The Cyanide Monograph

The Cyanide Monograph
SECOND EDITION
EDITED BY:
Terry I. Mudder, Ph.D.

and
Michael M. Botz, M.S., P.E.
MINING JOURNAL BOOKS LIMITED

LONDON
Preface
The Cyanide Monograph, Second Edition, is a collection of over 30 full-length technical papers
covering several aspects of cyanide and mining. These papers have been edited, and in some
cases revised and expanded, from their original form by Dr. Terry Mudder and Mr. Michael
Botz. Completion of this volume would not have been possible without the contributions of the
many authors indicated in the papers, and we greatly appreciate the time and effort of each of the
authors.
This volume has been divided into six sections to cover both broad and narrow issues associated
with the use of cyanide in mining. The first section provides a general perspective regarding the
use of cyanide in mining, a description of its environmental behaviour, and the analysis and
significance of low levels of cyanide in the environment. In the second section, the toxicological
properties of cyanide and its related compounds are examined with respect to humans and
wildlife. The third section addresses the important topic of cyanide recovery and recycling, a
practice which is becoming more widespread in the mining industry due to its many direct and
indirect advantages. Active and passive biological treatment of cyanide and its related
compounds are discussed in the fourth section, and several detailed case studies are presented in
this respect. The fifth section continues with a review of chemical and physical treatment
methods for the removal of cyanide and its related compounds, a topic which is of interest to
many of the mining operations utilizing cyanide. Finally, the sixth section concludes with an
examination of several mine closure aspects, particularly in regard to water management and
heap leach operations.
As with the first edition of this volume, the intention is to discuss many of the topics of concern
to mining professionals and those connected to the mining industry. While this work will serve
as a useful reference to many, it will not take the place of practical judgment and a willingness to
conceive, design, operate, monitor and close mine sites in a responsible manner. Those
individuals who do possess these characteristics will find this volume a useful companion.
Terry I. Mudder, Ph.D. Michael M. Botz, M.S., P.E.

Sheridan, Wyoming USA Joliet, Montana USA
June 2001
Second Edition
THE CYANIDE MONOGRAPH
TABLE OF CONTENTS
SECTION 1: CHEMISTRY, FATE AND ANALYSIS
Making Sense of Cyanide ........................................................................................................... 1

A Global Perspective of Cyanide .............................................................................................. 11
The Sources and Environmental Significance of Low Levels of Cyanide .................................. 27
Modeling of Natural Cyanide Attenuation in Tailings Impoundments ....................................... 45
SECTION 2: TOXICOLOGICAL PROPERTIES
The Ecotoxicological Properties of Cyanide.............................................................................. 63

Human Cyanide Toxicity .......................................................................................................... 99
Development of Site-Specific Discharge Criteria Through Toxicological Testing ................... 120
Site-Specific Aquatic Life Criteria for Weak Acid Dissociable Cyanide.................................. 130
Derivation of Aquatic Life Criteria for Total and Iron Cyanide ............................................... 150
Strategies and Standards for Control of Bird Mortality at Mining Operations.......................... 178
SECTION 3: RECOVERY AND REUSE
The Recovery of Cyanide from Slurries .................................................................................. 202

Cyanisorb Cyanide Recovery Process Design, Commissioning and Early Performance........... 241
Recovery of Cyanide from Mill Tailings ................................................................................. 265
Cyanide Recovery Applications for CCD Circuits................................................................... 299
Processes for the Recovery of Cyanide from Thiocyanate ....................................................... 307
i Mudder & Botz

Second Edition
THE CYANIDE MONOGRAPH
TABLE OF CONTENTS (Continued)
SECTION 4: ACTIVE AND PASSIVE BIOLOGICAL TREATMENT
Microbial Treatment of Industrial and Hazardous Wastes ....................................................... 326

The Homestake Wastewater Treatment Process: Part 1 ........................................................... 350
The Homestake Wastewater Treatment Process: Part 2 ........................................................... 365
Combined Aerobic and Anaerobic Biological Treatment of
Tailings Solution at the Nickel Plate Mine .............................................................................. 388
Introduction to the Biopass System: An Alternative Passive
Treatment Process for Closure of Spent Heap Leach Pads....................................................... 419
The Biopass System Phase I: Laboratory Evaluation............................................................... 441
The Biopass System Phase II: Full-Scale Design and Construction ......................................... 470
SECTION 5: CHEMICAL AND PHYSICAL TREATMENT
An Overview of Cyanide Treatment and Recovery Methods ................................................... 481

Mine Water Treatment with Activated Carbon ........................................................................ 501
Overview of Water Treatment Methods for Thiocyanate Removal .......................................... 509
Review of Mine Water Nitrate Removal Technologies............................................................ 518
Process Water Management and Treatment at the Golden Cross Mine .................................... 523
SECTION 6: HEAP LEACH DECOMMISSIONING AND CLOSURE
Closure Concepts .................................................................................................................... 543

Solution Management During Decommissioning of Heap Leach Operations ........................... 553
Solution Management and Closure Alternatives for Precious Metals Heap Leach Facilities .... 571
Geochemical Study of Leach Pad Cyanide Neutralization at
Brohm Mining Corporation, South Dakota.............................................................................. 589
ii Mudder & Botz

CHAPTER 1
Chemistry, fate and analysis
● Making sense of cyanide

● A global perspective of cyanide
● The sources and environmental significance of low
levels of cyanide
● Modeling of natural cyanide attenuation in tailings
impoundments
MAKING SENSE OF CYANIDE
Prepared By:
Terry Mudder, Ph.D.
Originally published as a booklet by The Gold Institute in August 1999
Reprinted with permission of The Gold Institute, 1112 16th Street N.W., Suite 240, Washington,
D.C. (USA) 20036
Making Sense of Cyanide
1.0 INTRODUCTION
Cyanide has been used in industry for over a century. Although cyanide is commonly thought of
as a deadly substance, it is nonetheless a widely used chemical essential to the modern world.
Public concern about cyanide is valid and understandable. Much of the media attention and
reaction from the public has arisen from the perception of a lack of scientific knowledge about
cyanide and/or erroneous reports of impacts on human health and the environment. Fear
frequently dictates our feelings in the absence of knowledge. Fear is often more marketable than
knowledge. Fear is routinely employed as a tool against unpopular ideas or entities. The fear of
cyanide is routinely employed as a tool against mining. Science and common sense are needed
to counter the effects of fear. Science provides facts, while common sense promotes familiarity.
The reality is that products generated from cyanide are in ever increasing demand around the
world. The reality is that the benefits of cyanide are many and its products are used safely each
day by hundreds of millions of people. The reality is that no substitutes are available for
cyanide. The reality is that the elimination of cyanide results in a much less desirable and safer
life style. The reality is that people in developed and emerging countries will not condone
lowering their standard of living. The reality is that we must live with cyanide and strive to
educate ourselves about it.
People do not, will not, and cannot live in a risk free environment. Risk free environments do
not exist and cannot be mandated or legislated. The purpose of this document is to disperse
technical information in a manner that alleviates fears about cyanide and provides an
understanding of the interrelationship between this chemical, people, and the environment. It’s
hoped that the information provided in this document will broaden the reader’s perspective about
the benefits of cyanide when used prudently and properly.
2.0 CYANIDE SOURCES AND USES
Cyanide was first used commercially in New Zealand over a century ago in the extraction and
recovery of gold and silver. Although chemical replacements for cyanide have been investigated
for decades, it remains the lixiviant of choice in the base and precious metals industry
worldwide. The superiority of cyanide to other chemicals is due to a combination of availability,
effectiveness, cost, and an ability to use it with acceptable risk to people and the environment.
About 80% of the world production cyanide is used annually in the production of organic
compounds such as nylon, plastics, and pharmaceuticals. A little less than 20% of the cyanide is
used in the mining industry. Elimination of gold and silver mining would not eliminate the need
for or use of cyanide.
2 T. Mudder
Cyanide originates from both manmade and natural sources. Ironically, cyanide has been
postulated by many scientists as the first organic compound on earth, from which the chemical
building blocks of life evolved. Cyanide is formed, excreted, and degraded naturally by
hundreds of animals, plants, insects, fungi, and bacteria. The levels of cyanide produced upon
digestion of certain plants can cause death in some animals and exceed limits for hazardous
wastes. Some of the plants include apricots, bean sprouts, cashews, cherries, corn, lentils,
potatoes, and soybeans.
We come in daily contact with cyanide and its derivatives through foods and products.
According to the 1981 USEPA cyanide exposure and risk assessment document and the 1995
U.S. Department of Health and Human Services cyanide toxicological profile, over 90% of the
cyanide released to the atmosphere in the U.S. originates from automobile exhaust. Over two-
thirds of the cyanide, entering surface waters is discharged from municipal sewage treatment
plants. As an anti-caking agent in road salt, as much or more cyanide can be released into the
environment during a single winter in a major northeastern city as is released annually from all
United States mining operations.
3.0 CYANIDE TOXICITY, EXPOSURE, AND RISK
Cyanide is generally considered a short-term or acute toxicant. Cyanide is neither carcinogenic,

mutagenic, tetratogenic, nor bioaccumulative. Cyanide is readily metabolized to thiocyanate.
The mechanisms and rates of cyanide toxicity have been identified and quantified for many
animals. There are many chemicals more toxic than cyanide. The relative toxicity of cyanide
can be illustrated by comparing it to that of chlorine, the main ingredient in common household
bleach. Chlorine is more widely used than cyanide and in larger quantities. Chlorine and its
derivatives are equally or more toxic than cyanide to people and aquatic life. There are chemical
alternatives to chlorine and none for cyanide. Based upon the reasoning used in support of a
recent ban on cyanide in the State of Montana, chlorine should be abandoned as a disinfectant for
public water supplies in the United States, regardless of the health implications.
The risk of accidental death due to cyanide exposure in the United States is quite rare and many
thousands of times less than the risk of either dying in a vehicle accident or from simply falling
down. Nearly all of the accidental and intentional fatalities resulting from cyanide exposure
have occurred in and around the home and not in the workplace. Based upon information from
both Canadian and U.S. federal health and safety agencies, there have been only three accidental
deaths this century in the North American mining industry possibly arising from cyanide
exposure. Two of the deaths occurred in Canada in 1952 and 1961 based upon records from the
Ontario Department of Labour. The third death occurred in Arizona at a small mining operation
in 1986 according to records kept by the U.S. Mine Health and Safety Administration.
In this case, a man, who worked with cyanide, became ill on the job. He was taken to a hospital
where he died some days later. The Emergency Medical Personnel did not administer a cyanide
antidote since there were no indications of cyanide poisoning. There was either no or conflicting
medical opinions and data regarding these fatalities, and no direct confirmation that cyanide was
the cause of death of any of the three individuals. Cyanide was used in the area in which each of
the facilities occurred, and was therefore speculated as the cause.
3 T. Mudder
The manufacture, transport, storage, use, and disposal of cyanide are strictly regulated in the
United States and can be managed safely. Countries throughout the world have stringent
standards and regulations limiting exposure of humans, livestock, wildlife, and aquatic
organisms to cyanide. There are severe civil and criminal penalties arising from the accidental
and intentional violation of these standards and regulations. Nonetheless, there are risks
associated with the use of cyanide, and accidents can and do occur. Not all countries regulate
cyanide to the same extent that it is in the United States. When environmental impacts due occur
from cyanide in less regulated countries such incidents are sometimes used in an attempt to
justify the need for more controls and legislation in the United States.
Mining operations in the United States continuously update and improve their environmental
monitoring, reporting, and compliance programs through internal and external training seminars
and audits. In response to concerns raised by the public and environmental community, mining
companies have promulgated environmental mission statements, guidelines, and/or codes of
ethics. No degree of legislation can eliminate completely risks or impacts to the environment. If
an accident does occur, mining companies in the United States have established rigorous
emergency response procedures.
Environmental impacts resulting from mining operations are often attributed to cyanide, whether
its involved or not. This situation arises from the perception that mining and cyanide are
synonymous or the desire to portray mining in a negative light. Such situations have arisen in
both the United States and in other countries. Cyanide has not been associated with long-term
environmental impacts at mining sites in the United States. The long-term environmental issues
of most concern are related to generation of acidic mine drainage, geo-technical stability, and
bonding.
One such situation was the failure of the tailings dam at the Los Frailes Mine in southern Spain
in April 1998. One U.S.-based environmental group stated in 1998 “while news reports of the
associated massive fish kill did not mention cyanide or related compounds in the wastes, their
presence seems likely given the nature of the metals extracted at this site”. Cyanide was not
being used at this zinc recovery operation. This type of speculation is completely unjustified and
creates unwarranted fear about cyanide. Such statements require verification of the facts, as well
as the reliability of their sources.
A similar situation involving a dam failure occurred at the Omai Gold Mine in Guyana in 1995
releasing about 3.2 million cubic meters of mine tailings to a local river. The tailings did contain
total cyanide at levels of 20-30 mg/l, about 80% of it being metal complexed. A technical
review team including members of the World Health Organization (WHO) was assembled on
behalf of the government. The principle concern with respect to cyanide was the protection of
aquatic life in and people along the Essequibo River.
4 T. Mudder
The WHO team reported no fish kills in this river and no cases of cyanide poisoning. The
concentration of cyanide did not exceed the drinking water standard in the river. The initial
release of tailings containing solids and cyanide directly into the smaller Omai River did produce
immediate impacts on aquatic life, causing the death of about 350 fish. Within a week following
the release, the total cyanide concentration in the Omai River was near detection. A month later,
fish were seen in the Omai River near the point of release of the tailings. The longer-term
impacts to the Omai River were the result of deposited tailings, which were subsequently
removed. There was no evidence of any impact to aquatic life in the Essequibo River. At no
time did cyanide reach levels in this river that were a serious threat to human life. The exposure
to cyanide was transient and no persistent toxic effects were noted in aquatic life, people, or
livestock.
Two situations that have arisen in the United States include the Summitville Gold Mine in
Colorado and the Zortman-Landusky Gold Mines in Montana. It has been assumed that the
environmental impacts at these mines were associated primarily with cyanide. Both mines used
cyanide in the recovery of gold and silver. Although minor spills of cyanide did occur at these
sites during operations, they were not responsible for the most severe long-term environmental
impacts to local surface waters and fisheries, according to the State regulatory agencies
overseeing these mines. The most severe environmental damage and ongoing long-term impacts
were caused by the release of acid-and-metal containing drainage from waste rock dumps and/or
historic mine portals.
In May 1998 at the Homestake Mine located in the Black Hills of South Dakota several tonnes of
cyanide containing tailings were accidentally released into a local stream. The results of an
ongoing in-stream bio-monitoring program required and approved by the State regulatory
agencies have shown that the fish and aquatic insects in the stream have nearly recovered in a
year without additional stocking. In contrast to a common belief that cyanide is persistent in the
environment for many years, such a rapid recovery demonstrates that cyanide does not result in
long-term environmental impacts.
Another situation occurred in the Kyrgyz Republic in the former Soviet Union in May 1998. In
this case, a truck carrying about 20 tonnes of cyanide to the Kumtor Mine left the road, releasing
about two tonnes of its cargo into a local stream. The cyanide was transported in solid form but
not in sealed steel containers, as is the usual case in the United States. Several thousand people
living in two downstream villages were understandably frightened and potentially exposed to
cyanide.
5 T. Mudder
A commission was formed of a team of experts including members of Natural Resources Canada
and Health Canada that visited the site. The commission investigated the short and long-term
impact of the cyanide spill on air, water, soil, vegetables, plants, fish, and milk. The commission
concluded that the cyanide levels in air were below occupational and industrial hygiene
guidelines. There was no exposure to cyanogen chloride. The cyanide levels in the soils did not
reach levels harmful to humans or animals. No carcinogenic, tetratogenic, mutagenic,
reproductive, neurotoxicological, or long-term effects were expected. Within the first 48 hours,
up to sixteen people reported to the hospital that could have been exposed to cyanide. No
medical evidence was provided confirming that cyanide exposure had occurred. No confirmed
deaths due to cyanide exposure occurred within the first 72 hours. With a few days, fish were
again seen in the river near the site of the spill.
This regrettable and avoidable accident was used to prompt calls for stricter regulations of
cyanide worldwide. However, this accident involved human error. The transportation
regulations in this particular situation were recommended for review with respect to the cyanide
packaging and containment used in transportation.
The regulations and requirements for cyanide in the United States are stringent and effective, as
evidenced by the hundreds of millions of tonnes of cyanide that have been safely used in the
United States with no major environmental incidents. Direct comparisons between countries
exhibiting different regulatory processes and requirements must be conducted carefully in a
realistic manner to avoid misconceptions and unjustified conclusions.
These situations illustrate the need to factually understand the sources and causes of
environmental impacts at mine sites. Although cyanide may be responsible for adverse impacts
at a particular mine site, relentless emphasis on it can be misleading and divert attention from
more important long-term environmental issues. No short or long-term physiological impacts to
humans occurred as the result of the cyanide related incidents discussed. There were no
indications that the cyanide related compounds were responsible for any short or long-term
environmental impacts at any of these sites. These situations and incidents illustrate that major
environmental impacts can and do occur as the result of mining.
However, these impacts are rarely the result of cyanide and are often unjustifiably blamed on
cyanide. When impacts from cyanide do arise, the effects are transient and the recovery of the
environment occurs in a short period. We must focus our efforts on the most common causes of
environmental impacts from mining to create an even safer industry.
Every effort must be made to avoid such incidents involving cyanide or any other widely used
and potentially toxic chemical. Safety is the number one priority at mining operations in the
United States with ongoing awareness and training programs. No level of legislation will
eliminate the risks associated with cyanide. When incidents do occur, the causes and sources
must be identified and corrective action taken.
6 T. Mudder
In the United States shipments of cyanide are accompanied by Material Safety Data Sheets
(MSDS) that provide the chemistry and toxicity data, instructions in case of accidents,
emergency telephone numbers for assistance, and other information from the manufacturer.
Shipments of cyanide are inventoried and checked against delivery records to ensure proper and
continuous surveillance. Personnel using cyanide are trained in workplace safety, medical
response, and the use of cyanide antidotes.
The environmental fate of cyanide and its related compounds have been widely studied and
documented in surface and ground water, soils, and the atmosphere. Because of the many
reactions and transformations that it undergoes naturally, cyanide does not persist in the
environment. Hundreds of literature publications and reference texts are available regarding all
aspects of cyanide and its related compounds. Some of the older publications were general in
nature, while newer publications provide quantitative information regarding cyanide and its
impacts on and fate in the environment. It is important to review and reference the newer
documents to provide the most accurate and current information about cyanide, otherwise
speculative statements supported with out-of-date information can once again create unjustifiable
fears in the public.
Considering the global usage of cyanide, the environmental impacts associated with it have been
minor when compared with other chemicals. Cyanide has been used safely around the world for
many decades. Its chemistry, analysis, environmental fate, handling, use, and treatment are well
understood. There are no suitable substitutes for cyanide. At present, the only alternative to
using cyanide is its elimination, along with the products arising from it. Although research
should continue regarding any chemical, there is no environmental or economic justification for
eliminating cyanide.
4.0 CYANIDE CHEMISTRY, ANALYSIS, AND TREATMENT
There are several forms of cyanide potentially present in mine process solutions. Related to
cyanide are additional compounds formed through interactions with the ore, water treatment, and
natural attenuation. These compounds include ammonia, cyanate, nitrate, and thiocyanate. In
the rate case in which alkaline chlorination is used for cyanide destruction at a mining operation,
chloramines can also form as a reaction by-product. The forms of cyanide most often discussed
from a monitoring and compliance standpoint include free, weak acid dissociable (WAD), total,
and amenable to chlorination. Analytically, the “toxicologically significant” or ecologically
important” forms of cyanide are differentiated most accurately from the others by the WAD
cyanide procedure. This procedure is widely used by industry and regulatory agencies for
compliance and monitoring purposes.
7 T. Mudder
The WAD analytical procedure measures free and the weakly metal complexed forms of
cyanide. Subtraction of the WAD cyanide value from the total cyanide value obtained from a
split sample provides a measure of, the essentially non-toxic and stable, iron cyanide levels
present. In theory, the WAD and cyanide amenable to chlorination (CATC) procedures should
yield nearly identical results, since these two methods report the same forms of free and metal
complexed cyanide. Over the years, the CATC method has been replaced almost completely by
the more reliable WAD procedure for toxicological testing, compliance, and monitoring
purposes. If applied and conducted properly, the total and WAD cyanide procedures produce
reliable and meaningful results. The sensitivity of these methods is sufficient to quantify levels
of cyanide that could be harmful to people and the environment.
Problems arise when these analytical methods are extended beyond their capabilities in an
attempt to quantify cyanide at levels approaching a detection limit and below which
environmental impacts would occur. The environmental significance of low levels of cyanide in
surface waters has been a concern to industry, commercial laboratories, and regulatory agencies
for many years. Although these levels are lower than those typically associated with adverse
impacts to people or the environment, there remains an ongoing concern with regulatory
agencies and the public as to the meaningfulness of these levels of cyanide and their sources.
Unfortunately, too much emphasis is placed upon the significance of these often unreliable low
values of cyanide when they are reported in surface and ground waters.
In order to protect the environment and people, reasonable levels of protection should be
provided through promulgation of standards that not only protect designated beneficial uses, but
also can be achieved through treatment and analyzed accurately using approved methods. There
is a need for consensus among industry, State and federal regulatory agencies, and commercial
laboratories regarding the most appropriate cyanide analytical procedures and their applicability.
The USEPA has initiated an internal long-term investigation and evaluation of cyanide analytical
techniques, in hopes of resolving long-standing uncertainties surrounding these measurements.
The technical data are available with which to make informed decisions about protection of
human health and the environment.
It is imperative that the interpretation of cyanide data be tempered with an understanding of the
reality of the problems associated with its analysis and the need to quantify cyanide levels below
which no measurable impacts are occurring. Over the years, commercial chemical laboratories
have lowered their reporting and detection limits for WAD and total cyanide from the original or
traditional level of 0.02 mg/l to lower than 0.005 mg/l in many instances.
The gradual lowering of these limits has come in spite of the fact that the analytical procedures,
reagents, and instrumentation have remained essentially the same, as has the inherent error in its
accuracy and precision. In large part, the lowering of detection and reporting limits has resulted
from regulatory mandates and competitive marketing without the necessary scientific
justification or rationale. This trend has contributed to the frequent misinterpretation of low
level cyanide data generated by commercial laboratories and reported to government agencies for
monitoring and compliance purposes. The result is the creation of needless fear that manmade
contamination and impacts from cyanide have occurred, when indeed they have not.
8 T. Mudder
Cyanide in its various forms is monitored frequently at multiple locations within various
solutions and natural waters in and around mining sites. The analytical data is reported on a
regular basis to both State and federal regulatory agencies and is available to the public. The
analytical procedures for WAD and total cyanide are accurate and reliable at levels protective of
people and the environment. The USEPA has recently promulgated a new method for the
analysis of very low levels of free cyanide.
There are robust and reliable chemical, physical, and biological technologies for the removal of
cyanide and its related compounds operating at dozens of mining operations throughout the
world. These processes either alone or in combination are capable of achieving effluent levels
protective of the environment.
The recovery of cyanide is again being accomplished at mining operations around the world,
through application of the modern Cyanisorb Process. Cyanisorb is a commercial process that
allows the recovery of over 90% of the cyanide used as at a mining operation for recycle and
reuse, thereby avoiding many of the potential environmental problems. Cyanide treatment and
recovery facilities have been operating successfully for many years with no measurable
environmental impacts. Modern cyanide recovery plants have been or are operating in
Argentina, Brazil, New Zealand, and the United States.
5.0 CYANIDE RELATED COMPOUNDS
There are several compounds routinely found in process solutions related to cyanide in some
chemical manner. These compounds include ammonia, cyanate, nitrate, and thiocyanate. In a
rare instance in which alkaline chlorination is used for cyanide destruction, residual chloramines
could be present in an effluent. Cyanogen chloride is formed as a transient intermediate during
alkaline chlorination. It exists in solution for a very short time, due to the elevated pH used in
this cyanide destruction process. The potential release of cyanogen chloride to the atmosphere
during alkaline chlorination has not created a major human health or environmental issue.
Reliable and accurate analytical methods are available for all of these compounds at levels that
are environmentally meaningful. In the case of cyanide, ammonia, nitrate, and chloramines, the
USEPA has extensively reviewed their toxicity and issued ambient water quality criteria
documents. Regulatory agencies have promulgated surface and ground water standards for these
compounds for protection people and the environment.
Awareness of the presence of cyanate and thiocyanate in process solutions originally grew out of
research conducted by Environment Canada and the Canadian mining industry many years ago.
There are many literature references and documents addressing the toxicity of these compounds
to various organisms. The mechanisms of cyanate and thiocyanate formation and degradation
are well understood and have been modeled and quantified. The mechanism of cyanide
detoxification involves conversion to thiocyanate. Although many research organizations and
government agencies have investigated the toxicity of cyanate and thiocyanate to various
organisms, no standards have been promulgated due to their inherently low toxicity and the lack
of documented impacts to people or the environment.
9 T. Mudder
In the early 1990’s, serious concerns arose regarding the impacts on wildlife and waterfowl in
contact with process solutions stored in tailings impoundments. The primary concern was
cyanide. Lowering of the WAD cyanide to below 50 mg/l has resolved this environmental
problem although residual concentrations of ammonia, cyanate, nitrate, and thiocyanate
remained in solution without treatment. A similar standard for WAD cyanide and protection of
migratory birds and waterfowl has been adopted at mining operations in other countries.
The published and documented acute toxicities of cyanate and thiocyanate for various organisms
indicate they are several hundred to over a thousand fold less toxic than cyanide. The average
concentrations of these compounds in process solutions are below levels considered harmful to
humans or the environment.
Access to process solutions containing cyanate and thiocyanate is limited at mine sites using
institutional controls and physical restrictions. The potential for exposure to these chemicals is
low, when compared to other industrial and domestic settings. These two compounds are less
toxic and less dangerous than many of the chemical ingredients in common household products
we are exposed to each day, such as cleansers, insect repellents, spray paints, and weed killers.
The low relative risk associated with cyanate and thiocyanate compared with other industrial and
household chemicals is borne out in the statistics reported annually by poison control centers in
the United States.
In the rare situation in which one or more of these constituents are determined to be a potential
cause or source of an environmental impact on people or wildlife, treatment processes are
available to lower their concentrations to acceptable levels. If treated discharges containing
these compounds enter the environment, State and federal regulatory agencies require bioassays
using sensitive organisms and in-stream bio-monitoring programs to quantify the overall toxicity
of the effluent and to ensure that adverse impacts do not occur.
Additional monitoring and oversight by the public or government agencies is not warranted on
the basis of the number and degree of impacts resulting from exposure to the cyanide related
compounds of cyanate and thiocyanate. Additional scrutiny or regulations will eliminate the
risks associated with human error.
The other cyanide related compounds have been well characterized and are strictly regulated.
The key to limiting impacts to cyanide is to continue on-site training of employees and off-site
education of the public. The key to limiting environmental impacts of mining is to focus upon
their actual and not perceived sources and causes.
Although cyanide can be toxic to humans and produce adverse effects on the environment, our
knowledge of cyanide and its related compounds is sufficient to use it safely. Unfortunately
accidents resulting from human error have and will continue to infrequently occur. However, the
overall safely and environmental record associated with cyanide is excellent, when compared
with other industrial chemicals. Clearly, the benefits of cyanide outweigh its detriments and our
society and lives would be adversely impacted without it and its products.
10 T. Mudder
A GLOBAL PERSPECTIVE OF CYANIDE
Prepared By:
Terry Mudder, Ph.D.

Mike Botz, M.S., P.E.
Originally published in Proceedings of the 2001 SME Annual Meeting and Exhibit, Denver,
Colorado, February 26-28, 2001
Reprinted with permission of The Society for Mining, Metallurgy, and Exploration, Inc. (SME),
8307 Shaffer Parkway, Littleton, Colorado (USA) 80127-5002
A Global Perspective of Cyanide
ABSTRACT
There are currently more that 460 mines worldwide that utilize cyanide for gold and silver
extraction. Despite this large number of cyanide-related mining operations, there have been no
published accounts during the previous 25 years of the death of humans due to cyanide as a
direct consequence of major mining-related environmental incidents. All published accounts of
human deaths due to mining-related environmental incidents have been the result of physical
inundation with tailings or waste rock materials. It appears that major mining-related
environmental incidents have not been concentrated in any geographic location, are likely to
occur regardless of the size of the mining company and do not occur more frequently with a
specific type of mining activity. Several cyanide treatment and recovery technologies have been
widely demonstrated to reliably control cyanide levels in mining solutions. With proper use of
these technologies, tailings cyanide concentrations can be maintained at levels protective of
wildlife while reducing the potential for adverse environmental incidents. The development of
an international cyanide code of practice or management plan is recommended and should take
into consideration the adoption of a weak-acid-dissociable (WAD) cyanide standard that
maintains the levels entering a tailings impoundment below 50 mg/L.
1.0 HISTORY, SOURCES AND USES OF CYANIDE
Since its commercial introduction in New Zealand over a century ago, cyanide has been used
worldwide in the extraction of gold and silver. Although chemical replacements for cyanide
have been investigated for decades, it remains the exclusive lixiviant of choice due to a
combination of availability, effectiveness, economics, and an ability to use it with acceptable risk
to humans and the environment. Currently, there are about 875 gold and silver operations in the
world, of which about 460 utilize cyanide. On shown on Figure 1, the gold and silver mines are
found throughout the world. Although confidence in and trust of the mining industry has been
declining, nonetheless the demand for metals, minerals, and other raw materials continues to
steadily rise throughout the world.
As shown on Figure 2, about three 1.4 million tonnes of hydrogen cyanide are produced annually
worldwide, of which only about 13% is converted into sodium cyanide and used for the
extraction of gold and silver. The remaining 87% of the hydrogen cyanide is used in the
production of a wide range of items such as adhesives, computer electronics, fire retardants,
cosmetics, dyes, nylon, paints, pharmaceuticals, Plexiglas, rocket propellant, and road and table
salts.
The benefits of cyanide are many and its products are used safely by hundreds of millions of
people worldwide everyday. The elimination of gold and silver mining would not eliminate the
risks associated with cyanide or mining, but would negatively affect the lives of many people.
12 T. Mudder & M. Botz

Canada
Australia & 9%
South Pacific United States
26% 16%
Asia
7% Latin America
13%
Europe
2%
Africa
27%
Figure 1. Distribution of World Mines That Use Cyanide
Used By
Mining
13%
Used By
Other
Industries
87%
Figure 2. Industrial Uses of Hydrogen Cyanide

Cyanide originates from both manmade and natural sources. Ironically, many scientists have
postulated cyanide as the first organic compound on earth, from which the chemical building
blocks of life evolved. Cyanide is formed, excreted, and degraded naturally by thousands of
animals, plants, insects, fungi, and bacteria. The levels of cyanide potentially produced and
released upon digestion or cooking of cyanogenic plants can reach hundreds of parts per million.
Ingestion of these plants can cause death in animals and chronic poisoning in humans. Some of
the cyanide producing plants include almonds, apricots, bamboo, bean sprouts, cassava, cashews,
cherries, lentils, olives, potatoes, sorghum, and soybeans.
2.0 THE RISK AND EXPOSURE OF CYANIDE TO HUMANS
Public concern regarding the safety and environmental aspects of cyanide is valid and
understandable, considering its historical uses and several recent mining incidents which have
involved cyanide. In spite of these concerns, cyanide remains vital to a large number of
industries and is handled in a safe and environmentally sound manner at hundred of sites
worldwide.
Nonetheless, cyanide is potentially toxic, and like most chemicals, if it is mishandled or misused
can result in severe impacts to humans and the environment. Humans at work and at home come
in daily contact with cyanide and its derivatives through foods we eat and products we use. In
addition to mining, there are dozens of other occupations in which workers come in frequent
contact with cyanide. Although potential worker exposure to cyanide is comparatively high in
the mining industry, there have been only a few purported accidental deaths worldwide over the
last century. In the United States, there are a few accidental deaths each year due to cyanide
exposure, nearly all of which are the result of accidents and intentional suicides in the home.
Accidental death due to cyanide exposure within the general population is very low, and
thousands of times less than the risk of either dying in a vehicle mishap, from drowning, or from
simply falling down. The risk of dying from cyanide exposure is less than that of being struck
by lighting. The highest exposures of the general population to cyanide in the United States arise
from automobile exhaust and cigarette smoking. Most of the cyanide and related compounds
entering surface waters originates in effluents from municipal sewage treatment plants. It has
been estimated that more cyanide enters surface waters in the United States annually as an anti-
caking agent in road salt than from the entire mining industry. The best-known example of
human cyanide poisoning from a natural source involves the ingestion of cyanogenic plants and
particularly cassava in several countries of Africa.
Although the record regarding cyanide use has been exemplary and stringent safeguards and
standards exist regulating its manufacture, transport, storage, use, and disposal, nonetheless
accidents involving cyanide do occur, sometimes with severe impacts. However, reductions in
the number of incidents and resultant impacts are possible, with the first steps involving a change
in attitude and an increase in awareness. Along with attitude and awareness, come the
realization and acceptance of the fact that no level of regulation has eliminated all risk from our
daily lives.

3.0 THE TOXICIY OF CYANIDE TO WILDLIFE
Other than humans, there are three basic groups of animals, which are of concern with respect to
cyanide exposure. The first group includes the terrestrial animals like mammals, reptiles, and
amphibians. The second group involves migratory birds and waterfowl, while the third group
involves aquatic life forms. With respect to the first group, adverse impacts to terrestrial animals
resulting from exposure to cyanide solutions at precious metals operations have been limited, due
to the proximity to human activities and implementation of exclusion techniques.
In 1991, the United States General Accounting Office (GAO) conducted a study of 119 active
precious metal operations using cyanide in Arizona, California, and Nevada. A total of 31
inadvertent releases of cyanide were reported in generally remote and arid areas. The GAO
concluded that the impacts resulting from these releases were not serious and that from a
regulatory standpoint, appropriate containment designs and engineering standards are available
to protect terrestrial animals. In contrast, the United States National Response Center, which
provides a nationwide emergency service for reporting of chemical spills, handled nearly 30,000
incidents in 1999.
Of equal or greater environmental concern is the exposure of domestic and wild animals to
cyanogenic plants and to cyanide containing devices placed in the ground and used to control
nuisance predators, like the coyote. Decades ago, the United States Department of Agriculture
issued a pamphlet to farmers and ranchers regarding the dangers of their livestock ingesting
cyanogenic plants.
With respect to migratory birds and other waterfowl, the primary concern has been exposure of
these animals to open solution ponds and tailings impoundments containing elevated cyanide
levels. This issue was of serious concern during early part of the last decade, particularly in
North America and Australia. Through a cooperative effort between industry and government,
this environmental concern has been virtually eliminated either by covering smaller process
ponds with nets or floating balls, or by lowering the weak acid dissociable (WAD) cyanide levels
entering large tailings impoundments. The WAD cyanide contained in tailings slurries
discharged into impoundments can be destroyed through treatment or recovered and reused. A
level of 50 mg/l WAD cyanide in the tailings slurry entering an impoundment has been
extensively used as a regulatory guideline providing protection of animals coming in contact
with the stored solution. In practice, the resultant WAD cyanide level is reduced well below 50
mg/l within the tailings pond due to ongoing natural attenuation.

The most vulnerable component of the ecosystem to potential adverse impacts from exposure to
cyanide is aquatic life. Aquatic organisms are generally the most sensitive to the toxicological
effects of cyanide and cannot physically avoid it upon entering their environment. The primary
issue relating to exposure of aquatic life arises from the inadvertent release of untreated process
solutions containing elevated levels of cyanide into nearby surface waters. In general, elevated
and acutely toxic levels of cyanide are associated exclusively with the extraction of gold and
silver, since only very low concentrations of cyanide are sometimes used in the beneficiation of
base metals as a floatation reagent. The problem does not extend to excess tailings solutions that
have been treated prior to discharge. There are excellent examples of treated process solutions
arising from gold and silver operations being discharged into sensitive aquatic ecosystems for
many years without adverse environmental impacts.
4.0 CYANIDE CHEMISTRY, ANALYSIS AND TREATMENT
There are several forms of cyanide potentially present in process solutions associated with the
extraction of gold and silver. Related to cyanide are additional compounds formed through
interactions with the ore, water treatment, and natural attenuation. Historically, the forms of
cyanide most frequently discussed included free, weak acid dissociable (WAD), total, and
amenable to chlorination (CAC). Over the years, the WAD analytical procedure has been
adopted by industry and the regulatory authorities for measurement of the “toxicological
significant” or “ecologically sensitive” forms of cyanide. The WAD analytical procedure
measures free and weakly complexed forms of cyanide. Subtraction of the WAD cyanide value
from the total cyanide value provides a measure of the essentially non-toxic and stable iron
cyanide level present. Applied and conducted properly, the total and WAD cyanide procedures
produce reliable and meaningful results that can be used for compliance and monitoring
purposes. The sensitivity of these methods is sufficient to quantify the forms and levels of
cyanide that could be harmful to humans and the environment.
Problems arise when these analytical methods are extended beyond their capabilities in an
attempt to quantify cyanide at levels approaching detection and below which environmental
impacts occur. Unwarranted concern and emphasis is placed upon the significance of unreliably
low values of cyanide. In order to protect humans and the environment, reasonable levels of
protection can be provided through promulgation of standards that not only protect designated
uses of surface and ground water, but also can be achieved through treatment and analyzed
accurately using approved methods. There is a need for consensus amongst industry,
governmental agencies, and commercial laboratories regarding the most appropriate cyanide
analytical procedures and their applicability.
It is imperative that the interpretation of cyanide data be tempered with an understanding of the
reality of the problems associated with its analysis at levels below which no measurable impacts
are occurring. Appropriate criteria and standards can be promulgated for weak acid dissociable
(WAD) limits that are both quantifiable and protective of humans and the environment.

There are robust and reliable chemical, physical, and biological technologies for removal of
cyanide and its related compounds operating at dozens of mining operations throughout the
world. These processes alone or in combination are capable of achieving effluent levels
protective of the environment. In general, there are four chemical oxidation technologies that are
currently being used to destroy cyanide. These technologies include copper catalyzed hydrogen
peroxide, Caro’s acid, the sulfur dioxide/air process, and alkaline or breakpoint chlorination.
These processes have used in full-scale applications throughout the world for decades. In the
event a higher quality effluent is needed than can be produced by one of the chemical oxidation
technologies, advanced treatment in the form of granular activated carbon can be employed as a
polishing process. Cyanide has been successfully treated passively and actively using a variety
of aerobic and anaerobic biological treatment processes. As a substitute to cyanide destruction,
the recovery of cyanide is again being accomplished at mining operations throughout the world.
In this process, about 90% of the WAD cyanide can be recycled through recovery and reuse in
the metallurgical process. There are many distinct environmental advantages including a
lowering of transportation risks and the potential for contamination of groundwater beneath
tailings impoundments.
The success of these processes has demonstrated that cyanide-containing solutions can be treated
and discharged into the environment safely and on a continuous basis. The use of treatment
facilities and discharge of effluent to maintain site and operational water balances is preferable to
attempting to maintain a “zero water balance” with no provision for treatment under extreme
climatologic conditions. Incorporating the ability to treat and discharge solution safely into the
environment should be encouraged in the initial stages of mine development and design. Many
of the major environmental incidents that occur at gold and silver operations have involved the
inadvertent release of tailings solutions and slurries containing elevated cyanide concentrations
into nearby surface waters. The major result of these releases of cyanide was the acute or short-
term toxicological impacts to aquatic life.
The scientific knowledge regarding the chemistry, analysis, environmental fate, toxicity, and
treatment of cyanide has increased dramatically over the last two decades. Although cyanide can
be toxic to humans and produce adverse effects on the environment, this knowledge of cyanide
and its related compounds is of sufficient depth to use it safely. Unfortunately, accidents
resulting from human error have and will continue to infrequently occur. The key to limiting
environmental impacts from cyanide and mining is to focus on the actual and not perceived
sources and causes.

5.0 ENVIRONMENTAL INCIDENTS RELATED TO CYANIDE AND MINING
Environmental incidents due to mining operations are often attributed to cyanide, whether it is
involved or not. This situation arises from the perception that mining and cyanide are
synonymous, or a simple desire to portray mining in a negative light.
Cyanide is not generally associated with long-term environmental impacts. The impacts of
cyanide are usually acute or short-term in nature, lasting on the order of hours to days. In
contrast, long-term environmental impacts from mine sites are generally associated with the
release tailings slurries, which once deposited in and along surface waters may be susceptible to
oxidation and the slow release of acidic and metals containing drainage. The long-term
environmental concerns may often evolve into economic issues associated with the financial
surety and stability of the mining companies themselves.
To begin a discussion regarding development of a global code of practice for cyanide

management, a review of the major environmental incidents associated with mining and their
underlying causes is appropriate. A summary of major environmental incidents associated with
all types of mining operations worldwide during the part 25 years is presented in Table 1. The
information in Table 1 was taken from a variety of published sources. This review was not
intended to be completely comprehensive and was somewhat skewed due to differences in
reporting requirements of such incidents in different nations. A major incident was defined as
one involving a release of several thousand cubic meters or more of tailings slurry or solution, or
a release of sodium cyanide, with resultant impacts to humans and ecological systems, in
particular aquatic life.
As indicated, there have been more than 30 major incidents over last 25 years, or about one
incident per year. These incidents have involved junior, intermediate, and large mining
companies. As shown in Figure 3, the incidents have occurred throughout the world and have
involved transportation accidents, pipe failures, and tailings dam related causes.
The tailings dam related causes, which accounted for the majority environmental incidents, have
included overtoppings, and geotechnical failures due to design/construction flaws and
earthquakes. Based upon the antidotal information associated with these incidents, the release of
cyanide has not been directly responsible for any of the human fatalities. It appeared that human
fatalities have been the result of physical inundation by the tailings themselves, such as washing
away of homes. The major environmental impacts of cyanide have been associated with short-
term effects leading to injury and mortality of aquatic life.
A more detailed examination of the environmental incidents related strictly to gold and silver
mining operations is presented in Figure 4. As with all mining- related environmental incidents,
they have been distributed throughout the world with the major causes having been related to a
water management or engineering/construction aspect of tailings dams. The percentage of
incidents related to transportation has been slightly higher for the gold and silver operations than
mining in general. In both of the transportation related incidents, non-traditional methods were
employed to transport the cyanide to the mining operation.


By Location By Cause
Africa Transport
6% North Pipe Failure Accident
Asia 18% 6%
America
9%
28%
Australia &
South Pacific
24% Latin America
15% Dam Mishap
Europe 76%
18%
By Mine Type Involving Cyanide
Unknown
Other 9% Cyanide
15% Present
Precious 27%
Metals
43%
Base Metals Cyanide Not

42% Present
64%
Figure 3. Summary of Major Mining-Related Environmental Incidents Since 1975

By Location By Cause
Africa North Pipe Failure Transport
14% America Accident
14%
21% 14%
Asia Latin America
14% 7%
Europe
7%
Australia &
South Pacific Dam Mishap
37% 72%
Figure 4. Summary of Major Mining-Related Environmental Incidents Since 1975 in the Gold Industry

As is discussed in the next section, adherence to the many codes of practice and management
plans that exist for cyanide throughout the world could reduce a portion of the incidents that have
occurred. One specific area not addressed in the various codes and management plant relates to
the levels of cyanide allowed in tailings impoundments. The lowering of WAD cyanide levels in
tailings impoundments could dramatically reduce the risk of adverse short-term impacts to
aquatic life. With respect to environmental impacts, aquatic organisms are the most frequently
affected component of the ecological system. A recommended target level of less than 50 mg/l
WAD cyanide for tailings slurries entering impoundments would not only protect wildlife but
also lower the risk of adverse impacts to the environment in the event of an inadvertent release.
A comparison of the recent environmental incidents related to the tailings dam failures in Spain,
Guyana, and Romania provides additional insight into this issue. The large dam failure in Spain
did not involve cyanide, although severe short-term and potentially long-term impacts to humans
and the environment occurred. In this incident, a large release of tailings entered a large river
system. In the case of the dam failure in Romania, a large release of tailings containing elevated
cyanide levels entered a major river system resulting in severe impacts to aquatic life hundreds
of kilometers downstream. In contrast in Guyana, release of a large quantity of tailings into a
small stream resulted in significantly less impacts to aquatic life due to the much lower WAD
cyanide levels.
From the information available regarding major mining related environmental incidents, a
dramatic reduction in the risk of short-term adverse impacts could realized by lowering WAD
cyanide levels to below 50 mg/l prior to discharge into a tailings impoundment. However, in
order to achieve a major reduction in impacts resulting from mining operations, there must be
increased emphasis on water management practices and tailings dam safety.
6.0 CYANIDE REGULATIONS, MANAGEMENT AND CODES
The manufacture, transport, storage, use, and disposal of cyanide can be managed safely and are
strictly regulated in many countries worldwide. Countries throughout the world have stringent
narrative and numerical standards and criteria limiting exposure of humans, livestock, wildlife,
and aquatic organisms to cyanide. Many countries have severe civil and criminal penalties
arising from the accidental and intentional violation of these standards and regulations.
Nonetheless, there are risks associated with the use of cyanide, and accidents do occur. Not all
countries regulate cyanide to the same degree. When environmental impacts do occur from
cyanide in less regulated countries, these incidents are sometimes exploited in an attempt to
justify the need for more controls and legislation worldwide, when adoption, acceptance,
implementation, and enforcement of existing regulations, standards, codes of practice, and
management plans are the solution.

The mining of metals and minerals has become and will remain a global industry with companies
operating on six continents. In order to remain a sustainable industry worldwide, mining
companies in association with governments, environmental organizations, and other stakeholders
and stockholders must adopt an attitude and code of practice toward environmental stewardship
that incorporates the concepts of transparency and verification. Many mining companies and
operations worldwide are continuously updating and improving their environmental monitoring,
reporting, and compliance programs through internal and external employee training and audits.
In response to concerns raised by the public, mining companies have instituted environmental
mission statements, guidelines, and codes of ethics. However, no degree of legislation can
eliminate completely risks or impacts to the environment. If an accident occurs, responsible
mining companies have established rigorous emergency response procedures.
There are both general and specific codes of practice and management plans that have been
developed for cyanide around the world. The goal should not be to create more regulations but
to utilize the operational experience and technical expertise associated with the various cyanide
management and codes of practice to formulate a single unified document for global application.
Adherence to that code and management plan is essential and requires acceptance of an alliance
and association of many stakeholders and stockholders. This experience and expertise can be
combined with a wealth of new scientific information to produce a consensus for cyanide
management in the precious metal mining industry.
7.0 CONCLUDING REMARKS
There are currently more that 460 mines worldwide which utilize cyanide for gold and silver
extraction. Despite this large number of cyanide-related mining operations, there have been no
published accounts during the previous 25 years of the death of humans due to cyanide as a
direct consequence of major mining-related environmental incidents. All published accounts of
human deaths due to mining-related environmental incidents have been the result of physical
inundation with tailings materials.
It appears that major mining-related environmental incidents have not been concentrated in any
geographic location, are likely to occur regardless of the size of the company and do not occur
more frequently with a specific type of mining activity. Furthermore, most major incidents have
been the result of some sort of dam overtopping, breaching, geotechnical failure, or earthquake.
The banning of cyanide from mining will not eliminate the risk of environmental impacts due to
mining.
Several cyanide treatment and recovery technologies have been widely demonstrated to reliably
control cyanide levels in mining solutions. With proper use of these technologies, tailings
cyanide concentrations can be maintained at levels protective of wildlife while reducing the
potential for severe environmental incidents.

The development of a code of practice or management plan should take into consideration
adoption of a WAD cyanide standard that maintains the levels entering an impoundment below
50 mg/l. In conjunction with lowering of the WAD cyanide levels, further review of dam design
and water management practices should be undertaken.
8.0 ACKNOWLEDGMENT
The assistance of Mr. Steven Vick in providing geotechnical information for this publication is
gratefully appreciated.
9.0 BIBLIOGRAPHY
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THE SOURCES AND ENVIRONMENTAL SIGNIFICANCE
OF LOW LEVELS OF CYANIDE
Prepared By:
Terry Mudder, Ph.D.
Originally published by Mining Journal Books in The Cyanide Monograph, First Edition, Mining
Journal Books Limited, London, England, United Kingdom, June, 1998
The Sources and Environmental Significance of Low Levels of Cyanide
1.0 BACKGROUND INFORMATION
The environmental significance of low levels of total and weak acid dissociable (WAD) cyanide
has been a concern to industry, commercial laboratories, and regulatory agencies for nearly two
decades. The concerns arise from the inability to confirm the presence or absence of low levels of
reported cyanide in its various forms and to verify the sources of the cyanide being either manmade
and/or natural.
For purposes of this discussion, low levels of total cyanide are those below about 0.10 mg/l and for
WAD cyanide levels below about 0.05 mg/l. Although these particular levels are lower than those
typically associated with adverse impacts to either humans or aquatic life, there remains an
ongoing concern with the regulatory agencies and regulatory communities as to the
meaningfulness of these levels of cyanide and their potential sources. Unfortunately, too much
emphasis is placed upon the significance and reliability of these low levels of cyanide when they
are reported in the analysis of surface or groundwater. In order to protect the environment and
human health, efforts should be directed toward establishing reasonable levels of safety through
promulgation of standards that can not only be achieved through treatment, but also analyzed
accurately.
There are three possible scientific explanations for the appearance of low levels of total and WAD
cyanide in surface waters of treated effluents. The first is analytical error in the measurement of
cyanide. The second is the detection of naturally produced cyanide excreted by plants,
microorganisms, and insects. The third explanation is the release and detection of manufactured
cyanide. Each of these potential reasons for the presence and/or improper reporting of cyanide is
discussed in the following sections. The current status and applicability of methods for the
analysis of cyanide in the mining industry remains in a state of flux. The USEPA has initiated an
internal long-term investigation and evaluation of cyanide analytical techniques, in hopes of
resolving the long-standing uncertainties surrounding this measurement. It is imperative that the
interpretation of cyanide analytical data be tempered with an understanding of the reality of the
problems associated with its analysis.
Over the years, commercial chemical laboratories have lowered their reporting and detection limit
for total and WAD cyanide from the original or traditional level of 0.02 mg/l to lower than 0.005
mg/l in some instances, in spite of the fact that the analytical procedure, its reagents, and
instrumentation have remained essentially the same, as has the inherent error in its accuracy and
precision. In large part, the lowering of detection limits has resulted from regulatory mandates
without the necessary scientific justification or rationale. This trend has contributed to the frequent
misinterpretation of cyanide data generated by commercial laboratories and reported to
government agencies for monitoring and compliance purposes.
28 T. Mudder
The forms of cyanide most often discussed from a monitoring and compliance standpoint include
free cyanide, WAD cyanide, and total cyanide. Analytically, the "toxicologically significant"
forms of cyanide are differentiated from all others by the WAD cyanide procedure. The WAD
cyanide procedure measures the forms of free and weakly metal complexed forms of cyanide.
Subtraction of the WAD cyanide value from the total cyanide value obtained from a split sample
provides a measure of the iron cyanide present in the sample. In the event a total cyanide analysis
does not yield detectable cyanide, the corresponding WAD cyanide analysis would, in theory, also
yield a non-detectable result. The procedures for measurement of total and was cyanide are
described in Part 4500 of the 19th Edition of Standard Methods, generally considered the primary
authoritative reference text for analysis of water and wastewater.
The most commonly employed total cyanide analysis for compliance and monitoring purposes
involves manual distillation under strongly acidic conditions and a vacuum, with the addition of
magnesium chloride as a catalyst. Sulfuric acid is used to adjust downward the pH of the sample.
During the distillation, the free and metal complexed forms of cyanide are converted to the volatile
molecular HCN form, which is recaptured in a caustic scrubber. The strongly basic solution
containing the cyanide is then removed from the scrubber and subjected to a colorimetric analysis
using pyridine, barbituric acid, and chloramine-T as reagents. A reddish-blue color is formed in
the presence of cyanide, the intensity of which is related to cyanide concentration at a specific
wavelength of visible light using a spectrophotometer.
The entire procedure provides an indirect measurement of cyanide, unlike the direct analysis of a
metal using atomic absorption spectrometry. Constituents other than cyanide can react with the
reagents used in the procedure producing both positive and negative interferences, leading to
observed cyanide levels in a sample that are either higher or lower than the actual concentration.
In the case of WAD cyanide, the manual distillation procedure involves the more moderate pH of
4.5 and a buffer of zinc acetate and acetic acid. The identical colorimetric procedure is used to
quantify the cyanide captured in the caustic scrubber. The difficulty in measuring free cyanide has
been recognized by the USEPA in its ambient water criteria document for this constituent. The
USEPA did not establish a BAT (Best Achievable Technology) limitation for total cyanide, in
large part due to the problems associated with its analytical measurement, which the agency
indicated was unreliable below 0.20 mg/l (USEPA, 1982). The inherent variability in the total
cyanide analysis is shown on Figures 1 and 2, which include summaries of multiple analyses of a
distilled water blank and a low cyanide standard by two commercial laboratories (EGI, 1997).
Although the free forms of cyanide, which include molecular HCN and its anion (CN-), have been
traditionally considered by the USEPA as the most important from a toxicological and regulatory
standpoint, concerns relating to the inability to measure free cyanide and the potential toxicity
exhibited by other weakly bound metal cyanide complexes, other than those of iron, have
prompted other countries and State agencies in the western United States, such as Colorado, Idaho,
Montana, South Dakota, Nevada, and Washington, to employ the WAD cyanide method for
compliance and monitoring purposes at mining operations. For example, in South Dakota, the
groundwater protection standard for WAD cyanide is 0.75 mg/l, while a site-specific in-stream
aquatic life standard for WAD cyanide has been promulgated at 0.08 mg/l.
29 T. Mudder
0.50
Laboratory 1
0.40 Laboratory 2
CN (mg/L)
0.30
0.20
0.10
0.00
0 5 10 15 20 25 30
Sample Number
Figure 1. Analysis of a Total Cyanide Standard
30 T. Mudder
0.30
0.25
Laboratory 1
0.20 Laboratory 2
CN (mg/L)
0.15
0.10
0.05
0.00
0 5 10 15 20 25 30
Sample Number
Figure 2. Analysis of a Distilled Water Blank
31 T. Mudder
Several States within the U.S. have promulgated various mine closure, groundwater, and aquatic
life standards for cyanide using the WAD analytical procedure. The USEPA ambient water quality
criteria (AWQC) document for cyanide notes that the toxicity of cyanide is due to the presence of
free cyanide and that most of the metal cyanide complexes, particularly those of iron, are not very
toxic (USEPA, 1985).
In the AWQC document, it was further noted that measurement of free cyanide would provide a
more scientifically correct basis for compliance and monitoring purposes, but no reliable procedure
existed for measurement of free cyanide. As a result, the USEPA originally recommended the use
of the total cyanide procedure for measurement of free cyanide, although the agency noted that the
criteria may be overly protective for aquatic life using the total cyanide analysis. To compensate
for this problem, NPDES discharge permits in the United States have been issued using the WAD,
and not the total cyanide measurement. It should be kept in mind that even if WAD and total
cyanide detected or reported in low levels below 0.10 mg/l in an aqueous sample and these values
reflect the actual presence of cyanide from natural or manmade sources, these levels are lower than
those typically associated with causing toxicity to wildlife, aquatic life, or humans.
2.0 VARIABILITY AND INTERFERENCES IN THE ANALYSIS OF CYANIDE
There is inherent error associated with every analytical measurement. Such error may arise from
several random and systematic sources including sampling, instruments, reagents, and operator
variabilities. In the case of cyanide, these errors can be magnified in commercial laboratories by
the rapid and/or sequential analysis of samples containing elevated or low cyanide levels, such as
process solution or natural waters. In these cases carryover of cyanide can result if the glassware is
not cleaned thoroughly in between each sample analysis.
Additional errors arise from either negative or positive interferences caused by the presence of
other constituents already within an aqueous sample. Furthermore, positive or negative
interferences can arise from the addition of reagents used to counter the interferences caused by
naturally occurring constituents within the sample matrix. In interpreting analytical data, it is
important to understand that each measurement is not an exact value, but is associated with a
probable range of values influenced by the variability of the analytical procedure, laboratory
technician, and sample matrix involved.
For example, many mining solutions contain thiocyanate, which can break down during distillation
forming cyanide, resulting in a false positive or a higher than expected level of cyanide. The
interference is most prevalent in the total cyanide analysis in which a strong mineral acid is
employed during distillation. The interference created by the use of sulfuric acid during the
distillation step could be mitigated by using phosphoric acid, rather than sulfuric acid. However,
the use of phosphoric acid has yet to be accepted by the USEPA as part of the approved methods
for analysis of total cyanide.
32 T. Mudder
The impact of the thiocyanate interference on the total cyanide measurement using both sulfuric
and phosphoric acid is demonstrated in Table 1 (Smith and Mudder, 1991). The resultant total
cyanide values obtained on a prepared sample containing 0.25 mg/l were up to three times the
actual cyanide concentration. Both nitrite and nitrate can also affect cyanide analyses, since nitrite
can form HCN by reacting with both man-made and natural organic compounds during distillation,
and nitrate can be reduced to nitrite under anaerobic conditions thereby indirectly leading to the
formation of cyanide.
TABLE 1
Comparative Evaluation of Total Cyanide Methods Using
Different Acids With a Synthetic Metal Cyanide Solution
Containing Thiocyanate
Standard Reflux Total Cyanide Total Cyanide

Flask (CN) Thiocyanate Concentration with H2SO4 with H3PO4
(mg/l) (mg/l) (mg/l) (mg/l)
0.25 100.0 0.288 0.268
0.25 100.0 0.488 0.255
0.25 100.0 0.572 0.252
0.25 100.0 0.360 0.258
0.25 100.0 0.724 0.257
0.25 100.0 0.604 0.266
The presence of color or turbidity in an aqueous sample can also result in a positive interference in
a cyanide analysis due to the presence of natural organic substances, such as plant detritus and
suspended solids in an aqueous sample. Although distillation generally removes these
interferences some carryover could occur, resulting in the reporting total or WAD cyanide near
detection levels, even in samples containing no cyanide.
The required act of collecting and preserving a sample with caustic for subsequent analysis can
affect the numerical values obtained. In a study commissioned for and directed by the present
South Dakota Department of Environment and Natural Resources (DENR), using actual mining
solutions, a comparison was made of the effect of sample preservation on the WAD cyanide
analyses of split samples (ASCI, 1990). The results are presented in Table 2. Of particular
importance is the variation in WAD cyanide analyses below 0.10 mg/l. The variation in WAD
cyanide results between split preserved and unpreserved samples, at these low cyanide
concentrations reached a maximum of 0.05 mg/l.
33 T. Mudder
In several instances, the USEPA required preservation procedure for the analysis of cyanide
increased the resultant WAD cyanide levels. The effects of adding preservatives and reagents to
samples to control interferences due to oxidants and sulfides, two common interferences, was
evaluated in a second phase of the same study using actual mining solutions (Smith and Mudder,
1991). The results comparing the effects on total, WAD, and free cyanide analyses are presented
in Table 3. The study involved a single split solution sample, two analytical laboratories, and three
sample preparations, as well as unaltered samples. The WAD cyanide results produced
interlaboratory variations ranging from 0.03-0.11 mg/l, with an average variation of 0.08 mg/l.
TABLE 2
Comparison of WAD Cyanide Values from Preserved and Unpreserved Samples
Sample WAD Cyanide (mg/l) Unpreserved WAD Cyanide (mg/l) Preserved

No. (held 24 hrs) (held 6 days)
1 0.04 0.05
2 0.04 0.08
3 0.09 0.09
4 0.11 0.08
5 0.03 0.08
6 0.03 0.05
7 0.02 0.04
8 0.02 0.02
9 0.08 0.09
10 0.48 0.41
11 1.52 1.40
12 1.92 1.81
13 2.30 2.12
14 2.22 2.06
15 1.97 1.41
16 1.80 1.68
17 1.77 1.72
34 T. Mudder
TABLE 3
Effects of the Use of Preservatives for Oxidants and Sulfides on Cyanide Analyses
Laboratory A Laboratory B
(mg/l) (mg/l)
Total Cyanide Unfixed 1.80 2.30
Fixed for Sulfide 1.80 2.20
Fixed for Oxidants 1.30 2.30
Fixed for Oxidants and Sulfides 2.00 2.10
Wad Cyanide Unfixed 0.10 0.18
Free Cyanide Unfixed 0.03 0.07
The inherent variability of total cyanide analyses was again demonstrated in a fourth study
involving the analysis of groundwater at a mining site, suspected of being contaminated with
cyanide (DENR, 1996). The results of the study, which included both manual and automated total
cyanide analyses and several commercial analytical laboratories, are presented in Table 4. In this
study, both inter- and intra-laboratory variation in total cyanide analyses using the same procedure
ranged from <0.01 up to 0.03 mg/l. It is interesting to note that on more than one occasion, one
laboratory reported no cyanide at a detection limit <0.01 mg/l in a split sample for which another
laboratory reported cyanide at 0.03 mg/l. In this particular instance, a monitoring limit of <0.05
mg/l for total cyanide was eventually recommended for this particular mining operation by the
state regulatory agency since quantification at lower concentrations was considered unreliable.
35 T. Mudder
TABLE 4
Summary of Groundwater Analyses for Total Cyanide
Date Lab Method Total CN Date Lab Method Total CN Date Lab Method Total CN
(mg/l) (mg/l) (mg/l)
01/06/88 C M <0.01 11/18/89 C M <0.01 08/13/90 A A 0.01
04/20/88 A A <0.01 12/02/89 A A <0.01 08/13/90 B A <0.01
05/23/88 A A <0.01 12/13/89 A A 0.03 08/13/90 T M <0.25
06/14/88 A A <0.01 12/29/89 C M 0.02 08/13/90 A A 0.02
08/08/88 A A <0.01 01/02/90 A M,A 0.03 08/13/90 A A 0.02
01/19/89 A A <0.01 01/02/90 D M <0.01 08/22/90 A A 0.02
04/21/89 A A <0.01 01/02/90 C M 0.01 09/08/90 A A 0.04
05/22/89 A A 0.04 01/03/90 C M <0.01 09/14/90 A A 0.04
07/05/89 A A 0.01 01/04/90 C M <0.01 09/22/90 A A <0.01
07/25/89 A A 0.01 01/05/90 C M <0.01 09/28/90 A A 0.03
08/01/89 A A 0.01 01/09/90 C M <0.01 10/20/90 A A 0.02
08/01/89 A A 0.01 01/10/90 C M <0.01 10/27/90 A A 0.04
08/02/89 A A 0.02 01/11/90 C M <0.01 11/24/90 A A 0.02
08/02/89 A A 0.02 01/12/90 C M <0.01 12/15/90 B A 0.03
08/02/89 A A 0.02 01/18/90 C M <0.01 01/02/91 B A 0.02
08/02/89 E M 0.02 02/10/90 C M <0.01 01/07/91 A M,A 0.03
08/02/89 E M 0.02 02/27/90 C A <0.01 01/07/91 B A 0.03
08/02/89 D M <0.01 04/10/90 A A 0.03 01/19/91 A A <0.01
08/02/89 D M <0.01 04/10/90 C M <0.01 01/19/91 B A 0.02
08/14/89 A A 0.03 04/19/90 A A <0.01 01/24/91 B A 0.03
08/30/89 A A 0.02 04/19/90 C M <0.01 01/31/91 A A 0.01
09/05/89 A A 0.05 05/16/90 A A 0.01 03/15/91 A A <0.01
09/12/89 A A 0.01 05/16/90 C M <0.01 03/15/91 A A <0.01
09/12/89 A A 0.01 05/24/90 A M 0.02 03/18/91 A A 0.02
09/21/89 A A 0.01 07/05/90 A A 0.02 03/29/81 A A 0.02
09/28/89 A A 0.02 07/08/90 A A 0.02 04/02/91 A A 0.06
09/28/89 A A 0.02 08/06/90 B A 0.03 04/05/91 A A 0.02
10/21/89 A A <0.01 08/06/90 B A 0.03 04/09/91 A A 0.02
10/27/89 A A 0.03 08/06/90 A A 0.01 04/24/91 A A 0.03
11/10/89 A A 0.01 08/08/90 B A <0.01 05/04/91 B A <0.01
11/18/89 A A <0.01 08/09/90 B A 0.01 06/03/91 B A 0.02
11/18/89 A M <0.05 08/09/90 A A 0.01
Method Abbreviations: A = Automated Analysis

M = Manual Distillation
In summary, both other constituents as well as the reagents used to eliminate these interferences
can affect the measurement of cyanide. The potential impact of these interferences is more
pronounced at low cyanide levels approaching the detection limit of the procedure. In short,
accurate and reliable measurements of cyanide near the detection limits are frequently
unobtainable.
36 T. Mudder
Therefore, it is possible that low levels of reported cyanide for a particular treated effluent or
surface water merely represent routine analytical error and variation, rather than the actual
presence of cyanide. Based upon an awareness of the recognized variation inherent within
analytical measurement, and the impact of that variation on the determination of compliance at
constituent levels approaching detection, the USEPA initiated a general study, not yet complete, to
identify an appropriate procedure for distinguishing between detection and quantification. The
USEPA issued revised protocols requiring that quantification limits be calculated from a series of
low level constituent spikes into reagent grade water (USEPA, 1985).
The USEPA recognized that variable quantification was not achievable near the detection limit for
a particular constituent and a specific analytical procedure (CMA, 1990). Realizing that
compliance levels or effluent standards should not be set at or near the method detection limit or
MDL because of the analytical variability surrounding these values, the USEPA introduced the
term "minimum level" or ML. The ML represents the lowest level achievable by laboratories
within specified limits on a day to day basis during which hundreds of samples are analyzed in a
continuous and rapid manner (USEPA, 1994).
The ML is also referred to as the "practical quantification limit" or PQL. Due to the possibility of
an analytical procedure incorrectly indicating the presence of a constituent below the ML or PQL,
even though it is absent, the USEPA has recommended that for compliance purposes, any value
below the ML should be considered zero (USEPA, 1994). In order to ensure that a certified
commercial laboratory is producing sufficiently accurate and precise data, the USEPA routinely
requires the analysis of prepared samples as a method of quantifying quality control and assurance.
An example of the allowable variation in the analysis of total cyanide associated with actual
USEPA audit samples obtained from a commercial laboratory is presented in Table 5. As noted in
Table 5, the allowable variation is nearly 0.04 mg/l at the lowest prepared concentrations, which
ranged from below detection to 0.035 mg/l.
TABLE 5
Examples of Acceptable Variance Within USEPA Audit Samples
Acceptable Warning
Constituent True Value Limits Limits
Total Cyanide (mg/l) 0.02 <0.001-0.035 0.002-0.030
0.09 0.05-0.12 0.06-0.1
0.18 0.12-0.22
37 T. Mudder
In order to determine a site-specific reporting level or ML for total and WAD cyanide in various
mining effluents, an interlaboratory study was conducted for the South Dakota Department of
Environment and Natural Resources and three mining companies located in the Black Hills of
South Dakota (Schafer and Associates, 1995a and 1995b). The results of the ML or PQL study are
presented in Table 6. The MLs were determined using the proposed procedure of the USEPA and
were conservative, since the six commercial laboratories to which samples were sent were made
aware of the study, and therefore should have provided the highest level of precision and accuracy
achievable. The calculated reporting levels for total and WAD cyanide ranged from 0.04-0.11
mg/l and 0.02-0.08 mg/l, respectively, depending upon the sample matrix. Therefore, for a
particular effluent matrix, cyanide analytical results below those site-specific reporting levels
would not be considered quantifiable and would not be distinguishable from values just above or
below detection.
TABLE 6
PQL Values and Recommended Reporting Values in mg/l
NPDES Recommended
Discharge Reporting
Point Constituent Value
Mine A Total Cyanide <0.11
Discharge 001 WAD Cyanide <0.08
Mine B Total Cyanide <0.04
Mine C WAD Cyanide <0.02
Discharge 004
The magnitude of the variation noted in the USEPA audit samples, the site-specific ML or PQL
study, and the previous laboratory studies relating to interferences are consistent and verify that
substantial variation is inherent in the results reported from employing total and WAD cyanide
analytical procedures. As a result, it is possible that the reported data merely reflect the normal
error and variation inherent in the analysis of total or WAD cyanide, and not the actual presence of
cyanide.
38 T. Mudder
3.0 NATURAL SOURCES OF CYANIDE
It is commonly believed that the natural production of low levels of cyanide in its various forms
does not occur to any great extent in the global environment. In fact, the natural production of
cyanide is ubiquitous throughout the world. Cyanide and chemically related compounds are
formed, excreted, and degraded in nature by hundreds of species of bacteria, algae, fungi, plant,
and insects (Knowles, 1976 and U.S. Fish and Wildlife Service, 1991).
As a result, it would not be uncommon for low levels of cyanide to periodically or routinely appear
in background or ambient surface or groundwater samples which are not expected to contain this
constituent. Cyanide is naturally present in the biosphere in both simple and complexed forms.
Interestingly, for many decades cyanide and cyanide related compounds have been postulated as
the first organic compounds on earth, from which the remaining building blocks of life were
derived (Lehninger, 1970 and Oparin, 1938). Research has demonstrated that various amino acids
can form from hydrogen cyanide precursors under the environmental conditions thought to exist
during the early stages of earth's history and development.
Many biological systems, including higher plants, bacteria, fungi, algae, and animals produce
cyanogenic glycosides which liberate free cyanide upon hydrolysis (U.S. Fish and Wildlife
Service, 1991). At least 1,000 species of plants and microorganisms from 90 families have been
shown to contain one or more of nearly twenty compounds capable of producing cyanide (Seigler,
1976). About 800 species of higher plants from 70-80 families, including agriculturally important
species such as the cassava, flax, sorghum, alfalfa, bamboo, peach, pear, cherry, plum, corn,
potato, cotton, almond, and beans are cyanogenic (Eyjolfsson, 1970). The concentration of
cyanide produced upon hydrolysis or digestion of cyanogenic plants can range from a few to
several hundred mg/l (U.S. Fish and Wildlife Service, 1991).
Cyanide poisoning of livestock by forage sorghums and other cyanogenic plants is well
documented. The toxicity of cyanogenic plants to both domestic and wild ungulates has been
recognized for more than half a century. More than sixty years ago, the federal government issued
a pamphlet regarding the potential for poisoning of livestock with naturally produced cyanide from
cyanogenic plants (U.S. Department of Agriculture, 1932).
Fungi and bacteria are prevalent producers of cyanide. About 300 species from 52 genera of fungi
have been shown to be cyanogenic (Bach, 1956 and Locquin, 1944). One fungus, Fomes
scutellatus, can generate a free cyanide concentration in solution of about 65 mg/l or 65,000 ug/l.
It appears that cyanide production is widespread in fungi and is a normal metabolite (Knowles,
1976). Two species of bacteria are known to be cyanogenic, including Chromobacterium
violaceum, a common soil and fresh water organism, which has been shown to produce cyanide in
concentrations as high as 21 mg/l or 21,000 ug/l (Michaels and Corpe, 1965). In addition, 74 out
of 110 strains of Pseudomonas aeruginosa, found commonly in soil and fresh water habitats, have
been shown to produce cyanide (Castric, 1975). In addition to plants and microorganisms, insects
have been shown to produce cyanide in its molecular form HCN. Seven species of centipedes,
forty-six species of millipedes, three species of beetles, four species of moths, and three species of
butterflies have been shown to synthesize and excrete cyanide (Duffey, 1981). These insects and
arthropods excrete cyanide for defensive purposes.
39 T. Mudder
Many of the cyanogenic plants, fungi, and bacteria are ubiquitous in nature and can survive and
thrive under a wide range of environmental conditions. Although no definitive studies are often
taken during background investigations related to the permitting of mining operations or projects, it
is not unlikely that one or more of these cyanogenic species are or have been residents in a specific
area under investigation. It should also be noted that cyanogenic organisms can also produce
chemically and structurally related natural organic compounds, which could report as cyanide in its
analysis, thereby yielding yet another positive interference.
Many of the cyanogenic microorganisms reported in the scientific literature are commonly found
in a wide variety of chemical and physical environments, like those associated with mining
projects. Consequently, it is possible that naturally produced cyanide has been noted either
periodically or randomly during the ongoing monitoring of surface and groundwaters in the
vicinity of a mining project.
4.0 THE RELEASE OF MANUFACTURED CYANIDE
Other than analytical variation or the natural production of cyanide resulting in the appearance of
total and WAD cyanide in aqueous samples, there is the potential for release or discharge of
manufactured cyanide from manmade sources. Many proposed mining projects are located in
areas of substantial historic mining activity. Cyanide has been used since the turn of the century at
many of those defunct mining operations. Older tailings deposited at historical operations are a
possible source of low levels of particularly total cyanide, as it is slowly degraded and released to
surface or groundwaters in the vicinity of a newly operating or proposed mining project.
In addition, road salt can contribute to elevated levels of total cyanide in adjacent surface waters
(Ohno, 1989). Iron cyanide is often used as an anti-caking agent in both table and road salt, and
can be present in the salt in concentrations of up to many mg/kg. In the USEPA exposure and risk
assessment document for cyanide, it was estimated that about 940 metric tons of iron cyanide used
as an anti-caking agent in road salt enter U.S. surface waters each year (USEPA, 1981). The
quantity of cyanide used in salting roads annually for each of the cities of Chicago, Detroit, New
York, and Milwaukee ranged from 12-27 metric tons. In contrast, the USEPA estimated that about
2-20 metric tons of cyanide are released into U.S. surface waters by the entire ore mining and
dressing industry each year.
Based upon personal experience, the practice of pushing or dumping snow into streams has
resulted in the detection of total cyanide in surface water samples during routine monitoring. As a
result, the detection of low levels of cyanide in surface or groundwaters may not be the result of
release from a new mining operation.
40 T. Mudder
5.0 CONCLUSIONS
The detection of low levels of total or WAD cyanide may be the result of actual cyanide released
from natural or manmade sources, or may be the result of error or interferences in the various
cyanide analytical procedures. Before these potentially inaccurate or unreliable values become a
major regulatory concern or compliance issue, it is important that the magnitude of the total or
WAD cyanide values be placed into perspective with those concentrations that are considered
harmful to humans or the environment. Figure 3 presents a comparison of the various cyanide
standards and analytical detection and quantitation levels. As shown in Figure 3, there is no need
to pursue lower detection limits of questionable reliability when the appropriate standards are
several fold greater in magnitude.
All too often, very low levels of cyanide are determined to be a "signature" that a release from a
mining operation has occurred, when in fact no such situation exists. Long term monitoring and
bioassay data support the contention that total cyanide levels below 0.10 mg/l and WAD cyanide
levels below 0.05 mg/l that are present in mining related discharges are unreliable and are not of
concern with respect to protection of human health or aquatic life. Total and WAD cyanide
concentrations below these respective levels are best reported as "less than" values and should not
be employed for compliance purposes.
41 T. Mudder
42 T. Mudder
6.0 REFERENCES
ASCI, "An Evaluation of the Effectiveness of Rinsing Procedures on Cyanide Removal from Spent
Heap Leach Ore: Brohm Mining Company," prepared for the South Dakota Department of Health
and Natural Resources, Joe Foss Building, Pierre, South Dakota, September, 1990.
Bach, E., "The Agric Pholiota aurea, Physiology and Ecology," Dan. Bot. Ark., Volume 16, pp. 1-
220, 1956.
CMA, "Quantitation/Detection Limits for the Analysis of Environmental Samples," prepared by

the Chemical Manufacturing Association (CMA) and presented at the 13th Annual USEPA
Conference on the Analysis of Pollutants in the Environment, Norfolk, Virginia, May, 1990.
Castric, P., "Hydrogen Cyanide, A Secondary Metabolite of Pseudomonas aeraginosa," Canadian

Journal of Microbiology, Volume 21, pp. 613-618, 1975.
Duffey, S., "Cyanide and Arthropods," pp. 385-414, in Cyanide and Biology, Academic Press,
New York, New York, 1981.
Eyjolfsson, R., "Recent Advances in the Chemistry of Cyanogenic Glycosides," Fortschr. Chem.
Org. Naturst., Volume 28, pp. 74-108, 1970.
Environmental Geochemistry International (EGI), Balmain, NSW, Australia, personal

communication from Dr. Stuart Miller, February, 1997.
Knowles, C., "Microorganisms and Cyanide," Biological Reviews, Volume 40, pp. 652-680, 1976.
Lehninger, A., Biochemistry, Worth Publishers, New York, New York, 1970.
Locquin, M., "Degagement et Local station de l'acide Cyanohydrique chez. les Basidiomycetes et
les Ascomycetes," Bull. Soc. Linn., Volume 13, pp. 151-157, 1944.
Michaels, R., and Corpe, W., "Cyanide Formation by Chromobacterium violaceum," Journal of
Bacteriology, Volume 89, pp. 106-112, 1970.
Ohno, T., "Spectrophotometric Determination of Total Cyanide in Surface Waters Following

Ultraviolet Induced Photodecomposition," Analyst, Volume 114, pp. 857-858, 1989.
Oparin, A., The Origin of Life, The Macmillian Company, New York, 1938.
Schafer and Associates, Inc., "Wharf Resources MDL/PQL Determination for NPDES Permit
Compliance Monitoring," January 16, 1995a.
Schafer and Associates, Inc., "LAC Minerals (USA) -- Richmond Hill Mine MDL/PQL
Determination for NPDES Permit Compliance Monitoring," February 22, 1995b.
43 T. Mudder
Seigler, D.S., "Plants of the Northeastern United States that Produce Cyanogenic Compounds,"
Econ. Bot., Volume 30, pp. 395-407, 1976.
Smith, A. and Mudder, T., The Chemistry and Treatment of Cyanidation Wastes, Mining Journal
Books, London, England, United Kingdom, 1991.
South Dakota Department of Environmental and Natural Resources (DENR), "Assessment of

Surface Water Quality and the Aquatic Ecosystem of the Northern Black Hills," Volumes I and II,
prepared by Times Limited, Chadwick Ecological Services, and WQ Hydro Consulting, Pierre,
South Dakota, February, 1996.
U.S. Department of Agriculture, "Poisoning of Livestock by Plants that Produce Hydrocyanic

Acid," Leaflet No. 88, pp. 1-4, March, 1932.
U.S. Fish and Wildlife Service, "Cyanide Hazards to Fish, Wildlife, and Invertebrates: A Synoptic
Review," Biological Report 85(1.23), Contaminant Hazard Reviews Report 23, U.S. Department
of the Interior, December, 1991.
USEPA, "An Exposure and Risk Assessment for Cyanide", Office of Water, EPA-440/4-85-008,
Washington, D.C., December, 1981.
USEPA, "National Guidance for the Permitting, Monitoring, and Enforcement of Water Quality
Based Effluent Limitations Set Below Analytical Detection/Quantitation Levels," Washington,
D.C., March, 1994.
USEPA, Ambient Water Quality Criteria Document for Cyanide, PB85-227460, Washington,
D.C., January, 1985.
USEPA, "National Primary Drinking Water Standards, Volatile Synthetic Organic Chemicals;
Final Rule," 40CFR, Parts 141 and 142, 1985.
USEPA, "Development Document for Final Effluent Guidelines and New Source Performance
Standards for the One Mining and Dressing Point Source Category," Effluent Guidelines Division,
Office of Water, Washington, D.C., November, 1982.
44 T. Mudder
MODELING OF NATURAL CYANIDE ATTENUATION
IN TAILINGS IMPOUNDMENTS
Prepared By:

Terry Mudder, Ph.D.
Originally published in Mineral and Metallurgical Processing, Vol. 17, No. 4, pp. 228-233,
November 2000.
Modeling of Natural Cyanide Attenuation in Tailings Impoundments
ABSTRACT
Cyanidation tailings which are disposed in a surface impoundment experience a loss of cyanide
due to natural attenuation, frequently reducing the cyanide concentration to very low levels.
Quantifying cyanide losses in terms of impoundment geometry, local weather conditions and feed
solution chemistry has been largely empirical though in many cases mining operations rely on
surface impoundments to reduce cyanide to below an internally regulated concentration or below
an effluent limitation. To permit a more quantitative evaluation of cyanide losses in an
impoundment, a computer simulation was developed to estimate the losses of free, weak acid
dissociable (WAD) and total cyanide due to dissociation, photolysis and volatilization. Results of
the model are compared against data collected for a North American tailings impoundment during
1998.
1.0 INTRODUCTION
A typical milling and cyanidation circuit utilizes a surface impoundment for permanent storage of
tailings solids, and as illustrated in Figure 1 there are many factors which influence the overall
water and cyanide balance in an impoundment. Quantification of an impoundment water balance
is largely statistical due to the influence of weather conditions, however reasonable probability
bounds can be placed on the water balance to allow development of a useful site water
management plan. Conversely, quantification of an impoundment cyanide balance is more
difficult because of its dependence on the water balance, weather conditions, impoundment
geometry and tailings chemistry, all of which may vary significantly over the life of a mine.
Because of the complexity involved in completing an impoundment cyanide balance, such

balances are frequently not conducted even though cyanide losses in an impoundment directly
influence site operating costs, such as those associated with sodium cyanide purchases or
operation of a cyanide detoxification plant. For planned mining operations, coupling tailings
impoundment design with goals for minimizing or maximizing cyanide attenuation in an
impoundment would facilitate development of a cyanide management plan, result in the
development of more accurate site operating costs, potentially simplify impoundment closure and
address issues associated impoundment toxicity during the permitting stage.
Generally, the volume of water contained in an impoundment increases with time as the tailings
solids and their entrained liquid accumulate in the impoundment. However, in almost all cases
there is a net loss of cyanide from an impoundment as a result of natural cyanide attenuation.
46 M. Botz & T. Mudder

Hydrogen
Direct Precipitation Cyanide Reclaim
Cyanidation and Runoff Volatilization Evaporation Water Discharge
Tailings Water
Cyanide
DECANT
Supernatant
SOLUTION
Solution Pore Water from
Exchange
Solids Consolidation
Tailings with
Entrained Solution
Seepage from
Impoundment
Figure 1
Basic Water and Cyanide Balance for a Tailings Impoundment

Overall, natural attenuation is a complex process which may include the following routes of
cyanide losses from solution (Smith and Mudder, 1991):
• Volatilization
• Chemical Oxidation
• Biological Oxidation
• Hydrolysis
• Precipitation
• Complexation
• Sorption
These reactions may take place in the supernatant solution or in the tailings sediment, however the
predominant route of cyanide loss is typically ascribed to hydrogen cyanide volatilization from the
impoundment water surface. Schmidt et al. (1981) found from tests carried out in Canada that
volatilization of hydrogen cyanide accounted for 90% of cyanide removed from solution in a
tailings impoundment while a combination of other reactions accounted for the remaining 10%.
It has been found that the loss of hydrogen cyanide occurs according to a first order rate equation
(Simovic, 1984) which means that the rate of loss of hydrogen cyanide from an impoundment is
directly proportional to the hydrogen cyanide concentration in solution. Mathematically this is
represented by:
d[HCN ]
(1) = − K[HCN ]
dt
where [HCN] represents the molar concentration of aqueous hydrogen cyanide in the
impoundment supernatant solution, t is time and K is the first order rate constant. For a tailings
impoundment with a supernatant pond which is assumed to be completely mixed, the rate
constant k is given by:
A
(2) k =  Kv
V
where A is the surface area of the supernatant pond exposed to the atmosphere, V is the volume
of solution in the completely mixed portion of the supernatant pond and Kv is the first order
volatilization rate constant for hydrogen cyanide. Substituting this into Equation 1 yields:
d[HCN ] A
(3) = −  Kv[HCN ]
dt V

The significances of the parameters in Equation 3 are:
1. The term A/V is the inverse of the average depth of the impoundment, commonly referenced
as 1/Z. Note that as the surface area of the impoundment increases, the hydrogen cyanide
volatilization rate increases, and similarly, as the volume of the impoundment water body
increases, the hydrogen cyanide volatilization rate decreases. The term A/V is a physical
property of a tailings impoundment and not a function of weather conditions or solution
chemistry.
2. The hydrogen cyanide volatilization rate constant Kv is influenced by factors which accelerate
or slow the rate of hydrogen cyanide volatilization, including temperature, wind speed,
turbulence on the water surface and the degree of mixing in the impoundment water body.
This rate constant is dependent upon local weather conditions but is not normally a function of
the impoundment geometry or chemistry.
3. The product of Kv and A/V is the specific hydrogen cyanide volatilization rate constant and is
a physical property of an impoundment. This constant changes with time as weather
conditions vary or as the impoundment geometry changes, but does not vary with changes in
solution chemistry.
The terms A/V and Kv are a function of time according to changes in weather conditions and
impoundment geometry variations, therefore an exact solution to Equation 3 has not been
provided. Rather, the solution to Equation 3 is achieved by solving the equation for a discrete
time step according to impoundment geometry, weather conditions, and cyanide and metal
concentrations appropriate for the time step. Repeating the solution for a large number of time
steps yields the time-versus-concentration solution to the equation.
Integral with the time step calculations is the mathematical solution of cyanide equilibria relations
required to determine the value of [HCN] used in Equation 3. If there are no cyanide-complexing
metals in the impoundment solution, calculation of [HCN] in Equation 3 is straightforward,
however milling effluents typically contain copper, iron, nickel, zinc or other metals which
complicate the calculations. Even a small concentration of a complexing metal affects the
equilibrium concentration of hydrogen cyanide in solution, and in all cases complexing metals
decrease the equilibrium hydrogen cyanide concentration and the overall rate of hydrogen cyanide
volatilization. Note that although complexing metals lower the overall rate of hydrogen cyanide
volatilization, the volatilization rate constant does not change with the solution chemistry as it is a
physical property of an impoundment. The effect of the presence of complexing metals is to
lower the value of [HCN] used in Equation 3, thereby lowering the overall rate of hydrogen
cyanide volatilization. The effect of pH on the rate of hydrogen cyanide volatilization is similar in
that a lower pH favors the formation of hydrogen cyanide and thus increases its rate of
volatilization.

Table 1 lists the dissolved metal-cyanide complexes most commonly found in tailings
impoundment solutions. Using copper as an example, Figure 2 shows the equilibrium
concentrations of the three soluble copper-cyanide species for the case of 100 mg/L total cyanide
and 50 mg/L copper in solution at 25oC. As shown in Figure 2, approximately 20% to 40% of
cyanide is present as hydrogen cyanide at a pH in the range of 7.0 to 9.0, a typical pH range
observed in impoundment solutions. The influence of copper on the equilibrium hydrogen cyanide
concentration is illustrated by the dashed line in Figure 2 which shows the concentration of
hydrogen cyanide that would be present if there were no copper in solution. With no copper
present, approximately 60% to 100% of cyanide would be present as hydrogen cyanide at a pH in
the range of 7.0 to 9.0. This example illustrates the significant effect that complexing metals have
on the equilibrium concentration of hydrogen cyanide.
Table 1
Common Metal-Cyanide Complexes
Free Cyanide Copper Iron Cyanides Nickel Zinc Cyanides
Cyanides Cyanides
HCN Cu(CN)2- Fe(CN)6-3 NiCN+ ZnCN+
CN- Cu(CN)3-2 Fe(CN)6-4 Ni(CN)4-2 Zn(CN)20
Cu(CN)4-3 Ni(CN)5-3 Zn(CN)3-
Zn(CN)4-2
Zn(CN)5-3
As indicated in Table 1, iron forms two complexes with cyanide, with the Fe(III) complex being
the predominant specie found in surface impoundments. Iron-cyanide complexes are very stable
and dissociate only to a small degree under ambient conditions. However, these species are
photolytically active and readily dissociate in the presence of ultraviolet (UV) radiation with a
wavelength in the range of approximately 300 to 500 nm (Broderius and Smith, 1980). The rate
of photolysis is primarily dependent upon UV intensity, however pH, temperature and iron-
cyanide concentration have been found to influence the photolysis rate (Broderius and Smith,
1980). Therefore, in addition to the equilibrium dissociation of iron-cyanides, there is the
irreversible dissociation of iron-cyanides through photolysis which occurs in impoundments
exposed to UV. Iron-cyanide photolysis has been found to be first order and the rate equation is
written as:
d[Fe − CN ]
(4) = − Kuv[Fe − CN ]
dt
where [Fe-CN] is the molar concentration of the iron-cyanide species, t is time and Kuv is the
photolysis rate constant. The reaction mechanism for the photolytic decay of iron-cyanides is not
clearly understood. However, it has been observed that each mole of Fe(II) and Fe(III) cyanide
dissociates to yield 5 and 3 moles of free cyanide, respectively, out of the 6 moles of cyanide
bonded to the unreacted iron-cyanide species (Broderius and Smith, 1980). The fate of the
remaining 1 and 3 moles of cyanide, respectively, is not presently known.

100%
HCN Concentration
with 0 mg/L Cu 90%
HCN
80%
70%
mg/L of species as CN
CN-
60%
50%
Cu(CN)3 -2
40%
30%
Cu(CN)4 -3 CuCN(s)
Cu(CN)2- 20%
10%
0%
11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0
pH
Figure 2
Copper cyanide species distribution vs. pH (100 mg/L cyanide and 50 mg/L copper)

The photolysis rate constant for iron-cyanides is time dependent as a result of seasonal and daily
variations in UV intensity according to the position of the sun. As with Equation 3, the solution
to Equation 4 is achieved by solving the differential equation in a series of time steps along with
repetitive solution of metal-cyanide equilibria relations.
2.0 MODEL STRUCTURE
The present approach parallels the presentation of Simovic (1984), Simovic et al. (1984) and
Simovic and Snodgrass (1989) in that several reaction steps are included in calculating the rate of
hydrogen cyanide volatilization. Referencing Figure 3, it is assumed that metal-cyanide
complexes, including iron-cyanide complexes, exist in equilibrium with the cyanide anion and
metal cations according to values of individual equilibrium constants. At the same time, the
cyanide anion exists in equilibrium with aqueous hydrogen cyanide which volatilizes from solution
according to a location and time-dependent volatilization rate constant. Contributing to the
formation of the cyanide anion is the photolytic dissociation of iron-cyanides according to the
photolysis rate constant.
In the present work, it is assumed that metal-cyanides exist in equilibrium as indicated by the
reversible reactions in Figure 3. The validity of this assumption may be debatable and a model
developed by Simovic et al. (1984) was based on the premise that individual metal-cyanide species
are not in equilibrium, rather they experience first order decay with rate constants characteristic to
each metal. However, data collected by the authors, Broderius (1973) and Maracle (1992)
suggest that for reaction time periods on the order of weeks to months, the assumption of metal-
cyanide equilibrium is appropriate.
Functionally, each of the reaction steps illustrated in Figure 3 are quantified as follows:
Metal-Cyanide Equilibria and Cyanide-Hydrogen Cyanide Equilibrium

Mathematical solution of metal-cyanide equilibria as a function of pH and temperature is achieved
through numerical iteration according to equilibria constants for each metal-cyanide complex.
Equilibria constants are calculated as a function of temperature according to data presented by
Zemaitis et al. (1986) and Flynn and McGill (1995). Attendant with calculation of metal-cyanide
equilibria is mathematical determination of the cyanide-hydrogen cyanide equilibrium which gives
the concentration of aqueous hydrogen cyanide used in Equation 3. Typical results of this
procedure are presented in Figure 2 for a simple copper-cyanide system.

HCN(g)
Kv
Keq Ka M = metal cation (including iron)

M-CN CN HCN(aq) Keq = metal-cyanide equilibrium constant
Ka = HCN/CN acid dissociation constant
Kuv = photolysis rate constant
Kuv Kv = HCN volatilization rate constant
Fe-CN
Figure 3
Routes to Hydrogen Cyanide Volatilization

Iron-Cyanide Photolysis
Data presented by Zepp and Cline (1977) and Broderius and Smith (1980) is used in conjunction
with GCSOLAR, a photolysis rate model developed by the U.S. Environmental Protection
Agency (USEPA, 1988), to calculate photolysis rate constants. Much of the input data required
for the use of GCSOLAR with iron-cyanides is provided by Broderius and Smith (1980), though
physical and chemical properties of a specific impoundment are also required. Photolysis rate
constants can be calculated by GCSOLAR as an average over the depth of a water body for each
season of the year. The constants must be corrected for pH, temperature and iron-cyanide
concentration according to data presented by Broderius and Smith (1980).
Hydrogen Cyanide Volatilization

Calculation of the hydrogen cyanide volatilization rate constant is substantially empirical and
several methods have been presented (Smith et al., 1980; Thomas, 1990; USEPA, 1994; Sadek et
al., 1996; Eastern Research Group, 1997). In addition, published values of hydrogen cyanide
volatilization constants have a large range (Simovic, 1984; Simovic and Snodgrass, 1989; Murphy
and Robertson, 1979). The approach in the current model is to calculate the volatilization rate
constant according to the methods of Thomas (1990) and USEPA (1994) to provide an
approximate range of values for the rate constant. Time-versus-cyanide concentration data are
then generated for the range of hydrogen cyanide volatilization rate constants and the results are
assumed to bracket the solution. As variations in weather may be considered random and there is
a degree of uncertainty in the hydrogen cyanide volatilization rate constant, the physical and
chemical data for an impoundment and the site water balance, time-versus-cyanide concentration
results would be expected to represent a probabilistic solution rather than a exact solution.
The overall model calculation sequence is depicted in Figure 4. Calculations are conducted for a
series of discrete time steps in which metal-cyanide equilibria relations are solved, iron-cyanides
dissociate as a result of photolysis, and cyanide and metals are removed from solution through
precipitation and volatilization reactions. The time step for the iterative calculations is usually on
the order of 0.1 to 1.0 day and it is assumed during this time step that equilibrium is established in
solution and that photolysis and volatilization proceed according to an exponential decay function.
Note that during the iterative procedure, constants for equilibria, photolysis, solubilities and
volatilization are recalculated according to the time-dependent values of metals and cyanide
concentrations, pH, temperature, UV intensity, weather conditions and impoundment geometry.
Results from each iteration step are used in conjunction with the impoundment water balance to
calculate metals and cyanide concentrations as a function of time.

Initialize Model
Read initial metal and cyanide concentrations
Read pH and temperature variation by month
Calculate Constants
Equilibria
Iterate for Acid Dissociation
Time Step Photolysis
Volatilization
Solubility Product
Solve Equilibria
Cyanide-Hydrogen Cyanide
Metal-Cyanide
Photolysis
Iron-cyanide decay rate versus time of year
Check Solubility
Metal-Cyanides
Metal-Carbonates
Metal-Hydroxides
Precipitate Species if Necessary
Volatilize HCN
Adjust Total Cyanide Concentration
Write Results
Concentrations versus Time
Figure 4
Structure of Cyanide Attenuation Model

3.0 TAILINGS IMPOUNDMENT CASE STUDY
In 1998 the model was used to estimate the rate of loss of cyanide from a tailings impoundment at
an inactive mine site. At the time the modeling was completed, solution in the tailings
impoundment contained approximately 170 mg/L of total cyanide, which was present almost
exclusively as iron-cyanide. The situation for this impoundment was unique in that:
1. Greater than 98% of cyanide in the impoundment solution was iron-cyanide, therefore
calibration of the model could proceed specifically for the case of iron-cyanide photolysis. As
the rate of hydrogen cyanide volatilization is rapid relative to the rate of iron-cyanide
photolysis, the rate of cyanide loss from the impoundment would approximately equal the
photolysis rate and the applicability of GCSOLAR and the data of Broderius and Smith (1980)
could be evaluated. In addition, analytical data and UV spectrographic data for the
impoundment solution indicated that only Fe(III) cyanide was present, therefore calculations
proceeded assuming Fe(II) cyanide was not present in the impoundment solution.
2. Tailings were not being disposed in the impoundment, therefore the system represented a
batch cyanide decay situation rather than a continuous throughput or accumulation situation.
This removed some uncertainty associated with the development of an impoundment water
balance model.
Summaries of physical, chemical and weather data for the impoundment under consideration are
provided in Tables 2 and 3. The impoundment is located in the northern hemisphere, and as
indicated in Table 3, winter temperatures result in freezing of the pond surface for approximately
four to five months per year. In addition to these data, the UV absorbance of the impoundment
solution as a function of wavelength is presented in Figure 5. The absorption spectrum in Figure
5 is similar in shape to that presented in Broderius and Smith (1980) for Fe(III) cyanide,
supporting the assumption that only Fe(III) was present in the impoundment solution. The range
of UV of interest is from approximately 300 nm to 500 nm since essentially no light less than 300
nm penetrates the earth’s atmosphere (Goldman and Horne, 1983) and iron-cyanides are not
photolytically active above 500 nm.
Table 2
Impoundment Physical and Chemical Data Summary
Elevation, m 2,200
Average Solution Depth, m 6.10
Initial Total Cyanide, mg/L CN 172
Solution pH 8.2 to 8.9

0.80
0.70
Absorbance, cm-1
0.60
0.50
0.40
0.30
0.20
0.10
0.00
280 300 320 340 360 380 400 420 440 460 480 500
Wavelength, nm
Figure 5
Impoundment Solution Absorbance Spectrum

Model calculations for the impoundment were conducted to estimate the total cyanide
concentration over a period of five years. A summary of the results is presented in Figure 6 and
Table 4. There is good agreement between the calculated and actual cyanide concentrations
presented in Figure 6 and Table 4, and model was successful at forecasting the rate of iron-
cyanide photolysis for the first eight months of 1998 to within approximately ±10%. However,
several years of additional decay data for the impoundment would be required along with weather
records to further quantify the accuracy of the model.
The stepwise decrease in total cyanide over the five-year period is a result of the rapid photolysis
which occurs during summer months when the pond is not ice-covered followed by periods during
the winter when the UV intensity decreases and the pond is ice-covered. The calculations indicate
that after five years, the total cyanide concentration will decrease from 170 mg/L to less than
approximately 10 mg/L.
Calculated photolysis rate constants ranged from 2.62×10-5 to 21.4×10-5 hour-1 as an average over
the full depth of the water body for this specific impoundment. However, it was assumed that
when the impoundment is ice-covered, the photolysis rate constant is zero. This range of
photolysis rate constants corresponds to an Fe(III) cyanide half-life of approximately five months
to three years depending upon the time of year, however the average half-life during summer
months is approximately six months.
Table 3
Impoundment Weather Summary
Month Ice-Free Water
Surface Temperature
(oC)
January 0% 0.2
February 0% 0.2
March 0% 2
April 50% 3
May 100% 10
June 100% 14
July 100% 17
August 100% 15
September 100% 15
October 100% 5
November 50% 3
December 0% 0.2

200
180 Calculated
160 Actual
Total Cyanide, mg/L CN
140
120
100
80
60
40
20
0
0 6 12 18 24 30 36 42 48 54 60
Month
Figure 6
Total Cyanide Concentration vs. Time

Table 4
Impoundment Cyanide Concentration versus Time
Total Cyanide
mg/L CN
Actual Calculated
January, 1998 172 172
February, 1998 180 172
March, 1998 -- 172
April, 1998 173 168
May, 1998 170 160
June, 1998 138 143
July, 1998 121 123
August, 1998 110 104
September, 1998 92 88
October, 1998 76 83
November, 1998 -- 79
December, 1998 -- 79
4.0 CONCLUSIONS
At this time, only field data for iron-cyanide has been available for testing of the model, though
calibration of the model for copper, nickel and zinc affects on hydrogen cyanide volatilization are
underway. In the case study presented for the tailings impoundment, it was desired to estimate
the cyanide attenuation rate for use as a reference in planning water management at the site for
the next two to five years, and for this case the model was successful at estimating cyanide
concentrations for a minimum of about one to two years in advance.
5.0 REFERENCES
Broderius, S., 1973, “Determination of Molecular Hydrocyanic Acid in Water and Studies of the
Chemistry and Toxicity to Fish of Metal-Cyanide Complexes”, Ph.D. Thesis, Oregon State
University.
Broderius, S. and L.L. Smith, January, 1980, “Direct Photolysis of Hexacyanoferrate Complexes:
Proposed Applications to the Aquatic Environment”, USEPA Report 600/3-80-003.
Eastern Research Group, March, 1997, “Preferred and Alternative Methods for Estimating Air
Emissions from Wastewater Collection and Treatment”, Final Report, Prepared for the Emission
Inventory Improvement Program and the USEPA, Vol. II, Chapter 5.
Flynn, C.M. and S.L. McGill, 1995, “Cyanide Chemistry - Precious Metals Processing and Waste
Treatment”, US Bureau of Mines, NTIS Document PB96-117841.

Goldman, C.R. and A.J. Horne, 1983, Limnology, McGraw-Hill, New York, Chapter 3.
Maracle, K.J., 1992, “Cyanide Regeneration of Gold Mill Barren Solutions Using Hollow Fibre
Gas Membranes”, Master of Engineering Thesis, McMaster University, Ontario.
Murphy, K.L. and J.L. Robertson, 1979, “Factors Affecting Natural Degradation of Free and
Metal-Complexed Cyanides from Gold Milling Effluents”, A Literature Review for Fisheries &
Environment Canada, Burlington, Ontario.
Sadek, S.E., J.D. Smith, A.T. Watkin and R. Gebel, 1996, “Mass Transfer of Volatile Organics
from Large Open Basins”, Environmental Progress, Vol. 15, No. 2, pp. 82-92.
Schmidt, J.W., L. Simovic and E. Shannon, 1981, “Development Studies for Suitable
Technologies for the Removal of Cyanide and Heavy Metals from Gold Milling Effluents”,
Proceedings of the 36th Industrial Waste Conference, Purdue University, pp. 831-846.
Simovic, L., 1984, “Kinetics of Natural Degradation of Cyanide from Gold Mill Effluents”,
Master of Engineering Thesis, McMaster University, Ontario.
Simovic, L, W.J. Snodgrass, K.L. Murphy and J.W. Schmidt, December, 1984, “Development of
a Model to Describe the Natural Degradation of Cyanide in Gold Mill Effluents”, Conference on
Cyanide and the Environment, Tucson, Arizona, pp. 413-432.
Simovic, L. and W.J. Snodgrass, 1989, “Tailings Pond Design for Cyanide Control at Gold Mills
Using Natural Degradation”, Proceedings from Gold Mine Effluent Treatment Seminars,
Vancouver, British Columbia, pp. 58-81.
Smith, J.H., D.C. Bomberger and D.L. Haynes, November, 1980, “Prediction of the Volatilization
Rates of High-Volatility Chemicals from Natural Water Bodies”, Environmental Science &
Technology, Vol. 14, No. 11, pp. 1332-1337.
Smith, A. and T. Mudder, 1991, The Chemistry and Treatment of Cyanidation Wastes, Mining
Journal Books Ltd., London, Chapter 3.
Thomas, R.G., 1990, “Volatilization from Water” Chapter 15 in Handbook of Chemical Property
Estimation Methods, Edited by W.J. Lyman, W.F. Reehl and D.H Rosenblatt, Published by
American Chemical Society, Washington D.C.
USEPA, GCSOLAR Version 1.1, February, 1988, Available through the Center for Exposure
Assessment Modeling, Environmental Research Laboratory, Athens, Georgia.
USEPA, November, 1994, “Air Emissions Models for Waste and Wastewater”, EPA Document
453/R-94-080A.

Zemaitis, J.F., D.M. Clark, M. Rafal and N.C. Scrivner, 1986, Handbook of Aqueous Electrolyte
Thermodynamics, Design Institute for Physical Property Data, American Institute of Chemical
Engineers, New York.
Zepp, R.G. and D.M. Cline, April, 1977, “Rates of Direct Photolysis in Aquatic Environment”,
Environmental Science & Technology, Vol. 11, No. 4, pp. 359-366.

CHAPTER 2
Toxicological properties
● The ecotoxicological properties of cyanide

● Human cyanide toxicity
● Development of site specific discharge criteria through
toxicological testing
● Site specific aquatic life criteria for weak acid dissociable
cyanide
● Derivation of aquatic life criteria for total and iron cyanide
● Strategies and standards for control of bird mortality at
mining operations
THE ECOTOXICOLOGICAL PROPERTIES OF CYANIDE
Prepared By:
Karen Hagelstein, Ph.D., CIH

Terry Mudder, Ph.D.
Originally published in Proceedings of the Short Course on Management of Cyanide in Mining,

Australian Centre for Minesite Rehabilitation Research (now ACMER), Perth, Western
Australia, April 1997
The Ecotoxicological Properties of Cyanide
1.0 SOURCES AND USES OF CYANIDE
The objectives of this paper are to discuss the environmentally significant sources of cyanide, the
toxicology and metabolism of cyanide, and the environmental impacts on organisms due to
cyanide and its associated compounds.
The chemistry and toxicology of cyanide has been well studied in the laboratory, field studies
have assessed cyanide toxicity to waterfowl, and epidemiological studies have evaluated acute
and chronic human health effects. The toxicity of free cyanide has been evaluated at various
food web levels including: algae, macroinvertebrates, amphibians, fish, birds, and mammals.
The principal toxicological hazard of cyanide is acute exposures, such as rapid ingestion of
cyanide-containing forage or solutions. Mammalian chronic exposure to cyanide at sublethal
concentrations, in food or water, has not been shown to induce bioaccumulative effects due to
the rapid detoxification process and excretion of by-products. Exposures to cyanide in mining
solutions have been generally controlled with physical exclusion methods, with chemical
treatment and recovery of cyanide, and by maintaining the levels of WAD cyanide below 50
mg/l.
Anthropogenic cyanide uses and environmental sources result from the manufacturing of plastics
and synthetic fabrics, metal mining operations, electroplating baths, pesticidal agents,
intermediates in agricultural chemical production, cyanogenic drugs, and predator control
devices. Laetrile (an anticancer preparation made from apricot kernels), sodium nitroprusside (a
drug used to reduce high blood pressure), and simple aliphatic nitriles release cyanide upon
metabolism (ATSDR, 1995). Sodium cyanide production and consumption in North America
was 130,000 tons; about 90 percent was used in gold mining (The Gold Institute, 1996). About
84% of domestic HCN production is used to produce organic cyanides, also known as nitriles
(Towill et al., 1978).
Hydrogen cyanide vapor, because of its rapid lethal toxicity, has been used widely to fumigate
buildings, ships, and warehouses; to exterminate rabbits, rodents, and large predators; and in
horticultural practice to control insect pests that have developed resistance to other pesticides
(Ballantyne, 1988). Sodium cyanide was used for about 50 years by the U.S. Fish and Wildlife
Service against the coyote, in attempts to protect livestock, especially sheep. Environmental
impacts due to these applied sources of cyanide have attributed to only minimal additional deaths
in the food chain (i.e., 64 other birds, rodents, and mammals) in conjunction with approximately
1,000 targeted coyotes. Cyanide compounds have been used to collect various species of
freshwater fish in the Missouri and Mississippi River drainages and have been used illegally to
obtain Atlantic salmon and brown trout from rivers, leaving no visible damage to the fish
(Holden and Marsden, 1964).
Natural sources of cyanide include various species of arthropods, insects, bacteria, algae, fungi,
and higher plants (2,650 plant species) that form and excrete cyanide (Way, 1984). The most
widely distributed major food crop with a high content of cyanogenic glycosides is cassava, also
known as manioc. Cyanogenesis has an important role in plant defense against predatory
herbivores. Wildlife and livestock exposure to high concentrations cyanogenic plants can be
hazardous if consumed rapidly.
64 K. Hagelstein & T. Mudder

Various arthropod species such as centipedes and millipedes, and insects such as beetles, moths,
and butterflies secrete cyanide for defensive purposes in repelling predators such as amphibians
and birds (Duffy, 1981). Some species of soil bacteria suppress plant diseases such as tobacco
root rot caused by soilborne fungi, by producing metabolites, HCN, with antibiotic activity. A
wide variety of bacteria and fungi can degrade cyanide compounds (Towill et al., 1978). Dried
fungal mycelia are now sold commercially to detoxify cyanide in industrial wastes (Knowles,
1988). An estimate of the amount of cyanide released to the environment from natural biogenic
processes is not available.
2.0 ENVIRONMENTAL EXPOSURES TO AND RELEASES OF CYANIDE
2.1 Water
Anthropogenic sources are responsible for much of the point and nonpoint cyanide releases into
the environment. Table 1 presents the sources, monitored levels, and discharges of total
cyanides and hydrogen cyanide into the air, water, and soil environments from certain industrial
facilities as reported to USEPA's Toxics Release Inventory (TRI92, 1994) and as monitored from
other sources (ASTDR, 1995). About 90% of the total cyanides released to surface waters are
effluents from publically owned wastewater treatment (POTW) facilities. Metal finishing and
organic chemical industries account for the majority of cyanide influent to POTWs. The
nonpoint sources of cyanide released to water are usually comprised of agricultural and road
runoff, along with atmospheric washout. The predominant sources of cyanides found in urban
runoff samples were reported to be products of gasoline combustion and anti-caking ingredients
in road salts, including about two million pounds of sodium ferrocyanide per year in the
northeastern United States (Fiksel et al., 1981).
The atmospheric washout of hydrogen cyanide released to surface water and POTWs was
estimated at 3,947 and 330 pounds, respectively (TRI92, 1994). These combined releases
amount to approximately 0.1% of the total environmental release of hydrogen cyanide. The
major cyanide releases to water are discharges from metal finishing industries, iron and steel
mills, and organic chemical industries (Fiksel et al., 1981).
Process solutions from mining operations were typically found to contain >10 mg/liter as simple
cyanides; 20-80 mg/liter as weak acid dissociable cyanides (WAD), 20-190 mg/liter as total
cyanides, and 300-450 mg/liter as thiocyanate (Boucabeille et al., 1994). Effluents from the
cyanidation process used in precious metal extraction contain elevated levels of cyanide (Scott,
1985). However, the contribution of this source to the total cyanide discharge in water, however,
is insignificant (Fiksel et al., 1981). Thiocyanate has been found in concentrations ranging from
100 to 1,500 mg/liter in coal plant waste waters (ATSDR, 1995).
Background surface water concentrations in the U.S. reported to the USEPA STORET database
indicated cyanide levels averaged 3.5 ug/liter during 1970-1980s. However, seven states have
locales with cyanide concentrations above 200 ug/liter (Fiksel et al., 1981). Drinking water
exposure to cyanogen chloride, from the reaction of humic substances with chloramine, ranged
from 0.45 to 0.80 ug/liter in a 1988 survey of 35 U.S. water utilities (Jancangelo et al., 1989).

2.2 Soil
The major sources of simple and complex cyanide releases to soil appear to be disposal of
cyanide wastes in landfills and the use of cyanide-containing road salts. Cyanide and its
complexes have been identified in at least 415 of the 1,416 hazardous waste sites that have been
proposed for inclusion on the USEPA National Priorities List (NPL). Fifty-three of these sites
are related to mining, which accounts for <5.0% of the total NPL. In addition, only three of
these sites, or <0.30% of the total, list cyanide as a constituent of concern. The cyanide
contamination at these three sites was due to mismanagement and abandonment of the mines by
the operators (USEPA, 1991). The risk assessments associated with the sites were driven
primarily by concerns with metals and constituents other than cyanide.
The concentration of cyanide in the leachate from landfills has been monitored in the range of
0.005 -14.0 mg/liter based on fourteen out of forty-three landfills investigated (Venkataramani et
al., 1984). Wildlife and livestock around contaminated landfill soils do not constitute a major
exposure route, but the transport of cyanide into ground and surface waters could be
toxicologically significant. However, the concentrations of cyanide distributed in the air, soil,
and water media have not been thoroughly evaluated (HazDat, 1995).
According to TRI92, 1994, an estimated total of only 17 pounds of hydrogen cyanide, a
negligible amount of the total environmental release, was discharged by atmospheric washout to
land from U.S. manufacturing facilities in 1992 (Table 1).

Table 1
Sources and Releases of Environmental Cyanide

2.3 Air
Of the total cyanide (estimated at 44 million pounds per year) released to the air, which accounts
for about 60% of the environmental load of total cyanide, about 90% is due to the combustion
emissions from automobiles (Table 1). The average emission rates of cyanides from automobile
exhaust were 11-14 mg/mile and 1 mg/mile for cars without and with catalytic converters,
respectively, operating under optimum conditions (Fiksel et al., 1981). The second largest
source of cyanide emissions was reported to be from the manufacture of methyl methacrylate,
acrylonitrile, and hydrogen cyanide (Fiksel et al., 1981).
In 1992, the total amount of hydrogen cyanide released to the atmosphere was estimated at 2.34
million pounds (1,060 metric tons), which amounted to about 75% of the total environmental
release of HCN (TRI92, 1994). Sources of cyanide release, from facilities required to report,
included emissions from iron and steel production, coal combustion, petroleum refineries, oil
shale retorting processes, municipal solid waste incinerators, the combustion of acrylonitriles or
other nitrogen-containing plastics, cigarette smoke, volatilization from cyanide waste in landfills,
and direct release to the atmosphere from certain agricultural pest control activities (Fiksel et al.,
1981).
Most cyanide in the atmosphere exists as hydrogen cyanide gas and to a lesser extent particulate
cyanides (USEPA, 1984). Free hydrogen cyanide occurs only rarely in nature because of its high
reactivity. Hydrogen cyanide can potentially be transported over long distances from its
emission source and before reacting with photochemically generated hydroxyl radicals. Neither
photolysis nor deposition by rainwater are expected to be significant removal mechanisms. Only
2% of the tropospheric hydrogen cyanide is expected to be transported to the stratosphere
(Cicerone and Zellner, 1983), which means most of the cyanide remains in the lower altitudes.
The half-life (time needed for half of the material to be removed) of hydrogen cyanide in the
atmosphere is about 1-3 years (ATSDR, 1995).
Background concentrations of nonurban, troposphere hydrogen cyanide in the northern

hemisphere has been measured at 0.17 ppb (0.19 ug/m3) (Cicerone and Zellner, 1983). For
comparison, the cyanide monitored during New York City traffic measured about 0.057 ppm;
cyanide concentrations from sidestream cigarette smoke measured about 0.30 ppm; while
cyanide concentrations due to fire emissions measured about 2.8 ppm (Table 1).

2.4 Terrestrial Plants and Invertebrates
Table 2 presents the concentrations of cyanide in selected plants. The primary cyanide source in
food is cyanogenic glycosides, which through acid hydrolysis or by action of the enzyme B-
glucosidase can produce hydrogen cyanide (USEPA, 1980). Hydrogen cyanide release can occur
either during maceration or by breakdown in the gut. There are about 20 known cyanogenic
glycosides, all which differ considerably in bioavailability. The most widely distributed major
food crop with a high content of cyanogenic glycosides is cassava, also know as manioc.
Cassava is a staple food in human diets in over 80 countries where chronic cyanide consumption
is the main etiological factor in the debilitating tropical ataxic neuropathy and thyroid
dysfunction (Egekeze and Oehme, 1980). Other plants having comparatively high levels of
cyanide content include fruit pits (apricots, peaches, plums, cherries), sweet potatoes, corn,
bamboos shoots, linseed, lima beans, and millet (Way, 1984).
Of chief agricultural importance among plants that accumulate large quantities of cyanogenic
glycosides are the sorghums, Johnson grass, Sudan grass, corn, lima beans, flax, pits of stone
fruits (cherry, apricot, peach), vetch, linseed, sweet potatoes, bamboo shoots, southern mock
orange, millet, almonds, and cassava. High concentrations of thiocyanate (5 to 660 ug/g wet
weight) are also found in vegetables from the Brassica family (cabbages, kohlrabi, kale).
Cyanide poisoning of livestock by forage sorghums, such as Sudan grass and various hybrid
cultivars has led to the development of several variations of sorghums that have a reduced
capability of producing cyanide poisoning (Egekeze and Oehme, 1980).
Factors favoring cyanide build-up in cyanogenic plants include high nitrogen and low
phosphorus in soils and immature, rapidly-growing plants and leaves. Cyanide levels drop
rapidly after pollination (Biehl, 1984; Egekeze and Oehme, 1980). There are about 20 major
cyanogenic glycosides, of which usually only one or two occur in any plant.
Cyanogenic glycosides also occur in several species of arthropods, including the tiger beetle, leaf
beetle, zygaenid moths, polydesmid millipedes, and certain butterflies which seem to function as
protection against predators. (Nahrstedt, 1988).

Table 2
Background Cyanide Concentrations In Selected Plants
Concentration
Cyanogenic Plant Species (mg/kg)
Bamboo (Bambusa, Arundinaria, Dendrocalamus)
Tip Max. 8,000
Stem Max. 3,000
Stargrass, Cynodon plectostachyus, whole 180
Rose Family, Malus spp., Pyrus spp. Max. 200
Cassava, Manihot esculenta
Bitter varieties
Leaves 347-1,000
Roots 327-550
Dried roots 95-2,450
Stem 1,130
Mash 162
Bark
Total cyanide 1,351
Free cyanide 102
Peel
Total cyanide 1,390
Free cyanide 255
Pulp
Total cyanide 810
Free cyanide 53
Sweet varieties
Leaves 377-500
Roots 138
Dried roots 46-<100
Mash 81
Lima Bean, Phaseolus lunatus
United States 100-170
Burma 2,100
Puerto Rico 3,000
Java 3,120
Almond, Prunus amygdalus, nut
Bitter 280-2,500
Spicy 86-98
Sweet 22-54
Seeds, 4 species, Nigeria, whole, frequently consumed by humans
Phaseolus sp. 381-1,093
Vigna sp. 285-1,223
Cajanus sp. 208-953
Canavalia sp. 285-953
Sorghum, Sorghum spp., young plant, whole Max. 2,500
Reference: Eisler, 1991

2.5 Environmental Fate of Cyanide
Since hydrogen cyanide is a gas and has a relatively slow degradation rate in air, the atmosphere
will be the ultimate sink for this compound. Almost all of the hydrogen cyanide released to the
atmosphere remains in the lower troposphere (Cicerone and Zellner, 1983).
The environmental fate of HCN from surface waters is through volatilization, biodegradation,
and hydrolysis, and sorption. Volatilization and sorption are the two physical processes that
contribute to the loss of cyanide from surface water. At pH<9.2, most of the free cyanide in
solution exists as hydrogen cyanide, the volatile form. Volatilization rates are dependent upon
pH (lower pH, faster rates) and aeration. The most common alkali metal cyanides (sodium and
potassium cyanide) may be lost from surface water primarily through volatilization; whereas,
the sparingly soluble metal cyanides (copper, nickel, zinc) are removed from water
predominantly by sedimentation and biodegradation (USEPA, 1992).
Biodegradation of cyanide in natural surface waters is dependent on such factors as cyanide

concentrations, pH, temperature, availability of nutrients, and acclimation of microbes. Mixed
microorganisms in sewage or activated sludge acclimated to cyanide can biodegrade 100 mg/l or
more of most simple and complex cyanides (Gaudy et al., 1982). Under aerobic conditions the
biodegradation of cyanides and thiocyanate in waste waters, initially produces ammonia, which
is converted to nitrite and nitrate in the presence of nitrifying bacteria; whereas anaerobic
biodegradation under denitrification conditions may produce nitrogen. Complete biodegradation
of simple and metal complexed cyanides and thiocyanate from mining waste waters by various
species of Pseudomonas, Vibrionacas, and Enterobacterias has been reported (Boucabeille et al.,
1994). Sulfate ions were produced from thiocyanate degradation.
Analogous to the fate of cyanides in water, it is predicted that the biodegradation fate of cyanide
in soil would be dependent on cyanide concentrations, pH, temperature, metal content,
concentration of microbes, availability of nutrients, and acclimation of microbes. Upper limits of
200 and 2 ppm (mg/kg CN--), respectively, have been reported for uninhibited aerobic and
anaerobic biodegradation of cyanide in soil (Fueller, 1984). Cyanides are sorbed by various
natural media, including clays, biological solids, and sediments (ATSDR, 1995). However,
sorption is probably insignificant even for metal cyanides when compared to volatilization and
biodegradation (USEPA, 1992).
Volatilization of hydrogen cyanide would be a significant loss mechanism for cyanides from soil
surfaces at pH<9.2. Cyanide mobility is lowest in soils with high concentrations of free iron
oxides, positively charged particles, and clays (Callahan et al., 1979).
There are no data available to indicate that the toxicologically significant simple metal cyanides
and hydrogen cyanide bioconcentrate in aquatic organisms (USEPA, 1992). There is no
evidence of biomagnification of cyanides in the food chain (Towill et al., 1978).

3.0 TOXICOLOGY OF CYANIDE
3.1 Physiology of Cyanide Toxicity
The most common forms of cyanide in the environment are free cyanide, metallocyanide
complexes, and synthetic nitriles. Free cyanide, specifically HCN at pH 9.2 and lower, is the
primary toxic agent in the aquatic environment. The toxicity of complex cyanides is related to
their ability to release cyanide ions in solution; relatively small fluctuations in pH significantly
affect their biocidal properties. Total cyanides refers to all cyanide-containing compounds,
including simple and complex cyanides, cyanoglycosides, and free cyanide. The relation
between total cyanide and free cyanide in natural waters varies with receiving-water conditions,
degree of aeration, type of cyanide compounds present, exposure to daylight, and the presence of
other compounds.
All available evidence suggests that cyanides are neither mutagenic, teratogenic, nor
carcinogenic (Ballantyne, 1987). Moreover, there are no reports of cyanide biomagnification or
cycling in living organisms, probably owing to its rapid detoxification. Cyanide seldom persists
in surface waters and soils owing to complexation, sedimentation, microbial metabolism, and
loss from volatilization as previously discussed. Cyanide has beneficial pharmacological activity
and possibly has antineoplastic activity, as judged by a low therapeutic success against rat
sarcomas (USEPA, 1980).
Cyanides are readily absorbed through inhalation, ingestion, or skin contact and are readily
distributed throughout the body via blood (Towill et al., 1978). Inhalation and skin absorption
are the primary hazardous routes in cyanide toxicity in occupation exposure. Skin absorption is
most rapid when the skin is cut, abraded, or moist. Inhalation of cyanide salts is potentially
hazardous because the cyanide dissolves on contact with moist mucous membranes.
Cyanide is a potent a rapid-acting asphyxiant by inducing tissue anoxia through inactivation of

the cytochrome oxidase enzyme in the mitochondria. Tissue hypoxia causes a shift from aerobic
to anaerobic metabolism, resulting in the depletion of energy-rich compounds such as glycogen,
phosphocreatine, and adenosine triphosphate, and the accumulation of lactate with decreased
blood pH. The combination of cytotoxic hypoxia with lactate acidosis depresses the central
nervous system, resulting in respiratory arrest and death. If the absorption rate is significantly
greater than the detoxification rate, there will be a rapid accumulation of free cyanide in the
tissues and body fluids, resulting in the prompt onset of signs of acute cyanide poisoning.
Clinical symptoms in the first stage of acute cyanide poisoning include headache, vertigo, weak
and rapid pulse, nausea and vomiting. In the second stage, there are convulsions, falling, dilated
pupils, clammy skin, and a weaker and more rapid pulse. In the final stage, the heart beat
becomes irregular and slow, body temperature falls, there is cyanosis of the lips, face, and
extremities, coma, frothy bloody saliva flow from mouth and death (Way, 1981).

Chronic cyanide poisoning may develop after ingestion of significant quantities of cyanide or
cyanide precursors in their diets as well as by chronic inhalation of tobacco smoke. Effects are
exacerbated by dietary deficiencies in vitamin B12 and other water soluble vitamins, iodine, and
sulfur amino acids, as well as by low levels and insufficient distribution of detoxifying enzymes
such as rhodanese (Solomonson, 1981). Cyanide levels in mainstream cigarette smoke have
been reported to range from 0.28 to 0.55 mg per cigarette of hydrogen cyanide, with the ratio of
cyanide concentration in sidestream smoke to mainstream smoke ranging from 0.006 to 0.27
(Fiksel et al., 1981). The serum of smokers contains about three times higher cyanide and
thiocyanate concentrations than the serum of non smokers (ATSDR, 1995).
3.2 Detoxification
The majority of the absorbed cyanide reacts with thiosulfate in the presence of enzymes to
produce thiocyanate, which is excreted in the urine over a period of several days. Owing to this
rapid detoxification, animals can ingest high sublethal doses of cyanide over extended periods
without harm (Eisler, 1991). Species vary considerably in both the extent to which thiocyanate is
formed and the rate at which it is eliminated from the body; thiocyanate metabolites resulting
from the transulfuration process are about 120 times less toxic than the parent cyanide
compound. Thiocyanate may accumulate in tissues and has been associated with developmental
abnormalities and other adverse effects. The two enzyme systems associated with the
transulfuration process are the rhodanese and beta-mercaptopyruvate cyanide sulfurtransferase
which are limited by the availability of sulfur. Minor detoxification pathways for cyanide
include exhalation in breath as HCN and as CO2 from oxidative metabolism of formic acid,
conjugation with cystine, combining with vitamin B12 to form cyanocobalamin, which is
excreted in the urine and bile, and binding with methemoglobin in the blood (Ballantyne, 1987).
Cyanide concentrates in the erythrocytes through binding with methemoglobin (USEPA, 1980)
and free cyanide concentrations in plasma are an indicator of cytotoxicity. Cyanide accumulates
in mammalian blood, spleen, brain, and cerebrospinal fluid which are the biological samples
taken for analysis in cyanide poisonings.
The measured rates of detoxification of cyanide by a guinea pig and by a human are 0.076 and
<0.001 mg/kg/minute, respectively (Ballantyne, 1987). In addition to rapid metabolic
detoxification, cyanide antidotes, taken orally and by injection, can be and have been
administered successfully to both humans and other animals. These antidotes include amyl
nitrite, sodium nitrite, and sodium thiosulfate.
Different species of migratory birds have been found dead within and adjacent to unnetted or
uncovered tailings impoundments in which the total cyanide levels exceeded 200 mg/l.
However, injured birds that were still alive after 60 minutes of exposure to 200 mg/l often
survived, due to very rapid metabolism and detoxification of cyanide to thiocyanate (Clark and
Hothem, 1991, and Wiemeyer, 1986).

Tissue specific biochemical effects have been studied (Pritsos, 1996) with the mallard duck
exposed perorally to sublethal doses of free cyanide ranging from 0.25 mg KCN/kg body weight
(10 ppm) up to 80 ppm KCN. Two hours after exposure, the ATP levels in the brain, heart, and
liver were measured. The ATP depletions in the brain and liver were dose dependent. Using 1
mg/kg body weight of KCN (40 ppm), an initial decrease in ATP levels in all tissue occurred
with a subsequent increase approaching control levels within 24 hours. In the brain tissue, the
recovery was the most dramatic with increases in ATP levels above control levels at 12 hours
and a return to control levels within 24 hours.
Further research conducted with mallard ducks (Pritsos, 1996) monitored the detoxification
systems in the heart, liver, and brain tissues after cyanide exposure by measuring the enzymatic
activities of rhodanese and 3-MPS (3-mercaptopyruvate sulfurtransferase). After 1 mg/kg body
weight of KCN exposure, rhodanese and 3-MPS activities were found to be unchanged in heart
and liver tissues. However, the brain showed a 64% increase in rhodanese and 3-MPS activates,
which also had the fastest recovery of ATP levels. The conclusion was that different metabolic
rates and detoxification enzymes activities exist in different duck tissues.
These studies with mallard ducks exposed to 10-80 ppm KCN, demonstrate the expected
toxicological effects on the cytochrome oxidase system by measurable, dose dependent
reductions in liver and brain ATP levels. Significantly, detoxification mechanisms were not
overwhelmed by cyanide, since the ATP levels returned to control levels after 24 hours exposure.
Measurements of the detoxification enzyme activities validated that the mallard duck exposure to
40 ppm free cyanide did not impair the organism's physiological detoxification mechanisms,
since the enzyme levels returned to control levels within 24 hours.
3.3 Antidotes
The classic nitrite-thiosulfate treatment of cyanide poisoning, developed about 60 years ago, in
combination with excess oxygen is one of the antidotal combinations still employed. Livestock
treatment in cases of suspected cyanide intoxication consists of intravenous administration of
sodium nitrite at 10-20 mg/kg body weight followed by sodium thiosulfate at 30-40 mg/kg body
weight. However, a sodium thiosulfate dose of 500 mg/kg body weight or more, may be more
effective (Biehl, 1984). Once clinical signs have abated, 1 gram of activated charcoal per
kilogram body weight may be administered as a drench by way of a stomach tube (Biehl, 1984).
Cobalt compounds, such as hydroxocobalamin and its derivatives have been used to treat cyanide
poisoning for more than 100 years after confirmation of their efficacy with pigeons and rabbits
(Way, 1981).

4.0 CYANIDE TOXICITY TO AQUATIC ORGANISMS
The observed toxicity to aquatic life of simple and complex cyanides is attributed almost entirely
to molecular, undissociated HCN, derived from ionization, dissociation, and photodecomposition
of cyanide-containing compounds. The acute toxicity of stable silver cyanide and cuprocyanide
complex anions is much less than that of molecular HCN. Toxicity of aquatic organisms to
organic, nitrile compounds is similar to that of inorganic cyanides because they usually undergo
rapid hydrolysis in water to free cyanide (Towill et al., 1978). There is general agreement that
total cyanide concentrations in water overestimate the actual cyanide toxicity to aquatic
organisms, because it measures non-toxic forms of the compound and is subject to analytical
interferences. The other forms of cyanide that must be considered in developing criteria, include
iron cyanide and weakly bound metal cyanides measured with free cyanide as the WAD (weak
acid dissociable) cyanide analysis, the most analytically reliable index of toxicity in aquatic
pollution.
The cyanide effects on selected aquatic organisms are presented in Table 3. Fish were generally
the most sensitive organisms tested under controlled conditions. Algae and macrophytes were
comparatively tolerant; adverse effects were reported at >160 ug free cyanide per liter (Table 3).
Temperature and activity modify the lethality of HCN to juvenile rainbow trout (Leduc, 1988);
higher resistance to cyanide correlated with higher activity and temperatures suggesting a faster
detoxification rate or higher oxidative metabolism. Low levels of cyanide that were harmful
when applied constantly, may be harmless under seasonal or other variations that allow the
organism to recover and detoxify (Leduc, 1981). Additionally, acclimation by certain species of
fish to low sublethal levels of cyanide through continuous exposure might enhance their
resistance to potentially lethal concentrations (Leduc, 1981).
Cyanide acts rapidly in aquatic environments, does not persist for extended periods, and is highly
species selective; organisms usually recover quickly on removal to clean water. The target sites
for cyanide toxicity in freshwater organisms include the gills, egg capsules, and other sites where
gaseous exchange and osmoregulatory processes occur. Signs of acute distress include increased
ventilation, gulping for air at the surface, erratic swimming movements, muscular incoordination
convulsions, tremors, sinking to the bottom, and widely extended gill covers. Thiosulfate
administered in the water with cyanide reduced the toxicity of cyanide to fish, presumably by
increasing the detoxification rate of cyanide to thiocyanate (Towill et al., 1978).
Fish reproduction is affected by cyanide concentrations in the range of 10 to 100 ug HCN/liter,

in the reduced number of spawned eggs and the viability of the eggs by delaying the process of
secondary yolk deposition in the ovary (Eisler, 1991). Developmental abnormalities were
reported in embryos of Atlantic salmon after extended exposure to cyanide (Leduc, 1984). Other
adverse effects of free cyanide concentrations of 10 ug/liter to fish include delayed mortality,
pathology, impaired swimming ability and relative performance, susceptibility to predation,
disrupted respiration, osmoregulatory disturbances, and altered growth patterns.

Table 3
Effects Of Free Cyanide On Aquatic Organisms

Table 3
Continued

Stimulatory effects of cyanide include increased growth of fish during exposure to low sublethal
levels; also known as a hermetic effect, applicable to many other chemicals (Leduc, 1984).
Sodium cyanide has a stimulatory effect on oxygen-sensitive receptors in lungfish, amphibians,
reptiles, birds, and mammals (Smatresk, 1986), which internally assist respiratory activity.
Factors increasing the toxicity of free cyanide in aquatic ecosystems include low dissolved
oxygen, low pH, but not hardness other than the effect hardness or alkalinity has on pH. Additive
and synergistic toxicity of free cyanide to aquatic fauna (Atlantic salmon smolth) has been
reported in combination with ammonia and low dissolved oxygen (Alabaster et al., 1983). The
acute toxicity of cyanide on fish in solutions containing only free cyanide decreases with
increasing pH, indicating the molecular form (HCN) is more toxic (2.3 times) than the anionic
form (CN-).
The toxicity of iron cyanide is related to the free cyanide formed through chemical or photolytic
dissociation and not to the complex itself. The decomposition of solutions can yield toxic HCN.
In streams and rivers, natural conditions are minimally conducive to photolytic breakdown of
iron cyanide to produce free cyanide since the actual percentage of UV light reaching the earth's
surface is minimal and further scattering, reflection, and absorption occurs (Doudoroff, 1976).
According to a long-term study by Environment Canada, approximately 90% of the free cyanide
formed through decomposition of iron cyanides is removed from surface waters through
volatilization and about 10% through oxidation or hydrolysis (Simovic et al., 1984).
Several investigators have examined the effect of photodecomposition on the toxicity of mining
solutions with iron cyanide levels near 20 mg/liter. The percentage breakdown of iron cyanide
ranged from 0.80-2.5% based upon comparison of the average WAD and iron cyanide levels
(Smith and Mudder, 1991). Once breakdown occurs, the HCN is rapidly removed from solutions
through volatilization, hydrolysis, and biodegradation. There is no evidence that WAD cyanide
accumulates in holding ponds or receiving streams due to the breakdown of iron cyanide released
in treated mine effluents (Smith and Mudder, 1991).
Antagonistic are the toxic effects of cyanide and nickel, since the toxicity to fathead minnows
decreased as the water alkalinity and pH increased above 7.5 (Doudoroff, 1976). As the HCN
concentration increases from dissociation from the nickel cyanide at acidic pH values, the
tolerance limits decrease. In general, since natural waters and mining effluents are alkaline,
complexation with nickel is effective in reducing the relative toxicity of cyanide, as is the effect
listed with other metals.
The toxicity of the metal cyanide complexes of zinc and cadmium is comparable with the
toxicity of free cyanide since the complexes are weak and dissociate nearly completely. Toxicity
criteria should be derived on the basis of WAD cyanide to adequately reflect the toxicity of the
metal cyanide complexes and their potential to dissociate.

Similarly, cyanide and copper are independently toxic to aquatic organisms. However,
complexes of copper and cyanide reduce the toxicity of the individual molecules by an order of
magnitude. For fathead minnows the 24 hour mean tolerance limits for copper cyanide, copper
and free cyanide are 2.2 mg/liter, <0.10 mg/liter, and 0.25 mg/liter as cyanide, respectively
(Doudoroff, 1976).
Site specific water quality criteria have been derived from consideration of all the metal
complexed and WAD cyanide forms present in treated mine wastewater discharging into
Whitewood Creek, South Dakota and New Zealand streams. An instream final chronic value for
WAD cyanide of 0.08 or 0.10 mg/liter has been calculated to be protective of aquatic life (Smith
and Mudder, 1991).
5.0 CYANIDE TOXICITY TO BIRDS
5.1 The Most Sensitive Species to Oral Cyanide
The sensitivity to cyanide toxicity of different species of birds is not related to body size, but
appears to be associated more with their diet (Wiemeyer et al., 1986). Birds that feed
predominantly on flesh, such as owls and kestrels, are more sensitive to cyanide than species that
feed mainly on plant material. The exception to this generalization is the mallard duck, as
judged by comparisons of its oral lethal dosages or LD50 (lethal dosage for 50% of the
population) values with those of other birds (Eisler, 1991). A summary of the effects of cyanide
on selected species of birds is presented in Table 4 (Eisler, 1991). The toxicity data indicated
that the mallard duck, due to its high sensitivity and importance as a migratory waterfowl
species, was the best model organism for use in the laboratory evaluation of the toxic effects of
cyanide and in the establishment of safe exposure levels.
The acute oral toxicity of free cyanide in tap water or in the actual mining solution, when
expressed in terms of mg/kg for the mallard duck, was consistent with those literature values
reported (Wiemeyer, 1986) for sodium cyanide. Figure 1 is the cyanide dose versus mortality
relationship in the mallard duck illustrating an LD50 (lethal dosage resulting in 50% mortality)
of about 150-200 mg/liter (Fletcher, 1986 and 1987). Assuming mallard ducks weigh 1.0 kg and
the acute ingested dose is about 10 milliliters, the LD50 values were 2.5 and 3.2 mg/kg in tap
water and in mine effluent, respectively. Reported acute oral toxicity values for sodium cyanide
range from 4.0 mg/kg for the American kestrel to 36 mg/kg of body weight for the turkey vulture
(Table 4). The data demonstrates that the mallard duck is one of the most sensitive species and
provides an excellent model organism for toxicity evaluations due to its importance as a
migratory waterfowl species. The absorption of cyanide from solution requires some time, as
does the onset of its toxic effects. During this same time period, the bird's metabolism and
detoxification of cyanide are initiated.

It is interesting to note that if the total cyanide level exceeds 250 mg/kg in a solid material, as
measured by the USEPA proposed Reactive Cyanide Method, that material is considered a
hazardous waste under RCRA (USEPA, 1985). As a result, several of these plant species could
be classified as hazardous substances using such criteria. In contrast, the same 250 kg animal
must rapidly ingest about 20 liters (5.2 gallons) of a solution containing 50 mg/l WAD cyanide
to reach a lethal dose. Cattle, sheep, horses, and swine have a daily water intake ranging from
about 40 to 65 liters. Therefore, exposure to properly contained and monitored manmade
cyanide solutions may be of minor important compared with the exposure of animals to natural
sources of cyanide in plants.
Summarized in Figure 2 are the laboratory and field data reflecting cyanide toxicity values in
mallard ducks. In general, the mallard duck tolerates slightly higher concentrations of cyanide
when it is in solution with other effluent or process solution ions. Using this data, the LC1
(lethal concentration resulting in 1% mortality for free cyanide was estimated to be about 50
mg/liter and is used as the level below which no mortality would be expected (Table 4). The
LC1 estimate is conservative, since it assumes a low no effect level, as well as instantaneous and
complete absorption of oral cyanide without consideration of metabolic detoxification.

Table 4
Effects Of Free Cyanide On Selected Species Of Birds
Species Dose and Other Variables Effects
Mallard, Single oral dose of NaCN
Anas platyrhynchos 0.53 mg CN/kg body weight (BW), No deaths
equivalent to 1 mg NaCN/kg BW
1.1 mg CN/kg BW (2.0 mg NaCN/kg BW) About 6% dead
1.43 mg CN/kg BW (2.7 mg NaCN/kg BW) LD 50; 95% confidence interval (C.I.)
of 2.2 and 3.2 mg NaCN/kg BW
Turkey vulture Single oral dose of 19.1 mg CN/kg BW, Up to 80% of the cyanide in blood
equivalent to 36 mg NaCN/kg BW was present as free cyanide and the
remainder as bound cyanide
Single oral dose of 19.1 mg CN/kg BW, Average time to death was about 19
equivalent to 36 mg NaCN/kg BW min and ranged between 8 and 41
min; cyanide residues postmortem,
in mg CN/kg fresh weight (FW),
were 6.7 in blood (Max. 21) and
0.6 in liver (Max. 2.8)
Rock dove, 1.6 mg CN/kg BW, equivalent to 4.0 mg Minimum lethal dose when
Columba livia KCN/kg BW administered intravenously or
intramuscularly
Black vulture, Single oral dose, as NaCN No deaths in 60 min. Mean and
Coragyps atratus 1.6 mg CN/kg BW maximum blood CN concentrations,
in mg/kg FW, were 0.7 and 0.9,
respectively
2.4 mg CN/kg BW Some deaths within 30 min. Mean
blood CN residues in mg/kg FW,
were 0.7 in dead birds vs. 1.2
in those surviving 60 min
2.54 mg CN/kg BW Acute oral LD50; 95% C.I. of 2.3
and 2.8 mg CN/kg BW (4.4-5.3 mg
NaCN/kg BW)
3.7 and 19.1 mg CN/kg BW All dead within 16 min.; maximum
blood CN levels postmortem were
2.1 mg/kg FW in the low dose group
and 4.2 in the high dose group
Japanese quail,
Coturnix japonica Single oral dose, as NaCN Acute oral LD50 for adult females;
4.5 mg CN/kg BW 95% C.I. of 3.1 and 6.5 mg CN/kg
BW
5.5 mg CN/kg BW Acute oral LD 50 for adult males;
95% C.I. of 4.0 and 7.5 mg CN/kg
BW

Table 4
(Continued)
American kestrel, 2.12 mg CN/kg BW, as NaCN Acute oral LD50; 95% C.I. of 1.6
Falco sparverius and 2.8 mg CN/kg BW
Domestic chicken, 0.6 mg CN/kg BW, equivalent to 1.5 mg Lethal
Gallus domesticus KCN/kg BW
0.78 mg CN/kg BW, as KCN Sublethal; thiocyanate excretion
increased 10 times after 10 min
and returned to normal levels
after 3.5 h; the total thiocyanate
collected was equivalent to 85% of
the administered dose
1.3 mg CN/kg BW, as KCN Lethal
Single oral dose, as NaCN
3.2 mg CN/kg BW, equivalent to 6.0 mg No deaths in 30 min; maximum CN
NaCN/kg BW levels, in mg/kg FW, were 1.1 in
blood and 0.06 in liver
6.4 mg CN/kg BW Some deaths in 30 min; maximum CN
levels, in mg/kg FW were 1.6 in
11.1 mg CN/kg BW Acute oral LD50; 95% C.I. of 6.4
and 19.1 mg CN/kg BW
25.4 CN/kg BW Advanced signs of acute poisoning;
death probable within 30 min;
maximum CN levels, in mg/kg FW,
were 1.5 in blood and 0.6 in liver
Dietary route
Fed cassava diets containing 4, 37, 70, or At all dietary levels, there was no
103 mg total cyanide per kilogram significant effect on survival,
ration to day-old chicks for 8 weeks growth, histology, haemoglobin,
hematocrit, or lymphocyte number;
however, serum thiocyanate levels
increased in a dose-dependent
manner
Fed diets containing 135 mg HCN/kg
Chicks, 20-day exposure
Growth and food intake significantly
depressed; plasma thiocyanate
Adults, 14-day exposure concentration increased
Urinary excretion of thiocyanate
increased 5 times in laying hens
Eastern screech-owl, 4.6 mg CN/kg BW, equivalent to 8.6 mg
Otus asio NaCN/kg BW Acute oral LD50; 95% C.I. of 3.8
and 5.4 mg CN/kg BW
European starling, 9.0 mg CN/kg BW, as NaCN
Sturnus vulgaris Acute oral LD50; 95% C.I. of 4.8
and 17 mg CN/kg BW
Andean condor, Single oral dose of 19.1 mg CN/kg BW
Vultur gryphus (36 mg NaCN/kg BW) Blood sampled immediately after
death contained 1.2 mg free CN
per litre and 0.5 mg bound CN
per litre
Reference: Eisler, 1991

Figure 1: Cyanide Dosage - Mortality Relationship in the Mallard Duck

Figure 2: Summary of Cyanide Toxicity to Mallard Ducks

5.2 Summary of Bird Mortalities at U.S. Mines
In the U.S., the federal Fish and Wildlife Service has jurisdiction regarding the protection of
birds under the 1991 Migratory Bird Treaty Act and the Endangered Species Act. The
requirement and goal of these acts is "zero mortality" at mining operations. During the later part
of the 1980's, as the number of mining operations in the southwestern U.S. increased sharply, the
number of bird mortalities also increased. The problem related to the establishment of new
solution ponds and tailings impoundments at the mining operations, which served as short term
resting areas for migratory birds and waterfowl in arid regions of the country.
Since the solution ponds and tailings impoundments were not covered and the cyanide levels
were at process strength, mortalities resulted. During the period of 1984 through 1989, about
9,000 wildlife deaths were reported at 59 mining operations located in the states of Arizona,
California, and Nevada. Nearly 70% of the total wildlife mortalities were reported at 53 mining
operations in Nevada. A summary of the wildlife mortalities, by year and number of mining
operations, is presented in Table 5 (Clark and Hothem, 1991). It shows that the number of
mining operations increased from 1986-1990, while the number of mortalities per operation fell
from 143 to 17 mortalities per mine as control strategies were developed. Based upon data
collected from 1990-1995, bird mortalities declined from nearly 1,300 birds to 221, or about an
80% reduction (The Gold Institute, 1996).
The magnitude of the mining-related bird deaths can be placed in perspective with other sources
of bird mortality statistics. Research conducted by Dr. William Jackson, professor emeritus of
biology, Bowling Green State University, revealed that ten billion birds are estimated to die
annually in the U.S., with 80 million birds dying from flying into windows and one million per
year colliding with radio and TV towers. About 12 million ducks are killed per year by hunters
(The Gold Institute, 1996).

Table 5
Wildlife Mortalities Reported By Nevada Mine Operators
Number of
Year Total Mines Mortalities
Mortalities Reporting Per Mine
1986 1,426 10 143
1987 1,488 32 47
1988 2,346 50 47
1989 1,955 57 34
1990 1,643 95 17
Reference: Clark and Hothem, 1991
The nearly 9,000 deaths in five years at 59 mining operations were less than one tenth of a
percent (<0.10%) of the total number of birds taken by hunters in those three states in one year,
which translated into about fifty-four million (54,000,000) birds over the same six year (1984-
1989) period. The primary issue was that the hunters could legally shoot the birds with a license,
while the mining operations were in violation of the Migratory Bird Treaty Act (GAO, 1991).
Most of the of the other animal mortality at the mining operations included rodents, rabbits,
amphibians, and reptiles (Henny et al., 1994).
In conjunction with the self-monitoring conducted by the various mining operations, the U.S.
Fish and Wildlife Service conducted a "spot" tour of seventeen mines in Nevada. A summary of
their observations are presented in Table 6 (Henny et al., 1994). The pond or impoundment sizes
examined ranged from 1-159 ha, while the WAD cyanide levels ranged from 8.4-216 mg/l.

Table 6
Weak Acid Dissociable Cyanide In Tailings Ponds
Discharge Pipe
Mine No. Pond Dead Detoxified
Size (ha) Birds WAD CN pH
(mg/L)
9 100 No 216 7.6 Yes
4 1 No 197 10.6 No
2 5 No 138 11.3 No
10 15 Yes 81 10.3 No
13 80 Yes 62 10.6 No
12 100 No 59 6.0 Yes
5 80 No 53 10.1 No
14 10 No 52 10.7 No
8 150 No 48 10.7 No
15 70 No 34 10.8 ?
3 1 No 30 NA Yes
7 5 No 26 11.4 No
16 70 No 23 10.5 ?
1 40 No 20 9.3 Yes
11 20 No 18 10.6 Yes
6 40 No 18 9.4 Yes
17 70 No 8.4 10.9 Yes
Reference: Henry et al., 1994
Although mortality was noted in the ponds at 81 and 62 mg/l, none were noted at the lower
WAD cyanide levels. Live birds were observed at all of the operations except at the mines
exhibiting the three highest WAD cyanide levels in their ponds. Some of the solutions had been
detoxified with hydrogen peroxide or by other means prior to their disposal in the ponds. No
mortalities were noted at WAD cyanide levels below 59 mg/l.
With the implementation of proven control strategies of hazing, stretch nets, and floating plastic
balls over impoundments, as well as treatment technologies, the issue of bird mortality has been
nearly eliminated and is not generally considered a major environmental problem at mining
operations.

6.0 CYANIDE TOXICITY TO MAMMALS
The toxicity data for selected mammals is presented in Table 7. Exposure to cyanide
experimentally via single oral LD50 doses ranging from about 4-24 mg HCN/kg body weight
reflected a wide range of mammalian species including the rats, mice, rabbits, dogs, and coyote.
Livestock found dead near a cyanide disposal site had been drinking surface water runoff from
the area that contained up to 365 mg/l free cyanide. No human cases of illness or death in the
U.S. due to cyanide ingestion from water supplies are known (USEPA, 1980). No known
accidental fatalities have occurred in the mining industry from cyanide poisoning in North
America during the past 20 years (The Gold Institute, 1996).
Illustrated on Table 7 are the various physiological systems and mammalian animals tested with
similar toxic target organ responses to inhaled cyanide. The acute health effects of inhaling
cyanide are respiratory failure and death at concentrations ranging from 100-1000 ppm.
Intermediate and chronic effects at lowest observable effect levels ranged from 1-100 ppm HCN.
The major target organs include the respiratory, neurological, cardiovascular, thyroid, systems
with less serious effects on other systemic functions. The airborne presence of cyanide can be
detected by most humans at concentrations around 1.0 ppm HCN, as a bitter almond-like
sensation to the olfactory system and has a vapor pressure of 630 mm Hg at 20oC (Eisler, 1991).
Some humans (20-40%) are genetically insensitive to the odor of cyanide.
The concentration of HCN immediately hazardous to human health is 50 ppm, the occupational
short-term (15 minute) exposure limit recommended is 5.0 ppm (NIOSH, 1994). As a chemical
asphyxiant, cyanide's oxygen depleting effects are most critical to the brain and heart. A
combination of rapid breathing, convulsions, and lactate acidosis leading to unconsciousness are
symptoms of acute cyanide poisoning.
Skin surfaces, especially abraded sites, wounds, and mucous membranes are penetrable,
permeable surfaces for cyanide uptake and its acutely toxic effects. In one case, liquid HCN ran
over the hand of a worker wearing a fresh air respirator. He collapsed into unconsciousness in
five minutes, but ultimately recovered (USEPA, 1980). Mammalian deaths were recorded at
dermal applications between 2.3 mg/ HCN/kg body weight for abraded skin and 100 mg HCN/kg
body weight for intact skin (Eisler, 1991).
Chronic exposures to low levels of cyanide in the air, diet, or water are generally metabolized,
excreted and not accumulated. The detoxification rate for humans is <0.001 mg/kg body weight
per minute (Ballantyne, 1987) which is affected by the individual's aerobic metabolic rate and
capacity, by adequate nutritional intakes, and by concurrent exposures or health problems.
Chronic high cyanide levels from dietary or tobacco smoke sources, increases blood plasma of
thiocyanate and goiters in mammals; effects are exacerbated by dietary deficiencies in vitamin
B12, iodine, and sulfur amino acids, as well as by low levels and insufficient distribution of
detoxifying enzymes such as rhodanese (Solomonson, 1981).

Table 7
Cyanide Toxicity to Mammals
Species & Dose Exposure Variables & Effects References
Livestock
>200 mg HCN/kg BW Lethal
15-20 kg Sudan grass per animal daily Lethal to 13 cattle, 21 sick Bapat and Abhyanker, 1984
Dog
2 mg NaCN/kg BW Recovery in 30 min., no adverse effects in 15 USEPA, 1985a
months
24 mg NaCN/kg BW Lethal, single oral dose Christel et al., 1977
150 mg NaCN/kg BW Exposure 30 days in diet, no measurable effect
on food consumption, blood chemistry,
behaviour or organ histology USEPA, 1985a
Coyote
4.1 mg NaCN/kg BW LD50, single oral dose Sterner, 1979
8 mg NaCN/kg BW Immobilized in 9 min., death within 41 min. Sterner, 1979
African Giant Rat

1,000 mg KCN/kg BW Exposure 12 weeks to weanlings, adverse effects Tewe, 1988
on growth when cassava peel exceeds 7.8% of
the ration
Mouse
8.5 mg KCN/kg BW LD50, single oral dose USEPA, 1989
3.4 mg CN/kg BW LD50, single oral dose USEPA, 1989
1,000 mg KCN/L drinking water Exposure 40 days, inhibition of cytochrome Buzaleh, 1989
oxidase activity
Rabbit
2.5 mg HCN/kg BW LD50, single oral dose
5.1 mg NaCN/kg BW LD50, single oral dose
5.8 mg KCN/kg BW LD50, single oral dose
12.8 mg NaCN/kg BW Lethal in 22 mins. Ballantyne, 1987
20 mg of acrylonitrile Inhalation HCN from combustion, lethal in 12-16 Yamamoto et al., 1979
mins.
Lab White Rat
3.6-4.2 mg HCN/kg BW LD50, single oral dose
5.1-5.7 mg NaCN/kg BW LD50, single oral dose Ballantyne, 1987
8 mg CN/kg BW Exposure 21 days, liver normal USEPA, 1989
21 mg CN/kg BW Exposure 21 days, increased liver weight USEPA, 1989
750 mg CN/kg BW Exposure 8 weeks, diet KCN, no measurable Tewe and Maner, 1985
effects on growth
3,778 mg HCN/m3 Inhalation, 10 sec., LC50 Ballantyne, 1987
151-173 mg HCN/m3 Inhalation, 30-60 min., LC50 Ballantyne, 1987
Domestic Pig
96 mg CN/kg ration Exposure 72 days, cassava peel, no effect on Tewe and Pessu, 1982
food consumption or protein metabolism

Of primary concern for wildlife and stock animals is their exposure through ingestion of
cyanogenic or cyanide-producing plants, such as bamboo, sorghum, certain fruits, lima beans,
and cassava. Neuropathies associated with cyanide intoxication such as due to cassava ingestion,
in humans and domestic animals include nerve deafness, optic atrophy, and ataxia as well as
inflammations of mucous membranes. The detoxification product thiocyanate can cause goiter
by inhibiting the absorption of iodine (Way, 1981). A summary of the potential cyanide
production from different plant species is presented in Table 2.
The recommended limits of cyanogenic plants are less than 200 mg/kg HCN in the diet of
livestock animals (Table 7). Sorghum, cassava, bamboo, and lima beans can produce up to 2,000
mg/kg or ppm of total cyanide, following ingestion of the plant material (Eisler, 1991).
Assuming consumption of 4.0 mg of HCN per kilogram of body weight by a range animal could
be fatal (to the most sensitive animals), ingestion of only 0.50 kg of plant material capable of
producing 2,000 mg HCN/kg would be necessary to cause death in 250 kg animal.
Poisoning of herbivorous ungulates is more prevalent under drought conditions, when these
mammals become less selective in their choice of forage and dry growing conditions also
enhance cyanogenic glycoside accumulations in certain plants (Towill, 1978). In general, cattle,
sheep, horses, and pigs, in that order, are most vulnerable to cyanogenic plants. Deer and elk
have been observed to graze on forages that contain a high content of cyanogenic glycosides.
However, cyanide poisoning has not been reported in these species (Towill et al., 1978).
Management of cyanide-containing plants may effectively control potentially adverse

mammalian exposures to dietary cyanide. Hay and silage should be properly cured in order to
minimize cyanide content before feeding to livestock (Egekeze and Oehme, 1980). Selective
breeding of plants with low cyanide content will help reduce livestock and wildlife poisoning,
but the most advisable prevention method at present is to prohibit grazing on field where
cyanogenic plants are present (Egekeze and Oehme, 1980) or eradicate the cyanogenic plants.
The toxicity of the products from cyanide degradation in the environment are presented in Table
8. The lethal dosages to mammals and amphibians, via the oral and subcutaneous routes are
tabulated for ammonia, ammonium carbonate, ammonium sulfate, ammonium thiosulfate,
potassium thiocyanate, disodium thiosulfate, magnesium thiosulfate, and sodium nitrate. The
most sensitive organism to ingestion of these products is the frog whose LD50 = 300 mg
potassium thiocyanate/kg body weight. The most sensitive organism to subcutaneous exposure
to these products is the guinea pig whose lowest published lethal dose was 150 mg potassium
thiocyanate/kg body weight. In general, free cyanide exhibits greater toxicity than the products
from cyanide degradation processes. Therefore, criteria which protect against cyanide toxicity
should also be protective of these degradation products.

Table 8
Toxicological Data For Cyanide Related Compounds
Organism Compound Dosage Route Effect
Rat ammonia 350 mg/kg oral LD50
Frog ammonium 250 mg/kg sub-cutaneous Lowest published lethal dose
carbonate
Domestic Animal ammonium 3,500 mg/kg oral Lowest published lethal dose
sulphate
Guinea Pig ammonium 600 mg/kg oral Lowest published lethal dose
thiocyanate
Mouse ammonium 330 mg/kg oral Lowest published lethal dose
thiocyanate
Guinea Pig ammonium 1,098 mg/kg oral LD50
thiosulphate
Frog potassium 300 mg/kg oral Lowest published lethal dose
thiocyanate
Rabbit potassium 500 mg/kg oral Lowest published lethal dose
thiocyanate
Human potassium 428 mg/kg oral Lowest published lethal dose
thiocyanate
Guinea Pig potassium 150 mg/kg sub-cutaneous Lowest published lethal dose
thiocyanate
Pigeon potassium 500 mg/kg sub-cutaneous Lowest published lethal dose
thiocyanate
Rabbit disodium 4,000 mg/kg sub-cutaneous LD50
thiosulphate
Frog disodium 6,000 mg/kg sub-cutaneous LD50
thiosulphate
Mouse magnesium 850 mg/kg sub-cutaneous LD50
thiosulphate
Rat sodium nitrate 3,236 mg/kg oral LD50
Rabbit Sodium nitrate 2,680 mg/kg oral LD50
Reference: Registry of Toxic Effects of Chemical Substances

National Institute for Occupational Safety and Health (NIOSH)
U.S. Dept. of Health and Human Services
Washington, D.C., Volumes 1 and 5, 1985-1986

7.0 CYANIDE CRITERIA FOR ENVIRONMENTAL PROTECTION
The release of cyanide to the environment is due to both nonpoint and point sources arising from
combustion, manufacturing and processing of cyanides, with most of the emissions ending in the
air. Wildlife and livestock exposures to environmental cyanide are likely due to primarily
natural sources. Selective breeding of plants with low cyanide content will help reduce livestock
and wildlife poisoning, but the most advisable prevention method at present is to prohibit grazing
on field where cyanogenic plants are present (Egekeze and Oehme, 1980) or eradicate the
cyanogenic plants. Cyanide has low persistence in the environment due to volatilization,
hydrolysis, oxidation, and precipitation and is not accumulated or biomagnified in any mammal
or food web studied. Recommended cyanide criteria for protecting marine organisms, birds,
livestock, and humans and their reference documents are found in Table 9.
The chemistry and toxicology of cyanide in wildlife and humans has been well studied. The
acute toxicity of cyanide is based on tissue hypoxia caused by free cyanide; orally, inhaled, or
dermally. Cyanide complexes in wastewaters may contain toxicologically significant
concentrations of metals ions. The toxicity of free cyanide has been evaluated at various food
web levels including: algae, macroinvertebrates, amphibians, numerous species of fish, birds
(quails, vulture, condors, owls, and kestrels), and mammals (rodents, coyote, dog, pig, livestock,
and man). Fish are generally the most sensitive representatives of aquatic toxicity. The principal
toxicological hazard of cyanide is acute exposures at high concentrations, such as rapid ingestion
of cyanide-containing forage.
Mammalian chronic exposure to cyanide at sublethal concentrations, in food or water, has not
been shown to have adverse, bioaccumulative effects due to rapid detoxification and excretion
processes (Eisler, 1991). Exposures to cyanide in mining solutions have been generally
controlled with physical exclusion methods, with chemical treatment and recovery of cyanide,
and/or by maintaining the levels of WAD cyanide below 50 mg/liter. These cyanide criteria are
based on laboratory and field investigations, consensus among regulators and provide
conservatism by protecting the most sensitive organisms from the lowest adverse effect levels,
which provides protection for other avian and mammalian members of the ecosystem.

Table 9
Cyanide Criteria Proposed for Environmental Protection

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mill effluents". Wastewater Technology Center, Environment Canada, Dec. 12-14, 1984.
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evidence for two chemoreceptor loci". Am J. Physiol. 251(1, Part 2):R116-R125, 1986.
Smith, L.L., Jr., S.J. Broderius, et al., "Acute and chronic toxicity of HCN to fish and
invertebrates". U.S. Environmental Protection Agency Report 600/3-79-009, 129 pages, 1979.
Smith, A., and Mudder, T., The Chemistry and Treatment of Cyanidation Wastes, Mining
Journal Books, London, England, December, 1991.
Solomonson, L.P., "Cyanide as a metabolic inhibitor". In B. Vennesland, E.E. Conn, C.J.

Knowles, J. Westley, and F. Wissing, eds., Cyanide in Biology, Academic Press, New York,
l981.
Sterner, R.T., "Effects of sodium cyanide and diphacinone in coyotes (Canis latrans):
applications as predicates in livestock toxic collars". Bull. Environ. Contam. Toxicol. 23:211-
217, 1979.
Tewe, O.O., "Performance, nutrient utilization and cyanide metabolism in African giant rats
(Cricetomys gambianus Waterhouse) fed varying dietary levels of cassava peels". Anim.
Technol. 39:88-82, 1988.
Tewe, O.O., and J.H. Maner, "Cyanide, protein, and iodine interaction in the performance and
metabolism of rats". J. Environ. Pathol. Toxicol. Oncol. 6:69-77, 1985.
Tewe, O.O. and E. Pessu, "Performance and nutrient utilization in growing pigs fed cassava peel
rations containing different cyanide levels". Nutr. Rep. Int. 26:51-58, 1982.
The Gold Institute, Gold Issues Briefing Book, Washington, DC, 1996.
Thompson, R.S., "Measurement of the inhibition of amino acid uptake. A toxicity test procedure
using mussels". In G. Persoone, E. Jaspers, and C. Claus, eds., Proc. Int. Symp. Ecotoxicol.
Test. Mar. Environ., Ghent, Belgium, September, 1983.
Towill L.E., J.S. Drury, B.L. Whitfield, et al., "Reviews of the environmental effects of
pollutants. V. Cyanide". EPA Health Effects Research Laboratory, Office of Research and
Development, Cincinnati, OH. NTIS PB28-9920, 1978.

Toxics Release Inventory 1992 (TRI92), National Library of Medicine, National Toxicology
Information Program, Bethesda, MD, 1994.
USEPA, "Ambient water quality criteria for cyanides". U.S. Environmental Protection Agency,
USEPA, Rep. 440/5-80-037, 72 pp., 1980.
USEPA, "Health effects assessment for cyanide". EPA/540/1-86-011. Response prepared by the
Office of Health and Environmental Assessment Environmental Criteria and Assessment Office
for the Office of Solid Waste and Emergency Response, 1984.
USEPA, "Basis for Listing Hazardous Waste," 40 CFR 261, App. VII, EPA, 1985.
USEPA, "Cyanide". Rev. Environ. Contam. Toxicol. 107:53-64, 1989.
USEPA, "Mining Waste NPL Site Summary Reports for Cimarron Mining Site in New Mexico
and the Silver Mountain Mining Site in Washington," final drafts, prepared by Science
Applications International Corp., Falls Church, Virginia, June 21, 1991.
USEPA, "Drinking water criteria document for cyanide", 1992.
Venkataramani, E.S., Ahlert, R.C., Corbo, P., "Biological treatment of landfill leachates." CRC
Crit. Rev. Environm. Control, 14:333-376, 1984.
Way, J.L., "Pharmacologic aspects of cyanide and its antagonism". In B.Vennesland, E.E. Conn,
C.J. Knowles, J. Westley, and F. Wissing, eds., Cyanide in Biology, Academic Press, New York,
l981.
Way, J.L., "Cyanide intoxication and its mechanism of antagonism". Ann. Rev. Pharmacol.
Toxicol. 24:451-481, 1984.
Weimeyer, S., Scott, J., Anderson, M., Bloom, P., and Stafford, C., "Environmental
Contaminants in California Condors". J. Wildlife Management, 52:238-247, 1986.
Wiley, R.W., "A review of sodium cyanide for use in sampling stream fishes". N. Am. J. Fish.
Manage. 4:249-256, 1984.
Yamamoto, K., et al., "A blood cyanide distribution study in the rabbits intoxicated by oral route
and by inhalation". Z. Rechtsmed. 83:313-317, 1979.
Yasuno, M., S. Fukushima, F. Shioyama, J. Hasegawa, and S. Kasuga, "Recovery precesses of

benthic flora and fauna in a stream after discharge of slag containing cyanide". Verh. Int. Ver.
Theor. Angew. Limno. 21:1154-1164, 1981.

HUMAN CYANIDE TOXICITY
Prepared By:
Steven Baskin, Pharm.D., Ph.D., FCP, FACC, DABT, FATS

Thomas Brewer, M.D., FACP
Originally published in as “Cyanide Poisoning”, Chapter 10 in Textbook on Military Medicine,

Edited by F.R. Sidell, E.T. Takafuji and D.R. Franz, Department of the Army, United States of
America, Chemical Casualty Care Division, MMCC Supplemental Training Series, 1997.
Reformatted and reprinted with permission of Steven I. Baskin, Pharm.D., Ph.D., Team Leader,
Biochemical Toxicology, Pharmacology Division, United States Army Medical Research
Institute of Chemical Defencse, Aberdeen Proving Ground, Maryland 21010-5400
This publication was prepared by a U.S. government employee. This work was performed in
accordance with duties as a federal employee. All copyright regulations were within the
guidelines of the U.S. rules and regulations for a federal employee.
Cyanide Poisoning
1.0 INTRODUCTION
Cyanide, long considered a toxic, deadly substance, has been used as a poison for thousands of
years. It was not highly successful as a chemical warfare agent in World War I, possibly
because of the way it was delivered. The effects of a high dose of cyanide are quick, and death
occurs within minutes. Antidotes are effective if administered in time.
Cyanide is ubiquitous. It is present in some foods, in the products of combustion of synthetic

materials, and is widely used in industry. Much of the cyanide used is in the form of salts, such
as sodium, potassium, or calcium cyanide. The cyanides of military interest are the volatile
liquids hydrocyanic acid (hydrogen cyanide, HCN; North American Treaty Organization
[NATO] designation: AC) and cyanogen chloride (NATO designation: CK) (Table 1).
Although substances containing cyanide had been used for centuries as poisons, it was not until
1782 that cyanide itself was identified. It was first isolated by the Swedish chemist Scheele, who
later may have died from cyanide poisoning in a laboratory accident.
TABLE 1
CHEMICAL, PHYSICAL, ENVIRONMENTAL, AND
BIOLOGICAL PROPERTIES OF CYANIDES
Properties Hydrogen Cyanide (AC) Cyanogen Chloride (CK)
Chemical and Physical
Boiling Point 25.7oC 12.9oC
Vapor Pressure 740 mm Hg 1,000 mm Hg
Density:
Vapor 0.99 at 20oC 2.1
Liquid 0.68 g/mL at 25oC 1.18 g/mL at 20oC
Solid Crystal: 0.93 g/mL at -40oC
Volatility 1.1 × 106 mg/m3 at 25oC 2.6 × 106 mg/m3 at 12.9oC
Appearance and Odor Gas: Odor of bitter almonds Colorless gas or liquid
or peach kernels
Solubility:
In Water Complete at 25oC 6.9 g/100 mL at 20oC
In Other Solvents Completely miscible in Most organic solvents
almost all organic solvents (mixtures are unstable)
Environmental and Biological
Detection ICAN: M254A1 kit M256A1 kit
Persistency:
In Soil <1 h Nonpersistent
On Materiel Low Nonpersistent
Skin Decontamination Water; soap and water Water; soap and water
Biologically Effective Amount:
Vapor (mg-min/m3) LCt50: 2,500-5,000 LCt50: 11,000
(time dependent)
Liquid (mg/kg) LD50 (skin): 100 --
ICAD: individual chemical agent detector
LCt50: the vapor or aerosol exposure [concentration × time] that is lethal to 50% of the exposed population
LD50: the dose that is lethal to 50% of the exposed population
100 S. Baskin & T. Brewer

Cyanide Poisoning
Military Uses
Since the days of ancient Rome, cyanide and the derivatives of this highly toxic substance have
been used as weapons.1 Nero used cherry laurel water, which contains cyanide as its chief toxic
component, to poison members of his family and others who displeased him. Napoleon III
proposed the use of cyanides to enhance the effectiveness of his soldiers’ bayonets during the
Franco-Prussian War.
During World War I, in late 1915 and early 1916, the French were the only proponents for using
cyanide and its derivative, hydrocyanic acid. This was made by distilling a concentrated solution
of potassium cyanide with dilute sulfuric acid. Its use, however, proved to produce less than its
desired effect. A highly volatile gas and lighter than air, hydrocyanic acid persisted for only a
few minutes in the open air; this made it difficult to disperse a lethal concentration (also, the
munitions used had a small payload). The effects of cyanide were not cumulative. In addition,
the Germans, on learning of its use, equipped their troops with a mask that was capable of
filtering out the gas. These combined factors made hydrocyanic acid less effective as a weapon.
About September 1916, the French tried another cyanide-based poison, cyanogen chloride,
which is heavier and less volatile than hydrocyanic acid and which had a cumulative effect on its
victims. Cyanogen chloride was produced by chlorinating a saturated solution of potassium
cyanide at 0oC (32°F). Its toxicity was similar to that of hydrocyanic acid, but cyanogen chloride
was more effective at low concentrations (it irritated the eyes and lungs). Cyanogen chloride
also had a delayed toxic effect similar to such lung irritants as chlorine and phosgene. At high
concentrations, cyanogen chloride is capable of killing by rapidly paralyzing the respiratory
system's nerve center.2
At about the same time that the French launched cyanogen chloride, the Austrians introduced
their own poisonous gas, which was derived from potassium cyanide and bromine. The resulting
cyanogen bromide was highly volatile, yet it had only a quarter of the volatility of hydrocyanic
acid and was less toxic. Cyanogen bromide had a strong irritating effect on the conjunctiva and
on the mucous membranes of the respiratory system; however, because it corroded metals and
was unstable in storage (gradually polymerizing into a toxicologically inert substance), the
Austrians abandoned its use.2
During World War II, the Nazis employed hydrocyanic acid adsorbed onto a dispersible
pharmaceutical base (Zyklon B) to exterminate millions of civilians and enemy soldiers in the
death camps.3,4 Zyklon B was a fumigant and rodenticide. One of its uses in the United States
and other countries was to rid ships of rodents.
In the late 1980s, reports indicated that cyanide-like agents may have been used against the
inhabitants of the Syrian city of Hama5 and the inhabitants of the Kurdish city of Halabja, Iraq,6
and possibly in Shahabad, Iran, during the Iran-Iraq War.7 Based on this recent history, acute
cyanide poisoning continues to constitute a threat for U.S. soldiers in future conventional or
nonconventional conflicts.

Cyanide Poisoning
Nonmilitary Uses
There has been little use of cyanide by the military; most of the information on cyanide
poisoning has been from civilian experience in poisoning, fires, and industrial accidents. Most
people probably contact cyanide in some form almost every day. Hundreds of thousands of tons
of cyanide are manufactured annually in this country. Cyanide is used in many chemical
syntheses, electroplating, plastics processing, gold and silver extraction, tanning, metallurgy, and
as a fumigant. Cyanides are in some foods; are pyrolysis products of many substances; and have
gained notoriety for their use in executions, homicides, and suicides.
Cyanide poisoning has been reported8 from eating chokecherries, bitter almonds, and apricot
pits. In addition, cyanide is found in lima beans and cassava beans and roots. Cassava is a staple
in certain countries and is blamed for the high incidence of tropical ataxic neuropathy in those
areas.
Combustion of synthetic products that contain carbon and nitrogen, such as plastics and synthetic
fibers, releases cyanide. Cigarette smoke contains cyanide; the nonsmoker averages 0.06 ug/mL
of cyanide in blood, whereas the smoker has 0.17 ug/ mL.9 The effects of cyanide and of carbon
monoxide, also formed in fires, are additive because they both contribute to tissue hypoxia by
different mechanisms. The two gases are major causes of combustion-related fatalities.10 In
residential fires, cyanide poisoning may be more significant than has previously been
appreciated. The short half-life of cyanide in blood contributes to the low concentrations of
cyanide found in fire victims when blood is drawn after the victims reach the hospital.
TABLE 2
BLOOD CYANIDE LEVELS IN VICTIMS OF
SMOKE INHALATION
Total Subjects Blood Cyanide Levels
(Mean ± SD)
Fire Victims* (N=109)
Survivors (N=66) 21.6 ± 36.4 umol/L (P<0.001)
Fatalities (N=43) 116.4 ± 89.6 umol/L (P<0.001)
Controls (N=114) 5.0 ± 5.5 umol/L
*Of the 66 fire victims who survived, 9 had blood cyanide levels above 40 umol/L and 3 had levels above l00
umol/L. Of the 43 fire victims who died, 32 had blood cyanide levels above 40 umol/L and 20 had levels above l00
umol/L.
Data source: Baud FJ, Barriot P, Toffis V, et al. Elevated blood cyanide concentrations in victims of smoke
inhalation. N Engl J Med. 1991:325(25):Fig 1:1763.
From April 1988 through April 1989, a team of French investigators11 collected samples - on the
scene - from 109 victims of residential fires in and around Paris, France. The data they gathered
were compared with data from a control group (N = 114) of individuals whose injuries were not
caused by fire.

Cyanide Poisoning
Blood cyanide concentrations were much higher in the fire victims than in the control group
(Table 2), and victims who died had significantly higher levels (>5-fold) than victims who
survived. Contrary to what previous researchers have concluded, the results from this study
"suggest that cyanide poisoning may prevail over carbon monoxide poisoning as the cause of
death in some fire victims.”11 Therefore, military medical officers need to be aware that victims
of smoke inhalation from fires may be suffering the effects of cyanide poisoning, and might
benefit from early antidotal cyanide therapy.
In addition, cyanide is used by governments, terrorists, corporations, and individuals to achieve

various economic, beneficial, humanitarian, or harmful ends:
• Cyanide is the agent used in "gas chambers," in which a cyanide salt is dropped into an
acid to produce HCN. (These chemicals - an acid and a cyanide salt - were found in
several subway restrooms in Tokyo, Japan, in the weeks following the release of nerve
agents in Tokyo in March 1995.)12
• It was illicitly placed in bottles of Tylenol (acetaminophen, manufactured by McNeil1

Consumer Products Co., Fort Washington, Pa.) in the Chicago area in 1982, killing seven
people.13
• In 1978 near Port Kaituma, Guyana, the followers of the Reverend Jim Jones drank a
grape-flavored drink laced with cyanide, and more than 900 children and adult members
of the People's Temple committed mass suicide.14
• Furthermore, cyanide is a metabolic product of ingested Laetrile (an alleged cancer

chemotherapeutic compound not available in this country) and may have been
responsible for the deaths of some patients who took this substance.
Chronic ingestion of cyanide in the form of organic cyanogens is a public health problem in
areas such as East Africa and Southeast Asia. Several common plants contain cyanogenic
glycosides15,16; ingestion coupled with improper processing of such cyanogenic glycosides can
result in death. Consumption of foodstuffs such as cassava result in tropical neuropathies in
Africa17 and in other diseases, such as tropical thyroid disease and tobacco amblyopia.
2.0 BIOCHEMICAL BASIS FOR POISONING
Although cyanide is known to bind and inactivate several enzymes, it is thought to exert its
ultimate lethal effect of histotoxic anoxia by binding to the active site of cytochrome oxidase,
thereby stopping aerobic cell metabolisml8,19 after an initial effect on excitable tissue. The
binding to the cytochrome oxidase can occur over minutes. A more rapid effect appears to occur
on neuronal transmission. No antagonists are known for the latter reaction, although it appears
to be feasible to develop competitive antagonists for cyanide at a cytochrome oxidase-binding
site.20

Cyanide Poisoning
The most important route of cyanide excretion is by formation of thiocyanate (SCN-), which is
subsequently excreted in the urine.17 Thiocyanate possesses a less inherent toxicological hazard
than cyanide, cyanate, or isocyanate. Thiocyanate formation is catalyzed directly by the enzyme
rhodanese (EC 2.8.1.1) and indirectly via a spontaneous reaction between cyanide and the
persulfide sulfur products of the enzymes 3-mercaptopyruvate sulfurtransferase (EC 2.8.1.2)21
and thiosulfate reductase (EC number unassigned). The mechanisms of all three enzymes22 as
well as the pharmacokinetics of thiocyanate formation23 have been studied. Although 3-
mercaptopyruvate functions to convert cyanide to this cyanate, its instability and sulf-auto-
oxidation at a basic pH may mask this effect.24 The enzymatic routes are efficient but have an
insufficient capacity for detoxification in acute poisoning because of lack of sulfur donors. The
mitochondrial sulfurtransferase reactions are exploited by the administration of sodium
thiosulfate (used in therapy and discussed later in this chapter) in the treatment of acute
poisonings. It is still not known with any certainty, however, what specific endogenous sulfur
sources participate in the formation of thiocyanate from cyanide.25
A minor route of metabolism is the oxidation of cyanide to cyanate (CNO-), which occurs via
enzymatic and nonenzymatic pathways. The interaction of cystine and cyanide to form 2-amino
thiazoline 4-carboxylic acid and its tautomer accounts for approximately 20% of cyanide
metabolism. This increases with toxic doses of cyanide. However, the protection conferred by
forming cyanate derivatives is limited because of the cell's inability to utilize oxygen during
cyanide intoxication.
Combined, these metabolic routes detoxify 0.017 mg of cyanide per kilogram of body weight per
minute in the average human. Cyanide is one of the few chemical agents that does not follow
Haber's law, which states that the Ct (the product of concentration and time) necessary to cause a
given biological effect is constant over a range of concentrations and times. For this reason, the
LCt50 (the vapor or aerosol exposure that is lethal to 50% of the exposed population) for a short
exposure to a high concentration is different from a long exposure to a low concentration.
Cyanide Pharmocokinetics and Pharmocodynamics
Cyanide appears to display first-order kinetics during the period of initial toxicity.23 The volume
of distribution for cyanide appears to change as the blood levels of the chemical change,26 but
these alterations probably reflect the marked intracellular sequestration of the molecule. Animal
studies27,28 show a differential disposition of inhaled HCN, with the highest tissue levels found in
the lung, heart, and brain. These data seem to corroborate the evidence from other animal
studies and from clinical reports that emphasize the importance of these organs in cyanide
toxicity. Ingestion of cyanide results in much higher levels in the liver than does inhalation; this
is a useful differential point in forensic investigations. Cyanide also has wide-ranging
cardiovascular effects, including a poorly understood increase in vascular resistance in the early
phases of poisoning29 and a marked increase in cerebral blood flow in dogs.30

Cyanide Poisoning
Data from rodent studies suggest that a single, acute administration of a cyanide salt leads either
to death or to complete recovery. However, data from HCN inhalational studies in dogs, rabbits,
monkeys, and humans suggests that death may be delayed for up to 8 days.31,32 The neurological
sequelae of cyanide intoxication may be delayed for up to a year.1 These delayed changes in
regional sensitivities of the brain are thought to be due to hypoxic stress and are analogous to
those seen following sublethal carbon monoxide poisoning.
Toxicity
Although they are generally considered to be very toxic substances, when compared with other
lethal chemical warfare agents, cyanides are among the least toxic. The LCt50 for hydrogen
cyanide (hydrocyanic acid) is generally stated to be 2,500-5,000 mg-min/m3 ; for cyanogen
chloride, about 11,000 mg-min/m3. (Comparable values for the nerve agents are 10-200 mg-
min/m3; for sulfur mustard, 1,500 mg-min/m3 ; and for phosgene, 3,000 mg-min/m3.)
The estimated intravenous dose that is lethal to 50% of the exposed population (LD50) of
hydrogen cyanide for man is 1.0 mg/kg, and the estimated LD50 for liquid on the skin is about
100 mg/kg.
The effects from cyanide poisoning are those of progressive histotoxic tissue hypoxia. The
symptoms, signs, and physical findings are directly related to the dose of cyanide, the route of
exposure, and the type of cyanide compound. In addition to the effects described below,
cyanogen chloride also produces irritation of the eyes and mucous membranes similar to that
produced by riot control agents.
On a military battlefield, casualties will be from exposure to cyanide gas; this can be fatal within
minutes after exposure to high concentrations. An initial hyperpnea (15 sec after exposure), due
to the effect of cyanide on the chemoreceptor bodies, is closely followed by a loss of
consciousness (30 sec after exposure). This progresses to apnea (3-5 min after exposure),
cessation of cardiac activity (5-8 min after exposure), and death.
After exposure to lower concentrations, or exposure to lethal amounts via the oral or
percutaneous routes, the effects are slower to develop. For example, after ingestion of a lethal
dose of a cyanide salt, the casualty might have 15 to 30 minutes of survival time during which an
antidote could be administered.
Prominent early signs and symptoms of cyanide poisoning include a transient hyperpnea,
headache, dyspnea, and findings of general central nervous system (CNS) excitement, including
anxiety, personality changes, and agitation progressing to seizures.33 Diaphoresis, flushing,
weakness, and vertigo may also be present. Late-appearing indications of CNS depression, such
as coma and dilated, unresponsive pupils, are prominent signs of cyanide intoxication.33-35 These
signs are not specific for cyanide poisoning, which makes the distinction from other types of
poisoning very difficult without a history of exposure. The telltale odor of bitter almonds cannot
be used as a guide because 40% to 60% of the population is unable to detect the odor.36

Cyanide Poisoning
Because the toxic effect of cyanide is to block tissue uptake and utilization of oxygen, the
casualty is transiently flushed and may have other, related signs of poor tissue oxygen extraction.
For example, funduscopic examination shows an equally bright red color for retinal arteries and
veins because of poor oxygen extraction. Increased oxygenation of venous blood is also
responsible for a "cherry-red" skin color, but this sign may not always be present.
Laboratory Findings
Relevant laboratory findings include an early decreased arteriovenous difference in the partial
pressure of oxygen (PO2) with progressive lactic acidosis.
Timely measurements of blood and urine concentrations for suspected intoxicants are useful in
guiding clinical therapy, especially when there is toxicity associated with the treatment agents.
Unfortunately, analysis of cyanide in biological fluids is a difficult task for a variety of reasons.37
Also, measurements of blood cyanide concentrations are almost never available during the
treatment phase. Blood concentrations of cyanide and associated clinical effects are shown in
Table 3.
Documentation of blood cyanide levels is useful in confirming the clinical diagnosis and in
subsequent follow-up investigations. The red blood cells contain most of the cyanide in the
blood, so an assay of whole blood is necessary. Furthermore, cyanide levels tend to fall in stored
samples because of the compound's short half-life, and this process can only partially be limited
by optimal storage conditions. Therefore, the time of sampling and the conditions of storage are
very important factors to consider and record.
Cyanide concentrations in tissue, such as liver, lung, spleen, and heart, may be more accurate
indicators of the blood cyanide intoxication levels. Estimates of tissue levels are necessary
adjunctive studies in forensic cases.38 For details on collecting and analyzing blood and tissue
for cyanide, see Assay Techniques for Detection of Exposure to Sulfur Mustard, Cholinesterase
Inhibitors, Sarin, Soman, GF, and Cyanide, Technical Bulletin Medical 296.39
TABLE 3
BLOOD CONCENTRATIONS OF CYANIDE
AND ASSOCIATED CLINICAL EFFECTS
Cyanide
Concentration (ug/mL) Signs and Symptoms
0.2-0.5 None
0.5-1.0 Flushing, tachycardia
1.0-2.5 Obtunded
2.5-3.0 Coma
≥3.0 Death
Reprinted from Rumack BH. Cyanide poisoning. In: Newball HH, ed. Respiratory care of chemical casualties. In:
Proceedings of the Symposium on Respiratory Care of Chemical Casualties. Fort Detrick, Frederick, Md: US Army
Medical Research and Development Command; 28-30 November 1983:186.

Cyanide Poisoning
Principles of Therapy
An understanding of the toxicology and pathophysiology of cyanide poisoning leads directly to

the principles of therapy: eliminate further exposure, and institute supportive and specific
antidotal therapy. (The specific antidotes are discussed separately in the section that follows.) In
addition to the difficulties of diagnosing cyanide poisoning, each of the specific antidotal
therapies discussed in this chapter has its own inherent toxicity. This knowledge should temper
their use in the typical field medical treatment facility and other emergency setting.
Elimination of Further Exposure
The first principle of therapy is the obvious one: eliminate any potential source of continuing
cyanide poisoning:
• Remove the patient from an environment containing cyanide.

• Remove all contaminated clothing; rinse skin with soap and water or water alone if there
is liquid on the skin.
• Gavage and administer activated charcoal if cyanide was ingested.
Following these steps can significantly decrease the amount of poison that has to be eliminated
from the body.40
Supportive Therapy
Possibly the most important elements of therapy are general supportive actions, which, by
themselves, can effect the recovery of most casualties without further risk from specific antidotal
therapy.41 They are probably the only indicated therapies for casualties of cyanide poisoning
who arrive conscious at the emergency medical treatment station.
As early as 1840, Blake42 found that the lethal effects of cyanide are neutralized by mechanical
resuscitation. The use of hyperbaric oxygen in cyanide intoxication is still controversial.
Supplemental oxygen with or without assisted ventilation clearly augments the effect of specific
antidotes in animal studies; however, despite encouraging reports,43,44 there is inconclusive
evidence of further benefit from the use of hyperbaric oxygen.
Lactic acidosis resulting from anaerobic metabolism should be treated by intravenous

administration of sodium bicarbonate, and seizures should be controlled by the administration of
anticonvulsants such as diazepam.45 Because correction of deficiencies in tissue perfusion and
oxygenation is the ultimate goal of supportive therapy and is also important for the success of
specific antidotal therapy, it is critically important to maintain an effective cardiac rhythm; this
can be accomplished with cardiopulmonary resuscitation, if necessary, in the early stages of
treatment.

Cyanide Poisoning
Specific Antidotal Therapy
Casualties with advanced toxicity from a large amount of cyanide may require specific antidotal
therapy in addition to the vigorous supportive therapy outlined above. The recommended agents
or components of specific antidotal therapies for cyanide poisoning vary according to country
and medical custom (Table 4). This diversity seems to be based, in part, on where the drugs
were initially developed and used. The aims of the recommended therapies are generally similar,
however, in that one drug is given for immediate relief from the histotoxic effect of cyanide
complexed with cytochrome oxidase.
In most of the regimens discussed below, the action of displacing cyanide from cytochrome
oxidase is accomplished by the formation of methemoglobin. Methemoglobin removes cyanide
from the extracellular fluid space and, by so doing, displaces cyanide from the intracellular fluid.
The second component of most regimens is sodium thiosulfate, which is given as a specific
antidote to augment the systemic clearance of cyanide via thiocyanate formation by sulfur
transferases.
TABLE 4
CYANIDE ANTIDOTAL COMPOUNDS IN USE
Antidote
(Route of Administration) Country
Sodium nitrite and United States1, Yugoslavia2
sodium thiosulfate (IV)
4-Dimethylaminophenol Germany3,4
(IV or IM) and sodium
thiosulfate (IV)
Dicobalt edetate (IV) United States5, Netherlands6
Hydroxocobalamin (IV) United States7,8, France9
IM: intramuscular: IV: intravenous Sources: (1) Chen KK. Rose CL. Clowes GHA. Methylene blue. nitrites and
sodium thiosulfate against cyanide poisoning. Proc Soc Exp Biol Med. 1933;31:250-251. (2) Binenfeld Z. Antidote
therapy in cases of poisoning by some heavy metals and cyanides and its risks. Farm Glas. 1971;27:1-6. (3) Bright
JE. Marrs TC. A model for the induction of moderate levels of methaemoglobinaemia in man using 4-
methylaminophenol. Arch Toxicol. 1982;50:57-64. (4) Kiese M. Methemoglobinemia: A Comprehensive Treatise.
Cleveland, Ohio: CRC Press; 1974. (5) Marrs TC, Swanston OW. Bright JE. 4-Dimethylaminophenol and dicobalt
edetate (Kelocyanor) in the treatment of experimental cyanide poisoning. Hum Toxicol. 1985;4:591-600. (6) Nagler
J. Provoost RA. Parizel G. Hydrogen cyanide poisoning: Treatment with cobalt EOTA. J Occup Med. 1978;20:414-
416. (7) Cottrel1JE. Casthely P. Brodie JD. Patel K. Klein A, Turndorf H. Prevention of nitroprusside-induced
cyanide toxicity with hydroxocobalamin. JAMA. 1978;298:809-811. (8) Mushett CW. Kelley KL. Boxer GE.
Rickards JC. Antidotal efficacy of vitamin B12a (hydroxocobalamin) in experimental cyanide poisoning. Proc Soc
Exp Biol Med. 1952;81:234-237. (9) Yacoub J. Faure J. Morena H. Vincent M. Faure H. Acute cyanide poisoning:
Current data on the metabolism of cyanide and treatment with vitamin B12a . Eur J Toxicol. 1974;7:22-29.

Cyanide Poisoning
3.0 SPECIFIC ANTIDOTES
The clinical use of most antidotes is based on animal experiments46 and on extrapolations made
from a small number of clinical cases. Comparing results from animal studies has limitations
because of the differences in experimental design from one study to another as well as marked
interspecies differences in cyanide and drug metabolism. Moreover, the studies were not
designed to resemble the usual emergency medical or battlefield scenario. The disparity of
antidotes for cyanide is due to the following factors47,48:
• the small number of patients;

• the fact that most cyanide victims understandably receive several treatment agents;
• the lack of readily available, adequate analysis of blood and tissue concentrations: and
• the limited comparison studies that are available in animal models.
Antidotes are usually unnecessary if the casualty is conscious.
Drugs Used in the United States
Nitrites
Amyl nitrite and sodium nitrite, with or without sodium thiosulfate, are used as antidotes for
cyanide.49 The antidotal action of amyl nitrite was first noted as early as 1888.50
The oxidized form of heme iron (Fe3+) in methemoglobin has a higher binding affinity for
cyanide than does cytochrome oxidase. The preferential binding of cyanide to methemoglobin to
form cyanomethemoglobin frees cytochrome oxidase to resume its role in aerobic metabolism.51
In the United States and other countries, sodium nitrite has been used as the methemoglobin-
inducing drug of choice.
In addition to methemoglobin formation, both sodium and amyl nitrite cause significant
vasodilatation, which warrants careful monitoring of blood pressure. Marked vasodilatation with
orthostatic hypotension, dizziness, and headache, in addition to the unpredictable levels of
methemoglobin formed,52 limit the utility of amyl nitrite in an upright casualty. Therefore, if a
casualty is conscious and able to stand, he should not receive any nitrite. These factors, together
with other concerns, have caused amyl nitrite to be removed from the cyanide antidote kit in the
U.S. Army formulary for field units.
Sodium nitrite is available in the Lilly Cyanide Antidote Kit (manufactured by Eli Lilly and
Company, Indianapolis, Ind.) in 10-mL ampules containing 300 mg for intravenous
administration. (The kit also contains amyl nitrite encased in glass "pearls," which are meant to
be broken so the drug can be inhaled.) The solution of sodium nitrite (30 mg/mL) should be
given to an adult intravenously over 5 to 15 minutes, with careful monitoring of blood pressure.
A single dose is sufficient to raise the methemoglobin 1evel to 20% in an adult,53 and a second
dose, up to half as large as the initial one, can be given. Methemoglobin levels should be
monitored if possible and kept below 35% to 40%, the range that is associated with oxygen-
carrying deficits caused by methemoglobin itself.54

Cyanide Poisoning
Because most automated clinical analyzers do not detect cyanomethemoglobin, the residual
normal hemoglobin capable of oxygen transport can be overestimated by measuring total
hemoglobin only. Methemoglobin-inducing substances should not be given to fire victims, even
if cyanide intoxication is suspected, because neither methemoglobin nor carboxyhemoglobin
(formed by carbon monoxide) transport oxygen. Alternative therapy in this situation consists of
administering oxygen, thiosulfate, and other standard supportive measures.
In children, sodium nitrite can cause lethal methemoglobin levels if the dose is too high. The
recommended dose for children is 0.33 mL of the 10% solution per kilogram of body weight.
34,55
Some data indicate that nitrites exert their action by a mechanism other than methemoglobin
formation. It has been suggested that the protective effect is due to the vasodilating effect of
nitrite.52 Several α-adrenergic antagonists (e.g., chlorpromazine, promethazine, promazine, and
phenoxybenzamine) that cause vasodilatation also antagonize cyanide toxicity.56,57 Further
information is needed to determine the mechanism or mechanisms by which chlorpromazine and
phenoxybenzamine reverse cyanide intoxication.57
Several alternative methemoglobin-forming drugs that have different pharmacological properties

from sodium nitrite have been investigated and used in other countries (see Table 4).
Other Methemoglobin-Forming Drugs
4-Dimethylaminophenol (4-DMAP), p-aminopropionphenone (PAPP), p-

aminoheptanoylphenone (PAHP), and p-aminooctanoylphenone (PAOP) are also
methemoglobin-forming compounds that have protective effects against cyanide. 4-DMAP was
proposed as a fast-acting antidote with low toxicity.58,59 This German-developed compound is
used in the German military and by the civilian population. In humans, intravenous injection of
4-DMAP (3 mg/kg) can produce a level of 15% methemoglobin within 1 minute.60 In dogs, a
dose of 4-DMAP that produces a 30% level of methemoglobin will save animals that have
received 2 to 3 LD50 of cyanide.61
The disadvantages of 4-DMAP are (1) the appearance of necrosis in the area of injection after
intramuscular administration and (2) the possibility that extremely high levels of methemoglobin
may occasionally result. Increases in pain, fever, and muscle enzymes also occur after
intramuscular administration of the drug. 4-DMAP has been reported to produce positive results
in the Ames test, which suggests that the compound may be a mutagen. PAHP appears to be the
safest phenone of the series.62
Thiosulfate and Other Sulfur Donors
Thiosulfate has been used primarily with sodium nitrite in a fixed antidotal regimen. The
standard dose of sodium thiosulfate, which is supplied in the Lilly Cyanide Antidote Kit in 50-
mL ampules, is 50 mL of the 250 mg/mL (12.5 g), given intravenously. A second treatment with
half of the initial dose may be given. The pediatric dose is 1.65 mL per kilogram of body
weight.55

Cyanide Poisoning
The utility of thiosulfate is limited because of its short biological half-life and its small volume
of distribution.23 This combination of pharmacological properties, in addition to the suggestion
that the presence of cyanide increases the intracellular availability of the thiosulfate,63 indicates
that this compound probably cannot be used as a prophylactic but only as an antidote.
Compounds containing the more-lipophilic sulfane sulfur (R-S-S-) or compounds that can be
actively transported into the cells may be more beneficial as cyanide antagonists,64-66 but none
are commercially available.
Other Therapeutic Drugs
Cobalt Salts
Cobalt salts have been shown to be an effective means for binding cyanide in vitro and in
vivo.67,68 Kelocyanor, the cobalt salt of ethylenediamine-tetraacetic acid (EDTA), which is
commercially available in Europe but not in the United States, is administered intravenously.69
In comparison studies against nitrite and hyposulfite, the cobalt chelate was thought to be
superior31; however, in other studies the nitrite-thiosulfate combination was found to be
superior.70
The drawback of cobalt compounds is their rather severe toxicity. Cardiac effects such as angina
pectoris and ventricular arrhythmias, edema around the eyes, vomiting, and death have been
observed.71 A clinical caveat is that severe toxicity from cobalt can be seen even after initial
recovery from acute cyanide poisoning.
Hydroxocobalamin
Hydroxocobalamin (vitamin B12a) is an effective antagonist of cyanide intoxication that binds

cyanide directly without forming methemoglobin. It is useful under certain conditions such as in
fire victims who may already have a decreased concentration of functioning hemoglobin.72 It
has a low toxicity even at high doses.73 In addition, in vitro cyanide studies74 have shown a
greater affinity for hydroxocobalamin than for cytochrome oxidase. Sodium thiosulfate can
improve the protection provided by hydroxocobalamin alone.46
There are several disadvantages in the clinical use of this drug. In rare instances, urticaria can
result from hydroxocobalamin administration. More importantly, hydroxocobalamin has a
relatively short shelf life because it decomposes in light. It may cause tachyphylaxis, which may
limit its usefulness.75 The cost of the drug is high, in part because so much is needed on a molar
basis. At 1,346 grams per mole of hydroxocobalamin, a dose of at least 4 g is needed to
neutralize a lethal amount of cyanide.

Cyanide Poisoning
Investigational Drugs
Prophylactic Drugs
PAPP and PAOP are also aminophenol derivatives. PAPP may not be active against cyanide
intoxication; its metabolite, p-hydroxylaminopropiophenone, may be the active compound. This
could account, in part, for the fact that cyanide toxicity itself changes the pharmacokinetics of the
antidote.76 PAPP reduces cyanide levels within red blood cells,77 and its effect is greatly
enhanced in the presence of sodium thiosulfate.78 PAPP, PAHP, and PAOP all have
pharmacokinetics that may allow for prophylactic administration.62,79 Prophylactic
methemoglobin formation could present its own problems, however, for victims of smoke
inhalation or in other settings where high levels of carbon monoxide occur .33,80
A number of 8-aminoquinoline analogs of primaquine have also been studied as potential

prophylactic drugs because they create elevated methemoglobin levels of long duration. Only
preliminary information is available regarding the methemoglobin-forming potential of these
drugs in humans.62,81,82
Cyanohydrin-Forming Drugs
Aldehydes and carbonyl-related compounds (such as pyruvate, α-ketoglutaric acid, glyoxal, and
reducing sugars) form cyanohydrins from cyanide. This action may be a mechanism for
improving the protection provided by nitrites.83 Steinberg and Thomas84 found that glyoxal
trimer may be the most effective compound of the group that they examined. The relatively
short half-lives of these reversible reactions and the drug dose required85 may limit the clinical
utility of this class of compounds.24
4.0 SUMMARY
Cyanide, an ancient compound, is often associated with murders and assassinations. Because of
the high amount needed to cause death and the inefficient weapons in which it was used, cyanide
was not an effective chemical weapon in World War I; however, it was possibly used by Iraq
against the Kurds in the Iran-Iraq War during the late 1980s.
Cyanide causes intracellular hypoxia by inhibiting the intracellular electron transport

mechanism, the cytochrome enzymes. After inhalation of a large amount of cyanide - as either
hydrocyanic acid or cyanogen chloride - the onset of effects is within seconds, symptoms are
few, physical findings are scanty, and death occurs within minutes.
The antidotes used in the United States, sodium nitrite and sodium thiosulfate, are quite effective
if given before cessation of cardiac activity.

Cyanide Poisoning
5.0 ACKNOWLEDGMENT
The authors thank Michael P. Whitmer and Eric W. Nealley, U.S. Army Medical Research
Institute of Chemical Defense, and Adam S. Szczepaniak, Jr., Wood Technical Library,
Aberdeen Proving Ground, Maryland, for their excellent technical assistance.
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USAMRDC Report 7583-14: 1-75.

DEVELOPMENT OF SITE SPECIFIC DISCHARGE
CRITERIA THROUGH TOXICOLOGICAL TESTING
Prepared By:
Terry Mudder, Ph.D.

Fred Fox
Jim Whitlock
Steve Marshall
Originally published in Proceedings of the Cyanide and the Environment Conference, edited by
Dirk van Zyl, Ph.D., Volume 1, pp. 109-117, Tucson, Arizona, December 11-14, 1985
Development of Site-Specific Discharge Criteria Through Toxicological Testing
ABSTRACT
Employment of aquatic toxicological testing for the selection of viable wastewater treatment
alternatives and the development of site specific water quality criteria is increasing. The increase
in its usage is due to recognition that such testing is cost effective in solving environmental
problems and its use should no longer be considered merely an elaborate research tool. There is a
growing spirit of compromise and cooperation surfacing between industry and the regulatory
agencies in an attempt to, through rational and practical approaches, solve long standing
environmental problems. This paper deals with an approach undertaken at the Homestake Mine
in Lead, South Dakota. The approach followed flexible guidelines recently proposed in a new
water quality criteria development document published by the EPA. The problem dealt with
development of an acceptable underwater treatment alternative that would provide an effluent
compatible with the designed use classifications of Whitewood Creek, the receiving stream.
1.0 INTRODUCTION
The use of aquatic toxicological testing in selecting environmentally acceptable wastewater

treatment alternatives and establishing site specific water quality criteria is increasing rapidly, due
to many factors. Regulatory agencies (state and federal) have recognized that previously
calculated water quality and waste load allocation criteria are in certain instances unnecessarily
stringent and unwarranted. Enforcement of these criteria may be impractical, leading to public
outcry when violations remain unenforced. Both industry and regulatory agencies recognize that
construction of tertiary or advanced wastewater treatment facilities in certain instances may result
in effluents exhibiting adverse aquatic life effects. These toxicological effects are often
attributable to chemical and/or physical factors in the treated effluent which result from a toxic
component previously unidentified through chemical analysis. This situation often arises when
treatment plant process alternatives are evaluated on a numerical basis only. The reluctance of
industry to invest millions of dollars in research, development, and construction of "state of the
art" treatment facilities in an attempt to meet criteria which are technically unachievable or
unnecessarily stringent. Finally, there is a spirit of compromise and cooperation developing
between industry and regulatory agencies to attempt rational and practical approaches in
1
establishing site specific criteria which will assure protection of beneficial use classifications.
This paper deals with the employment of an aquatic toxicological testing program currently in
progress at the Homestake Mine in Lead, South Dakota. The purpose of the program is to
establish site specific water quality criteria and waste load allocations to assure protection of the
beneficial uses of the receiving stream, Whitewood Creek, a cold water marginal trout fishery.
Development of a treatment facility and subsequent development of water quality criteria relied
significantly upon the use of toxicological testing and the guidelines proposed in the recent draft
2
of the EPA aquatic life protection and criteria development document.
121 T. Mudder et al.

2.0 HISTORICAL PERSPECTIVE
On September 3, 1976, the United States Environmental Protection Agency (EPA) issued to the
Homestake Mine in Lead, South Dakota, National Pollutant Discharge Elimination System
(NPDES) Permit No. SD-0000043. The permit contained discharge effluent limitations derived
from Best Practicable Control Technology requirements under the Clean Water Act and South
Dakota water quality standards applicable to Whitewood Creek, the receiving stream. Effective
July 1, 1977, the NPDES permit required Homestake to meet very low effluent limitations
principally designed to attain and maintain the existing beneficial use classifications of Whitewood
Creek below the mine's discharge.
On July 1, 1978, the mine was not in compliance with the permit limitations, despite its attempt to
implement Best Practicable Control Technology for the destruction of cyanides and heavy metals
in the discharge. At this time, it became clear that accurate and precise laboratory analysis to
measure the very low levels in the permit was also a problem.
Numerous treatment technologies representing the Best Available Technology were tested at the
mine prior to the selection of a biological treatment process. Construction of a treatment facility
was initiated during March of 1983 and completed and placed into continuous operation by
August 15, 1984.
If the treated effluent discharged by the mine will not interfere with the attainment and
maintenance of the existing designated beneficial uses of Whitewood Creek under South Dakota
water quality standards, the State will initiate a proceeding to consider modification of its water
3
quality criteria for Whitewood Creek.
In order to assure attainment and maintenance of the designate uses for the receiving stream and
to be certain that the mine can properly analyze for and meet future permit limits, an aquatic
toxicological testing program was integrated into the treatment selection program during the
spring of 1980.
The program consisted of 1) conducting a bioassessment of the receiving waters, 2) cooperating

with State and Federal agencies in modifying South Dakota's surface water quality standards to
reflect laboratory testing procedures developed at the mine and allow for development of site
specific criteria for water quality standards, and 3) constructing and utilizing an on site aquatic
toxicological testing facility.

3.0 BIOASSESSMENT AND USE ATTAINABILITY ANALYSIS
The first step toward development of site specific water quality criteria and waste load allocations
is to establish the beneficial use classification of the discharger's receiving system. In the case of
the Homestake Mine, the receiving system is a small cool water stream, Whitewood Creek. A
4
bioassessment was completed in accordance with proposed EPA guidelines and protocol at a
cost of approximately $300,000. The actual thirteen month study (March 1981-March 1982) was
conducted and designed by a team of university professors, experts in their respective fields, in
cooperation with the South Dakota Department of Water and Natural Resources (DWNR) and
EPA Region VIII. The study was conducted along Whitewood Creek and two reference streams,
Spearfish Creek and Sand Creek. The study assessed the physical, chemical, and biological
characteristics of the receiving stream, defining the stream's existing environmental conditions and
potential future beneficial uses.
The physical characteristics investigated included surficial geology, stream discharge, stream
morphometry, and sediment size classifications and quantification. In addition, chemical analyses
were conducted on samples collected from surface waters, sediments and the biota. The
biological investigations included a survey of riparian vegetation (including percent cover),
qualitative and quantitative macrobenthos, algae, diatoms, and existing fisheries. The detailed
study fulfilled the requirements of a water body survey and formed the basis for a petition to
request a modification of the beneficial use classification of Whitewood Creek from a "cold water
permanent fish life propagation" classification to "cold water marginal fish life propagation". The
latter classification, which was granted, protects for stockings of catchable size trout, but does not
provide protection for reproduction. The results of the study concluded the habitat was limited
due to low hydraulic flows and excessive summer water temperatures. In addition to the petition
for reclassification of Whitewood Creek, Homestake initiated further specific changes to the
South Dakota water quality regulations to upgrade them technically and to make them consistent
5
with current scientific thinking. The changes required modification of the surface water quality
regulations through public hearing and final approval by the South Dakota board of water
management. They included allowances for toxicological testing and its use in setting site specific
water quality criteria. Advances in analytical techniques, specifically the methodology for analysis
of weak acid dissociable cyanides, (considered by Homestake an important potential form of
toxicologically significant cyanides), were also accepted by the water management board and are
6,7
presently incorporated into South Dakota laws.

4.0 TOXICOLOGICAL TESTING FACILITY
In conjunction with the water body assessment and the upgrading of the surface water quality
regulations, Homestake constructed a toxicological testing facility located adjacent to the site of
the new biological wastewater treatment facility. The primary test organisms include Daphnia,
macroinvertebrates (stoneflies and caddisflies), and trout (rainbow and brown). Dilution water is
pumped continually through the bioassay facility from a pumping station located along
Whitewood Creek approximately one mile above Homestake's discharge. The dilution water
provides flowing fresh water for the stock fish population and for test purposes. A bioassay
facilities manual details the specific protocol employed in the laboratory and is utilized as an
8
educational tool to train bioassay technicians. The basic toxicological testing procedures are in
9 10 11
accordance with procedures specified by ASTM , Standard Methods , and the EPA .
The toxicological testing facility was built with a two-fold purpose in mind. First, to evaluate and
compare the toxicological effects of various treatment process alternatives. Secondly, to utilize
the toxicity data from the process selected for eventual development of site specific water quality
criteria and waste load allocations.
4.1 Alternative Treatment Selection
The first use of the facility is of particular importance, as emphasis on specific parameter removal
through routine numerical evaluations could result in "treated effluents" that meet numerical
limits, but still exhibit considerable toxicity. The toxicological characteristics are due to pollutants
associated with or produced through breakdown of target parameters not analyzed for and/or
removed through further treatment. The employment of whole effluent testing aids in minimizing
these possible oversights. One example involved numerical and toxicological comparisons of the
copper catalyzed hydrogen peroxide process and the biological process as alternatives for the
treatment of Homestake's wastewaters. In terms of specific parameter removal, the two treatment
alternatives were comparable, based solely upon numerical evaluations of the treated effluents
(such as copper and total cyanide removal). However, toxicological evaluations of the effluents
indicated the chemical treatment effluent to be quite toxic as compared to the effluent from the
biological treatment pilot plants. Further chemical analyses indicated the chemically treated
effluent contained significant concentrations of ammonia, not found in the biologically treated
wastewater. The ammonia constituted a parameter which would require further treatment to
remove if the chemical treatment alternative was to be employed. As a result of comparative
numerical and toxicological evaluations, the biological treatment alternative was found feasible
and environmentally acceptable at a considerable cost savings over other process alternatives.
Design of the biological treatment facility was completed and a full scale treatment plant was
constructed and placed into continuous operation on August 13, 1984. A comparison of the
various treatment plant alternatives tested can be found in a recent paper presented at the AIME
12
conference in Los Angeles.

The use of toxicological testing aided significantly in the development and selection of a "state of
the art" innovative treatment process. The reduced capital and operational costs could save
millions of dollars over the design life of the facility, while providing an environmentally
acceptable compatible with the designated beneficial use of the receiving stream.
4.2 Site Specific Water Quality Criteria Development
With the completion of the bioassessment, modification of the existing water quality regulations,
and the construction of the treatment facility, the final step is to establish discharge criteria which
are consistent with existing water quality criteria. The criteria development as generally outlined
in the proposed EPA guidelines involves three phases: selection of parameters of concern,
recalculation of water quality criteria on a site specific basis, and a toxicological testing program
to establish the final permit values for the parameters of interest. The process requires frequent
meetings between key technical personnel from industry and the regulatory agencies with
emphasis on flexibility, cooperation, and practicality. Due to the beneficial use classification of
Whitewood Creek as a "cold water marginal" trout fishery, the approach to developing adequate
criteria and the degree and type of toxicity testing is quite novel. With input from all parties, it
was agreed that the first step of the process would require the establishment of a list of potential
parameters which are of a concern from a water quality and beneficial use aspect. The second
phase of the process involves recalculating the site specific water quality criteria for these
13
parameters using existing ambient water quality criteria documents for each parameter.
Based upon the recalculated water quality criteria and comparison of these values with historical
background and untreated discharge water quality analyses, the list may be narrowed to those
parameters of primary concern. These parameters form the basis for the third phase of the
process, the toxicological testing program, which itself involves three modes: 48 hour range
finding toxicity tests, 96 hour flow through tests to establish acute toxicities, and 45 day long
term tests to establish chronic toxicities and long term effects.
The first mode of testing involves conducting a series of 48 hour static range finding toxicity tests
using the primary organism of interest (most sensitive species, trout) to establish an approximate
range of lethal concentrations (LC50's) for each of the parameters of interest.
The choice of test concentrations is made on the basis of past testing and available literature
centered on the organisms and parameters of interest. The results of this and other range finding
tests produce toxicity information which is utilized to select a range of parameter concentrations
to use in the second mode of testing, the 96 hour flow through toxicity tests.
In meetings prior to the initiation of the toxicity testing program, it is mutually agreed that the
results of the 96 hour tests would be used to derive instantaneous note-to-exceed in-stream water
quality criteria, based upon an acceptable percent death. This approach was in agreement with
the degree of protection to be afforded to the stocked fish population to maintain the beneficial
use classification.

In order for this data, as well as subsequent long term test data, to be utilized in developing waste
load allocations for Homestake, a low flow value for Whitewood Creek had to be established.
The 7Q25 value selected was 4.5 cfs (2000 gpm) and was derived by extrapolation of low flow
conditions from adjacent water shed basins and through examination of existing flow records
maintained by Homestake and the USGS. Using the design dry weather flow for the treatment
plant of 2600 gpm (3.75 MGD), the resulting critical effluent dilution was 56%. It was decided to
operate the flow through tests (both acute and long term) at this effluent/dilution water ratio in all
aquaria, except the control. Using this fixed effluent concentration as the base ratio, concentrated
solutions of the various test parameters are spiked into the aquaria with the use of a multichannel
metering pump to create a series of test concentrations from which a 96 hour acute LC50 value
could be obtained. This procedure allows one to study the effects of an individual parameter with
the background matrix of the whole effluent present during the test.
No provision for control of water temperature is provided as the wastewater and dilution water
temperature fluctuate considerably during the course of a year. Control of the water temperatures
would not reflect actual stream conditions and may lead to difficulties when attempting to
extrapolate such information to real situations. As a result, it was decided the testing program
would encompass the two most critical temperature periods, that of winter and late summer, both
of which correspond to minimum flow conditions.
Following establishment of the maximum in stream values through the 96 hour test program, the
final mode of toxicity testing involves conducting a series of long term, or chronic, tests to
establish a 30 day average discharge value and subsequent waste load allocation. Since the
beneficial use classification focuses upon maintenance of a stocked fish population and not
reproduction, the purpose of these tests involving spiked effluent is to gather data on general
external appearance, internal organ appearance, bioaccumulation, and of course, death.
Based upon surveys and information obtained from local game, fish, and parks personnel,
approximately 95% of the stocked fish are removed from a stocked stream section within 45-90
days. As a result, the long term tests will be conducted for 45 days to simulate a protection
period. Again, a base effluent concentration of 56% is used into which concentrated solutions of
each test parameter are spiked to produce a series of test concentrations. These concentrations
are selected through examination of the test results from the previous 96 hour flow through tests.
Organisms are fed throughout the long term test, which constitutes the only major difference in
test protocol between the two tests. In addition to the testing of fish, indigenous
macroinvertebrates which serve as food source organisms for the fish will also be included in the
toxicity testing program. The insects tested include primarily stoneflies and caddisflies, as these
species were the predominant organisms found in the receiving stream during the water body
assessment.

5.0 CAPITAL AND OPERATING COSTS OF THE TOXICITY FACILITY
Table 1 presents itemized costs of construction of the bioassay facility and the associated dilution
water pumping station. Capital costs will vary considerably from site to site. These costs
represent an upper value, with considerable cost savings possible in both construction of the
facility and the dilution water feed system. An approximate cost of operation is presented in
Table 2, for the various test modes. Neither of these costs reflect the capital cost expended
previously for the new Homestake Analytical Chemistry Laboratory.
Table 1
Capital Costs Of Construction Of The
Toxicological Testing Facility
Expenditure Purpose Cost($)
Building $30,000.00
Internal piping $15,000.00
Aquaria $ 3,200.00
Pumps, dilutor system, metering system, tubing,

glassware, etc. $ 6,000.00
Dilution water pumping system

Pump house/pump $ 3,500.00
Stream modification for water source $ 5,000.00
4" buried water supply line to bioassay facility $12,000.00
TOTAL $74,700.00

Table 2
Operating Costs Of The Bioassay Facility
Test Type
Expenditure Purpose
48 Hour 96 Hour 45 Day
Static Flow Through Flow Through
Bioassay Technician Time $ 92.00 $ 276.00 $ 2,162.00

($11.50/hr)
$ 390.00 $ 1,170.00 $ 8,190.00
Chemical Analysis ($5.00/analysis)
(in house)
------ ------- $ 1,500.00
Fish Tissue Analysis
$ 100.00 $ 100.00 $ 500.00
Supervision ($20/hr)
TOTALS $ 582.00 $ 1,546.00 $12,352.00
6.0 CONCLUSION
The use of toxicological testing as an aid in selection of wastewater treatment alternatives and in
the establishment of site specific water quality criteria is increasing rapidly. The implementation
of such testing in an environmental program is cost effective and its use should no longer be
considered merely an elaborate research tool, but rather a practical and sound approach to solving
environmental problems. The capital expenditures by Homestake are far outweighed by
considerable cost savings in developing an innovative wastewater treatment alternative, while
providing a treated effluent which is environmentally compatible with the beneficial use
classifications of its receiving stream. Also, the Homestake example has shown that industry and
regulatory agencies can work together effectively to solve complicated environmental problems.

7.0 REFERENCES
1. Edelman, L.H., Walline, R.E., "Developing a Cooperative Approach to Environmental

Regulation", National Resources Lawyer, Volume XVI, No. 3, pg. 489.
2. Water Quality Standards Handbook, United States Environmental Protection Agency,

Office of Water Regulations and Standards, Washington, D.C., December 1983.
3. Consent Decree, Civil No. 78-5094, United States of America, State of South Dakota vs.
Homestake Mining Company, February 1980.
4. Herricks, E.E., "Bioassessment of Whitewood Creek, Lawrence and Meade Counties,

South Dakota", 1982. Prepared for Homestake Mining Company, Lead, S.D.
5. Proposed modifications to amend Surface Water Quality Standards, ARSD Chapter

74:03:02, April 1984, Homestake Mining Company, Lead, S.D.
6. Mudder, T.I., Whitlock, J.L., Sharp, C., "Summary of the Toxicological Significance and
Analytical Methodology for Free and Complexed Cyanides", December 1, 1981.
7. "Workshop, Cyanide From Mineral Processing", Chapter 5, Utah Mining and Mineral
Resources Research Institute, February 2-3, 1982, Salt Lake City, Utah.
8. "Facilities and Operational Manual for the Homestake Mining Company Aquatic
Toxicological Testing Facility", the Homestake Mine, Lead, S.D., First Edition, July 1981.
9. Proposed Standard Practice for Conducting Acute Toxicity Tests on Aqueous Effluents
with Fishes, Macroinvertebrates and Amphibians, Draft 3, June 1, 1983. (T.A.
Abrahamsen, Tech Bldg 311, Kingsport, Tenn. 37662, E-47.01)
10. Standard Methods for the Examination of Water and Wastewater, 15th Edition, 1980, pp.
615-743.
11. Methods for Measuring the Acute Toxicity of Effluents to Aquatic Organisms, 3rd
Edition, EPA-600/4-82-000, November 1982.
12. Mudder, T.I., Whitlock, J.L., "Biological Treatment of Cyanidation Waste Waters",
presented at the annual AIME conference in Los Angeles, CA, February 1984.
13. "Ambient Water Quality Criteria", U.S. Environmental Protection Agency, National
Technical Information Service, October 1980.

SITE-SPECIFIC AQUATIC LIFE CRITERIA
FOR WEAK ACID DISSOCIABLE CYANIDE
Prepared By:
Terry Mudder, Ph.D.

Australian Centre for Minesite Rehabilitation Research (now ACMER), Perth, Western Australia,
April 1997
Site-Specific Aquatic Life Criteria for Weak Acid Dissociable Cyanide
1.0 INTRODUCTION
Cyanide is commonly used in the beneficiation of gold and silver in the mining industry. The
wastewaters generated at these mining facilities contain varying concentrations and forms of
cyanide. The concentrations of cyanides found in the wastewaters are dependent upon the
quantity of precipitation and degree of dilution associated with a mine site, and the metallurgical
consumption of demand for cyanide needed for efficient extraction of silver and/or gold.
As a result of using cyanide as a process reagent, the treated wastewater discharge from a mining
operation can contain low levels of metal complexed cyanides, although its free forms are usually
destroyed to levels below detection during treatment. From an aquatic life standpoint, the metal
complexed cyanides, as measured by the weak acid dissociable (WAD) analysis, constitute the
toxicologically significant forms.
The historical approach taken by the USEPA of permitting cyanide on the basis of its free forms is
not appropriate when considering mining discharges. In order to more accurately assess the
potential impacts to aquatic life exposed to these forms of cyanide, site-specific acute and chronic
criteria for WAD cyanide have been derived and implemented for mining discharges in North
America, and recently for the Golden Cross Mine, located near the city of Waihi on the north
island of New Zealand.
In general, the site-specific criteria for WAD cyanide have been developed for protection of all life
stages of trout species and their associated primary food sources, the aquatic insects (i.e. mayflies,
caddisflies, and stoneflies). By comparison, other aquatic species that are as or less sensitive than
the species for which the site-specific criteria were developed will also be protected at or below
the acute and chronic WAD cyanide levels derived herein.
The appropriate toxicological data base for development of site-specific criteria is available from
the extensive and detailed whole effluent bioassays conducted by Homestake Mining Company
(HMC), the South Dakota Department of Environment and Natural Resources (DENR), and
Region VIII of the USEPA, located in Denver, Colorado. The toxicological studies examined the
acute, chronic, and sub-lethal effects of cyanidation solutions on trout and aquatic insects in
Whitewood Creek, a cold water permanent trout fishery, located in the Black Hills of South
Dakota in the United States. The majority of these studies were conducted in the flow through
toxicological testing facility located at the Homestake Mine in South Dakota, and at the Fisheries
Bioassay Laboratory (FBL) located on the campus of Montana State University (MSU) in
Bozeman, Montana in the United States.
In addition, there is now long term whole effluent toxicity and instream monitoring data for the
discharges from the biological treatment plant at the Homestake Mine, which has been in
operation for ten years, and from the chemical treatment plan at the Golden Cross Mine, which
has been in operation for about two years. The results of ongoing water quality monitoring and
compliance programs at these two mining facilities indicate that the discharge of these two treated
effluents, which were permitted using similar instream WAD cyanide levels, have not and are not
causing adverse impacts to their respective receiving streams or the resident aquatic life.
131 T. Mudder
This document sets forth a rational and scientific approach leading to the derivation of site-
specific acute and chronic criteria for WAD cyanide and the protection of sensitive and important
species of aquatic life.
2.0 THE CHEMISTRY OF CYANIDE
Because cyanide is an excellent complexing reagent, its use in the metallurgical circuit results in
the complexation and solubilization of other metals from the ore. The types of metal complexes
and their concentrations result from characteristics specific to the ore and the metallurgical
process being employed.
There are three principle forms of cyanide present in a wastewater generated at a mine. These
include free cyanide, weakly complexed cyanide, and strongly bound or complexed cyanide. Free
cyanide exists in two forms including molecular hydrogen cyanide (HCN) and the cyanide anion
-
(CN ). These two forms are in equilibrium with one another in solution, with the concentration of
the dominant form being dependent upon the pH of the solution. As shown on Figure 1 at a pH
of 8 nearly all the free cyanide is in the HCN form, while at a pH of 10.5 nearly all the free
cyanide is present as the anion.
The free forms of cyanide, considered the most toxic forms of the compound, are the most readily
removed forms through treatment. Conventional chemical, physical, and biological cyanide
treatment processes can reduce the levels of free cyanide in solution to either non-detectable or
environmentally acceptable concentrations. A summary of the various reactions associated with
cyanide are shown on Figure 2.
The second form of cyanide present in mine wastewaters includes the weakly bound metal cyanide
complexes. The predominant metals associated with the complexes include copper, nickel, and
zinc, because these metals are commonly found in elevated levels in the ore. The toxicity of these
complexes with regards to aquatic life arises primarily from the free cyanide produced through
dissociation, and secondarily from the complex itself and any free metal yielded through
breakdown of the complex. Analytically, these forms of cyanide are measured using one of
several methods, with the weak acid dissociable (WAD) cyanide methods of ASTM, Method C,
and Standard Methods being the preferred procedures (1, 2). Although other forms of metal
complexed cyanide report either completely or partially as WAD cyanide including mercury,
cadmium, and lead, the metals are usually present in very low levels and are not a major
environmental concern.
Although the regulation of cyanide and derivation of aquatic life criteria have focused upon the
free form historically, the trend among regulatory agencies and scientists is to consider the weakly
bound forms in conjunction with the free forms. For example in South Dakota the groundwater
standard is written in terms of WAD cyanide, while in Nevada and Montana the heap leach rinsing
criteria are written in terms of WAD cyanide, as are certain effluent criteria in other countries
including Canada and New Zealand.
132 T. Mudder
Figure 1: Relationship Between HCN and CN- with pH
100%
90%
80%
70%
Free Cyanide Present as HCN
60%
HCN CN-
50%
40%
30%
20%
10%
0%
6.0 7.0 8.0 9.0 10.0 11.0 12.0
pH
133 T. Mudder
Figure 2: The Cyanide Cycle
134 T. Mudder
The third form of cyanide which occurs in a mine wastewater includes the strongly bound metal
cyanide complexes of iron and cobalt. Cobalt is usually present in very low levels and is relatively
non-toxic, leaving iron cyanide the predominant stable metal cyanide complex. The iron in the
complex may be either in the ferrous or ferric form, both of which form very strong cyanide
complexes. The iron cyanide complex itself is non-toxic and exhibits toxicity only through its
breakdown to form WAD or free cyanide. The toxicity of iron cyanide becomes a concern only
when its concentration reaches a level that sufficient WAD or free cyanide is formed through its
breakdown and dissociation.
Analytically, the metal complexed forms of cyanide are quantified by one of two methods
including the total cyanide and WAD cyanide (i.e. Method-c cyanide) procedures. The total
cyanide procedure reports all forms of cyanide including free and metal bound cyanides, including
the relatively non-toxic and stable iron cyanides. The WAD cyanide procedure reports all forms
of cyanide except cyanide bound to iron. In the event breakdown of iron cyanide occurs, the free
or other weakly complexed cyanide formed is reported by the WAD cyanide procedure.
Because the ratio of iron to WAD forms of cyanide fluctuates, a total cyanide analysis does not
provide the information needed to quantify the toxicologically significant forms of cyanide. In
terms of reliability and accuracy, the interferences associated with the total cyanide analysis are
well documented. Due to varying degrees of reproducibility, the method is not suitable for
compliance purposes when considering mining wastewaters. The WAD cyanide procedure is
reliable and is not affected by chemical interferences as is the total cyanide analysis (3). The
accuracy and reproducibility of the WAD cyanide method makes it the preferred choice for
monitoring and compliance requirements associated with wastewater discharges in several states
and countries.
The measurement of free cyanide by conventional methods (i.e. ion selective electrode or
titration) is not accurate to the levels considered toxic to aquatic life. Because the WAD cyanide
procedure reports free as well as weakly bound metal cyanide, it provides a conservative measure
of the toxicologically significant forms of cyanide. The WAD cyanide method is currently a
certified procedure found in the 17th edition of Standard Methods. The method was not accepted
by EPA prior to the publication of the cyanide criteria document. At present, the EPA
recommends the total cyanide analytical procedure and a practical quantification limit (PQL) of
0.01 mg/l, although the PQL in practice is often much higher.
Therefore, based upon the inaccuracy of the total cyanide method in determining low and
environmentally significant levels of cyanide, the reliability of the WAD cyanide procedure, and
the importance of the WAD cyanide from a toxicity viewpoint, the WAD cyanide method is
recommended for development of site-specific aquatic life criteria.
The chemical dissociation of the various cyanide complexes is summarized in Tables 1 and 2 (3).
As shown in the tables, the metal cyanide complexes of iron, copper, mercury, and silver are very
stable. The rates of chemical dissociation and release of free cyanide are affected by several
factors including the intensity of light, water temperature, pH, total dissolved solids, and complex
concentration. The liberation of free cyanide through photolysis is most pronounced for the iron
cyanide complexes.
135 T. Mudder
As shown in Table 2, the free cyanide concentration formed through dissociation is very low for
the complexes of iron, mercury, copper, and silver. With regards to nickel, cadmium, and zinc,
the complexes are quite weak and susceptible to varying degrees of dissociation. With regards to
the development of criteria for the very weak complexes, the conservative approach is to assume
the metals exist in their free forms.
Table 1: Metal Cyanide Complexes in Order of Decreasing Stability in Water

Metal Cyanide Complex Chemical Formula Dissociation Constant
-3 -52
Hexacyanoferrate (III) or Ferricyanide [Fe(CN)6] 1.0 x 10
-4 -47
Hexacyanoferrate (II) or Ferrocyanide [Fe(CN)6] 1.0 x 10
-2 -42
Tetracyanomercurate (II) [Hg(CN)4] 4.0 x 10
-2 -28
Tricyanocuprate (I) [Cu(CN)3] 5.0 x 10
-2 -22
Tetracyanonickelate (II) [Ni(CN)4] 1.0 x 10
-2 -21
Dicyanosilverate (I) [Ag(CN)2] 1.0 x 10
-2 -17
Tetracyanocadminate (II) [Cd(CN)4] 1.4 x 10
-2 -17
Tetracyanozincate (II) [Zn(CN)4] 1.3 x 10
Table 2: Free Cyanide Concentration Released at Various Levels

of Total Cyanide, pH = 7 and 25oC
Concentration (mg/l) of the Metal Cyanide Complex and the
Respective Free Cyanide Levels
Complex 1 mg/l 10 mg/l 100 mg/l 1,000 mg/l
-2
[Hg(CN)4] 0.00002 0.00003 0.000045 0.00007
-1
[Ag(CN)2] 0.00009 0.0002 0.0004 0.0009
-2
[Cu(CN)3] 0.0003 0.00054 0.00097 0.0017
-3
[Fe(CN)6] 0.0002 0.00032 0.0004 0.0006
-4
[Fe(CN)6] 0.0012 0.0016 0.0022 0.0031
-2
[Ni(CN)4] 0.135 0.215 0.340 0.539
-2 (1)
[Cd(CN)4] 2.30 3.64 5.77
-2 (1)
[Zn(CN)4] 2.26 3.59 5.68
Note:
(1) Calculations indicate that at this dilution the two complexes are essentially completely
ionized.
In the formulation of site-specific criteria for cyanide, the important issues include consideration
of its various forms and selection of appropriate analytical techniques for monitoring and
compliance purposes.
136 T. Mudder
3.0 THE AQUATIC TOXICITY OF CYANIDE
The primary concern in a receiving stream is the protection of the resident aquatic species and
ecosystem. The organisms of concern include various species of aquatic insects and fish. From a
toxicity and regulatory standpoint, it is the level of free cyanide in either the molecular or anionic
form which is of most interest. Cyanide toxicity is not affected by hardness and due to its labile
nature bioaccumulation is not an issue. Although cyanide is not an accumulative toxicant, the
metals bound to cyanide can bioconcentrate resulting an adverse environmental impacts.
The toxicity and metabolism of free cyanide is well documented. The lethal toxicity of free
cyanide is due to the inability of tissue to utilize oxygen to support aerobic life processes. The
pharmacological pathway involves irreversible complexation of the iron in the cytochrome oxidase
system, resulting in depression of the central nervous system and hypoxia.
All of the conventional and advanced cyanide treatment processes can reduce the free cyanide
concentrations in an effluent to environmentally acceptable levels. The USEPA recognizes the
problem of how to establish criteria for cyanide in the cyanide water quality document (4). It
recommends that free cyanide be the regulated form and a free cyanide analytical procedure be
employed, because the total cyanide method is too conservative as it measures relatively stable
non-toxic forms of the compound. As noted by Doudoroff, a regulatory limit based upon total
cyanide is not a defensible water quality criterion, because the total cyanide concentration is not
toxicologically meaningful (5).
Free cyanide in aquatic ecosystems is a non-hardness related parameter. There is no evidence that
hardness affects the toxicity of free cyanide, other than the effect hardness or alkalinity has on pH,
a parameter which does affect the free cyanide level. The acute toxicity of cyanide to fish in
solutions containing only free cyanide decreases with increasing pH, indicating the molecular form
(i.e. HCN) is more toxic than the anionic form (6). It has been estimated that the toxicity of the
molecular form of cyanide is about 2.3 times as toxic as the anionic form (5). Although the
relationship of the free cyanide forms may be of value, it is not important with regards to most
streams because the pH is usually below 8.3 and any free cyanide present exists in the molecular
form.
In general, fish species are more sensitive to the toxic effects of cyanide than are the aquatic
insects. For example, the final acute values or FAV's for free cyanide from the EPA criteria
document range from 0.064-0.125 mg/l for various sensitive fish species to 2.49 mg/l for the
midge (4). In general, fish are more sensitive to the toxic effects of free cyanide than are the
aquatic insects. A FAV for free cyanide of 0.063 mg/l provides protection for the cladocerans,
the bluegill, the fathead minnow, the yellow perch, and the brook trout. Employment of a
criterion based upon a sensitive fish species generally provides an adequate level of protection for
the remaining aquatic species.
Criteria based upon free cyanide alone are not appropriate, due to presence of other potentially
toxic forms of cyanide and the lack of accurate analytical techniques for free cyanide. The use of
the total cyanide procedure is too conservative and is subject to a variety of analytical
137 T. Mudder
interferences. The other forms of cyanide which must be considered include iron cyanide and the
weakly bound metal cyanides, which are measured along with free cyanide by the WAD cyanide
analysis.
138 T. Mudder
Iron cyanide exists in two forms in a mine wastewater, either as the ferrous or ferric compound,
both of which are very stable. As shown in Table 2, over 100 mg/l of either iron cyanide is
needed to yield a free cyanide concentration approaching the recommended criteria. This level of
dissociation was also noted in research conducted by Cherryholmes, who found that after 30 days
a 0.01 M solution of potassium iron cyanide (1,560 mg/l as CN) kept in the dark at a pH of 6.9 or
above contained only a 0.01 mg/l free cyanide level (6). The ferrous cyanide forms initially during
metallurgical processing and is slowly oxidized to the more stable ferric form over time. Rarely,
does the cyanide levels bound to iron approach 100 mg/l in a mining solution based upon ten
years of experience and work related to over 40 mining projects. The iron cyanide levels are
usually in the range of <1-20 mg/l. The stability of the iron cyanides is further exemplified by the
conditions associated with their analysis. In order to decompose the iron cyanide complex and
release the free cyanide, the pH of the sample is reduced to <1.0 with concentrated sulfuric acid
and the sample refluxed for 1-2 hours. As a result, under normal conditions in a stream (i.e.
ambient temperature and near neutral pH), iron cyanide is not subject to rapid chemical
breakdown.
The toxicity of iron cyanide is related to the free cyanide formed through chemical or photolytic
dissociation and not to the complex itself. As stated by Doudoroff, the complexes are not
themselves materially toxic, but their photodecomposition in irradiated solutions can yield much
highly toxic HCN (5).
Although the iron cyanides are considered non-toxic under normal conditions, the potential for
photolytic breakdown of the compounds is of some concern. These concerns have resulted from
various laboratory studies which showed that in closed and sealed systems under high intensity
ultraviolet radiation nearly complete breakdown of iron cyanide forming free cyanide occurs.
Unfortunately, the studies did not represent realistic natural conditions and did not take into
account natural attenuation through volatilization, hydrolysis, and oxidation.
In small streams and rivers, the extent of photolytic breakdown is minimal. In the event free
cyanide is formed through chemical or photolytic dissociation, it is quickly removed from solution
through volatilization. According to long-term research conducted by Environment Canada,
approximately 90% of the free cyanide formed through decomposition of iron cyanides is
removed from surface waters through volatilization and about 10% through chemical oxidation or
hydrolysis (7). The breakdown of iron cyanides to form free cyanide is the rate limiting step, and
once free cyanide is generated it is rapidly removed from solution through volatilization.
The percentage of ultraviolet radiation reaching the earth's surface is limited and is attenuated
significantly as light passes through the atmosphere. The actual percentage of uv light within the
electromagnetic spectrum which reaches the earth's surface is less than 10% (8). Of this 6%,
additional attenuation occurs as the result of many factors including scattering, reflection, and
absorption. Scattering alone reduces the percentage of available uv light by an additional 25%.
Reflection which increases as the angle of incidence increases at the water surface is particularly
important in rapidly moving streams, and can account for an additional 20% attenuation.
139 T. Mudder
Once the remaining light passes through the air and water surface, further attenuation occurs
through chemical reactions with oxygen, humic acids, and other reduced inorganic substances. As
a result, the quantity of light available for breakdown of iron cyanides is quite limited in surface
waters. If breakdown does occur, the free cyanide is rapidly attenuated.
As noted by Doudoroff, "because the penetration of sunlight, and especially that of ultraviolet, is
limited, photolysis of the iron cyanide complexes in most of the receiving waters exposed to
sunlight probably is not nearly as rapid as that observed in aquarium tests. Free cyanide produced
by the photolysis is continuously lost to the atmosphere or otherwise eliminated. Therefore,
concentrations of free cyanide lethal to fish may not often be attained even in surface waters
receiving large amounts of the iron cyanide complexes" (9).
There are no reported incidents in the mining industry involving discharges of effluents containing
elevated levels of iron cyanides which have resulted in the production of free cyanide levels
leading to toxic effects in a receiving system or its aquatic ecosystem.
From the period 1980-1986, detailed toxicological testing was conducted both at Homestake
Mining Company (HMC) and at the Fisheries Bioassay Laboratory (FBL) at Montana State
University to accurately simulate the rate and degree of photolytic breakdown of the iron cyanide
complexes and to quantify the toxicological effects on rainbow trout (10, 11). The tests were
conducted in accordance with standardized and USEPA accepted protocols. The work at
Homestake Mining Company was conducted under the supervision of both the state and federal
regulatory agencies, while the work at Montana State was conducted under the direction of Dr.
Vance Thurston, a noted aquatic toxicologist. These tests in conjunction with others investigating
toxicity of cyanide and aquatic insects, were employed in the development of a site-specific
chronic criteria for WAD cyanide of 0.08 mg/l by the South Dakota Department of Environment
and Natural Resources (DENR) for application to Whitewood Creek, a cold water permanent
trout fishery located in the Black Hills.
In a preliminary set of 96-hour flow through tests conducted at the FBL, fingerling rainbow trout
were exposed to varying concentrations of both ferrous and ferric cyanide in covered aquaria
using 18-hour photoperiods. The light sources were Spectralite tubes placed near the aquaria
surface. This light source was chosen as it best simulates natural light conditions, particularly in
the ultraviolet region of the electromagnetic spectrum.
The results of the acute tests are presented in Tables 3 and 4. In the dark, the LC50 or FAV's for
ferrous and ferric cyanide ranged from 869-939 mg/l and 869-1210 mg/l, respectively. These
values are consistent with other literature data. At a maximum light intensity of 680 lux, using an
18-hour photoperiod in covered aquaria, the FAV's for ferrous and ferric cyanide averaged 35
mg/l and 31.2 mg/l, respectively. During the testings the aquaria were well lit throughout. The
corresponding WAD values ranged from 0.15-0.42 mg/l under maximum light conditions, which
indicated the breakdown of the iron cyanide to be <2.0%. The corresponding criterion maximum
concentration, or CMC, for ferrous and ferric cyanide were about 17.5 mg/l and 15.6 mg/l,
respectively. The CMC, which is numerically equal to one-half the FAV, is employed as the
maximum not-to-exceed instream aquatic life criterion.
140 T. Mudder
In a second series of 48-hour static screening tests conducted at the FBL, Daphnia magna were
exposed to varying concentrations of both ferrous and ferric cyanide under differing light and
ventilation conditions. The percent mortalities for the two iron cyanides are presented in Tables 5
and 6. The tests conducted in the dark utilized covered containers, while the bioassays conducted
under elevated intensity simulated natural light conditions utilized uncovered containers to
promote ventilation.
Although no LC50 values could be calculated due to insufficient mortality, the results indicated
that the FAV values for ferrous and ferric cyanide were in the range of 4-<18 mg/l and >3-6 mg/l,
respectively.
Table 3: Summary of 96-hour LC50 Values Obtained

for Ferrocyanide and Rainbow Trout
Light Mean Mean WAD CN Total CN
Regime Light Mean Temperature Mean D.O. 96-hr LC50 96-hr LC50
o
Test Hours of Intensity pH C mg/l mg/l mg/l
No. Light/Dark lux (range) (range) (range) (95% C.I.) (95% C.I.)
1074 0/24 0 -- 9.4 8.44 -- 752
(9.4-9.5) (7.03-8.85) (474-1190)
1077 0/24 0 -- -- -- -- >867
1078 0/24 0 7.95 9.4 8.83 -- 939
(7.89- (9.4-9.5) (8.76-8.97) (828-1064)
8.01)
1088 18/6 330 7.77 15.7 8.22 -- 220
(7.66- (15.4-16.1) (8.01-8.49) (184-261)
7.94)
1090 18/6 330 7.83 15.2 7.85 -- 232
(7.75- (15.2-15.4) (7.64-8.11) (178-302)
7.95)
1980 18/6 680 7.33 9.6 7.93 0.15 33.30
(7.30- (9.6-9.7) (7.77-8.17) (0.13-0.17) (28.7-37.9)
7.34)
1083 18/6 680 7.55 9.5 8.37 0.17 37.4
(1) (1)
(7.50- (9.5-9.6) (8.16-8.58) ( - ) ( - )
7.57)
Note:
(1) Confidence interval not calculable by method used.
141 T. Mudder
Table 4: Summary of 96-hour LC50 Values Obtained

for Ferricyanide and Rainbow Trout
Light Mean Mean Mean WAD CN Total CN
Regime Light Mean Temperature D.O. 96-hr LC50 96-hr LC50
o
1075 0/24 0 7.87 9.3 8.18 -- 1210
(7.46-8.23) (9.46-9.4) (7.03- (1060-1380)
8.85)
1076 0/24 0 7.96 9.3 8.88 -- 869
(7.75-8.17) (9.2-9.4) (8.70- (860-1110)
9.01)
1079 0/24 0 -- -- -- -- 869
1081 18/6 330 7.33 9.6 7.91 -- 69.6
(7.30-7.34) (9.5-9.7) (7.61- (54.7-88.5)
8.11)
1082 18/6 330 7.56 9.6 8.28 -- >541
(7.53-7.58) (9.5-9.7) (8.09-
8.43)
1085 18/6 680 7.78 10.3 8.26 0.42 44.2
(7.76-7.80) (10.1-10.7) (8.13- (0.36-0.45) (38.2-51.0)
8.34)
1987 18/6 680 7.96 16.0 8.69 0.40 38.8
(7.89-8.06) (15.8-16.1) (8.58- (0.36-0.43) (25.0-60.2)
8.83)
1089 18/6 680 7.89 16.0 8.16 0.31 10.8
(7.79-7.10) (15.5-16.4) (8.05- (0.30-0.32) (9.93-13.1)
8.37)
142 T. Mudder
To further investigate the photolytic chronic or long-term toxicity of iron cyanides on rainbow
trout, a series of 45-day bioassays were conducted at the HMC toxicological laboratory. The test
utilized juvenile rainbow trout with an average initial size and weight of 7.1 cm and 3.8 grams,
respectively. The fish were exposed to a 16-hour photoperiod in covered aquaria. Lighting was
again accomplished using Spectralite fluorescent tubes, which simulated accurately natural light
conditions. The fish were exposed to a constant background matrix of 56% treated effluent from
the HMC biological treatment plant and 44% receiving stream water. Into the whole effluent
chemical matrix various concentrations of ferric cyanide were introduced into a series of duplicate
aquaria. The average ferric cyanide concentration ranged from <0.02 mg/l as total cyanide in the
control to 22.6 mg/l in 100% effluent. The corresponding average WAD cyanide concentrations
resulting from the combined chemical and photolytic breakdown of iron cyanide ranged from
<0.02-0.19 mg/l. The various ferric cyanide concentrations were fed into the aquaria via a multi-
channel peristaltic pump.
Table 5: Preliminary Acute Toxicity Data for

Ferricyanide and Daphnia
Percent Mortality
Dark, No Ventilation Light, Good Ventilation
Ferricyanide mg/l as CN (Tests 702 & 705) (Test 703)
2,350 100 --
470 100 --
235 100 --
47 100 30
23 100 30
11 70 50
6 60 60
4.7 -- --
3 40 10
2.3 -- --
1.5 20 0
0.7 0 0
0 0 0
143 T. Mudder
TABLE 6: Preliminary Acute Toxicity Data for

Ferrocyanide and Daphnia
Percent Mortality
Dark, No Ventilation Light, No Ventilation
Ferricyanide mg/l CN (Test 700) (Test 699)
1,825 100 --
365 100 --
182 100 100
36 82 80
18 70 30
3.6 -- 10
1.8 -- 10
1.8 -- 13
A summary of the chemical analyses associated with the test are presented in Table 7. Following
45 days of exposure, no mortalities were noted in any test concentration of iron cyanide, which
reached a maximum of 30.0 mg/l. No differences in growth factors (K-factors) were noted
between controls and exposed organisms. No bioaccumulation was noted and no physiological
abnormalities were noted following external and internal necropsies of the fish. The results
demonstrated conclusively that a sensitive fish species can be exposed to very high concentrations
of iron cyanide without experiencing toxic effects. The primary concern related to the WAD
cyanide which formed through the breakdown of the iron cyanides and accumulated in the test
solutions. The test was quite valuable because it utilized an actual treated mine effluent as a
background matrix, a long-term test period under elevated light conditions, and a sensitive aquatic
species.
The percentage breakdown of iron cyanide increased as the concentration of the compound
decreased. The percentage breakdown ranged from 0.80-2.5% based upon comparison of the
average WAD and iron cyanide levels. The results were in accordance with the previous test
work conducted at the FBL, in which the average percentage breakdown of ferricyanide at the
highest light intensity was 1.2% (i.e. 0.38 mg/l WAD cyanide/31.2 mg/l total cyanide x 100 =
1.2%). Assuming the 6% uv radiation reaching the earth's surface results in 100% breakdown of
iron cyanide, attenuation to 0.3% through scattering and reflection alone (i.e. 6 x 0.25 x 0.20 =
0.30) reduces the total breakdown to about 5%.
144 T. Mudder
TABLE 7: Summary of Iron Complexed Cyanide Chronic Toxicity Test (1)

(5) (2)
Aqu. % ml/min Mean Max Min Mean Max Min Std. Mean Max Min Std. Max Min
# Eff Spike Total Std. WAD CN- Dev. Fe Dev. Mean
Cyanide Dev Temp
365-66 0 0 0 0 0 0 0 0 0 0 1.3 0.8 1.7 0.3 4.2 7.0 2.0
367-68 56 0 0.47 0.59 0.30 0.09 0.03 0.03 0.03 0.005 0.9 1.2 0.6 0.2 12.4 14.0 10.0
369-70 56 1 1.62 2.00 1.16 0.24 0.04 0.08 0.02 0.02 1.2 1.5 0.8 0.2 -- -- --
371-72 56 20 22.58 30.00 18.75 3.2 0.19 0.31 0.12 0.06 8.0 9.7 7.2 0.8 -- -- --
373-74 56 5 6.22 5.70 4.94 0.23 0.11 0.16 0.08 0.03 2.5 3.0 2.1 0.2 -- -- --
375-78 56 11 10.96 11.50 10.50 0.38 0.15 0.20 0.11 0.03 4.7 5.0 4.3 0.5 -- -- --
(3) (3) (4)

Aqu. % Mean Mean Mean Mean Mean Mean Mean Mean Mean Mean Mean Mean Mean
# Eff Do NH3-N Alk Hard Cond. Cu Ni Zn Pb Cr Cd As Ag
365-66 0 11.0 <0.5 180 257 450 0.005 0.012 0.017 0.019 0.002 0.002 0.008 0.001
367-368 56 8.8 >0.5 107 485 1266 0.025 0.041 0.029 0.034 0.004 0.004 0.040 0.002
Notes:
(1) All values reported as mg/l, unless otherwise stated.
o
(2) Reported as C
(3) Reported as mg/l As CaCO3
(4) Reported as µmhos/cm
(5) For all calculated means and standard deviations n=10
The test data demonstrate that the breakdown of iron cyanide under conditions similar to ambient
in which the natural attenuation of cyanide is not maximized, results in minimal formation of
WAD cyanide or free cyanide. Furthermore, iron cyanide levels near 20 mg/l do not exert acute
or chronic toxicity to the sensitive rainbow trout. In the event breakdown of the iron cyanide
does occur in a pond or stream along with buildup of free cyanide, the free cyanide formed would
be reported by the WAD cyanide analysis. There is no evidence that breakdown of iron cyanide
and accumulation of WAD cyanide occurs in either holding ponds or flowing receiving systems.
Examination of data from various tailings ponds indicates the ratio of total to WAD cyanide
remains constant over time and accumulation of WAD forms of cyanide does not occur. As
mentioned previously, the rate limiting step in reduction of the cyanide content in a tailings pond
is breakdown of the complex. Once breakdown occurs, the free cyanide is rapidly removed from
solution primarily through volatilization.
To investigate the breakdown of total cyanide, HMC monitored the receiving stream at several
locations below the wastewater treatment plant discharge. A comparison of the total to WAD
cyanide levels yielded a relatively constant ratio, which indicated breakdown of iron cyanide to
form increased and accumulated levels of WAD cyanide was not occurring (Mudder and
Whitlock, unpublished results). Data of this type indicates that concerns regarding the
downstream formation of WAD cyanide following discharge of relatively low levels of iron
cyanide are not warranted.
145 T. Mudder
The scientific reasoning for preferring the WAD cyanide versus the total cyanide method for
compliance and monitoring purposes was the recognition that iron cyanide was inherently non-
toxic at the concentrations normally associated with mining solutions. Furthermore, the total
cyanide analytical method itself is unreliable at the lower environmentally relevant levels.
Historically, only the free form of cyanide measured as total cyanide has been included in the
regulatory process. Compliance using the total cyanide measurement includes the cyanide bound
to iron, which is non-toxic in moderate levels under natural conditions. However, the other
weakly bound metal cyanide complexes which are reported along with free cyanide using the
WAD cyanide procedure, do exhibit both direct and indirect toxicity, and must be considered.
The trend in the U.S. and other countries is to utilize the WAD cyanide procedure for monitoring
and compliance purposes where protection of aquatic life is a major concern. The WAD cyanide
procedure does not report cyanide bound to iron, but does report the free cyanide produced
through breakdown of the complex.
The WAD cyanide analysis reports not only free cyanide, but cyanide bound to copper, nickel,
and zinc. These three metal complexes include those predominantly associated with mining
effluents. These compounds exhibit varying degrees of stability, and tendencies for breakdown
and release of free cyanide when compared to the iron cyanides. In addition, these compounds
exhibit varying degrees of inherent toxicity. From a treatment standpoint, these compounds and
forms of cyanide are the most readily degradable. As mentioned previously, the WAD cyanide
analysis is reliable, and measures those forms of cyanide considered toxicologically significant.
Of the forms reporting as WAD cyanide, free cyanide is the most readily degradable from a
treatment viewpoint. Following treatment, the effluent normally contains non-detectable and/or
non-toxic levels of free cyanide (i.e. <0.01 mg/l). As a result, the primary concern with regards to
aquatic or mammalian toxicity, are the other forms of WAD cyanide. As a rule, metal complexed
cyanide is less toxic than free cyanide. In addition, the toxicity of the complexed metal is lower
than an equal level of the free ionic form of the metal. There is no evidence to support the
existence of a hardness relationship with the toxicity of WAD cyanide other than effect hardness
has on pH.
The concentration of metals in cyanidation wastewaters varies over several orders of magnitude.
In general, there is sufficient cyanide present in mining wastewaters to complex the available
metals. The metal cyanide complexes of major and minor importance include those of mercury,
cadmium, zinc, nickel, iron, copper, silver, and gold.
In early work examining the toxicity of metal complexed cyanides and certain fish species, the
concentrations of harmful action for zinc cyanide, cadmium cyanide, copper cyanide, and nickel
cyanide were found to be 0.10 mg/l, 0.30 mg/l, 1.0 mg/l, and 30 mg/l as cyanide, respectively (9).
Considerable reduction in the toxicity of the four metals and cyanide was noted in the tests.
Unfortunately, little information concerning the test conditions and fish species used was included
in the publication.
146 T. Mudder
In subsequent experiments, the pH of the test solutions were controlled in the range of 6.5-8.0.
The 96-hour median tolerance limits for nickel cyanide and fathead minnows at pH 6.6 and 8.0
were 0.42 mg/l and 7.3 mg/l as cyanide, respectively (9). The tolerance limits decreased 10-13
fold when the pH was decreased from 7.8 to 7.5. As a result, the acute toxicity of dilute nickel
cyanide solutions is determined primarily by the free molecular HCN concentration which results
from dissociation. The observation includes the fact that free nickel ion is relatively non-toxic to
aquatic life, even in low hardness waters. Although there is evidence to support direct toxicity of
the complex itself, a equally large database suggests the opposite hypothesis is valid.
As stated by Doudoroff, the practical implications of the nickel cyanide toxicity data indicates
nickel is very effective in protecting fish from lethal effects of cyanide in alkaline waters (i.e. pH
>7.5), but is not effective in acidic waters (i.e., pH <6.5). Since, natural waters and mining
effluents are generally alkaline, complexation with nickel is effective in reducing the relative
toxicity of cyanide. In addition, free cyanide formation through dissociation at acidic pH values is
slow, and once formed will be rapidly lost from the water column through natural attenuation (i.e.
volatilization, hydrolysis, and oxidation). It is interesting to note that the complexing ability of
nickel forms the basis for a specific cyanide analytical procedure.
With regards to nickel cyanide, the toxicity varies in accordance with pH, and is quite pronounced
at acidic pH levels in the range of 6.5. The detailed investigations on the influence of pH on
nickel cyanide toxicity have supported the assumption that the toxicity of the complex is
attributable to the free cyanide formed through dissociation. In general, the toxicity of waters
containing nickel cyanide can be estimated by calculating the free cyanide concentration resulting
from dissociation of the complex.
The toxicity effects of nickel cyanide have been studied more extensively than any other metal
cyanide complex. In early experiments conducted by Doudoroff using fathead minnows, about
20-40 percent of the organisms died within 168 hours at a total cyanide concentration of
0.50 mg/l. The cyanide present was complexed prior to the experiments by mixing of solutions of
nickel sulfate and sodium cyanide until nickel precipitated. It was determined that the toxicity of
various solutions increased with time after introduction of the test organisms. An increase of 0.50
unit in pH of a test solution with sodium hydroxide was sufficient to induce recovery of fish
already affected by the nickel cyanide present in the solution. The mole ratio of cyanide to nickel
was about 4.0 in the various tests.
In terms of silver cyanide, the metal cyanide complex formed is very effective in preventing the
occurrence of free cyanide in solution. For example, at a pH of 7.0 and 8.0, greater than 80
percent and 99 percent of the cyanide still remains bound to silver in dilute solutions of the
complex. In addition, very low levels of silver are noted in discharges from mining operations due
to recovery processes. Cyanide and silver occur in an approximate 2/1 molar ratio. Although free
silver ion is very toxic to aquatic life, there is generally sufficient cyanide to promote complete
complexation. Once the complex is formed it is quite stable, and there is no tendency for
dissociation at the pH associated with mining effluents or natural waters. Concerns with silver
cyanide toxicity and criteria development should be focused upon the free metal and cyanide
concentrations existing in solution.
147 T. Mudder
Work conducted by Broderius indicated the extent of dissociation of the silver cyanide complex
with pH was minimal as were its toxic effects on bluegills. For example, the mean survival times
for bluegills at a silver cyanide concentration of 10 mg/l as cyanide and pH values of 7.5 and 8.5
were 29 and 31 hours, respectively (9). The molar ratio of cyanide to silver is again 2/1. The 96-
hour median tolerance limit of silver cyanide was estimated from additional research to be
somewhat below 7.0 mg/l as cyanide.
Numerous studies have been conducted concerning the toxicity of free cyanide and the metal
cyanide complexes of zinc and cadmium. These complexes are weak in nature and dissociate
nearly completely at low concentrations in natural waters. The results of toxicity tests comparing
free cyanide and these two metal cyanide complexes indicates there is no definitive relationship
with regards to synergism or antagonism between the metal and cyanide.
The importance of the stability of either zinc or cadmium cyanide should be ignored when
establishing criteria for the metals or cyanide. In this instance, criteria should be derived or
selected assuming free metal and free cyanide, and the results similar to those previously discussed
concerning the toxicity of these particular metal complexes must be ignored.
The copper cyanide complex offers additional insight into the toxicity of the WAD forms of
cyanide. The observed molar ratio for cyanide to copper varies from 2/1 to 3/1. For calculation
-28
purposes the dissociation constants employed for a ratio of 2/1 or 3/1 are 4 x 10-24 and 5 x 10 ,
respectively. At the concentrations present in treated mining effluents (i.e. <0.50 mg/l), the
tricyanide complex begins to dominate. At concentrations of copper cyanide below 0.20 mg/l as
cyanide, the tricyanide complex is the dominant form.
Pronounced detoxification of both cyanide and copper when combined has been demonstrated by
several researchers. For example, Doudoroff found the 24-hour median tolerance limit for copper
cyanide, copper, and free cyanide with fathead minnows to be about 2.2 mg/l as cyanide, <0.10
mg/l, and 0.25 mg/l, respectively (9). These results have been confirmed in testing conducted at
Homestake Mining Company (Mudder, unpublished results). Both copper and cyanide are quite
toxic to aquatic organisms, especially trout, and dissociation of the complex produces two species
of potential concern.
In addition, there is evidence to support the complex itself is toxic, as several tests indicated low
LC50 values in solutions of non-detectable or non-toxic concentrations of free cyanide. The 48-
hour median tolerance limit for copper cyanide and bluegills in slightly alkaline solutions was
estimated by Broderius at 9.0 mg/l as the complex and 4.0 mg/l as cyanide. Data was obtained
indicating the penetration of the complex into the fish tissue. The toxicity of the copper cyanide
complex was very similar to that of the free metal, resulting in coagulated mucus on the gills and
body surfaces of the fish. However, at the pH of mining effluents and natural waters, and the
levels of the complex in treated effluents, there is little tendency for dissociation, and a distinct
reduction in toxicity of both copper and cyanide occurs upon complexation.
148 T. Mudder
In further research conducted by HMC, several series of acute and chronic static and flow-
through bioassays were performed over a three to four-year period to investigate the toxicity of
WAD and copper cyanides. A series of acute 96-hour flow-through bioassays were conducted
examining specifically the toxicity of copper cyanide and rainbow trout (12). In those tests the
"no effect levels" or calculated FAV's for WAD cyanide ranged from 0.16-0.42 mg/l with an
average WAD cyanide value of 0.29 mg/l.
In another series of chronic bioassays using juvenile rainbow trout, the long-term effects (i.e. 45
days) of iron cyanide and the WAD cyanide resulting from its breakdown were examined. The
bioassay involved a series of covered, flow-though aquaria into which a constant background
matrix of 56% treated effluent and 44% Whitewood Creek water flowed. Into this chemical
matrix various concentrations of ferricyanide were introduced. The aquaria were subjected to an
18-hour daylight period. No deaths were reported in 45 days at mean WAD cyanide
concentrations in the five aquaria ranging from 0.03-0.19 mg/l with an average final chronic value,
or FCV, of 0.10 mg/l. The maximum "No Effect Level", or NOEL, ranged from 0.03-0.31 mg/l
with an average value of 0.16 mg/l. The test solutions contained all complexed metal cyanides in
an actual background chemical matrix of treated cyanidation or process wastewater. The results
of the study are presented in Table 7.
In addition to zero mortality, there was no indication of bioaccumulation of metals or cyanide, no

difference in growth factors, and no evidence of external or internal physiological effects based
upon examination of each fish following the test period. This test was conducted using USEPA
approved bioassay procedures. Very strict control of flow rates and testing conditions was
practiced. Particular attention was paid to the analytical procedures to ensure accurate and
reliable results.
From the similar research conducted at the FBL, the results of which are presented in Table 4, the
FAV's for young rainbow trout and WAD cyanide resulting from the breakdown of ferric cyanide
under intense light, low ventilation conditions ranged from 0.31-0.42 mg/l with an average FAV
of 0.38 mg/l. The study involved the formation of WAD cyanide from the breakdown of ferric
cyanide, the predominant form of iron cyanide in a mine wastewater effluent. Although ferrous
cyanide exhibited a higher toxicity than the ferric form, its levels in the effluent are minimal due to
the biological oxidation and chemical precipitation which occur during treatment.
In the case of the Golden Cross Mine and the Waitekauri River located on the north island of
New Zealand, the conservative and average NOEL or FCV of 0.10 mg/l was used as the instream
site-specific aquatic life criterion for WAD cyanide. This particular site-specific chronic criterion
took into account the presence of all the primary metal complexed cyanides. As noted previously,
in further testing conducted by HMC, the average FAV for copper cyanide, which is measured as
WAD cyanide, was 0.29 mg/l. Using this toxicity data coupled with a site-specific acute to
chronic ratio, a site-specific FCV for copper cyanide can be determined. Division of the site-
specific FAV of 0.29 mg/l by a factor of two generates a site-specific CMC or criterion maximum
concentration of 0.15 mg/l WAD cyanide.
149 T. Mudder
A site-specific ACR of 3.8 is obtained for copper and WAD cyanide by division of the average
FAV obtained for ferric and WAD cyanide of 0.38 mg/l at the FBL by the average FCV of 0.10
mg/l obtained for ferric and WAD cyanide in the HMC toxicity studies. Division of the site-
specific FAV for copper cyanide of 0.29 mg/l, previously discussed, by the corresponding ACR of
3.8 results in a site-specific FCV for copper and WAD cyanide of 0.08 mg/l. In situations where a
treated mine wastewater discharge contains predominantly copper cyanide, the 0.08 mg/l FCV for
WAD cyanide would be more appropriate than application of the 0.10 mg/l FCV, which was
derived from consideration of all the metal complexed and WAD cyanide forms present in a
treated mine wastewater, including copper, nickel, and zinc cyanide. In any event, the free
cyanide levels associated with this range of WAD cyanide, regardless of the metal complexed
form involved, would not be quantifiable based upon the equilibrium concentrations presented
previously in Table 2.
However, both these FCV's are conservative and are not distinguishable analytically, due to the
inherent variability associated with the WAD cyanide measurement. As a result, application of an
instream FCV for WAD cyanide of 0.08 to 0.10 mg/l as a monthly average would be acceptable,
conservative, and protective of the aquatic life for which it was originally derived. The site-
specific CMC of 0.15 mg/l WAD cyanide would in turn become the daily maximum not-to-exceed
instream aquatic life standard.
4.0 REFERENCES
1. Standard Methods, Part 4500-CN, Section I, Weak and Dissociable Cyanide, p. 4-38, 17th
Edition, APHA-AWWA-WPCF, 1989.
2. ASTM Annual Book of Standards, Section D2036, Method-C, Weak Acid Dissociable
Cyanides, p. 121, 1985.
3. Mudder, T. and Smith, A., The Chemistry and Treatment of Cyanidation Wastes, Mining
Journal Publications, London, England, in press, November, 1991.
4. Ambient Water Quality Criteria Document for Cyanide, PB85-227460, USEPA,

Washington, D.C., January, 1984.
5. Doudoroff, P., A Critical Review of Recent Literature on the Toxicity of Cyanides to Fish,
American Petroleum Institute, Washington, D.C., 1979.
6. Cherryholmes, K., "Biological Degradation of Complex Iron Cyanides in Natural Aquatic

Systems", the 7th Annual Symposium on Aquatic Toxicology.
7. Simovic, L., et al., "Development of a Model to Distribute the Natural Degradation of

Cyanide in Mill Effluents", Wastewater Technology Center, Environment Canada,
December 12-14, 1984.
8. Limnology, Wetzel, R., W.B. Saunders Company, Philadelphia, 1975.
150 T. Mudder
9. Doudoroff, P., Toxicity to Fish of Cyanide and Related Compounds, EPA-600/3-76-038,

USEPA, Duluth, Minnesota, April, 1976.
10. Marshall, S. and Fox, F., "The Long Term Toxicity of Treated Effluent to Rainbow
Trout", Toxicity Test SG-45D-WWTD-EFF-II, Homestake Mining Company, Aquatic
Toxicity Laboratory, Lead, South Dakota, June, 1985.
11. Meyn, E., Zajdel, R., and Thurston, R., "Acute Toxicity of Ferrocyanide and Ferricyanide
to Rainbow Trout", Technical Report No. 84-1, Fisheries Bioassay Laboratory, Montana
State University Bozeman, Montana, June, 1984.
12. Triennial Review of the South Dakota Surface Water Quality Standards, Uses Assigned to
Lakes, and Uses Assigned to Streams, ARSD 74:03:02 - 74:03:04, prepared by the South
Dakota DENR, Pierre, South Dakota, February, 1989.
151 T. Mudder
DERIVATION OF AQUATIC LIFE CRITERIA
FOR TOTAL AND IRON CYANIDE
Prepared By:
Terry Mudder, Ph.D.
Originally written in 1995 and first published in The Cyanide Monograph, published by Mining
Journal Books, London, England, United Kingdom, June 1998
Derivation of Aquatic Life Criteria for Total and Iron Cyanide
1.0 THE NATURAL ATTENUATION AND PHOTOLYSIS OF IRON CYANIDE
The forms of cyanide important from a treatment and toxicity standpoint include free cyanide,
weak acid dissociable (WAD) cyanide, and total cyanide. Analytically, the forms of cyanide are
distinguished and quantified by either the weak acid dissociable or total cyanide method. The
weak acid dissociable method measures all forms of cyanide, except those bound to primarily iron.
The total cyanide method measures all forms of cyanide including the stable iron complexed
form. Subtraction of the WAD cyanide value from the total cyanide value provides a measure of
the iron cyanide present in a sample. Although the free cyanide forms have been generally
considered the most important from a toxicological standpoint, concerns relating to the toxicity
and breakdown of other metal complexed cyanides have prompted several State regulatory
agencies in the western United States to recommend the WAD cyanide method for compliance
and monitoring purposes in the mining industry. The derivation of the site-specific criteria for
WAD cyanide are discussed in detail elsewhere (SDDENR, 1996).
The scientific reasoning for preferring the WAD cyanide versus the total cyanide method for
compliance and monitoring purposes was the recognition that iron cyanide was inherently non-
toxic at the concentrations normally associated with mining solutions. Furthermore, the total
cyanide analytical method itself is unreliable at the lower environmentally relevant levels.
Although the total cyanide level within an effluent can remain constant from analysis to analysis,
the toxicity of the effluent would increase or decrease as the ratio of WAD to iron cyanide
increased or decreased. The chemical stability of iron cyanide, which exists in both the ferrous
and ferric forms, is very high as evidenced by the conditions associated with its analysis. In order
to decompose the complex in the total cyanide analysis, the pH of a sample is reduced to <1.0
with concentrated sulfuric acid and refluxed for a period of 1-2 hours. Under the ambient
conditions occurring in a stream, iron cyanide is not subject to chemical dissociation. However,
although the total cyanide level within an effluent remains constant from analysis to analysis, the
toxicity of an effluent could increase or decrease, as the proportion of WAD cyanide within the
total cyanide measurement increases or decreases.
151 T. Mudder
Table 1: Metal Cyanides Complex Ions in Order of Decreasing

Stability in Water
(1)
Name Formula Dissociation Constant
-3 -52
-4 -47
-2 -42
Tetracyanomercurate (II) [Hg(CN)4] 4.0 x 10
-2 -28
Tricyanocuprate (I) [Cu(CN)3] 5.0 x 10
-2 -22
Tetracyanonickelate (II) [Ni(CN)4] 1.0 x 10
-1 -21
Dicyanosilverate (I) [Ag(CN)2] 1.0 x 10
-2 -17
Tetracyanocadminate (II) [Cd(CN)4] 1.4 x 10
-2 -17
Tetracyanozincate (II) [Zn(CN)4] 1.3 x 10
Note:
(1) The Roman numerals indicate the oxidation state of the metal atom.
The very high stability of both iron cyanides (i.e., ferrocyanide and ferricyanide) is demonstrated
by the comparison of dissociation constants for various metal complexes presented in Table 1
(Caruso, 1975). The ferro- and ferri-cyanide complexes exhibit the lowest potential for
dissociation under normal conditions. As shown in Table 2, even at 1,000 mg/l of either iron
cyanide, the resultant free cyanide levels produced do not exceed the USEPA recommended
aquatic life criteria of 0.005 mg/l (Caruso, 1975; and USEPA, 1984). The toxicity of iron
cyanide is related to the free cyanide formed through chemical or photolytic dissociation and not
to the complex itself. As stated by Doudoroff, "these complexes are not themselves materially
toxic, but their photodecomposition in irradiated solutions can yield much highly toxic HCN"
(Doudoroff, 1976; and Doudoroff, 1979).
152 T. Mudder
Table 2: Free Cyanide Concentration Released at Various Levels

of a Metal Cyanide Complex
(1,2)
Complex 1 mg/l 10 mg/l 100 mg/l 1,000 mg/l 100,000 mg/l
-2
[Hg(CN)4] 0.00002 0.00003 0.000045 0.00007 0.00018
-1
[Ag(CN)2] 0.00009 0.0002 0.0004 0.0009 0.0041
-2
[Cu(CN)3] 0.0003 0.00054 0.00097 0.0017 0.0054
-3
[Fe(CN)6] 0.0002 0.0032 0.0004 0.0006 0.0012
-4
[Fe(CN)6] 0.0012 0.0016 0.0022 0.0031 0.0061
-2
[Ni(CN)4] 0.135 0.215 0.340 0.539 1.324
-2 (3)
[Cd(CN)4] 2.30 3.64 5.77 14.49
-2 (3)
[Zn(CN)4] 2.26 3.59 5.68 14.28
Notes:
(1) All values in mg/l.
(2) Free cyanide levels calculated at pH = 7 and 25C.
(3) Calculations indicate that at this dilution the two complexes are completely ionized.
Although the iron cyanides are considered non-toxic under normal conditions, it is the potential
for the production of free cyanide through photolytically enhanced chemical dissociation of these
compounds, which has been of concern for many years. These concerns have resulted primarily
from various laboratory studies which showed that in closed systems and/or under high intensity
radiation nearly complete breakdown of iron cyanide forming free cyanide occurs. Unfortunately,
the studies were generally conducted under artificial and not ambient conditions, and did not take
into account natural attenuation through volatilization, hydrolysis, and oxidation (Asperger, 1952;
Asperger, et al., 1960; MacDiarmid and Hall, 1953; and Ohno, 1967).
In addition, there have been reports that releases of very high concentrations of iron cyanides to
surface waters from photographic processing facilities and other industries, has resulted in fish
kills due to the photolytic breakdown of these metal cyanide complexes (Burdick and Lipschuetz,
1950; and Kobayashi and Mori, 1973). These reports are extremely rare and the wastewaters
described contained other constituents in addition to the very high levels of iron cyanide, far in
excess of concentrations associated with mining effluents. There are no reported incidents in the
mining industry involving discharges of effluents containing elevated levels of iron cyanides which
have resulted in the production of free cyanide levels leading to toxic effects in a receiving system
or its aquatic ecosystem. Iron cyanide has been discharged in varying levels from mining
operations for many years throughout the world.
153 T. Mudder
It is interesting to note that the quantity of iron cyanides released directly or indirectly into surface
waters in the United States, used as anti-caking agents in road and table salt, is between one and
two orders of magnitude greater than the total quantity of cyanide entering the environment
through discharges from mining operations (USEPA, 1981). In the exposure and risk assessment
for cyanide prepared by the USEPA, releases of cyanide from the mining industry accounted for
only 0.01-0.20% of the total releases of cyanide to the environment (USEPA, 1981).
Furthermore, the USEPA stated that risks to aquatic organisms would be highly localized in the
immediate vicinity of a major point source discharge, due to the rapid attenuation of free cyanide
through volatilization.
Although most of the metal cyanide complexes are photolytically active, only the iron cyanides are
susceptible to absorption of wavelengths of light commonly associated with the higher energy
ultraviolet or visible light reaching the surface of the earth (Broderius, 1973; and Moggi, et al.,
1966). The rate of a photochemical reaction in aqueous solution is dependent upon the solar
irradiance at the solution surface, the radiative transfer from into the solution, and the
transmission of sunlight in the solution. Through absorption by components in the atmosphere,
the intensity of light in the ultraviolet and visible region of the solar spectrum decreases with
decreasing wavelength, such that essentially no light is transmitted to the surface of the earth
below about 300 nm (Bener, 1972). The metal cyanide complexes, reporting as WAD cyanide,
either absorb light in the ultraviolet region below 300 nm or the far-infrared region below 5,000
-1
cm , which is associated with very low energy.
As a result, the main mechanism for breakdown of metal cyanide complexes, reporting as WAD
cyanide, is through chemical dissociation, which is controlled primarily by pH and temperature.
The iron cyanide complexes do absorb radiation above 300 nm, with ferricyanide, the oxidized
form, exhibiting a strong absorption band near 420 nm. The absorption specra for the two iron
cyanides are shown on Figure 1, taken from the research of Broderius and Smith (Broderius and
Smith, 1980).
Since the chemical dissociation of the iron cyanides is very limited due to the extreme stability of
these compounds, the environmental importance of these compounds relates to the potential for
photolytically enhanced breakdown under ambient or natural conditions encountered at mining
operations throughout the world. The earlier research conducted on the photolytic breakdown of
iron cyanides was conducted in laboratories for research purposes, and as mentioned earlier, did
not simulate accurately natural conditions. The actual percentage of the electromagnetic specrum,
and in particular that portion of the specrum associated with ultraviolet light, reaching the earth's
surface is quite limited and is attenuated significantly as light passes through the atmosphere.
Only a few percent of the ultraviolet light actually reaches the earth's surface (Wetzel, 1975; and
Odum, 1971). The specral distribution of extraterrestrial radiation is shown on Figure 2, taken
from the work of Gates (Gates, 1965).
154 T. Mudder
Figure 1: Specific Sunlight Absorption Rates of

Hexacyanoferrate (II) and (III) Complexes as a Function
Of Wavelength at Midday and Mid-Summer, Latitude 40° N
155 T. Mudder
As is shown on Figure 2, the percentage of light at wavelengths below about 0.40 microns or 400
nm is strongly attenuated by the atmosphere, clouds, and in particular plants. For example, very
limited diffuse light would reach a pond or stream surface surrounded by tree cover. The
remaining light is further attenuated by reflection at the water's surface, and by sorption and
scattering within the water column.
The key to predicting the importance of the photolytic breakdown of iron cyanides relates to the
accurate measurement of light intensity or energy available for this reaction under varying
environmental conditions. In order to aid in the prediction of the photolytic breakdown of
chemicals in the environment, a fundamental model was developed that took into account all of
the contributing variables (Zepp and Cline, 1977). In addition, this research included laboratory
methods with which the various influences on the rate coefficients for photodecomposition could
be quantified. A computer model was developed, which could be obtained from the authors for
the purposes of determining the photolytic decay rate or coefficient for a specific chemical of
interest in water.
Employing the fundamental relationships put forth by Zepp and Cline, the USEPA undertook to
examine and develop the fundamental rate coefficients for the iron cyanides (Broderius and Smith,
1980). In this classic work of Broderius and Smith, the theoretically and experimentally derived
maximum rates of photodecomposition under natural conditions were established for both iron
cyanides, along with the affects that water depth, turbidity, sky conditions, change of season, and
diurnal fluctuations had on reducing the photodecomposition rates. In addition to determining the
various rates of photodecomposition, the minimum volatilization rates of free cyanide were also
empirically derived for various concentrations. Both photodecomposition of the iron cyanides
and volatilization of free cyanide in solutions were determined to be first order, following an
exponential curve dependent upon the initial concentration of either iron or free cyanide,
respectively.
In natural waters, the loss of cyanide is controlled almost exclusively through volatilization or
stripping of HCN from solution, which is in turn controlled by pH, temperature, and mixing or
turbulence. In natural waters, since the pH is usually at or below about 8.5, any free cyanide
present is almost entirely in the HCN form. In the event free cyanide is formed through chemical
or photolytic dissociation, it is quickly removed from solution through volatilization. According
to long-term research conducted by Environment Canada, approximately 90% of the free cyanide
formed through decomposition of iron cyanides is removed from surface waters through
volatilization and about 10% through chemical oxidation or hydrolysis (Simovic, 1984; and
Simovic and Snodgrass, 1989). In addition to volatilization, further attenuation of light occurs
through chemical reactions with oxygen, humic acids, and other reduced inorganic substances. As
a result, the quanta of light available for breakdown of iron cyanides is quite limited in surface
waters. If breakdown of iron cyanide does occur, the free cyanide is rapidly converted to HCN
gas at ambient pH values and lost through volatilization or other attenuation mechanisms.
156 T. Mudder
Figure 2: Principles and Concepts Pertaining to Energy in Ecological Systems
157 T. Mudder
As noted by Doudoroff, "because the penetration of sunlight, and especially that of ultraviolet, is
limited, photolysis of the iron cyanide complexes in most of the receiving waters exposed to
sunlight probably is not nearly as rapid as that observed in aquarium tests. Free cyanide produced
by the photolysis is continuously lost to the atmosphere or otherwise eliminated. Therefore,
concentrations of free cyanide lethal to fish may not often be attained even in surface waters
receiving large amounts of the iron cyanide complexes" (Doudoroff, 1976; and Doudoroff,
1979).
As concluded by Broderius and Smith, the relatively small concentration of HCN formed from the
photolysis of iron cyanide is of minimal toxicological importance below a depth of about 50-100
cm in most well-mixed natural waters likely to receive this compound as a pollutant. Under
ambient conditions, the rate of HCN volatilization is much more rapid from surface waters than is
observed in the laboratory, due primarily to the increased mixing, turbulence, and/or wind action.
On the other hand, the rates of photodecomposition of iron cyanides under ambient or natural
conditions are much lower than the maximum rates observed in the laboratory, due to the various
mechanisms available for attenuation of light. In order for the photolysis of iron cyanide to be an
important environmental pathway for the production of HCN, the rate of photolysis must be
sufficiently greater than the volatilization rate to allow the accumulation of cyanide of a toxic
form and in toxic levels within the water column.
During the 1980's, following the work of Broderius and Smith, an intense research and field
verification program was undertaken by several researchers and Environment Canada, to further
quantify, verify, and compare the rates of volatilization, dissociation, and photodecomposition of
the various metal cyanide complexes. The results of the research efforts were formulated into a
computer driven mathematical model for the prediction of the rates of decay of the natural
attenuation or degradation of cyanide in impoundments containing process solutions at mining
operations (Simovic, 1984; Simovic and Snodgrass, 1989; and Wastewater Technology Centre,
1997). The research demonstrated that the rate limiting step in the natural attenuation of
degradation or loss of cyanide within static impoundments was the dissociation of its metal
complexes and not the volatilization of HCN, once it was formed. Although the natural
attenuation of the iron cyanide complexes was found to be the only photolytically enhanced
dissociation reaction of importance, the resultant increased decomposition rate was still less than
the rate of HCN volatilization, due to the array of light attenuation mechanisms described earlier.
The basic reactions involved in the natural attenuation of metal complexed and free cyanides are
shown on Figure 3 (Simovic, 1984). As shown on Figure 3 and demonstrated in the research, the
rate of volatilization (kv) was greater than k1 or kuv.
158 T. Mudder
Figure 3: Conceptual Cyanide Degradation Model
The demonstration of these findings are found in the many investigations of the natural
attenuation of cyanide in surface waters associated with mining operations. Regardless of the
surface water configuration or ambient conditions examined, the monitoring of the decay of total
cyanide, and more specifically iron cyanide, does not result in an accumulation of WAD cyanide,
the measurement of which would report any breakdown products, such as HCN. A typical
example of the simultaneous decay of total and WAD cyanide in a static holding pond or
impoundment is shown on Figure 4 (Simovic and Snodgrass, 1989).
159 T. Mudder
Figure 4: Model Validation for a Shallow Process Solution Holding Pond
In another study conducted in Australia, process solution was pumped from a large impoundment
into a small, shallow pond used for the watering of stock. The pond was about fifteen feet square
and about one foot deep. The specific purpose of the study was to examine the decay of iron
cyanide under worst case conditions (i.e. shallow pond and high light intensity) to determine if the
accumulation of free cyanide would occur to the extent that toxicity to cattle could occur
(Environmental Geochemistry International, 1988). As shown in Figure 5, the rate of total or iron
cyanide decay was rapid under the temperature and light intensity conditions exhibited near the
mine site. However, the decay of WAD cyanide was also rapid with no accumulation of free
cyanide occurring, indicating that HCN was quickly volatilized from solution even under static
conditions.
160 T. Mudder
Figure 5: Decant Decay Test Results – No UV Light
As would be expected, the rate of loss or volatilization of HCN from a flowing surface water
would be even more rapid than in a pond due to the additional mixing and turbulence occurring
within such a system. Furthermore, the rate of photolysis would usually be less in a flowing
stream due to shading from the surrounding topography, plants, and other constituents in the
water that could attenuate light (i.e. humic and fulvic acids). An excellent study area has been
provided below the discharge of the biological treatment facility located at the Homestake Mine in
the Black Hills of South Dakota, near the towns of Lead and Deadwood. This treatment facility
has been discharging treated wastewater containing low levels of total and WAD cyanide for over
a decade. The receiving stream is shallow and is readily exposed to solar insolation below the
discharge. In the summer, stream temperatures often exceed 20 degrees C.
161 T. Mudder
The total and WAD cyanide levels have been monitored at various points downstream below the
discharge for more than a decade. The data indicate that although the total and WAD cyanide
levels decline downstream due to attenuation and dilution, there has been no accumulation of
WAD cyanide, as would be expected if the rate of decomposition of iron cyanide was greater than
the rate of HCN volatilization. The stream currently supports a reproducing brook and brown
trout fishery. A summary of the water quality data is presented in Appendix A for the two
stations (SDDENR, 1996). The first surface water sampling station, HMC#35S, is located just
below the mixing zone, while the second station, HMC#36S, is located at a point further
downstream on Whitewood Creek. Due to the recognition that iron cyanide is not a major
environmental concern in effluents discharged into surface waters, several states, such as
Washington, Idaho, and South Dakota, have altered water quality standards from total to WAD
cyanide for protection of aquatic life. Furthermore, several state and federal agencies use a WAD
cyanide standard or guideline for protection of waterfowl and migratory birds, groundwater
quality, and to monitor closure at mining operations.
2.0 TOXICOLOGICAL DATA FOR IRON CYANIDE AND AQUATIC LIFE
Although iron cyanide, and therefore total cyanide, may not be of a toxicological concern to
aquatic life when discharged at low levels from mining operations, nonetheless it would be useful
to have some information regarding the relative toxicity of these compounds under conditions
which could maximize the contribution of photodecomposition. Clearly, iron cyanide, in either of
its two forms, is not toxic at very high concentrations under reduced light or dark conditions, due
to its very limited dissociation. Although the volatilization of HCN formed through the photolytic
breakdown of iron cyanide is rapid, some indication of the toxicity of iron cyanide under enhanced
light conditions would be useful in establishing acceptable levels in discharges below which
guidelines or standards would not be necessary.
In order to address these questions and concerns, detailed toxicological testing on iron and total
cyanide was conducted during the early 1980's in the Homestake Mining Company (HMC)
Toxicological Testing Facility and in the Fisheries Bioassay Laboratory (FBL) at Montana State
University to accurately and conservatively simulate the rate and degree of photolytic breakdown
of the iron cyanide complexes and to quantify the toxicological effects of rainbow trout (Marshall,
et al., 1985; and Meyn, et al., 1984). The tests were conducted in accordance with standardized
and accepted protocols.
The research at Homestake Mining Company was conducted under the supervision and with the
approval of both the State of South Dakota and federal (USEPA) regulatory agencies, while the
work at Montana State was conducted under the direction of Dr. Vance Thurston, an well known
and respected aquatic toxicologist, who originally developed the USEPA ammonia criteria.
162 T. Mudder
The results of these tests, in conjunction with those of others investigating the toxicity of cyanide
and aquatic insects, were employed in the development of a site-specific acute and chronic criteria
for total cyanide, WAD cyanide, and the protection of sensitive aquatic life. In a preliminary set
of 96-hour flow through tests conducted at the FBL, fingerling rainbow trout were exposed to
varying concentrations of both ferrous and ferric cyanide in covered aquaria using 18-hour
photoperiods. The light sources were Spectralite tubes placed near and directly above the surface
of the covered aquaria. This light source was chosen as it best simulates natural light conditions,
particularly in the ultraviolet region of the electromagnetic spectrum. The results of the acute
tests conducted at the FBL are presented in Tables 3 and 4. In the dark, the LC50 or FAV's for
ferrous and ferric cyanide ranged from 869-939 mg/l and 869-1210 mg/l, respectively. These
values are consistent with other literature data. At a maximum light intensity of 680 lux, using an
18-hour photoperiod in covered aquaria, the FAV's for ferrous and ferric cyanide averaged 35
mg/l and 31.2 mg/l, respectively. During the testings the aquaria were well lit throughout. The
corresponding WAD values ranged from 0.15-0.42 mg/l under maximum light conditions, which
indicated the breakdown of the iron cyanide to be <2.0%. The corresponding CMC's for ferrous
and ferric cyanide were about 17.5 mg/l and 15.6 mg/l, respectively.
163 T. Mudder
Table 3: Ferrocyanide Toxicity Test Summary of Test Conditions

and 96-h LC50 Values Obtained

o
1074 0/24 0 -- 9.4 8.44 -- 752

(9.4-9.5) (7.03-8.85) (474-1190)
1077 0/24 0 -- -- -- -- >867
1078 0/24 0 7.95 9.4 8.83 -- 939

(7.89-8.01) (9.4-9.5) (8.76-8.97) (828-1064)
1088 18/6 330 7.77 15.7 8.22 -- 220

(7.66-7.94) (15.4-16.1) (8.01-8.49) (184-261)
1090 18/6 330 7.83 15.2 7.85 -- 232

(7.75-7.95) (15.2-15.4) (7.64-8.11) (178-302)
1980 18/6 680 7.33 9.6 7.93 0.15 33.30

(7.30-7.34) (9.6-9.7) (7.77-8.17) (0.13-0.17) (28.7-37.9)
1083 18/6 680 7.55 9.5 8.37 0.17 37.4

(1)
(7.50-7.57) (9.5-9.6) (8.16-8.58) ( - ) ( - )(1)
Source: Meyn, 1984

Note:
(1) Confidence interval not calculable by method used.
164 T. Mudder
TABLE 4: Ferricyanide Toxicity Tests Summary of Test Conditions

and 96h LC50 Values Obtained
o
1075 0/24 0 7.87 9.3 8.18 -- 1210

(7.46-8.23) (9.46-9.4) (7.03-8.85) (1060-1380)
1076 0/24 0 7.96 9.3 8.88 -- 869

(7.75-8.17) (9.2-9.4) (8.70-9.01) (860-1110)
1079 0/24 0 -- -- -- >1.14 >877
1081 18/6 330 7.33 9.6 7.91 0.24 69.6

(7.30-7.34) (9.5-9.7) (7.61-8.11) (0.23-0.26) (54.7-88.5)
1082 18/6 330 7.56 9.6 8.28 >0.50 >541

(7.53-7.58) (9.5-9.7) (8.09-8.43)
1084 18/6 680 ---- ---- ---- >0.61 >731
1085 18/6 680 7.78 10.3 8.26 0.42 44.2

(7.76-7.80) (10.1-10.7) (8.13-8.34) (0.36-8.34) (38.2-51.0)
1087 18/6 680 7.96 16.0 8.69 0.40 38.8

(7.89-8.06) (15.8-16.1) (8.58-8.83) (0.36-0.43) (25.0-60.2)
1089 18/6 680 7.89 16.0 8.16 0.31 10.8

(7.79-7.10) (15.5-16.4) (8.05-8.37) (0.30-0.32) (9.96-13.1)
Source: Meyn, 1984
165 T. Mudder
In a second series of 48-hour static screening tests conducted at the FBL, Daphnia magna were
exposed to varying concentrations of both ferrous and ferric cyanide under differing light and
ventilation conditions. The percent mortalities for the two iron cyanides are presented in Tables 5
and 6. The tests conducted in the dark utilized covered containers, while the bioassays conducted
under elevated intensity simulated natural light conditions utilized uncovered containers to
promote ventilation. Although no LC50 values could be calculated, the results indicated that the
FAV's for ferrous and ferric cyanide were in the range of 4 to <18 mg/l and >3 to 6 mg/l,
respectively. The no effect level of NOEL for these organisms ranged from about 1.5-3.6 mg/l
for ferricyanide.
Table 5: Preliminary Acute Toxicity Data for Ferricyanide and Daphnia

Percent Mortality
Dark, No Ventilation Light, Good Ventilation
-
Ferricyanide mg/l CN (Tests 702 & 705) (Test 703)
2,350 100 --
470 100 --
235 100 --
47 100 30
23 100 30
11 70 50
6 60 60
4.7 -- --
3 40 10
2.3 -- --
1.5 20 0
0.7 0 0
0 0 0
166 T. Mudder
Table 6: Preliminary Acute Toxicity Data for Ferrocyanide and Daphnia

Percent Mortality
Dark, No Ventilation Light, No Ventilation
-
Ferricyanide mg/l CN (Test 700) (Test 699)
1,825 100 --
365 100 --
182 100 100
36 82 80
18 70 30
3.6 -- 10
1.8 -- 10
0 0 13
To further investigate the photolytic chronic or long-term toxicity of iron cyanides on rainbow
trout, a series of 45-day bioassays were conducted at the HMC toxicological laboratory. The test
utilized juvenile rainbow trout with an average initial size and weight of 7.1 cm and 3.8 grams,
respectively. The fish were exposed to a 16-hour photoperiod in covered aquaria. Lighting was
again accomplished using Spectralite fluorescent tubes, which simulated accurately natural light
conditions. The fluorescent tubes were placed directly above the covered aquaria, providing a
high level of illumination throughout the water column. The fish were exposed to a constant
background matrix of 56% treated effluent from the HMC biological treatment plant and 44%
receiving stream water.
Into the whole effluent chemical matrix various concentrations of ferric cyanide were introduced
into a series of duplicate aquaria. The average ferric cyanide concentration ranged from <0.02
mg/l as total cyanide in the control to 22.6 mg/l in 100% effluent. The corresponding average
WAD cyanide concentrations resulting from the combined chemical and photolytic breakdown of
iron cyanide ranged from <0.02-0.19 mg/l. The various ferric cyanide concentrations were fed
into the aquaria via a multi-channel peristaltic pump.
A summary of the chemical analyses associated with the HMC test are presented in Table 7.
Following 45 days of exposure, no mortalities were noted in any test concentration of iron
cyanide, which reached a maximum of 30.0 mg/l. No differences in growth factors (K-factors)
were noted between controls and exposed organisms. No bioaccumulation was noted and no
physiological abnormalities were noted following external and internal necropsies of the fish.
167 T. Mudder
Table 7: Summary of Iron Complexed Cyanide Chronic Toxicity Test (1)
(5) (2) Min

Aqu. % ml/min Mean Max Min Mean Max Min Std. Mean Max Min Std. Max
# Eff Spike Total Std. WAD CN- Dev. Fe Dev. Mean
Cyanide Dev Temp
365-66 0 0 0 0 0 0 0 0 0 0 1.3 0.8 1.7 0.3 4.2 7.0 2.0
367-68 56 0 0.47 0.59 0.30 0.09 0.03 0.03 0.03 0.005 0.9 1.2 0.6 0.2 12.4 14.0 10.0
369-70 56 1 1.62 2.00 1.16 0.24 0.04 0.08 0.02 0.02 1.2 1.5 0.8 0.2 -- -- --
371-72 56 20 22.58 30.00 18.75 3.2 0.19 0.31 0.12 0.06 8.0 9.7 7.2 0.8 -- -- --
373-74 56 5 6.22 5.70 4.94 0.23 0.11 0.16 0.08 0.03 2.5 3.0 2.1 0.2 -- -- --
375-78 56 11 10.96 11.50 10.50 0.38 0.15 0.20 0.11 0.03 4.7 5.0 4.3 0.5 -- -- --
(3) (3) (4)

Aqu. % Mean Mean Mean Mean Mean Mean Mean Mean Mean Mean Mean Mean Mean
# Eff Do NH3-N Alk Hard Cond. Cu Ni Zn Pb Cr Cd As Ag
365-66 0 11.0 <0.5 180 257 450 0.005 0.012 0.017 0.019 0.002 0.002 0.008 0.001
367-368 56 8.8 >0.5 107 485 1266 0.025 0.041 0.029 0.034 0.004 0.004 0.040 0.002
Notes:
(1) All values reported as mg/l, unless otherwise stated.
o
(2) Reported as C
(3) Reported as mg/l As CaCO3
(4) Reported as µmhos/cm
(5) For all calculated means and standard deviations n=10
The results demonstrated conclusively that a sensitive fish species at an early life stage can be
exposed to relatively high concentrations of iron cyanide without experiencing toxic effects. The
primary concern related to the WAD cyanide which formed through the breakdown of the iron
cyanides and accumulated in the test solutions. The toxicity tests was quite valuable since they
utilized an actual treated mine effluent as a background matrix, a long-term exposure period under
elevated light conditions, and sensitive aquatic species. In general, the brook, brown, and
rainbow trout are the most sensitive fresh water organisms with respect to chronic cyanide
toxicity, and protection of these very sensitive species would provide protection of other resident
aquatic life. The percentage breakdown of iron cyanide increased as the concentration of the
compound decreased. The percentage breakdown ranged from 0.80 - 2.5% based upon
comparison of the average WAD and iron cyanide levels. The results were in accordance with the
previous test work conducted at the FBL, in which the average percentage breakdown of
ferricyanide at the highest light intensity was 1.2% (i.e. 0.38 mg/l WAD cyanide/31.2 mg/l total
cyanide x 100 = 1.2%).
168 T. Mudder
The individual percentage breakdowns of iron cyanide from the long-term test were as follows:
(1) [0.04 mg/l WAD cyanide] / [1.62 mg/l total cyanide] x 100 = 2.5%
The toxicity of iron cyanide (i.e. both ferro and ferri forms) was related to the WAD cyanide
concentration which formed as a result of the photolytic breakdown of the corresponding total
cyanide. Monitoring of WAD cyanide provided a method of monitoring iron cyanide
concentrations reported by the total cyanide analysis. Development of a regression line relating
the breakdown of total cyanide to form WAD cyanide using the data above produced the
following equations:
2
(1) ln [WAD cyanide in mg/l] = 0.59 [In total cyanide in mg/l] - 3.28 (r = 0.95)
(0.59 [In total cyanide(mg/l)] - 3.28)
(2) WAD cyanide (mg/l) = e
The test data demonstrated that the breakdown of iron cyanide under light conditions typically
more intense than ambient, n which the photolysis of cyanide was enhanced, resulted in minimal
formation of WAD cyanide or free cyanide. The WAD cyanide concentrations formed were
higher than the free cyanide levels noted by Broderius for the long term dissociation of similar
levels of iron cyanide kept in the dark (Broderius, 1973).
Furthermore, iron cyanide levels in the range of 20-30 mg/l did not exert acute or chronic toxicity
to the sensitive rainbow trout. Development of total or iron cyanide criteria based upon
protection of the rainbow trout, a very sensitive aquatic organism, would provide an adequate
level of protection for most other freshwater fish and aquatic insects. In the event instream iron
cyanide levels remain below levels noted in the test work, then no measurable adverse impacts
would likely occur and the regulation of total cyanide in a permit would not be warranted. In the
event breakdown of the iron cyanide does occur in a pond or stream along with buildup of free
cyanide, the free cyanide formed would be reported by the WAD cyanide analysis. There is no
evidence that breakdown of iron cyanide and accumulation of WAD cyanide occurs in turbulent
receiving systems.
It is interesting to note that the WAD cyanide levels resulting from the photolytically enhanced
breakdown of iron cyanides was much higher than would be expected to cause toxicity, based
upon other research conducted with free cyanide. As a result, either the WAD cyanide generated
is of another form than free cyanide and/or the free cyanide being released is in turn complexed to
a less toxic form. In either case, the WAD cyanide formed through the breakdown of iron
cyanide is much less toxic than has been reported for free cyanide itself.
169 T. Mudder
Examination of data from various tailings ponds indicates the ratio of total to WAD cyanide
generally remains constant over time, and accumulation of WAD forms of cyanide does not occur.
As mentioned previously, the rate limiting step in reduction of the cyanide content in a surface
water feature is breakdown or dissociation of the metal cyanide complex. Once breakdown
occurs, the free cyanide is rapidly removed through volatilization primarily.
To investigate the breakdown of total cyanide, HMC has monitored the receiving stream at
several locations below the wastewater treatment plant discharge. A comparison of the total to
WAD cyanide levels generally yielded a relatively constant ratio, which indicated breakdown of
iron cyanide to form increased and accumulated levels of WAD cyanide was not occurring. A
summary of this instream water quality data is presented in Appendix A, as mentioned earlier.
This type of observation indicates that concerns regarding the downstream formation of WAD
cyanide following discharge of relatively low levels of iron cyanide are not warranted. The next
section of the memorandum addresses the calculation of site-specific aquatic life criteria for total
cyanide. The instream biomonitoring data collected below the point of discharge and the mixing
zone has indicated that a thriving and viable permanent trout fishery exists and there has been no
evidence of adverse impacts to the local aquatic ecosystem. The discharge of treated mine water
from HMC has been occurring for over a decade.
3.0 DERIVATION OF AQUATIC LIFE CRITERIA FOR TOTAL CYANIDE
The numerical acute and chronic criteria are derived to protect aquatic life from the impacts of
short and long term toxicity, respectively. The acute criterion, also termed the criterion maximum
concentration (CMC), is calculated by dividing an experimentally obtained final acute value
(FAV) by a factor of two. The primary form of iron or total cyanide in a mine water discharge, if
present, is ferric cyanide, because of the ongoing oxidation processes that occur naturally in a
tailings impoundment and/or are created artificially through treatment.
As noted in Table 4, the lowest FAV for total (ferric) cyanide and rainbow trout was
experimentally determined to be 10.8 mg/l. Division of this FAV by two results in a CMC of 5.4
mg/l. The CMC of 5.4 mg/l becomes the maximum iron cyanide level, measured as total cyanide,
that should be allowed instream during a 24 hour period.
In contrast to the acute criteria, there are two approaches available for calculating site-specific
chronic aquatic life criteria, based upon the toxicological and photochemical data generated for
iron cyanide and rainbow trout. The first approach involves division of an appropriate FAV for
iron cyanide and rainbow trout by an appropriate acute/chronic ratio (ACR). The second
approach available for deriving a site-specific total cyanide final chronic value (FCV) incorporates
the concept of photolytic breakdown of iron cyanide, which was discussed earlier. Since a site-
specific ACR did not exist for WAD, total, or metal cyanides, the extensive toxicity testing
program, previously discussed, was initiated by HMC in the early 1980's.
170 T. Mudder
As a result of over three years of examining the toxicological effects of various forms of cyanide
on several species of trout and aquatic insects, a site-specific ACR of 3.8 was derived for metal
complexed cyanides (SRK, 1991). Division of the lowest FAV for iron cyanide of 10.8 mg/l,
taken from Table 4, by the site-specific ACR of 3.8 developed for HMC results in a FCV for total
and iron cyanide of 2.8 mg/l (10.8/3.8 = 2.8). In contrast, the average ACR reported in the
USEPA ambient water quality criteria document for free cyanide and all freshwater and marine
organisms is 8.56. Division of the average FAV of 31.2 mg/l for ferricyanide and trout obtained
at the FBL, taken from Table 4, by the average USEPA ACR for cyanide of 8.56 yields another
FCV for total cyanide of 3.6 mg/l. The average FAV for total cyanide was calculated using the
three lowest LC50 values reported in Table 4, which were 44.4, 38.8, and 10.8 mg/l.
As noted earlier, the second approach available for derivation of site-specific chronic criteria for
total cyanide considers the concept of photolytic breakdown of iron cyanide and the resultant
formation of WAD cyanide levels, which are considered of most importance toxicologically.
Employing the site-specific instream FCV for WAD cyanide of 0.08 mg/l derived for HMC during
its extended toxicity testing program and the previously derived regression equation relating
breakdown of total cyanide to WAD cyanide formation, the resulting FCV determined through
back calculation is 4.0 mg/l. The derivation assumed a percentage breakdown for iron cyanide of
2.0% (0.08/0.02 = 4.0), which was typical of the data obtained from the various toxicological
tests conducted by HMC or the FBL.
In summary, the recalculated site-specific acute value or CMC for total and iron cyanide is 5.4
mg/l. The value of 5.4 mg/l represents the upper level of iron cyanide (reported as total cyanide)
that should not be exceeded in a stream or river, in order that the resident aquatic life are
protected from short term toxicity. The maximum daily acute value or CMC should be
determined on the basis of a single grab or 24 hour composite sample. With respect to protection
against long term toxicity or sub-lethal and chronic effects, the allowable instream FCV for iron
cyanide (reported as total cyanide) would be based upon a 30 day average concentration. The
site-specific FCV for iron or total cyanide is 2.8 mg/l, based upon the minimum of the three
calculated FCV's of 2.8, 3.6, and 4.0 mg/l presented earlier. These site-specific criteria were
derived on the basis of protecting several of the most sensitive freshwater aquatic organisms, and
should provide a useful baseline for protection for other warm and cold water species of aquatic
life.
The CMC and FCV, which are used to protect aquatic life from short and long term toxic effects,
respectively, are then applied as instream criteria. The FCV also is called the Criterion Maximum
Concentration or CCC. The allowable discharge or effluent limitations are in turn calculated by
multiplying each of these instream criteria by an appropriate dilution factor, which is based upon
the ratio of the stream flow to that of the discharge volume. Site-specific acute and chronic
criteria for total and WAD cyanide, like those derived herein, have been employed in determining
the need for and selection of effluent standards for two actual mining operations, one of those
being the Homestake Mine discussed in this document, while the other was the Golden Cross
Mine in New Zealand. These gold mines have been discharging treated water containing low
levels of metal complexed cyanides into sensitive trout streams for many years.
171 T. Mudder
The protection of the fisheries at these two mining operations is very important and of major
concern, since their discharges account for twenty to over fifty percent of the entire stream flow.
However, the discharge of treated water from these mining operations has yet to produce any
measurable adverse impacts on the resident aquatic life in their receiving streams. These actual
field situations have provided long-term proof that the metal complexed cyanides can be
discharged within reasonable limits to provide protection of aquatic life.
Based upon the experimental and actual instream monitoring data presented, the site-specific
CMC and FCV or CCC values derived of 5.4 mg/l and 2.8 mg/l, respectively, would be protective
of very sensitive fresh water aquatic life residing in streams or other lotic water systems, since
these values are protective of the young trout. Although these site-specific criteria for iron and
total cyanide are conservative and protective of very sensitive aquatic life species, it is useful to
compare them with other data regarding the toxicity of iron cyanides to other aquatic organisms
under varying light conditions.
As reported earlier, the lowest no effect level reported by the FBL in its testing program was 1.5
mg/l for ferricyanide, the predominant form of in a treated effluent, and Daphnia magna. In the
research of Burdick and Lipschuetz, referenced earlier, toxicity tests with fish under varying light
conditions indicated the toxic value for either iron cyanide to be between 1.0-2.0 mg/l. In a
separate study examining the toxicity of iron cyanide to fathead minnows under varying light
conditions up to 8,000 foot candles, the 96 hour LC50 was reported to be greater than 1.0 mg/l
(Terhaar et al., 1972).
Based upon the long term instream monitoring data presented in Appendix A, the average WAD
cyanide values in the receiving stream below the HMC discharge at the edge of the mixing zone
was 0.037 mg/l. Using the equation presented above for the breakdown of iron cyanide under
elevated light conditions, the corresponding total cyanide value would be about 1.0 mg/l. The
range of WAD cyanide values at the edge of the mixing zone were 0.02-0.19 mg/l, which
correspond to a range of total or iron cyanide values of <0.50 mg/l to over 20.0 mg/l.
Finally, the lowest FAV for iron cyanide and trout obtained by the FBL was 10.8 mg/l. Division
of this value by the USEPA ACR for cyanide of 8.56 would result in another very conservative
site-specific chronic criterion or CCC of 1.3 mg/l.
Based upon the additional toxicity available, a much more conservative instream chronic value or
CCC of 1.0 mg/l could be employed for iron or total cyanide, since no adverse aquatic life effects
were reported at or below this level. The more conservative CCC of 1.0 mg/l could be
considered a no effect level, or NOEL. The corresponding site-specific CMC would be set at the
original site-specific chronic value of 2.8 mg/l. The corresponding WAD cyanide site-specific
acute and chronic criteria, described elsewhere, would be applied in conjunction with the site-
specific values for total cyanide (SDDENR, 1996). In the event the anticipated resultant instream
total cyanide levels are expected to be below any of the site-specific criteria for total or iron
cyanide, no standard other than for WAD cyanide for be required. These lower site-specific
criteria for iron and total cyanide would be employed in the event very sensitive species of aquatic
life, other than those examined, were believed to be present.
172 T. Mudder
Both of these sets of site-specific acute and chronic criteria for iron and total cyanide are very
conservative and were derived taking into account consideration of the photolytical
decomposition of these compounds, although there is no instream or effluent biomonitoring data
suggesting that discharges from mining operations containing these compounds at these levels
have produced adverse impacts on resident aquatic life, as the result of photolytic breakdown.
4.0 REFERENCES
Asperger, S., "Kinetics of the Decomposition of Potassium Ferrocyanide in Ultra-Violet Light",

Transactions of the Faraday Society, Volume 48, pp. 617-624, 1952.
Asperger, S., Murati, I., and Pavlovic, D., "Kinetics and Mechanism of the Decomposition of
Complex Cyanides of Iron (II) and Molybdenum (IV)", Journal of the Chemical Society, pp. 730-
736, 1960.
Bener, P., "Approximate Values of Intensity of Natural Ultraviolet Radiation for Different
Amounts of Atmospheric Ozone", U.S. Army Report DAJA 37-68-C-1017, Davos Platz,
Switzerland, 1972.
Broderius, S., "Determination of Molecular Hydrocyanic Acid in Water and Studies of the
Chemistry and Toxicity to Fish of Metal-Cyanide Complexes", Ph.D. Thesis, Oregon State
University, Corvallis, Oregon, 1973.
Broderius and Smith, "Direct Photolysis of Hexacyanoferrate Complexes-Proposed Applications

to the Aquatic Environment", USEPA Environmental Research Laboratory, Duluth, MInnesota,
EPA-600/3-80-003, January, 1980.
Burdick, G. and Lipschuetz, M., "Toxicity of Ferro- and Ferricyanide Solutions to Fish, and
Determination of the Cause of Mortality", Transactions of the American Fisheries Society,
Volume 78, pp. 192-202, 1950.
Caruso, S.C., "The Chemistry of Cyanide Compounds and Their Behavior in the Aquatic
Environment," Carnegie Mellon Institute of Research, June 1975.
Doudoroff, P., Toxicity to Fish of Cyanide and Related Compounds, EPA-600/3-76-038,

USEPA, Duluth, Minnesota, April 1976.
Doudoroff, P., A Critical Review of Recent Literature on the Toxicity of Cyanides to Fish,
American Petroleum Institutes, Washington, D.C., 1979.
Environmental Geochemistry International, personal communciation from Dr. Stuart Miller,

Balmain, New South Wales (NSW), Australia, February, 1997.
Gates, D., "Radiant Energy, Its Receipt, and Disposal, Meterological Monographs, Volume 6, pp.
1-26, 1965.
173 T. Mudder
Kobayashi, T. and Mori, K., "Formation of Compounds Toxic to Fish from Ferro- and
Ferricyanides by Photodecomposition (Occurence of Toxicity to Fish by Photodecomposition of
Complex Cyanides)", Mizu. Shori. Gijutsu., Volume 14, Number 6, pp. 575-579, 1973.
MacDiarmid, A. and Hall, N., "Illumination-pH Effects in Solutions of Complex Cyanides",

Journal of the American Chemical Society, Volume 75, pp. 5204-5207, 1953.
Marshall, S. and Fox, F., "The Long Term Toxicity of Treated Effluent to Rainbow Trout,"
Toxicity Test SG-4D-WWTD-EFF-II, Homestake Mining Company, Aquatic Toxicity
Laboratory, Lead, South Dakota, June 1985.
Meyn, E., Azjdel, R., and Thurston, R., "Acute Toxicity of Ferrocyanide and Ferricyanide to
Rainbow Trout," Technical Report No. 84-1, Fisheries Bioassay Laboratory, Montana State
University, Bozeman, Montana, June 1984.
Moggi, L., Bolletta, F., Balzani, V., and Scandola, F., "Photochemistry of Coordination
Compounds-XV Cyanide Complexes", Journal of Inorganic Nuclear Chemistry, Volume 28, pp.
2589-2597, 1966.
Ohno, S., "The Photochemistry of Aqueous Hexacyanoferrate (II) Solutions. I. Photo-Aquation

Reaction at 3660 A", Bulletin of the Chemical Society of Japan, Volume 40, pp. 1765-1769,
1967.
Odum, E., Fundamentals of Ecology, Third Edition, W. B. Saunders Company, Philadelphia, Pa.,
1971.
Simovic, L., "Kinetics of Natural Degradation of Cyanide from Gold Mill Effluents", Master of
Science Thesis, McMaster University, Hamilton, Ontario, Canada, 369 pages, 1984.
Simovic, L. and Snodgrass, W. "Tailings Pond Design For Cyanide Control At Gold Mills Using
Natural Attenuation", Proceedings of the Gold Mining Effluent Treatment Seminars, sponsored
by Mining Association of British Columbia, Environment Canada, and Ministry of Energy, Mines,
and Petroleum Resources, Vancouver, B.C., Canada, February 15-16, 1989.
South Dakota Department of Environment and Natural Resources (SDDENR), Assessment of the
Surface Water Quality and the Aquatic Ecosystem of the Northern Black Hills, prepared by Times
Limited, Bozeman, Montana for the SDDENR, February, 1996.
Terhaar, C., Ewell, W., Dziuba, S., and Fassett, D., "Toxicity of Photographic Processing
Chemicals to Fish", Photographic Science and Engineering, Volume 16, Number 5, 1972.
USEPA, An Exposure and Risk Assessment for Cyanide, Office of Water Regulations and
Standards, EPA-440/4-85-008, Washington, D.C., December, 1981.
USEPA, Ambient Water Quality Criteria Document for Cyanide, PB85-227460, Washington,
174 T. Mudder
D.C., January 1984.
Wastewater Technology Centre, Industrial Division, "Natural Degradation Model for Prediction
of Cyanide Levels in a Tailings Pond, 867 Lakeshore Road, Burlington, Ontario, Canada L7R
4L7, February, 1997.
Wetzel, R., Limnology, W.B. Saunders Company, Philadelphia, 1975.
Zepp, R. and Cline, D., "Rates of Direct Photolysis in Aquatic Environment", Environmental
Science and Technology, Volume 11, Number 4, pp. 359-366, 1977.
175 T. Mudder
APPENDI X A
176 T. Mudder
177 T. Mudder
STRATEGIES AND STANDARDS
FOR CONTROL OF BIRD MORTALITY
AT MINING OPERATIONS
Prepared By:
Karen Hagelstein, Ph.D., CIH

Terry Mudder, Ph.D.

Australian Centre for Minesite Rehabilitation Research (now ACMER), Perth, Western Australia,
April 1997
Strategies and Standards for Control of Bird Mortality at Mining Operations
1.0 INTRODUCTION AND BACKGROUND INFORMATION
Cyanide has been used for nearly a century on a worldwide basis for the recovery of metals.
Although, our knowledge of its chemistry, analysis, environmental fate, toxicity, and treatment
has grown dramatically in the last decade, various myths, misconceptions, and fears still exist
regarding this chemical. Cyanide, unlike some of the metals with which it combines in water, is
not persistent in the environment. In nearly all instances, the long term adverse effects (if any)
that arise at a mining site are not related to cyanide.
The primary environmental concerns of cyanide relate to the potential for adverse impacts on
humans and other animals. The impact of cyanide on human health in the mining work place has
been minor when compared to that of other chemicals and physical hazards associated with other
industries. In fact, there have been no reported human deaths by accidental cyanide poisoning in
the mining industry in North America during this century (Mudder and Smith, 1994). Although
cyanide can be a toxic compound, it has been manufactured, shipped, stored, and used safely at
hundreds of mining operations worldwide for many decades.
In the case of animals, there are three groups which are of a concern with respect to exposure to
cyanide. The first group includes mammals, reptiles, and amphibians. Within the mammal group
are included both domestic stock and wild animals, such as cattle and deer respectively. The
second group includes aquatic life forms, such as macroinvertebrates and fish. The third group
includes migratory birds and other waterfowl, which can come in contact with solution ponds and
tailings impoundments.
With respect to the first group of animals, reports of exposure to cyanide solutions at mining
operations resulting in adverse effects have been minimal. From a regulatory standpoint, the U.S.
General Accounting Office (GAO) has conducted a recent study of mining operations in the
southwestern United States, and found appropriate containment designs and engineering
standards have been promulgated to mitigate the problems associated with exposure of humans,
mammals, birds, reptiles, and amphibians to cyanide solutions (GAO, 1991).
1.1 Domestic Stock Ingestion of Cyanide-Containing Plants
Of primary concern for wildlife and stock animals is their exposure, through ingestion, to
cyanogenic or cyanide producing plants, such as bamboo, sorghum, certain fruits, lima beans, and
cassava. For example, sorghum, cassava, bamboo, and lima beans can produce up to 2,000
mg/kg or ppm of total cyanide, following ingestion of the plant material (U.S. Fish and Wildlife
Service, 1991). A summary of the potential cyanide production from different plant species is
presented in Table 1. Assuming consumption of 4.0 mg of HCN per kilogram of body weight by
a range animal could be fatal, ingestion of only 0.50 kg of plant material could be necessary to
cause death in a 250 kg animal.

Table 1
Background Concentrations of Cyanide in Selected Plants
Concentration
Cyanogenic Plant Species (mg/kg or mg/L)
Bamboo, (Bambusa, Arundinaria, Dendrocalamus)
Tip Max. 8,000
Stem Max. 3,000
Stargrass, Cynodon plectostachyus, whole 180
Rose family, Malus spp., Pyrus spp. Max. 200
Cassava, Manihot esculenta
Bitter varieties
Leaves 347-1,000
Roots 327-550
Dried roots 95-2,450
Stem 1,130
Mash 162
Bark
Total cyanide 1,351
Free cyanide 102
Peel
Total cyanide 1,390
Free cyanide 255
Pulp
Total cyanide 810
Free cyanide 53
Sweet varieties
Leaves 377-500
Roots 138
Dried roots 46-<100
Mash 81
Lima bean, Phaseolus lunatus
United States 100-170
Burma 2,100
Puerto Rico 3,000
Java 3,120
Almond, Prunus amygdalus, nut
Bitter (280-2,500)
Spicy (86-98)
Sweet (22-54)
Seeds, 4 species, Nigeria, whole, frequently consumed by humans
Phaseolus sp. (381-1,093)
Vigna sp. (285-1,223)
Cajanus sp. (208-953)
Canavalia sp. (285-953)
Sorghum, Sorghum spp., young plant, whole Max. 2,500
Notes: Values are in milligrams total cyanide per kilogram fresh weight or millgrams per liter.

In contrast, the same 250 kg animal must rapidly ingest about 20 liters of a solution containing 50
mg/l cyanide to reach the same lethal level. The daily consumption of water by cattle, sheep,
horses, and swine ranges from about 4-65 liters (Clark et al., 1977). These examples demonstrate
that potential exposure to properly contained and monitored manmade cyanide solution ponds and
impoundments is less important compared with the exposure of animals to natural sources of
cyanide through ingestion of cyanogenic plants. The level of cyanide produced through ingestion
of these plants can exceed the 250 mg/kg (ppm) USEPA limit that is employed to characterize a
hazardous waste (USEPA, 1985).
1.2 Waterfowl and Migratory Bird Protection
Depending upon whether or not a project contains an open pit and/or is designed as a "zero
discharge" facility with a no release policy to local surface waters, there may or may not be
concerns regarding the protection of the aquatic life, the most sensitive organisms to the
toxicological effects of cyanide. Of the three groups of animals potentially at risk due to cyanide
exposure at a proposed mining operation, the migratory birds and waterfowl are most important.
The remainder of the report focuses upon the potential impacts to birds, the biochemistry and
toxicology of cyanide compounds, control strategies and standards needed for their protection
during operation of the mine.
2.0 THE HISTORY OF BIRD MORTALITY AT MINES IN THE U.S.
In the U.S., the federal Fish and Wildlife Service has jurisdiction regarding the protection of birds
under the Migratory Bird Treaty Act and the Endangered Species Act. The requirement and goal
of these acts is "zero mortality" at mining operations. During the later part of the 1980's, as the
number of mining operations in the southwestern U.S. increased sharply, the number of bird
mortalities also increased. The problem related to the establishment of new solution ponds and
tailings impoundments at the mining operations, which served as short term resting areas for
migratory birds and waterfowl in arid regions of the country.
Since the solution ponds and tailings impoundments were not covered and the cyanide levels were
at process strength, mortalities resulted. During the period of 1984 through 1989, about 9,000
wildlife deaths were reported at 59 mining operations located in the states of Arizona, California,
and Nevada. Nearly 70% of the total wildlife mortalities were reported at 53 mining operations in
Nevada. Over 90% of the total mortalities were migratory birds (USEPA, 1991). A summary of
the wildlife mortalities, by year and number of mining operations, is presented in Table 2. It
shows that the number of mining operations increased from 1986-1990, while the number of
mortalities per operation fell sharply as control strategies were developed and implemented. With
the implementation of proven control strategies and technologies, the issue of bird mortality has
been virtually eliminated and is not generally considered a major environmental problem at mining
operations. Based upon data collected from 1990-1995, bird mortalities declined from nearly
1,300 birds to 221 in that time period (The Gold Institute, 1996).

Table 2
Wildlife Mortalities Reported by Nevada Mine Operators
Number of
Year Total Mines Mortalities
Mortalities Reporting Per Mine
1986 1,426 10 143
1987 1,488 32 47
1988 2,346 50 47
1989 1,955 57 34
1990 1,643 95 17
The magnitude of the mining-related bird deaths can be placed in perspective with other sources
of bird mortality statistics. The nearly 9,000 deaths in six years at 59 mining operations were less
than one tenth of a percent (<0.10%) of the total number of birds taken by hunters in those three
states in one year, which translated into about fifty-four million (54,000,000) birds over about the
same six year (1984-1989) period. The primary issue was that the hunters could legally shoot the
birds with a license, while the mining operations were in violation of the Migratory Bird Treaty
Act (GAO, 1991). Most of the of the other animal mortality at the mining operations included
rodents, rabbits, amphibians, and reptiles (Henny, Hallock, and Hill, 1994).
Research conducted by Dr. William Jackson, professor emeritus of biology, Bowling Green State
University, revealed that ten billion birds are estimated to die annually in the U.S., with 80 million
birds dying from flying into windows, and one million per year colliding with radio and TV
towers. About 12 million ducks are killed per year by hunters (The Gold Institute, 1996).

3.0 WATERFOWL PROTECTION STRATEGIES
3.1 Physical Methods of Deterring Waterfowl
As a result of the concern regarding bird mortality at mining operations, a workshop and
conference, sponsored by the Nevada Mining Association (NMA), the Nevada Department of
Minerals (NDM), and the Nevada Department of Wildlife (NDW), was held in Reno, Nevada in
March, 1990 (NMA et al., 1991). At this conference, representatives from government, industry,
academia, and consulting met to discuss the bird mortality issue and exchange experiences
regarding effective, as well as ineffective, control strategies. A trial and error approach had been
used in examining the effectiveness of several physical control strategies. The strategies examined
included the techniques of hazing and netting to eliminate the contact of birds with the solution
ponds or larger impoundments. The hazing techniques included the use of pennants, noise
cannons, loud music, and individuals in boats. The hazing techniques proved to be ineffective as a
primary control strategy, although workers at some operations still patrol the larger
impoundments to facilitate the removal of birds.
Netting of the entire surface of a process pond or impoundment has been an effective means of
excluding birds from contact with a cyanide solution. Netting is still practiced today for covering
smaller process ponds containing barren or "preg" solutions, in which the cyanide levels must be
maintained at full strength for metallurgical purposes. In addition to netting smaller process
ponds, the use of floating plastic balls is on the rise in the U.S. These "Bird Balls" are used to
cover the entire surface of the pond and also aid in minimizing the loss of free cyanide due to
volatilization. Each black plastic ball is about 10 cm in diameter, has a wall thickness of about 4
mm, and weighs about 40 grams. About 100 of the UV-stable balls are required to cover an area
of one square meter. They are manufactured by Euro-Matic Ltd. and exclusively marketed in the
United States by Wildlife Control Technology (Mining Environmental Management, 1996).
3.2 Cyanide Recovery and Treatment
Although larger impoundments can be netted, there were severe engineering and maintenance
problems associated with this control strategy. The preferred approach for larger impoundments
has shifted to chemically treating the solution or slurry to lower cyanide levels prior to discharge
into a larger tailings impoundment, using one of two well-proven technologies.
The primary chemical treatment technologies include the Inco SO2/air and copper-catalyzed
hydrogen peroxide processes. Weak acid dissociable (WAD) cyanide has also been removed at
full scale on both a continuous and emergency basis through precipitation using ferrous sulfate.
Cyanide can also now be recovered and recycled from either slurries or solutions at full scale
using the commercial Cyanisorb Process. The Cyanisorb Process is being used at full scale
facilities at the Golden Cross Mine on the North Island of New Zealand, and at the Delamar Silver
Mine located in Idaho, U.S. These cyanide removal technologies have been reviewed in two
publications (Smith and Mudder, 1991 and Mining Environmental Management, 1995).

At the 1990 conference sponsored by the Nevada Mining Association, Neveda Department of
Minerals, and Nevada Department of Wildlife, and represented by the mining industry, regulators,
and scientists, a consensus was that "50 mg/l cyanide or less was a good number, with no
mortalities at those operations" (Kay, 1990). The lowering of WAD cyanide levels in unnetted
ponds to below 50 mg/l was recommended as a regulatory guideline by both a federal regulatory
agency (U.S. Fish and Wildlife Service, 1991), and the Nevada Department of Wildlife (Kay and
McQuivey, 1989). The 50 mg/l WAD cyanide guideline is routinely employed in the western
United States.
Onsite observations of the effectiveness of the 50 mg/l WAD cyanide guideline have been
reported at mining operations in Nevada. At the Paradise Peak mine, owned and operated by
FMC Gold Company, the detoxification of a process solution and destruction of cyanide with
hydrogen peroxide was conducted over a six-day period using hydrogen peroxide. During the
six-day period, the cyanide levels were reduced from 500 mg/l to less than 50 mg/l. Along with
this decrease in cyanide levels there was a dramatic decline in bird mortality, which is shown on
Figure 1. Since the detoxification was completed, a total of 29 mortalities were reported in 1989,
a reduction of nearly 97% from the mortalities reported in 1986 (Castrantas, 1988).
Figure 1: Avian Mortality at a Gold Mine in Nevada

Field results obtained by FMC Gold Company were consistent with those noted at the Echo Bay
McCoy-Cove Mine, Nevada, where the tailings slurry is being treated using the Inco sulphur
dioxide/air process to reduce the WAD cyanide levels to less than 50 mg/l. The numbers of
mortalities declined dramatically following implementation of water treatment.
In conjunction with the self-monitoring conducted by the various mining operations, the U.S. Fish
and Wildlife Service conducted a "spot" tour of seventeen (17) mines in Nevada. A summary of
their observations are presented in Table 3. The pond or impoundment sizes examined ranged
from 1-159 ha, while the WAD cyanide levels ranged from 8.4-216 mg/l. Although mortality was
noted in the ponds at 81 and 62 mg/l, none were noted at the lower WAD cyanide levels. Live
birds were observed at all of the operations except at the mines exhibiting the three highest WAD
cyanide levels in their ponds. Some of the solutions had been detoxified with hydrogen peroxide
or by other means prior to their disposal in the ponds. No mortalities were noted at WAD
cyanide levels below 59 mg/l.
Table 3
Annual Bird Deaths in Australia
Estimated
Cause of Death Deaths/Year
Predation by introduced species foxes 96,000,000
feral cats 300,000,000
600,000
Accidents (car and aircraft strikes)
2,000,000
Game hunting ducks 400,000
"damage control" (ducks)
250,000
Wild bird farming Mutton birds 10,000
Emu farming
<1,000
Tailings Storage Facilities (TSFs)
400,000,000
TOTAL 100,000
Remainder dying from "natural" causes

0.00019%
Precentage of bird deaths in TSFs 0.00024%
- of all deaths
- of deaths from other than "natural" causes

The key concern since the early 1990's relates to determining the form and level of cyanide that is
toxicologically important and defining an appropriate standard to protect migratory birds and
waterfowl which come in contact with larger unnetted process ponds and tailings impoundments.
The next section provides a discussion of cyanide biochemistry and toxicology.
4.0 CYANIDE TOXICOLOGY
4.1 Biochemistry of Cyanide Toxicity
The toxicological target of cyanide in all experimental animals and humans has been establised for
many years to be the terminal oxidative respiratory enzyme in the mitochondria. The mechanism
-
of cyanide poisoning is the production of an histotoxic anoxia or hypoxia by binding of the CN
+++
ion to the ferric iron (Fe ) of the cytochrome oxidase enzyme. The biochemical consequences
are the inhibition of oxidative phosphorylation, anaerobic metabolism with increased ADP levels,
decreased ATP production, and lactic acid accumulation with resultant decreased blood pH and
bicarbonate levels (Hall, 1987).
The combination of cytotoxic hypoxia with lactate acidosis will influence central nervous system
functions, causing disturbances of the conscious level and control functions (Marrs, 19987).
Extensive morphological, biochemical, and physiological evidence (Ballantyne, 1987) all implicate
the central nervous system and myocardium as the major target tissues for the lethal and sublethal
toxicity of cyanide. With respect to adverse effects other than acute toxicity, there is no scientific
evidence that cyanide is teratogenic, carcinogenic, or bioaccumulative in animals (Ballantyne,
1987)
Cyanide is rapidly detoxified through an enzyme transulfuration to thiocyanate, a compound

which is about two orders of magnitude less acutely toxic than cyanide and which is excreted in
the urine. The various forms of transulphurases and sulfur are interconverted by an enzyme,
rhodanese. An important biological effect making cyanide unavailable to exert toxicity is its
sequestration from plasma by erythrocytes, and then concentration by binding to hemoglobin.
Other minor pathways for detoxification include exhalation as HCN, oxidative methabolism to
carbon dioxide and formate, reaction with cystine to form 2-iminothiazoline-4-carboxylic acid,
and combination with hydroxocobalamin to form cyanocobalamin (Marrs, 1987).
The measured rates of detoxification of cyanide by a guinea pig and by a human are 0.076 and
0.17 mg/kg/minute, respectively (Ballantyne, 1987). In addition to rapid metabolic detoxification,
cyanide antidotes, taken orally and by injection, can be and have been administered successfully to
both humans and other animals. These antidotes include amyl nitrite, sodium nitrite, and sodium
thiosulfate.

4.2 The Toxicologically Significant Forms of Cyanide
The acute toxicity of free cyanide as compared to the acute toxicity of the metal complexed
cyanides is attributed primarily to the more rapid metabolic absorption of the free form of cyanide.
The primary toxic constituents in mining process solutions were the weak acid dissociable or
WAD forms of cyanide, and not iron cyanide (total cyanide), the metals, or other inorganic
-
compounds. The WAD forms of cyanide include its free forms (HCN and CN ) and the weakly
bound metal complexes of copper, nickel, and zinc (Clark and Hothem, 1991). Free cyanide is
rapidly absorbed from the avian digestive tract, while its formation and absorption from the
dissolved metal complexed cyanides are comparatively slow, even at low pH (Huiatt, et al., 1983).
A rapid rate of cyanide absorption is needed to induce acute toxicity, supporting the lower
toxicity noted with exposure to metal cyanide complexes.
The stability of metal cyanide complexes is demonstrated by the severe conditions required for
their analysis. In the case of WAD cyanide, the pH is adjusted to 4.5 with a buffer and the sample
is reflexed for 1.0 to 1.5 hours to complete its dissociation. These conditions are more rigorous
than those associated with the stomack of an animal. Even with low pH and elevated
temperature, the dissociation of these metal cyanide complexes is slow, and organisms are
provided an opportunity to metabolize/detoxify the free cyanide as it forms.
The substitution of WAD cyanide for free cyanide as a control parameter provides an additional
factor of safety and conservatism, since reduction to 50 mg/l WAD cyanide through treatment or
recovery results in nearly complete removal of free cyanide leaving only the less toxic metal
complexed forms of cyanide. Additionally, precipitation and runoff dilute pond solutions, while
natural attenuation also occurs, further reducing the WAD and free cyanide concentrations.
As has been demonstrated repeatedly in the field and scientific literature, the metal complexed
cyanides are less toxic individually than is free cyanide itself, due to the decrease in their rates of
dissociation and formation of free cyanide. As a result, an organism can tolerate a higher level of
complexed cyanide than free cyanide, since it can use its detoxification abilities to rapidly convert
the slowly forming free cyanide to thiocyanate.
Furthermore, under acidic conditions below a pH of 4.0, such as in the stomach, the WAD
cyanide metal complexes partically dissociate to free cyanide and an insoluble neutral metal
cyanide complex which precipitates, as is demonstated for copper and nickel cyanide in the
following equations:
-1 +
1. Cu(CN)3 + H = Cu(CN)2 (s) + HCN
-2 +
2. Ni(CN)4 + 2 H = Ni(CN)2 (s) + 2HCN
This process occurs for each of the WAD cyanide metal complexes and forms the basis for the
original AVR cyanide recovery and precipitation process developed in Canada many years ago.
In order to break down the neutral metal cyanide complexes a much lower pH was needed
coupled with an extended period of vigorous agitation. With these basic chemical concepts in
mind and the fact that detoxification to thiocyanate is relatively rapid, it is unlikely that the very
slow release of additional free cyanide, if it occurs, will contribute to long term chronic or

sublethal toxicity.
For example, based upon experience the following composition of a 50 mg/l WAD cyanide
solution would be typical of that associated with a cyanidation solution after treatment or
recovery and prior to its discharge into a tailings impoundment:
-
1. Copper Cyanide 30 mg/l as CN
-
2. Zinc cyanide 10 mg/l as CN
-
3. Nickel cyanide 5 mg/l as CN
-
4. Free cyanide 5 mg/l as CN
Under the acidic conditions of the stomach, the inital free cyanide concentration could eventually
increase to about 25 mg/l as about one-third of the copper cyanide breaks down, one-half of the
nickel and zinc cyanides break down, and the remaining neutral metal cyanides precipitate. A
portion of that cyanide would begin degradation through detoxification. Therefore, at a WAD
cyanide concentration of 50 mg/l, the free cyanide component could initially reach about 25 mg/l
in the stomach, assuming no further dilution or attenuation is occurring within the impoundment
prior to ingestion of solution by the bird.
Since most treated cyanide solutions contain virtually no free cyanide and it is difficult to
quantitate at low levels, WAD cyanide has become the form of choice for monitoring and
compliance of the "toxicologically significant" forms of cyanide. The WAD cyanide method is
used by industry, researchers, and government agencies for setting of aquatic life criteria,
groundwater protection standards, and operational and closure guidelines at mining operations.
4.3 The Sensitivity of the Mallard Duck to Cyanide Toxicity
The sensitivity to cyanide toxicity of different species of birds is not generally related to body size,
but appears to be associated more with their diet (Wiemeyer et al., 1986). Birds that feed
predominantly on flesh, such as vultures, owls, and kestrels, are more sensitive to cyanide than
species that feed mainly on plant material. The exception to this generalization is the mallard
duck, as judged by comparisons of its oral lethal dosages or LD50 (lethal dosage for 50% of the
population) values with those of other birds (U.S. Fish and Wildlife Service, 1991). A summary
of the effects of cyanide on birds is presented in Table 4. The toxicity data indicated that the
mallard duck, due to its high sensitivity and importance as a migratory waterfowl species, is an
excellent model organism for use in the laboratory evaluation of the toxic effects of cyanide and in
the establishment of safe exposure levels.
Different species of migratory birds have been found dead within and adjacent to unnetted or
uncovered tailings impoundments in which the total cyanide levels exceeded 200 mg/l. However,
injured birds that were still alive after 60 minutes of exposure to 200 mg/l often survived, due to
very rapid metabolism and detoxification of cyanide to thiocyanate (Clark and Hothem, 1991, and
Wiemeyer, 1986).

Table 4
Weak Acid Dissociable Cyanide in Tailings Ponds
at Gold Mines in Nevada, 1990
Pond Dead Discharge Pipe

Mine No. Size (ha) Birds Detoxified
WAD CN pH
(mg/l)
9 100 No 216 7.6 Yes
4 1 No 197 10.6 No
2 5 No 138 11.3 No
10 15 Yes 81 10.3 No
13 80 Yes 62 10.6 No
12 100 No 59 6.0 Yes
5 80 No 53 10.1 No
14 10 No 52 10.7 No
8 150 No 48 10.7 No
15 70 No 34 10.8 ?
3 1 No 30 NA Yes
7 5 No 26 11.4 No
16 70 No 23 10.5 ?
1 40 No 20 9.3 Yes
11 20 No 18 10.6 Yes
6 40 No 18 9.4 Yes
17 70 No 8.4 10.9 Yes
Tissue specific biochemical effects have been studied (Pritsos, 1996) with the mallard duck
exposed perorally to sublethal doses of free cyanide ranging from 0.25 mg KCN/kg body weight
(10 mg/l) up to 80 mg/l KCN. Two hours post exposure, the ATP levels in the brain, heart, and
liver were measured. The ATP depletions in the brain and liver were dose dependent. Using 1
mg/kg body wieght of KCN (40 mg/l), an inital drop in ATP levels in all thissue occured with a
subsequent increase approaching control levels in 24 hours. In the brain tissue, the recovery was
the most dramatic with increases in ATP levels above control levels at 12 hours and then a return
to control levels at 24 hours.
Further research conducted with mallard ducks (Pritsos, 1996) monitored the detoxification
systems in the heart, liver, and brain tissues after cyanide exposure by measuring the enzymatic
activities of rhodanese and 3-MPS (3-mercaptopyruvate sulfurtransferase). After 1 mg/kg body
weight of KCN expousre, rhodanese and 3-MPS activities were found to be unchanged in heart
and liver tissues. However, the brain showed a 64% increase in rhodanese and 3-MPS activites,
which also had the fastest recovery of ATP levels. The conclusion was that different metabolic
rates and detoxification enzymes activities exist in different duck tissues.

Figure 2: Summary of Cyanide Toxicity to Mallard Ducks

These studies with mallard ducks exposed to 10-80 ppm KCN, demonstrate the expected
toxicological effects on the cytochrome oxidase system by measurable, dose dependent reductions
in liver and brain ATP levels. Significantly, detoxification mechanisms were not overwhelmed by
cyanide since the ATP lelves returned to control levels by 24 hours post exposure. Measurements
of the detoxification enyzme activities validated that the mallard duck exposure to 40 ppm free
cyanide did not impair the organism's physiological detoxification mechanisms since the enzyme
levels returned to control levels in 24 hours.
The acute oral toxicity of free cyanide in tap water or in the actual mining solution, when
expressed in terms of mg/kg for the mallard duck, was consistent with those literature values
reported (Wiemeyer, 1986) for sodium cyanide. Summarized on Figure 2 are the laboratory and
field data reflecting cyanide toxicity values for mallard ducks. Assuming mallard ducks weigh 1.0
kg and the acute ingested dose is about 10 milliters, the LD50 (lethal dosage resulting in 50%
mortality) values were 2.5 and 3.2 mg/kg in tap water and in mine effluent, respectively.
Reported acute oral toxicity values for sodium cyanide range from 4.0 mg/kg for the American
kestrel to 21 mg/kg for the domestic chicken (Table 4). The data demonstrated that the mallard
duck was one of the most sensitive species and provided an excellent model organism for toxicity
evaluations due to its importance as a migratory waterfowl species.
Assuming the "no effect" or no observable effect level (NOEL) for a 1.0 kg duck is 0.50 mg
CN/kg, taken from Table 4, consumption of 8.0-10.0 ml of a 50 mg/l WAD cyanide solution
would result in a body level of 0.40-0.50 mg CN/kg, which is at or below the lowest no effect
level for this sensitive bird. The absorption of cyanide from solution requires some time, as does
the onset of its toxic effects. During this same time period, the bird's metabolism and
detoxification of cyanide are initiated. As a result, the estimate is conservative, since it assumes a
low no effect level, as well as instantaneous and complete absorption of cyanide without any
consideration of detoxification.
4.4 Toxicological Studies Involving Actual Cyanidation Solutions
Other laboratory and field studies provided further support for the 50 mg/l WAD cyanide
regulatory guideline. For example, FMC Gold Company conducted detailed toxicological
evaluations to develop a dose-mortality relationship employing both single and multiple exposures
of mallard ducks to free cyanide in tap water and in actual mining solutions. Although nearly all
of laboratory evaluations have been conducted using free cyanide, the approach is conservative
since, in general, the metal complexed cyanide are less toxic than its free forms.
In the first study, the acute oral LC50 (the lethal concentration resulting in 50% mortality) value
for cyanide and the mallard duck was determined by exposing different sets of five male and five
female, 20-week old organisms, to varying concentrations (0-265 mg/l) of total cyanide in tap
water (Fletcher, 1986). Following administration of the single dose the ducks were observed for
a period of seven days. The LC50 value for combined male and female ducks was 181 mg/l based
on total cyanide, as shown on Figure 3.

Figure 3: Cyanide Dosage – Mortality Relationship in the Mallard Duck
In a second toxicity evaluation, solution collected from an effluent holding pond at a gold mining
operation in Nevada was used and the total cyanide levels were adjusted through the addition of
sodium cyanide to achieve concentrations ranging from 107-332 mg/l. Again several sets of five
male and five female mallard ducks were exposed to the different cyanide levels and observed for
seven days. The resulting LC50 was calculated to be 212 mg/l based on total cyanide.
All of the mortalities occured within the first three hours following treatment and all surviving
birds appeared normal at the seven day sacrifice. The LC50 of 212 mg/l obtained with effluent was
consistent with the first LC50 of 181 mg/l obtained in tap water (Figure 3).
FMC Gold Company conducted a subsequent study to evaluate the effect of multiple oral
exposures to mallard ducks (Fletcher, 1987). Mallard ducks were exposed to a cyanide-
containing process solution as the sole source of drinking water for a period of seven days. The
cyanide level in the solution was 83 mg/l and was adjusted with additional sodium cyanide to
achieve several test concentrations ranging from 37.5-300 mg/l total cyanide.
Five male and five female 19-24 week old ducks were exposed over the range of concentrations
using buffered tap water as the control solution. Mortalities resulted from exposure to
concentrations above 75 mg/l total cyanide and all but three mortalities occurred within the first
day of exposure. The LC50 value was calculated as 158 mg/l based upon total cyanide and 136
mg/l based upon free cyanide.

An evaluation of the dosage mortality data from all of the studies allowed FMC Corporation to
calculate a level below which the risk of avian mortality should be negligible with respect to a
process solution. The data demonstrated that the acute toxicity of free and/or complexed cyanide,
as reported by the weak acid dissociable (WAD) analysis, was the primary concern and not the
toxicity of other constituents. Using the data, the LC1 (lethal concentration resulting in 1%
mortality) for free cyanide was estimated to be about 50 mg/l and was used as the level below
which no mortality would be expected. This value is equivalent to a single oral dose of free
cyanide of about 0.73 mg/kg and is well below the literature reported values. As mentioned
previously, the experimentally derived dosage mortality curve is shown on Figure 3. A summary
of the above cyanide toxicity data for mallard ducks and field/laboratory studies evaluating
cyanide-containing solutions, is presented on Figure 2.
5.0 SUMMARY
This review of cyanide toxicity to waterfowl and stategies to control bird mortalities indicated the
following facts:
1. The mallard duck has proven an excellent species as a model for evaluation of the toxicity of
cyanide containing solutions to birds and in particular waterfowl.
2. The free form of cyanide is its most toxic form, with the lethal dosage to mallard ducks having
been established at 4.0 mg/kg. The "no effect" level or no-observable effect level (NOEL) is
about 0.50 mg/kg free cyanide (CN) for the mallard duck. This is approximately the single
intake of water (10 mls) or ingested dose a mallard duck consumes from an impoundment or
pond.
3. Process solution is comprised of primarily metal complexed cyanides following treatment and
release to an impoundment. The toxicities of the metal complexed forms of cyanide are
typically several fold less than those of free cyanide. A margin of safety or conservatism exists
in applying 50 mg/l WAD cyanide as a guideline or standard, since a typical 50 mg/l WAD
cyanide solution entering a tailings impoundment is only partially convertable to free cyanide
and is further diluted and attenuated by a factor of several fold.
4. Biochemical mechanisms in mallard ducks function to detoxify ingested doses of up to 40 mg/l

free cyanide as measured by respiratory enzyme levels, which returned to normal within 24
hours.
5. Field surveys have confirmed that bird mortalities have diminished dramatically when WAD
cyanide concentrations are below the 50 mg/l guidance level. Until research indicates
differently, the recommended and preferred exclusion strategy is to cover the surface of the
smaller process ponds with nets or balls and/or to reduce the WAD cyanide levels in larger
tailings impoundments to below 50 mg/l. Additionally, a regimented observation program
should be implemented to record bird contacts within and along the tailings impoundment, in
order that an adjustment in the WAD cyanide control level can be made, if needed, on a site-
specific basis.

6.0 REFERENCES
Allen, C.H. 1990, "Mitigating impacts to wildlife at FMC Gold Company's Paradise Peak Mine".
Pages 67-71 in Proceedings of the Nevada Wildlife/Mining Workshop, 27-29 March 1990, Reno,
Nev. Available from Nevada Mining Assoc., 3940 Spring Drive, Reno, Nev. 89502.
Ballantyne, B., "Toxicology of Cyanides", Chapter 3 in Clinical and Experimental Toxicology of

Cyanides. Edited by B. Ballantyne and T.C. Marrs, Wright Publishers, Bristol, England, U.K.,
1987.
Castrantas, H., "Cyanide Detoxification of a Gold Mining Tailings Pond with Hydrogen
Peroxide", paper presented at the Randol Gold Forum 88, January 23, 1988.
Clark, J., Viessman, W., and Hammer, M., Water Supply and Pollution Control, third edition, IEP
Publishers, New York, 1977.
Clark, D. and Hothem, R., "Mammal Mortality at Arizona, California, and Nevada Gold Mines
Using Cyanide Extraction", California Fish and Game, Volume 77, pp. 61-69, 1991.
Fletcher, D.W., "Acute Oral Toxicity Studies with Cyanide in Mallard Ducks", Report 186/0942
and 186/0943, FMC Corporation, December 30, 1986.
Fletcher, D.W., "Simulated Exposer Study with Cyanide Effluent in Mallard Ducks", Report
186/0944, FMC Corporation, January 6, 1987.
General Accounting Office (GAO), "Increased Attention Being Given to Cyanide Operations", a
report to the Chairman of the Subcommittee on Mining and Natural Resources, GAO/RCED-91-
145, June, 1991.
Hall, T.C., "Clinical toxicology of cyanide: North American clinical experiences,", Chapter 12 in
Clinical and Experimental Toxicology of Cyanides. Edited by B. Ballantyne and T.C. Marrs,
Wright Publishers, Bristol, England, U.K., 1987.
Hallock, R. J., 1990. "Elimination of migratory bird mortality at gold and silver mines using
cyanide extraction". Pages 9-17 in Proceedings of the Nevada Wildlife/Mining Workshop, 27-29
March 1990, Reno, Nev. Available from Nevada Mining Assoc., 3940 Spring Drive, Reno,
Nevada.
Henny, C., Hallock, R., and Hill, E., "Cyanide and Migratory Birds at Gold Mines in Nevada,
USA", Ecotoxicology, Volume 3, pp. 45-58, 1994.
Huiatt, J., Kerrigan, J., Oslo, F., and Potter, G., Cyanide from Mineral Processing, Utah Mining
and Minerals Institute, Salt Lake City, Utah (USA), 1983.

Kay, F. and McQuivey, R., "Migratory Birds and Toxic Mine Ponds: The Nevada Experience",
Gold and Silver Recovery Innovations Phase IV, Randol International, Ltd., Sacramento,
California, November, 1989.
Kay, F., "Nevada Department of Wildlife's Role: Past, Present, and Future". Presented at
Proceedings of the Nevada Wildlife Mining Workshop, Reno, Nevada, March, 1990.
Marrs, T.C., "Clinical and experimental toxicology of cyanides: an overview", Chapter 23 in

Clinical and Experimental Toxicology of Cyanides. Edited by B. Ballantyne and T.C. Marrs,
Wright Publishers, Bristol, England, U.K., 1987.
Mining Environmental Management, Technology Section, pp. 4-16, Mining Journal Ltd., June,
1995.
Mining Environmental Management, Technology Section, p. 23, Mining Journal Ltd., June, 1996.
Mudder, T. and Smith, A., "An Environmental Perspective on Cyanide", Proceedings of the
Mining Environmental Management Conference, Mining World News and Mining Journal Ltd.,
October 16-19, Reno, Nevada, 1994.
Nevada Mining Association, Nevada Department of Minerals, and the Nevada Department of
Wildlife, Proceedings of the Nevada Wildlife Mining Workshop, Reno, Nevada, March, 1990.
Pritsos, C. and Juntao, M., "Biochemical Assessment of Cyanide-Induced Toxicity in Migratory

Birds from Gold Mining Hazardous Waste Ponds", Proceedings of the International Congress on
Hazardous Waste:Impact on Human and Ecological Health, Atlanta, Georgia (USA), June, 1995.
Pritsos, C.A. and Ma, J., "Tissue specific bioenergetic effects and increased enzymatic activities
following acute sublethal peroral exposure to cyanide in the mallard duck". Toxicol. Appl.
Pharmacol., in press, 1996.
Smith, A., and Mudder, T., The Chemistry and Treatment of Cyanidation Wastes, Mining Journal
Books, London, England, December, 1991.
The Gold Institute, Gold Issues Briefing Book, Washington, DC, December, 1996.
U.S. Fish and Wildlife Service, "Cyanide Hazards to Fish, Wildlife, and Invertebrates: A Synoptic
Review", U.S. Department of the Interior, Biological Report 85(1.23), Containment Hazard
Reviews Report 23, December, 1991.
USEPA, 1985, "Basis for Listing Hazardous Waste". 40 CFR 261, App. VII, EPA, 1985.
USEPA, "RMZ Briefing on Cyanide", Office of Pollution Prevention and Toxic's Cyanidation
Mining Initiative and Mining Inquiry, November, 1991.

Weimeyer, S., Scott, J., Anderson, M., Bloom, P., and Stafford, C., "Environmental
Contaminants in California Condors", J. Wildlife Management, 52:238-247, 1986.

Table 5
Cyanide Effects on Selected Species of Birds
Mallard, Single oral dose of NaCN
Anas platyrhynchos 0.53 mg CN/kg body weight (BW), No deaths
equivalent to 1 mg NaCN/kg BW
1.27 mg CN/kg BW (2.4 mg NaCN/kg About 33% dead
BW) LD 50; 95% confidence interval
1.43 mg CN/kg BW (2.7 mg NaCN/kg (C.I.)
BW) of 2.2 and 3.2 mg NaCN/kg BW
Turkey vulture
Up to 80% of the cyanide in blood
Single oral dose of 19.1 mg CN/kg BW, was present as free cyanide and the
equivalent to 36 mg NaCN/kg BW remainder as bound cyanide
Average time to death was about 19

Single oral dose of 19.1 mg CN/kg BW, min and ranged between 8 and 41
equivalent to 36 mg NaCN/kg BW min; cyanide residues postmortem,
in mg CN/kg fresh weight (FW),
were 6.7 in blood (Max. 21) and
0.6 in liver (Max. 2.8)
Rock dove,
Columba livia Minimum lethal dose when
1.6 mg CN/kg BW, equivalent to 4.0 mg administered intravenously or
KCN/kg BW intramuscularly
Black vulture,
Coragyps atratus
Single oral dose, as NaCn No deaths in 60 min. Mean and
1.6 mg CN/kg BW maximum blood CN concentrations,
in mg/kg FW, were 0.7 and 0.9,
respectively
Some deaths within 30 min. Mean
2.4 mg CN/kg BW blood CN residues in mg/kg FW,
were 0.7 in dead birds vs. 1.2
in those surviving 60 min
Acute oral LD50; 95% C.I. of 2.3
2.54 mg CN/kg BW and 2.8 mg CN/kg BW (4.4-5.3 mg
NaCN/kg BW)
All dead within 16 min; maximum
3.7 and 19.1 mg CN/kg BW blood CN levels postmortem were
2.1 mg/kg FW in the low dose
group
and 4.2 in the high dose group
Japanese quail,
Coturnix japonica
4.5 mg CN/kg BW Acute oral LD50 for adult females;
BW
5.5 mg CN/kg BW Acute oral LD 50 for adult males;
BW

TABLE 5
(continued)
American kestrel, 2.12 mg CN/kg BW, as NaCN Acute oral LD50; 95% C.I. of 1.6
Falco sparverius and 2.8 mg CN/kg BW
Domestic chicken, 0.6 mg CN/kg BW, equivalent to 1.5 mg Lethal

Gallus domesticus KCN/kg BW
0.78 mg CN/kg BW, as KCN Sublethal; thiocyanate excretion
increased 10 times after 10 min
and returned to normal levels
after 3.5 h; the total thiocyanate
collected was equivalent to 85% of
the administered dose
1.3 mg CN/kg BW, as KCN Lethal
3.2 mg CN/kg BW, equivalent to 6.0 mg No deaths in 30 min; maximum CN
NaCN/kg BW levels, in mg/kg FW, were 1.1 in
6.4 mg CN/kg BW Some deaths in 30 min; maximum
CN
levels, in mg/kg FW were 1.6 in
11.1 mg CN/kg BW blood and 0.12 in liver
25.4 CN/kg BW and 19.1 mg CN/kg BW
Advanced signs of acute poisoning;
death probable within 30 min;
maximum CN levels, in mg/kg FW,
Dietary route were 1.5 in blood and 0.6 in liver
Fed cassava diets containing 4, 37, 70, or
103 mg total cyanide per kilogram At all dietary levels, there was no
ration to day-old chicks for 8 weeks significant effect on survival,
growth, histology, hemoglobin,
hematocrit, or lymphocyte number;
however, serum thiocyanate levels
increased in a dose-dependent
Fed diets containing 135 mg HCN/kg manner
Chicks, 20-day exposure
Growth and food intake significantly

Adults, 14-day exposure depressed; plasma thiocyanate
concentration increased
Urinary excretion of thiocyanate
Eastern screech-owl, 4.6 mg CN/kg BW, equivalent to 8.6 mg increased 5 times in laying hens
Otus asio NaCN/kg BW
European starling, 9.0 mg CN/kg BW, as NaCN and 5.4 mg CN/kg BW
Sturnus vulgaris
Andean condor, Single oral dose of 19.1 mg CN/kg BW and 17 mg CN/kg BW


Vultur gryphus (36 mg NaCN/kg BW)
Blood sampled immediately after
death contained 1.2 mg free CN
per liter and 0.5 mg bound CN
per liter

Figure 4: Northparkes Mines, Australia

Figure 5: Cyanide Consumption Resulting from

the CIP Treatment of Oxide Gold Ore

Figure 6: Total Bird Mortality Versus Cyanide (mg/l WAD)

CHAPTER 3
Recovery and reuse
● The recovery of cyanide from slurries

● Cyanisorb cyanide recovery process design,
commissioning and early performance
● Recovery of cyanide from mill tailings
● Cyanide recovery applications for CCD circuits
● Processes for the regeneration of cyanide from thiocyanate
THE RECOVERY OF CYANIDE FROM SLURRIES
Prepared By:
Terry Mudder, Ph.D.

Adrian Goldstone
Originally published in Proceedings of the International Gold Expo Conference, p. 107, Reno,
Nevada, September 7-9, 1989
The Recovery of Cyanide from Slurries
1.0 INTRODUCTION
The use of cyanide for extraction of precious metals has been practiced for nearly a century, since
it was first employed in New Zealand in 1898. Cyanidation is an efficient process capable of
extracting minute amounts of gold from complex chemical and mineral matrices. In theory, a
solution of 100 mg/l of free cyanide can provide the maximum rate and extent of gold dissolution.
In practice, concentrations of 200-800 mg/l of total cyanide are often required for gold and silver
recovery.
The metal extraction process may involve either vat or heap leach, with recovery being
accomplished through zinc precipitation or activated carbon adsorption. The milling, extraction,
and recovery processes produce waste streams including barren solutions, tailings slurries, and
excess decant water. Qualitatively, the chemistry of these waste streams are similar containing a
variety of constituents including cyanide complexes, metals, and in-organics (i.e. ammonia,
thiocyanate, cyanate, sulfate, and nitrates). Quantitatively, the waste streams vary substantially
exhibiting concentrations ranging over several orders of magnitude. A summary of the chemical
composition of various barren solutions and slurries are presented in Table 1.
The excess solutions and solids are normally disposed of in an impoundment. Several potential
problems may result from disposal including contamination of groundwater, exposure of wildlife
and water fowl to elevated cyanide concentrations, and impacts on surface water environments
following discharge of treated or untreated effluents.
There is a need to mitigate these problems and to minimize potential adverse environmental
impacts. The conventional approach involves treatment of mill tailings or decant solutions and
lining of impoundments, while ignoring the options associated with recycle of process solutions
and reagents. The capital and operating costs of wastewater treatment and tailings disposal are
substantial and often dictate the economic viability of a mining project. Treatment costs are
increasing sharply due to more stringent environmental regulations and the need for more
sophisticated and advanced technologies.
In conjunction with treatment and solid waste disposal costs, are the rapidly increasing costs of
water and reagents, particularly cyanide. The cost of cyanide has risen sharply due to world-wide
demands and shortages. The spot-market price for cyanide in certain instances is several times
higher than the average price. The cost of cyanide is a primary concern in remote areas where
cyanide availability is limited.
As a result, every attempt must be made to reduce reagent consumption through recycle and
recovery to minimize the costs of production and of environmental protection. One excellent
approach involves recovery and recycle of cyanide from process solutions and slurries.
Historically the process, termed acidification, volatilization, and reneutralization or AVR, has
been employed in the recovery of cyanide from clarified barren or decant solutions.
203 T. Mudder & A. Goldstone

Table 1
Chemical Composition Of Barren Solutions And Tailings Slurries
(1)
Parameter Range of Concentrations
Arsenic <0.02 - 10.0
Cadmium <0.005 - 0.10
Chromium <0.02 - 0.10
Copper 0.10 - 400.0
Iron 0.50 - 40.0
Lead <0.01 - 0.10
Manganese 0.10 - 20.0
Mercury <0.0001 - 0.05
Nickel 0.02 - 10.0
Selenium <0.02 - 6.0
Silver <0.005 - 2.0
Zinc 0.05 - 100.0
Total Cyanide 0.50 - 1000.0
WAD Cyanide 0.50 - 650.0
Free Cyanide <0.01 - 200.0
Ammonia-N <0.10 - 50.0
Thiocyanate <1.0 - 2000.0
Hardness (as CaCO3) 200 - 1500
Sulfate 5 - 10000
o
Temperature (in C) 0 - 35
Flow (in gpm) 1 - 6000
(1) All values in mg/l, unless otherwise stated.

Although cyanide recovery has been employed in the full-scale recovery of cyanide from
solutions, only recently has considerable interest in the process resurfaced, particularly for
application with tailings slurries. This paper describes in detail the history, chemistry,
applications, advantages, and costs of various cyanide recovery processes.
Emphasis is placed on the development of the Cyanisorb Process for recovery of cyanide from
slurries. This process has been tested and proven through an extensive pilot plant evaluation for
application at Cyprus Gold's proposed Golden Cross Mine in New Zealand, and would represent
the first full-scale application of cyanide recovery from slurries.
2.0 HISTORY OF CYANIDE RECOVERY PROCESSES
The recovery of cyanide from mining solutions through acidification, air stripping, and
reabsorption was originally known as the Mille Crows Process (1). The process involved
acidifying clarified barren solution, then stripping the HCN formed and reabsorbing it from the
air stream with a caustic or milk of lime spray. The process was employed at the Flin Flon Mine
operated by Hudson Bay Smelting and Mining Company from about 1930-1975 (2,3).
The Canadian mining operation involved cyanidation of gold bearing tailings originating from
the flotation of a copper-zinc ore. To condition the barren solution for stripping, the pH was
first adjusted downward to 2.5 with sulfuric acid supplied from the zinc electrolytic plant.
The acidified solution was then passed through a series of four stripping towers packed with
wooden grids. The towers were constructed of concrete and measured about 5m x 2m x 7.5m
in height. The stripping towers were operated in a series, each connected to one of four
concrete absorption tunnels by means of closed loop recycled air streams.
3 3
The air and liquid volumes in each stripping loop were about 56,000 m /hr and 107 m /hr,
resulting in an air to liquid ratio of about 525/1. The HCN entrained in the air stream was
reabsorbed by contacting the air stream with lime slurry sprays and recollected in a central
storage tank. The stripping process required high volumes of low pressure air. In this
application a reduction in total cyanide of 92 percent was achieved by lowering the cyanide
concentration from 560 mg/l to 44 mg/l.
The major problem associated with the system was the buildup of gypsum and copper
thiocyanate precipitates on the packing internals, which required manually cleaning every two to
four months. The problem arose due to the very low pH and high sulfate concentrations
generated, two problems minimized in modern adaptations of the process. The process was
utilized for economic, not environmental reasons and was limited to the stripping of cyanide
from clarified barren solutions, not slurries. During the 1930's there were about seven cyanide
regeneration plants in operation utilizing various designs, but only limited information was
available concerning these facilities (4). The plants were utilized in conjunction with silver
recovery primarily and were located in remote regions of the world.

From the mid-1930's into the 1950's, a full-scale cyanide regeneration or recovery process was
utilized by the Real Del Monte Company in Pachuca, Hidalgo, Mexico (5). The stripping of free
cyanide was conducted at an acidic pH, employing sulfuric acid generated on-site through the
burning of sulfur. The volatilization stage and absorber stages were combined alternately and
operated in series. The system was enclosed and the air recycled at 100 percent humidity to
minimize evaporation. A total cyanide recovery of about 93 percent was achieved with about a
60 percent removal realized through each of the three stripper stages. The operation was
originally designed to treat about 350 tonnes of solution per day and was later expanded to
accommodate about 1,100 tonnes of solution per day. The free cyanide was concentrated until
a 5 percent solution was obtained and then recycled to the metallurgical circuit. However, the
process was restricted to recovery of cyanide from clarified barren solutions only.
In the 1970's the process was reinvestigated and modernized by CANMET and McNamara (6).
The renewed interest in the process was due to the increasing costs of both cyanide and its
treatment. In the CANMET study, a bench-scale laboratory apparatus was employed to
investigate the recovery of cyanide from six actual barren waters. The study summarized for the
first time the various chemical reactions associated with the process. The process was referred
to as acidification, volatilization, and reneutralization or the AVR process, which is the current
terminology for cyanide recovery and regeneration from solutions.
The study advocated the use of single complete mix aeration basins about 1.5m in depth instead
of stripping towers, to minimize the mechanical problems associated with scaling and plugging
of media or internals, and to minimize pressure drop and horsepower requirements. It was
recommended that aeration in a full-scale operation be accomplished using multiple rows of fine
bubble diffusers.
The AVR process was evaluated as a primary wastewater treatment alternative, utilizing pH
values below 2.0 to facilitate removal of total and iron complexed cyanides through
precipitation. Greater than 99 percent removal of total cyanide was achieved in the studies, with
treated effluents containing total cyanides ranging from 0.10 to 4.0 mg/l. In addition, the
investigation of metals precipitation was undertaken, demonstrating excellent removal
efficiencies were achievable following reneutralization with lime. However, the process was
confined to solution treatment as it was considered not feasible for treatment of tailings slurries.
In addition, the use of basins and fine bubble diffusers increased the horsepower requirements
compared to towers, due to the increased pressure losses encountered in the system.
The AVR process was further investigated as a primary alternative for treatment of mine decant
water from 1985-1987 (Mudder, unpublished results). The tests employed a small pilot plant
operated in batch mode using barren waters obtained from a silver mining operation. The pilot
plant design involved two 0.3m diameter 2.5m polyethylene columns connected in series.

One column served as the stripping chamber, while the other served as the absorption chamber.
About 200 L of actual decant solution were utilized per experiment in conjunction with coarse
bubble diffusers, as it was found turbulence was a more important factor in stripping of cyanide
than the size of the bubble. The coarse bubble diffusers simplified the process, while maintaining
process performance. Total cyanide levels were routinely reduced from an average of 330 mg/l
to less than 2.0 mg/l.
Also in the mid-1980's, investigations were conducted at the Noranda Research Center aimed at
designing a cyanide recovery process employing packed towers and plastic, media (7). Stripping
towers significantly reduced the surface area required for the AVR process, as well as the
horsepower requirements due to the reduced pressure losses through the system.
Employing information derived in a bench-scale study, a continuous flow pilot plant system was
designed and operated. The data obtained in the pilot study was utilized in the development of a
3
design for a full-scale stripping system to treat about 2,000 m /d of barren solution, utilizing an
air to liquid ratio of 330.
The pilot plant evaluations indicated the total cyanide levels could be reduced from about 4,000
mg/l to about 120 mg/l, for an overall removal efficiency of 97 percent. The stripped cyanide
was reabsorbed in a second packed tower using a counter current caustic solution. The process
employed a pH of 2.5 and considerable precipitation of copper thiocyanate and calcium sulfate
was realized. It was noted that the precipitated solids would eventually reduce the stripping
efficiency, and mechanical cleaning of the media would be necessary and difficult. The study
demonstrated that use of modern mass transfer technology and materials could be employed in
the removal and recovery of cyanide from clarified barren solutions.
A full-scale packed tower cyanide recovery system was designed and operated from 1985-1987
by Golconda Engineering and Mining Services at the Beaconsfield Gold Mine in Tasmania (8).
The process was termed the C.R.P. or Cyanide Regeneration Process. Initially, a continuous
flow pilot plant operation was conducted to establish the appropriate air to liquid ratio, stripping
time, and caustic requirements for the absorber. The full-scale facility was designed to treat
1,200 tonnes/d of clarified barren water using a system of multiple packed aeration towers. A
schematic of the full-scale facility is presented in Figure 1.

Figure 1: Beaconsfield C.R.P. Flowsheet
The plant was designed using the most modern mass transfer technology, plastic media, and
cyanide monitoring equipment. The system was designed for maximum safety incorporating an
enclosed negative pressure system. Fan exhausts were monitored routinely for HCN with
3 3
typical values of <1.0 mg/m , which were 1/10 of the 8-hour 10.0 mg/m TLV for free cyanide.
Cyanide recoveries of nearly 95 percent were reported in the full-scale system.
The various laboratory, pilot plant, and full-scale cyanide recovery facilities described have
demonstrated that application of mass transfer technology coupled with state-of-the-art
monitoring equipment and engineering design approaches can be employed in the construction
and operation of full-scale cyanide recovery systems. However, it has been widely believed that
the cyanide recovery process can not be extended to slurries, due to the problems associated
with the chemical and physical properties of low pH slurries and the lack of adequate materials
and equipment.

Since 1985, an intensive research effort has been undertaken to expand the capabilities of the
process to slurries, while minimizing the chemical and mechanical problems associated with past
systems. The work involved both detailed laboratory and continuous flow pilot plant
evaluations conducted for Cyprus Gold of New Zealand, to develop and design the first full-
scale commercial cyanide recovery system for tailings slurries to be installed at the proposed
Golden Cross Mine near Waihi, New Zealand.
Based on the test results, a full-scale cyanide recovery system utilizing packed towers would be
3
built to treat 200 m /hr of a 35 percent tailings slurry from a WAD cyanide level of 200 mg/l to
less than 10 mg/l. The commercial cyanide recovery process for which patent applications have
been filed and a patent is pending is known as the Cyanisorb Process.
The following sections of the paper focus on the chemistry, performance, applications, and
economics of the cyanide recovery from solutions and slurries, with emphasis on the cyanide
recovery system proposed for the Golden Cross Mine.
3.0 PROCESS DESCRIPTION AND CHEMISTRY
Cyanide recovery processes utilize the volatility of HCN at a lowered pH (i.e. Figure 2) to strip
free cyanide from solution or slurry and recover it in usable form (i.e. NaCN or Ca(CN)2). The
volatility of free molecular cyanide (HCN) is related to its Henry's Law Constant, which is
affected by several factors including viscosity, hydrogen bonding, pH, and temperature (7). The
transfer of hydrogen cyanide from a solution or slurry to air is liquid film limited, and high
volumes of low pressure air (i.e. <0.5 psi) are required to create the necessary air to liquid
contact to facilitate its removal.
There are several factors which affect the rate and extent of HCN removal from slurries or
solutions through air stripping. These factors include:
1. The pH of the solution

2. The form of cyanide
3. The concentration of cyanide
4. The temperature of the slurry or solution
5. The pressure maintained within the recovery system
6. The air to liquid ratio
7. The mechanical dispersion equipment
8. The viscosity of the solution or slurry
9. The liquid to air contact period

Figure 2: Relationship Between HCN and CN- with pH

Figure 3: Schematic of the Cyanide Recovery Process

A great deal of information is available regarding the effects of these design parameters on the
recovery of cyanide from clarified solutions, but limited data is available concerning the treatment
of tailings slurries. The current cyanide recovery processes are upgraded versions of the original
Mills Crowe Process previously discussed. A schematic of the generalized cyanide recovery
process is presented on Figure 3.
The process is conducted in three stages. The first stage known as acidification, involves
lowering of the wastewater pH in the range of 1.5-8.5 with the use of concentrated mineral acid.
The acid employed most commonly is sulfuric acid, due to its relatively low cost and ease of
availability. In addition, the handling, storage, and feeding of sulfuric acid is quite common in
industry.
The potential problems associated with sulfuric acid include an increase in sulfate and total
dissolved solids concentrations and the potential for precipitation of calcium sulfate or gypsum in
oversaturated solutions. The pH of the solution or slurry is monitored in-situ continuously. The
acidification step must be enclosed to prevent escape of HCN gas and requires about 10 to 20
minutes to complete. The reduction of HCN during the acidification step is about 10 to 15
percent of the total cyanide concentration.
The pH of a solution, slurry, or sludge is lowered in accordance with the stability of the particular
complexes from which the cyanide will be recovered. For the recovery of free cyanide from
simple cyanides (i.e. NaCN and Zn(CN)2), a pH in the range of 4.5 to 8.5 is employed. For
recovery of weak acid dissociable (WAD) cyanide, the pH is lowered to about 4.0. For removal
of iron complexed cyanide the pH is lowered to less than 2.0. In this case, an insoluble metal iron
cyanide complex forms, and precipitates from solution. The best approach is to utilize a near
neutral or basic pH when possible to minimize precipitation problems and an increase in total
dissolved solids.
From the acidification stage, the acidified solution or slurry containing HCN passes into the
cyanide stripping or volatilization stage, which consists of either open or packed towers, a series
of complete mix reactors, or a shallow aeration basin. The volatilization system is sealed to
prevent escape of HCN laden air and to allow efficient recovery of cyanide. All configurations
are applicable to either slurries or clarified solutions. A stripping efficiency in the range of 90-99
percent is possible. In the case of complete mix reactors or aeration basins, coarse bubble
diffusers are employed in the bottom of the reactors, and the reactors are sealed to eliminate
release of HCN gas to the atmosphere. The use of diffusers provides air for agitation of the
solution as well as stripping of the free cyanide. Mechanical agitation does not provide the
necessary turbulence to facilitate stripping of HCN.
The free cyanide produced through volatilization is entrained in an air stream, passed upflow
through a packed tower, and reabsorbed into a caustic solution moving counter current to the air
flow. The caustic solution is then returned to the metallurgical circuit for reuse. The pH of the
caustic solution is maintained in the range of 10.5-11.5.

Once the solution or slurry is free of recoverable free cyanide, it enters the reneutralization stage
of the process. In this stage, the pH is readjusted to 9.0-10.5 with lime, to precipitate residual
metals and to add buffering capacity. With cyanide removed, the metals are released in free form
into solution, allowing precipitation to low levels as their stable and insoluble carbonate and
hydroxide complexes. The addition of buffering capacity is important in the event a slurry being
treated exhibits the potential for acid generation through sulfide oxidation.
The lime may be supplied as thickened sludge from other treatment processes if present on site.
The simplified chemistry of the process is presented in the following reactions:
(1) Ca(CN)2 + H2SO4 = 2HCN + CaSO4 (acidification)

++ -2
(2) M(CN)2 + H2SO4 = 2HCN + M SO4
(3) HCN/H2O = HCN/Air (volatilization)
(4) HCN + NaOH = NaCN + H2O (absorption)
++ -
(5) M + 2OH = M(OH)2 (precipitation/reneutralization)
(6) Na4Fe(CN)6 + 2CuSO4 = Cu2Fe(CN)6 (red/brown) + 2Na2SO4 (iron cyanide removal)
-
The process chemistry indicates that the initial phase of recovery involves conversion of CN to
HCN and initiation of breakdown and of precipitation of neutral metal cyanide complexes. The
extent of the conversion dependent on the pH chosen for recovery and forms of cyanide being
recovered. At very low pH values, precipitation of iron complexed cyanide occurs as the copper-
iron cyanide complex, which accounts for the removal of this portion of the total cyanide.
4.0 PROCESS PERFORMANCE
As discussed previously, excellent overall stripping and recovery efficiencies of total and WAD
cyanides from barren and decant solutions are achievable by any of the recovery processes
mentioned. In the case of the three full-scale systems described above, overall removal
efficiencies ranged from 92 to 99 percent. In the case of the Flin Flon Mine, the total cyanide
level was reduced from 560 mg/l to 44 mg/l. The performance of the Golconda C.R.P. facility is
presented in Table 2. The initial total and free cyanide levels of 200 mg/l and 10-30 mg/l were
reduced to <5.0 mg/l and <0.50 mg/l, respectively. The residual cyanide levels were reduced
further once the treated effluent was passed through a carbon adsorption column prior to
discharge.
In addition, the copper, nickel, and zinc concentrations were all reduced to <1.0 mg/l in the
treated effluent. The level of treatment obtained was consistent with that achievable by any
chemical and/or biological treatment process currently used in the mining industry. The cyanide
regeneration process also enhanced the recovery of gold from solution through carbon adsorption.

Table 2
Performance Of The Beaconsfield CRP Plant
Solution Free Tota Cu Fe Ni Zn Au Ag

CN l CN
Feed Liquor 10-30 200 200 50-100 1-2 5-30 0.05- 0.05-
0.08 0.2
Clarified Liquor to 110 115 <1.0 <1.0 <1.0 <1.0 0.08 <0.02
Regeneration
Regeneration Discharge 2.0 5.0 <1.0 <1.0 <1.0 <1.0 0.08 <0.02
Aeration Discharge 0.2-0.5 2-4 <1.0 <1.0 <1.0 <1.0 0.08 <0.02
Carbon Column Discharge 0.1-0.3 1.2 <1.0 <1.0 <1.0 <1.0 0.01 <0.02
Similar results were obtained in the pilot scale batch studies evaluating the removal and recovery
of WAD and total cyanide from actual decant water (Mudder, unpublished results). Repeated
trials were conducted, each using 200 L samples of decant water. A summary of influent and
effluent chemistries before and after cyanide recovery are presented in Tables 3 and 4. Greater
than 99 percent removal of total and WAD forms of cyanide was realized, as well as excellent
removal of various metals following pH adjustment and precipitation. The results compared
favorably with those obtained in the CANMET laboratory evaluations, which are presented in
Table 5. The removal efficiencies for metals in the CANMET studies were excellent and ranged
from about 80-99 percent.

Table 3
Chemical Characteristics Of Untreated Tailings Impoundment Water
Parameter (1,2) Concentration Range Average Concentration

Arsenic ------ 0.36
Cadmium ------ 0.01
Chromium ------ 0.01
Cobalt ------ 0.21
Copper 2.6 - 2.7 2.6
Iron ------ 16.0
Lead 0.08 - 0.20 0.14
Mercury 0.01 - 0.024 0.016
Nickel ------ 0.20
Silver 2.0 - 2.1 2.0
Zinc 91.9 - 96.4 93.3
Thiocyanate 30.1 - 36.6 33.6
Total Cyanide 310 - 340 330
Method-C Cyanide 270 - 320 294
Ammonia (as N) 19.0 - 19.6 19.3
pH (in pH units) 10.4 - 10.5 10.4
(1) All concentrations in mg/l, unless otherwise stated.

(2) All values are the result of direct analysis of the samples.

Table 4
Chemical Characteristics Following Cyanide Recovery
Parameter (1,2) Concentration Range Average Concentration

Arsenic 0.01 - 0.02 0.01
Cadmium 0.004 - 0.004 0.004
Chromium <0.01 - <0.02 <0.02
Cobalt 0.15 - 0.18 0.16
Copper 0.28 - 0.55 0.39
Iron 0.05 - 0.09 0.07
Lead 0.05 - 0.20 0.10
Mercury 0.013 - 0.015 0.014
Nickel 2.05 - 0.10 0.09
Silver 0.5 - 1.1 0.9
Zinc 0.04 - 0.13 0.09
Thiocyanate 27.4 - 36.6 31.3
Total Cyanide 1.3 - 2.3 1.7
Method-C Cyanide 0.7 - 1.6 1.2
Ammonia (as N) 13.8 - 21.3 18.6
Nitrate (as N) 20.0 - 31.4 25.4
Sulfate 1200 - 1600 1450
pH (in pH units) 9.5 - 9.8 ------
(1) All concentrations in mg/l, unless otherwise stated.

(2) All values are the result of direct analysis of the samples.

Table 5
Results Of The Canmet Bench-Scale Avr Studies
Mine and Barren Solution Parameter Concetration (1)

Chemistry Before _______________________________________________________
and After AVR CN(2) SCN Cu Zn Ni Fe
Kerr Addison
- Barren Feed 60 47 14 10 6 0.8
- AVR Treated Effluent <0.10 <1 0.3 0.01 0.05 <0.1
Dome
- Barren Feed 23 -- 12 8 2 --
- AVR Treated Effluent <0.10 14 0.09 0.2 0.2 0.2
Giant Yellowknife
- Barren Feed 260 50 77 98 6 11
- AVR Treated Effluent <0.10 57 0.3 0.1 <0.03 <0.03
Hollinger Ross
- Barren Feed 610 540 310 82 1 11
- AVR Treated Effluent 4.16 300-370 4 <0.01-8.0 0.2 <0.03-0.08
Pamour
- Barren Feed 990 1530 310 86 230 1
- AVR Treated Effluent <0.1-3 1180-1320 0.3 - 2 <0.01 0.1-2 <0.03-.01

(2) Total cyanide as measured by the picric acid colorimetric method.
The results from the various laboratory, pilot plant, and full-scale systems demonstrate the
effectiveness of the processes for the recovery and reuse of cyanide from clarified barren and
decant solutions. In addition, the results demonstrate the reliability in predicting full-scale
operation based upon data obtained from laboratory or pilot plant investigations. The
reabsorption of cyanide following stripping is a well documented and proven process capable of
recovering between 95 to 99 percent of the stripped cyanide.

However, it is still widely believed that the approaches and equipment utilized in the treatment of
solutions are not suitable for the recovery of cyanide from slurries. In order to expand the
applicability of cyanide recovery from solutions to slurries, extensive laboratory and pilot plant
investigations have been undertaken on behalf of Cyprus Gold of New Zealand since 1986 to the
present (Mudder, unpublished results). The investigations have proven the effectiveness of
recovering cyanide from tailings slurries. The next section of the paper details the investigations
and the results of those studies.
5.0 RECOVERY OF CYANIDE FROM SLURRIES
5.1 Introduction
Although recovery of cyanide from solutions is desirable, recovery of cyanide from slurries is
optimal for a variety of reasons including:
1. Elimination of sedimentation or clarification prior to treatment of the barren solution,

thereby reducing both metallurgical capital and operating costs.
2. Recovery of an expensive reagent is realized, which significantly reduces operating

costs and the hazards associated with the manufacture, transport, and storage of
cyanide.
3. Reduction of the total and WAD cyanide content entering the tailings impoundment,
thereby minimizing the toxicity effects of cyanide on wildlife, and significantly reducing
the potential for generation of leachate containing unacceptable levels of metals and
cyanide.
4. Elimination of a lining requirement in many applications.
5. Reduction of total cyanide in mine backfill to acceptable levels, thereby eliminating the
need for wash plants in certain instances.
6. Reduction of total cyanide and metals concentrations in the decant water and associated
cyanide containing wastewaters, significantly decreases the costs, while increasing the
reliability and performance of downstream treatment processes.
7. Minimizing generation of undesirable treatment by-products such as ammonia and

cyanate which exhibit their own inherent toxicity and may require significant capital
outlays for treatment.
The need for development of treatment processes for recovery of cyanide is essential to the
success of current and future mining operations. The requirement stems from concerns over the
volatility of the gold price and the realization that more stringent environmental regulations will be
developed restricting the concentrations of cyanide discharged into tailings impoundments and
remaining in solid wastes.

The best application of cyanide recovery is as a pre-treatment process prior to discharge of

tailings into an impoundment. The operational problems and costs associated with achieving high
treatment efficiency under low pH conditions minimize its value as a primary treatment
alternative. It is best suited for reduction of WAD and total cyanide to levels in the range of 5-20
mg/l. By lowering the level of metals and cyanide requiring downstream treatment, lower effluent
levels can be reached.
The impoundment into which the tailings are discharged should be designed to enhance cyanide
degradation, thereby minimizing downstream treatment requirements. If downstream treatment of
decant water is required prior to discharge to a surface water, conventional chemical or biological
treatment should be employed as these processes are best suited for this purpose. The use of
chemical or biological treatment for slurries is unwarranted or impractical in most cases from both
an environmental and economic standpoint. The next section details the approach taken by
Cyprus Gold to develop the first full-scale cyanide recovery process for the tailings slurry at the
proposed Golden Cross Mine.
5.2 Bench and Pilot Plant Scale Investigations
A series of bench scale laboratory tests were first utilized in the study of cyanide recovery from
slurries. A schematic of the laboratory apparatus is presented on Figure 4. The slurry utilized
was obtained from associated metallurgical tests. The chemistry of the tailings slurry and the
experimental results are presented in Table 6. The pH of the slurry was lowered into the proper
range with sulfuric acid, utilizing a 2.0-hour stripping period, and reneutralization with lime to a
pH of about 9.5 - 10.0.
These experiments completed at the Department of Science and Industrial Research (DSIR) in
Wellington, New Zealand, were conducted to verify the effectiveness of the process, but not to
optimize chemical usage or obtain design information. The results indicated that WAD cyanide
levels of 218 mg/l could be reduced to less than 10.0 mg/l. The increase in total cyanide was due
to solubilization of iron and formation of the stable iron cyanide complex. The change in
chemistry noted indicated the need to examine each application and each slurry individually to
determine potential changes in the slurry chemistry. An overall removal of cyanide of greater than
95 percent was achieved. The apparatus simulated a complete mix reactor. Air flow rates of 80
and 100 L/min were employed along with 10 L slurry samples.
Employing the data and basic knowledge of the process, a continuous flow pilot plant program
was designed to investigate the recovery of cyanide using either complete mix reactors in series
or stripping towers.
The pilot plant program was undertaken to verify the laboratory results and to obtain the
necessary design information for the full-scale cyanide recovery system. The slurry used in the
pilot plant study was obtained from the Martha Hill Gold Mine located in the town of Waihi,
New Zealand.

Figure 4: The Cyanide Recovery Laboratory Apparatus

Table 6
Chemistry Of Tailings Slurry Before And After Cyanide Recovery
Before After Cyanide Recovery

(1)
Parameter Cyanide Recovery Trial 1 Trial 2
pH (in pH units) 10.4 9.7 10.2
Total Alkalinity (as CaCO3) 575 170 169
-
Total CN 218 29.4 24.6
-
WAD CN 213 7.4 6.8
Total Hardness (as CaCO3) 307 2170 2030
Sulfate 360 2525 2350
SCN 34 37 38
As 0.8 0.8 0.7
Ca 123 869 814
Cd <0.01 <0.01 <0.01
Cr 0.02 <0.02 <0.02
Co 0.16 0.33 0.30
Cu 4.7 6.0 6.1
Fe 1.3 8.7 6.7
Pb <0.1 <0.1 <0.1
Mn 0.01 0.02 0.02
Hg 0.0155 0.0004 0.0001
Ag 0.15 0.04 0.04
Zn 0.64 0.01 0.06
Air Flow (L/min) ------ 80 100

The slurry exhibited chemical and physical characteristics similar to those anticipated at the
Golden Cross Mine and provided an excellent continuous untreated feed for the pilot plant
program. The form of the WAD cyanide was predominantly free and a basic pH was selected for
the volatilization process.
In the first phase of the study, the use of multiple complete mix reactors in series was
investigated, along with various aeration periods and air flow rates. Course bubble flexcap
diffusers were used to facilitate recovery of free cyanide and to minimize buildup of total
dissolved solids and precipitates
The results of the aeration basin studies are summarized in Tables 7 and 8. At slurry feed rates
3 3 2
ranging from 0.5-2.2 m /hr, air flow rates ranging from 2.4-6.0 m /m min, aeration periods
ranging from 138-312 minutes, and a slurry depth of 1.3m, WAD cyanide was reduced from 150-
230 mg/l to 15-67 mg/l. The results in Table 8 indicated that in multiple baffled systems of 3-5
complete reactors, the bulk of the cyanide removal occurred within the first hour of aeration
regardless of air flow, pH, or influent cyanide concentrations. However, there was a marked
difference in relative cyanide removal within the first hour depending on the air flow rate. No
mechanical problems were encountered with the equipment or diffusers although certain
deficiencies were noted in the actual battle construction. No buildup of chemical precipitates
were noted.
In the second phase of the study, the recovery of cyanide from slurries was investigated using a
packed tower. A schematic of the tower is presented in Figure 5. The tower was packed with
about 3m of either 50 or 75mm plastic media. The influent distribution system consisted of a
ceramic multiple weir trough assembly and a demister. The media was supported by a multiple
beam ceramic gas injection plate. The stripping column was about 0.5m in diameter and 6m in
height. The parameters investigated included mass transfer efficiency, media size, air to liquid
ratios, flooding characteristics, cyanide removal efficiencies, and required packing height. A
summary of the tower performance is presented in Table 9.

Table 7
Results Of The Continuous Flow Pilot Plant
Study Using Complete Mix Reactors
Slurry Feed Influent No. of Total Aeration Effluent

Rate Influent WAD CN- Air Flux Slurry Depth Reactors Period WAD CN-
3
Trial (m /hr) (pH) (mg/l) m3/m2/min (m) In Series (min) (mg/l)
1 1.7 9.6 230 4.5 1.3 1 138 67
2 1.7 9.6 150 4.5 1.3 1 138 43
3 2.2 9.6 228 4.6 1.3 1 106 67
4 2.2 9.7 228 3.9 1.3 1 106 67
5 1.7 9.7 198 4.4 1.3 3 138 60
6 1.8 9.7 195 4.5 1.3 3 130 52
7 2.2 9.8 168 2.4 1.3 3 106 84
8 2.2 10.0 182 4.5 1.3 5 92 61
9 0.5 10.0 207 4.5 1.3 5 312 26
10 0.5 10.0 157 2.8 1.3 5 312 28
11 0.5 10.0 198 4.5 1.3 5 312 23
12 0.5 10.0 170 4.5 1.3 5 312 22
13 0.5 10.0 203 4.5 1.3 5 312 23
14 0.5 10.0 179 6.2 1.3 5 312 16
15 0.5 10.0 171 8.8 1.3 3 187 16
16 0.5 9.9 161 4.5 1.3 5 312 19
17 0.5 9.0 176 6.0 1.3 5 312 15

Table 8
Results Of The Continuous Flow Pilot Plant
Study Using Complete Mix Reactors
Influent Air Flux Complete Mix Aeration Period

Effluent
CN- m3/m2/min Reactor Stage (min) CN-
198 4.5 1 63 33
2 125 31
3 187 27
4 250 25
5 312 24
179 6.2 1 63 21
2 125 20
3 187 17
4 249 18
5 312 14
171 8.8 1 63 16
2 125 15
3 187 16
Table 9
Pilot Plant Stripper Tower Test Results
Test Run No. 1 2 3 4 5 6 7 8

Slurry Flow (m3/hr) 2.37 2.37 1.94 2.17 2.54 2.1 2.21 2.33 239
Air Flow (m3/hr) 845 845 839 839 839 2126 2126 1484 1400
No. of Tower Passes 1 1 1 1 1 1 1 1 2
Air/Liquid Ratio 357 357 432 387 330 1012 962 637 586
Influent WAD CN- 182 182 156 166.4 166.4 1924 192.4 197.6 19.1
-
Effluent WAD CN 36.6 24.5 45.1 23.5 22.7 15 13.7 18.3 5.6
Test Run No. 9 10 11 12 13

3
Slurry Flow (m /hr) 236 245 4.1 4.0 4.17 4.0 3.9 3.7 5.0 4.6
3
Air Flow (m /hr) 1615 1615 2137 2137 2581 2581 1364 1364 1682 1682
No. of Tower Passes 1 2 1 2 1 2 1 2 1 2
Air/Liquid Ratio 684 659 571 534 619 645 349 369 336 365
-
Influent WAD CN 223.6 22.0 174 25 193 22 179 35 184 35
Effluent WAD CN- 23.9 6.0 29 7.0 26 7.0 43 13 40 14

Figure 5: Schematic of the Stripping Tower

At air to liquid ratios of about 500-700, influent WAD cyanide concentrations ranging from 174-
224 mg/l were effectively reduced to <10.0 mg/l in two passes of the tower packed with the
75mm media. With the 50mm media, similar results were obtained at air to liquid ratios <500.
The goal of the studies was to reduce WAD cyanide to <10.0 mg/l, which was achieved. Pressure
drops of about 100mm water gauge were measured through the 3m of 50mm mass transfer media.
Schematics for the layout of the full-scale Cyanisorb Process using either three complete mix
reactors in series or two stripping towers are presented in Figures 6 and 7. Based on a
comparison of performance versus cost and ease of operation, the use of towers were selected as
the preferred process configuration. The preferred configuration involves two single pass towers
about 4.0m in diameter and 10.0m in height operated in parallel, with a third tower as a stand-by
unit. Testing continues to identify any long-term mechanical or physical problems with the
process. Following cyanide removal, the slurry pH will be readjusted to 9.5 to precipitate free
metals, prior to disposal of the slurry in the impoundment.
Figure 5: Schematic of the Cyanide Recovery System Employing Towers

Figure 7: Schematic of the Cyanide Recovery System Employing Complete Mix

Reactors
In conjunction with development and design of the Cyanisorb process, additional experiments and
calculations were prepared to evaluate the impact of the cyanide recovery circuit on cyanide and
metals levels in the tailings impoundment and associated leachates.
The effect of cyanide recovery on cyanide concentrations at various points in the Golden Cross
water management system are summarized in Table 10. These calculations were prepared by
M.P.A. Williams and Associates, located in Melbourne, Victoria, Australia (9). The results of the
analysis indicated that total cyanide levels entering and exiting the tailings impoundment were
reduced from 186.0 to 30.0 mg/l and 42.0 to 9.0 mg/l, respectively. In addition, the total cyanide
in the untreated feed to the wastewater treatment facility was reduced from 14.0 mg/l to about
5.0 mg/l. Prior to incorporation of the cyanide recovery system into the metallurgical process a
tailings washing system was required, which was subsequently eliminated at a substantial cost
savings to the project.

Table 10
Estimated Cyanide Concentrations With And Without
Cyanide Recovery At The Golden Cross Mine
Cyanide Concentrations(2)
Without Cyanide Recovery With Cyanide Recovery

(1)
Solution Total CN- Total CN- WAD CN-
Tailings slurry to impoundment 186 30 10
Pumped decant from pond (3,4) 42 9 <.01
Mine backfill going underground ---- 11 3.7
Mine water pumped out ---- 1.2 0.39
Influent to water treatment plant 14 4.7 0.06
(1) Values taken from Golden Cross water management system model.
(2) All values in mg/L, unless otherwise stated.
(3) A first order decay rate was utilized in conjunction with dilution to calculate cyanide
values. The decay rate for total cyanide used prior to cyanide recovery was 0.0014/hr. The
total cyanide values after cyanide recovery were calculated using dilution only, while a decay
rate of 0.006/hr was used for WAD cyanide.
(4) The residence time in the pond before and after cyanide recovery was 14.7 and 56.4 days,
respectively.
In addition, the impact of cyanide recovery on the anticipated chemistry of the tailings seepage
was investigated through a series of laboratory decay experiments conducted by Stuart Miller and
Associates, located in Sydney, Australia (10). The expected chemistry of the tailings liquor and
seepage with and without cyanide recovery is presented in Table 11. The results of cyanide decay
and metals attenuation in entrained tailings liquor are presented in Table 12. By reducing WAD
cyanide in the tailings liquor, the free metals formed quickly precipitated into the tailings mass.
As a result, the potential for elevated cyanide and metals levels in the seepage was significantly
reduced. The improvement in seepage chemistry reduced long-term treatment requirements after
mine closure and monitoring requirements, as well as other environmental liabilities.
Figure 8 presents the anticipated cyanide decay curves for the decant water and entrained tailings
liquor at the Golden Cross Mine. By lowering the WAD cyanide levels entering the
impoundment, very low levels of residual metals and cyanide will result, minimizing the impacts
on wildlife and groundwater, while significantly reducing downstream treatment requirements.
The expected WAD cyanide levels will be more than an order of magnitude less than typical
values found in decant and pore waters.

Table 11
Expected Chemistry Of Tailings Liquor
And Seepage At The Golden Cross Mine
Tailings Liquor Tailings Seepage

Without Cyanide With Cyanide Without Cyanide With Cyanide
(1)
Parameter Recovery Recovery Recovery Recovery
pH 10-11 9.5-10 9.5-10 8.0-9.5

Hardness (CaCO3) 750 2000 ----- 2000
Alkalinity (CaCO3) 1000 200 300-500 ------
Sodium 400 400 300-400 300-400
Calcium 200-300 800 300-600 800
Sulfate 1000 2500 1000-2000 2500
Total CN 150-220 25-30 50 25-
30
WAD CN 150-220 5-10 20-30 <1.0
Cadmium <1.0 0.1 <0.005 <0.01
Chromium <0.02 <0.02 0.002-0.02 <0.02
Cobalt 0.1 0.3 0.1-0.5 0.25
Copper ------- ----- 5.0-10.0 <0.5-1.0
Iron 1.0-5.0 5-10 5 8-10
Lead 0.001-0.1 <0.1 <0.001 <0.1
Mangansese 0.05-0.1 <0.02 0.03-0.05 <0.1
Mercury 0.001-0.009 <0.0005 0.001-0.005 <0.0001
Nickel 0.01 0.05 ------- ------
Selenium 0.01-0.4 0.1 <0.05 ------
Zinc 0.5-3.0 0.01-0.1 2.0-4.0
0.1
SCN 30-40 30-40 ------- ------

Table 12
Cyanide Decay In Entrained Liquor Flollowing Cyanide Recovery (1)
Parameter Initial 1 Week 2 Weeks 4 Weeks 8 Weeks 12 Weeks

pH 10.2 9.7 9.1 9.8 9.8 9.3
SO4 2525 2525 2580 2530 2370
2390
Ca 858 858 858 858 808
805
Total hardness 2140 2140 2140 2140 2013
2008
(as CaCO3)
Total CN 29.4 29.4 31.3 25.5 27 26
WAD CN 6.8 6.6 5.5 3.8 2.1 1.51
Cd 0.1 <0.01 <0.01 <0.01 <0.01 <0.01
Co 0.33 0.25 0.2 ---- ---- ----
Cu 6 4.3 2.9 2.1 0.63 0.16
Fe 8.7 8.9 9 9.3 9.3 9.5
Zn 0.01 0.03 0.01 <0.01 0.01 0.01
Pb <0.1 <0.1 <0.1 <0.1 ---- ----
Mn 0.02 0.02 <0.01 0.01 0.02 0.02
Ag 0.04 0.01 0.01 0.02 0.02 0.02
Cr 0.02 ---- ---- <0.02 ---- ----
Hg 0.0002 <0.0001 <0.0001 <0.0001 ---- ----
Cyanide Decay In Tailings Decant Following Cyanide Recovery (1)

Exposure Time pH Total CN- WAD CN-
Initial 10.2 29.4 6.8
1 day 8.0 29.4 ----
3 days 8.2 30.0 ----
7 days 8.3 30.0 ----
14 days 8.0 31.9 ----
28 days 7.3 32.0 0.33

Figure 8: Cyanide Decay Characteristics in Decant and Pore Waters
The results of the laboratory and pilot plant investigations have proven the viability of the
Cyanisorb Process for recovery of cyanide from slurries. In addition to the recovery of cyanide,
there were further environmental advantages relating to the disposal of tailings and the potential
for groundwater contamination. The next section of the paper examines the economic aspects of
cyanide recovery from solutions and slurries.
6.0 ECONOMICS OF CYANIDE RECOVERY PROCESSES
In applications where treatment of tailings prior to disposal is warranted, there are several
economic advantages to cyanide recovery systems. First, the operating costs associated with
chemical treatment are eliminated, while second, a useful and expensive reagent (i.e. cyanide) is
recovered. The cost recovery more than offsets the cost of the cyanide recovery system. Third,
the cyanide recovery systems are simple in design and operation, thereby minimizing operator
requirements and the degree of automated control. Fourth, the capital costs of cyanide recovery
systems are less than for either chemical or biological treatment facilities. Incorporation of a
cyanide recovery system into the metallurgical circuit reduces downstream cyanide and metals
levels, and thereby further reduces the capital and operating costs of treatment by reducing the
size of the treatment facility and the period of time treatment is required following mine closure.
The economic advantages are in addition to the environmental advantages discussed in the

previous section.
Examination of the proposed Golden Cross cyanide recovery system provides an excellent
example of the economics of the process (11). The anticipated capital cost for the Cyanisorb
Process is about $(NZ) 2,200,000. There are several direct capital cost benefits due to
incorporation of cyanide recovery. First, there is no need for the backfill wash plant which would
have cost about $(NZ) 600,000. Second, there are substantial reductions in downstream
treatment requirements associated with the hydrogen peroxide treatment facility.
The excess process water accumulating in the decant pond will be treated and discharged to a
local river. By incorporating cyanide recovery, there is a significant decrease in untreated cyanide
concentrations, thereby decreasing chemical costs. The reduction in cyanide minimizes the
ammonia formed via natural attenuation and chemical treatment to such an extent that nitrification
is not required. These modifications in treatment capacity reduce the original capital cost estimate
for cyanide, metals, and ammonia treatment from about $(NZ) 6,300,000 to $(NZ) 3,700,000.
The overall capital cost savings is $(NZ) 3,200,000 compared to the $(NZ) 2,200,000 cost of the
cyanide recovery system.
Based on the pilot plant results, estimates of the cost of cyanide recovery have been prepared on a
per tonne basis. The cost per day to operate the cyanide recovery process including sulfuric acid,
power for the air supply, caustic, and lime is $(NZ) 1.10/tonne. The cost assumes a power
requirement of 150 kw at a cost of $(NZ) 0.08/kw-hr, and chemical costs 3 to 5 times higher than
in the United States.
In terms of operating cost credits, there is a return for recovered cyanide and caustic contained in
the scrubber solution. Assuming a 90 percent recovery from a 200 mg/l WAD cyanide slurry, the
operating cost credit is $(NZ) 2.17/tonne. The calculations assumed a sodium cyanide cost of
$(NZ) 3.30/kg. The cyanide usage rate is low and assuming a more realistic cyanide
concentration of 300 mg/l and a 90 percent recovery, the operating cost credit increases to $(NZ)
3.23/tonne of ore processed.
Introduction of the cyanide recovery system reduces the downstream WAD cyanide concentration
requiring treatment from about 45.0 mg/l to 4.0 mg/l. On the basis of hydrogen peroxide
consumption alone, there is a decrease in operating chemical costs of $(NZ) 1.08/tonne, assuming
a peroxide cost of $(NZ) 1.56/kg for 50 percent solution, and a 250 percent theoretical excess of
peroxide.
The net operating cost benefit for the cyanide recovery process is $(NZ) 2.15/tonne of ore (i.e.
$2.17 + $1.08 - $1.10) or $(NZ) 1,550,000 for a 720,000-ton-per-year operation. The net
operating cost savings amounts to over $(NZ) 12,000,000 during the eight-year life of the mine.
There are additional cost savings due to decreases in operating staff and other chemicals utilized
(i.e. copper sulfate) in the hydrogen peroxide treatment facility. Furthermore, there is no need to
line the impoundment as would be case in many installations in the U.S. Lining of an
impoundment designed for the Golden Cross Mine would require a several million dollar
expenditure, and would be very difficult to install due to the terrain. The anticipated capital
operating cost savings are significant in an application of low cyanide containing slurries and high

chemical and power costs, with greater benefits realized in more typical mining installations.
The operating costs associated with Golconda C.R.P. including chemicals, power, and labor were
$(AUS) 1.07/tonne, with a cost recovery of $(AUS) 2.13/tonne of solution treated. Nearly 70
percent of the cost savings were attributed to the additional gold recovery following cyanide
recovery. These values are quite consistent with those anticipated at the Golden Cross Mine.
Similar cost estimates were recently completed for two existing mining operations in the United
States. The first mine is a 15,000 ton/day operation exhibiting a slurry flow of about 5,000 gpm
and a free cyanide level of 125 mg/l. The estimated capital and operating costs were $3,500,000
and $0.31/ton of ore processed, respectively. A summary of the costs are presented in Tables 13
and 14. Using a cost of $0.70/lb for NaCN and a 90% recovery, the recoverable value of cyanide
was about $0.59/ton. The net recoverable value was about $0.28/ton or $1,200/day. These
calculations did not take into account either the mass of cyanide present in the recycled and
untreated decant water, or the royalty fee. The corresponding operating costs for chemical
treatment would have ranged from about $1.00-$1.50/ton.

Table 13
Estimated Capital Cost For Cyanide Recovery
Item Total Cost

Stripping Towers $ 125,000
Absorber Towers 125,000
Tower Internals
Demisters 100,000
Distributers 100,000
Support Gratings 50,000
Packing 250,000
Reactors 100,000
Mixers 60,000
Fans 75,000
H2SO4 Feed System + Storage 50,000
Lime Feed System + Storage 105,000
NaOH Feed System + Storage 20,000
Subtotal Equipment Costs $1,160,000

Installation Factor x 3.0
TOTAL CAPITAL COST $3,480,000

Table 14
Operating Expenses
Item Cost per Tone of Ore

(1)
H2SO4 $ 0.09
(2)
CaO $ 0.04
(3)
Electrical $ 0.02
(4)
NaOH $ 0.16
(5)
Operator $ 0.01
$ 0.31
(1)
Based on $0.04/lb for 93% H2SO4.
(2)
Based on $0.04/lb CaO.
(3)
Based on the current mine price of $0.04/kw
-hr.
(4)
Based on 48% caustic solution at $0.18/lb.
(5)
Based on $35,000 per year.

The second mine is a 3,500 ton/day operation exhibiting a slurry flow of 1,100 gpm and a wad
cyanide level of about 600 mg/l. The estimated capital and operating costs were $2,000,000 and
$0.73/tone of ore processed, respectively. A summary of the costs are present in Tables 15 and
16. Employing a cost of $0.70/lb for NaCN and a 95% recovery, the recoverable value of cyanide
was $2.83/ton of ore processed. The net recovered value was $2.10/ton or $2,600,000/year. The
corresponding costs for chemical treatment were several dollars per ton of ore processed.
Table 15
Estimated Capital Cost For Cyanide Recovery
Item Total Cost
Stripping Towers $ 75,000
Absorber Towers 75,000
Tower Internals
Demisters 60,000
Distributers 60,000
Support Gratings 30,000
Packing 100,000
Reactors 35,000
Mixers 50,000
Fans 30,000
H2SO4 Feed System + Storage 25,000
Lime Feed System + Storage 100,000
NaOH Feed System + Storage 15,000
Subtotal Equipment Costs $ 655,000

Installation Factor x 3.0
TOTAL CAPITAL COST $1,965,000

Table 16
Operating Expenses
Item Cost per Tone of Ore

(1)
H2SO4 $ 0.20
(2)
CaO $ 0.07
(3)
NaOH $ 0.40
(4)
Electrical $ 0.03
(5)
Operator $ 0.03
$ 0.73
(1) Based on $0.05/lb for 93% H2SO4.

(2) Based on $0.04/lb CaO.
(3) Based on 48% NaOH soltion of $0.18/lb.
(4) Based on the current mine price of $0.04/kw
-hr.
(5) Based on $35,000 per year.
Based on the estimated operating costs for the two mines, an average cost of about $0.50/ton of
ore processed was obtained. There was an economy of scale for capital costs which ranged from
about $575/ton for the 3,500 ton/day mine to about $250/ton for the 15,000 ton/day mine.
These examples clearly demonstrate the economic and environmental viability of the cyanide
recovery process. The economic advantages when coupled with the environmental advantages
yield an efficient pre-treatment alternative for slurries or solutions containing cyanide.
7.0 THE FUTURE OF CYANIDE RECOVERY
As mentioned previously, the real advantage of cyanide recovery from slurries includes the
lowering of cyanide and metals levels entering a tailings impoundment, thereby minimizing
downstream treatment and the potential for surface and groundwater and groundwater
contamination.
Cyanide recovery is not well suited as a primary treatment process, when very low levels of
residual cyanide are required (i.e. <1.0 mg/l), although in many instances these levels are
achievable. However, by lowering the initial cyanide level entering an impoundment and
enhancing natural attenuation, downstream cyanide values are lowered, allowing for more
effective and reliable treatment. By lowering the downstream cyanide level, conventional
chemical or biological treatment processes can be employed to reduce the residual concentrations,
which in most instances are not achievable when treating the higher influent cyanide and metals
levels.

With increasing concern over groundwater and wildlife issues, there will be increasing pressure to
more closely regulate cyanide entering tailings impoundments. Cyanide recovery processes solve
the problem in an economically and environmentally acceptable manner. In addition, cyanide
recovery allows the use of higher cyanide levels during metals recovery, thereby increasing the
flexibility of existing or proposed metallurgical circuits.
Once a solution or slurry is deposited in an impoundment, every attempt should be made to

configure the impoundment to enhance natural degradation, thereby reducing the concentrations
of cyanide and metals requiring treatment. The design of tailings impoundments to enhance
natural attenuation or degradation has been practiced successfully in Canada for several years.
In the event excess decant water must be discharged and natural attenuation alone or in
conjunction with cyanide recovery cannot yield an acceptable effluent, additional treatment is
required. In this instance, the residual cyanide and metals concentrations will have been lowered
sufficiently to allow the use of conventional biological or chemical treatment to achieve the
desired effluent quality. The first choice is biological treatment, where applicable, due to its
simplicity, performance, and low operating costs. In the event biological treatment is not
practical, due to low temperatures, then selection of one of the chemical treatment processes is
necessary (i.e. hydrogen peroxide, sulfur dioxide, or chlorine). The use of conventional chemical
treatment processes are expensive when treating slurries or solutions containing elevated cyanide
levels. In addition, process performance is often not sufficient to reduce elevated influent
concentrations to environmentally acceptable levels. However, these processes are well suited as
downstream treatment alternatives once the cyanide and metals concentrations have been reduced
through cyanide recovery.
Water management and wastewater treatment at a mining operation demands an integrated

approach, to minimize the generation of poor quality water requiring treatment. No single
solution can solve every water quality problem at a mining facility.
There are several additional cyanide recovery processes on the market or under development. In
most cases the processes involve an intermediate cyanide concentration step (i.e. ion exchange)
which significantly increases both the cost and complexity of the recovery operation. Many of
these processes are in the pilot plant or bench scale testing phase and have not been utilized in a
full-scale design.
The recovery of cyanide from solutions is a well established process, resulting in substantial
capital and operating cost savings while minimizing persistent cyanide disposal and environmental
problems. Attention has shifted to the recovery of cyanide from slurries, as this application
provides significant environmental as well as economical benefits.
Following detailed laboratory and pilot plant evaluations, the recovery of cyanide from slurries
has been demonstrated. The information would be employed in the first full-scale process for the
recovery of cyanide from slurries at the Golden Cross Mine operated by Cyprus Gold of New
Zealand. The Cyanisorb Process for which a patent is pending would be in operation at the
mining facility in the fall of 1990.


8.0 REFERENCES
(1) Lawr, C.W., "Cyanide Regeneration or Recovery as Practiced by the Compania

Beneficiadore de Pachuca", Technical Report No. 208-B-20, American Institute of
Min., Metall., and Pet. Engineers, 1929.
(2) Davies, D., Robertson, D.J., Kirkwood, W., and Goodman, J.,"Cyanide and
Regeneration Plant and Practice at Flin Flon", Trans. Can. Inst. Min. Metall., Vol.
XLIX, pp. 130-142, 1946.
(3) McQuiston, F.W. and Shoemaker, R.S, "Gold and Silver Cyanidation Plant Practice
Monograph", Amer. Inst. Min., Metall., and Pet. Engineers.
(4) Dorr, J., Cyanidation and Concentration of Gold and Silver Ores, McGraw Hill, New
York, 1936.
(5) Seeton, F., "The application of Cyanide Regeneration to the Treatment of Refractory,
Complex, or Copper Bearing Ores as Practiced by Compania de Real Del Monte Y
Pachuca", Pachuca, Hidalgo, Mexico, Denver Equipment Company, journal source
unknown, ca. 1950.
(6) McNamara, V., "Acidification Volatilization Reneutralization Treatment Process for

Decontamination of Canadian Gold Mill Effluenta", CANMET, Energy, Mines and
Resources Report MRP/MSL 78-223, 1978.
(7) Avedesian, M., Spira, P., and Kanduth, H., "Stripping of HCN in A Packed Tower",
Can. J. Chem. Engineering, Vol. 61, pp. 801-806, December 1983.
(8) Kitney, M., "Cyanide Regeneration From Gold Tailings-Golconda's Beaconsfield

Experience", Perth Gold '88 Conference, pp. 89-93, 1988.
(9) Williams, P., M.P.A. Williams and Associates, Melbourne, Victoria, Australia, Personal
Communication.
(10) Miller, S., Stuart Miller and Associates, Sydney, Australia, Personal Communication.
(11) Goldstone, A., Environmental Coordinator, Cyprus Gold New Zealand, Waihi, New
Zealand, Personal Communication.

ACKNOWLEDGEMENTS
The authors would like to acknowledge the following individuals for their input during the
project. Alan Fricker and Barry Judd of the Department of Science and Industrial Research in
Wellington, New Zealand, for their aid during the initial laboratory bench-scale studies. David
Peterson of Harrison Grierson Consultants in Aukland, New Zealand, for his contribution on the
design of the cyanide reabsorption system. Tony Truman, Max Wilkinson, and Greg Berti of
Davy McKee in Melbourne, Australia, for their assistance in the design and operation of the
continuous flow pilot plant evaluations. Waihi Gold Company for supplying the tailings slurry for
the studies. Gene Andrews, Bellevue, Washington, for his estimates of capital and operating costs
for the Canadian cyanide recovery system, and Bill Byers of CH2M Hill in Corvallis, Oregon, for
his insight and expertise in the field of mass transfer technology.

CYANISORB CYANIDE RECOVERY PROCESS
DESIGN, COMMISSIONING AND EARLY PERFORMANCE
Prepared By:
Adrian Goldstone
Terry Mudder, Ph.D.
Originally presented at the Northwest Mining Association Annual Meeting, Spokane, Washington
(USA) in December 1992 and subsequently published in The Cyanide Monograph, First Edition,
Mining Journal Books, London, England, United Kingdom, June 1998
Cyanisorb Cyanide Recovery Process Design, Commissioning and Early Performance
ABSTRACT
Cyprus Minerals Golden Cross project in New Zealand has been the site of the first recent
commercial application of a cyanide recovery process on gold tailings. The process, known as
CYANISORB, is in use at Golden Cross due to stringent environmental requirements on the
project and the economic advantages cyanide recycling offered. The CYANISORB plant was
commissioned in December of 1991 and has been operating successfully since then.
Commissioning performance was well within expectations and performance since then has
exceeded expectations.
The plant relies on acidification of the tails into the slightly acidic range and agitation for 10-15
minutes, followed by air stripping in a packed tower. The loaded air is scrubbed in caustic
solution in a second packed tower prior to being recycled into the stripping tower. The absorbed
cyanide and caustic solution is returned to the leach plant. The tailings are re-neutralized and
disposed of into a tailings pond.
The plant, although not full optimized, is stripping 90% of the 220ppm WAD cyanide from the
tailings. All process parameters are within those observed from pilot and design studies and
reagent consumption is currently being optimized. Only minor design difficulties have been
encountered and all have been, or can be, corrected. A second plant is performing similarly well
at the NERCO De Lamar mine in Idaho.
1.0 INTRODUCTION
The CYANISORB technology was developed by Cyprus Gold New Zealand Ltd. for the Golden
Cross joint venture (Cyprus Gold N.A. and Todd Corporation of N.Z.) during 1988 and 1989.
CYANISORB was developed by the project team in response to stringent environmental
standards on tailings dam design and water discharge criteria. The process was fully tested at
laboratory and pilot scale.
Full scale design was completed in 1989 and 1990 and the prototype full scale facility was built at
Golden Cross (GC) in 1990 and 1991. The plant was commissioned by the GC team in December
of 1991 and has been operating continuously since then. As the full implications and benefits of
the technology became apparent Cyprus embarked on a patenting and licensing program. A
second plant is now operating under license to Cyprus at the NERCO De Lamar silver mine in
Idaho in the U.S. The aim of this program has been to scale up the successful pilot program to a
full scale design that is economically and technically feasible and to build and commission the
prototype plant so that its performance is within expectations based on the test program.
242 A. Goldstonee & T. Mudder

2.0 SETTING
Cyprus' Golden Cross project is on the east side of the North Island of New Zealand about 100
km S.E. of Auckland city. The operation consists of an open pit/underground mine with a
conventional crushing, grinding, and CIL/CIP circuit. Gold and silver stripped from carbon is
recovered through a zinc precipitation circuit. Tailings are treated in a CYANISORB plant to
recycle residual cyanide to the CIP plant prior to discharge of tailings to an impoundment.
Golden Cross is in an area of high environmental sensitivity with strong local support for stringent
control over the mining industry. The site borders a national forest park, and a year round
positive water balance requires constant discharge of treated water to a local trout fishery.
Early in the permitting and regulatory phase engineering was started, particularly in the area of
water and environmental management and waste disposal. It was in this setting that it became
apparent that some form of tailings detoxification was going to be necessary. Technical and
economic feasibility of downstream water treatment and of tailings disposal and the protection of
groundwater hinged on maintaining a relatively low tailings cyanide concentration at deposition.
A number of tailings chemical detoxification alternatives were considered and evaluated. When
overall performance and economics of each was considered it was decided to commence
development of recycle technology. The historically well known Acidification Volatilization
Reneutralization (AVR) process (McNamara 1978) was chosen for development and application.
The process had not seen recent use or development and had only been applied to clear solutions
and not to slurries or in the pH range proposed. However, its basic simplicity and probable cost
efficiency made it the most attractive alternative.
A successful development program including bench and pilot scale testing followed. The decision
to include the revised and reconfigured process, named CYANISORB, was taken in 1990. The
full scale plant was constructed as an integral component of the metallurgical plant and
commissioned in December 1991. The reasoning leading up to this development work and
description of the perceived advantages is given in Williams & Goldstone (1989). A detailed
analysis of the development work, testing and pilot program and performance predictions are
given in Mudder & Goldstone (1989). This paper describes the project at the detailed engineering
phase and follows the commissioning and first year performance of the full scale plant. A second
plant was commissioned at the De Lamar silver mine in Idaho in May 1992. The development
history and justification for the decision to build this plant is similar to that for GC. The De
Lamar CYANISORB plant is retrofit to an existing 3000 tpd CCD Merrill-Crowe plant.
3.0 PLANT DESIGN CRITERIA
The generalized plant feed and effluent design criteria for the GC CYANISORB plant are shown
in Table 1. The effluent criteria are driven primarily by regulatory requirements. Apart from
these effluent quality criteria the other primary design requirement was to build a plant that was
inherenty safe to operate and forgiving should component failure occur. The secondary criterion
was to build a plant which was simple to operate and reliable.

Table 1
Golden Cross Cyanisorb Feed & Effluent Criteria
Item Units Feed Effluent
Ore Throughput tonnes/hr 90

3
Slurry Flow Rate m /hr 213
Slurry Density % 34
Slurry SG /l 1.26
Slurry pH pH units 9.5-11.0 9.0-9.5
Slurry Viscosity cP 500
Particle Size P80 micro m 38
3
[CN WAD] Max g/m 300 30
3
[CN WAD] Normal/Design g/m 200 20
3
[Cu] Max g/m 10
At the conclusion of the pilot study a preferred configuration had been chosen for the application
of the technology at GC. The plant had also been operated across a range of conditions that
covered those applicable to GC and data gathered from operating regimes covering an acceptable
range of performance conditions. Operating experience with the pilot plant also assisted with the
design of proper safety features and systems.
A generalized flow sheet is shown in Figure 1. The basic configuration chosen is described
below. Acidification is carried out in a stirred tank reactor to allow mixing and reaction time.
H2SO4 is used as the reagent. The slurry is then pumped to towers, packed with 50mm plastic
pall rings. The slurry falls through the packing and counter current air is drawn through an inlet
at base of tower. Recycle air is used. Absorption of the HCN from the air is carried out in a
second, proprietary, tower packed with high efficiency media and with circulating NaOH as the
reagent. Discharge air returns to the stripper. Tailings reneutralization is carried out in stirred
tank reactors to allow for control to required pH. Lime is used as the reagent. The system is
maintained under negative pressure, with a bleed maintained by small independent fans. All tanks
are covered and air swept.
The GC plant is designed with two independent stripping - absorption trains. A single
acidification system feeds both stripper towers and each tower discharges to the same "bottom"
tank. The bleed air system is shared and each absorber tower discharges regenerated NaCN to a
single regenerated cyanide tank. The detailed process flow diagram for GC is shown in Figure 2.

Figure 1: Generalized Flow Sheet

Figure 2: Golden Cross Process Flow Diagram (by Permission of Davy McKee)

The acidification and air stripping section of the system were those that received the most
development attention. Pilot plant data was used to generate constants for use in design from
theoretical principles (Perry 1984). The data was also used in parallel to design the full scale plant
using empirical methods. The two methods produced consistent full scale design requirements
and criteria, after margins for variability were properly applied. This consistency and the success
of the pilot plant operation allowed confidence in our ability to scale up from pilot to commercial
application. Final design was, however, a function of this design approach and of comfort and
factors of conservatism for designers and operators. Some of the design and operating issues for
the system are described below.
4.0 PLANT DESIGN
4.1 Acidification
In this section sulfuric acid is mixed with the tailings slurry in an agitated tank to provide a
solution pH in the required range. The 98% acid is diluted to 10% prior to addition, as if higher
strength acid is added localized reactions quickly consume acid and overall acid consumption
increases. In the historical application of the AVR process, concentrated acid and low pH was
also found to lead to gypsum formation and scaling. At GC a pH of 7.0 to 8.0 is adequate for
stripping although this will vary for each application.
One concern in the acidification section relates to the possible attack of tailings solids by the acid
and loss of inherent neutralizing capacity or even initiation of sulphide oxidation in high sulphide
materials. This concern was tested using leaching trials conducted on pilot plant effluent and
found not to be an issue (Miller 1989). This is probably due to the diluted acid being added, and
to the pH range that the process works at (5.0-8.0). The pH change is restricted to the solution
component of the slurry and no evidence of attack on tailings solids has been observed from the
current process design. Acid consumption varies between slurries and needs to be tested under
the expected range of conditions and target pH. For the pH regime used at GC acid consumption
3
is in the range 1.2 to 1.5 kg/m of tailings slurry. The second function of the acidification stage is
- -
to allow sufficient reaction time for the formation of HCN from CN and the dissociation of CN
from its metal complexes. If sufficient time is allowed here, to maximize HCN formation,
stripping efficiency will be improved.
As with acid consumption, acidification time is dependent on specific tailings chemistry. The GC
plant allows an average of 10-15 minutes and the DeLamar plant 15-20 minutes. As the
proportion of CYANISORB treated water, used as mill make up from the tailings pond, increases
recirculating metal loads decrease. Thus in retrofit plants the chemistry of the slurry reporting to
-
the CYANISORB plant then exhibits decreasing levels of complexed CN . That is the level of
complexing with metals such as Zn and Cu decreases and the efficiency of the acidification section
improves. This is being demonstrated by the operation of the DeLamar plant (Hampton pers
comm 1992).

4.2 Stripping
In this section large volumes of air are contacted with thin films of the acidified slurry. The HCN
in solution in the slurry is extremely soluble and subject to strong hydrogen bonding and even
through HCN gas is very volatile, and most of the free cyanide present at pH<8 is present as HCN
there is still a significant barrier to overcome in stripping the dissolved HCN into the air.
The slurry is pumped to the top of a stripping tower and flows into a distribution system. The
effectiveness of this system in distribution system. The effectiveness of this system in distributing
the slurry evenly over the tower packing is critical to the success of the plant. Uneven
distribution, even if the slurry is redistributed in the packing, would reduce the effective stripping
height of the tower packing.
There is evidence from observation of the packing, however, that the slurry is not well distributed
by the packing itself and poor distribution at the top of the tower is reflected closely by
distribution at the bottom of the tower. If the slurry is concentrated into one vertical zone of the
packing, then slurry film depth on the packing is greater and much of the counter current air is not
in contact with slurry at all. Although poor distribution has been observed in both the GC and
DeLamar plants, this has not caused a problem due to the conservatism of the design. This is
discussed further in section 7.
The key design parameters for the tower itself are its cross sectional area, its packed height and
the type of packing chosen. Packing height and cross sectional area were assessed both
empirically from pilot plant data and using modern mass transfer theory by generating constants
from pilot data for use in mass transfer equations. Tower cross sectional area is determined
empirically by design slurry flux and the design air flux or the air:slurry ratio. Packing height is
-
determined empirically by observed stripping efficiency, feed CN concentration, and target
removals or residuals. In an empirical sense the difference between the pilot and full scale plants
was that the pilot plant used fresh air in the stripper while the full scale plant uses recycle air.
Recycle air has a residual of HCN which will theoretically reduce the "driving force" and lower
stripping efficiencies in the bottom sections of the tower.
The pilot plant was modified during the NERCO test work and now includes an absorber and
recycle air system. As figure 3 shows, however, this has little quantitative effect. Figure 3 shows
a representative stripping curve from the GC pilot data and theoretical efficiency with recycle air
(4ppm residual at stripper air inlet). These values are compared with a value calculated from the
NERCO test work (Omofoma & Hampton, 1992) and actual values from the two full scale plants.
Stripping performance is discussed more fully in the next section.
-
Mass transfer (transfer of gas from solution to gas phase) of the CN is affected by a number of
-
factors. As described already the form of the CN and the solution pH are major factors which
affect the concentration of HCN and its volatility. The volatility of HCN is theoretically related to
its Henry's Law Constant (HLC) which has to be derived from test data (Table 2, equation 1).
The HLC is also affected by several factors, including the viscosity of the liquid the gas is
dissolved in and the temperature, as well as hydrogen bonding and pH as described above.

Figure 3: Pilot & Actual Stripping Efficiencies

Table 2
Fundamental Mass Transfer Equations
EQUATION 1. Y*=Hx
Y*=HCN mole fraction in air at equilibrium
H=Henry's Law Constant atm/mole fraction
x=HCN mole fraction in slurry
and lnxi-lnx0=GH/Qt
xi=HCN mole fraction in inlet slurry

x0=HCN mole fraction in outlet slurry
G=Air flow rate g mole/hr
H=HLC
Q=Slurry Quantity g mole
t=Time hrs.
EQUATION 2. KLa=Na/hA xlm
3
KLa=Volumetric MTC kmole HCN/m hr
2
Na=Interphase mass transfer rate kmole HCN/m hr
h=Total stripping height m
2
A=Tower cross sectional area m
xlm=Log mean of driving force
0 0 0 0
=(x -x)2-(x -x)1/ln[(x -x)2/(x -x)1]
0
x =mole fraction HCN in slurry with equilibrium with air HCN
x=mole fraction HCN in slurry
1=Top of tower packing
2=Bottom of tower packing
EQUATIONS 3. C1=(L/G)(Dair/Dslurry)0.5
C2=[G2(a/E3)psi(mu)0.2]/DairDslurry9.8067
2
L=Liquid (slurry) rate kg/m s
2
G=Gas (air) rate kg/m s
3
Dair=Air density kg/m
3
Dslurry=Slurry density kg/m
3
a/E =Packing factor (for 50mm pall rings = 82/m)
mu=Slurry viscosity cP
psi=Dwater/Dslurry or1/slurry specific gravity
C1 and C2 are then used to find an operating point and estimate packing pressure drop.

Other factors which are ingredients in mass transfer are those that overcome the considerable
limitations to transfer from solution, i.e. turbulence, liquid:air contact period and mass ratios, and
the pressure maintained in the air:liquid contact environment.
It can be argued that theoretical mass transfer of CN WAD becomes less applicable lower in the
- -
packing as less of the residual CN is present as HCN and more is present as CN metal complex.
The mass transfer equations (Table 2, equation 2) and the calculation of constants such as Henry's
Law Constant do not recognize solution reactions such as the dissociation formation of HCN in
this system and calculate HCN transfer solely. In addition, the calculation of constants from the
experimental data is subject to variability in the data. When appropriate ranges are applied to the
constants a greater range of design possibilities emerge. Table 3 documents all of the relevant
theoretical and empirical design values finally chosen for the full scale plant and compared these
with the ranges used in the pilot plant. Also included are the averaged estimates of HLC and
Mass Transfer Coefficient (MTC) used in the design study.
The operation of the plant suggests that the air:slurry ratio can be considerably reduced from the
design value and that the liquid rate or slurry flux can be increased without any significant drop in
performance. At start up the GC plant was operated within the design ranges but since start up
there has been considerable variation in the operating parameters without unduly affecting process
performance. Packing type should be chosen to give the greatest stripping efficiency per unit
height and the lowest maintenance and operating cost.
The function of the packing is to create as much slurry surface area as possible and to create
conditions where high volumes of turbulent air can be passed over the slurry surfaces and through
the packing voids. The aim is to maximize mass transfer of HCN with minimum pressure drop.
Plastic pall rings were the chosen packing and ring diameter was evaluated in the pilot study.
Larger rings have the advantage of being less susceptible to mechanical blockage and being
subject to lower pressure drops and therefore lower operating costs and potentially lower
maintenance costs. Larger rings, however, have the disadvantage of having lower surface areas
and lower packing factors and ultimately lower mass transfer efficiency.
Pilot evaluation showed that smaller 50mm pall rings handled the slurry without any difficulty and
that pressure drops through the packing were within a reasonable range. There was no observed
advantage to larger 75mm rings. The performance and reliability of the 50mm packing in the full
scale plant has been consistent with pilot results and with theoretical generalized pressure drop
correlations (Table 2, equation 3). There has been no blockage by the slurry and pressure drops
are in the range 20 to 30 mmH2O/m packing. Checking of the packing during maintenance shut
downs has shown no abrasion or damage, no fouling and no sign of slurry bridging or build-up.
4.3 Absorption
The function of this section of the plant is to remove the HCN gas from the air stream prior to its
recycle to the stripper tower. The absorber is a packed tower with a high rate circulation of
NaOH solution through the packing. Solution is bled off periodically to recycle NaCN to the
leach plant and made up with fresh NaOH to maintain pH and effective absorption.

The absorber system is chemically the exact opposite of the stripping system and involves the
transfer of HCN from the gas phase into solution. The same chemical and reaction principles
apply. The exception here is that absorption is carried out in a solution of NaOH which has low
viscosity and few complicating reactions in the solution. Because this system is much more
consistent with the requirements of mass transfer theory and because the scrubbing of HCN from
air is a not uncommon process, this section of the plant did not require any basic research. The
absorber system was included as a separate item in the plant supplied as a package by a vendor of
this type of technology.
The key to the operation of this section of the plant is the pH maintained in the circulating NaOH
solution and the maximum concentration of NaCN. The values used in the GC and DeLamar
plants are shown in Table 3. Both of these are a function of operational efficiency, HCN emission
rules and the impact on stripping of residual HCN. In both full scale plants the consumption of
NaOH is significantly above that theoretically predicted. The reasons for this are not completely
clear and there is considerable focus on this aspect of the operation at both plants. This is
covered in a later section.

Table 3
Design And Operating Data Comparisons
Units GC Pilot GC Final GC Operating De Lamar
Plant Study Design Actual Actual
Packing Type 50mm.75mm 50mm pall 50mm pall 50mm
pall
Feed (CN WAD) g/m3 166-224 200-300 250
Liquid Rate m3/hr m2 4.3-11.2 6.8 est 6.8-12 5.4
Stripping pH pH units 7.0-8.0 6 6.0-8.5 6.5
Gas Rate g/m3 1785-5141 5310 est 3000-5000 4700
Gas: Liquid v/v 374-921 770 est 400-700 870
Process Constants:
HLC(1) atm/mol frac 2
MTC(2) kmol/m3hr 877
PLANT
CHARACTERISTICS(3)
m3/hr 2.17-5.6 100(per tower) 100-200 160
Slurry Feed % 10 10 10 10
Acid Addition Strength mins 3-10 20 20
Acidification Time cP 500-600 500 2500
Slurry Visc % solids 36 35 34-38 35
Slurry Density /l 1.29 1.28 1.28 1.27
Slurry SG mm 800 4300 4300 6100
Stripper Tower Diameter m 5 10 10
Stripper Tower Height m/hr 896-2581 77000 est 45000-75000 13600(70000)
Total Air Rate (per tower) 5-15
% of total 10 5.5
Bleed Air Rate m 2.7(4) 5.5 20-30 6.4
Stripper Packing Height mm H2O/m 5.0-25.0 30
Stripper Packing dP Vendor
Absorber Supply
pH units NA Package
Absorber Solution pH % NA 13-14
Regen NaCN Strength 21.7
Notes : (1) Henry's Law Constant

(2) Mass Transfer Coefficient-Estimated from Range of Pilot Values
(3) Both GC & De Lamar design utilize 2 independent, parallel,
stripper/absorber trains
(4) For increased height slurry was treated and discharged to a large tank and
then batch pumped through the tower.

4.4 Reneutralization
In this section lime is mixed with the stripped tailings prior to final discharge. The purpose of this
step is to create conditions which allow the precipitation of metals released from CN complexes
as stable hydroxides and carbonates into the tailings mass. Secondly the lime provides additional
buffering capacity as a precaution against sulphide oxidation and acid generation in the tailings.
At GC lime is added to the tailings as a lime slurry into agitated tanks with a 20-30 minute
residence time. Target pH is 9.5. There is some evidence that some of the metals released (Zn &
Cu) from CN WAD complexes are precipitating with iron cyanide complexes after stripping. This
is probably happening during stripping where pH is lower and some of the iron is probably
resolubilizing as pH is increased during reneutralization. Generally tailings chemistry is
environmentally much improved by the process.
The pH in the reneutralization section of the plant can also be controlled to a level below 9.5
-
where metal precipitation still occurs but where the residual CN is more easily naturally degraded
in the tailings pond. This is a practice which has proven effective at both GC and DeLamar with
resulting pond CN WAD levels below 5 ppm. In general, the ability to control solution chemistry
and change the acid-base accounting result for the tailings is a real advantage of the
reneutralization stage of the plant. The need for the quite long reaction time in this section of the
plant is, however, currently being evaluated. Given the consistent pH from the stripper towers it
is apparent that pH control is not as difficult as first thought. The agitated tanks and control loop
may be items which could be deleted or reconfigured in the next full scale design.
4.5 Safety
The creation of a safe working environment for employees must be a first priority in the design
construction and operation of any process or plant. The CYANISORB process generates HCN
gas within the plant. While it is technically and economically simple to engineer a safe system, it
should however be recognized that operators and communities are entitled to have their concerns
properly addressed, questions answered, and appropriate standards applied. The GC plant was
designed with this philosophy in mind. When a detailed design was available a full and
independent Hazard and Operability (HAZOP) study was carried out on the design.
HAZOP is a minute examination of process and instrumentation diagrams and mechanical

drawings where every single failure mode of every single component of the plant is examined and
all consequences are followed through. Any problems or concerns arising from this analysis are
addressed by design modifications. This approach has resulted in a general design which is not
only technically safe, well supported and backed up, but which people feel comfortable working
with and around. The basic safety features of the GC design were incorporated, with additional
site specific requirements, into the DeLamar design.

The key design elements related to safety in the process are:
1. The process is a closed circuit (except for slurry) with all of the process components being
enclosed within the equipment.
2. The system is continuously under negative pressure with any leakage into the process
rather than outward.
3. All tanks in the plant are air swept with air discharge into the process.
4. The plant is well supported with back up systems to avoid shut down of process
components and process equipment interlocks for complete shut down in the event of total
process component failure.
5. The section of plant where HCN gas is present is relatively small.
6. Area gas monitoring with local and remote reading and alarm functions are provided.
In addition, because such large volumes of process air are involved, the HCN gas streams are
relatively dilute. Operating procedures are as much a key to safe operation as good design. Well
trained operators with ready access to personal monitoring and safety equipment run both full
scale plants. Maintenance personnel complete standard checking and tag-out procedures prior to
opening or entering parts of the plant for maintenance purposes.
In neither operating plant has there been HCN gas detected around walkways, tanks or any other
area of the plant. In both plants stack emissions are well within allowable limits. In neither plant
has maintenance been difficult or dangerous. The technology used to provide these safety
features is standard, and well tried and proven. The occupational health and safety risk with
CYANISORB is demonstrably no greater, perhaps less, than is associated with any plant where
cyanide solution is made up and used to leach gold from ores. There is very good acceptance,
and in fact genuine interest in the plant by operators at GC and DeLamar.
5.0 PERFORMANCE
The commissioning of a prototype plant generally involves degrees of uncertainty as to operation

and performance. The GC CYANISORB plant was no different in this respect with uncertainty
relating not just to quantitative stripping efficiency but also to areas such as packing pressure
drop, potential for flooding the towers, mechanical blockage of the packing, or some
unanticipated problem arising.

The GC plant was commissioned as a part of the whole metallurgical circuit commissioning.
Initially the plant was commissioned on water and then on ore slurry without added cyanide. The
slurry was recycled to the leach tanks until it was considered that cyanide leaching and recovery
could commence. This staged commissioning approach was used to ensure that the mechanical
aspects of the plant operated as planned without the complication of having cyanide in various
phases in the plant.
This commissioning stage was completed very quickly. Pressure drop through the packing was in
the low end of the predicted range and observations of the packing suggested that the slurry was
flowing through the packing as well as pilot test data anticipated. With these hurdles overcome
and commissioning of safety systems, interlocks, and instrumentation and mechanical systems
complete, cyanide was introduced to the circuit.
Over the next one to two weeks, it was confirmed that not only was the plant performing
mechanically well, it was also easy to operate, required no unexpected maintenance, and was
performing well in a process sense. Stripping of CN WAD of up to 95% during commissioning
was being achieved.
Some problems developed with level control loops in tanks where level controllers were
functioning incorrectly and with pH control loops where pH probes were poorly located for
control purposes. However, no problem developed in this period with the plant or process itself.
Because the plant was so easy to start, stop, run and maintain, focus was shifted to other aspects
of the metallurgical circuit where commissioning was running less smoothly.
Since that time, while attention has been directed at improving metallurgical performance, the
CYANISORB plant has received little attention. It has not been fully optimized and has been
running at process set points (airflow, pH, and slurry flow) little different from those used during
commissioning and an unknown distance from "optimum".
Apart from quantitative measures of performance such as packing pressure drop, which has been
described, the only real quantitative indicator of process performance is stripping efficiency and
NaCN returned to the metallurgical circuit. Figure 4 shows the influent and effluent CN WAD
concentrations to the stripper towers at GC for March through October of this year. Figure 5
shows the recovery as a percentage of CN WAD stripped.

Figure 4: March-October 1992 Influent & Effluent

CN WAD Concentrations – Golden Cross Cyanisorb

Figure 5: March-October 1992 % CN WAD Stripping

Running Mean – Golden Cross Cyanisorb
These samples are taken at the end of the CIL train and at the tailings sump. It has since been
found that the stripper feed pump from the acidification tank has on occasion not kept up with
tank inflow, and thus the tank has been overflowing. This tank overflows to the stripper bottom
tank and the high CN slurry mixes with the stripped slurry before being pumped to the tailings
sump where the effluent sample is taken. Thus, the effluent sample results have been skewed
toward higher CN WAD values by occurrences of low CN WAD discovery related to this non
process plant upset condition.
This problem is being addressed, but the data nevertheless shows a satisfactory performance for
this eight months of operation so early in the history of the process. Table 4 shows the monthly
averages for these figures and the average NaCN returns to the metallurgical circuit. The
CYANISORB plant at GC has provided, as a monthly average, between 0.6 kg/t and .8 kg/t
recycled NaCN to the leach circuit. Table 5 shows the comparative data for the DeLamar plant.
It is clear from this data that the plant is performing similarly to the GC plant and consistently
with pilot performance.

Table 4
Golden Cross Summary Data
[CN [CN Ore Slurry m3 Soln kg kg/t lb/t

WAD] WAD] Recovery Tonnes %Solids NaCN NaCN NaCN
Influent Effluent
March 255 26 90% 53946 36% 95904 41390 0.77 1.53
April 211 28 87% 55417 36% 98519 33978 0.61 1.23
May 210 30 86% 60305 36% 107209 36369 0.60 1.21
June 226 43 81% 50603 36% 89961 31026 0.61 1.23
July 215 32 85% 59071 36% 105015 36218 0.61 1.23
August 247 31 87% 63730 36% 113298 46121 0.72 1.45
September 202 29 86% 50695 36% 90124 29384 0.58 1.16
Table 5
De Lamar Summary Data
[CN [CN Ore Slurry m3 Soln kg kg/t lb/t

WAD] WAD] Recovery Tonnes %Solids NaCN NaCN NaCN
Influent Effluent
March Due to errors in measure-

April ment method on the
May 294 39 87% tailings in and out of the 67926 149748
June 283 33 88% Cyanisorb plant, actual 44233 97515
July 239 27 89% recoveries may be higher 61642 135895 1.55
August 228 25 89% and so regenerated cyanide 72812 160520 1.69
September 219 33 85% solution analyses are used 76227 168049 1.85
for the mass values to
the right.
The reason for the plant data from GC to be consistent with batch lab data but for the residual to
be higher than that seen in the GC pilot work (see Figure 3) is related to leach solution chemistry.
The lab data was generated from test work based on GC ores while the pilot test was carried out
using a small continuous stream of tailings from a plant which was already operating located
about 10 km from the GC deposit.

The residual is probably metal cyanide complex that is not dissociated fully at the pH being used
and is mostly likely to include copper and silver complexes. Short term test work carried out at
the GC plant showed that when acidification pH was dropped to around pH 5 that considerably
lower residuals were achieved. As yet, no longer term quantification of this relationship has been
attempted using the full scale plant and there is no operational or permit compliance reason to run
at a lower pH at GC.
It is likely that the pilot plant will be used on a tailings stream with a higher copper concentration
in the near future. Table 6 shows the GC tailings solution chemistry. The operating models
described in the next section give results consistent with this chemistry and plant performance.
Maintenance requirements have already been discussed.
TABLE 6
GOLDEN CROSS TAILINGS SLURRY
Fe Mn Cu Zn
O/P ORE <20 <5 <5 <1
U/G ORE <5 <1 <10 <1
6.0 COSTS AND ECONOMICS
6.1 Operating Cost
The main components of the operating cost for CYANISORB are:
- Power costs
- H2SO4 costs
- CaO costs
- NaOH costs
- Ops & Maint Overhead
Power costs are primarily associated with the operation of the process air fans which provide the
air flow for stripping and the air volumes in and pressure drop through the system. Operating
3
data suggests that current CYANISORB design consumes between 1.0 and 1.5 kWh/m of slurry
3
processed. At an average of $.04/kWh this is up to $.06/m or $.13/tonne for a 35% solids slurry
and 2.6 SG ore.

H2SO4 costs will vary with the slurry pH, solution buffering capacity and the acidification pH
3
used. Consumption of 1.4 to 1.5 kg 98% H2SO4/m of slurry processed appears to be the
maximum for acidification to a pH of about 7 or around 3.0 to 3.5 kg/tonne. At an average of
$.06/kg this is around $.18 to $.21/tonne. CaO consumption varies also with acidification pH and
3
target reneutralization pH. A consumption of about 0.2 kg/m or 0.5 kg/tonne appears to be the
norm. At $.07/kg this is less than $.05/tonne. NaOH costs are proving to be the largest
component of operating cost in both full scale plants. Presently NaOH is consumed in the
-
absorption process at a rate of around 3 kg NaOH/kg of CN absorbed. There is also
consumption of NaOH by the CO2 in the fresh bleed air. Stoichiometric calculations indicate this
3
should be around 0.0012kg NaOH/m of fresh air. In total, at a NaOH price of $.37/kg, NaOH
costs are up to $.609/tonne for an average application. This is higher than expected, and the
reasons and the program for optimizing or finding an alternative is described in the next section.
6.2 NaCN Recovery
The CYANISORB process provides an offset to this operating cost by returning regenerated
NaCN to the leach circuit. The returned NaCN for the operating plants was shown in Table 4.
Typically, using a current NaCN price of $1.10 to $1.20/kg, a return NaCN value of $.60/tonne
to $1.00/tonne can be achieved for an average operation. Any other offsets such as the NaOH
returned with the NaCN displacing CaO or NaOH additions to the metallurgical circuit are
ignored.
These figures, based on actual reagent consumption rates show that the net cost of the process
can vary between about $.50/tonne and break-even.
6.3 Other Savings
In addition to the low or possibly zero operating cost that can be achieved for CYANISORB, the
direct operating savings from not having to use a conventional tailings cyanide destruction
technology should be considered in any economic evaluation. Thus, a $1.00 to $2.00/tonne
additional benefit can be realized if CYANISORB is considered as an alternative to conventional
technologies.
7.0 OPERATING ISSUES AND ONGOING DEVELOPMENT
No issues have arisen in the operation of either of the full scale plants which unduly affect process
performance. No process issues have arisen that throw the process into doubt as a viable
technology in this area. There are, however, some operating issues that require attention where
design or operating optimization could improve process or economic performance.

7.1 Slurry Carry-over
Due to the high gas rates used in the process, some slurry is being carried over with the process
air through the ducts and into the absorber. There is also some carry-over from the absorber to
the process air fan.
Slurry carry-over to the absorber, although not in significant quantities, has the effects of
increasing the volume of and diluting the absorber solution. This is partly contributing to the high
NaOH addition rate being observed as transfer of solution and make up with fresh NaOH has to
be more frequent.
It is proposed at GC to fit an irrigated pad or some packing above the slurry distribution system
to try and trap the slurry particles from the air. An alternative being considered is to trap the
particles in a large chamber fitted to the duct prior to the absorber which would reduce the air
velocities. In any event, future plant design will mitigate this problem.
7.2 Slurry Distribution
The distribution of the slurry over the packing surface was uneven in both full scale plants. In
each case the slurry is flowing in only about half the length of the final distribution launders and
thus there are dead zones in the packing. consideration being given to increasing the slurry
loading on the towers may help overcome this problem by increasing velocities in the launders.
Modifications are, however, being made to each existing plant.
7.3 NaOH Consumption
As already described, there is considerable incentive to decreasing operating costs in this area.
Apart from work on optimizing the operation of the absorber, there is also study on alternatives
being carried out. Absorbing into NaOH was chosen because there was unlikely to be any
problem with chemical fouling of tower packing as there may be with time. Now, however, it
seems appropriate to review that decision to look at absorption into lime slurry as an alternative.
Lime scrubbing is a relatively common unit operation and could be applicable here.
The second alternative here is being less actively pursued and is considered a more distant
possibility. It is to absorb the HCN directly to the mill slurry stream after pH adjustment and
prior to being fed to the leach tanks. This would require a tower between the milling circuit and
the leach circuit, but would negate the need for any reagent and the transfer of regenerated
NaCN.
7.4 Design and Cost Review
The process has been demonstrated to be not only successful but also reliable. It is appropriate
now, then, to reduce some of the design conservatism and change the prototype nature of the
plant in future designs.

Cyprus, in conjunction with Davy International, are undertaking a thorough review of process
design and detailed engineering of CYANISORB plant. A generic plant design, of average size,
will be prepared based on operating experience and a new capital estimate prepared. Using this
information cost curves for varying plant capacity will also be developed. This information will be
made available to potential users of the CYANISORB technology and used in evaluating
feasibility in potential applications.
8.0 SUMMARY
Cyprus set out in 1988 to develop, test, design, build and operate a tailings detoxification plant
that made residual cyanide available to the process again by recycle rather than destroying it in an
oxidation process. A successful piloting program led to full scale design and construction of a
plant in a Cyprus NZ operation.
The aim of the program has been achieved via the successful operation of the prototype plant and
recovery of around 90% of the excess tailings cyanide which would have otherwise been wasted.
The plant has proved to be easy to operate and its operation is reasonably consistent with
empirical and theoretical predictions of its operation and performance. A second plant has been
operating under license in the US since mid 1992 and is similarly successful. A program of design
and operating optimization is now in place.
9.0 REFERENCES
Hampton, P., DeLamar Silver Mine, Personal Communication, 1992.
McNamara, V., "Acidification Volatilization Reneutralization Treatment Process for

Decontamination of Canadian Gold Mill Effluents," CANMET, Energy, Mines & Resources
Report MRP/MSL 78-223, 1978.
Miller, S., "Evidence on Waste Geochemistry," Water Right Tribunal Hearing into Golden Cross
Project Water Right Applications, Hauraki Catchment Board, Te Aroha, NZ, 1989.
Mudder, T. and Goldstone, A., "The Recovery of Cyanide from Slurries," in Proceedings of
International Gold Expo, Sept. 7-9, Reno, Nevada, 1989.
Omofoma, M., and Hampton, P., "Cyanide Recovery in a CCD Merrill Crowe Circuit: Pilot
Testwork of a CYANISORB Process at the NERCO DeLamar Silver Mine," Randol Gold
Conference, Vancouver, 1992.
Perry, R., and Green, D. (Eds), Perrys' Chemical Engineers Handbook, 6th Edition, McGraw Hill,
1984.
Williams, M.P.A. and Goldstone, A., "Water Management and Water Treatment at Golden
Cross," in Proceedings of 3rd International Mine Water Congress, Melbourne, Australia, October,

1989.
10.0 ACKNOWLEDGEMENTS
The authors would like to acknowledge the contributions of individuals and organizations to this
program at both Golden Cross and DeLamar. These include; Paul Hampton, who has added
much to the original R&D work; the Department of Scientific & Industrial Research in NZ, who
contributed to the original program; Davy McKee, who contributed to the pilot work and
completed detailed engineering at Golden Cross; the commissioning and operations teams at both
Golden Cross and DeLamar; Brian Burdett, who runs the Golden Cross plant; and the
management of Cyprus Gold Co. in the US and Australia (Messrs. Lampard, Martin & Metcalf);
and particularly Dave Ingle in New Zealand, whose encouragement and trust allowed us to
conclude a successful program.

RECOVERY OF CYANIDE FROM MILL TAILINGS
Prepared By:
James Stevenson, P.E.

Terry Mudder, Ph.D.
Alan Wilder
Robert Richins
Brian Burdett
Originally presented at the Northwest Mining Association Annual Meeting in Spokane,

Washington (USA) in November 1994 and subsequently published in The Cyanide Monograph,
First Edition, Mining Journal Books, London, England, United Kingdom, June 1998
Recovery of Cyanide from Mill Tailings
1.0 INTRODUCTION AND OBJECTIVES
Cyanide has been used to extract gold and other metals from ore since the first extraction
processes were employed in 1898 in New Zealand and Africa. Cyanide is also used in industries
such as metal finishing and pesticide manufacturing.
Sodium cyanide production in the United States is estimated to be approximately 140,000 tons
per year, 90% of which is used in the mining industry. Wastes produced by cyanidation industries
are commonly treated by destroying cyanide. With a global price averaging greater than $0.50
per pound, and based on the amount produced only by the United States, it is likely that more
than $140 million worth of sodium cyanide is destroyed by the mining industry each year.
TM
This paper presents design and operation details of the Cyanisorb cyanide recovery process.
TM
Two mining operations currently use Cyanisorb to recover approximately 90% of cyanide from
tailings.
TM
A history of cyanide recovery and details of Cyanisorb process design are presented in Sections
2.0 and 3.0. Section 4.0 compares two cyanide destruction processes and natural degradation of
TM
cyanide in tailings ponds. Applications of Cyanisorb in the mining industry are discussed in
Section 5.0 and conclusions are presented in Section 6.0.
1.1 Cyanide Chemistry

-
Free cyanide may exist in solution as the CN anion or molecular HCN. The proportion of each
species in solution is a function of pH, as shown in Figure 1-1. The acid dissociation constant
- o
(pKa) for HCN/CN equilibrium in water is 9.31 at 20 C. Therefore at a pH of 9.31, cyanide
o -
solutions at 20 C theoretically contain approximately 50 mol% CN and 50 mol% HCN. The
equilibrium relation is represented by:
+ -
HCN ↔ H + CN (1-1)
Cyanide forms complexes with metals such as iron, mercury, copper, nickel, silver, gold, cadmium
and zinc. Metal-cyanide complex solution equilibria is described by:
2-x ++ -
M(CN)x ↔ M + xCN (1-2)
Iron cyanide complexes, although soluble, are very stable and essentially non-toxic.
-
Weak Acid Dissociable (WAD) cyanide includes CN , HCN and weakly complexes cyanides such
as mercury, zinc, cadmium, copper, nickel and silver-cyanides, while free cyanide includes only
-
CN and HCN.
Typical gold and silver recovery operations are confronted with wildlife mortality concerns when
tailings pond WAD cyanide concentrations exceed approximately 50 mg/L, increased gold and
silver costs associated with tailings cyanide destruction, and increased environmental risks
associated with potential impoundment liner leakage.
266 Stevenson et al.

Figure 1-1: Relationship Between HCN and CN- with pH

In lieu of cyanide destruction, recovering 90% of cyanide from tailings solutions may provide the
following benefits:
• Reduced cyanide consumption and associated mine operating costs.

• Reduced or eliminated tailings pond liner requirements.
• Reduced potential for liability due to environmental contamination.
• Reduced tailings pond reclamation requirements.
• Reduced post-closure monitoring requirements.
• Reduced or eliminated wildlife mortalities.
2.0 CYANIDE RECOVERY
Cyanide recovery has been employed on a limited basis since the 1930's using the less
sophisticated Acidification Volatilization Reabsorption (AVR) technology, however operating
costs render the technology economically unfavorable. The process is not currently thought to be
a viable economic alternative to cyanide destruction due to excessive operating costs.
TM
The Cyanisorb process exhibits some similarity to conventional AVR technology, however,
TM
Cyanisorb employs high efficiency packed towers to strip cyanide from either slurries or clear
TM
solutions at a near-neutral pH. Cyanisorb recovers both free cyanide and metal-cyanide
complexes, while AVR employs shallow aeration basins, high-pressure air blowers and a low pH
to recover free cyanide and precipitate metal-cyanide complexes. AVR operating costs are
prohibitively high due to power costs and acid consumption necessary to achieve a very low pH.
TM
A comparison of the Cyanisorb and AVR processes is presented in Table 2-1.
Table 2-1
CyanisorbTM and AVR Process Comparison
Parameter AVR Process CyanisorbTM Process

pH <2 6 to 8
Pressure Drop >80" water (>20 kPa) <20" water (<5 kPa)
Stripping Method Basins Packed Towers
Cyanide Recovery 90% 90%
Recoverable Cyanide Free WAD
Solutions Slurry or Clear Solution Slurry or Clear Solution
Operating Costs High Low

TM
2.1 Cyanisorb Operations
2.1.1 Golden Cross Mine
The Golden Cross operation consists of an open-pit and underground gold mine with a
conventional crushing, grinding, and carbon-in-pulp/carbon-in-leach (CIP/CIL) circuit with
Merrill Crowe zinc precipitation for gold recovery. Prior to disposal in the tailings pond, slurry
TM
tailings are stripped of cyanide at a pH of approximately 7.5 using the Cyanisorb process.
Mill throughput is approximately 2,400 tons per day (TPD) (2,180 metric tons per day [MTPD]),
and CIP/CIL slurry tailings average 34% solids with a specific gravity of 1.26. Slurry WAD
cyanide concentrations range from 150 mg/L to 350 mg/L, averaging 200 mg/L. The
TM
Cyanisorb process recovers approximately 90% of tailings cyanide, producing a slurry effluent
with approximately 20 mg/L cyanide.
2.1.2 DeLamar Silver Mine

TM
A Cyanisorb process was commissioned at the NERCO DeLamar silver mine in southwest
Idaho in May, 1992. The ore milling and silver recovery operation consists of crushing, grinding,
a CIP circuit and Merrill Crowe zinc precipitation for silver recovery. Effluent slurry from the
3,500 TPD (3,180 MTPD) mill consists of approximately 40% solids with a specific gravity of
1.27 and an average of 250 mg/L cyanide.
Due to the presence of zinc-cyanide complexes in mill tailings resulting from the Merrill Crowe
process, cyanide stripping is performed at a pH of approximately 5.5. Cyanide is currently
recovered from the clarified tailings.
TM
The Cyanisorb process was installed at the site in response to migratory bird fatalities in the
TM
tailings pond. Cyanisorb reduces the clarified tailings solution from approximately 250 mg/L
cyanide to less than 20 mg/L.
TM
3.0 CYANISORB DESIGN
3.1 Process Flow Diagram

TM
An optimized Cyanisorb facility design was completed in 1994 to provide accurate capital and
operating cost data for recovery from a 2,500 TPD (2,270 MTPD) milling operation. Details of
the conceptual design are presented in the following sections.

TM
A process flow diagram for the Cyanisorb facility is presented in Figure 3-1. The flow diagram
incorporates only one stripping tower and one recovery tower, however in practice two
independently operated stripping/recovery trains are used to provide flexibility and stability of
operation. Cyanide recovery consists of four unit operations: 1) conversion of cyanide and
metal-cyanide complexes to HCN; 2) stripping of HCN from tailings in a packed tower; 3)
recovery of HCN gas into a basic solution in a packed tower; and 4) pH adjustment of stripped
tailings.
The basic process unit operations include:
Dissociation Section:
Two conversion tanks are operated in series with acid addition to the first tank. Retention time in
each tank is approximately 15 minutes with an effluent target pH of 8.0. Control of pH is
accomplished using multiple pH probes in the second tank and a controller to adjust the acid feet
rate to the first tank.
Stripping Section:
Slurry from the second conversion tank is pumped to the stripping tower where HCN is removed.
Tower diameter and packing height are a function of air flow rate, slurry flow rate, temperature,
packing size and type, and slurry viscosity. A liquid to gas ratio (L/G) (expressed in English units
3 3
as gpm/1,000 SCFM or in metric units as m slurry/m air) in the range of 9.4 to 15 GPM/1,000
3 3
ACFM (1/500 to 1/800 m slurry/m air) is the operating target.
Recovery Section:
HCN laden air from the stripping tower is directed to a second packed tower where HCN is
recovered into a basic solution. Sodium carbonate or sodium hydroxide solutions may be used for
this purpose. Cyanide recovery in the tower is typically in excess of 99%, with cyanide
concentrations in air at the tower outlet less than 5 ppm. Air exiting the recovery tower is
recycled to the stripping tower inlet.
Neutralization Section:
One neutralization tank is used to adjust the pH of stripped slurry to 9.0 to 10.5 using lime.
Retention time in the tank is approximately 30 minutes. Control of pH is accomplished using
multiple pH probes and an adjustable lime feed rate.
Fan Sections:
A process fan is used to supply air to the stripping and recovery towers in quantities sufficient to
maintain the desired L/G. Pressure drop through the entire air recirculation system is usually less
than 20" of water (5 kPa).
The conversion tanks, neutralization tank, stripping tower and recovery tower are operated at a
negative pressure to prevent loss of HCN gas. A bleed fan is used to maintain the pressure below
atmospheric at the process fan outlets.

Figure 3-1: CyanisorbTM Process Flow Diagram

3.2 Capital Costs

TM
The capital cost for a Cyanisorb facility designed to recover cyanide from a 2,500 TPD (2,250
MTPD) milling operation with a 35% solids tailings slurry is estimated to be approximately $3,7
million, in third quarter 1994 U.S. dollars.
TM
Operating specifications for the Cyanisorb facility are listed below:
• Maximum of 30 minutes retention time in conversion step.

• Maximum of 30 minutes retention time in neutralization step.
• Two packed stripping towers.
• Two packed recovery towers.
• 93% cyanide recovery; 300 mg/L influent; 20 mg/L effluent.
• 35% solids slurry.
• Slurry specific gravity of 1.30.
• 2,500 TPD (2,270 MTPD) mill capacity.
• Maximum of 20" water (5 kPa) pressure drop through the system.
Project costs as a percentage of the total project budget are outlined below:
Structural Excavation and Fill 0.9%

Concrete 3.4%
Structural Steel and Structures 8.6%
Piping and Ducting 19.7%
Process Equipment 30.0%
Electrical 18.1%
Instrumentation 5.6%
General Equipment 0.6%
Miscellaneous 0.3%
Freight 2.1%
Engineering and Construction Management 10.7%
TOTAL: 100.0%
Special considerations incorporated into the design include freeze protection, secondary
containment for reagent storage and process equipment, maintenance of a negative air pressure in
the system and an emergency power source for the bleed fans.
Capital costs for 1,000, 5,000 and 10,000 TPD (910, 4,550, and 9,100 MTPD) facilities are
estimated according to the "six-tenths rule" based on $3.7 million for a 2,500 TPD mill and 35%
solids in slurry tailings. Capital cost estimates are shown in Table 3-1.

Table 3-1
CyanisorbTM Capital Cost Estimates
Mill Capacity Estimated Capital Cost

1,000 TPD (900 MTPD) $2,100,000
2,500 TPD (2,250 MTPD) $3,700,000
5,000 TPD (4,550 MTPD) $5,600,000
10,000 TPD (9,000 MTPD) $8,500,000
3.3 Operating Costs

TM
Operating costs for a Cyanisorb facility at a 2,500 TPD (2,270 MTPD) mill were estimated
using a 90% plant availability. A 2,500 TPD (2,270 MTPD) mill with a 35% solids tailings
3
stream with a specific gravity of 1.30 equates to approximately 920 gpm (210 m /hr) of slurry fed
TM
to the Cyanisorb facility. If solids were removed from the tailings slurry, the resultant clear
3
solution would have a flow rate of 775 gpm (175 m /hr).
Estimated operating costs for the 2,500 TPD (2,270 MTPD) facility are presented in Table 3-2
assuming sodium carbonate is used to recover HCN. It is assumed that tailings consist of 35%
solids with 300 mg/L WAD cyanide. Included are costs for reagents, power, operations and
maintenance (O&M), royalty and credit for recovered cyanide. Operating cost without
considering cyanide credit is approximately $0.80 per ton of ore ($0.88 per metric ton of ore). A
credit of approximately $1.05 per ton of ore ($1.16 per metric ton of ore) is realized for cyanide
recovery, equating to an overall operating credit of approximately $0.25 per ton of ore ($0.28 per
metric ton of ore), or a credit of $235,000 per year.
Table 3-2
Estimated Operating Costs (1)
2,500 TPD Facility
Description Unit Cost Usage $/hour $/day $/year $/ton ore
Lime (CaO) 0.04 $/lb 92 lb/hr 4 88 32,237 0.04
Sulfuric Acid (93.5%) 0.04 $/lb 330 lb/hr 13 317 115,632 0.13
Sodium Carbonate 0.05 $/lb 438 lb/hr 22 526 191,813 0.21
Power 0.04 $/kW hr 392 kW 16 376 137,357 0.15
O&M (2) 18 420 153,300 0.17
Royalty (3) 11 264 96,185 0.11
Subtotal: 83 1,990 726,524 0.8
Sodium Cyanide (credit) 0.60 $/lb 183 lb/hr 110 2,635 961,848 1.05
Total: -27 -645 -235,324 -0.26
(1) 90% plant availability
(2) Based on 50% manpower at $35/hr.
(3) 10% of recovered NaCN value

Sulfuric acid consumption varies with ore chemistry, solution buffering capacity and operating
pH. Usage is typically 3.3 pounds of sulfuric acid per ton of ore (1.7 kg sulfuric acid per metric
ton of ore) at a pH of 8.0. At a cost of $0.04 per pound ($0.09 per kg) of 93.5% sulfuric acid,
costs are approximately $317 per day or $0.13 per ton of ore ($0.14 per metric ton of ore).
Lime consumption varies with degree of acidification and desired tailings discharge pH. Typical
lime usage is estimated to be 1.0 pound of CaO (1.3 pounds Ca(OH)2) per ton of ore (0.5 kg CaO
(0.7 kg Ca(OH)2) per metric ton of ore). With a purchase price of $0.04 per pound ($0.09 per
kg), lime costs are approximately $88 per day or $0.04 per ton of ore ($0.04 per metric ton of
ore).
Cyanide is recovered from HCN laden air as sodium cyanide. With a 93% recovery from tailings,
approximately 4,400 pounds (2,000 kg) per day of sodium cyanide is recovered. Assuming a
purchase price of $0.60 per pound ($1.32 per kg), sodium cyanide recovery credit is
approximately $2,635 per day, or $1.05 per ton of ore ($1.16 per metric ton of ore).
Sodium carbonate could potentially be used to recovery HCN from air in the recovery towers.
-
Approximately 4.5 pounds of sodium carbonate is required for each pound of CN recovered.
With a purchase price of $0.05 per pound ($0.11 per kg), $526 of sodium carbonate is used per
day, or $0.21 per ton of ore ($0.23 per metric ton of ore).
Operating costs associated with using sodium hydroxide to recover cyanide are presented in Table
3-3. Use of sodium hydroxide results in an operating cost of $0.13 per ton of ore ($0.14 per
metric ton of ore). The Golden Cross and DeLamar facilities currently use sodium hydroxide for
HCN recovery.
Table 3-3
Estimated Operating Costs (1)
2,500 TPD Facility
Sodium Hydroxide Option

Lime (CaO) 0.04 $/lb 92 lb/hr 4 88 32,237 0.04
Sodium Hydroxide (50%) 0.19 $/lb 330 lb/hr 63 1,505 549,252 0.6
Power 0.04 $/kW hr 392 kW 16 376 137,357 0.15
O&M (2) 18 420 153,300 0.17
Royalty (3) 11 264 96,185 0.11
Subtotal: 124 2,970 1,083,962 1.19
Total: 14 335 122,114 0.13

Other cost savings such as reduced liner requirements and reduced treatment costs were not
incorporated into the above estimates. Evaluation of the Golden Cross facility indicated a
$330,000 savings due to eliminating a backfill wash plant. Reduced metals, cyanide and ammonia
in tailings pond water resulted in a capital savings of $1.43 million due to reduced tailings pond
water treatment requirements. Additionally, the tailings pond at Golden Cross did not require
lining, resulting in unquantified cost savings. Overall, savings were $1.76 million plus the cost
2
associated with lining a 60 acre (240,000 m ) tailings pond.
Estimated operating costs for 1,000, 5,000, and 10,000 TPD (910, 4,550, and 9,100 MTPD)
facilities are presented in Table 3-4. The costs are based on the following assumptions:
• O&M costs are equivalent to the 2,500 TPD (2,270 MTPD) facility.
• Power costs are scaled according to the six-tenths rule.
• Sodium carbonate is used to recover HCN.
As evidenced in Table 3-4, operating costs decrease as mill capacity increases due to the increased
amount of sodium cyanide recovered.
TM
Estimated conditions for net-zero operating costs for Cyanisorb are presented in Table 3-5 as a
function of tailings cyanide concentration and mill capacity. Depreciation is not included in
estimated operating costs. As shown in Table 3-5, the net annual operating cost of operating a
TM
Cyanisorb process at a 2,500 TPD (2,270 MTPD) facility with 200 mg/L cyanide in the slurry
effluent is zero dollars per year.
Table 3-5
Estimated Net-Zero Operating Conditions as a Function
Of Mill Capacity and Tailings Cyanide Concentration
Mill Capacity WAD Cyanide

Concentration
1,000 TPD (910 MTPD) 330 mg/L
2,500 TPD (2,270 MTPD) 200 mg/L
5,000 TPD (4,550 MTPD) 180 mg/L
10,000 TPD (9,100 MTPD) 160 mg/L

Table 3-4
Estimated Cyanisorb Operating Costs (1)
1,000 TPD
Lime (CaO) 0.04 $/lb 37 lb/hr 1 35 12,895 0.04
Sodium Carbonate 0.05 $/lb 177 lb/hr 9 212 77,555 0.21
Power 0.04 $/kW hr 226 kW 9 217 79,190 0.22
O&M (2) 18 420 153,300 0.42
Royalty (3) 4 102 37,318 0.1
Subtotal: 46 1,114 406,510 1.11
Total: 4 91 33,334 0.09
5,000 TPD
Lime (CaO) 0.04 $/lb 184 lb/hr 7 177 64,474 0.04
Sodium Carbonate 0.05 $/lb 876 lb/hr 44 1,051 383,688 0.21
Power 0.04 $/kW hr 594 kW 24 570 208,138 0.11
O&M (2) 18 420 153,300 0.08
Royalty (3) 22 527 192,370 0.11
Subtotal: 141 3,379 1,233,233 0.68
Sodium Cyanide (credit) 0.60 $/lb 366 lb/hr 220 5,270 1,923,696 1.05
Total: -79 -1,892 -690,463 -0.38
10,000 TPD
Lime (CaO) 0.04 $/lb 368 lb/hr 15 353 128,947 0.04
Sulfuric Acid (93.5%) 0.04 $/lb 1,320 lb/hr 53 1,267 462,528 0.13
Sodium Carbonate 0.05 $/lb 1,752 lb/hr 88 2,102 767,376 0.21
Power 0.04 $/kW hr 900 kW 36 864 315,360 0.09
O&M (2) 18 420 153,300 0.04
Royalty (3) 44 1,054 384,739 0.11
Subtotal: 253 6,061 2,212,250 0.61
Sodium Cyanide (credit) 0.60 $/lb 366 lb/hr 439 10,541 3,847,392 1.05
Total: -187 -4,480 -1,635,142 -0.45

4.0 CYANIDE DESTRUCTION
Several processes are employed to destroy cyanide and metal-cyanide complexes in mine milling
wastes. The more commonly applied methods include hydrogen peroxide, SO2/air, and natural
degradation. A comparison of these destruction processes is presented in the following sections.
4.1 Cyanide Destruction with SO2/Air
SO2/air based processes are employed to destroy cyanide and cyanide-metal complexes in gold
and silver mine milling wastes. The process has been applied to tailing slurries, barren solution
bleeds, pond waters and heap leach rinse solutions. Cyanide concentrations are generally reduced
to below 1.0 mg/L. Process chemistry is described by Smith and Mudder and Palmer, et al.
Table 4-1 outlines the estimated capital and operating costs associated with treating 500 and
1,000 GPM of clear solution and slurry with varying cyanide concentrations. SO2 dosages were
estimated to be 5 pounds per pound of cyanide destroyed (5 kg/kg) for clear solutions and 7
pounds per pound of cyanide destroyed (7 kg/kg) for slurries. Purchase cost for SO2 is estimated
to be $0.09/lb ($0.20/kg).

Table 4-1
Estimated SO2/Air Treatment Costs
Estimated Capital Cost Estimated Operating Cost

$/day
10 mg/L
500 gpm clear solution $1,300,000 613
1,000 gpm clear solution $2,000,000 697
500 gpm slurry $1,300,000 622
1,000 gmp slurry $2,000,000 771
50 mg/L
1,000 gpm clear solution $2,000,000 1,362
500 gpm slurry $1,300,000 991
1,000 gmp slurry $2,000,000 1,508
100 mg/L
500 gpm clear solution $1,300,000 1,362
500 gpm slurry $1,300,000 1,451
1,000 gmp slurry $2,000,000 2,429
200 mg/L
500 gpm slurry $1,300,000 2,372
1,000 gmp slurry $2,000,000 4,271
300 mg/L
500 gpm slurry $1,300,000 3,293
1,000 gmp slurry $2,000,000 6,113
NOTES:
1. Slurry composed of 35% solids
2. Slurry has specific gravity of 1.30

4.2 Cyanide Destruction with Hydrogen Peroxide
Hydrogen peroxide is used to oxidize cyanide and weakly-complexed cyanides with copper ions in
solution acting as a catalyst. Process chemistry is described by Smith and Mudder and Higgs.
3
The capital cost of constructing a facility to treat 3,100 GPM (700 m /hr) of tailings pond water
with an average cyanide concentration of 9.5 mg/L was estimated to be approximately $3.2
million. Costs include engineering design, earthwork, facility equipment and construction. The
process included hydrogen peroxide addition, coagulation using ferric sulfate, and clarification.
3
Capital costs of similar facilities designed to treat 500 and 1,000 GPM (115 and 230 m /hr) are
estimated to be approximately $1.1 million and $1.6 million, respectively.
Table 4-2 outlines the estimated capital and operating costs associated with treating 500 and
3
1,000 GPM (115 and 230 m /hr) of clear solution and slurry with varying cyanide concentrations.
Dosages of hydrogen peroxide were estimated to be 5 pounds of peroxide per pound of cyanide
destroyed (5 kg/kg) for clear solutions and 9 pounds of peroxide per pound of cyanide destroyed
(9 kg/kg) for slurries. Purchase price of hydrogen peroxide is assumed to be $0.35 per pound
($0.77/kg) of active product.

Table 4-2
Hydrogen Peroxide Treatment Costs
Estimated Capital Cost Estimated Operating Cost

$/day
10 mg/L
500 gpm slurry $1,100,000 866
1,000 gmp slurry $1,600,000 1,211
50 mg/L
500 gpm slurry $1,100,000 1,810
1,000 gmp slurry $1,600,000 3,099
100 mg/L
500 gpm slurry $1,100,000 2,990
1,000 gmp slurry $1,600,000 5,459
200 mg/L
500 gpm slurry $1,100,000 5,350
1,000 gmp slurry $1,600,000 10,179
300 mg/L
500 gpm slurry $1,100,000 7,710
1,000 gmp slurry $1,600,000 14,899
NOTES:
1. Slurry composed of 35% solids
2. Slurry has specific gravity of 1.30

4.3 Natural Degradation
Precious metals recovery operations commonly employ impoundments for tailings disposal,
clarifying mill water for reuse, and storing wastewater for eventual discharge from the site.
Cyanide concentrations in mill tailings solutions may range from less than 10 mg/L to more than
300 mg/L, but typically range from 25 to 250 mg/L. Through natural degradation in tailings
ponds, cyanide levels are often decreased to less than 20 mg/L, and in a properly designed tailings
pond, to less than 5 mg/L.
Natural degradation of cyanide is controlled by the rate at which metal-cyanide complexes are
-
converted to free cyanide (i.e. CN and HCN). The pH of pond water is lowered by the
dissolution of atmospheric carbon dioxide, inducing a change in the cyanide equilibrium
concentration according to Equation 1-1. Conversion of cyanide complexes to free cyanide is
affected by pH, temperature, pond geometry and the intensity of ultraviolet light incident on the
pond.
Ultraviolet light destabilizes metal-cyanide complexes and catalyzes their dissociation into
dissolved metals and free cyanide, as shown in Equation 4-1.
2-x ++ -
M(CN)x = M + xCN (4-1)
Equilibrium between the cyanide anion and dissolved HCN is governed by water pH, as shown in
Figure 1-1. At a solution pH less than approximately 8.5, cyanide is predominantly in the form of
dissolved HCN. HCN is stripped to the atmosphere from the surface of the pond, which drives
the equilibrium of Equation 4-1 such that further metal-cyanide complex dissociation occurs
according to LeChatelier's principle. This step is relatively fast when compared to the rate of
metal-cyanide complex dissociation.
The formation of metal cations in the presence of water with a pH of 7 to 8 will result in the
partial precipitation of the respective insoluble hydroxide or carbonate. As a consequence, low
concentrations of cyanide and metals in pond solutions can result. Environmental conditions
favoring natural degradation include shallow ponds with a large surface area, wind and a pH less
than 8.5.
If the concentration of cyanide influent to a pond is less than 20 mg/L, metal-cyanide complex
dissociation will result in low cyanide concentrations in pond water as well as that entrained as
pore water within tailings sediment. Experimental data has shown that cyanide will degrade in
pond water and in pore water under both aerobic and anaerobic conditions.
Metal-cyanide complexes moving through tailings sediment will dissociate and form dissolved free
metals. Anaerobic conditions present in the tailings may promote the reduction of sulfate to
sulfide, further decreasing dissolved metal concentrations as metal-sulfides precipitate. If the
tailings are sufficiently deep, the resultant pore water will contain low levels of cyanide and
dissolved metals.
At the Golden Cross mine in New Zealand, a tailings pond liner was not required due to the

quality of water entrained in the tailings.
Published data documents a significant reduction in cyanide concentrations in tailings ponds at

several Canadian mines. Figure 4-1 shows shallow tailings pond cyanide concentration as a
function of time for the Domes Mine in Timmins, Ontario. As evidenced, cyanide concentrations
were decreased to less than 5 mg/L after four months.
Figure 4-1: Cyanide Degradation in Shallow Holding Pond

At the Dome Mine in Timmins, Ontario

5.0 CYANISORBTM APPLICATIONS

TM
Cyanisorb processes may be installed in any of several configurations, depending on site-
TM
specific conditions and mill operations. Ideally, the Cyanisorb process is incorporated into the
overall design of mining and milling operations. The following sections present several
TM
applications of Cyanisorb .
5.1 Recovery Following Cyanidation and Before CIP
Recovering cyanide from pregnant solutions prior to a CIP circuit has been shown to increase
gold recovery by reducing competition among active species for carbon adsorption sites.
Oxidation of cyanide in the presence of activated carbon may account for nearly 50% of cyanide
losses. Removing cyanide prior to gold adsorption on activated carbon reduces cyanide oxidation
catalyzed by carbon. Figure 5-1 shows a schematic of cyanide recovery prior to gold adsorption.
Cyanide recovery from pregnant solutions is applicable to both slurries and clear solutions.
Cyanide concentrations in leaching solutions are typically higher than encountered in tailings
solutions, the former ranging from 200 to 600 mg/L. Stripping of cyanide from pregnant
solutions does not appear to cause gold, iron and copper-cyanide complexes to dissociate or
precipitate.
Figure 5-1: CyanisorbTM Pregnant Solution Cyanide Recovery

5.2 Recovery from Mill Tailings
Mill tailings cyanide concentrations typically range from 100 to 500 mg/L in a slurry with 20% to
TM
50% solids. A Cyanisorb facility would recover approximately 90% of this cyanide, depending
on the concentration of metal-cyanide complexes. A schematic of cyanide recovery from mill
tailings is shown in Figure 5-2.
Figure 5-2: CyanisorbTM End-of-Milling Cyanide Recovery

5.3 Recovery into Mill Slurry Prior to Cyanidation
As an alternative to recovering cyanide with a solution containing sodium carbonate or sodium

hydroxide, volatilized HCN could be recovered by mill slurry being fed to the leaching circuit.
Mill slurries fed to leach tanks typically have a pH of roughly 10.5 and therefore could replace the
basic solutions already considered. Existing air blowers used to pre-aerate slurry in the leaching
circuit could be used to move air from the stripping towers into the leach tanks. Figure 5-3 is a
schematic of cyanide recovery into mill slurry. Pilot or full-scale application of this option has yet
to be tried.
Packed towers identical to those used to strip HCN from mill tailings could also be used to
recover cyanide. The towers could operate in a manner similar to the stripping towers though
mass transfer would be from air to slurry phase. Slurry being fed to the leaching circuit would be
pumped to the top of packed towers where HCN would be absorbed. Effluent from the towers
would be directed to leaching tanks. Use of packed towers to recover cyanide would eliminate
the need for high-pressure blowers necessary to sparge HCN laden air into leach tanks.
Figure 5-3: CyanisorbTM Cyanide Recovery into Feed Pulp

5.4 CyanisorbTM Coupled with Natural Degradation
It is common practice to dispose tailings in an impoundment without first reducing Cyanide

TM
concentrations. If Cyanisorb were used to reduce tailings cyanide concentrations to less than
20 mg/L, prior to disposal in a tailings pond, the following benefits could be realized:
• Cyanide consumption would be reduced.

• Wildlife mortalities due to elevated tailings pond cyanide concentrations would be reduced or
eliminated.
• Liability due to cyanide leakage from tailings pond would be reduced.
• Requirements for tailings pond liners could be reduced.
Additionally, if treatment of pond water is required prior to discharge, operating costs associated
with chemical destruction of residual cyanide would be reduced in proportion to the mass of
cyanide recovered.
5.5 CyanisorbTM Coupled with SO2/Air or Hydrogen Peroxide

TM
Reductions in chemical treatment costs can be realized if Cyanisorb is used to decrease the
mass of cyanide being destroyed. Cyanide recovery and treatment options are presented in the
following sections.
5.5.1 Mill Slurries
Destruction and recovery costs as a function of initial cyanide concentration are shown in Figure
5-4. Assumptions used in estimating costs are:
• 35% solids in slurry.

• Slurry s.g. = 1.30.
• 2,500 TPD mill capacity (920 GPM slurry).
Cyanide recovery costs decrease as the concentration of cyanide increases due to the increased
amount of cyanide recovered per pound of solution processed.

Figure 5-4: Cyanide Recovery and Destruction Costs for 920 gpm Slurry

5.5.2 Tailings Pond Water
Discharge of tailings pond water may be necessary at mines with a positive water balance. Cost
estimates for recovering cyanide from mill slurries and for chemically destroying cyanide in clear
solutions are presented in Tables 4-1, 4-2, and 5-1.
Table 5-1
Cyanide Recovery and Destruction Operating Costs
2,500 TPD Mill Capacity
Description Operating Cost(1)

$/ton $/year
Cyanisorb, 920 GPM slurry, from 300 mg/L to 20 mg/L cyanide -$0.26 -$0.24 million (credit)
Hydrogen Peroxide, 920 GPM slurry, from 300 mg/L to <1 mg/L cyanide $5.48 $5.0 million
SO2/Air, 920 GPM slurry, from 300 mg/L to <1 mg/L cyanide $2.26 $2.1 million
Hydrogen Peroxide, 920 GPM slurry, from 20 mg/L to <1 mg/L cyanide $0.64 $0.58 million
SO2/Air, 920 GPM slurry, from 20 mg/L to <1 mg/L cyanide $0.37 $0.33 million
5.6 Installation at Existing Facilities

TM
Cyanisorb appears well suited for addition to an existing milling operation, however the most
TM
efficient application of Cyanisorb appears to be during design of milling operations. During
design of a new mill, the potential exists to offset the cost of pond with installation of a
TM TM
Cyanisorb process. Cyanisorb can provide significant operating cost savings when installed
where chemical destruction is currently used.
TM
Table 5-1 shows the estimated operating costs associated with Cyanisorb and SO2/air and
hydrogen peroxide cyanide destruction processes.
6.0 ECONOMIC MODEL
6.1 Introduction
TM
This model is used to estimate capital and operating costs for Cyanisorb cyanide recovery,
hydrogen peroxide cyanide destruction and SO2/air cyanide destruction processes. Both metric
units and English units can be used for input and output variables, however the model does not
provide automatic conversion of units.

Rows preceded with an asterisk (*) denote input parameters which are supplied by the user.
Columns marked "TYPICAL VALUE" provide an estimate for some parameters if the user isn't
certain of an appropriate value to input. Rows not marked with an asterisk should not be altered
as the cells contain formulas which would be destroyed.
Two models are available: one titled "SLURRY" for use in predicting process performance with
tailings slurries (e.g. CIP tailings); and one titled "CLEAR" for use in predicting process
performance with clear solutions (e.g. pond decant water). All dollar values given are U.S.$.
The following sentences provide a brief description of the model corresponding to each section of
the output. The tailings properties section provides the properties of the slurry or clear solution,
and calculates the mass flow of cyanide. The operating specifications section provides
information regarding operation of the facility. The reagent costs section provides unit costs for
reagents and power, and should be adjusted according to an individual site's purchase cost. The
reagent usage section specifies the rate of usage for each reagent and power. Typical values have
been taken from operating data from existing plants or from published data. Actual usage would
vary on a site-specific basis.
Capital cost and power usage are calculated from information provided in the estimate basis
section. The input parameters provide the basis for scaling capital cost and power consumption
estimates according to the "six-tenths rule", and are based on the design completed by UniField in
1994. The basis for capital estimates is:
Flow Rate: 920 gpm

Capital Cost: $3.7 Million
Power Usage: 392 kW
If the basis for the cost estimate is different, this section should be adjusted accordingly. The
scaling factor and royalty charge can be changed to suit a particular application.
6.2 Scaled Costs
Calculated estimates for capital cost and power consumption is output in this section. The cell
formulas may need to be changed if the ESTIMATE BASIS is changed, otherwise the cells
should not be altered.
6.3 Operating Costs
Components of operating costs are detailed in this section. None of the rows contain user input
parameters and cells in this section should not be altered. Note that capital depreciation is not
included in the estimate, as the method will vary from site to site. Detailed summaries of the
TM
operating cost comparisons for Cyanisorb , the INCO process, and hydrogen peroxide for both
solutions and slurries are presented in Tables 7-1 through 7-6.







7.0 CONCLUSIONS
The following conclusions are based on the information presented in preceding sections:
1. Cyanide recovery from mill tailings prior to chemical destruction or disposal in a tailings
pond may provide the following benefits:
• Reduced cyanide consumption and associated operating costs.

• Reduced or eliminated tailings pond liner requirements.
• Increased gold recovery.
• Reduced or eliminated wildlife mortalities.
• Reduced potential for liability due to environmental contamination.
• Reduced tailings pond reclamation requirements.
• Reduced post-closure monitoring requirements.
TM
2. Cyanisorb operating costs decrease with increasing influent cyanide concentrations. For
a 2,500 TPD (2,270 MTPD) mill with 35% solids tailings slurry at 300 mg/L WAD
cyanide, the following operating costs associated with utilizing the following solutions for
cyanide recovery are estimated:
Sodium Carbonate: -$0.26 per ton ore (credit)

Sodium Hydroxide: $0.13 per ton ore
TM
3. Reductions in chemical treatment costs can be realized if Cyanisorb is used to decrease
3
the mass of cyanide being destroyed. Detoxifying 920 gpm (210 m /hr) of tailings slurry
prior to disposal in a tailings pond is estimated to cost $2.1 million per year when using
SO2/air to destroy cyanide, and $5.0 million per year when using hydrogen peroxide.
Operating costs are decreased by approximately $1.8 million and $4.4 million per year if
TM
Cyanisorb is used to decrease cyanide concentrations to 20 mg/L prior to cyanide
destruction with SO2/air or hydrogen peroxide, respectively.
TM
4. Applications of Cyanisorb to milling operations include:
• Cyanide recovery from pregnant slurries or clear solutions.

• Cyanide recovery from tailings slurries or clear solutions.
TM
5. Advantages of Cyanisorb when compared to AVR include:
• Lower operating costs.

• Recovery of WAD cyanide.
• Lower pressure drop through process.
• Higher operating pH.

TM
6. Assuming an installation cost of $3.7 million for a Cyanisorb process at a 2,500 TPD
(2,270 MTPD) milling operation producing a tailings effluent with 35% solids, estimated
payback periods for the following cyanide treatment and destruction scenarios are as
follows:
A. Existing facility using hydrogen peroxide to destroy 300 mg/L cyanide in 920
TM
slurry tailings retrofitted with Cyanisorb to reduce slurry to 20 mg/L cyanide
prior to cyanide destruction from 20 mg/L to <1 mg/L.
TM
Operating cost without Cyanisorb : $5,000,000/year
TM
Operating cost with Cyanisorb : $340,000/year
Resultant savings: $4,660,000/year

_______________
Payback period: 0.8 years
B. Existing facility using SO2/air to destroy 300 mg/L cyanide in 920 GPM slurry
TM
tailings retrofitted with Cyanisorb to reduce slurry to 20 mg/L cyanide prior to
cyanide destruction from 20 mg/L to <1 mg/L.
TM
Operating cost without Cyanisorb : $2,100,000/year
TM
Operating cost with Cyanisorb : $90,000/year
Resultant savings: $2,010,000/year

_______________
Payback period: 1.8 years
UniField wishes to thank Mr. Brian Burdett and Mr. Darren Wolfenden at the Golden Cross Mine
TM
for their help in developing this paper and for providing Cyanisorb design and operating
information. The support of Dr. Terry Mudder of Times Limited in providing technical direction
and review is appreciated, as well as the engineering and economic input from Mr. Al Wilder of
Coeur d'Alene Mines Corporation.

9.0 REFERENCES
Chemical Marketing Reporter, October 1, 1993.
Fricker, A.G., "Recovery of Cyanide from Pregnant Gold Pulps", Presented at the Randol Gold
Forum, Reno, Nevada, 1990.
Goldstone, A.J., T.I. Mudder, "Cyanisorb Cyanide Recovery Process Design, Commissioning and
Early Performance", Unreferenced Publication.
Mudder, T.I., Personal Communication, August 1994.
Mudder, T.I., A.J. Goldstone, "The Recovery of Cyanide from Slurries", Paper Presented at the
96th Annual Northwest Mining Convention, Spokane, Washington, December 5-7, 1990.
Omofoma, M.A., A.P. Hampton, "Cyanide Recovery in CCD-Merril Crowe Circuit: Pilot
Testwork of Cyanisorb Process at NERCO DeLamar Silver Mine", Paper Presented at the Randol
Gold Conference, Vancouver, British Columbia, 1992.
Palmer, S.A.K., M.A. Brenton, T.J. Nunni, D.M. Sullivan, N.F. Surprenant, "Metal/Cyanide
Containing Wastes", Pollution Technology Review No. 158, Noyes Data Corporation, New
Jersey, pp. 662-675, 1988.
Simovic, L., W.J. Snodgrass, "Tailings Pond Design for Cyanide Control at Gold Mills Using
Natural Degradation", Paper Presented at Gold Mining Effluent Treatment Seminars, Vancouver,
British Columbia, Feb. 1989.
Smith, A., T.I. Mudder, "Chemistry and Treatment of Cyanidation Wastes", Mining Journal
Books Ltd., London, 1991.
T.W. Higgs Associates Ltd., "Technical Guide for the Environmental Management of Cyanide in
Mining", British Columbia Technical and Research Committee on Reclamation of Cyanide Sub-
Committee, 1992.
Ulrich, G.D., "A Guide to Chemical Engineering Process Design and Economics", John Wiley &
Sons, New York, p. 268, 1994.
TM
UniField Engineering, Inc., "Schedule A Engineering Report, Cyanisorb Cyanide Recovery
Facility", 1994.
UniField Engineering, Inc., "Preliminary Facility Design Report", 1993.
Wilson, H.R., "Tailings Management Program - An Operating Success, Echo Bay's Lupin Mine",
Paper Presented at the Gold Mining Effluent Treatment Seminars, Vancouver, British Columbia,
February 1989.

CYANIDE RECOVERY APPLICATIONS FOR CCD CIRCUITS
Prepared By:

Terry Mudder, Ph.D.
Originally presented at the Randol Gold & Silver Forum, Denver, Colorado, April 26-28, 1998
Cyanide Recovery Applications for CCD Circuits
1.0 INTRODUCTION
Cyanidation of silver ores typically requires higher concentrations of cyanide in comparison to

gold ores to affect similar leaching rates and metal recoveries. The requirement for high cyanide
concentrations in a silver ore leaching circuit may translate into higher operating costs, however-
with operation of an acidification-volatilization-reabsorption (AVR) plant to recover and recycle
tailings cyanide, cyanide consumptions can be significantly reduced. At each of the currently
operating AVR plants in the world, overall cyanide consumptions have been reduced by
approximately one-half by recovering and recycling tailings cyanide. In addition, the AVR plants
have reduced final tailings cyanide concentrations to less than 20 to 30 mg/L WAD cyanide and
reduced potential adverse impacts to wildlife in the tailings impoundments. This paper presents
an analysis of the application of AVR to a generic silver ore leaching operation which has a
CCD/Merrill-Crowe circuit included in the metallurgical plant.
2.0 REFERENCE PLANT DESCRIPTION
The acidification-volatilization-reabsorption (AVR) process has been practiced for more than 50
years at approximately ten sites worldwide. Generally, the process consists of acidifying mine
tailings to convert soluble cyanides to hydrogen cyanide, stripping hydrogen cyanide from
solution and recovering the hydrogen cyanide gas into sodium hydroxide or lime to yield a
concentrated solution of recovered cyanide. Details of the process are presented by Smith and
Mudder (1991), Omofoma and Hampton (1992) and Botz et al. (1995).
To determine the effects of incorporating cyanide recovery into a silver ore cyanidation
operation, conceptual process designs were completed for a reference milling and leaching
operation. A description of the reference operation selected for this evaluation is presented in
Table 1. The 1 million tonne per year reference plant was modeled in METSIM and includes a
conventional grinding circuit followed by agitated tank cyanidation of pulp at 45% solids.
Precious metals recovery from the leached pulp is conducted in a 5-stage countercurrent
decantation (CCD) circuit and pregnant solution overflowing from the first stage CCD thickener
is directed to a Merrill-Crowe circuit. The leach circuit is operated with 600 mg/L of weak-acid-
dissociable (WAD) cyanide in leach tailings.

Table 1
Reference Plant Milling and Leaching Operation
Mill Throughput, tonnes per year 1,000,000
Mill Availability 90%
Leach Pulp % Solids 45%
Leach Tailings WAD Cyanide, mg/L as CN 600
CCD Circuit Wash Ratio, tonnes wash water per tonne solids 3.5:1
Number CCD Stages 5
Interstage CCD Wash Efficiency 97%
Dissolved Value Recovery in CCD Circuit 98.1%
CCD Thickener Underflow % Solids 50%
Cyanide Recovery Efficiency, % WAD CN 95%
Two options for recovering cyanide in the reference plant were considered in this evaluation:
Case 1
Referencing Figure 1, the first evaluation was conducted assuming that a portion of barren
solution exiting the Merrill- Crowe circuit is directed to an AVR plant for cyanide recovery. The
flowrate of solution directed to the AVR plant is controlled according to the volume of wash
water required in the CCD circuit, while the remaining barren solution is directly recycled to the
grinding circuit without cyanide recovery. Effluent from the AVR plant contains a low
concentration of cyanide, therefore the CCD circuit would function to wash both metals and
cyanide from the pregnant pulp. Final tailings are discharged to the tailings impoundment from
the number 5 CCD thickener underflow at a concentration of approximately 12 mg/L of WAD
cyanide. A summary of the water and cyanide balances for Case 1 is provided in Table 2. The
AVR plant for Case 1 processes approximately 409 m3/hour of Merrill-Crowe barren solution
with a W AD cyanide concentration of approximately 203 mg/L.

Fresh NaCN Wash Water
Ore Tailings Pulp

Crushing & 5-Stage CCD
Leach Circuit
Grinding Circuits Circuit
Pregnant Solution
Au/Ag Product
Merrill-Crowe
Circuit
Recycle Barren Solution
Barren Solution
Recovered NaCN Barren Bleed

AVR Plant
(optional)
Figure 1
AVR-CCD Configuration - Case 1
Case 2
The evaluation for-Case 2 was conducted using the same metallurgical circuit described for Case
I except that the AVR plant processes tailings pulp from the number 5 CCD thickener underflow.
In this configuration, the cyanidation, CCD and Merrill-Crowe circuits all operate with high
cyanide concentrations since cyanide is not removed from solution until the pulp tailings are
discharged from the CCD circuit. A flowsheet for Case 2 is presented as Figure 2, while Table 2
provides a summary of the water and cyanide balances. The AVR plant for Case 2 processes
approximately 160 m3/hour of tailings pulp at 50% solids and 600 mg/L of W AD cyanide.
Table 2
Water and WAD Cyanide Balances for the Reference Plants
Case 1 Case 2
m3/hour m3/hour mg/L kg/day mg/L kg/day
Pulp Solution CN NaCN CN NaCN
Pregnant Pulp to CCD 186 143 600 3,872 600 3,872
Wash Solution to CCD -- 409 10 188 600 11,089
Pregnant Solution from CCD -- 435 203 3,999 600 11,797
#5 CCD Thickener Underflow Pulp 160 117 12 61 600 3,165
Barren Tailings Pulp to Impoundment 160 117 12 61 30 158

Recovered NaCN
Fresh NaCN Wash Water
Ore Crushing & 5-Stage CCD Tailings Pulp

Leach Circuit AVR Plant
Grinding Circuits Circuit
Pregnant Solution
Merrill-Crowe
Barren Solution
Circuit
Recycle Barren Solution
Au/Ag Product
Figure 2
AVR-CCD Configuration - Case 2
Though the data presented in Table 2 are based on a simplified analysis, the following are
observed in regard to design of the AVR plant:
1. Recovery of cyanide from Merrill-Crowe barren solution in Case I results in a relatively

large hydraulic design of the AVR plant as a result of dilution occurring in the CCD
circuit. In addition, the cyanide concentration is diluted in the CCD circuit from 600
mg/L in the pregnant pulp to approximately 200 mg/L in the clarified pregnant solution.
The Case I configuration yields the lowest tailings cyanide concentration and minimizes
the concentration of cyanide recirculating in the- CCD circuit, however a larger AVR
plant is required.
2. Recovery of cyanide from tailings pulp in Case 2 is advantageous in that a smaller

volume of pulp is processed and the pulp cyanide concentration is not diluted as a result
of washing in the CCD circuit. The Case 2 configuration yields a lower tailings cyanide
concentration while minimizing the size of the AVR plant.
3.0 ECONOMIC ANALYSIS
Construction and operating costs for the two reference plants were developed according to data
gathered from pilot and full-scale AVR plants. The economics were based on typical US mine
site conditions and reagent purchase prices as outlined in Table 3. Construction cost estimates
include equipment purchase and installation plus plant design costs. Operating costs include
reagents, power, labor and maintenance.

Table 3
Operating Cost Basis
Sulfuric Acid (98%), $/kg $0.10
Sodium Hydroxide (100%), $/kg $0.40
Lime (CaO), $/kg $0.06
Sodium Cyanide, $/kg $1.30
Power, $/kW-hour $0.05
Labor, $/hour $20
A summary of the reference plant construction and operating costs are presented in Table 4.
Construction costs for the two plants are similar, though the hydraulic throughputs are 409 and
160 m3/hour for Cases 1 and 2, respectively. In terms of a constructed cost as a function of
hydraulic throughput, the plant designed for pulp service is more expensive relative to the clear
solution plant due to the additional and more robust equipment required for pulp service. The
operating cost for Case 2 is significantly lower than for Case 1 due to the more concentrated
cyanide pulp being processed under Case 2. However, with either plant the operating costs of
$1.10 and $0.82 per kilogram of recovered sodium cyanide are less than the $1.30 per kilogram
cost for newly purchased sodium cyanide. In each case nearly $1.5 million per year of sodium
cyanide is recovered and the value of cyanide discharged to the tailings impoundment is reduced
to less than $75,000 per year. These economics are even more attractive when compared to
cyanide destruction alternatives for which operating costs generally range from $0.50 to $1.00
per kilogram of sodium cyanide destroyed.
Table 4
Reference Plants Economic Summary
Case 1 Case 2
AVR Plant Constructed Cost 5,500,000 $4,500,000
AVR Plant Operating Cost, $/kg recovered NaCN $1.10 $0.82
Value of Recovered Cyanide, $/year $1,500,000 $1,400,000
Value of Cyanide Discharged to Tailings Impoundment, $/year $26,000 $67,000
4.0 OPERATING PLANTS
The Kinross DeLamar Mining Company in the USA currently operates a gold/silver cyanidation
plant with a 5-stage CCD circuit and Merrill-Crowe circuit. At this operation, approximately 350
m3lhour of Merrill-Crowe barren solution is processed for cyanide recovery in an AVR plant,
which affects the removal of greater than 95% of the influent WAD cyanide. As a result of
operating the AVR plant, the concentration of WAD cyanide in final tailings is reduced to less
than 30 mg/L and the concentration of cyanide in the tailings impoundment is reduced to less
than 10 mg/L as a result of natural degradation.

The flowsheet for this plant is similar to that presented in Figure 1, though the AVR plant feed
solution contains approximately-350 to 500 mg/L of WAD cyanide and a CCD circuit wash ratio
of less than 3.5:1 is used. This AVR plant has been in operation for approximately 6 years and
has decreased the site's sodium cyanide purchases by more than one-half since commissioning of
the AVR plant. The operating cost for the plant is estimated to be approximately $0.70 to-$0.80
per kilogram of recovered sodium cyanide.
The DeLamar plant was originally designed to operate with tailings pulp from the number 5
CCD thickener underflow, however due to solids build-up in the stripping towers the plant was
subsequently switched to clear solution operation. The solids build-up was due primarily to
gypsum precipitation and this required shut-down and cleaning of the stripping towers every six
to nine months. Since a 5-stage CCD circuit was already in operation at the site, transfer to clear
solution was readily accomplished, but serious concerns regarding the ability of an AVR plant to
operate with a tailings pulp were raised. In response, UniField constructed and operated several
stripping towers to test varying designs and their ability to both resist and accommodate solids
build-up. Following several successful long-term pilot tests, the redesigned stripping tower
operated with greater than 95% efficiency, resisted solids build-up, allowed quick access for
internals inspection and efficient operations were maintained with as much as 2.5 centimeters of
solids build-up. The proprietary stripping tower design has been included in the AVR plant
constructed at AngloGold’s Cerro Vanguardia mine in Argentina which was placed into
operation in September, 1998.
A summary of AVR plants operating or under construction is provided in Table 5. In general,

these plants have reduced overall sodium cyanide consumptions at the sites by approximately
one-half and yielded investment paybacks of two to four years.
Table 5
Summary of AVR Cyanide Recovery Plants
Plant Leach Commissioning AVR Plant Feed Solution
Tonnage Date WAD CN or Pulp
(tonnes/day) (mg/L)
Golden Cross – New Zealand 1,800 1991 150 to 200 Pulp
DeLamar – USA 3,700 1992 350 to 500 Solution
Rio Paracatu – Brazil 1,000 1998 1,000 to 1,500 Solution
Cerro Vanguardia – Argentina 2,000 1998 600 to 1,200 Pulp

5.0 SUMMARY AND CONCLUSIONS
The analysis presented in this paper is relative to the application of AVR to a Merrill-Crowe
operation, however AVR has broad applicability to most cyanide-containing pulps or clear
solutions. In general, an AVR plant can recover cyanide from a solution or pulp containing 150
mg/L or more of WAD cyanide for less than the purchase price of sodium cyanide. In addition,
since an AVR plant recovers most of the cyanide contained in tailings pulp or barren solution,
leach circuits can be operated at very high cyanide concentrations with only a minor increase in
the overall cyanide consumption. For proposed silver leaching operations, incorporation of an
AVR circuit would significantly reduce concerns associated with optimizing silver extractions
while minimizing the leach cyanide concentration since a majority of cyanide is recycled with an
AVR process.
Given an equal choice between operation of an AVR plant with clear solution or pulp, the
selection would be clear solution due to ease of design, operation and maintenance associated
with clear solutions. However, reliable and efficient handling of pulp in an AVR plant has been
demonstrated and the choice of clear solution versus pulp is now based upon the preferred
metallurgical circuit configuration and minimizing the cost for cyanide recovery.
6.0 REFERENCES
Smith, A. and T. Mudder, "Chemistry and Treatment of Cyanidation Wastes", Mining Journal
Books Limited, London, 1991.
Omofoma, M. and A. Hampton, "Cyanide Recovery in a CCD Merrill-Crowe Circuit: Pilot

Testwork of a Cyanisorb Process at the NERCO DeLamar Silver Mine", Presented at Randol
Gold Forum, Vancouver, British Columbia, 1992.
Botz, M., J. Stevenson, A. Wilder, R. Richins, T. Mudder and B. Burdett, "Cyanide Recovery
and Destruction", Engineering & Mining Journal, pp. 44-47, June, 1995.

PROCESSES FOR THE REGENERATION OF
CYANIDE FROM THIOCYANATE
Prepared By:

Dimitri Dimitriadis
Tony Polglase
Wayne Phillips
Rudolf Jenny
Originally published in Proceedings of the 2000 SME Annual Meeting and Exhibit, Salt Lake
City, Utah, February 28 – March 1, 2000
Processes for the Recovery of Cyanide from Thiocyanate
ABSTRACT
Cyanidation processes for the extraction of gold or silver frequently involve the processing of
sulfur-containing solids which react with cyanide to form thiocyanate. The formation of
thiocyanate is an undesired side-reaction, and in many cases thiocyanate formation results in a
prohibitively high cyanide consumption. With the increasing number of gold and silver mining
projects which involve the processing of sulfide ores or concentrates or which utilize a biological
sulfur oxidation process, more attention has been focused on minimizing thiocyanate formation
and in treating solutions to eliminate toxicity associated with thiocyanate. Though not yet
commercially applied, there are several processes available to recover cyanide from thiocyanate
to both reduce tailings toxicity and allow the reuse of cyanide otherwise lost to thiocyanate
formation. This paper presents an overview of processes available for recovering cyanide from
thiocyanate along with estimated operating costs for the processes. Pilot testing data suggests
that in some cases, cyanide can be recovered from thiocyanate for approximately the same cost
as newly purchased cyanide.
1.0 INTRODUCTION
It is generally believed that thiocyanate (SCN-) is formed during cyanide leaching operations as a
result of reactions between cyanide (CN-) and sulfur species, including solid or dissolved sulfur.
Examples of these reactions include the following:
(1) Elemental Sulfur So + CN- → SCN-

(2) Sulfide S-2 + CN- + H2O + ½O2 → SCN- + 2OH-
(3) Thiosulfate S2O3-2 + CN- → SO3-2 + SCN-
Depending on the sulfur content of solids in contact with cyanide, resultant concentrations of
thiocyanate in solution may range from a few mg/L to well over 1,000 mg/L in some cases. In
an extreme case, it has been found that cyanidation circuits following biological sulfur oxidation
processes may contain in excess of 5,000 mg/L of thiocyanate as a result of cyanide interactions
with oxidized and partially oxidized sulfur species. High thiocyanate concentrations are also
commonly found in cyanidation circuits processing high sulfide ores or concentrates.
Some process and environmental impacts associated with thiocyanate formation in a

metallurgical circuit include the following:
1. It is becoming increasingly common to utilize bacterial oxidation circuits for the pre-
treatment of sulfide-containing ores and concentrates to liberate gold for subsequent cyanide
leaching operations. The bacteria used in these oxidation circuits are sensitive to cyanide and
thiocyanate, and concentrations of these species in excess of approximately 10 mg/L are
toxic. Therefore, it is important in these circuits that cyanide and thiocyanate-containing
solutions be segregated from bacterial oxidation circuits. This is accomplished by
maintaining separate solution circuits for bacterial oxidation and cyanide leaching, or by
treating excess cyanidation solutions for cyanide and thiocyanate removal.
308 M. Botz et al.

2. While not commonly regulated in water discharges, thiocyanate may be toxic to aquatic
species. If a water discharge is subject to compliance with a toxicity test, such as the
USEPA’s Whole Effluent Toxicity (WET) test, thiocyanate may be of concern. Since
thiocyanate is not destroyed in most cyanide detoxification processes, an additional treatment
technology may be required if thiocyanate removal is necessary.
3. If it is assumed that sodium cyanide is purchased for $1.30 per kilogram, then each kilogram
of thiocyanate formed in a leaching circuit indirectly costs about $1.10 as a result of
increased cyanide consumption. Referencing Table 1, this could translate into an operating
cost well in excess of $1.0 million per year for a thiocyanate concentration greater than 1,000
mg/L in a cyanide leaching circuit.
Table 1
Operating Cost Associated with Thiocyanate Formation
Thiocyanate Concentration Annual NaCN Cost Due to
(mg/L) Thiocyanate Formation
500 $0.8 million
1,000 $1.5 million
5,000 $7.0 million
Note: Calculated for a solution flow of 150 m3/hour and NaCN
purchase price of $1.30 per kilogram.
As noted in the following sections, the cost of cyanide regeneration may be less than that
associated with thiocyanate destruction due to the chemical behavior of thiocyanate in low pH
systems.
2.0 THIOCYANATE CHEMISTRY
Regeneration of cyanide from thiocyanate requires the simultaneous chemical reduction of

carbon and the oxidation of sulfur in the SCN complex to yield free cyanide and sulfate. This
process is illustrated in the following half-reaction for the oxidation of thiocyanate to cyanide (all
potentials are relative to the Standard Hydrogen Electrode):
(4) SCN- + 4H2O → SO4-2 + CN- + 8H+ + 6e-

Eo = -0.490 V
Referencing Table 2, in this reaction carbon is reduced from C(IV) to C(II) while sulfur is
oxidized from S(-II) to S(VI). This reaction has been investigated with chemical oxidants and
electrolytically, however to date there have been no full-scale applications of such a process.
309 M. Botz et al.

A significant difficulty encountered with thiocyanate oxidation to cyanide is the tendency to

fully oxidize thiocyanate to cyanide then to cyanate:
(5) CN- + H2O → OCN- + 2H+ + 2e-

Eo = 0.169 V
If this reaction occurs, the first step via Reaction (4) would result in the regeneration of free
cyanide, but this cyanide would subsequently be destroyed via Reaction (5) by further oxidation
to cyanate. Therefore, to affect the regeneration of cyanide from thiocyanate, it is necessary to
promote the completion of Reaction (4) while minimizing the extent of Reaction (5).
Several researchers have noted that Reaction (4) will take place at an acidic pH, and in this case
aqueous hydrogen cyanide is formed in lieu of the free cyanide anion:
(6) SCN- + 4H2O → SO4-2 + HCN + 7H+ + 6e-

Eo = -0.399 V
Under acidic conditions, it has been found that Reaction (5) does not occur to a significant extent
and that cyanide regeneration via Reaction (6) may proceed to near completion. Note that
Reaction (6) is acid-generating, therefore there is a tendency for the reaction to naturally lower
the solution pH thereby preventing cyanide oxidation via Reaction (5). This behavior is
advantageous in a cyanide regeneration system, as described below.
3.0 REGENERATION CHEMISTRY
Thermodynamics suggest that cyanide regeneration via Reaction (6) is possible provided that the
reaction environment has an oxidation potential greater than approximately –0.4 V. This
potential could be provided as an induced voltage, or in reference to Table 3, by a suitable
chemical oxidant. Note that although thermodynamic data in Table 3 suggest that several
oxidants would be suitable to affect cyanide regeneration from thiocyanate, including oxygen,
only a few have been demonstrated to affect this reaction at an appreciable rate. A summary of
the chemistry associated with the oxidants listed in Table 3 is presented in the following sections.
Table 2
Oxidation States of Thiocyanate-Related Compounds
Element Oxidation State
Compound Formula
C N S O
-
Cyanide CN +2 -3
Thiocyanate SCN- +4 -3 -2
-
Cyanate OCN +4 -3 -2
Thiosulfate S2O3-2 +2 -2
-2
Sulfite SO3 +4 -2
Sulfate SO4-2 +6 -2
310 M. Botz et al.

Table 3
Half-Reactions for Oxidants (Relative to the Standard Hydrogen Electrode)
Oxidant Oxidant Half-Reaction Eo (V)
Oxygen O2(g) + 4H+ + 4e- → 2H2O 1.229
Chlorine Cl2(g) + 2e → 2Cl
- -
1.361
Hydrogen Peroxide H2O2 + 2H + 2e → 2H2O
+ -
1.763
Caro’s Acid H2SO5 + 2e- → SO4-2 + H2O 1.974
Sulfur Dioxide SO2(g) + O2(g) + 2e → SO4
- -2
2.303
Ozone O3(g) + 6H + 6e → 3H2O
+ -
4.532
Oxygen
The obvious advantage of utilizing oxygen for cyanide regeneration from thiocyanate would be
its relative inexpensive availability in atmospheric air. However, work of the author’s suggests
that if the regeneration reaction does take place with oxygen, it is prohibitively slow for practical
application, and therefore additional information is not presented here relative to oxygen. At this
time, work is being conducted by the authors to evaluate the possibility of using oxygen for this
reaction in the presence of solid and aqueous catalysts.
Chlorine
Chlorine has been widely used for cyanide destruction, though this process typically takes place
at a pH above about 10.0 and results in the complete oxidation of thiocyanate and/or cyanide to
form cyanate. At a low pH chlorine may partially oxidize thiocyanate to yield cyanide (Flynn
and McGill, 1995), as illustrated in the following reaction.
(7) SCN- + 3Cl2(g) + 4H2O → SO4-2 + HCN + 7H+ + 6Cl-
In addition, chlorine is known to oxidize cyanide to cyanate via the following reaction:
(8) CN- + Cl2(g) + H2O → OCN- + 2H+ + 2Cl-
Reagent demands associated with cyanide regeneration (Reaction (7)) and complete thiocyanate
destruction (Reaction (7) plus Reaction (8)) with chlorine are summarized in Table 4. Note that
the estimated lime demands are also shown in Table 4 as needed to neutralize acid generated in
the reactions.
Hydrogen Peroxide
Similar to chlorine, hydrogen peroxide has been widely used for cyanide destruction and has also
been demonstrated to affect the regeneration of cyanide from thiocyanate at a low pH (Wilson
and Harris, 1960a and 1960b). The reaction of thiocyanate with hydrogen peroxide to yield free
cyanide is:
(9) SCN- + 3H2O2 → SO4-2 + HCN + H+ + 2H2O
311 M. Botz et al.

In addition, hydrogen peroxide is known to oxidize cyanide to cyanate in the presence of a

soluble copper catalyst via the following reaction:
(10) CN- + H2O2 → OCN- + 2H2O
Reagent demands associated with cyanide regeneration and complete thiocyanate destruction
with hydrogen peroxide are summarized in Table 5.
Although Soto et al. (1995) indicate that hydrogen peroxide is not a sufficiently strong oxidant to
affect the oxidation of thiocyanate to cyanide, it has been well established that this can be done
(Wilson and Harris, 1960a and 1960b; Orbán, 1986). Wilson and Harris (1960b) focused on
determining the reaction sequence and stoichiometry for complete thiocyanate oxidation with
hydrogen peroxide, however experimental data showing the formation of free cyanide as an
intermediate were also presented. In one of the experiments, a less than stoichiometric dosage of
hydrogen peroxide partially oxidized thiocyanate, with 75% of the reaction products being free
cyanide and 25% being other cyanide-related compounds. It was also noted that the presence of
dissolved copper resulted in the rapid catalytic oxidation of cyanide to cyanate, even at a low pH,
thereby destroying any regenerated cyanide.
Therefore, with this reaction it is critical to ensure that the dissolved copper concentration is
sufficiently low to minimize the catalytic oxidation of cyanide to cyanate.
Table 4
Stoichiometric Reagent Demands for
Thiocyanate and Cyanide Oxidation with Chlorine
Reaction Reagent Demand
Cyanide Regeneration 3.67 g Cl2/g SCN regenerated
3.86 g CaO/g SCN regenerated
Complete Thiocyanate Destruction 4.90 g Cl2/g SCN destroyed
4.83 g CaO/g SCN destroyed
Table 5
Thiocyanate and Cyanide Oxidation with Hydrogen Peroxide
Cyanide Regeneration 1.76 g H2O2/g SCN regenerated
Complete Thiocyanate Destruction 2.35 g H2O2/g SCN destroyed
312 M. Botz et al.

Caro’s Acid
Caro’s acid, also known as peroxymonosulfuric acid, has the chemical formula H2SO5 and is
generated through the reaction of sulfuric acid with hydrogen peroxide. Caro’s acid is a
relatively strong oxidant and is increasingly being used for the destruction of cyanide in the
mining industry. At a low pH, Caro’s acid is capable of regenerating cyanide from thiocyanate
(Smith and Wilson, 1966), as illustrated in the following reaction:
(11) SCN- + 3H2SO5 + H2O → 4SO4-2 + HCN + 7H+
In addition, Caro’s acid is known to oxidize cyanide to cyanate via the following reaction:
(12) CN- + H2SO5 → OCN- + SO4-2 + 2H+
with Caro’s acid are summarized in Table 6.
Sulfur Dioxide
Sulfur dioxide based processes may be the most widely used for cyanide destruction in the
mining industry, though thiocyanate destruction with this process is typically less than 10% at
reaction conditions required for efficient cyanide destruction. The use of sulfur dioxide and
oxygen for thiocyanate oxidation to regenerate cyanide has not been thoroughly investigated,
though the following reaction may occur at an acidic pH:
(13) SCN- + 3SO2(g) + 3O2(g) + 4H2O → 4SO4-2 + HCN + 7H+
In addition, sulfur dioxide and air are known to oxidize cyanide to cyanate in the presence of a
soluble copper catalyst and oxygen via the following reaction:
(14) CN- + SO2(g) + O2(g) + H2O → OCN- + SO4-2 + 2H+
with sulfur dioxide are summarized in Table 7.
Ozone
Ozone is a strong oxidant and widely used for water and wastewater treatment for the oxidation
of contaminants. Relative to cyanide destruction, ozone use is typically limited to small-volume
and low-concentration systems due to its relatively high cost in comparison to other oxidants
such as chlorine, hydrogen peroxide and sulfur dioxide. However, it has been well documented
that ozone is efficient at regenerating cyanide from thiocyanate (Layne et al., 1984; Jara et al.,
1996). The thiocyanate and cyanide oxidation reactions which occur with ozone are:
(15) SCN- + O3(g) + H2O → SO4-2 + HCN + H+
(16) CN- + 1/3O3(g) → OCN-
313 M. Botz et al.

with ozone are summarized in Table 8. Note that the redox reaction for ozone listed in Table 3 is
not that typically listed in published compilations of redox potentials. However, as described in
a following section, the experimentally observed stoichiometry for ozone oxidation of
thiocyanate to regenerate cyanide is approximately one mole of ozone per mole of thiocyanate
oxidized. This indicates that the reaction as listed in Table 3 applies to the ozone-thiocyanate
oxidation system at an acidic pH.
Table 6
Thiocyanate and Cyanide Oxidation with Caro’s Acid
Cyanide Regeneration 5.90 g H2SO5/g SCN regenerated
Complete Thiocyanate Destruction 7.86 g H2SO5/g SCN destroyed
Table 7
Thiocyanate and Cyanide Oxidation with Sulfur Dioxide and Air
Cyanide Regeneration 3.31 g SO2/g SCN regenerated
Complete Thiocyanate Destruction 4.41 g SO2/g SCN destroyed
To date, the majority of experimental work conducted using chemical oxidants to regenerate
cyanide from thiocyanate has been performed using ozone. Representative results are presented
in Figure 1 which shows the concentration of cyanide-related compounds as a function of time in
an ozonation reactor (Layne et al., 1984). Referencing Figure 1, during the first 20 minutes of
the reaction there is a rapid decrease in the thiocyanate concentration which corresponds to a
rapid increase in the cyanide concentration. Beyond 20 minutes of reaction time, the cyanide
concentration begins to decrease, and at 40 minutes the cyanide concentration approaches zero.
Through most of the reaction there is a gradual increase in the concentration of cyanate (OCN-),
indicating that the oxidation of cyanide to cyanate competes with thiocyanate oxidation, though
this reaction rate is relatively slow. At approximately 20 minutes of reaction time the cyanide
concentration is a maximum and cyanide regeneration is approximately 75%. These results
parallel those presented by Kemker et al. (1980) in which a maximum cyanide regeneration of
approximately 80% to 85% was observed at a pH of 10.0.
314 M. Botz et al.

Figure 1
Ozone Oxidation of Thiocyanate
Source: Layne et al. (1984)
315 M. Botz et al.

Results presented in Figure 1 were generated at a solution pH of 11.2, however Soto et al. (1995)
indicate that the ozonation reaction and subsequent regeneration of cyanide is pH dependent.
Referencing Figure 2, it appears that above a pH of approximately 10.0, cyanide formed through
the oxidation of thiocyanate is subsequently oxidized to cyanate. The rate of cyanide oxidation
to cyanate decreases as the pH decreases, with negligible oxidation below a pH of approximately
4.0. This observation is explained by the pH behavior of cyanide in solution where at a high pH
cyanide is present in solution as CN- and is susceptible to attack by ozone. However, at a low
pH, cyanide will be present primarily as HCN which is less susceptible to attack by ozone.
Table 8
Thiocyanate and Cyanide Oxidation with Ozone
Cyanide Regeneration 0.83 g O3/g SCN regenerated
Complete Thiocyanate Destruction 1.10 g O3/g SCN destroyed
The effect of dissolved copper on the oxidation rate of cyanide to cyanate by ozone is quite
significant and a copper concentration in excess of approximately 10 to 50 mg/L results in
significant oxidation of cyanide to cyanate at any pH. The catalytic action of copper to promote
cyanide oxidation to cyanate has been observed by many others and forms a basis for several
cyanide destruction patents (Mathre, 1971; Neville, 1980; Borbely et al., 1984). However,
removal of copper from solution to less than approximately 10 mg/L reduces cyanide oxidation
to a low level and accommodates the regeneration of cyanide from thiocyanate. Processes
available for the removal of copper from cyanide leach solutions are discussed in Botz and
Parodi (1997) and Botz (2001).
4.0 ELECTROLYTIC OXIDATION OF THIOCYANATE
In addition to chemical oxidation of thiocyanate, an induced electric potential can also be used to
provide the oxidizing environment to regenerate free cyanide. Electrolytic oxidation of
thiocyanate to regenerate cyanide has been researched on a small-scale, but to date there have
been no full-scale applications.
The reactions representing the electrolytic oxidation of thiocyanate to yield cyanide, cyanate and
sulfate are (Byerley and Enns, 1984):
(17) SCN- + 4H2O → CN- + SO4-2 + 8H+ + 6e-

Eo = -0.490
(18) SCN- + 5H2O → OCN- + SO4-2 + 10H+ + 8e-

Eo = -0.325 V
316 M. Botz et al.

Figure 2
Effect of pH on Ozone Oxidation of Thiocyanate
Source: Soto et al. (1995)
317 M. Botz et al.

In addition to the above reactions which occur at the anode of an electrolytic cell, water is
oxidized at the anode to yield oxygen gas according to:
(19) 2H2O → O2 + 4H+ + 4e-

Eo = -1.229 V
Occurring simultaneously at the cathode is the reduction of water to form hydrogen gas:
(20) 2H2O + 2e- → H2 + 2OH-

Eo = -0.828 V
Other reactions in addition to Reaction (20) will also occur at the cathode if suitable compounds
are present in solution. For example, the copper-cyanide complexes will react at the cathode to
give elemental copper, while at the anode thiocyanate will oxidize to yield free cyanide
(Dickson, 1989). It has been experimentally observed that Reactions (17) through (20) occur
simultaneously at the cathode and anode, respectively, however reaction conditions can be
controlled to maximize cyanide regeneration according to Reaction (17).
Byerley and Enns (1984) presented experimental data for electrolytic oxidation of thiocyanate
using synthetic solutions at varying pH values. It was found that approximately 80% cyanide
regeneration could be affected with a solution pH of approximately 2.0 to 2.5, with significantly
lower regeneration efficiencies observed at neutral to alkaline pH values. This was explained by
the pH behavior of cyanide solutions in which free cyanide is present primarily as the cyanide
anion at high pH values and this complex is susceptible to oxidation to cyanate. At low pH
values, cyanide is present primarily as undissociated hydrogen cyanide, which is less susceptible
to electrolytic oxidation to cyanate.
Representative electrolytic cyanide regeneration data presented by Byerley and Enns (1984) is
provided in Figure 3. As indicated, after approximately 200 minutes of reaction time, the
cyanide regeneration is about 82% at a final solution pH of 2.4. Similar experiments conducted
at a pH of 10.7 gave a maximum cyanide regeneration of 13% after approximately 30 minutes of
reaction time, however beyond 30 minutes the regeneration efficiency decreased and approached
zero at 120 minutes. Byerley and Enns (1984) indicated that electrical power usage for the
regeneration of cyanide from thiocyanate is approximately 0.03 kW-hour per gram of
thiocyanate oxidized.
318 M. Botz et al.

Figure 3
Electrolytic Oxidation of Thiocyanate
Source: Byerley and Enns (1984)
319 M. Botz et al.

5.0 PILOT TESTING RESULTS
In 1998 and 1999, TVX Hellas investigated the possibility of regenerating cyanide from
thiocyanate at its Olympias project in Greece. Gold and silver ore at the Olympias project is
refractory and near complete oxidation of mineral sulfides is required to permit efficient
extraction of gold and silver via cyanidation. In laboratory and pilot studies conducted with
bacterially oxidized ore samples, it was observed that cyanide reactions with oxidized and
partially-oxidized sulfur species resulted in a significant generation of thiocyanate in the
proposed leach process. Thiocyanate concentrations in the tailings ranged from a low of about
2.5 g/L to a high in excess of 12 g/L in the tests conducted. The high amount of thiocyanate
formed in the process was responsible for approximately 90% of the total cyanide consumption
in the circuit, and as a result, options for recovering cyanide from thiocyanate were investigated.
Following a review of regeneration process options, TVX proceeded with small-scale pilot
testing of ozone oxidation of thiocyanate to regenerate free cyanide. The following is a summary
of this testwork which was conducted using a synthetic thiocyanate solution and samples of
laboratory-generated tailings pulp.
Pilot Tests
Pilot testing of the ozone regeneration of cyanide from thiocyanate was conducted by Ozonia at
their laboratory in Bern, Switzerland in 1998. Pilot testing involved the continuous pumping of
pulp or solution through a bubble column reactor which was sparged with ozone-containing gas.
During this time, ozone consumption and concentrations of thiocyanate, cyanide and cyanate
were monitored and the cyanide regeneration efficiency as a function of pH, ozone dosage and
time was determined. For the first one to two hours of reaction time, the pulp or solution pH was
allowed to decrease from an initial value of approximately 10.5 to less than 2.0 according to the
acid-generating reaction:
(21) SCN- + O3(g) + H2O → SO4-2 + HCN + H+
Results for one test conducted with a synthetic thiocyanate solution prepared with potassium
thiocyanate are presented in Table 9. For this test, the reactor was operated for a total of nine
hours, and the average cyanide regeneration efficiency was 85%. The overall cyanide balance
calculated for this test with thiocyanate and total cyanide analyses closed to within 95% to 99%,
indicating that oxidation of cyanide to cyanate was not significant. The consumption of ozone
during this test was approximately 0.93 grams per gram of oxidized thiocyanate, or about 1.12
moles of ozone per mole of oxidized thiocyanate. This is in close agreement with the
stoichiometry of Reaction (21) and data published by Palmer et al. (1988) and represents about
10% excess ozone consumed in the process.
Ozone was fed to the bubble column reactor as a gas mixture with oxygen, and as a result a
portion of regenerated cyanide was volatilized from the reactor as hydrogen cyanide gas. On
average, approximately 5% of the cyanide was volatilized as HCN, while the remaining 95%
reported in the solution discharged from the reactor. Data in Table 9 for the treated solution
include cyanide volatilized from the reactor, which was absorbed in an off-gas caustic scrubber.
320 M. Botz et al.

A similar test was conducted with laboratory-generated tailings pulp to assess the impact of
solids on the performance of the ozone reaction with thiocyanate. The test was conducted with
pulp at approximately 40% solids and the average cyanide regeneration efficiency during the test
was about 50%. A summary of results from this test are presented in Table 10.
The cyanide regeneration efficiency for the test involving pulp was significantly less than that
observed using clear solution. For the test with pulp, approximately 10% of the feed thiocyanate
went unreacted, 50% was converted to free cyanide and 20% was converted to cyanate (OCN).
Accordingly, a total of approximately 80% of the feed thiocyanate was accounted for in
thiocyanate, cyanide and cyanate analyses, while the remaining 20% was unaccounted for in the
mass balance. It is anticipated that the unaccounted for thiocyanate in the mass balance may
have been precipitated as a metal-cyanide and/or metal-thiocyanate complexes due to solution-
solid reactions at the low pH conditions. Also, the relatively high amount of thiocyanate
converted to cyanate was likely due to the presence of copper in solution which acted to catalyze
the oxidation of thiocyanate fully to cyanate. Testwork at Ozonia is ongoing to further define
reactions of ozone in a pulp system and to evaluate reaction conditions for optimal cyanide
regeneration efficiency. As with the solution test, hydrogen cyanide gas from the bubble column
reactor was collected in a caustic scrubber, and for this test approximately 15% of cyanide
reported to this scrubber.
In summary, this testwork demonstrated that cyanide can be efficiently regenerated from
thiocyanate in a clear solution system, while less efficient regeneration can be affected in a pulp
system.
6.0 ESTIMATED OPERATING COSTS
Order of magnitude operating cost estimates were developed for the oxidation processes to allow
a quantitative comparison of various oxidants. These costs are presented in US dollars and
include only costs associated with oxidation reagents, lime for neutralization and power, as
summarized in Table 11. Costs presented in Table 11 reflect stoichiometric reagent dosages,
though in practice actual reagent dosages would likely be greater than stoichiometric.
Construction costs are not presented as the processes require specialized equipment, the costs for
which cannot be accurately defined at this time.
A summary of estimated operating costs for cyanide regeneration and for complete thiocyanate
destruction to form cyanate is presented in Table 12. Note that the cost for thiocyanate
destruction does not include the cost of lost sodium cyanide, which is approximately $1.10 per
kilogram of thiocyanate destroyed. Therefore, the net total cost for thiocyanate destruction
would be the costs indicated in Table 12 plus approximately $1.10 per kilogram of destroyed
thiocyanate.
321 M. Botz et al.

Overall, it appears that the ozone oxidation process would be the least expensive of the processes
considered, however within the accuracy of these estimates, the chlorine, sulfur dioxide and
electrolytic processes would have similar operating costs. Note that the ozone, chlorine and
sulfur dioxide processes appear to be capable of regenerating cyanide for less than the purchase
cost of new sodium cyanide. Relative to the solution chemistry following treatment with each of
the oxidants considered, it appears that all except the ozone, hydrogen peroxide and electrolytic
processes would yield high total dissolved solids (TDS) concentrations.
To date, there have been no full-scale operations in which cyanide has been regenerated from
thiocyanate. However, in cyanidation operations where high cyanide consumption is attributed
to thiocyanate formation, it appears that several oxidation technologies would be suitable for the
regeneration of cyanide from thiocyanate. Specifically, these regeneration technologies appear
well-suited to metallurgical operations where a bacterial sulfur oxidation process is employed or
where sulfide concentrates are leached. With a system involving the regeneration of cyanide in a
clear solution, the cost of cyanide regeneration would approximately equal the value of
recovered sodium cyanide, and it appears that cyanide regeneration would be less expensive than
thiocyanate destruction.
Table 9
Cyanide Regeneration Pilot Testing Results for Clear Solution
Feed Solution Chemistry pH 10.5
0 mg/L Total CN
2,580 mg/L SCN
Bubble Column Reactor Residence Time 1.5 hours
Average Ozone Dosage 14% by weight O3 in O2
97% of stoichiometric requirement
Average Treated Solution Chemistry pH 1.50
950 mg/L Total CN
380 mg/L SCN
Average Cyanide Regeneration Efficiency 85%
322 M. Botz et al.

Table 10
Cyanide Regeneration Pilot Testing Results for Pulp
Feed Pulp Chemistry pH 10.4
60 mg/L Total CN
5,300 mg/L SCN
0 mg/L OCN
170 mg/L Cu
Bubble Column Reactor Residence Time 3.4 hours
Average Ozone Dosage 14% by weight O3 in O2
106% of stoichiometric requirement
Average Treated Pulp Chemistry pH 1.80
1,230 mg/L Total CN
440 mg/L SCN
760 mg/L OCN
Average Cyanide Regeneration Efficiency 50%
Table 11
Reagent Purchase Costs
Reagent Purchase Cost
Ozone $0.90/kg
Chlorine $0.30/kg
Hydrogen Peroxide $1.25/kg
Caro’s Acid $1.00/kg
Sulfur Dioxide $0.25/kg
Lime (CaO) $0.08/kg
Power $0.05/kW-hour
Note: Ozone production cost assumes 18 kW-hour per
kilogram of O3 including the cost for purified O2
production.
Table 12
Approximate Operating Costs for Thiocyanate Oxidation Processes
Cyanide Regeneration Thiocyanate Destruction
Process ($/kg regenerated NaCN) ($/kg destroyed SCN)
Ozone $0.97 $1.07
Sulfur Dioxide $1.35 $1.49
Chlorine $1.67 $1.86
Electrolytic $1.78 --
Hydrogen Peroxide $2.69 $3.02
Caro’s Acid $7.34 $8.25
323 M. Botz et al.

8.0 REFERENCES
Borbely, G.J., E.A. Devuyst, V.A. Ettel, M.A. Mosoui and K.J. Schitka, “Cyanide Removal from
Aqueous Streams”, US Patent 4,537,686, August, 1985.
Botz, M.M., “Processes for the Removal of Copper from Cyanide Leach Solutions”, Paper
Presented in The Cyanide Compendium, Edited by T.I. Mudder and M.M. Botz, Mining Journal
Books Limited, London, In Press, 2001.
Botz, M.M. and G. Parodi, “Removal of Copper from Cyanide Leach Solutions”, Proceedings of
Randol Copper Hydromet Roundtable, Vancouver, B.C., pp. 217-219, November, 1997.
Byerley, J.J. and K. Enns, “Electrochemically Treating Aqueous Thiocyanate Solutions”,

Canadian Patent 1,188,250, 1985.
Byerley, J.J. and K. Enns, “Electrochemical Regeneration of Cyanide from Waste Thiocyanate
for Cyanidation”, CIM Bulletin, pp. 87-93, January, 1984.
Dickson, G.C., “The Regeneration of Cyanide from Milling Solutions Containing Copper
Cyanide Complexes and Thiocyanates”, Published in Proceedings of Gold Mining Effluent
Treatment Seminars, Vancouver, British Columbia, pp. 265-277, February, 1989.
Flynn, C.M. and S.L. McGill, Cyanide Chemistry: Precious Metals Processing and Waste
Treatment, NTIS Document PB96-117841, 1995.
Jara, J., H. Soto and F. Nava, “Regeneration of Cyanide by Oxidation of Thiocyanate”, US

Patent 5,482,694, January, 1996.
Kemker, G.H., Roadcap, S.J. and R. Sitchin, “The Ozonolysis of Aqueous Solutions of Phenol
and Thiocyanate”, NTIS Document ORNL/MIT-318, 1980.
Layne, M.E., Singer, P.C. and M.I. Lidwin, “Ozonation of Thiocyanate”, Proceedings of the
Conference on Cyanide and the Environment, Vol. 2, Edited by D. Van Zyl, Tucson, Arizona,
pp. 433-455, 1984.
Mathre, O.B., “Destruction of Cyanide in Aqueous Solutions”, US Patent 3,617,567, November,

1971.
Neville, R.G., “Method for the Removal of Free and Complex Cyanides from Water”, US Patent
4,312,760, January, 1982.
Smith, A. and T.I. Mudder, The Chemistry and Treatment of Cyanidation Wastes, Mining
Journal Books Limited, London, 1991.
Orbán, O., “Oscillations and Bistability in the Cu(II)-Catalyzed Reaction between H2O2 and
KSCN”, Journal of the American Chemical Society, Vol. 108, pp. 6893-6898, 1986.
324 M. Botz et al.

Palmer, S.A.K., M.A. Breton, T.J. Nunno, D.M. Sullivan and N.F. Surprenant, Metal/Cyanide
Containing Wastes, Pollution Technology Review No. 158, Noyes Data Corporation, New
Jersey, 1988.
Smith, R.H. and I.R. Wilson, “The Mechanism of the Oxidation of Thiocyanate Ion by
Peroxymonosulphate in Aqueous Solution, I. Stoichiometry of the Reaction”, Australian Journal
of Chemistry, Vol. 19, pp. 1357-1363, 1966.
Soto, H., Nava, F., Leal, J. and J. Jara, “Regeneration of Cyanide by Ozone Oxidation of
Thiocyanate in Cyanidation Tailings”, Minerals Engineering, Vol. 8, No. 3 pp. 273-281, 1995.
Wilson, I.R. and G.M. Harris, “The Oxidation of Thiocyanate Ion by Hydrogen Peroxide, I. The
pH-Independent Reaction”, Journal of the American Chemical Society, Vol. 82, pp. 4515-4517,
1960a.
Wilson, I.R. and G.M. Harris, “The Oxidation of Thiocyanate Ion by Hydrogen Peroxide, II. The
Acid Catalyzed Reaction”, Journal of the American Chemical Society, Vol. 83, pp. 286-289,
1960b.
325 M. Botz et al.

CHAPTER 4
Active and passive biological treatment
● Microbial treatment of industrial and hazardous wastes

● The Homestake wastewater process: Part 1
● The Homestake wastewater process: Part 2
● Combined aerobic and anaerobic biological treatment of
tailings solution at the Nickel Plate mine
● Introduction to the Biopass System
● The Biopass System Phase I: Laboratory evaluation
● The Biopass System Phase II: Full scale design and
construction
MICROBIAL TREATMENT OF
INDUSTRIAL AND HAZARDOUS WASTES
Prepared By:
Terry Mudder, Ph.D.
Originally written for and presented at the Annual Meeting of the American Institute of Chemical
Engineers, New York, New York, November, 1987
Microbial Treatment of Industrial and Hazardous Wastes
1.0 INTRODUCTION
Development of novel technologies for the treatment of industrial and hazardous wastes is
increasing rapidly. Particular attention is being focused upon the use of biological treatment
either along or in combination with chemical and physical treatment processes. Aerobic and
anaerobic microbial treatment processes have been successfully employed in the destruction
and/or removal of organic compounds, inorganics, and metals. The paper details the
fundamentals and applications of microbial processes for the treatment of industrial and hazardous
liquid wastes. Included are discussions of waste types and characteristics, fundamentals of
microbial treatment, descriptions of the basic treatment processes, approaches to microbial
treatment, and sources of information concerning the microbial treatment of liquid wastes.
2.0 WASTE TYPES AND CHARACTERISTICS
The discussion of microbial or biological treatment focuses primarily on treatment of liquid wastes
versus disposal and/or treatment of solid wastes. The generation of liquid wastes arises from
several sources including chemical industries, government installations, pharmaceutical
companies, mineral industries, textile manufacturers, and agricultural practices. A liquid waste
may be of continuous or intermittent flow which originates from a chemical process, a leachate
formed through the interaction of precipitation or runoff with a solid hazardous waste, a
contaminated groundwater, seepage from a containment site or container, or wastewater stored in
containers or impoundments.
The liquid waste may contain a variety of components including organic compounds, inorganic
constituents (i.e. sulfur compounds, nitrogen compounds, fluoride, or elevated dissolved solids)
and/or metals. These components occur in a wide range of concentrations and are present in
either relatively pure form or combined in a complex chemical matrix. It is essential to completely
characterize the liquid waste chemically to identify the parameters which are treatable or toxic, or
may serve as trace nutrients for the microorganisms. The anticipated volume and temperature
ranges of the liquid waste must also be identified.
An understanding of the chemical and physical characteristics of the wastewater is required to

assess the potential for microbial treatment and to determine if pre-treatment or dilution of the
liquid waste is necessary.
The options for final disposal of the treated wastewater include discharge to a surface or
groundwater, reuse and recycle as process water, or land application. The degree and type of
treatment required is dictated by the beneficial uses associated with the preferred points of
discharge. The beneficial uses may include stock watering, irrigation, process water, potable
water, recreational, and/or aquatic life protection. The regulated parameters and criteria
associated with the classifications vary considerably from region to region and state to state. In
the case of aquatic life protection toxicological testing may be required to determine an acceptable
level of treatment and to establish final discharge limits. In many cases microbial treatment can
result in the generation of a low toxicity and environmentally acceptable effluent in a relatively
simple and cost effective manner.
327 T. Mudder
In addition to the biologically treated wastewater, consideration must be given to the disposal of
waste biological solids or sludge produced during treatment. Depending upon the liquid waste
treated, the excess biological solids may contain a wide range of components (i.e. organics and
metals) in varying concentrations. The sludge may be suitable for land application as a fertilizer
or due to the sorption of refractory and toxic substances may yield a sludge which requires
specialized handling and disposal measures. In the event the sludge contains elevated metals
concentrations, metals recovery may be an economically viable option.
3.0 FUNDAMENTALS OF AND FACTORS AFFECTING MICROBIAL

TREATMENT
3.1 Fundamentals of Microbial Treatment
Aerobic and anaerobic biological processes have been successfully employed in the treatment of a
wide variety of industrial and hazardous liquid wastes. The microorganisms primarily responsible
for biological degradation include a diverse group of anaerobic and aerobic bacteria. These
single-celled microorganisms exhibit a wide range of metabolic functions and are capable of
degrading a wide range of chemical structures and concentrations.
Table I includes a partial listing of the various organic compounds which have been successfully
treated by the aerobic activated sludge process (1). In general, aerobic bacteria are capable of
degrading a broader range of chemical structures, are less susceptible to toxicity or inhibition, can
perform degradations in a shorter time period, and can survive in a wider range of environments
than anaerobic organisms. Certain species of bacteria (i.e. the Pseudomonas genus) can utilize
many different organic compounds as carbon and energy sources, while other species utilize only
one type of compound as their sole source of carbon and energy.
Bacteria utilize a combination of extracellular and intracellular adaptive and constituative enzymes
in the biochemical breakdown and assimilation of the organic and inorganic compounds present in
liquid wastes. These compounds, along with various nutrients (i.e. nitrogen, phosphorous, and
trace metals) are degraded and/or assimilated for the purposes of energy production and cell
synthesis. The extracellular enzymes found on the cell wall or in the capsule layer surrounding the
cell wall aid in the breakdown of larger and more complex molecules, converting these
compounds to smaller, more soluble by-products. The breakdown products are then transported
into the bacterial cell for conversion to cellular material and energy through the use of intracellular
enzymes. The chemical composition of the cell wall and capsule layer also accounts for the
properties responsible for adsorption and absorption of various refractory organics and heavy
metals. Extracellular and intracellular enzymes are either adaptive and constituative in nature.
Constituative enzymes are present at all times and have evolved following many successive
generations and mutations resulting from exposure of a bacterial species to specific compounds.
The production of adaptive enzymes which are not normally present, may be stimulated by the
presence of a particular compound or class of compounds, which the bacteria utilize as alternative
carbon and/or energy sources if preferred substrates are not available.
328 T. Mudder
The type and versatility of adaptive and constituative enzymes is dependent upon the species of
bacteria being utilized. The success of microbial treatment of industrial and hazardous wastes is
dependent upon isolating and identifying bacterial species which possess the specific adaptive and
constituative enzymes capable of breaking down the target compounds present in the liquid waste.
Therefore, it is essential an initial literature review be conducted to identify potential organisms
capable of degrading the particular wastewater components of interest.
329 T. Mudder
Table I
A Partial Summary Of Organic Compounds Proven
Degradable Through Aerobic Biological Treatment
Class of Compounds Example Compounds
Aliphatic Aldehydes and Ketones Acetaldehyde

Acetone
Camphor
Cyclohexanone
Furfural
Mesityl Oxide
Aliphatic and Aromatic Carbonyl Compounds Acetic Acid

Oleic Acid
Phthalic Anhydride
Organic Nitrile Compounds Acetonitrile

Ethylene Cyanohydrin
Toluene Diisocyanate
Aromatic Hydrocarbons Benzene

Creosote
Naphthalene
Styrene
Xylene
Carboxylic Acids Acrylic Acid

Fatty Acids
Salicylic Acid
Alcohols Cyclohexanol
Glycerine
Methyl Amyl Alcohol
Sorbitol
Aliphatic Amines Aminoethylethynol Amine

Cyclohexylamine
Morpholine
Triethylene Tetramine
Urea
Esters Amyl Acetate

Di-n-buthyl Phthalate
Methyl Acrylate
Methyl Methacrylate
Vinyl Acetate
330 T. Mudder
Table I (Continued)
A Partial Summary Of Organic Compounds Proven
Degradable Through Aerobic Biological Treatment
Class of Compounds Example Compounds
Aromatic Nitrogen Containing Compounds Acridine

Aniline
2,4-Dinitraoniline
B-naphthylamine
Pyridine
O-toluidine
4-Nitrotoluene
Phenols Butyl Phenol

Phenol
Cresol
Diethylstibestrol
Nonyl Phenol
Xylenol
Organophosphorous Pesticides Methyl Parathion

Demeton
Guthion
Miscellaneous Compounds Benzene Sulfonic Acid

Hydroquinone
Dimethyl Sulfate
Carbamate Pesticides
Chlorinated Hydrocarbons
331 T. Mudder
3.2 Factors Affecting Microbial Treatment
Once the specific liquid waste has been characterized and appropriate bacterial species have been
identified, it is essential a suitable environment be provided for the growth and reproduction of the
bacteria. The critical environmental factors include:
1. Temperature
2. pH
3. Oxygen levels
4. Nutrient availability
The optimal temperature range for aerobic and anaerobic treatment is 10-30° C and 25-45° C,
respectively. The optimal pH range for aerobic and anaerobic treatment is 6-9 and 6.5-7.5,
respectively. Oxygen must be absent in anaerobic systems, while in aerobic systems the dissolved
oxygen level should be maintained above 1-2 mg/L. It is common for industrial and hazardous
wastes to contain insufficient levels of the required nutrients, nitrogen and phosphorous.
Depending upon the bacteria utilized nitrogen can be added as ammonia or nitrate, while
phosphorous is supplied through addition of phosphoric acid, regardless of the bacterial process
employed. The initial carbon/nitrogen/phosphorus ratio should be in the range of 100/5/1 for
aerobic systems and 100/10/2 for anaerobic systems.
Even though the proper bacterial species and environment have been provided, microbial
treatment may not occur for several interrelated factors, including:
1. Elevated influent concentrations

2. Inadequate treatment or degradation periods
3. The presence of toxic and/or inhibitory substances
4. Insufficient acclimation periods
In certain cases the compounds targeted for treatment, although known to the degradable, are
present in sufficient concentration to induce bacterial inhibition or toxicity. Lowering of the
influent concentrations through dilution may be required to initiate treatment. In addition, many
of the compounds present in the industrial and hazardous wastewaters require greater degradation
or treatment periods than utilized in conventional biological treatment processes. The advantage
of increasing degradation periods and decreasing influent parameter concentrations has been
shown in a recent study investigating the anaerobic treatment of various organic priority
pollutants(2).
In general, the organic compounds found in industrial and hazardous liquid wastes are more
difficult to degrade biologically than those present in domestic sewage. In addition, the presence
of toxic and inhibitory substances reduce the effective rate of degradation below its optimal level.
332 T. Mudder
These compounds demand a significant expenditure of energy in their breakdown and generally
yield limited quantities of available energy and carbon for subsequent utilization by the bacteria.
As a result, the growth rates for the bacteria are slow and relatively long reaction and hydraulic
retention times are necessary to provide complete assimilation of the waste. Since the energy and
cell yield associated with the breakdown of these compounds is limited, a larger microbial biomass
must be maintained in terms of mean cell residence time and sludge age. Typical reaction periods
range from several hours to several days or longer, in the case of aerated or facultative lagoons
and ponds. Sludge ages as high as several weeks may result with mixed liquor suspended solids
concentrations reaching several thousand mg/L.
Another factor affecting biological treatment is the presence of toxic and/or inhibitory
components in the untreated industrial or hazardous wastewater. These components usually
include either refractory organics or metals which are not amenable to biological treatment. The
toxicity of these components may result from either acute or chronic effects. Acute effects result
in immediate toxicity to the bacterial population, while chronic effects result from long term
exposure of the bacterial population to these wastewater components. The chronic effects result
from the cumulative buildup of these substances in the biological floc or film through sorption
processes. Although initially these components may be present in non-toxic concentrations,
toxicity results from the gradual accumulation of these components within the biomass of the
treatment system. The problem is particularly acute in suspended growth biological treatment
systems in which biomass is recycled for process control purposes. Therefore, sorption of
refractory wastewater components is advantageous from a treatment viewpoint only to the point
toxicity or inhibition occurs.
The study of metals removal and toxicity in biological treatment systems provides an excellent
example of these effects. A summary of the extent of metals removal through aerobic biological
treatment is presented in Table II(3). A study of the removal of metals through anaerobic
treatment is also available(4). The mechanisms and factors affecting the removal of metals
through biological treatment processes have also been investigated (5, 6, 7). As indicated in
Table II, substantial removal of heavy metals is achievable through microbial treatment.
The actual removal efficiency for a particular system is affected by the influent metals levels, the
form of the metals, and the contact period between biomass and liquid waste. If the
concentrations of metals in the untreated wastewater are sufficiently elevated toxicity may result
in the microbial treatment process. A summary of threshold concentrations for metals tolerable in
the activated sludge process are presented in Table III(8). These levels may be used as a guide in
determining if direct treatment of the industrial or hazardous liquid waste under consideration is
possible. The actual level of a metal which causes toxicity is dependent upon the biological
system employed, the bacterial species utilized, the form of the metals, and the period of time the
biomass and metals are in contact.
333 T. Mudder
Table II
Summary Of Heavy Metals Removal
Efficiencies Through The Activated Sludge Process(1)
Metal Removal Efficiency (%)
Arsenic 25
Barium 47
Cadmium 39
Chromium 57
Copper 33
Iron 72
Mercury 69
Manganese 25
Nickel 21
Lead 56
Selenium 79
Zinc 65
Note: (1) Removal efficiencies calculated from data obtained over time at a
single activated sludge facility.
334 T. Mudder
Table III
Threshold Inhibition/Toxicity Metals Levels
For Aerobic Activated Sludge Processes
Metal Ion Concentration (mg/l) Type of Activated

Sludge Process
Silver <0.03 Carbonaceous
Vanadium 10.0 Carbonaceous
Zinc 2.0-10.0 Carbonaceous

1.0 Nitrification
Nickel 1.0-2.5 Carbonaceous

1.0-2.0 Nitrification
Chromium (VI) 10.0 Carbonaceous

1.0 Nitrification
Chromium (III) 10.0 Carbonaceous
Lead 10.0 Carbonaceous
Iron 15.0 Carbonaceous
Copper 1.0-10.0 Carbonaceous

1.0-2.0 Nitrification
Cadmium 5.0 Carbonaceous

1.0 Nitrification
335 T. Mudder
Refractory organic compounds may also exhibit toxic and inhibitory effects in microbial treatment
systems. The literature contains many excellent references concerning the fate and effects of
refractory and toxic organic compounds in both aerobic and anaerobic systems (9,10). A review
of the literature is essential to determine if a particular organic compound of interest is present at
a concentration which is potentially degradable, inhibitory, or toxic.
If the factors of compound degradability and toxicity cannot be mitigated through dilution, then
pre-treatment of wastewater is required to remove or reduce the concentration of the compound
to tolerable levels. Removal of metals is accomplished most efficiently and economically through
conventional chemical precipitation. The removal of problem organics may require specialized
chemical treatment (i.e. oxidation) or physical treatment (i.e. adsorption). The use of chemical
treatment may involve complete destruction and removal of refractory and toxic compounds or
partial treatment to alter the structure of these compounds to lend them more amenable to
microbial treatment. The preferred chemical oxidants include ozone and hydrogen peroxide
employed in conjunction with or without catalysts (i.e. ultraviolet light or a metal). The effects of
catalyzed and un-catalyzed chemical oxidation on organic compounds has been summarized in a
WPCF manual of practice (11). The enhancement of biodegradability through chemical pre-
treatment of biorefractory pollutants is well documented and should be considered as a possible
combined treatment scheme (12,13). The enhancement of biodegradability through physical and
biological treatment is best illustrated by the combined activated carbon to a conventional
activated sludge process aids in removal and concentration of refractory organics through
adsorption, thereby increasing treatment efficiency while reducing potential toxic effects.
A further factor affecting biodegradability involves acclimation. Initial short term investigations
of microbial treatment of industrial or hazardous liquid wastes are often unsuccessful, although
the previously mentioned considerations have been addressed. The process of acclimation
involves repeated exposure of successive bacterial generations or populations to gradually
increasing concentrations of compounds or wastewaters of interest. The acclimation process
affords the microbial population time to physiologically adjust to a new environment and to
promote stimulation of enzyme production. Repeated exposure of the bacterial population may
induce biochemical mutations which enhance the species' ability to utilize specific wastewater
components as sources of carbon and energy. The acclimation period required varies from
species to species and wastewater to wastewater and usually ranges from a few days to several
weeks. The effect of acclimation on biodegradability is shown in Table IV (16). The results
demonstrate that biogradability is significantly enhanced through acclimation of the biomass
involved in the biodegradation. The degree of enhanced biodegradability achievable through
acclimation must be determined experimentally through laboratory or pilot plant investigations.
336 T. Mudder
TABLE IV
EFFECT OF ACCLIMATION ON DEGRADATION
OF VARIOUS CHLORINATED ORGANICS
Percent Biodegraded
Concentration of
Test Compound Test Compound (mg/l)
First Third
Culture Subculture
2-Chlorophenol 5.0 86 100

10.0 83 100
Pentachlorophenol 5.0 19 100

10.0 16 100
p-chlorol-m-cresol 5.0 78 100

10.0 76 100
Chlorobenzene 5.0 89 100

10.0 30 100
2-Chloroethyl vinyl ether 5.0 76 100

10.0 52 100
Bis (2-chloroisopropyl) ether 5.0 85 100

10.0 63 100
PCB-1242 5.0 37 66
337 T. Mudder
In certain cases the degree of biodegradation achievable can be increased during acclimation and
treatment with the addition of a co-metabolite. The co-metabolite may exhibit a chemical
structure similar to or different from those present in the liquid waste. The purpose of the coo-
metabolite is to provide an interim carbon source on which the bacterial culture can grow and/or
to stimulate production of microbial enzymes which can aid in the degradation of substances
present in the wastewater. Examples of the employment of acclimation and co-metabolites to
enhance the degree and rate of biological treatment are available in two recent studies
investigating the degradation of chlorinated organics (17, 18). In addition to enhancing the
degree and rate of biodegradation, acclimation also produces microbial populations which are
more resistant to mass or hydraulic shock loads, thereby increasing the stability and reliability of
overall biological treatment process (19).
The next section of the paper includes discussions of the various attached and suspended growth
processes available for the microbial treatment of industrial and hazardous liquid wastes. The last
section of the paper includes a discussion of the experimental procedures employed in laboratory
and pilot plant investigations of microbial treatment of industrial and hazardous liquid wastes.
4.0 PROCESSES AND APPLICATIONS OF MICROBIAL TREATMENT
4.1 Introduction
There are a variety of attached growth and suspended growth systems available for the aerobic
and anaerobic treatment of liquid hazardous wastes. The treatment processes include:
Attached Growth Systems:
rotating biological contactors (RBC's)

packed bed reactors (upflow and downflow)
biological filters and towers
Suspended Growth Systems:
sequencing batch reactors (SBR's)

facultative ponds/aerated lagoons
complete mix activated sludge
All of the above systems have been employed in the treatment of liquid hazardous wastes. The
choice of one system versus another is based upon several reasons including engineer preference,
economic considerations, space requirements, and treatment efficiency. Treatment efficiency is
determined through either laboratory or pilot plant studies. These systems may be designed as
permanent facilities or mobile facilities. In the case of mobile facility, the system is set up and
operated until the liquid hazardous waste has been treated and then disassembled and moved to a
new site and reassembled. This approach, if applicable, can reduce overall treatment costs
significantly.
338 T. Mudder
4.2 Attached Growth Biological Treatment Systems
The attached growth systems involve the use of media either fixed or moving, synthetic or natural,
onto which the bacterial film develops with time. The RBC utilizes a central shaft onto which are
attached cylindrical sheets of corrugated polyethylene. The media and shaft rotate in the
wastewater at 1-2 rpm, with the media submerged either partially or completely. The use of
submerged shafts and media is employed in anaerobic applications. The media configuration
results in a treatment system requiring limited space, but possessing very high surface areas to
facilitate contact between the bacteria and liquid waste.
In aerobic RBC systems, oxygen is supplied through an air header or natural aeration. The shafts
are driven either mechanically or by forced air. The submerged RBC is an emerging technology
employed in both aerobic and anaerobic treatment applications.
The packed bed reactors and biological filters utilize fixed media beds through which the liquid
waste passes either upflow or downflow. The media employed in the packed bed reactors
consists of either a fine grain inert material (i.e. sand) or activated carbon. The media used in
biological filters is usually plastic of either the cross flow, vertical flow, or random dump types.
The use of plastic media facilitates the construction of deep filters exhibiting high surface areas
(i.e. high ft2/ft3 ratios) resulting in excellent treatment efficiencies and long media life. The
current preference is the cross flow type media with either 45 or 60 degree internal laterals. This
media configuration produces high levels of treatment efficiency with a minimum of operational
problems (i.e. media clogging and short-circuiting). Both the packed bed reactors and biological
filter have been successfully employed in aerobic and anaerobic systems treating liquid industrial
and hazardous wastes.
The hydraulic and mass loading rates associated with these systems vary significantly depending
upon the liquid waste characteristics. As a result, the design of these systems are determined
through laboratory and pilot plant studies. The anaerobic biological filter and packed bed systems
are operated upflow to promote anoxic conditions and facilitate filter cleaning. The aerobic
biological filter systems are operated either upflow or downflow and require air or pure oxygen to
maintain aerobic conditions in the systems. The packed bed reactors develop very large biomass
concentrations which significantly reduces the overall size of the system. However, an air or
oxygen source is required with the packed bed aerobic systems due to the extremely high biomass,
which may not be necessary in the case of biological filters or RBCs.
In general, attached growth systems are less costly and easier to operate than conventional
suspended growth activated sludge systems. Although effluent recycle may be utilized in attached
growth systems, recycle of biomass is not required as with suspended growth systems. Since the
attached growth processes involve single pass treatment systems, the potential for buildup of toxic
and refractory components is minimized in comparison with suspended growth systems. In
addition, the attached growth processes are well suited to low organic loadings and limited
bacterial reproduction associated with the treatment of many industrial and hazardous liquid
wastes.
339 T. Mudder
Attached growth systems produce significantly lower volumes of sludge than suspended growth
systems, thereby minimizing sludge handling and disposal requirements. Sludge production
becomes an important consideration in the event the sludge contins undesirable levels of
refractory and potentially toxic substances. In terms of process efficiency, the attached growth
systems compare favorably with the relatively high treatment efficiencies achievable with
conventional suspended growth microbial treatment systems.
4.3 Suspended Growth Biological Treatment Systems
The suspended growth processes requiring mention include the complete mix activated sludge
system, sequencing batch reactors (SBR), facultative ponds, and aerated lagoons. There are
several adaptations of the activated sludge system of which the complete mix configuration is
preferred in the treatment of industrial and hazardous liquid wastes. In such a system the income
waste is immediately diluted by the contents of the reactor thereby reducing the potential for
operational problems associated with shock loadings.
It is the easiest activated sludge system to design and operate, and is well suited to the relatively
high biomass and long sludge ages required for treatment of industrial and hazardous liquid
wastes. It is the most widely employed activated sludge process for these applications and
produces a relatively high treatment efficiency. However, the process if susceptible to operational
problems which may occur from the excessive sludge ages (i.e. poor settling) and biomass
recycling (i.e. toxics accumulation) required to maintain process viability.
The sequencing batch reactor (SBR) is a relatively new aerobic suspended growth process and is
very similar in design and operation to the laboratory draw and fill reactor (29-31). The sequence
of operation involves filling a reactor with raw liquid waste, followed by a degradation and
aeration period, a settling period, and a decant cycle during which the treated wastewater is
removed through siphoning or pumping. The time periods for the cycles vary according to the
characteristics of the liquid waste being treated. The system requires a series of reactors in the
event a continuous flow is being treated. As with the attached growth systems, the SBR is well
suited as an intermittent and/or mobile treatment facility. Very high levels of treatment efficiency
are possible with the SBR.
The final suspended growth systems requiring mention include the facultative lagoons and aerated
ponds. Both of these systems have been employed in the treatment of industrial and hazardous
liquid wastes. These systems exhibit the advantage of simplified design and operation, but exhibit
the disadvantages of reduced treatment efficiencies, significant surface area requirements, and
seasonal operational problems, particularly in cold climates. The applications of these systems is
limited, but may be useful in specific instances as influent pre-treatment or effluent post-treatment
polishing processes.
340 T. Mudder
4.4 Modifications of Microbial Treatment Processes
As previously mentioned, all of the microbial treatment systems discussed can be employed in
conjunction with other chemical or physical treatment systems. These combined systems are
utilized to enhance or promote microbial treatment through removal or alteration of potentially
toxic or inhibitory wastewater components. Chemical oxidants such as ozone or hydrogen
peroxide aid in the removal of undesirable organics or formation of modified chemical structures.
The modified compounds resulting from partial oxidation are often more susceptible to biological
degradation and may serve as co-metabolites, thereby enhancing the effectiveness of treatment.
Physical treatment usually involves incorporation of granular or powdered activated carbon into
the microbial treatment process for the purposes of removing and concentrating undesirable
refractory organic compounds. The combination of chemical and physical treatment processes
with microbial treatment can significantly increase overall treatment performance in a more cost
effective manner than employment of a single treatment process.
Another modification of combined treatment involves the use of packed bed anaerobic reactors
for treatment of liquid wastes containing sulfates and metals. Through bacterial conversion
sulfate is reduced to sulfide, which then serves as a chemical precipitating reagent for removal of
heavy metals. The process requires the addition of a supplemental carbon source to support the
growth and reproduction of the bacteria. A modification of the system has been successfully
employed in the removal of selenium through biological conversion of selenite and selenate to
elemental selenium.
A final modification of microbial treatment involves in-situ treatment of soils or groundwaters

contaminated with liquid wastes. The process if termed biorestoration (32-34).
The process involves injection of bacterial seeds, nutrients, and oxygen into contaminated soil or
groundwater to promote degradation and treatment. A well field is placed down gradient to
collect the percolating water and to facilitate recycle of the wastewater through the contaminated
soil. The number of cycles required is dependent upon site geology, hydrology, and contaminant
type. Oxygen can be supplied through the addition of low concentrations of hydrogen peroxide
which is chemically converted to oxygen in-situ. Alternatively, the recirculated water or solvent
solution is brought to the surface for treatment. The process, if effective, can efficiently clean up
soil and groundwater contamination at a fraction of the cost associated with other remedial
actions.
The final section of the paper discusses the approaches utilized in evaluating and designing
biological processes for the treatment of industrial and hazardous liquid wastes through laboratory
and pilot plant investigations.
341 T. Mudder
5.0 LABORATORY AND PILOT PLANT EVALUATIONS

OF MICROBIAL TREATMENT
5.1 Introduction
Due to the varied chemical and physical characteristics of liquid industrial and hazardous wastes,
it is necessary to evaluate the potential for microbial treatment through either laboratory studies
or field pilot plant studies. The information obtained from these investigations is utilized in ;the
development of a final treatment facility design.
The first step toward development of a biological treatment system involves a complete
characterization of the liquid waste. With an understanding of the chemical components of the
liquid waste, the next step involves a search of literature to evaluate the potential for biological
treatment and to identify microbial species capable of treating the chemical components of
interest. The search for suitable bacterial species and treatment systems is augmented significantly
through the use of computerized information retrieval systems (i.e. DIALOG) (35). These
systems facilitate the examination and screening of years of information from hundreds of journals
and publications in a few hours. Following characterization of the liquid waste and completion of
the literature review, the potential for biological treatment can be evaluated. If the evaluation
indicates microbial treatment is a possibility, the next step involves isolation of appropriate
bacterial species and initiation of laboratory and pilot plant investigations.
5.2 The Microbial Seed
The success of biological treatment lies in locating microbial species capable of degrading the
liquid waste components of interest. The microbial seed used in the subsequent laboratory and/or
pilot plant studies can be obtained from several sources, including:
1. Existing biological wastewater treatment facilities

2. The site or facility at which the liquid waste is generated or stored
3. Commercial manufacturers or suppliers of microorganisms
4. The American Type Culture Collection (ATCC), the national depository for pure
microbial species
The aerobic or anaerobic microbial seed should be composed of cultures obtained from several
sources to ensure the largest population of bacteria exhibiting the widest range of biochemical
capabilities is employed in the subsequent experimental studies. This approach maximizes the
potential for isolating bacteria with the preferred or ideal metabolic capabilities.
342 T. Mudder
The best source of mixed cultures is found in existing biological treatment facilities treating liquid
wastes containing chemical components of similar or identical structure. The bacterial population
associated with these wastewaters has previously undergone the processes of acclimation and
adaptation. The next source of microbial seed may be found at the site or facility where the liquid
waste is generated or stored. Sources for aerobic organisms include soils or solids which are in
contact with the atmosphere and the liquid waste of interest. This interface may be found at the
edge of a sump, a lagoon, an open drum, or an effluent outfall. The search for anaerobic seeds
involves location of an anoxic zone of slimes or solids which is saturated with or an intermittent
contact with the liquid waste of interest. Mixed samples of these solids from several areas
provide an excellent microbial seed source. In certain cases, preliminary plating studies are
necessary to ensure viable populations of microorganisms are present.
The third and fourth sources for microbial seeds include companies which manufacture and sell
specialized bacteria for the purpose of treating industrial and hazardous liquid wastes and the
American Type Culture Collection (ATCC), the national depository of pure microbial cultures
located in Maryland (36).
Following identification of potential microbial species capable of degrading the liquid waste of
interest, pure cultures of the organisms or similar species may be available for purchase from these
sources in sufficient quantity to conduct the necessary laboratory and/or pilot plant investigations.
The selection of suitable microbial species and seed sources is determined from the initial
literature review.
If possible, microbial seeds from all the available sources should be obtained. The association and
cooperation of several independent bacterial species exhibiting different metabolic capabilities is
often required for the successful degradation of the organic and inorganic components of interest.
For example, the degradation of a particular component initiated by one species of bacteria may
result in the formation of by-products toxic to the bacteria, thereby terminating the degradation
process.
Addition of a second bacterial species capable of degrading the by-product can complete the
degradation cycle yielding a viable treatment process. Once the appropriate bacterial species have
been identified and sources of the microbial seeds have been obtained, the initiation of laboratory
and/or pilot plant investigations can be undertaken.
343 T. Mudder
5.3 Laboratory Investigations of Microbial Treatment
A laboratory investigation of microbial degradation is utilized primarily to evaluate the potential

for biological treatment and to obtain information for design of subsequent pilot plant systems.
The potential for microbial degradation is evaluated initially through a bench scale screening
study, utilizing either the traditional river die-away or modified shake flask procedure. The
screening study involves the use of several 1-2 liter open or closed reactors and several mixed
microbial seed sources. Either actual waste spiked with nutrients or a synthetic waste consisting
of a standardized media containing the compounds of interest is employed in the reactors. An
acclimation period involving several adaptive transfers with or without co-metabolites proceeds
the degradation period. During the study the reactor solutions are routinely analyzed to monitor
the progress of degradation through an appropriate analytical technique (i.e. GC, TOC, LC,
GC/MS). Recently, a universal apparatus and procedure has been developed to study the
anaerobic and aerobic biological degradation of organic compounds (37). The equipment and
procedures are also adaptable to the study of chemical (i.e. hydrolysis and photolysis) and physical
(i.e. sorption and volatilization) degradation processes.
Alternative laboratory degradation systems include static draw and fill reactors, chemostats, and
packed columns. Open draw and fill reactors and chemostats (i.e. flow through systems) are
employed in the study of aerobic suspended growth treatment processes using diffused air for
mixing and aeration. A closed system with mechanical mixing is used to study anaerobic
processes. The systems following addition of actual or synthetic wastewater, microbial cultures,
and nutrients are operated continuously using reaction periods ranging from 12-48 hours.
Additional microbial seed or nutrients are added as required.
The packed column systems, constructed of plastic or glass, are employed in the study of either
aerobic or anaerobic attached growth systems. The packing used in the columns include plastic
media, course sand, or granular activated carbon. The columns are seeded and operated initially
either upflow or downflow with 100% recycle to establish biological growth on the media. The
size of columns varies from 2"-6" in diameter with initial flow rates ranging from 0.10-0.50
2
gpm/ft . The length of the column is varied according to the reaction period desired, which
ranges from 4-24 hours. The system is operated in such a manner to ensure uniform and complete
wetting of the column packing and to prevent column flooding or short-circuiting.
The preliminary screening studies are conducted to examine and verify the conditions and
microbial seeds best suited for degradation of the liquid waste under consideration. The
information being sought in these studies includes the following:
1. The best microbial seed

2. The optimal nutrient requirements
3. The need for a co-metabolite
4. The appropriate acclimation period
5. The extent and rate of degradation
6. The potential for toxicity and inhibition
7. The requirement for pre-treatment of the liquid waste
344 T. Mudder
As mentioned, the liquid waste used in the studies is either the actual waste or a synthetic waste
containing the target compounds of interest. Initially, nitrogen and phosphorus are added to the
liquid waste which has been diluted or pre-treated to minimize potential inhibitory or toxic effects.
A microbial seed mixture is prepared from the available sources and the liquid waste is
inoculated. The organisms are then slowly acclimated by exposing the microbial seed to fresh
liquid waste over a period of several days to weeks.
During the acclimation period co-metabolites may be added to the degradation systems to
enhance and initiate biological growth. Once degradation has been established the microbial seeds
are exposed to gradually increasing concentrations of liquid waste to determine the optimal rate
and extent of degradation possible. If known refractory and toxic substances are present in the
liquid waste (i.e. organics and metals) the liquid waste is initially conditioned or pre-treatment
through an appropriate chemical or physical process.
The time required for the screening process varies from weeks to months and is dependent upon
several factors including the degree of prior knowledge and experience with treatment of the
waste, the ability to locate suitable microbial seeds, and the required acclimation period. The cost
of a laboratory screening study ranges from approximately $50,000 to $150,000. Once the
screening process has been completed and biological degradation has been demonstrated, the
resulting data is employed in the subsequent design of the pilot plant systems. The pilot plant
investigations are conducted to obtain the necessary information for the final process design of the
full scale treatment facility. The next section of the paper provides a discussion of these pilot
plant systems.
5.4 The Design of Pilot Plant Systems
Pilot plant facilities for both the attached growth and suspended growth processes are either
fabricated or obtained in mobile or skid-mounted form from an appropriate equipment vendor or
firm specializing in the design of microbial treatment systems. The cost of a pilot plant study
ranges from approximately $150,000 to $450,000, depending upon the complexity of the design,
the cost of labor and construction materials, and the degree of analytical and toxicological testing
required. Pilot plant systems are normally operated for a period of 6 months to 2 years to obtain
the necessary information for the design of the full scale facility.
Although the primary purpose of a pilot plant testing program involves development of design
data for the full scale facility, secondary purposes include establishing operating conditions and
identifying operational problems. Operation of the pilot plant system also provides insight into
the types and degree of control systems required for the full scale design. With regards to
suspended growth systems, particular emphasis is placed on establishing aeration and mixing
requirements, sludge ages, sludge production and wasting rates, sludge settling characteristics,
reaction periods, and preferred mixed liquor suspended solids concentrations. Sludge analyses are
required to examine the potential for accumulation of refractory and toxic substances.
With regards to attached growth systems, emphasis is placed on developing a range of operational
loading and effluent recycle flow rates, determination of appropriate media, and establishment of
air requirements in the case of aerobic systems. Several types of media are examined to identify
345 T. Mudder
the media with the best flow characteristics and least potential for plugging.
Very little information is available on pilot plant system design and operation for the study of
microbial degradation or industrial and hazardous liquid wastes. A review of the literature and
engineering experience are essential in the design operation of these systems. Regardless of the
degree of preliminary planning, modifications are common during the course of the investigations.
Pilot plant systems are generally operated on a continuous basis with flow rates ranging from 1-10
gpm. The initial design information is obtained from the literature, engineering experience, and
the preliminary laboratory studies. Particular attention should be placed on the selection of
pumps, valves, construction materials, and other equipment used in the systems, as the equipment
must operate continuously with minimal problems on a 24 hour basis. In addition, a significant
degree of analytical support is required in these studies. Consideration of how and where the
analytical support will be obtained must be determined prior to the initiation of the testing
program. Approximately 50% of the cost of such programs is related to the daily samples and
analyses required to monitor the pilot plant systems. A minimum of one full time technician is
required to maintain and operate the pilot plant systems with further analytical and engineering
support being supplied either in-house or through an outside firm. Additional technical and
engineering support is required as significant changes in the pilot plant testing protocol, design,
and operation may occur during the course of the study.
6.0 CONCLUSIONS
The use of microbial processes in the treatment of industrial and hazardous liquid wastes is well
established. Both aerobic and anaerobic attached and suspended growth biological processes
have been employed in the treatment of liquid wastes containing a variety of organic compounds,
inorganic constituents, and metals.
The process of developing a microbial treatment system involves an initial literature review
followed by laboratory and pilot plant investigations. The extent of microbial treatment may be
enhanced through its combination with other chemical and physical treatment processes. The
success of microbial treatment is dependent upon isolating appropriate bacterial seeds and
optimizing their metabolic capabilities through appropriate pre-treatment and conditioning of the
liquid waste. Critical factors include supplying the necessary nutrients, growth stimulators (i.e.
co-metabolites), and acclimation periods, while minimizing the potential for toxic and inhibitory
effects.
Microbial treatment can provide a simple and cost effective solution to the treatment of liquid
wastes, while providing high quality, environmentally acceptable effluents.
346 T. Mudder
7.0 REFERENCES
1. Ottinger, R., Blumenthal, J., Dal Porto, D., Gruber, G., Sandy, M., and Shih, C.,
"Recommended Methods of Reduction, Neutralization, Recovery, or Disposal of
Hazardous Wastes", Volume X, U.S.E.P.A., EPA-670/2-73-053-J, August, 1973.
2. Johnson, L. and Young, J., "Inhibition of Anaerobic Digestion by Organic Priority

Pollutants", J. Water Pollution Control Federation, Vol. 55, P. 1441, 1983.
3. Esmond, S. and Petrasek, A., "Trace Metal Removal", Industrial Water Engineering, pp.
14-17, May/June, 1974.
4. Rivera, A., "Removal of Heavy Metals in a Packed Bed Upflow Anaerobic Reactor", J.
Water Pollution Control Federation, Vol. 55, pp. 1450-1456, December, 1983.
5. Nelson, P., Chung, A., and Hudson, M., "Factors Affecting the Fate of Heavy Metals in
the Activated Sludge Process", J. Water Pollution Control Federation, Vol. 55, pp. 1323-
1333, August, 1981.
6. Cheng, M., Patterson, J., and Minear, R., "Heavy Metals Uptake by Activated Sludge", J.
Water Pollution Control Federation, Vol. 47, p. 362, February, 1975.
7. Rudd, T., Sterritt, R., and Lester, J., "Complexation of Heavy Metals by Extracellular
Polymers in the Activated Sludge Process", J. Water Pollution Control Federation, Vol.
56, pp. 1260-1268, December, 1984.
8. Berkowitz, J., et al., "Physical, Chemical, and Biological Treatment Technologies for
Industrial Wastes", Vol. I, U.S. Dept. of Commerce, NTIS, PB-275-287, November,
1976.
9. Johnson, L., and Young, J., J. Water Pollution Control Federation, Vol. 55, pp. 1441-
1449, December, 1983.
10. Gaudy, A. and Gaudy, E., Microbiology for Environmental Engineers, McGraw Hill Book
Company, New York, 1980.
11. Removal of Hazardous Wastes in Wastewater Facilities-Halogenated Organics, Task

Force on Refractory Organics (Mudder, T., co-author), Manual of Practice No. FD-11,
Water Pollution Control Federation, 1986.
12. Medley, D. and Stover, E., "The Effects of Ozone on the Biodegradability of Biofreactory
Pollutants", J. Water Pollution Control Federation, Vol. 55, pp. 489-494, May, 1983.
13. Jones, B., et al., "Effects of Ozonation and Ultraviolet Irradiation on Biodegradability of
Oil Shale Wastewater Organic Solutes", Water Research, Vol. 19, p. 1421, 1985.
347 T. Mudder
348 T. Mudder
14. Garcia-Orozco, J., Hector, R., and Eckenfelder, W., "Modeling and Performance of the
Activated Sludge-Powdered Activated Carbon Process in the Presence of 4,6-Dinitro-o-
cresol", J. Water Pollution Control Federation, Vol. 58, pp. 320-325, April, 1986.
15. Weber, W., Corfis, N., and Jones, B., "Removal of Priority Pollutants in Integrated
Activated Sludge-Activated Carbon Treatment Systems", J. Water Pollution Control
Federation, Vol. 55, pp. 369-376, April, 1983.
16. Tabak, H., et al., "Biodegradability Studies with Organic Priority Pollutant Compounds",
J. Water Pollution Control Federation, Vol. 53, p. 1503, 1981.
17. Abelson, P., Science, Vol. 23, No. 4763, August, 1986.
18. Kim, C. and Maier, W., "Acclimation and Biodegradation of Chlorinated Organic
Compounds in the Presence of Alternate Substrates", J. Water Pollution Control
Federation, Vol. 58, pp. 157-164, February, 1986.
19. Gaudy, A. and Rozich, A., "Response of Phenol-Acclimated Activated Sludge Process to
Quantitative Shock Loading", J. Water Pollution Control Federation, Vol. 57, pp. 795-
804, July, 1985.
20. Obayashi, A. and Gorgan, J., Management of Industrial Pollutants by Anaerobic

Processes, Industrial Waste Management Series, Lewis Publishers, Inc., 1985.
21. Proceedings of the Industrial Waste Conferences, published annually by the Water
Pollution Control Federation.
22. Proceedings of the Purdue Industrial Waste Conferences, published annually by Purdue
University, Department of Civil and Environmental Engineering.
23. DIALOG Information Services, a computerized information and data retrieval system,
3460 Hillview Drive, Palo Alto, California 94304.
24. Removal of Hazardous Wastes in Wastewater Facilities-Halogenated Organics, Task

Force on Refractory Organics (Mudder, T., co-author), Manual of Practice No. FD-11,
Water Pollution Control Federation, 1986.
25. Kiang, Y. and Metry, A., Hazardous Waste Processing Technology, Ann Arbor Science
Publishers, 1982.
26. Journal of the Water Pollution Control Federation and annual literature reviews, Water
Pollution Control Federation, Washington, D.C.
27. Cheremisinoff, P., "Biotechnology: Treating Industrial/Municipal Wastes and

Wastewater", Pollution Engineering, Vol. XIX, p. 74, September, 1987.
349 T. Mudder
28. Weber, W. and Matsumoto, M., "Feasibility of Intermittent on-site Treatment of

Hazardous Wastes", Proceedings of WPCF Industrial Waste Symposia, p. 111, 58th
Annual Conference, 1985.
29. Hersbrun, P., Irvine, R., and Malinowski, K., "Biological Treatment of Hazardous Waste
in Sequencing Batch Reactors", J. Water Pollution Control Federation, Vol. 57, pp. 1163-
1167, December, 1985.
30. Hsu, E., "Treatment of a Petrochemical Wastewater in Sequencing Batch Reactors",

Environmental Progress, Vol. 5, p. 41, 1986.
31. Ying, W., et al., "Biological Treatment of a Landfill Leachate in Sequencing Batch
Reactors", Environmental Progress, Vol. 5, p. 41, 1986.
32. Wilson, J., et al., "In Situ Biorestoration as a Ground Water Remediation Technique",
Ground Water Monitoring Review, Fall, 1986.
33. Heyse, E., et al., "In Situ Aerobic Biodegradation of Aquifer Contaminants at Kelly Air
Force Base", Environmental Progress, Vol. 5, p. 207, 1986.
34. McMurty, D. and Elton, R., "New Approach to In-Situ Treatment of Contaminated
Groundwaters", Environmental Progress, Vol. 4, p. 168, 1985.
35. DIALOG Information Services, a computerized information and data retrieval system,
3460 Hillview Drive, Palo Alto, California 94304.
36. The American Type Culture Collection, 12301 Parklawn Drive, Rockville, Maryland
20852.
37. Mudder, T. and Musterman, J., "Testing Protocol for the Biodegradation of Volatile and
Slightly Soluble Organic Priority Pollutants", Proceeding of the Industrial Waste
Conference, Water Pollution Control Federation Annual Conference, 1986.
350 T. Mudder
THE HOMESTAKE WASTEWATER TREATMENT PROCESS
PART 1: DESIGN AND STARTUP OF A FULL SCALE FACILITY
Prepared By:
Jim Whitlock
Terry Mudder, Ph.D.
Updated and published in The Cyanide Monograph, First Edition, Mining Journal Books,
London, England, United Kingdom, June 1998
The Homestake Wastewater Treatment Process
Part 1: Design and Startup of a Full Scale Facility
ABSTRACT
Homestake mine in Lead, South Dakota, has developed and implemented a full scale (5.5 MGD)
attached growth aerobic biological treatment process to effectively remove all toxic parameters
from cyanidation wastewaters. The process consists of three biological phases: (1) the use of
mutant strains of bacteria to degrade cyanide, thiocyanate and ammonia, (2) bio-adsorption of
heavy metals and suspended solids on the biofilm and (3) utilization of a bioassay toxicity testing
facility to evaluate treatment efficiency and to develop site specific water quality criteria.
Emphasis is on the use of compatible living systems to treat and evaluate treatment of toxic
wastewaters.
1.0 INTRODUCTION
The Homestake Mining Co. Biological Wastewater Treatment Plant began full scale operation in
August of 1984, culminating seven years of intensive research, development, design and
construction. The research team at Homestake developed the process and designed a plant to
utilize specific microbial flora to degrade and detoxify contaminated wastewater; treating a
3
maximum of 21,000 M /d (5.5 MGD). Treatment consists of degradation via biological pathways
which effectively remove cyanide, thiocyanate and ammonia (a cyanide degradation by-product)
through oxidative processes and accomplishes the adsorption of toxic metals. Metals of concern
are nickel, copper, lead and zinc.
Treated, filtered effluent is discharged from the plant into Whitewood Creek. The creek has been
classified as a cold water marginal trout fishery by the State of South Dakota, to be stocked with
catchable size trout. As Homestake Mine's effluent seasonally makes up a large portion of the
flow in Whitewood Creek, it is essential that treated effluent be of high water quality to protect
the designated beneficial uses of the creek.
Pilot plant and full scale wastewater treatment plant effluent has been rigorously tested using a
flow through bioassay toxicity testing facility to validate research efforts and to insure the
compatibility of effluent with the uses assigned to the receiving stream.
2.0 HISTORICAL PERSPECTIVE
In 1977, construction was completed of the national award winning Grizzly Gulch Tailings
Impoundment Dam and an intensive research program was initiated by Homestake Mining
Company to develop analytical methodologies for toxic parameters and to develop a treatment
methodology to meet or exceed stream standard requirements. Almost all available chemical and
physical treatment processes were researched and pilot tested including acidification/volatilization,
ozonation, Cominco, ion exchange, activated carbon adsorption, Prussian Blue precipitation,
alkaline chlorination, and copper catalyzed hydrogen peroxide.
Chemical analysis and bioassay effluent evaluations of these treatment schemes led to the
conclusion that although some methods were superior to others, no individual or conjunctive
351 J. Whitlock & T. Mudder

processes would achieve the desired treatment levels.

The desired goal of more efficient treatment and production of an effluent of suitable quality for
discharge into a trout stream led to the research and development of the biological treatment
methodology presently utilized at Homestake's wastewater treatment plant.
Isolation and modifications to the bacterium began in the spring of 1981 (ref. 1 and 2). United
States Patents Nos. 4,440,644 and 4,461,834 were granted in 1984 on process characteristics and
the specific mutant strain of bacterium involved in the oxidative process.
Research in analytical methodology led to refinements in the total cyanide method; recognition
and quantification of interferences in analysis and establishment of method-C cyanide analysis
(ASTM ref. 3) as the most appropriate method for this particular wastewater (ref. 3).
Bioassay research directed at the toxicity of complex cyanide species (ferro-ferricyanides,

thiocyanate and weak acid dissociable cyanides) determined that the weak acid dissociable forms
as measured by method-C cyanide analysis are the toxicologically significant forms of cyanide
(ref. 4). Subtraction of method-C values from total cyanide values quantifies the concentrations
of cyanides of reduced toxicity.
3.0 MICROBIOLOGY
Utilization of bacteria to degrade cyanide and thiocyanate on a scale larger than laboratory bench
scale had not been previously accomplished even though the available literature indicated that
certain strains of bacteria possessed the capacity to degrade cyanides. Many of these biological
reactions, such as degradations, oxidations and metal accumulation or ingestion cannot be
duplicated by chemical processes, or at least not at the very rapid reaction rates accomplished by
microorganisms. Biological treatment is also advantageous in that chemical compounds acting as
a food source may be degraded without alteration of the liquid matrix to the degree caused by
chemical processes. Thus, effluent is more likely to be compatible with the natural water of a
receiving stream.
Homestake researchers isolated a specific strain of bacteria indigenous to process waters at the
Homestake Mine. They gradually acclimated these organisms to increased concentrations of
cyanide and thiocyanate in the matrix (Table 1) developing a mutant strain of bacteria with
increased capacity to degrade cyanides.
The predominant species of bacterium have been found unable to grow microaerophilically (in the
presence of small amounts of oxygen or in an atmosphere of hydrogen). Minimal growth
requirements are not complex and organic compounds serve as the energy and carbon source.
These organisms would best be categorized as aerobic heterotrophs.
The predominant bacterium is a gram negative rod (.7-1.4 um), motile by means of a single polar
flagellum approximately three times the body length. Optimum growth occurs at 30C with
limitations at 5-42C. Metabolism is respiratory, never fermentative. The optimum pH range for
the bacterium is 7.0-8.5. Nitrates and nitrites are not reduced and H2S is not produced; all of

these factors are critical to both the treatment process and structural features of the plant.
These bacteria oxidize free and complexed cyanides to carbonate and ammonia and metals are
adsorbed, ingested and precipitated as in Equation (1).
-
MxCNy + 4H2O + O2 Bacteria M-biofilm + 2HCO 3 + 2NH3 (1)
The order of rate of degradation from the most rapid to the least is Zn, Ni, Cu, and Fe for metal
complexed cyanides. Iron cyanides have been shown to be degraded as well as adsorbed in the
process with rates of degradation occurring to a much higher degree than indicated by the
literature.
Thiocyanate degradation is similar and is rapidly accomplished even though the literature
suggested that biological oxidation of thiocyanate is limited above pH 7.6 with the optimum range
being 6.7 to 7.2.
- -2 -
SCN + 5/2O2 + 2H2O Bacteria SO4 + HCO 3 + NH3 (2)
Following degradation of thiocyanate/cyanide and metals removal through adsorption, the

ammonia produced as a by-product from cyanide oxidation must be detoxified. This is
accomplished in the nitrification stage by means of a common pair of aerobic autotrophic bacteria
(used only inorganic material as a source of nutrients, inorganic carbon is the sole source of
carbon). The degradation and nitrification stages are represented in Figure 1.
+ - +
NH4 + 3/2O2 Bacteria NO 2 + 2H + H2O (3)
-2 -3
NO2 + 1/2O2 Bacteria NO3 (4)
Ammonia is oxidized to nitrite slowly and then rapidly to nitrate. The two microbial floras in the
degradation stage and nitrification stage are normally non-competitive as limited by the change in
thiocyanate/cyanide and ammonia concentrations. Thiocyanate and cyanide act as a food source
for the degradation stage bacteria and are toxic to the nitrifying bacteria. Ammonia acts as a food
source for the nitrifiers and along with diminishing food source may act to control competition
from the cyanide degrading bacteria. An upset in the effectiveness of cyanide degradation will
adversely affect the nitrification stage and recovery of the nitrifying bacteria is several times
slower than recovery for cyanide degraders. Thus the rate limiting factor incorporated into the
treatment plant design is based on the slower recovery rate of nitrifiers. Reactions rates for
thiocyanate, cyanide and ammonia are generally zero order down to low concentrations (Figure
1).

Figure 1: Biological Degradation of Ammonia, Cyanide and Thiocyanate
4.0 TREATMENT PLANT DESIGN
The treatment plant (flow diagram Figure 2) is an aerated attached growth biological system
incorporating the use of 48 Rotating Biological Contactors (RBC's) followed by clarification and
pressure sand filters with dual media beds. The wastewater consists of a proportioned blend of
tailings impoundment decant water and mine water with predetermined ratios controlled by a
thiocyanate monitor developed at the Homestake Mine. Regulation of the blended waters
controls influent bacterial food source concentrations and wastewater temperature as the mine
water is a constant 25C.
The wastewater to be treated contains most of the nutrient requirements of the bacteria.
However, phosphorous and carbonate, (energy and carbon source essentials, respectively) must
be supplemented by chemical addition.
Influent chemical additions consist of phosphorous as H3PO4 and carbonate as Na2CO3 (soda
ash). Effluent chemical additions which are available on a demand basis, are ferric chloride for
additional metals removal and polymer for increased clarification effectiveness.

Figure 2: Schematic of the Biological Treatment Plant
The 48 RBC's are arranged in a mirror image plant design; with 24 discs per side. The
wastewater flow is perpendicular to the disc with five discs per train. In general, the first two
discs per train accomplish thiocyanate/cyanide removal and metals accumulation and the
remaining three discs accomplish nitrification. The individual discs are fitted with aeration
headers and electronic load cells for supplemental aeration and biofilm thickness monitoring. The
discs are approximately 40% submerged and rotate at variable speeds of 0.5-1.5 RPM by
reversible drives. Physical dimensions of each disc are 3.65 M in diameter and 7.6 M in length
and constructed of corrugated biofilm of 9,290 m (100,000 sq. ft.) of 13,935 M (150,000 sq. ft.)
depending upon the density of the media. The first two stages are the weight of the biofilm. Each
RBC is housed in an individual insulated fiberglass cover. Bacterial film attached to the RBC may
approach an average weight of 18,140 Kg (40,000 pounds) (ref. 5).

5.0 ANALYTICAL RESEARCH
The selection, design, and testing of treatment methodologies is largely dependent upon precise
and accurate chemical analysis performed upon a complex matrix wastewater. The complexity
and unreliability of various methods for the analytical measurement of trace levels of cyanide in
wastewater led to an extensive research program (ref. 4) to evaluate and develop accurate cyanide
methods. The EPA Total Cyanide Method substituting phosphoric acid for sulfuric and the
ASTM Method C Cyanide method were found to be reliable for Homestake's specific wastewater.
Total cyanide measures free and metal complexed cyanides with the exception of iron complexed
cyanides. Method-C cyanide values represent the forms of cyanide which are highly toxic; iron
complexed cyanide toxicity is relevant only to the degree to which photo-decomposition to form
free cyanide occurs. Method-C cyanide was found to be free of many interferences which plague
the total method.
6.0 TOXICITY TESTING RATIONAL
A treatment method based solely on chemical analysis of an effluent may result in unexpected
toxicity due to the following factors: synergistic/antagonistic effects, toxic parameters which were
overlooked in analysis, lethal concentration values which have not been quantified, or physical
factors such as stress on the organism to be tested. An effluent testing program based on a
combination of accurate analytical testing for chemical parameters and whole effluent testing
greatly reduces the probability of selection of a treatment program which will not meet the
objectives for which is was designed.
7.0 TOXICITY TESTING FACILITY AND PROGRAM
A bioassay facility was constructed to test whole effluents as well as individual parameters
utilizing trout and daphnia and macroinvertebrates collected from the actual receiving stream.
Acute and chronic testing regimes were conducted to test treatment effectiveness and to develop
site-specific water criteria to protect for the beneficial uses assigned to the receiving stream.
The four phases of this program consisted of: (1) conducting a bioassessment of the receiving
stream and comparative background waters, (2) input to the modification of South Dakota
Surface Water Quality Standards to incorporate new proven analytical methodologies and allow
for site-specific criteria development for water quality standards, (3) design and construction of
the bioassay toxicity testing facility, and (4) development of procedures and protocol for
operation of the testing facility (ref. 6).
The mode of testing involved 48 hour static range finding tests followed by 96 hour flow through
tests. Finally 45 day long term flow through tests are used to establish maximum in stream
concentration limits and 30 day average concentration limits respectively. Fingerling rainbow
trout (a highly sensitive test organism) were selected for the bioassay along with caddisflies,
stoneflies, midges, and daphnia as representatives of the food chain for the trout.

The utilization of the bioassay toxicology testing as a central tool in the evaluation of treatment
methodologies and development of site-specific water quality criteria is an extremely valuable
research aid as well as cost effective method. Toxicity testing insures that the treatment scheme
provides an effluent that is compatible with the dynamic aquatic system into which it is
discharged.
8.0 FULL SCALE PLANT PERFORMANCE
Characteristics of the wastewaters to be blended are listed in Table 1 and may be described as a
high volume low toxic contaminant concentration wastewater. A dynamic chemical reaction
characterization of the tailings impoundment is presented in Figure 3.
Table 1
Wastewater Characteristics
Parameter Mine Water Tailings Impoundment

Water
Thiocyanate 1.00-16.00 110.00-240.00
Total Cyanide 0.10-0.50 7.00-30.00
Method-C Cyanide 0.02-0.10 4.00-20.00
Iron 0.10-10.00 1.50-6.00
Copper 0.07-1.60 1.40-6.00
Nickel 0.01-0.04 0.20-0.40
Zinc 0.01-0.10 0.01-1.50
Ammonia-N 5.00-6.00 less than 1.0
Phosphorous-P trace trace
pH 5.00-6.50 7.00-9.50
o o
Temperature 70-85 F 34.70 F
Notes: All values in mg/L except temperature and pH.


Figure 3: The Tailings Impoundment Cyanide Cycle

The actual wastewater ratio is varied throughout the year from 70/30 mine/tailings impoundment
wastewater ratio in the winter to 50/50 mine/tailings impoundment wastewater ratio in the
summer. Strict control is designed and maintained over the blending of the wastewaters to insure
proper waste loading to the RBC's. Results of this blending process are presented in Table 2 for
the period of January 1985 through May 1985. Minimum and maximum values are a result of
adjustments in blend ratios as well as changes in the chemical composition of the wastewaters,
particularly the tailings impoundment decant water.
Table 2
Summary Of Full Scale Plant Performance
January 1985 - June 1985
MIN MAX VAR. MEAN STD. DEV.

Influent CNT* 1.96 6.35 1.068 4.49 1.034
Effluent CNT 0.14 0.67 0.0119 0.3688 0.1091
Influent CNC** 1.07 5.23 0.8131 3.178 0.9071

Effluent CNC 0.02 0.14 0.00049 0.03558 0.0222
Influent Cu 0.31 0.73 0.0091 0.5041 0.09526

Effluent Cu 0.01 0.07 0.00011 0.03358 0.0106
Notes: All values in mg/L
*CNT (Total Cyanide)

** CNC (Method-C Cyanide)
Biological degradation and bioadsorption in the biofilm effectively removes 92% of the total
cyanide, 99% of the method-C cyanide (loosely complexed cyanides) and 95% of copper and
other toxic heavy metals based on mean values, Table 2. Reductions are presented graphically for
total cyanide, method-C cyanide, and copper in Figures 4, 5 and 6, respectively.

Figure 4: Influent Total Cyanide vs. Effluent Total Cyanide
Figure 5: Influent Method-C Cyanide vs. Effluent Method-C Cyanide

Figure 6: Influent Copper vs. Effluent Copper
Method-C cyanide in the effluent is almost totally comprised of copper cyanide as the ratio in
Figure 7 indicates. Subtraction of method-C cyanide from the total cyanide values results in a
value for iron cyanides; predominately ferricyanides. Copper cyanide is effectively degraded to a
greater degree than iron cyanide due to the significantly greater dissociation constant for copper
cyanide complexes, Figure 8. The removal of iron cyanide complexes is dependent upon
adsorption as well as biodegradation.
Seasonal variation of cyanide concentrations in the tailings impoundment water demonstrate a

consistent ratio between total cyanide and method-C cyanide. This trend would indicate that even
though biodegradation in the dam would favor more rapid reduction of copper cyanide, photolysis
of iron cyanides must proceed at a rate which keeps the ratio constant, Figure 9.

Figure 7: Effluent Method-C Cyanide vs. Effluent Copper
Figure 8: Effluent Total Cyanide vs. Effluent Method-C Cyanide

Figure 9: Influent Total Cyanide vs. Influent Method-C Cyanide
9.0 CONCLUSIONS
Selection of the biodegradation process was based on the following advantages: (1) treatment
efficiency equalled or generally exceeded all other tested methodologies, (2) bioassay effluent
evaluations gave biodegradation a substantially better rating, (3) biological treatment is less
subject to upset and recoveries from upset do not substantially effect the water quality of the
effluent as would large chemical additions, (4) the effluent produced by living systems is highly
compatible with living systems in the receiving stream, and (5) plant construction costs and daily
operational costs are substantially lower than for chemical systems.
Full scale treatment, based on at least a 200:1 scale up factor from the pilot plant yielded similar
or improved efficiencies over pilot plant efficiencies.

10.0 REFERENCES
1. T. I. Mudder and J. L. Whitlock, "Biological Treatment of Cyanidation Wastewaters,"

Proceedings of the 38th Industrial Waste Conference, Purdue University, (1983) 279-287.
2. T. I. Mudder and J. L. Whitlock, "Biological Treatment of Cyanidation Wastewaters,"

paper presented at 1984 SME-AIME Annual Conference Feb. 26, 1984, Los Angeles,
CA.
3. Standard Methods for the Examination of Water and Wastewater, 15th Edition, 1980.
4. J. L. Whitlock, C. W. Sharp and T. I. Mudder, "Summary of the Toxicological

Significance and Analytical Methodology for Free and Complexed Cyanides," December
1, 1981 (Homestake Mining Co. document).
5. J. L. Whitlock and T. I. Mudder, "Biodegradation and Bioaccumulation Technology in the

Treatment of Cyanide and Heavy Metal Contaminated Wastewater," 2nd Western
Regional Conf. on Precious Metals and Environment, Rapid City, SD 1984.
6. T. I. Mudder, F. D. Fox, J. L. Whitlock and Steve Marshall, "Development of Site

Specific Discharge Criteria Through Toxicological Testing," 1984.

THE HOMESTAKE WASTEWATER TREATMENT PROCESS
PART 2: OPERATION AND PERFORMANCE
Prepared By:
Terry Mudder, Ph.D.

Fred Fox
James Whitlock
Terry Fero
Greg Smith
Ron Waterland
Jim Vietl
Updated and published in The Cyanide Monograph, First Edition, Mining Journal Books,
Part 2: Operation and Performance
1.0 INTRODUCTION
In certain industrial processes, such as the beneficiation of gold and silver, cyanide is an essential
reagent. The free and metal complexed cyanides, heavy metals, thiocyanate, and ammonia
contained in wastewaters generated from these processes are potentially toxic to aquatic life. The
compounds and metals must be removed from the wastewater prior to its discharge into aquatic
environments.
Since 1977, personnel at the Homestake Gold Mine in Lead, South Dakota, have been engaged in
3
research to develop a process to treat a maximum of 20,000 m /d (5.3 mgd) of cyanidation
wastewaters. Various treatment processes were pilot plant tested and evaluated on both a
numerical and toxicological basis in an on-site flow-through bioassay facility. The treated
wastewater is discharged into a mountain stream serving as a cold water marginal trout fishery,
stocked seasonally with catchable-size brown trout.
Construction of a treatment facility based upon various chemical and/or physical treatment
processes tested never materialized, due either to inadequate treatment performance, residual
effluent toxicity, or prohibitive capital and operating costs.
Beginning in 1981, biological treatment was examined and evaluated on a pilot plant scale. The
testing yielded a simple, cost effective process, the performance of which exceeded all
conventional processes, while producing an effluent compatible with the beneficial use of the
receiving stream. Pilot plant testing of the biological treatment process was conducted from 1981
through 1982. Engineering and construction of the facility was conducted from 1983 through
1984. Startup of the plant was initiated in August 1984, and has been in operation over one year.
The general design of the facility includes flow equalization, 48 low and high density rotating
biological contactors, supplemental chemical addition for bacterial growth and residual
solids/metals removal, secondary clarification, and multi-media pressure and filtration, as shown in
Figure 1.

Figure 1: The Homestake Mine Biological Wastewater Treatment Facility
2.0 DISCHARGE REQUIREMENTS
Whitewood Creek, the receiving stream, is located in the Northern Black Hills in South Dakota.
3
The average flow is approximately 0.40 m /s (14 cu ft/s) with a critical or 25 year low flow of
3
0.13 m /s (4.5 cu ft/s). The low flow was established through hydrologic and habitat analyses to
determine the minimum flow required to maintain the beneficial uses of Whitewood Creek. The
most stringent beneficial use classification pertaining to water quality is a cold water marginal
trout fishery. Due to inherent physical habitat limitations, periodic low flows, and naturally
elevated water temperatures, the stream is not considered suitable to support a permanent trout
fishery. The beneficial use designation is the result of a detailed eighteen-month bioassessment
1
and subsequent reclassification of the receiving stream.

In order to assure long term maintenance of the beneficial use of the receiving stream, several
parameters were targeted for subsequent treatment and removal from the wastewater. The
parameters included metal complexed cyanides of iron and copper, ammonia, copper, total
3
suspended solids, pH, temperature, and flow. The design discharge flow of 14,160 m /d (3.74
mgd) will be utilized in conjunction with the critical low flow of Whitewood Creek to calculate
waste load allocations from instream water quality criteria. Water quality criteria are developed
through site specific analyses involving various recalculation procedures and toxicological testing.
Through the use of the site specific analysis, a few parameters of initial concern were
systematically eliminated. Final NPDES permit limitations are to be determined through
additional site specific toxicological testing.
3.0 WASTEWATER CHARACTERISTICS AND CHEMISTRY
The parameters of interest within the combined raw wastewater and respective concentrations are
presented in Table 1. The concentration ranges were established through a water monitoring
program, encompassing a four year period with analyses performed in the Homestake analytical
laboratory. Prior to treatment, wastewaters are blended to a specific ratio via a flow equalization
system.
Table 1
Wastewater Characteristics*
Combined
Decant Influent
Constituent Mine Water (process water) Wastewater
Thiocyanate 1.0-16.0 110.0-250.0 45.0-75.0
Total cyanide 0.10-1.0 7.0-35.0 0.50-10.0
Weak acid dissociable cyanide 0.02-0.10 4.0-25.0 0.50-5.0
Iron 0.10-5.0 1.50-6.0 0.50-2.0
Copper 0.07-1.5 0.50-2.50 0.10-1.50
Nickel 0.01-0.04 0.10-0.30 0.10-0.50
Zinc 0.01-0.10 0.01-0.75 0.10-0.50
Ammonia (as N) 5.0-6.0 1.0-7.0 6.0-22.0
Phosphorus (as P) 0.10 0.10 0.90-1.0
Hardness (as CaCO3) 650-850 400-450 600-700
Alkalinity (as CaCO3) 150-250 50-200 220-270
pH 7.0-9.0 7.0-9.0 7.5-8.5
o
Temperature ( C) 20-32 1-25 10-25
*
All values in mg/L except pH and temperature

The mine water chemical characteristics, presented in Table 1, indicate the concentrations of the
parameters of interest are normally low, except for periodic elevated concentrations of ammonia
and thiocyanate. The mine water is pumped continuously from the underground workings of the
mine and originates from a variety of sources, the predominate being water used for cooling,
drilling, and dust suppression. A minor amount of mine water is contributed by natural
3 3
infiltration. The daily flow of mine water ranges from 650 m /2 (1200 gal/min) to 13,100 m /d
3
(2,400 gal/min) with an average of 10,900 m /d (2,000 gal/min). Since the mine water
temperature remains inherently warm throughout the year, the combined influent wastewater
o o
temperature is maintained above 15.5 C (60 F), enabling the biological processes to proceed
efficiently and effectively. The desired influent wastewater temperature is achieved through
blending of mine and process waters, controlled by the flow equalization system.
The process water originates from the Grizzly Gulch tailings impoundment located approximately
three miles from the wastewater treatment facility. The impoundment receives 4,082,400 kg/day
(4,500 tons/day) of tailings in a 30% slurry. The process water decants from the solids within the
3
tailings impoundment forming a free water body of approximately 1,604,000 m (1,300 acre-ft).
The decant water is then recycled via a floating barge pump assembly to the flow equalization
basins located above the mill complex. A major portion of the recycled decant water is utilized in
the mill and metallurgical processes. A minor portion is blended with mine water and gravity fed
to the wastewater treatment facility. The volume of decant water treated varies seasonally from
3 3
approximately 1,635 m /d (300 gal/min) in the winter to 2,725 m /d (500 gal/min) in the summer.
The chemical characteristics of the decant (process) water are presented in Table 1. The seasonal
fluctuations in parameter concentrations result from a complex interaction of chemical, physical,
and biological reactions, including hydrolysis, precipitation, photolysis, volatilization, dilution, and
microbial degradations. The parameter concentrations reach maximum values in winter as the
various natural degradation reactions are curtailed due to near freezing water temperatures and
ice cover. During late spring and early summer the ice cover dissipates allowing the water to
warm and mix. The warmer water temperatures coupled with spring precipitation and snow melt
result in increased natural degradation and dilution, lowering parameter concentrations to
minimum summer values. The seasonable variations in the parameter concentrations dictate the
volume of decant water to be treated to maintain design hydraulic and mass loading criteria for
the wastewater treatment facility.
The various constituents within the wastewater originate from several sources. Thiocyanate
(SCN), found principally in the decant water, forms as a result of interaction of free cyanide with
various reduced sulfur species present in the ore (pyrite and pyrrhotite), according to the
following reaction:
- -
(1) FexSx+1 + CN = FexSx + SCN
The formation of thiocyanate during the cyanidation process constitutes a major cyanide demand.
The thiocyanate produced, along with cyanide, represents the primary food source for the
treatment process bacteria.

The metals of interest (iron, copper, nickel, and zinc) are found naturally in the ore and are
solubilized by cyanide during the cyanidation process, thus forming the metal complexed cyanides.
The metal complexed cyanides are divided into two categories. The first category contains the
+2 +3
iron complexed cyanides (Fe and Fe ), which are extremely stable and exhibit the greatest
resistance to treatment. The second category contains the weak acid dissociable forms of metal
complexed cyanides (copper, nickel, and zinc), or the "toxicologically significant" forms of
cyanide. Free cyanide is included in this category, but is virtually nonexistent in the raw
wastewater.
Ammonia in the raw wastewater is contained in both the mine and decant water. Ammonia found
in the miner water results from solubilization of gaseous ammonia produced during blasting.
Ammonia forms in the decant water as a result of natural breakdown of thiocyanate and metal
complexed cyanides. The breakdown is mediated through chemical and/or biological processes
according to the following reactions:
- -2 -
(2) SCN + 2H2O + 5/2O2 = SO4 + HCO3 + NH3
- -
(3) CN + 2H2O + 1/2O2 = HCO3 + NH3
The metals released during the oxidation of the metal complexed cyanides are removed from
solution through chemical precipitation and/or bacterial adsorption into the biofilm.
The alkalinity of the raw wastewater is important as insufficient alkalinity results in incomplete
nitrification within the treatment process. The bacterial breakdown of thiocyanate and cyanide
within the treatment process coupled with inherent ammonia in the raw wastewater produced
transient ammonia concentrations up to 25 mg/L as N. Since the raw wastewater alkalinity is
insufficient to meet nitrification demands, alkalinity is supplied in the treatment process through
the addition of soda ash (Na2CO3). Extremely high hardness values (650-750 mg/L as CaCO3) of
the influent wastewater result from excessive amounts of lime consumed in the cyanidation
process for pH control and from the massive quantities of cement employed in the cement-sand
backfill procedure. The backfill procedure is utilized in filling mined out areas to provide support
and improve structural integrity of the underground environment.
4.0 SITE SPECIFIC WATER QUALITY CRITERIA DEVELOPMENT
In order to provide data for modification of existing surface water quality regulations and
receiving stream classification, Homestake constructed a toxicological testing facility in addition
to conducting the water body assessment (bioassessment). The facility is located adjacent to the
wastewater treatment facility. The primary test organisms include Daphnia, macroinvertebrates
(stoneflies and caddisflies), and trout (rainbow and brown). Dilution water is pumped
continuously through the bioassay facility from a pump station located on Whitewood Creek,
approximately one mile above the wastewater discharge. The dilution water provides flowing
fresh water to maintain a stock fish population and for test purposes. A bioassay facilities manual
details specific protocol employed in the laboratory and serves as an educational tool to train
2
bioassay technicians. The basic toxicological testing protocol is in accordance with procedures

3 4
specified by Standard Methods and the EPA.
The toxicological testing facility has a two-fold purpose. First, to evaluate and compare the
toxicological effects of various treatment process effluents upon the receiving stream ecology.
Secondly, to utilize the toxicity data from the process selected for eventual development of site
specific water quality criteria and waste load allocations. The first use of the facility is of
particular importance, as emphasis on specific parameter removal through routine numerical
evaluations of pilot plant effluents could result in "treated effluents" that meet numerical limits,
but still exhibit considerable toxicity.
The residual toxicity is due to pollutants associated with or produced through the breakdown of
target parameters not analyzed for and/or removed through initial treatment. The employment of
whole effluent toxicity testing minimizes possible oversights. The use of toxicological testing
aided significantly in the development and selection of a "state-of-the-art" innovative biological
treatment process.
With the completion of the bioassessment, modification of the existing water quality regulations,
and the construction of the treatment facility, the final step at Homestake is to establish discharge
criteria which are consistent with calculated water quality criteria. The criteria development as
outlined in the proposed EPA guidelines involves three phases: 1) a selection of parameters of
concern, 2) recalculation of water quality criteria on a site specific basis, and 3) a toxicological
testing program to establish the final permit values for the parameters of interest. This process
requires frequent meetings between key technical personnel from industry and the regulatory
agencies with emphasis on flexibility, cooperation, and practicality.
Due to the beneficial use classification of Whitewood Creek as a "cold water marginal" trout
fishery, the approach to developing adequate criteria and the degree and type of toxicity testing is
quite novel. With input from all parties, it is agreed that the first step of the process would
require the establishment of a list of potential parameters which are of concern from a water
quality and beneficial use aspect. The second phase of the process involves recalculating the site
specific water quality criteria for these parameters using existing ambient water quality criteria
5
documents for each parameter. Based upon the recalculated water quality criteria and
comparison of these values with historical background and untreated discharge water quality
analyses, the list is narrowed to those parameters of primary concern. These parameters form the
basis for the third phase of the process, the toxicological testing program, which itself involves
three modes: 1) 48 hour range finding toxicity tests, 2) 96 hour flow-through tests to establish
acute toxicities, and 3) 45 day long term tests to establish chronic toxicities and long term effects.

The first mode of testing involves conducting a series of 48-hour static range finding toxicity tests
using the primary organism of interest (most sensitive species, rainbow trout) to establish an
approximate range of lethal concentration (LC50's) for each of the parameters of interest. The
choice of test concentrations is made on the basis of past testing and available literature review on
the organisms and parameters of interest. The results of this and other range finding tests produce
toxicity information which are utilized to select a range of parameter concentrations to use in the
second mode of testing, the 96 hour flow-through toxicity tests. In meetings prior to the initiation
of the toxicity testing program, it was mutually agreed that the results of the 96 hour test would
be used to derive instantaneous not-to-exceed in-stream water quality criteria. This approach is in
agreement with the degree of protection to be afforded to attain and maintain the beneficial use
classifications of the receiving stream.
In order for this data and subsequent long term test data to be utilized in developing waste load
3
allocations, a 25 year critical low value of 0.13 m /s (4.5 cu ft/s) was established. Using the
3
average dry weather design flow for the treatment plant of 14,160 m /d (3.74 mgd), the resulting
critical effluent concentration is 56%. It was decided to operate the flow-through tests (both
acute and long term) at this effluent/receiving stream ratio in all aquaria, except the control.
Using the fixed effluent concentration as the base line ratio, concentrated solutions of the various
parameters of interest are to be delivered via a metering pump to the aquaria to create a series of
test concentrations from which 96 hour acute LC50 values are to be obtained. The procedure
allows examination of an individual parameter in the background water chemistry matrix of the
while effluent combined with receiving street water, thereby simulating actual discharge
conditions.
Following establishment of the maximum in-stream values through the 96 hour test program, the
final mode of toxicity testing involves conducting a series of 45 day long term, or chronic, tests to
establish a 30 day average discharge value and subsequent waste load allocation. Since the
beneficial use classification focuses upon maintenance of a stocked fish population, and not
reproduction, the purpose of these tests involving spiked effluent is to gather data on general
external appearance, internal organ appearance, bioaccumulation, and mortality. The long term
tests are conducted for 45 days to simulate an in-stream protection period. Again, a base effluent
concentration of 56% is used into which concentrated solutions of each test parameter are spiked
to produce a series of test concentrations. These concentrations are selected through examination
of the test results from the previous 96 hour flow-through tests. Organisms are fed throughout
the long term test, which constitutes the only major difference in test protocol between the two
tests. In addition to the testing of fish, indigenous macroinvertebrates which serve as food source
organisms for the fish are included in the toxicity testing program. The insects tested include
stoneflies, caddisflies and midges, as these species were the predominant organisms found in the
receiving stream during the water body assessment. Currently, the program outlines above is in
the crucial long term testing phase from which final discharge criteria will be developed.

5.0 EVALUATION OF TREATMENT PROCESS ALTERNATIVES
Prior to the development of the biological treatment process, several chemical and physical
treatment processes were evaluated on a pilot plant scale, either alone or in combination. A
summary of the processes with respect to parameter removal and pilot plant description is
presented in Table 2. These processes include acidification/volatilization, ozonation, ion
exchange, prussian blue precipitation/oxidation, carbon adsorption, alkaline chlorination, and
copper catalyzed hydrogen peroxide. The INCO sulfur dioxide oxidation process was not pilot
plant evaluated as estimates of chemical usage and operational costs rendered the process
impractical for the application. This phase of the pilot plant testing program indicated the copper
catalyzed hydrogen peroxide process yielded the best treatment alternative. The process removed
metal complexed cyanides, including the stable iron cyanides, but did not remove ammonia,
thiocyanate, and residual copper, all of which were potentially toxic and required tertiary
treatment for their removal. The process required excessive amounts of costly chemicals and an
elaborate design resulting in expected high operating and capital costs. Therefore, research was
directed toward evaluation and development of a biological treatment process capable of
overcoming limitations associated with other treatment alternatives, while producing a high-
quality, low toxicity effluent, simply and cost-effectively.

Table 2: Summary Of Chemical/Physical Treatment Processes

Summary of Parameter Removal
Treatment Process Comment

Total Method-C
Thiocyanate Cyanide Cyanide Ammonia Metals
Ozonation yes no yes -- no The pilot plant consisted of two 152 mm (6 in.) diam 5.5 mm (18 ft) plexiglass columns packed with 16 mm (5/8 in)
diam Pall rings. The columns were operated in series with the pilot plant flow, pH, and reaction time being 0.19 L/s
- -
(3.0 gpm), 8.0, and 2.5 hr, respectively. Excessive ozone demand if SCN is present (2.8g O3/gCN and 4.2g O3/gSCN
). A staged sealed reactor with off-gas recycle would be required along with staged O3 injection due to its low
- -
solubility. High capital and O/M costs if SCN is present as it is oxidized in preference to CN . Also a high level of
operator expertise is required.
Acidification/ -- yes Yes No No The pilot plant consisted of a three-cell Denver flotation unit with the cells operated in series to achieve a 4.0 hr
3
volatilization residence time at 0.05 L/s (0.80 gpm). The pH, air flow rates, and acid consumption were 3.0-4.0, 0.071 m /s (150
scfm), and 100 mg/L (0.0008 lb per gal) of H2SO4, respectively. Excessive air, power, acid and base requirements
rendered the process cost prohibitive.
Carbon Adsorption no no yes -- no The pilot plant consisted of two 150 mm (6 in) dia. plexiglass columns 2.4 m (8 ft) in length packed with 1.5 m (5 ft)
2
of 12 mesh Westates GAC carbon. The two columns were operated in series of flow rates varying from 1.4-2.4 L/m s
-
(1-5 gal/min/sq ft). SCN total cyanide, and metals broke through quickly. Significant removal of method-c cyanide
was realized. The carbon adsorption process was examined primarily as a polishing process for the biological
treatment process. Regeneration of the carbon was not examined. Initial capital costs and projected operating costs
were prohibitive.
Ion exchange no yes yes -- yes The pilot plant consisted of 152 mm (6 in) dia. plexiglass columns 3.0 m (10 ft) in length containing a resin dept of
0.9-1.5 m (3-5 ft). The resins tested were all of the strong base type, such as A-101-D, as the metal cyanide complexes
2
were negatively charged. An 8% NaOH solution was employed for backwash for 45 min at 3.4 L/m s (5 gal/min/sq
- -
ft). SCN breaks through quickly, irreversibly poisoning the resins. Ion exchange should be used only when SCN is
not present and provides an acceptable polishing process in its absence. Other resins tested include A-102 and A-109.
2
Flow rates of 1.4-3.4 L/m s (2-5 gal/min/sq ft) were examined. A-7 was also examined but lost its exchange capacity
following successive regeneration.
Alkaline chlorination yes no yes yes yes The pilot plant consisted of three 210 L (55 gal) Nalgene barrels operated in series to produce a chlorine contact period
of 45 min. The pilot plant flow was 0.19 L/x (3.0 gal/min). Bleach was employed as the chlorine source and caustic
was used for pH control (10.5-11.0). Following the oxidation sequence was clarification with polymer addition and
pressure sand filtration. Sulfite and CO2 were employed for residual Cl2 destruction and pH adjustment, respectively.
- -
Ammonia could be destroyed if breakpoint Cl2 was used. Excessive Cl demand if SCN is present (4.9 gCl2/gSCN and
- -
2.8 gCl2/gCN ). Process most viable for SCN and iron cyanide free wastewaters.
Copper catalyzed No yes yes no yes The pilot plant consisted of several 210 L (55 gal) Nalgene barrels operated in series to achieve a 2.5 hour contact
hydrogen peroxide period. The pilot plant flow rates varied from 0.13-0.20 L/s (2.0-3.0 gal/min). 100 mg/L of H2O2, 10 mg/L of Cu, and
with ferric chloride 20.0 mg/L of FeCl3 were employed. The pH was maintained at 9.0 with either caustic or lime. The process was
addition for operated at ambient temperatures. Following the oxidation sequence was a clarification step followed by pressure sand
residual metals filtration. Excessive chemical requirements and costs rendered the process cost prohibitive for this application.
removal

Although full scale biological treatment of cyanidation wastewaters was not practiced in the
mining industry, a literature review indicated biological oxidation of free cyanide, metal
complexed cyanides, thiocyanate, and their corresponding breakdown products was possible. To
test the viability and versatility of biological treatment, a variety of suspended growth and
attached growth biological systems were evaluated on a pilot plant scale. A description of the
systems tested and a summary of their performance are presented in Table 3.
The biological processes tested included activated sludge, trickling filters, rotating biological
contactors, biotowers, and the EIMCO biological aerated filter. The use of a supplemental
organic carbon source (domestic sewage) was examined and abandoned when it was found that
cyanide and thiocyanate could serve as sole carbon sources. Initially, several plate cultures were
prepared from various process solutions and several bacteria were isolated capable of degrading
both metal complexed cyanides and thiocyanate. The isolated organisms were identified as
various species of Pseudomonas, which during the course of many decades had acclimated and
adapted to the elevated concentrations of cyanides and thiocyanate present in the waste streams.
The sources of these cultures were used to seed and initiate growth in the various biological
systems evaluated.
The biological process involves two separate bacterial oxidation steps to facilitate complete
assimilation of the wastewater. The first step involves the oxidative breakdown of cyanides and
thiocyanate, and subsequent adsorption/precipitation of the free metals into the biofilm. The first
step is represented by the following equations:
-
(4) MxCNy + 2H2O + 1/2O2 = M-biofilm + HCO3 + NH3 M = Fe, Cu, Ni, Zn
- -2 -
(5) SCN + 2H2O + 5/2O2 = SO4 + HCO3 + NH3
The second step of the assimilation converts ammonia to nitrate through conventional
nitrification. The ammonia concentration requiring oxidation fluctuates in accordance with the
initial influent ammonia concentration and the ammonia produced through breakdown of cyanide
and thiocyanate. The nitrification step proceeds according to the following reactions:
+ - +
(6) NH4 + 3/2O2 = NO2 + 2H + H2O
- -
(7) NO2 + 1/2O2 = NO3
Originally, it was thought the Pseudomonas species were responsible for complete assimilation of
the wastewater, including oxidation of cyanide, thiocyanate, and ammonia. However, elevated
ammonia and nitrate concentrations were found in the various pilot plant effluents indicating
incomplete nitrification. Sludge was obtained from the local sewage treatment plant and the
various attached growth biological pilot plants were seeded with nitrifying bacteria. Within two
weeks the ammonia and nitrate effluent concentrations decreased significantly.
Three additional factors were noted. First, the rotating biological contactor pilot plants exhibited
the best nitrification. Secondly, there was insufficient alkalinity to complete nitrification and soda
ash addition was implemented. Thirdly, phosphorus was required as a nutrient and addition of

phosphoric acid was initiated.

Table 3: Summary Of Biological Treatment Processesa

Total Method-C Comment
Thiocyanate Cyanide Cyanide Ammonia Copper
Pilot plant influent 60.0 - 10.0 5.60 - 2.10 4.10 - 1.30 6.0 - 1.0 1.00 - 0.40 The pilot plant influent is varied throughout the year from a ratio of 70/30 mine/decant (tailings impoundment)
wastewater in winter to 50/50 mine/decant wastewater ratio in the summer. The pollutant concentrations are
highest in the winter with temperatures falling to 10C in the wastewater.
2.0 m RBC pilot 1.0 0.30.10 0.05 - 0.02 0.50 0.06 - 0.02 The pilot plants were furnished by Envirex. The original feasibility study was undertaken with the use of a 0.5 m
plant effluent RBC pilot plant. The 2.0 m pilot plant was operated with the first and second stages unbaffled. Supplemental
3
aeration was fed to each stage of the pilot plant at an equivalent rate of 4.2 m /min (150 cu ft/min). Stripping of
3 2 2
biomass required 0.17 m /min (600 cu ft/min). The total surface area of the pilot plant was 743 m (8000 ft ). The
pilot plant was operated at flow rates of 0.13-0.50 L/s (2.0-8.0 gal/min). Effluent values recorded in this table were
obtained on clarified and sand filtered effluent. The rate controlling oxidation in the overall design was nitrification.
Laboratory bench 1.0 0.27 - 0.27 0.06 - 0.06 -- 0.35 - 0.12 The bench scale reators consisted of 5 L (1.3 gal) plexiglass cylinders operated on a 24 hour draw and fill cycle.
scale activated sludge Sludge ages examined ranged from 10 to 40 days. Activated sludge from the local sewage treatment plant was
utilized for the initial biomass along with microbial seed from Homestake sources. Eventually aeration periods from
4-24 hours were examined. The system failed at 60 days due to metals accumulation and toxicity.
6.6 m biotower 1.0 0.87 - 0.30 0.08 - 0.04 -- 0.10 - 0.04 The pilot plant consisted of a 0.6 m (2 ft) dia. steel pipe 6.6 m (22 ft) in height packed with KORO-Z plastic media
2 2
supplied by B.F. Goodrich Co. Maximum flow rate achieved was 0.17 L/m s (0.25 gal/min/sq ft) with 0.17 L/m s
(0.25 gal/min/sq ft) recycle flow. Supplemental air was provided countercurrent to the gravity wastewater flow.
Nitrification data is not meaningful as soda ash was not added to the raw wastewater feeding into the biotower.
Trickling filters were also examined. The pilot plants consisted of two 1.8 m/0.15 m dia. (6 ft/6 in dia.) plexiglass
columns operated in series of flow rates similar to those of the biotower. The trickling filters were either packed
with 16 mm (5/8 in) dia. Pall rings or crushed rock 13 mm (1/2 in) dia. The performance of the trickling filters was
slightly less than the biotower.
Biological aerated 1.0 1.00 - 0.60 0.06 - 0.02 1.2 - 0.7 0.03 - 0.03 The pilot plant was supplied by Eimco. The pilot plant consisted of two .30 m dia. (1 ft) plexiglass columns
filter (BAF process) containing 1.8 m (6 ft) of their patented media. The columns were operated in parallel and in series. The data
2
presented in this table was from the series operation. Hydraulic flow rates were varied from 0.27-1.0 L/m (0.40-
1.50 gal/min/sq ft). Supplemental aeration was added countercurrent to the gravity wastewater flow.
a
All values in milligrams per liter

Investigation of process kinetics yielded additional information. Analysis of the various stages of
the RBC pilot plant indicated the oxidation of cyanide and thiocyanate proceeded nearly five times
faster than the oxidation of ammonia. Also, residual cyanide and metals concentrations hindered
the nitrification process. The nitrification process was identified as the controlling step in the
overall assimilation of the wastewater and became a deciding factor in the subsequent process
design phase. The kinetics for oxidation of metal complexed cyanides, thiocyanate, and ammonia
were generally zero order at concentrations exceeding 0.5 mg/L, 1 mg/L, and 4 mg/L
respectively. Below these concentrations all reactions shifted to higher orders.
Although the activated sludge process exhibited high levels of total cyanide removal, slow
microbial growth evidenced by excessive sludge ages (20-30 days) coupled with rapid
accumulation of metals caused the system to fail at 60 days due to metals toxicity. In general, the
attached growth processes tested yielded good quality, low toxicity effluents. However, the
superior performance of the RBC coupled with its cost effective design and anticipated low
operating costs made it the process of choice for incorporation into the overall treatment plant
design.
6.0 DESIGN
The process design of the wastewater treatment facility involved three steps. First, a 0.5 meter
diameter RBC pilot plant was obtained in early 1981 and a feasibility study was conducted in
parallel with the other biological treatment processes. The results of the feasibility study
identified the RBC to be the process of choice. Next, a 2.0 meter diameter pilot plant was
obtained and operated through 1982. The results of the pilot study were utilized in the final scale-
up and process design which was completed in early 1983. The RBC pilot plant was operated at
19-38 L/min (5-10 gal/min) with a scale-up factor of approximately 250. Construction of facility
began in the fall of 1983 and was completed in the summer of 1984. Start-up of the full scale
facility commenced in August of 1984.
The process flow sheet for the facility is presented in Figure 2. Integral to the overall design and
operation of the facility is the flow equalization system. This system allows precise control of
both mine and decant water flows and corresponding ratios. The mine water flow, which
originates from underground, varies according to the sequential operation of two pumps. With
3
one pump in operation a flow rate of approximately 6,540 m /d (1,200 gal/min) reaches the
surface and flows continuously to the treatment plant by gravity. Periodically during a 24 hour
3
period, both pumps are operational increasing the total flow to the surface to 13,100 m /d (2,400
gal/min). The excess flow is stored in the mine reservoir and gravity fed via a separate line to the
3
treatment facility at a controlled flow rate of approximately 4,360 m /d (800 gal/min). The result
3
is a continuous steady flow of mine water to the treatment facility of approximately 10,900 m /d
(2,000 gal/min).

Figure 2: The Process Flow Diagram for the Biological Wastewater Treatment Facility

The return decant flow from the tailings impoundment is pumped to a stand pipe adjacent to the
mill reservoir. The decant flow rate to the plant is controlled via an automated valve located at
the bottom of the stand pipe. The excess decant flow feeds into the mill reservoir to be used as
recycled process water. The automated valve allows precise control of the desired decant flow
rate to the treatment facility. The flow is varied seasonally to achieve desired parameter
concentrations and loading criteria in the combined raw wastewater.
The various mine and decant flows are blended prior to chemical additions which occur in the
influent or chemical feed building. In the chemical feed building, the blended wastewater passes
through a Parshall flume and drops into an influent rapid mix tank. The contact time within the
mix tank is approximately one minute which varies according to influent flow. At this point,
concentrated phosphoric acid is added as a nutrient producing an influent phosphorus
concentration of 1 mg/L as P. The acid is fed via chemical feed pumps from a fiberglass storage
tank containing a one year supply of phosphoric acid. For alkalinity supplementation, soda ash is
fed as a 3%-6% slurry via a chemical feed system located adjacent to the chemical feed building.
The soda ash requirement is determined by the anticipated alkalinity necessary to complete
nitrification and produce a residual effluent alkalinity of 125 mg/L as CaCO3.
Once conditioned, the raw wastewater flows by gravity through an open channel to the first stage
rotating biological contactors (RBC's). The design incorporates 48 biodiscs arranged in five
consecutive stages, with 24 shafts distributed symmetrically on either side of the influent channel.
The first and second stage shafts are placed in twelve basins, with six basins adjacent to either
side of the influent channel. The flow is distributed to the twelve first stage shafts via manually
operated V-notch slide gates. The wastewater then passes through an influent well which
distributes the flow evenly across the entire length of the first stage shaft with the use of V-notch
weirs. The flow distribution system minimizes short-circuiting and contributes to even growth
within the biodiscs. The first and second stages are housed in a common basin which at present is
operated unbaffled to promote a complete mix configuration. The complete mix operation aids in
distribution of biomass between the first and second stages and minimized excessive growth on
first stage shafts. At any one time approximately eight of these basins are in operation. The
dominant Pseudomonas species located on the first and second stages are responsible for
oxidation of cyanide and thiocyanate, and adsorption of metals.
The wastewater leaving the second stages enters an intermediate collection channel prior to
redistribution into the third, fourth, and fifth stages of the process responsible for nitrification.
The 24 third, fourth, and fifth stage biodiscs are arranged in eight common basins. Fiberglass
removable baffles are located between consecutive stages to promote a plug flow configuration
and greater treatment efficiency. The flow into the third stages is regulated in an identical manner
as the first stages.

All 48 shafts are housed outside in separate insulated fiberglass covers. Each shaft is equipped
with a five horse power direct drive package. The drive packages include reversible variable
speed capabilities and can be operated manually or automatically.
2
The first and second stage shafts are low density units possessing approximately 9,300 m
2
(100,000 ft ) of surface area. The remaining three stages are high density units possessing
2 2
approximately 13,950 m (150,000 ft ) of surface area. Each shaft is supplied with supplemental
air via an air header and coarse bubble diffusers located directly under the shaft center. The air
3
system consisting of three positive displacement blowers can deliver 3-9 m /min (100-300 cu
ft/min) to each shaft. Biomass weight is controlled either through reversal of shaft director or the
3
use of an additional blower which can deliver up to 21 m /min (700 cu ft/min) of air to any
individual first, second, or third stage shaft. Shaft weight is monitored by hydraulic load cell
measurements or automatically with temperature compensated electronic load cells.
Following treatment, the wastewater passes from the fifth stage into one of two open effluent
channels and is combined before entering the secondary clarifier. Prior to entering the secondary
clarifier the treated wastewater passes through a second rapid mix chamber located in the
chemical feed building. At this point, either a coagulant (FeCl3) or an organic polymer (ultrion)
can be introduced to aid in settling of the sloughed suspended biomass. All chemicals added
either to the influent wastewater or treated effluent are housed and fed from one facility which
combines chemical handling and spill containment in the event of an emergency situation.
The circular secondary clarifier is 27 m (90 ft) in diameter with a wetted side wall depth of 3 m
(10 ft). The clarifier is a center feed type with a double sided effluent weir located approximately
1.2 m (4 ft) from the interior wall. The clarifier is covered with a fiberglass cover to minimize
wind action and temperature loss during winter operation. The rake mechanism travels at three
revolutions per hour to maximize continuous sludge removal. The settled solids are fed by gravity
to a pump house, combined with sand tailings and pumped 2.9 miles to Grizzly Gulch tailings
impoundment for ultimate disposal. Two existing 24 m (80 ft) square concrete reservoirs were
retrofitted with influent flow distribution and effluent weirs to be employed as emergency
clarifiers in the event of a clarifier failure, eliminating the need for a second clarifier.
The clarified wastewater is filtered prior to discharge through existing pressure sand filters
retrofitted with multi-media consisting of 7.1 cm (18 in) of anthracite coal, 5.9 cm (15 in) of
30/40 garnet, and 2.3 cm (6 in) of 8/12 garnet. The filters are operated at a loading rate of 2.0-
2
2.7 L/m .s (3-4 gal/min/sq ft). The filtered wastewater passes through a second Parshall flume
and down a 60 m (200 ft) natural cascade allowing for re-aeration and cooling prior to contact
with the receiving stream.

7.0 OPERATION, MONITORING, AND CONTROL
The entire treatment facility is monitored and controlled via a Bailey Network 90 control system.
The operator interface unit (OIU) from which the operators monitor and control the facility is
located in the wastewater treatment plant laboratory. The system allows the operator on duty to
monitor flow (water and air), chemical feed rates, pump operations, biodisc speed and weight,
clarifier operation, and various influent and effluent wastewater characteristics. In addition to the
monitoring capabilities, the operator can control mine and decant water flows, operate air
compressors and adjust air flows, operate sand filter pumps, operate the biodiscs and vary speeds,
control the chemical feed pumps and vary feed rates, and waste sludge.
The treatment facility maintains an analytical laboratory for process monitoring and control. Once
per eight-hour shift, influent and effluent samples are collected for analysis of temperature, pH,
copper, phosphorus, alkalinity, ammonia, nitrite, thiocyanate, and turbidity. An additional 24
hour composite effluent sample and influent grab sample are collected and analyzed in the
Homestake analytical laboratory each day. The samples are analyzed for all the above mentioned
parameters and also total cyanide, weak acid dissociable cyanide, hardness, and a number of
metals. The data collected in the Homestake analytical laboratory is utilized as a quality control
monitor on the wastewater treatment laboratory and satisfies regulatory requirements. A daily
operating log is maintained at the treatment facility along with analytical, instrument, and
maintenance logs.
8.0 START-UP
In June of 1984, prior to the start-up of the wastewater treatment facility, four operators were
hired to provide for continuous three shift operation of the facility. A plant supervisor is present
during dayshift. Construction, maintenance, and electrical support is supplied by various
Homestake departments responsible for those activities. A training manual was developed
covering basic environmental engineering principles, fundamental chemistry, mathematics, and
microbiology, as well as the design, process control and regulatory requirements of the
wastewater treatment facility. The operators were subjected to a four week classroom training
program followed by two weeks of orientation at the treatment facility.
On August 3, 1984, mine water flow was initiated to the plant with emphasis on achieving a
steady flow and distributing flows evenly to the first and third stages. During the next three
weeks the facility was made fully operational, with the start-up sequence as follows:
(1) With flow established through the plant and all tanks/basins filled, examinations for
leakage were made.
(2) The static weights of all shafts were then recorded.

(3) All shafts were aligned and rotated against flow to examine drive package operation and
speed control equipment.
(4) The air compressors were started, and the air system balanced via individual air flow
3
meters to yield 3 m /min (100 cu ft/min) per biodisc.
(5) The stripping air blower was placed in operation and utilized to aerate the influent and
intermediate channels.
(6) The fiberglass baffles were removed from between the first and second stages.
(7) Effluent from the existing 2 meter diameter pilot plant was fed via a 2.54 cm (1 in)
diameter hose to the influent blend tank to seed the biodisc plant.
(8) The influent rapid mix turbine was started, as were the phosphoric acid and soda ash feed
systems.
(9) The effluent rapid mix turbine and coagulant/polymer feed systems were checked.
(10) The clarifier drive was started and the sludge withdrawal value operated.
(11) Decant flow was initiated to the facility, as well as collection and analysis of influent,
intermediate, and effluent channel samples.
(12) The control system was actuated and its various monitoring and control capabilities tested.
(13) All flow meters were then calibrated.
(14) The sand filter pumps were started and the clarified wastewater filtered.
(15) After 10 days of operation the third stage biodiscs were seeded with 38 L (10 gal) each of
return activated sludge from the local sewage treatment plant to promote nitrification.
Within 30 days the effluent quality had stabilized and within 60 days the plant was operating at
near design flow. Over the next six months the various mechanical and process problems which
arose were rectified. It took approximately six months to rectify problems associated with the
control system. The operators currently are controlling and programming the system with
proficiency, while maintenance is performed by a company electrician. Following the initial 30
days of acclimation, no significant plant shutdowns have occurred, resulting in a stabilized effluent
of high quality.

9.0 PERFORMANCE
Performance data for the wastewater treatment plant for the first year of operation from
September 1984 through August 1985 are presented in Table 4. The treated effluent quality was
remained consistently high despite minor mechanical and process problems encountered during
the plant start-up and shakedown period. A summary of the overall performance for the
treatment plant from January 1992 through September 1995 is presented in Table 5. The rapid
recovery of the receiving stream was underscored by recent fish inventory studies conducted by
the Department of Game, Fish, and Parks in cooperation with the Department of Water and
Natural Resources. The results of those studies indicated significant populations of native brook
trout and stocked brown trout migrated into the section of receiving stream below the wastewater
discharge. The fish examined by a pathologist were healthy, indicating no signs of physical or
physiological abnormalities and no significant accumulation of trace metals. Furthermore, in a
recently completed 45 day long term chronic flow-through bioassay conducted at critical low flow
baseline conditions (56% effluent/44% receiving stream), no signs of undesirable effects were
noted in a test population of 40 juvenile rainbow trout.
Several interesting process characteristics and problems which arose during start-up of the facility
deserve discussion. Periodically, fluctuations in nitrification performance were noted and were
attributed to insufficient alkalinity present in the wastewater. The fluctuations were most notable
when effluent alkalinity at 125 mg/L as CaCO3 or higher resulted in consistent nitrification and
low effluent ammonia values (<0.15 mg/L as N). Another interesting situation arose as a result of
the excessive hardness present in the mine water. The sand backfill operations which have
increased significantly in the last two years had resulted in a rapid increase in suspended cement
(lime) and dissolved water hardness in the mine water. The combination of high wastewater
temperature, pH, and hardness resulted in precipitation of calcium carbonate on the biodiscs. The
problem was not noted earlier since the massive increases in cement usage began in 1983, one
year after the pilot plant testing program. The chemical precipitation caused three problems.
First, the chemical film developing on the discs decreased the performance and efficiency of the
biofilm. Secondly, the weight of chemical film contributed dead weight to the shafts which was
difficult to strip. Thirdly, once sloughed, the dense chemical/biological floc settled in the basins
and became anaerobic. Investigations focused upon the backfilling procedure, with emphasis on
reducing suspended material and dissolved water hardness underground. By discontinuing
backfilling of certain areas, continuous addition of flocculent during backfill, and modification of
the cement type, the suspended material was virtually eliminated and the dissolved water hardness
reduced by 200 mg/L as CaCO3. As a result, the disc film became increasingly biological in
nature, process performance increased, shaft weights decreased and were controlled effectively,
and sloughed solids deposition was reduced.

Table 4
Treatment Plant Performance And Proposed Effluent Limits(1,2)
Influent Effluent
Parameters Wastewater Wastewater
Copper
maximum 0.73 0.13
minimum 0.17 0.01
average 0.49 0.05
standard deviation 0.92 0.02
n 159 85
Total Cyanide
maximum 6.35 0.67
minimum 0.75 0.06
average 3.39 0.31
n 165 318
Weak acid dissociable cyanide

maximum 5.23 0.14
minimum 0.31 0.01
average 2.34 0.03
n 165 200
Total suspended solids

maximum - 16.0
minimum - 1.0
average - 3.0
standard deviation - 2.3
n - 318
Ammonia (as N)
maximum 10.40 0.35
minimum 0.98 0.10
average 5.31 0.12
n 165 165
pH
maximum 9.0 8.35
minimum 7.5 7.13
average - -
standard deviation - -
n - -
Notes:
(1) All data total analyses in mg/L except pH.
(2) All values daily maxima, minima and averages except proposed permit limits which are
daily maximum concentrations.

Table 5
Summary Statistics For Homestake Wastewater Treatment Facility Effluent
Number
Constituent of Minimum Mean2 Median Maximu S.D.2
Data m
Points1
Field pH 1187 4.50 8.02 8.03 8.69 0.300
Total Alkalinity 1184 0.3 95.6 78.0 1402 76.09
TSS 1338 0.0 3.1 3.0 47.5 1.86
Total Ammonia-N 1338 <0.10 0.27 0.10 5.7 0.28
Total Nitrate-N 1000 <0.10 21.9 22.0 258 10.8
Total Phosphate 1155 0.01 0.16 0.09 38.0 1.24
WAD Cyanide 1339 0.02 0.03 0.02 0.50 0.022
Total Cyanide 1157 0.02 0.37 0.19 1.37 0.34
Total Hardness 404 550 966 960 1890 106
Total Arsenic 185 0.0009 0.04 0.04 0.074 0.012
3
Dissolved Arsenic 48 0.004 0.04 0.04 0.066 0.011
Total Cadmium 185 <0.001 0.003 0.0009 0.039 0.004
3
Dissolved Cadmium 49 0.00400 0.007 0.006 0.032 0.005
Total Chromium 184 <0.01 0.003 0.001 0.013 0.003
3
Dissolved Chromium 47 0.004 0.006 0.006 0.010 0.001
Total Copper 185 0.001 0.04 0.032 0.28 0.02
3
Dissolved Copper 49 0.019 0.03 0.03 0.04 0.006
Total Lead 183 <0.001 0.076 0.05 0.44 0.097
3
Dissolved Lead 49 <0.001 0.056 0.05 0.09 0.016
Total Nickel 176 <0.01 0.027 0.02 0.36 0.034
Total Silver 185 <0.001 0.002 0.0009 0.008 0.002
3
Dissolved Silver 49 0.002 0.005 0.005 0.007 0.001
Total Zinc 176 <0.01 0.01 0.009 0.15 0.014
Total Iron 154 <0.01 0.27 0.28 0.76 0.21
Notes:
(1) Data from 1/1/92 through 9/14/95
(2) Non-Detects (LOD values) were not adjusted for any statistics presented in
BWWTF tables.
(3) 1992 only

Another operational problem which arose during start-up focused on solids separation and sludge
bulking. The problem resulted from excessive hydraulic retention times within the plant basins
and channels and elevated wastewater temperatures. The excessive hydraulic retention times
produced significant solids deposition throughout the plant. Under these conditions, the
Pseudomonas species produced through decapsulation and cell lysing significant quantities of
extracellular material. The stringy polymeric material bound the settled sloughed solids within the
clarifier into mats which surfaced following rapid denitrification promoted through excessive
sludge ages and solids retention times. Elevated summer wastewater temperatures caused by hot
supplemental air entering the water, naturally high wastewater and air temperatures accelerated
the process of extracellular slime/polymer production. The problem was significantly reduced by
increasing hydraulic movement through the plant and minimizing wastewater temperatures.
Hydraulic retention times and solids deposition was reduced through increased aeration of
channels, reducing the number of shafts in operation, and the filling in of third stage influent wells
with gravel. In addition, continuous sludge withdrawal from the clarifier was initiated together
with an increase in sludge rake revolutions. Temperature was minimized by opening of biodisc
cover doors and observation ports while reducing supplemental air flow to the minimum
necessary to maintain dissolved oxygen levels at approximately 4 mg/L.
With respect to the design of the biodisc plant, several observations are notable:
(1) No process performance problems were encountered during winter operation with
o
temperature losses through the plant being on the order of 2 C.
(2) No mechanical or maintenance problems were encountered during winter operation as a

result of the outdoor placement of the biodiscs and direct drive packages.
(3) The control of shaft weight through rotation reversal has been effective while use of air to
encourage stripping has been relatively ineffective. Shaft reversal resulted in shaft weight
reductions up to 6,600 kg (3,000 lbs).
(4) The electronic load cells, once calibrated to hydraulic load cell readings, have produced
consistently accurate weights.
(5) The ability to remove baffles has been effective in distributing weight evenly between first
and second stage biodiscs by promoting a complete mix configuration within the common
basin housing the first and second stage biodiscs.
(6) The flow distribution system has been effective in maintaining even growth across the
biodiscs.
(7) The operating costs for the plant, including personnel, power, and chemicals has been
approximately $700/day.

10.0 CONCLUSIONS
Over the course of four years, Homestake Mining Company has developed and proven a novel
process for the treatment of cyanidation wastewaters. The facility constructed was put into
operation with minimal difficulty as a result of careful and deliberate planning throughout the
development, design, construction, and start-up phases of the facility. The effluent has been of
consistently high quality as evidenced by the rapid recovery of the receiving stream which
presently supports a viable trout fishery. Through a highly cooperative technical relationship
developed between Homestake and the various state and federal regulatory agencies, a solution
has been realized to a long standing environmental problem.
11.0 REFERENCES
1. Herricks, E., et al., "Bioassessment of Whitewood Creek, Lawrence and Meade Counties,
South Dakota", 1982. Prepared for Homestake Mining Company, Lead, South Dakota,
and the South Dakota Department of Water and Natural Resources.
2. Mudder, T., Fox, F., Marshall, S., and Whitlock, J., Facilities and Operations Manual for
the Homestake Aquatic Toxicity Testing Facility, 2nd Edition, Homestake Mining
Company, Lead, South Dakota, November, 1983, 97 pp.
3. Standard Methods for the Examination of Water and Wastewater, 15th Edition, 1980, pp.
615-743.
4. Methods for Measuring the Acute Toxicity of Effluents to Aquatic Organisms, 3rd
Edition, EPA-600/4-82-000, November, 1982.
5. Water Quality Standards Handbook, U.S.E.P.A., Office of Water Regulations and

Standards, Washington, D.C., December, 1983.

COMBINED AEROBIC AND ANAEROBIC
BIOLOGICAL TREATMENT OF TAILINGS SOLUTION
AT THE NICKEL PLATE MINE
Prepared By:
Barry Given
Brenda Dixon
Gary Douglas
Rino Mihoc
Terry Mudder, Ph.D.
Originally published in The Cyanide Monograph, Mining Journal Books, First Edition, London,
England, United Kingdom, June 1998
Combined Aerobic and Anaerobic Biological Treatment
of Tailings Solution at the Nickel Plate Mine
1.0 BACKGROUND
During closure of the Homestake Nickel Plate Mine, located in south central British Columbia,
there is a need to treat and release seepage collected from and solution stored in the tailings
impoundment into a nearby trout stream. Several water management and treatment alternatives
were considered including land application, biological treatment, breakpoint chlorination,
hydrogen peroxide, and the INCO SO2/Air process, which was already in use at the mine. The
constituents of concern included not only cyanide and metals, but also thiocyanate, ammonia, and
nitrate. There were secondary concerns with elevated levels of total dissolved solids and sulfate.
The treatment process selected had to be operated in compliance with very stringent numerical
criteria and a narrative requirement that the effluent had to be non-toxic, as demonstrated by a 96
hour toxicity test using trout and 100% effluent. An INCO SO2/Air process for the destruction
of cyanide and removal of metals was already in operation at the mine.
Through extensive bench and continuous flow pilot plant scale evaluations, the decision was made
to use a combined aerobic and anaerobic biological treatment system for removal of residual
cyanide, thiocyanate, ammonia, and nitrate coupled with the new HDS process for removal of
residual metals. Biological treatment was chosen because the chemical oxidation processes
involving hydrogen peroxide and sulfur dioxide do not remove thiocyanate, ammonia, and nitrate.
Although breakpoint chlorination does remove these three constituents, it is very expensive and
produces residual TDS and chloride concentrations that are too high for fresh water fish to
tolerate.
The basic biological process utilized expertise and experience associated with the original
biological treatment process still in use at the Homestake Gold Mine located in Lead, South
Dakota in the United States. The attached growth biological treatment process at the Homestake
Gold Mine involves several stages of rotating biological contactors or RBC's for the aerobic
oxidation and destruction of cyanide, thiocyanate, and ammonia.
Although the use of biological treatment in the mining industry is somewhat rare and novel, the
application at the Nickel Plate Mine offered an extension of its uniqueness in that the existing
metallurgical plant used in the extraction of gold and silver was retrofitted into the full scale
biological treatment facility with only minor modifications, resulting in substantial cost savings.
The full scale combined biological and chemical treatment facility now in operation consists of the
following three separate steps:
1) a combined activated sludge treatment step for the conversion of thiocyanate

(SCN) to ammonia (NH3) and for the oxidation of the NH3 formed to nitrate
(NO3),
2) a denitrification treatment step to reduce NO3 to nitrogen gas (N2), and
3) a High Density Sludge (HDS) - ferric sulfate treatment step to precipitate arsenic
(As), some sulfate (SO4) and other residual metals in the effluent.
389 B. Given et al.

The full scale treatment system includes reagent make-up, storage, metering, and control
equipment for lime, soda ash, methanol, phosphoric acid, sulfuric acid and polyelectrolyte. Air
compressors provide the air for the biological processes. A propane-fired submerged combustion
water heater is used to raise the feed water temperature to approximately 20° C to optimize the
biological processes. The full scale treatment system was started in October, 1996, at a flow rate
of 25 to 50 gpm and then gradually increased to a flow rate of 200 gpm once the system was
meeting effluent specifications. The plant was then operated for several months at the 200 gpm
rate. The rate is to gradually increased to 350 gpm during the spring months to complete the
removal of the tailings pond solution. At that point the flow rate will be reduced over time to
match the seepage pump-back rate, which is on the order of 125 gpm.
This paper provides a discussion of and presents data from the development and operation of the
combined full scale combined biological treatment process. These discussions include the decant
or reclaim water characteristics, basic process chemistry, the original bench and pilot plant
evaluations, design considerations, effluent limitations, and full scale operational data
2.0 RECLAIM WATER CHARACTERISTICS
The anticipated range of chemical characteristics associated with the tailings impoundment
solution or reclaim water prior to treatment are provided below. These chemical characteristics
are expected to change and fluctuate to a certain degree following cessation of beneficiation due
to ongoing natural degradation processes, precipitation and evaporation.
Cations and Anions

pH 7.5 to 8.0
Alkalinity as CaCO3 200-400 mg/L CaCO3
Total Cyanide 2-7 mg/L
WAD-CN 0.2-3 mg/L
Cyanate (CNO) 200-350 mg/L
Thiocyanate (SCN) 500-1400 mg/L
Ammonia (NH3) 50-100 mg/L as N
Nitrate 10-50 mg/L as N
Nitrite 1 mg/L as N
Sulfate 2500-4000 mg/L
Chloride 800-900 mg/L
Metals (mg/L)
As 0.5-3.0
Ca 800-900
Cu 0.3-2
Fe <0.03
Ni 0.05-0.5
Zn <0.002-0.02
390 B. Given et al.

The focus of the combined biological treatment process is on the removal of cyanide, thiocyanate,
ammonia, and nitrate, while chemical treatment using the existing HDS process is on removal of
residual metals through precipitation.
3.0 EFFLUENT CRITERIA
The overall treatment system has been developed and designed to achieve the following effluent
criteria. Permit criteria are also included for comparison.
Process Effluent Process Design Permit

Parameter Units Criteria Criteria
pH 6.5-8.5
TSS 25
Total CN 0.2
Total CN + SCN 3.0
Cyanide-WAD 0.1 0.2
Cyanate <5
Thiocyanate mg/L SCN <5
Ammonia N mg/L N 10 1.0
Nitrate N mg/L N 10 10
Nitrite N mg/L N 1
Sulphate SO4 mg/L SO4 1800 3500 to 4500
Toxicity LC50 100%
Metals
Aluminum 0.5
Arsenic 0.07 0.07
Antimony 0.05
Cadmium 0.005
Calcium 800
Chromium 0.02
Cobalt 8
Copper 0.2 0.04
Iron 0.5 0.5
Lead 0.1
Manganese 0.2
Molybdenum 0.25
Nickel 0.1
Potassium 65
Sodium 2500
Zinc 0.1
391 B. Given et al.

4.0 BENCH AND PILOT PLANT SCALE EVALUATIONS
Once the decision was made to evaluate biological treatment for removal of thiocyanate,
ammonia, and nitrate, as well as cyanide and cyanate, an extensive bench and pilot plant scale
program was undertaken to examine the reliability and effectiveness of various attached and
suspended growth systems. The two biological systems chosen for evaluation included the
activated sludge suspended growth process for removal of thiocyanate, ammonia, and nitrate, and
rotating biological contactors (RBC's), an attached growth process for removal of thiocyanate and
ammonia.
The removal of thiocyanate and ammonia involve aerobic microbial processes, while the removal
of nitrate involves an anaerobic bacterial process. In the case of aerobic processes supplemental
oxygen is provided through diffusers, while the anaerobic process requires the exclusion of
oxygen. Since the RBC is constructed in such a manner that it is partially out of the wastewater
and exposed to the atmosphere, this system in this configuration is not suitable for anaerobic
applications. The activated sludge system utilizes stirred tanks, and as a result, are suitable for
anaerobic applications, such as nitrate removal, by simply covering the tanks to exclude oxygen.
In general, the activated sludge process is more suitable for treating high concentrations of
constituents due to its ability to accommodate the large suspended biomass levels generated
during treatment. The RBC process is more suitable to lower constituent concentrations, such as
dilute industrial wastewaters, and is also less susceptible to upsets through rapid changes in mass
loading.
Both the RBC and activated sludge systems were shown capable of treating thiocyanate and
ammonia to low levels. In addition, the covered, anaerobic activated sludge system was also
shown effective in treating nitrate to very low levels. A schematic of the combined activated
sludge and HDS pilot plant system is shown on Figure 1. The performance of the combined
aerobic and anaerobic activated sludge pilot plant system is shown on Figures 2-4. As shown on
Figure 2, once the biological processes were stabilized and acclimated, excellent removal of
thiocyanate and ammonia were achieved, with resultant conversion of the nitrogen in the
thiocyanate and ammonia to nitrate. In Figure 3, the removal of ammonia and production of
nitrate in the third aerobic activated sludge tank is shown. In Figure 4, the third anaerobic stage
of the activated sludge process, once stabilized, demonstrated excellent removal of nitrate through
conversion to nitrogen gas.
The continuous flow pilot plant evaluations were conducted from late 1995 through most of
1996. The initial bacterial seeds used in the pilot plant studies were obtained from several places
through the mine site at a liquid/solid/air interface, such as the interface of the tailings solution
and tailings beach areas, the seepage collection sumps, and at various locations throughout the
mill and metallurgical circuits.
Although both the attached and suspended growth processes were effective in treating
thiocyanate, ammonia, and nitrate, the activated sludge process proved more robust, yielding a
more consistent quality effluent than the RBC's. The superior performance of the activated sludge
392 B. Given et al.

process was likely related to the elevated constituent concentrations being treated, which in turn
led to high biomass production.
393 B. Given et al.

Figure 1: Water Treatment Pilot Plant
394 B. Given et al.

Figure 2: #1 Activated Sludge Tank Performance
395 B. Given et al.

Figure 3: #3 Activated Sludge Tank
396 B. Given et al.

Figure 4: Denitrification Tank
The generation of excessive biomass is not of concern with respect to the activated sludge
process, due to the ability to control the mixed liquor suspended solids (MLSS) concentrations
easily through wasting as needed. On the other hand, excessive build up of biomass on the RBC
can lead to inadequate oxygen transfer into the biofilm and poor distribution of liquid over its
surface. Although the RBC is easier to operate than an activated sludge process, there is less
ability to make process modifications as needed for improving performance. A summary of the
pilot plant performance for both the activated sludge and rotating biological contactor (RBC) is
presented in Table 1.
In addition to the performance considerations, it was determined that the existing metallurgical
circuit consisting of several large stirred tanks could be converted into a series of activated sludge
reactors with only slight mechanical modifications. These modifications included trimming the
prop blades to reduce shear of the biological floc, addition of diffusers to supply dissolved oxygen
for thiocyanate and ammonia removal, and covering of the final tanks with floating plastic balls to
exclude oxygen in the anaerobic denitrification step of the combined activated sludge process.
397 B. Given et al.

Table 1
Pilot Plant - Average Data For The Period May/96 - Aug/96
Parameter Reclaim Activated Sludge Circuit RBC Circuit

Aerobic Anaerobic HDS RBC Head
Circuit Circuit Circuit Circuit RBC #1 RBC #2
Units - mg/L unless noted Influent Effluent Effluent Effluent Effluent Effluent Effluent
Flow - L/min 9.1 9.1 9.1 0.4 1.4 5.4
Temp - deg C 20.1 21.1 17.9 15.0
pH 7.6 7.4 7.7 9.2 8.4 8.4 8.2
Dissolved Oxygen 4.9 0.4 4.7 3.5 2.9 5.5
Alkalinity 311.0 170.0 1027.0 293.0 1411.0 1308.0 582.0
Cyanide - Total 7.2 3.52 2.65 2.80 3.36 1.36
Cyanide - WAD 1.84 0.39 0.22 0.81 0.52
Thiocyanate - SCN 1245.0 0.6 1.1 1.1 139.0 104.0 15.9
Ammonia - NH3 - N 86.2 0.3 0.2 0.7 2.0 14.3 7.6
Nitrate - NO3 - N 48.0 450.0 1.1 1.3 18.8 6.4 29.7
Nitrite - NO2 - N 1.6 0.5 <0.5 <0.5 1.2 1.0 1.6
Sulphate - SO4 3410.0 5124.0 5444.0 5000.0 3566.0 2704.0
Phosphate - PO4 0.5 5.3 12.3 <0.3 29.1 19.5 8.1
Arsenic - Total 1.68 0.04
Cobalt - Dissolved 6.23 6.10 6.10 5.27 6.52 2.44
Copper - Total 1.70 0.20 0.03 0.03 0.40 0.35
Iron - Dissolved 0.13 0.12 0.10 0.09 0.10 0.07
Note 1 - RBC #1 had 1 liter/minute fresh water added to help reaction

Note 2 - RBC #2 had 4 liter/minute fresh water added to help reaction
The superior performance coupled with the ease with which a full scale system could be
constructed using existing equipment, were the reasons that the combined activated sludge
process was finally selected for full scale treatment of the tailings impoundment solution. The
next section provides a basic description of the process biochemistry associated with the various
stages of the combined activated sludge and HDS processes.
398 B. Given et al.

5.0 PROCESS BIOCHEMISTRY
5.1 Thiocyanate Oxidation
Thiocyanate is converted to ammonia, sulfate and carbon dioxide according to Equation (1).
- = +
SCN + 2H2O + 2O2 = SO4 + NH4 + CO2 (1)
Biological oxidation of thiocyanate is carried out by a number of aerobic, autotrophic organisms

which can use inorganic carbon sources, including Thiobacillus thiocyanoxidans, Thiobacillus
thioparus and Thiobacillus denitrificans. In addition, thiocyanate can be oxidized by several
species of the Pseudomonas genera, which are heterotrophic (require an organic carbon source).
Assuming a stoichiometric relationship for the oxidation of SCN, 0.34 gram of NH3 is generated
per gram of SCN oxidized and 1.1 g of oxygen is consumed per gram of SCN oxidized.
Theoretically SCN oxidation does not result in a change in pH, however testing has indicated that
the oxidation of thiocyanate does result in some consumption of alkalinity and a slight reduction
in pH, which is minor relative to consumption from the nitrification process.
The primary micro-organisms responsible for SCN oxidation are reportedly autotrophic and can
therefore use inorganic carbon sources such as CO2. However, since heterotrophic organisms
may also be responsible for SCN oxidation, a small amount of methanol is added to the first stage
aeration tank. Further benefits of methanol addition are derived from the resulting generation of
biomass and potential positive growth factors from the addition of an organic compound. A
reduction in SCN oxidation was noted when the addition of methanol was low.
5.2 Nitrification Process
Concurrent to thiocyanate oxidation, ammonia is oxidized by nitrifying organisms in two steps -

first to nitrite and then to nitrate according to Equations (2) and (3).
+ + -
NH4 1.5 O2 = 2H + 2H2O + NO2 (2)
- -
NO2 + 0.5 O2 = NO3 (3)
The oxidation of ammonia to nitrite and then nitrite to nitrate is carried out by two groups of
bacteria, Nitrosomonas and Nitrobacter. These organisms are autotrophic and therefore use
inorganic carbon sources.
399 B. Given et al.

In most nitrification processes, the oxidation of ammonia to nitrite is the rate limiting step,
therefore nitrite does not build up. However, at Nickel Plate, the rate of oxidation from nitrite to
nitrate appears to be slower than the rate of ammonia oxidation to nitrite. Therefore, under upset
conditions, when biomass concentrations are lower, nitrite will be present in the overflow. The
presence of nitrite in the overflow may be an early indicator of upset conditions prior to loss of
nitrification and noticeable increases in ammonia concentrations. At high biomass inventories,
however, both ammonia and nitrite (NO2) concentrations will be low and the system should not be
prone to upsets, i.e. NH3 < 0.3 mg/L as N and <0.1 mg/L NO2 as N. Nitrite residuals in the
effluent from the activated sludge system are not a major concern however, since nitrite is readily
reduced to nitrogen gas in the denitrification system downstream in the treatment process.
The combined nitrification reaction consumes alkalinity and releases acidity, therefore it is
necessary to control pH and maintain alkalinity to optimize the process. During the process, 7.2
kg of alkalinity (as CaCO3) is destroyed per kg of ammonia nitrogen oxidized. Alkalinity can be
supplied by either soda ash or lime. The lab scale and pilot plant tests initially utilized soda ash to
supply alkalinity, but switched to lime to reduce operating costs and complexity. There is some
concern with the exclusive use of soda ash for pH control, since the literature suggests that the
high sodium concentrations in the treated water from the used soda ash could be inhibitory to the
Nitrosomonas. The overall reaction for the nitrification process is provided in Equation (4).
2NH4HCO3 + 4 O2 + Ca(HCO3)2 = Ca(NO3)2 + 4 CO2 + 6H2O (4)
Both Nitrosomonas and Nitrobacter have long generation times and low cell mass yields. Sludge
age, therefore, is a critical factor in the nitrification process. Long sludge age can be achieved by
operating with a high biomass inventory and by maintaining long retention times. The nitrification
process is also markedly sensitive to temperature. Operating temperatures above 15° C are
desirable to achieve complete nitrification although potentially the system can be acclimatized to
operate at lower temperatures. At temperatures below about 11° C, problems were encountered
with the efficiency of the biological processes.
The nitrifying bacteria are also sensitive to low dissolved oxygen, low pH and the presence of
toxic compounds, such as metals. Dissolved oxygen concentrations at or above 2.0 ppm are
+
desirable. Oxygen consumption ratios are 3.22 mg O2/mg NH4 -N for Nitrosomonas and 1.22 mg
+
O2/mg NH4 -N for Nitrobacter.
pH in the range of 7.8 to 8.5 is theoretically optimal, with significant losses of efficiency below
7.0. However, the activated sludge system has been acclimatized to operate at a pH of 7.4
without a loss of efficiency.
5.3 Cyanide and Cyanate Removal
In addition to thiocyanate and ammonia oxidation, the aerobic portion of the combined activated
sludge process is capable of oxidizing and removing WAD cyanide and cyanate, another
breakdown product of cyanide produced during beneficiation and reporting to the tailings
impoundment.
400 B. Given et al.

Free cyanide, if present, can be oxidized biologically by a number of species of the genera of
Pseudomonas, Alcaligenes and Achromobacter to form cyanate which in turn hydrolyzes to form
ammonia. Alternatively cyanide can also be converted to thiocyanate by a number of organisms
including Chromobacterium violaceum that produce the enzyme rhodanese. This enzyme is
responsible for the detoxification of cyanide in mammals. Thiocyanate formed by rhodanese is
then converted to ammonia via Equation (1).
WAD-CN can be removed by metal complex absorption onto biomass and subsequent internal
decomposition to cyanate. Strong acid dissociable cyanides such as iron cyanide are not readily
treatable biologically, but can be removed in the process through precipitation.
The reclaim feed can contain appreciable concentrations of cyanate due to production as a by-
product of the Inco-SO2 Air cyanide destruction process. Cyanate hydrolyzes to form ammonia
under neutral to acidic conditions but can be quite stable under alkaline conditions.
- + -2 +
CNO + H + 2H2O = HCO3 + NH4 (5)
The lab and pilot test work has indicated that cyanate does not persist in the activated treatment
system and should not be of further concern.
5.4 Nitrate Removal and the Denitrification Process
The biological process of denitrification involves the conversion of nitrate and nitrite to gaseous
nitrogen species. The gaseous product is primarily nitrogen gas but also may contain nitrous
oxide or nitric oxide. The denitrification process is carried out by facultative bacteria of the
genera Pseudomonas, Micrococcus, Achromobacter and Bacillus under anaerobic conditions.
These organisms are heterotrophic and thereby require an organic carbon source. Methanol has
generally been used for this purpose due to its low costs. The conversion of nitrate to nitrogen
gas is a two step process. However, both steps are carried out by the same organisms.
The overall energy reaction for nitrate removal can be described by Equation (6).
- -
6NO3 + 5CH3OH = 5CO2 + 3N2 + 7H2O + 6OH (6)
-
On an empirical basis the methanol requirement for both energy and synthesis is 2.47 g/g of NO3
N removed. However, additional methanol may be required to consume any dissolved oxygen
present in the feed. Experience has indicated that the methanol requirement can vary from 1 to 3
-
g/g of NO3 N removed. The endogenous breakdown of biomass from the activated sludge system
upstream could supply some of the required organic carbon for nitrate removal. At low methanol
dosages, the denitrification rate will vary with the dosage, while changes at higher dosages should
not effect the rate.
401 B. Given et al.

-
Denitrification produces in the order of 3.5 g of alkalinity as CaCO3 per g of NO3 N removed,
requiring the addition of sulfuric acid to control pH in the optimum range of 6.5 to 7.5. The rate
of nitrate removal drops with temperature. The process will operate at temperatures as low as
5°C but generally requires temperatures greater than 10°C. The rate is very sensitive to
temperature with the rate doubling with each 4°C increase. The biomass yield of the
denitrification process is small. Therefore, maintaining high biomass inventories and sludge ages
will reduce the potential for upsets and loss of the process.
6.0 THE GENERAL COMBINED ACTIVATED SLUDGE PROCESS FLOWSHEET
6.1 The Combined Activated Sludge Process
The flowsheet for the combined full scale biological and chemical treatment process is shown
schematically on Figures 5-8. Reclaim water from the barge in the tailings impoundment is
pumped to the two internal reclaim tanks at the mill. The reclaim water is then heated in a
6
submerged combustion propane-fired heater rated for delivery of 4.0 x 10 BTU/h. The heater is
capable of raising the feed temperature to 25° C at 200 gpm. Under extreme conditions of minus
15° C air temperatures and a 15 mph wind, the system will ensure that the operating temperatures
are controlled between 15° and 20° C. The heater consists of an insulated tank, combustion air
preheater, burner, blower, combustion chamber, fuel trains and controls. Operation of the heater
will be controlled in the 1st aeration tank by taking manual temperature readings each day.
The activated sludge treatment system consists of three 38-foot diameter agitated aeration tanks
fitted with diffused air aeration systems. Process air is supplied by the existing Gardner-Denver
compressors in the mill. Lime and soda ash are added to the first aeration tank to control pH at
8.5. Most of the demand for alkalinity will be supplied by lime while soda is used to supplement
carbonate if this becomes necessary for SCN and NH3 removal. The bulk of the demand for
alkalinity is from the nitrification process. pH will be controlled with a PID controller.
Phosphoric acid is fed to the first aeration tank to supply phosphorous to the biological process.
Alternatively phosphoric acid may be added to the second reactor to reduce the impact of losses
in the first reactor due to lime addition. The phosphoric acid metering rate is set manually
according to analytical results from activated sludge thickener O/F samples. Currently, the
addition of phosphoric acid has not been required.
A small amount of methanol can be added to the first reactor to provide some organic carbon
(approx. 0.01 gpm at the design flow of 350 gpm). After commissioning it may be feasible to
reduce methanol addition due to organic carbon sourced from the breakdown of recycled
biomass. The rate of methanol addition is set manually according to overall performance of the
system.
The final stream added to the first aeration tank is recycled underflow sludge from the thickener
which provides the biomass necessary to carry out the biological treatment process. The second
and third stage aeration tanks provide additional retention time to complete the treatment process.
The overflow from each tank is sampled on an as required basis and assayed for SCN, NH3, NO3
402 B. Given et al.

and NO2.
403 B. Given et al.

Figure 5: Activated Sludge System Process Flowsheet
404 B. Given et al.

Figure 6: Denitrification Flowsheet
405 B. Given et al.

Figure 7: High Density Sludge Circuit Process Flowsheet
406 B. Given et al.

Figure 8: Reagent Feed Systems
407 B. Given et al.

Based on experience, oxidation of SCN is completed in the first reactor, while NH3 removal is
completed in subsequent reactors. The presence of nitrite is used to provide an early warning of
potential process upsets. The third reactor overflows to the center well of the 20 ft. thickener
(TA-04). The biomass settles in the thickener and be pumped from the sludge hopper by pump
M1021. The return sludge is pumped to the first aeration tank while the thickener overflow is
collected in the pump box and pumped to the denitrification process by pump M1022. The return
sludge pumping rate is set and controlled manually according to the plant flow rate. This rate is in
the range of 100 to 200% of plant flow rate. The activated sludge system discharge contains
significant amounts of nitrate (approx. 400 mg/L as N) but very low concentrations of thiocyanate
and ammonia (i.e. 0.3 mg/L SCN and 0.3 mg/L NH3 as N). The nitrate levels have decreased to
about 200 mg/l as N over time due to the continued decrease in SCN levels in the reclaim water
from the impoundment.
Overflow from the activated sludge system thickener is pumped to No. 5 aeration (38 ft dia.)
tank. This tank has low speed agitation to maintain the biomass in suspension without causing
significant oxygen transfer. Methanol is added at a rate of 900 ml/min at the design flow to
provide an organic carbon source for the denitrification process. The methanol metering rate is
set and controlled according to manual D.O. readings and on an assessment of overall
performance. The analyses of residual organics in the Hopper Clarifier O/F can be conducted as a
trouble shooting guide to set and control methanol feed rate.
Sulfuric acid is added to No. 5 aeration tank and controlled using a PID controller to maintain pH
in the 6.5 to 7.5 range. Supplemental phosphoric acid is metered to No. 5 aeration tank to
maintain a residual of 5 mg/L as P. Finally, underflow sludge from the hopper clarifier (TA-07) is
pumped to the first denitrification tank to provide active biomass. The denitrification reactor
overflows to the re-aeration reactor where air is supplied to strip nitrogen N2 gas, oxidize residual
methanol, and prevent rising sludge problems in the hopper clarifier. The amount of aeration
supplied to the re-aeration reactor is minimized to reduce the carry-over of dissolved oxygen.
The re-aeration tank overflows to a pump box and its contents are then transferred to the hopper
clarifier via two pumps M570 and M571. By mid-1997, a new 38-foot diameter clarifier was built
to replace the original hopper clarifier. The biomass is allowed to settle in the hopper clarifier and
is returned to No. 5 aeration tank at a rate of 100% to 200% of the reclaim flow rate (i.e. 350 to
700 gpm). The return sludge rate for the denitrification system is controlled manually.
The dissolved oxygen concentration of the denitrification tank will be monitored continuously.
Increases in dissolved oxygen in this reactor will require increases in the methanol usage. The
hopper clarifier overflow will be sampled daily and assayed for nitrate and nitrite. The overflow
from the hopper clarifier will flow by gravity to the High Density Sludge (HDS) treatment system.
408 B. Given et al.

6.2 The New HDS System
The flowsheet for the HDS treatment system which is used for the removal of arsenic, sulfate and
metals is provided in Appendix A and can be described as follows:
1) 38' thickener O/F from the denitrification circuit is fed to the distribution box at
HDS tank #1.
2) Sulfuric acid is added to the pump box to reduce pH to 5.5 to 6.5. This addition
rate is controlled by a PID controller from a probe mounted in the tails pump box.
However, this acid addition is no longer needed for arsenic removal.
3) Transfer Pumps M499 and M500, pump the contents of the tails pump box to the
first reactor (SO2 tank #1). Ferric sulphate is added in the transfer line upstream of
the reactor to provide a short contact time at a low pH. The ferric sulphate
solution metering rate is set and controlled manually.
4) Lime is added to the lime/sludge mix tank and controlled to control pH at 7.5 to
8.5 in the first reactor. Recycle sludge from the 110 ft thickener is combined with
the lime in the lime/sludge mix tank and then overflows to the first reactor (SO2
tank #1).
5) The first reactor is aerated to ensure than any ferrous iron present in the ferric
sulphate solution is oxidized. This reactor also contains a pH probe used to
control the lime addition rate to the lime/sludge mix tank. The first reactor tank
overflows to the second reactor which in turn overflows to the center well of the
110 ft thickener TA-13. This reactor is no longer in service.
6) A dilute polyelectrolyte solution is added upstream of the center well to provide

flash mixing, followed by flocculation in the center well.
7) The thickener separates out the suspended solids and generates thickened solids
that are recycled back to the lime/sludge mix tank. Solids recycle generates high
sludge densities, creates a high surface area to remove colloidal solids, maximizes
metals removal and precipitates gypsum.
8) A portion of the recycled solids are wasted periodically to the tailings pond to
maintain a constant solids inventory. The wasting strategy will include flow
restrictions and timer pump controls to prevent over-pumping and loss of sludge
inventory.
9) The thickener overflow will discharge to an overflow pump box and be pumped to
Leach Tank #2 via pumps M360 and M380 and then flow through Leach Tanks 3,
4 and 1 by gravity prior to the pipeline to 20 Mile Creek.
409 B. Given et al.

Monitoring will consist of daily sampling of the feed and overflow and assaying for total and
dissolved arsenic as well as assays for other metals including Co, Cu and Fe. The HDS process is
used to remove arsenic and sulphate through conventional ferric sulphate precipitation followed
by flocculation and solids removal in a high solids density recycle system. This system will also
precipitate other metals that may be present in suspension or solution in the denitrification system
overflow.
Arsenic co-precipitates with ferric hydroxide to form a basic ferric arsenate according to
Equations (7) and (8). Excess sulfate is also precipitated out as gypsum by lime as described in
Equation (9).
- -
2H3AsO4 + Fe2(SO4)3 + 3Ca(OH)2 = 2FeAsO4 2H2O + 3CaSO4 2H2O (7)
-
Fe2(SO4)3 + 3Ca(OH)2 + 6H2O = 2Fe(OH)3 + 3CaSO4 2H2O (8)
- ++ -
SO4 + Ca + 2H2O = CaSO3 2H2O (9)
Factors that affect arsenic removal and sludge stability in a treatment plant for arsenic using the
ferric sulphate HDS process can be summarized as follows:
Arsenic should be present as arsenate As(V) since some arsenite compounds have higher
solubilities than the equivalent arsenate. This should not be a significant factor at Nickel Plate
since the concentration of As is low and the reclaim water was exposed to oxidizing conditions in
-
the SO2 Air Process. Oxidation with air will not oxidize reduced As.
Iron dosage, i.e. ferric sulfate, should be set to maintain an Fe/As molar ratio greater than 5:1.
This ratio maximizes removal efficiency and ensures that the resultant sludge will be stable.
Commercial grades of ferric sulfate can contain an appreciable percentage of ferrous iron. Since
ferrous arsenates are more soluble than the equivalent ferric arsenate, it is good practice to
oxidize any ferrous present to ferric. The oxidation of ferrous to ferric is rapid under neutral pH
conditions. The use of air mixing in the arsenic precipitation reactor ensures that all ferrous iron
is oxidized to ferric iron.
Operating pH should be maintained in the 7-8 range to optimize arsenic removal. Removal under
acidic pH conditions relies on ferric arsenate solubility which is a minimum at pH 2. However,
low effluent concentrations at neutral pH are due to co-precipitation mechanisms that are in turn
influenced by the solubility of ferric hydroxide, which has a minimum solubility at pH 8.5 to 9.0.
Operating experience indicates that treatment efficiency is not overly sensitive to pH fluctuations,
if the Fe/As molar ratio is above 5:1.
Maintaining a high solids inventory using recycle and controlled sludge wastage can produce low
dissolved arsenic and suspended solids concentrations when coupled with proper flocculation.
Recycled sludge yields maximum settling rates and sludge densities which optimizes overall
performance.
410 B. Given et al.

A number of factors influence the effectiveness of polyelectrolyte addition, namely, type, charge,
charge densities, feed solution concentration, air entrainment, floc shear and dosage. Screening
and selection of a different polyelectrolyte can optimize suspended solids removal and improving
performance when problems occur.
7.0 OPERATING STRATEGY OF THE COMBINED

ACTIVATED SLUDGE/HDS SYSTEM
The strategy for operating the treatment plant will utilize a management structure and a
monitoring and control system that ensures that process problems are detected and corrected
before process upsets occur. Treatment system management will be the direct responsibility of a
Plant Manager (PM). The PM will direct the day-to-day activities of the operators on-shift, the
lab staff responsible for sample analyses as well as maintenance and other personnel assigned to
treatment plan operation.
The PM can assign his responsibilities to other individuals in the event of an extended absence.
The PM will still be responsible for management during normal days off on a call-out basis (if
necessary in an emergency situation).
The biological treatment systems at Nickel Plate are sensitive to specific operating conditions such
as temperature, pH and reagent addition rates. Loss of process due to upset conditions can
require a considerable period of time to rectify. Therefore, it is essential that the process be
monitored continuously. At times it may be necessary to change operating set points to improve
performance or correct problems. Decisions to change set-points and operating conditions can
only be made by the PM after a careful review of the situation.
The treatment system will be controlled based on maintaining set-points, regular sampling and
analyses of sampling, on-line controls and alarms and preventative maintenance of all mechanical
equipment. Process pumps that are critical to successful operation have standby pumps. Both the
main operating pumps and the standby pumps should be kept in good working order at all times
to ensure that a mechanical failure does not result in loss of the process.
A monitoring schedule for sampling and analyses of the individual effluent and sludge streams has
been developed for monitoring of the combined treatment system. This schedule will be subject
to modification based on operating experience with the full scale plant. It will be the
responsibility of the PM to select specific operating parameters or indices to operate the plant.
The PM will plot trends in the baseline data sets to select reliable operating parameters that can be
used to monitor and control the plant and ultimately reduce the intensity of the sampling and
analyses program. The objective will be to select one or two key parameters and to ultimately
rely on continuous physical parameters such as pH, conductivity, D.O. and turbidity. This will
permit setting alarms that will indicate a problem prior to process upsets occurring.
411 B. Given et al.

The operators will carry out the following tasks:
1) Receive and store all reagent shipments.
2) Maintain mechanical equipment in good work order.
3) Note and record all maintenance items requiring immediate attention on log.
4) Conduct all sampling and do physical tests for pH conductivity as instructed by the
PM.
5) Enter analytical data received from lab in computer file for review by the PM.
6) Calibrate instruments.
7) Maintain daily log for submission to PM for approval.
The duties of the wastewater treatment plant manager include:
1) Manage day-to-day activities of all staff assigned to the water treatment system.
2) Review and approve operators' daily log sheets.
3) Review equipment operation and schedule routine maintenance activities.
4) Review overall treatment system performance and make decisions regarding

changes to controlled parameters and set-points.
5) Prepare weekly report for submission to Homestake Canada, Inc.
The operators will be responsible for completion of a daily log that will be signed and sent to the
PM for approval. A sample of this log sheet is attached. This log will be modified based on
experience with operation of the full scale plant.
The PM will complete a summary of the information contained in the operators daily log as well
as a review of performance and an outline of any special activities being carried out in the
following week.
The instrumentation used to monitor and control the treatment operation is provided in Table 2.
All alarms points will have local enunciation as well as access via the MMI. The operators will be
required to record all alarm events on the daily log sheet for review by the PM. Alarms will
generally be due to mechanical problems that can be rectified directly by the operator.
Safety measures common to other areas for rotating equipment, fuel and electrical switch gear,
etc., also apply to the waste treatment system. The safety consideration unique to the waste
water treatment system are as follows:
412 B. Given et al.

1. The aeration tanks contain an air/water mixture that has a significantly lower density than
water and therefore lower buoyancy. Individuals that accidentally fall into these basins
would not have sufficient buoyancy to remain on the surface. Safety railings and chains
should remain in place at all times. All workers outside the safety railings should wear a
safety line and be assisted by a second worker who can provide assistance in the event of
an emergency.
2. The mixed liquor contains a high population of microorganisms including bacteria. These
organisms are not considered pathogenic because of their low optimum operating
temperatures. However, workers should still be reasonably careful when in contact with
mixed liquor or sludge to ensure that oral contact is not made. Latex gloves should be
worn when in contact with biomass.
3. Current lock-out procedures for lock-out of equipment during repair or maintenance of

rotating equipment.
4. Ferric sulfate will be delivered to site as a 60% solution in tanker truck quantities of
18,000 L and transferred to the ferric sulfate storage tank. Ferric sulfate will be metered
to the HDS process without dilution.
5. Quicklime will be delivered in bulk tanker truck and pneumatically loaded into the lime
silo for eventual slaking and transfer to the milk-of-lime stock tank.
6. Flocculent will be delivered in standard 25 kg bags. A 0.05 to 0.1% solution will be made
up using the existing equipment and delivered to the process as required.
7. Soda ash will be delivered to site in standard 1360 kg Flo Bins. A 10% solution of soda
ash will then be made up in the soda ash make-up tank and transferred to the soda ash
storage tank for delivery to the process.
413 B. Given et al.

Table 2
2nd Quarter 1997 Water Treatment Plant Data
Parameter Reclaim Activated Sludge Circuit

Aerobic Anaerobic HDS Permit Discharge
Circuit Circuit Circuit Criteria to
Units - mg/L unless Influent Effluent Effluent Effluent Hedley Creek
noted
Flow - US Gallons/min 328.3 319.1 40:1 Ratio
pH 7.26 7.90 7.30 7.58 7 - 10
Total Dissolved Solids 3940.0 4336.0 7500
Total Suspended Solids 8.8 22.0
Cyanide - Total 1.174 1.100 0.800 0.786 3.0 ppm CNt & SCN
Cyanide - WAD 0.392 0.203 0.080 0.085 0.200
Thiocyanate - SCN 527.0 0.1 0.3 0.5
Ammonia - NH3 - N 39.9 0.3 0.5 0.6 1.0
Nitrate - NO3 - N 14.1 159.1 1.0 1.1 10.0
Sulphate - SO4 2045.0 2880.0 2800.0 2811.0 3500
Arsenic - Total 0.300 0.210 0.180 0.012 0.07
Arsenic - Dissolved <0.01
Cobalt - Dissolved 2.62 2.15 1.65 1.68
Copper - Total 0.33 0.10 0.03 0.02 0.04
Copper - Dissolved 0.23 0.02 0.01 0.01
Iron - Total 0.33 0.33 0.32 0.22
Iron - Dissolved 0.04 0.05 0.06 0.05 0.50
414 B. Given et al.

10.0 START-UP PROCEDURES
10.1 Start-up
The start-up procedures used after an outage will be dependent on the nature of the outage and
the length of time the outage as occurred. In most cases, if the outage has been short, restarting
the system will simply involve restoring all mechanical operation and gradually increasing load
until the process has stabilized. A more complex start-up procedure would be required after the
loss of biomass due to wash-out or an extended shutdown.
11.0 TREATMENT THEORY
11.1 Activated Sludge Process
The activated sludge process consists of a reactor tank(s) followed by a settling chamber or
clarifier. The reactor(s) is fitted with aerators which add oxygen to the solution and provide
mixing. Feed enters the aerated reactor and contacts large numbers of aerobic microorganisms
including bacteria, protozoans and rotifers. The reactor contents are referred to as the Mixed
Liquor. The microorganisms withdraw dissolved and colloidal nutrients from the water and
produce cell mass. The clarifier then separates these organic solids from the liquid fraction and
reintroduces them to the reactor chamber, allowing the liquid fraction to exit the system. It is the
recycling of the cell mass that creates the very high cell densities in the Mixed Liquor which
allows efficient treatment of water.
The solids are kept in suspension in the reactor through mixing to provide good contact between
the microorganisms and their food. The settling chamber is quiescent, and allows agglomerations
of cells called flocs to settle by gravity.
The microbial composition of the Mixed Liquor is important to the formation of flocs and
therefore the settleability of the solids. Poor settleability causes a portion of the solids to be lost
from the clarifier which lowers the quality of the effluent. Better floc formation is partly achieved
by encouraging, through control of process parameters or regular inoculations, certain microbial
genera. Genera that form spheres and rods, such as Pseudomonas, Zoogloea and
Mycobacterium, will settle well while species forming filaments, such as Thiothrix and
Geotrichum will not. The presence of filamentous organisms cause a phenomenon called bulking.
Bulking is likely to prevent complete removal of solids in the settling chamber. The presence of
Protozoa and Rotifers is also important for their ability to consume dispersed, unflocculated or
incompletely flocculated bacteria which are difficult to settle. Contaminants such as metals may
also have an effect on flocculation and settleability.
The microbial performance may be controlled through a parameter called sludge age. The sludge
age is the length of time, on average, that solids are retained in the reactor. The proper sludge
age will optimize the rate of growth of the microorganism, and therefore the rate of uptake of
415 B. Given et al.

nutrients. Additionally, the organisms start to produce extra-cellular polymers at the proper age.
These polymers help to glue the organisms together to improve flocculation and settleability.
Optimum sludge age will vary according to the type of waste being treated.
Sludge age is controlled through a process called wasting. This involves the removal of a portion
of the cell mass on a regular basis. Once the optimal sludge age is reached, the wasting rate
should be equal to the rate of new cell growth.
The performance of the system also depends on the loading rate. The growth rate of the
organisms is dependent on the availability of their food; the growth rate will decrease with
crowding and competition. Treatment, however, depends on a large number of organisms; low
cell densities will reduce treatment effectiveness. There is an optimum loading rate between the
two extremes. This balance is measured by the Food to Microorganism ratio (F/M ratio). F/M
ratio may be controlled by varying the throughput of the plant (or sizing the plant for a certain
throughput), changing the sludge wasting and recycling rates, and also by changing the aeration
rate.
12.0 OPERATIONAL INDICES
12.1 Food to Microorganism Ratio (F:M)
An operating criteria commonly used to assess activated sludge plants is the F:M ratio. This ratio
is a measure of organic loading relative to biomass inventory and is calculated by dividing the
daily organic mass load by the mass of active biomass available to carry out treatment. In this
case, F:M could be defined by SCN and NH3 loadings relative to the biomass.
12.2 Sludge Volume Index (SVI)
SVI is a unit parameter commonly used to measure the settlement and compaction characteristic
of mixed liquor biomass. SVI is calculated by dividing the settled volume of the sludge obtained
by the 30 minute settleability test expressed as a percentage by mixed liquor suspended solids also
expressed as a percent. Values of 100 are considered typical of a well operated plant. High SVIs
are indicative of bulking sludge which can be due to a number of factors. These factors include
the presence of toxicity, low dissolved oxygen or organic overloading.
Common practice in treatment plan operation when a bulking sludge condition occurs is to waste
sludge to reduce total sludge inventory and to control loadings, if possible.
12.3 Sludge Age
The parameter "Sludge Age" or Mean Cell Residence Time (MCRT) is integral to the proper
operation of an activated sludge system. Failure to control this parameter will prevent the system
from operating as designed and lower the quality of the effluent.
416 B. Given et al.

Sludge Age is controlled through Sludge Wasting, which results in a reduction in the
concentration of biomass in the aeration tank (MLSS). Solids are customarily wasted from the
system by wasting return sludge from the final clarifier to the tailings pond.
The rate at which the sludge is wasted controls the sludge age. Once a desirable sludge age, or
mean cell residence time, is reached and the system is seen to be functioning properly, the sludge
wasting rate should match the biomass production rate in the reactor to give a constant MLSS
concentration.
The sludge age is important because it determines the microbial composition of the Mixed Liquor.
Slower growing microorganisms, such as nitrifiers, are at low concentrations when the sludge
age is low. A low sludge age may also result in poor settling characteristics and subsequent solids
loss with the effluent. The optimal sludge age for removal of carbonaceous material may differ
from the optimal sludge age for nitrification.
The plan performance is monitored by the plant operator to determine optimum sludge age. A
wasting strategy must then be implemented to control sludge age within a certain range.
12.4 Determination of Sludge Age and Sludge Wastage Rate
Sludge age can be calculated by dividing the total solids in inventory by the quantity of solids lost
and wasted from the system on a daily basis. The total solids inventory is equal to MLSS times
aeration tank volume. The quantity of solids lost from the system on a daily basis is equal to the
mean effluent suspended solids times the total discharge volume. The quantity of solids wasted
from the system is equal to the produce of sludge or mixed liquor concentration and volume
wasted.
Once a target Sludge Age is established, the sludge wastage rate can be calculated. For a system
where mixed liquor is wasted directly the calculation is as follows:
3
VW = 1/SA x V(m )
3
where: VW = volume (m ) to be pumped out per day
3
V = volume of tank(s) (m )
SA = sludge age in days
This calculation assumes that the quantity of solids lost with the effluent is minor relative to the
solids intentionally wasted from the system.
417 B. Given et al.

12.5 Microscopic Examination
A wide variety of microorganisms are present in untreated wastewater, especially from domestic
sources, although some raw industrial wastes may have low microorganism concentrations.
Biological treatment plants, however, carry high concentrations of bacteria which are essential to
carry out treatment. The bacteria convert soluble organic wastes into cell mass and other
inorganic and organic by-products that are used by other organisms. The bacteria present in
activated sludge are generally gram-negative and include Pseudomonas, Achromobacter,
Flavobacterium, Nocardia, Bdellovibrio, Mycobacterium, and two nitrifiers, Nitrosomonas and
Nitrobacter. Various filamentous bacteria may also be present; these include Sphaerotilus,
Beggiatoa, Thiothrix, Lecicothrix, and Geotrichum. In addition to bacteria which degrade the
organic waste, multi-cellular organisms such as protozoa and rotifers are often present to act as
effluent polishers. Protozoa consume dispersed bacteria that have not flocculated, while rotifers
consume small floc particles that have not settled. Poor settling effluent may contain high
concentrations of filamentous bacteria such as Sphaerotilus as well as fungi.
A microscopic examination of the mixed liquor is commonly conducted to evaluate the health of a
particular biomass. The presence of multicellular organisms, such as rotifers, is generally a good
indication that the sludge is healthy. The presence of large concentrations of filamentous
organisms and fungi would be indicative of a poorly settling sludge. This condition would
normally dictate that corrective action is required. The presence of filamentous organisms and
fungi can be due to high organic loading, presence of toxicants, low dissolved oxygen or lack of
nutrients.
Corrective action generally involves increased sludge wastage coupled with elimination of the
cause of the upset condition. A microscopic examination of the biomass can often provide an
early warning of problems requiring corrective action. Experience and record keeping are
essential to use microscopic examination as a control index.
13.0 OVERALL WATER TREATMENT PLANT PERFORMANCE AND COSTS
A summary of the overall water treatment plant performance for the second quarter of 1997 is
presented in Table 2. As is seen in Table 2, the full scale treatment plant is providing excellent
removal of WAD cyanide, thiocyanate, ammonia, and nitrate.
A summary of the individual reagents costs are provided in Table 3. A summary of the overall
cost of operation of the combined water treatment plant is presented in Table 4. As in seen in
these two tables, labor is the most significant individual cost followed by power and chemicals.
The overall cost is about $(US)0.02 per gallon of treated water, which is very low in comparison
to other widely used treatment processes.
418 B. Given et al.

The research, development, and implementation of the combined biological and chemical water
treatment process through retrofitting of the existing metallurgical circuit saved many millions of
dollars over other treatment processes, and demonstrated that such an approach is viable and
should be pursued in other mining applications. Consideration should be given at an early stage of
development of a beneficiation process to incorporate such concepts for closure.
A modification of the full scale biological treatment system is being used to treat and remove
nitrate from waste rock drainage. The modficated biological treatment system is an attached
growth process and involves the use of a series of sealed one meter diameter pipes in which
sections of high surface area plastic media have been placed. The entire biological treatment
system is sealed to exclude oxygen and methanol is added as a carbon source for the denitrifying
bacteria. This full scale system is treating up to 100 gpm and removing nitrate to less than 1.0
mg/l. Additional pilot plant work is under way to allow treatment of up to 200 gpm of waste rock
drainage using a modified configuration similar to the other full scale anaerobic treatment plant.
Table 3
1997 Water Treatment Plant Reagent Costs
Reagents Consumption Cost/M US Gallons

KG/M US Gallons US $
Methanol 3333 976.09
Ferric Sulphate 2113 430.15
Sulphuric Acid 1516 113.70
Phosphoric Acid 214 94.77
Soda Ash 3834 816.09
Lime 6023 602.30
Flocculant - Anionic 13 39.46
Flocculant - Cationic 50 180.36
Total Reagent Costs 3,252.93
419 B. Given et al.

Table 4
1997 Water Treatment Plant Costs
Cost/M US Gallons Cents/US Gallon

US $ US Currency
Reagent Costs 3,525.93 0.33
Propane 2,401.36 0.24
Power 3,673.47 0.37
Labor 7,959.19 0.80
Materials & Supplies 714.29 0.07
Repairs 714.29 0.07
Total Costs 18,715.51 1.87
420 B. Given et al.

INTRODUCTION TO THE BIOPASS SYSTEM:
AN ALTERNATIVE PASSIVE TREATMENT PROCESS
FOR CLOSURE OF SPENT HEAP LEACH PADS
Prepared By:
Terry Mudder, Ph.D.

Scott Miller
Luke Russell
Alan Cox
Dave McWharter
Originally presented at Northwest Mining Association Annual Meeting, Spokane, Washington,

December 1995
Introduction To The Biopass System:
An Alternative Passive Treatment Process For Closure Of Spent Heap Leach Pads
1.0 INTRODUCTION
1.1 Background
This paper presents a cyanide heap leach pad closure approach which utilizes physical stabilization
and lined containment of spent ore solids along with long-term biological passive treatment for
draindown of residual solutions. This is a cost effective alternative to the traditional approach to
heap leach pad closure which generally includes rinsing of spent ore with fresh or treated water
until compliance standards for solids and solutions are achieved.
Heap leach pad closure typically consists of both short-term and long-term goals. The short-term
goal is to eliminate process solutions, stabilize heap solids, and control erosion. The long-term
goal is to restore the site to a condition suitable for pre-mining uses of mineral exploration,
mining, livestock grazing and wildlife habitat by restoring useable vegetation similar to that which
existed on the site prior to disturbance. In addition, objectives include development and
implementation of a heap leach pad closure which eliminates maintenance requirements and the
potential for future environmental remedial action.
The traditional approach to heap leach pad closure is to rinse the heaps with several pore volumes
of fresh or treated water. The effluent from an initial rinse is often treated and recirculated until
the solutions passed through the heap meet the appropriate numeric and narrative water quality
standards. Column rinsing tests are often completed during project planning to determine the
number of pore volumes of fresh water required to rinse the heap to meet the closure criteria. A
traditional closure plan generally includes provisions to sample the rinse effluent and rinsed solids
to verify that the chemical requirements are being met. This closure approach, although a proven
technology for small heaps, presents a number of technical difficulties for large leach pads
including:
•
• Rinsing the heaps with multiple pore volumes requires years.
• Large quantities of solution requiring treatment or land application are generated.
• Due to preferential pathways in the heap, complete rinsing and detoxification is unlikely.
Recent evidence from actual heap leach operations indicates that numerical cyanide and pH
standards can routinely be met by rinsing, however, effluent standards cannot be achieved due to
leaching residual metals and other inorganics.

1.2 The Biopass System
An alternate approach is needed to allow stabilization of a heap leach pad that will meet the
existing closure objective in regard to control of long-term effluent flows and protection of waters
of the State. The alternative approach is to encapsulate the leach pad employing a vegetated soil
cover, and leave intact the liners to minimize the infiltration of future seepage and to collect and
treat any storm related seepage in a biological passive treatment cell. This concept for dealing
with residual drainage, if it occurs, from the spent leach pads is to convert one of the existing
solution ponds at the base of each pad into an in-situ anaerobic biochemical system, capable of
passively receiving and treating this drainage on an as needed and long term basis.
The basic system consists of an emptied and lined solution pond in which a layer of organic matter
is placed upon a set of evenly spaced perforated pipes which have been laid upon the liner to
receive and distribute any pad drainage. The organic matter, consisting of composted manure and
the distribution system are then covered with fill and a reclaimed soil and vegetative cover to
enclose the entire system to minimize infiltration, while promoting evapotranspiration and the
necessary anoxic conditions.
For purposes of this discussion, the passive in-situ anaerobic biochemical treatment system is
referred to as the "Biopass System.” The Biopass System finds its origins in the evaluation of
natural and manmade wetlands for treatment of low pH and metals containing drainage from
abandoned mine adits, waste rock disposal areas, and historical tailings. The drainage was initially
referred to as acid mine drainage (AMD), and more recently acid rock drainage (ARD).
During project planning, column rinse tests are routinely completed to evaluate closure
requirements for cyanide heap leach pads. The fresh water rinse requires three to five pore
volumes or more to achieve the water quality standards. For large heap leach pads, rinsing could
require hundreds of millions of gallons of fresh or treated water. Additionally, during rinsing
constituents such as mercury, arsenic, and selenium are mobilized above compliance standards.
The large quantities of fresh water required for rinsing and removal of other constituents
unrelated to the cyanide complexes make this approach problematic. Problems with this approach
include:
• Difficulty in detoxification, evaporation, or discharge of large quantities of residual rinse

solution.
• Generation and disposal of sludge.
• Numerical standards for certain metals or inorganics may not be attainable on either a short-
or long-term basis.
• The time needed to rinse the ore and evaporate the solutions from large heap leach pads may
take years.

Each heap leach pad closure should be designed to account for site-specific climatic and
environmental factors. The closure plan should be consistent with the long-term goal of restoring
the site to a condition suitable for the pre-mining land uses of mineral exploration, mining,
livestock grazing and wildlife habitat by restoring useable vegetation similar to that which existed
on the site prior to disturbance. In areas like Nevada there is little potential for infiltration of
precipitation through the rinsed ore to discharge in significant quantities due to the following
factors:
• Evaporation exceeds precipitation for all months of the year.

• Uptake of precipitation moisture by the ore is significant.
• The relatively low permeability of the soil cover material, in combination with
evapotranspiration will minimize infiltration.
The proposed procedure for stabilization of the heap will be to recirculate leach solution without
cyanide addition until the process is no longer economic. Once extraction is complete the leach
pad will be allowed to draindown, and will subsequently be physically stabilized by recontouring,
compacting, topsoiling and revegetation.
One of the process ponds at each leach pad will be converted to a bioreactor/ evaporator to treat
potential seepage from the heaps. A post-closure monitoring plan will be developed and
implemented to confirm that closure objectives are met. The closure plan revision and description
of the environmental setting as it relates to pertinent closure components are presented in detail in
the following sections.
2.0 GENERAL CLOSURE ACTIVITIES
2.1 Introduction
Under this alternative, the leach pad closure would require the following activities:
• Continue leaching ore while evaporating process solution until it is no longer economical.
• Draindown the leach pad and discharge solution to tailings facility if available for evaporation,
recirculate it to another heap leach pad as make up solution, land apply it, or evaporate the
residual solution on the heap leach pad.
• Recontour and compact the surface, spread topsoil and revegetate the leach pad.
• Construct a Biopass System with discharge to a leach field.
• Monitor short-term to verify that physical stabilization and closure objectives are being met.

2.2 Solution Management
At the completion of metals extraction all process solutions in the leach circuit are allowed to
draindown. Draindown solution is collected in the ponds at the facility and subsequently pumped
either to other leach pads for make up solution, pumped to a tailings impoundment for
evaporation or to a land application operation. Once draindown rates stabilize, all remaining
seepage is routed into the Biopass System, which is designed to accommodate expected long-term
seepage.
The reclaimed heaps will contain a residual moisture content after draindown, which is generally
immobile. Precipitation and extreme storm events can contribute moisture to a heap that is
discharged in a combination of the following processes:
• Evaporation or evapotranspiration.
• Uptake by spent ore raising the residual moisture content.
• Redistribute via unsaturated flow within the heap if the field capacity moisture content is
reached.
• Discharge from the heap, should the field capacity be exceeded or, if saturated conditions
occur at the base of the heap.
These processes can be modeled for each heap leach pad using an unsaturated flow code which
accounts for pad thickness, laboratory determined moisture release characteristics, and site-
specific climatic data.
Extensive research has been done on the theoretical and field measurements of infiltration and
evaporation from covers on mine waste facilities (Wilson, et al, 1993; Swanson, et al, 1994). The
unsaturated flow modeling can be designed to act as a quantitative closure evaluation regarding
the effectiveness of the selected closure alternatives. Climatic inputs to the system can be
modeled using site-specific precipitation and temperature data in conjunction with the synthetic
weather generator (WGEN) included as part of the Hydrologic Evaluation of Landfill
Performance (HELP) (USEPA, 1984) model. The WGEN model is used to simulate daily
precipitation, solar radiation and temperature for a one year period. These values are used as input
to the unsaturated flow model VS2DT (Lapalla, 1987) to approximate climatic conditions
through out the simulation period.
The unsaturated flow characteristics of both the topsoil and spent ore materials must be
determined empirically in the laboratory or estimated using information gathered during similar
investigations at other heap leach facilities. The laboratory characterization includes estimating
saturated hydraulic conductivity, residual moisture content, grain-size distributions, and moisture
characteristic curves.

2.3 Spent Ore Management
Reclamation plans generally call for recontouring the spent ore sideslopes to an overall angle of
2.5H:1V or 3.0H:1V. Often this will require pushing a portion of the spent ore outside of the
lined area. The consequences of placement of ore outside the lined area will depend upon the
final geochemical character of the ore and the potential for precipitation to infiltrate and discharge
from the leached ore. Five alternatives for protecting groundwater resources from effluent
leaching from spent ore were evaluated. They include:
• Placement of a low-permeability compacted soil liner under regraded ore.

• Extension of the geomembrane liner that presently underlies the leach pad.
• Creating an infiltration barrier over this portion of rinsed ore.
• Evaluation of the soil capacity to attenuate heavy metals through land application.
• No action.
2.4 Reclamation/Revegetation of the Heap Leach Pads
Following recontouring and compaction of the heap surface and spreading of topsoil, revegetation
of the spent ore will commence. Vegetation establishment on the leach pads will minimize
infiltration and deep percolation of precipitation into the leached ore and decrease erosion.
Infiltration and deep percolation will be minimized due to uptake within the heap and
evapotranspiration of rainfall by vegetation. The vegetation will also prevent the spent ore from
being eroded by either wind or water, by reduction of runoff flow velocities.
3.0 THE PASSIVE TREATMENT SYSTEM
3.1 Introduction
The primary goal with respect to decommissioning and closure of a spent heap leach pad involves
the prevention of long term deterioration of local surface and groundwater. According to
environmental regulations, the operation and site must be closed in a manner that will not degrade
the waters of the State. There are various methods for demonstrating that degradation of surface
and groundwater will not occur following closure.
The traditional approach has involved drilling and sampling the solids within the spent leach pad,
and subjecting those solids to leach tests either Meteoric Water Mobility Procedure (MWMP) or
Synthetic Precipitation Leaching Procedure (EPA Method 1312). The purpose of the extraction
test is to simulate the pad effluent that could originate from contact of infiltration with the spent
ore. A successful passage of the leach tests occurs if the resultant extraction solution does not
contain constituent levels greater than ten-fold their respective Maximum Contaminant Level
(MCL).

Unfortunately, compliance with the MWMP does not ensure that environmental impacts will not
occur. More recently, the assessment and prediction of potential water quality impacts following
closure of spent heap leach pads has included a Fate Transport Analysis (FTA), which involves
predictive mathematical modeling of the hydrological and chemical aspects of solutions and
seepage. In the current study, the hydrological modeling of the three spent heap leach pads has
indicated that once their surfaces are reclaimed, the quantity of precipitation and infiltration
entering the pads will be insufficient to generate drainage.
Closure of spent leach pads includes conversion of one of the existing solution ponds at the base
of each pad into an in-situ anaerobic biochemical system, capable of passively receiving and
treating this drainage on an as- needed and long-term basis. The basic Biopass System (Figure 1)
consists of an emptied solution pond in which first a layer of organic matter is placed upon a set
of evenly spaced perforated drain pipes, which have been laid in such a manner to receive and
distribute any pad drainage (Smith and Mudder, 1991). The organic layer and drain pipe is then
covered with fill and a reclaimed soil and vegetative cover to enclose the entire system to
minimize infiltration, while promoting evapotranspiration and the necessary anaerobic conditions.
Figures 2 and 3 illustrate a cross-section of the Biopass System.
In the course of evaluating the treatment performance of natural and manmade (i.e., engineered or
constructed) wetlands with respect to pH adjustment and metals removal, researchers found that
the vegetation communities removed only a few percent of the metals, generally well less than ten
percent (Sencindiver and Bhumbla, 1989; Environment Canada, 1990). The neutralization of
acidity and the precipitation of metals were occurring primarily in the anaerobic sediments beneath
the wetland, in which the bacterial reduction of sulfate yielded alkalinity and sulfide as
biochemical by-products (Kleinman, et al, 1986; Kleinman and Girtis, 1986). The sulfide
produced precipitated the metals as their very insoluble complexes, yielding very low residual
dissolved concentrations and very high removal efficiencies up to 99 percent.
Although wetlands have proved successful in treating ARD, several disadvantages have been
noted, which have limited their application. First, their effectiveness was limited in cold climates in
which the ground was frozen for extended periods of the year. Second, the wetlands did not
respond well to rapidly changing and elevated flows, which often occur in the spring in
mountainous regions, just as the plant and bacterial communities within the wetland are re-
establishing themselves. Third, the source of organic matter often became exhausted due to
ongoing bacterial activity, and required replacement from time to time. Fourth, the organic matter
or submerged anaerobic zone lost its metals removal capacity with time as its available sorptive
sites were occupied. Fifth, the metal removal efficiencies decreased with time due to short-
circuiting, which resulted in part from the continued precipitation of iron and aluminum
hydroxides within the submerged anaerobic zone.

With the Biopass System, and in this particular situation, many of the disadvantages of wetlands
can be circumvented, while taking advantage of the virtues of the bacterial and chemical processes
that occur in an anoxic environment. The performance of the Biopass System is not readily
affected by temperature as it is designed as an in-situ system in an area of moderate climate.
Second, the flows that potentially can enter the system are small and relatively constant. Third,
sufficient organic matter or compost can be placed in the system to accommodate the anticipated
long-term flux of constituents in the drainage, if it occurs. The fact that the organic layer will be
placed well below a compacted fill and vegetated surface promotes the necessary anoxic
conditions. Fourth, since the heap leach drainage is not acidic and does not contain elevated iron
or aluminum levels, the problems associated with precipitation of a large mass of metal hydroxides
within the organic layer is avoided.
The surface vegetation could be selected on the basis of specific metal uptake, as has been done
successfully in the rehabilitation of mine wastes (Morrey, 1993 and 1994). However, in the
current situation, the approach is to bacterially degrade the residual cyanide, while partially
reducing the residual nitrate and sulfate levels, and permanently fixing the precipitated the metals
within the subsurface organic layer. The fill and vegetative cover above the organic layer
promotes runoff and uptake of solution through capillary action. From a design perspective, the
primary concerns are associated with providing sufficient nutrients, moisture, and retention time
for stimulation of bacterial growth, acclimation, and degradation. During construction of the
system, the organic matter is wetted to promote anaerobic conditions, to supply the initial
moisture needed, and to encourage bacterial growth. The next section provides a discussion of
the basic biochemical processes that occur within the Biopass System.
3.2 Biological and Chemical Processes
The most important feature of the Biopass System is the organic layer into which the pad drainage
is directed, if it occurs. This layer contains the necessary nutrients and organic substrates to
support the growth of a diverse population of microorganisms, principally anaerobic and
facultative bacteria. Since the layer is placed many feet below the vegetated surface, anoxic or
anaerobic conditions are established along with a chemically reducing environment, as the organic
matter is degraded and the residual oxygen is depleted.
The anaerobic and chemically reducing environments promote the growth of the bacterial
population capable of uptake, treatment, sorption, and/or precipitation of cyanide, nitrate, sulfate,
and metals, the primary constituents of concern.

Figure 1: Biopass System Layout

Figure 2: Biopass System Cross Section

Figure 3: Biopass System Cell Detail

The initial chemical process that occurs as the drainage enters the Biopass System involves
physical sorption of a portion of the metals and complexed metal cyanides within the organic
layer, for example arsenic, copper cyanide, and mercury. The sorption of metals on both
inactivated and living biomass, even from solutions containing elevated total dissolved solids
levels, is well documented and forms the basis of several specialized treatment systems, such as
AlgaSORB and BIO-FIX, a treatment process being evaluated by the U.S. Bureau of Mines and
Department of Interior (Darnall and Gabel, 1989; Ferguson and Jeffers, 1991).
The sulfate entering the organic layer, which contains the necessary organic substrate, nutrients,
and bacterial seeds, is slowly converted to sulfide by one of several strictly anaerobic and
chemoheterotrophic bacteria which utilize sulfate as a terminal electron acceptor and organic
matter as their carbon source. The genus and species of bacteria most commonly associated with
sulfate reduction are named Desulfovibrio and D. desulfuricans. The basic sulfate reduction
reaction is as follows (Lapakko and Eger, 1981; Dvorak and McIntine, 1992; Maree and
Strydom, 1985):
-2 -1 -1 -2 -2
SO4 + 2 C3H4O3 (lactate) = 2 C2H4O2 (acetate) + 2 CO3 + S (1)
The carbonate or bicarbonate produced buffers the solution pH and neutralizes acidity if present.
The short chain compounds needed as substrate and a source of carbon will be provided by the
organic material. In addition to sulfate reduction, the same organisms can through a similar
biochemical process reduce the oxidized forms of selenium (i.e., selenite and selenate) to the
elemental metal (Baldwin, et al, 1985; Levine, 1924). The removal of selenium through the use of
anaerobic bacterial reduction has been investigated by Times Limited and more recently by the
U.S. Bureau of Mines in Salt Lake City (Adams, et al, 1993; Altringer, et al, 1991). The sulfide
and carbonate produced can combine with free and complexed monovalent and divalent cations,
such as cadmium, lead, nickel, mercury, silver, and zinc, to form very insoluble compounds
-2 +2
S + M = MS(s) (2)
-2 +2
CO3 + M = MCO3(s) (3)
With the organic layer within the Biopass System being in an anoxic and chemically reducing
environment, the metal sulfides will remain stable and insoluble. In conjunction with the bacterial
reduction of sulfate, nitrate is converted to nitrogen gas or is taken up as a nutrient through the
microbially mediated process of denitrification according to the basic following reaction (Water
Pollution Control Federation, 1983; Metcalf and Eddy, 1979; U.S. Environmental Protection
Agency, 1975):
- +
NO3 + 1.08CH4O (methanol) + H =
0.065C5H7O2N (biomass) + 0.47N2 + 0.76CO2 + 2.44H2O (4)

The genera of organisms principally responsible for denitrification include Pseudomonas,

Micrococcus, Achromobacter, and Bacillus. Although methanol is the preferred carbon source for
the engineered processes used in municipal wastewater treatment facilities, other organic
compounds found in composted manure, wastewater sludge, brewery wastes, and food processing
wastes can also be utilized by the microorganisms.
The other bacterially mediated reaction of importance is the anaerobic degradation of residual
cyanide. Although the aerobic oxidation of cyanide is well documented and forms the basis of full
scale heap leach decommissioning and mine water treatment facilities, for example at the
Homestake Mine in Lead, South Dakota, the degradation of cyanide under anoxic or anaerobic
conditions is less common (Canby, 1993; Altringer, et al, 1992).
However, anaerobic degradation of free and complexed cyanide does occur in solutions and in
tailings, although at a slower rate, according to one of the following reactions:
HCN + 3H2 = CH4 (methane) + NH3 (5)
HCN + 2H2O = NH4COOH (ammonia formate) (6)
The genera of bacteria responsible for anaerobic degradation of cyanide include Pseudomonas,
and other strictly anaerobic and facultative microorganisms. Cyanide can be used as a sole carbon
source or can be degraded in the presence of a co-metabolite supplied by substrates contained in
the organic material present in the Biopass System.
3.3 Anticipated Process Performance and Limitations
As discussed in the previous section, the primary biochemical processes at work in the Biopass
System include bacterial sulfate reduction, denitrification, and cyanide attenuation, coupled with
chemical precipitation and physical sorption of the metals. All of these processes have been
examined in bench scale, continuous flow pilot plant evaluations, and full scale natural and
manmade wetlands. In the present system, only partial sulfate reduction is necessary to form
sulfide and carbonate, which in turn will precipitate the residual metals as insoluble compounds.
All of the biological processes would be classified and would function as fixed film or attached
growth systems, similar to the trickling filters used in domestic wastewater treatment plants. As a
result, the discussion of the design, performance, and limitations of these systems has been based
upon the principles affecting attached growth biological treatment processes.
A review of the sulfate reducing efficiency of twenty-five constructed wetlands, provided a mean
removal efficiency of 22 percent (Kleinman and Girtis, 1986). In a study conducted by the U.S.
Bureau of Mines, an average of 24 percent sulfate removal efficiency was obtained from two
separate continuous flow systems (Dvorak and McIntine, 1992).

The lower percent reductions in sulfate were related partially to the exhaustion of organic matter
and short-circuiting through the wetland. However, in a system designed especially to maximize
sulfate reduction, removal efficiencies as high as 88 percent have been reported using sludge from
a domestic wastewater treatment plant as the organic carbon source (Maree and Strydom, 1985).
The untreated sulfate levels employed in the various studies ranged from about 1,000-3,000 mg/l.
In the case of most heap leach operations, the sulfate levels in the barren solutions from the three
heap leach pads range from about 2,100-4,300 mg/l.
Assuming only a partial reduction in sulfate levels, sufficient sulfide is produced to precipitate the
residual metals present in the untreated barren solutions. Although the bacterial reduction in
sulfate requires a reaction time of hours, the initial growth and acclimation period requires many
days. In the studies reviewed, the initial startup, growth, and acclimation period ranged from
about 9-35 days to attain maximum sulfate removal.
With respect to biological denitrification, the process is well defined and has been used in
municipal wastewater treatment applications for many years (Adams, et al, 1993; Altringer, et al,
1991; Water Pollution Control Federation, 1983). As with sulfate reduction, denitrification will
proceed at temperatures down to 10 degrees C, although a correction factor must be applied to
increase the capacity of the system to accommodate the slower growth and reaction rate of the
organisms.
In order to achieve nitrate removals of 90 percent or greater, a mass loading rate for
denitrification in the range of about 400 lbs N/day/cu ft of reactor and a hydraulic loading rate in
the range of 2.0 gpd/sq ft would be employed at the lowest temperatures in an attached growth
biological system. In the case of solids retention times (SRT) or startup periods for establishment
and acclimation of bacterial growth, the theoretical time required ranges from about 3-9 days,
with the actual SRT's ranging from 6-18 days using a safety factor of two. Since the Biopass
System would involve a less rigorously designed and operated passive process, with less control
and less efficient organic food sources, the SRT is increased by 25-50 percent above the upper
value of 18 days. Nitrate removal efficiencies of about 75 percent or greater are anticipated
producing treated levels below the MCL of 10 mg/l as N.
With respect to wad cyanide removal, the initial levels remaining in the pore solution are much
lower following draindown due to natural attenuation. Starting with an initial wad cyanide
concentration during leaching of >100 mg/l, the resultant solution wad cyanide level following
three months of natural attenuation assuming a pH of about 9.0, a conservative decay coefficient,
and a first order decay rate, would usually be well under 50 mg/l in temperate climates. The
anaerobic degradation of free and complexed cyanides up to 1,000 mg/l has been reported,
although cyanide levels of <100 mg/l have been more typically treated (Canby, 1993; Altringer, et
al, 1992). At initial wad cyanide levels of <50 mg/l, treated levels of <0.50 mg/l are achievable,
with treated levels of <0.20 mg/l being reported.

An initial growth and acclimation period of 10-15 days is usually needed, along with a
degradation period ranging from 10-15 days. For design purposes, a conservative total retention
time for growth, acclimation, and degradation on the order of 20-30 days is recommended for the
configuration of the Biopass System. The cyanide would be utilized for energy production, as
well as a source of carbon.
In the case of the removal of monovalent and divalent metal cations through sorption and sulfide
precipitation, an efficiency of 95 percent is reasonable based upon data gathered from bench,
pilot, and full scale sulfate reduction systems. Removal efficiencies of up to 99 percent have been
reported. A conservative removal efficiency of 50 percent is anticipated for selenium and sulfate,
although higher removal efficiencies up to 75 percent have been reported. With an average air
temperature in the fifties and an in-situ biochemical system, bacterial degradation and reduction
should proceed without climate inhibition. The levels of sulfate, nitrate, metals, and cyanide
present in the drainage would be within ranges that have been treated in bench, pilot, and full
scale anaerobic systems.
4.0 LABORATORY EVALUATION OF THE BIOPASS SYSTEM
In order to evaluate the performance of the Biopass System on a more quantitative basis, a long-
term continuous flow laboratory study was conducted. The study involved a series of six columns,
each filled with a different organic material and fed barren solution taken from a mining operation
in Nevada. The analysis of the various barren solutions contained straw only and served as a
control. The second, third, and fourth columns contained a composted cow manure. The
difference between these columns was based upon the hydraulic retention times used and whether
or not the organic material had been microbially seeded prior to its placement in the column. The
fifth and sixth columns contained much more expensive mushroom compost or peat mixed with
manure. The organic material placed in columns 2 through 6 was mixed with 5% straw to provide
additional surface for bacterial attachment and to minimize compaction.
The clear Plexiglas columns were six inches in diameter and eight feet in height. A positive
displacement pump was used to feed the columns at such a rate to create a fifteen to thirty day
empty bed retention period. The seeding of columns 1, 3, 4, 5, and 6 was accomplished by
spraying the organic matter prior to its placement within the column with a mixture of solutions
collected from various process ponds and soils from around the mine site. The six columns were
sealed to exclude air, with the effluent from each column reporting to a closed container adjacent
to the top of each column to aid in the removal of off-gases, such as hydrogen sulfide.
The presence and/or absence of sulfate reducing, general anaerobic, and denitrification bacterial
populations were monitored on a semi-quantitative basis with the use of Hach Chemical microbial
growth kits. The results of the analyses indicated that large populations of all three of these
bacterial types were present in the effluent from the columns. Once the columns filled with barren
solutions and effluent began appearing, solution samples were collected for analysis. The results
of those analyses are presented in Table 1.

As shown in Table 1, the straw column was the least effective in removal of the constituents of
interest. The remainder of the columns provided very high levels of treatment of cyanide, most
metals, and nitrate, with removal efficiencies exceeding 90% in many instances. The effluent
concentrations of cyanide, copper, mercury, selenium and nitrate were reduced to below drinking
water standards. The removal of arsenic varied from about 45-90%, while the removal of sulfate
reached about 80% in column 2. The results indicated that the more expensive mushroom
compost or peat mixtures did not provide a higher level of treatment. In addition, a retention time
of between 15-30 days appeared to be optimal. The pH remained steady and near neutral
throughout the study with increasing alkalinity’s being noted in the effluents from the columns. A
large negative Eh was noted in all of the columns, except the first one which contained straw only.
The laboratory study is more clearly defining the optimal retention time needed and also examines
the performance of the Biopass System under intermittent flow conditions, as would be seen in
the field. In addition, the organic material will be enhanced chemically in order to promote further
removal of metals, particularly arsenic.

Table 1
Column Effluent Test Results – Initial Sample
Column I.D.'s
#1 #2 #3 #4 #5 #6
Parameter Units Head (95010-5) (95010-6) (95010-4) (95010-8) (95010-9) (95010-10)
Eh mv 0 196 -360 -349 -330 -229 -354
pH pH units 9.17 4.77 8.09 7.93 7.94 8.31 8.53
Alkalinity, Total mg/L (CaCO3 143 288 8990 8940 7060 7970 10250
Sulfate mg/L 1850 2400 400 2000 700 10400 4500
Wad Cyanide mg/L 14 2.8 <0.2 <0.1 <0.2 <0.2 <0.2
Nitrate mg/L as N 55.6 45.8 0.8 0.5 0.8 0.8 0.8
Nitrite mg/L as N 12.2 <0.1 0.4 0.6 0.2 0.4 4.2
Arsenic mg/L 0.45 0.3 0.2 0.2 0.1 0.05 <0.1
Copper mg/L 10.3 4.7 <0.5 <0.5 <0.5 <0.5 <0.5
Mercury mg/L 0.164 0.007 <0.0002 <0.002 <0.0002 <0.0002 <0.0002
Selenium mg/L 0.41 0.24 0.03 0.02 <0.02 0.01 <0.001
Silver mg/L 0.31 <0.3 <0.3 <0.3 <0.02 <0.3 <0.3
Notes:
Column #1: 100% straw (control), seeded, target retention time = 30 days
Column #2: Premium 3 (composted cow manure/straw [5% by weight]), unseeded, target retention time = 30 days
Column #3: Premium 3 (composted cow manure/straw [5% by weight]), seeded, target retention time = 15 days
Column #4: Premium 3 (composted cow manure/straw [5% by weight]), seeded, target retention time = 30 days
Column #5: Mushroom Compost/straw (5% by weight), seeded, target retention time = 30 days
Column #6: Two-way (50% composted cow manure, 50% peat)/straw (5% by weight), seeded,
target retention time = 30 days

5.0 PROCESS DESIGN AND CONFIGURATION
Since the Biopass System is contained, the retention period for solution is on the order of many
weeks, providing maximum contact time for bacterial treatment and chemical precipitation
depending on site climate and infiltration. Therefore, there is no need to incorporate the volume of
organic material into the Biopass System to provide greater than a 30-day hydraulic retention
period, but there remains a need to incorporate sufficient organic material to complete the
bacterial treatment without periodically replenishing the carbon source. The organic material must
be carefully selected on the basis of both efficiency and economics. From an efficiency standpoint,
the organic material must not only provide the appropriate growth substrates for the individual
bacteria needed, but also a suitable matrix for initial sorption of cyanide and metals present in the
incoming drainage.
Consideration of economics must be included in an assessment, due to the relatively large volume
of organic material needed and the fact that specialty composted organic material can cost several
tens of dollars per ton. In general, the Biopass System costs only a fraction of that needed for
chemical detoxification. A sufficient quantity and volume of material must be incorporated into
the Biopass System to provide a long term supply of nutrients and substrate for treatment. The
organic material for various in-situ passive treatment systems can be obtained from a variety of
sources including peat, specialty compost, wood chips, straw or hay, food processing wastes, and
digested municipal sludges or animal waste. The organic material can be further bioaugmented
with specially adapted microbial seeds obtained in bulk form from specific suppliers.
In the current situation, the most suitable organic material would include a combination of
composted or animal waste mixed with 5-10% by weight straw or hay. The composted manure
provides the organic substrate, while the hay or straw provides interstitial surfaces onto which
bacterial films can develop and grow.
The volume of organic matter required is dependent upon the total mass of sulfate and nitrate that
could be degraded over time. The anticipated total mass of these two constituents would be
derived by multiplying their concentrations in the drainage by the estimated volume of drainage
exiting the pads. By assuming a required mass of organic matter per unit mass of sulfate or nitrate
reduced, a total volume and weight of organic matter can be calculated for incorporation into the
Biopass System design. Calculation of the total mass of organic matter needed on the basis of the
total mass of sulfate alone in the drainage is conservative, since the sulfate concentration is
typically an order of magnitude or greater than that of nitrate and only a portion of the sulfate will
be bacterially reduced over time.
The mass of organic matter required for sulfate reduction would be compared with the volume
needed to provide an appropriate treatment or retention period in days within the Biopass System.
The limiting factor of the two (i.e., mass versus retention period) would be used in the final
process design.

The general construction of the Biopass System would involve layering the organic matter in the
bottom of the lined solution pond, upon which a set of lateral, perforated plastic drain pipe would
be laid to equally distribute any drainage from the pads. The individual laterals would be joined at
the opposite end of the Biopass System into a single header with a riser extending above the inlet
pipe. The riser would make a 90 degree bend and pass through the liner out into the ground to
allow discharge of excess and treated solution, in the event sufficient drainage entered the Biopass
System to flood its bottom portion and the organic matter. Flooding of the organic matter would
not be of concern, since the bacterial processes are anaerobic. The inlet line into the Biopass
System would contain a one-way device to allow solution to enter, but would then close to
exclude oxygen.
Above the organic matter and drain pipes would be an additional compacted layer of fill material
and a final vegetated soil layer. The purpose of the two upper layers would be to maximize runoff,
while promoting removal of excess water through evapotranspiration. The volume of allowable
drainage that can enter the Biopass System before an excess and accumulation of water begins, is
being determined through additional hydrological modeling. A generalized schematic of the
Biopass System is presented on Figure 1.
In the event excessive draindown volumes and shortened retention periods are anticipated on an
infrequent basis, a second lined barren or pregnant pond could be used to receive partially treated
solution from the Biopass System through another distribution system. The second lined pond
would be filled with soil and vegetated with plant species specifically chosen for the particular
climate, and possessing the ability to absorb and evaporate excess solution and to selectively
concentrate residual metals.
6.0 CONCLUSIONS
The Biopass System provides an effective approach to treatment of long-term draindown from
heap leach pads and greatly reduces the need for and expense of chemical treatment or
detoxification of rinse solutions.
The continuous flow laboratory studies have demonstrated that the removal efficiencies for
cyanide, sulfate, nitrate and metals were equal to or greater than anticipated form the literature.
Currently, full scale Biopass Systems are being designed for installation at two mining operations
in Nevada, which are undergoing closure. The Nevada Department of Environmental Protection
has approved the basic design of the Biopass System for use as a primary heap leach closure
option.
In addition to closure of a heap leach operation, the Biopass System also finds utility in the long-
term treatment of leachate or seepage from tailings impoundments.

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Affected by low pH, Metal Contaminated Seepages (Acid Mine Drainage),” prepared by P. Lane
and Associates limited, Halifax, Nova Scotia, prepared for Environment Canada, Mine
Environmental Neutral Drainage (MEND) Program, Project No. E-278, Hall, Quebec, May,
1990.
Morrey, D., “The Role of Biotechnology in the Rehabilitation of Toxic Mining Wastes”, Golder
Associates Inc., Lakewood, Colorado, 1993.
Morrey, D., “The Application of Toxicity and Stress Tolerant Plant Species to the Reclamation of
Mining Wastes,” Golder Associates Inc., Lakewood, Colorado, 1994.
Mudder, T., and Goldstone, A., “The Recovery of Cyanide from Slurries”, Proceedings
International Gold Expo, Reno, Nevada, September 7-9, 1989.
Sencindiver, J., and Bhumbla, D., “Effects of Cattails on Metal Removal from Mine Drainage”,
Mine Drainage and Surface Mine Reclamation, Volume I, U.S. Bureau of Mines, IC9183,
Pittsburgh, Pennsylvania, pp. 359-369, 1988.
Smith, A., and Mudder, T., “The Chemistry and Treatment of Cyanidation Wastes”, Mining
Swanson, D.A., O’Kane, M., Wilson, G. W., and Barbour, S.L., “Monitoring and Prediction of
Atmospheric Fluxes through a Compacted Till Cover over Mine Waste Rock,” International Land
Reclamation and Mine Drainage Conference and the Third International Conference on the
Abatement of Acidic Drainage, Pittsburgh, Pennsylvania, April 24-29, 1994.
U.S. Environmental Protection Agency, “The Hydrologic Evaluation of Landfill Performance

(HELP) Model,” Vols. 1 and 2, User’s Guide for Ver. 1, EPA/530-SW-84-009 and EPA/520-
SW-84-010, Municipal Environmental Research Laboratory, Cincinnati, Ohio, 1984.
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Technology Transfer, October, 1975.

Water Pollution Control Federation, “Nutrient Control”, Manual of Practice, FD-7, 1983.
Wilson, G. W., Machibroda, R.T., Barbour, S.L., and Woyshner, M.R., “Modelling of Soil
Evaporation from Waste Disposal Sites,” In, Proceedings of the Joint CSCE-ASCE National
Conference on Environmental Engineering, Montreal, P.Q., July 12-14, 1993. pp. 281-288.

THE BIOPASS SYSTEM
PHASE I: LABORATORY EVALUATION
Prepared By:
Terry Mudder, Ph.D.

Scott Miller
Luke Russell
Alan Cox
Dave McWharter
Originally published in Mining Engineering, The Society of Mining, Metallurgy, Exploration, Inc.
(SME), Volume 47, Number 11, p. 1007, November 1995
Reprinted with permission of The Society of Mining, Metallurgy, and Exploration, Inc. (SME),
8307 Shaffer Parkway, Littleton, Colorado, 80217-5002
The Biopass System
Phase I: Laboratory Evaluation
1.0 INTRODUCTION
This paper presents a laboratory evaluation of the effectiveness of anaerobic biochemical

treatment of cyanide heap leach pad solutions. Long-term anaerobic biochemical treatment for
draindown of residual solutions offers a cost effective alternative to the traditional approach to
heap leach pad closure; which, generally includes rinsing of spent ore with fresh or treated water
until compliance with solids and solution standards are achieved.
The process of heap leach pad decommissioning and closure typically involves both short-term
and long-term goals. The short-term goal is to eliminate process solutions, stabilize the leach pad,
and control erosion. The long-term goal is to restore the site to a condition suitable for the pre-
mining operational uses of further mineral exploration and mining, livestock grazing and wildlife
habitat by restoring vegetation on the disturbed surfaces of site and ensuring that water coming in
contact with the site does not degrade the surface or groundwater. In addition, closure objectives
include development and implementation of a management plan which eliminates maintenance
requirements and the potential for future environmental remedial action.
The traditional approach to heap leach pad closure is to rinse the heaps with several pore volumes
of fresh and/or recycled treated water. The effluent from an initial rinse is often treated and
recirculated until the solutions passed through the heap meet the appropriate numeric and
narrative water quality standards. Column rinsing tests are often completed during project
planning to determine the number of pore volumes of fresh water required to rinse the heap to
meet the closure criteria. A traditional closure plan generally includes provisions to sample the
rinse effluent and rinsed solids (i.e. the Meteoric Water Mobility Procedure or USEPA 1312) to
verify that the chemical requirements are being met. This closure approach, although acceptable in
some instances for small leach pads, presents a number of technical difficulties for large leach pads
including:
• Rinsing the heaps with multiple pore volumes requires years.

• Large quantities of solution requiring treatment or land application are generated.
• Due to preferential pathways within the pad, complete rinsing and detoxification is unlikely
with respect to metals.
Recent evidence from actual heap leach operations indicates that numerical cyanide and pH
standards can routinely be met by rinsing, however, effluent standards for pH, metals, and other
inorganics are often not achievable, regardless of the extent of rinsing.
An alternate approach is needed to allow chemical and physical stabilization of a heap leach pad
that will meet the closure objectives with respect to control of long-term draindown or seepage
flows and protection of surface and groundwaters. The alternative approach is to stabalize the
leach pad employing a vegetated soil cover, and leave intact the liners to contain fugure seepages,
and to collect and treat any storm related seepage using a passive in situ biological treatment
system. The passive treatment option can eliminate the need for active or mechanical treatment
to achieve the inactive mine status that exists at closure.

The Biopass System
The approach for dealing with residual seepage or draindown, if it occurs, from the spent leach
pads is to convert one of the existing solution ponds at the base of each pad into an in situ
anaerobic biochemical system, capable of passively receiving and treating this drainage on an as-
needed and long-term basis. The basic system consists of an emptied and lined solution pond in
which a layer of organic matter is placed upon a drain layer comprised of sand and perforated
pipe. The organic matter, consisting of composted manure, or other similar organic material, and
the distribution system are then covered with fill and a reclaimed soil and vegetative cover to
enclose the entire system to minimize infiltration, while promoting evapotranspiration and the
necessary anoxic conditions. The system discharges to a leach field.
The passive in-situ anaerobic biochemical treatment system is referred to as the "Biopass System."
The Biopass System finds its origins in the evaluation of natural and manmade wetlands for
treatment of low pH and metals containing drainage from abandoned mine adits, waste rock
disposal areas, and historical tailings.
During project planning, column rinse tests are routinely completed to evaluate closure
requirements for cyanide heap leach pads. Fresh water rinse generally requires three to five pore
volumes or more to achieve the water quality standards. For large heap leach pads, rinsing could
require hundreds of millions of gallons of fresh or treated water. Additionally, during rinsing
constituents such as mercury, arsenic, and selenium are frequently mobilized above compliance
standards. The large quantities of fresh water required for rinsing and removal of other
constituents unrelated to the cyanide complexes make this approach problematic because of the
following:
• Difficulty in detoxification, evaporation, or discharge of large quantities of residual rinse

solution.
• Generation and disposal of chemical sludge.
• Numerical standards for certain metals or inorganics are not attainable on either a short- or
long-term basis.
• The time needed to rinse the ore and evaporate the solutions from large heap leach pads may
take years.
Each heap leach pad closure should be designed to account for site-specific climatic and
environmental factors. The closure plan should be consistent with the long-term goal of restoring
the site to a condition suitable for the pre-mining land uses of mineral exploration, mining,
livestock grazing and wildlife habitat by restoring useable vegetation similar to that which existed
on the site prior to disturbance.
In areas like Nevada there is little potential for infiltration of precipitation through the rinsed ore
to discharge in significant quantities due to the following factors:
• Evaporation exceeds precipitation for all months of the year.

• Uptake of precipitation moisture by the ore in post-closure conditions is significant.
• The relatively low permeability of the soil cover material, in combination with evapo-
transpiration will minimize infiltration.

The Biopass System
The proposed procedure for stabilization of a leach pad is to recirculate leach solution, while
enhancing its evaporation, and discontinuing cyanide addition until the process is no longer
economic. Once gold extraction is complete the leach pad is be allowed to draindown, and
subsequently physically stabilized by recontouring, compacting, topsoiling and revegetation.
Excess process solution is evaporated, land applied, or sent to another heap leach facility for
additional project use. One of the process ponds at each leach pad is converted to a Biopass
System to treat residual and stormwater seepage from the heaps. The quantity of drainage or
seepage expected, which is usually minimal, is determined using a finite differentce hydrological
model developed specifically for the unsaturated flow conditions that exist in a spent heap leach
pad. The use of the Biopass System eliminates both the technical and regulatory concerns
regarding long-term treatment and discharge of solutions from a decommissioned operation, and
allows for a shorter post-closure monitoring period.
The introduction of the Biopass System is a new and novel concept for heap leach closure, and to
a certain extent unproven. As a result, a long-term laboratory study was undertaken to evaluate
the Biopass System for use at closure. The laboratory study was conducted by Chemac
Environmental Services under the direction of Times Limited. Analytical services were provided
by ACZ Laboratories, located in Steamboat Springs, Colorado. The purpose of the laboratory
study was to evaluate the effectiveness of the Biopass System to treat leach pad draindown using
various organic materials exposed to varying operational conditions and constituent
concentrations.
The constituents of concern at the operations under consideration include wad cyanide, various
metals, nitrate, sulfate, and pH. The metals of interest included arsenic, copper, mercury,
molybdenum, selenium, silver, and zinc. These metals were chosen on the basis of their initial
elevated levels noted in the barren solutions. Four different types of organic matter were
examined, along with retention periods ranging from about 15-40 days. In addition, the use of
microbial seeds was examined, along with the impact of intermittent dosing of the Biopass
System. The remainder of this paper provides background information on the Biopass System
and the details and results of the laboratory study, along with conclusions and design
recommendations.
2.0 THE BIOPASS TREATMENT SYSTEM
2.1 Introduction
The primary goal with respect to decommissioning and closure of a spent heap leach pad involves
the prevention of long-term deterioration of local surface and groundwater. According to
environmental regulations, the operation and site must be closed in a manner that will not degrade
the waters of the State. There are various methods for demonstrating that degradation of surface
and groundwater will not occur following closure.

The Biopass System
The traditional approach has involved drilling and sampling the solids within the spent leach pad,
and subjecting those solids to leach tests either Meteoric Water Mobility Procedure (MWMP) or
Synthetic Precipitation Leaching Procedure (EPA Method 1312). The purpose of the extraction
test is to simulate the pad effluent that could originate from contact of infiltration with the spent
ore. A successful passage of the leach tests occurs if the resultant extraction solution does not
contain constituent levels greater than ten-fold their respective Maximum Contaminant Level
(MCL). Unfortunately, compliance with the MWMP does not ensure that environmental impacts
will not occur. More recently, the assessment and prediction of potential water quality impacts
following closure of spent heap leach pads has included a Fate Transport Analysis (FTA), which
involves predictive mathematical modeling of the hydrological and chemical aspects of solutions
and seepage.
Closure of spent leach pads includes conversion of one of the existing solution ponds at the base
of each pad into an in-situ anaerobic biochemical system, capable of passively receiving and
treating this drainage on an as- needed and long-term basis. The basic Biopass System (Figure 1)
consists of an emptied solution pond in which first a layer of organic matter is placed upon a set
of evenly spaced perforated drain pipes, which have been laid in such a manner to receive and
distribute any pad drainage. The organic layer and drain pipe is then covered with an effluent
solution collection system and a reclaimed soil and vegetative cover to enclose the entire system
to minimize infiltration, while promoting evapotranspiration and the necessary anaerobic
conditions. Figures 2 and 3 illustrate a cross-section of the Biopass System.
In the course of evaluating the treatment performance of natural and manmade (i.e., engineered or
constructed) wetlands with respect to pH adjustment and metals removal, researchers found that
the vegetation communities removed only a few percent of the metals, generally well below ten
percent (Sencindiver and Bhumbla, 1989; Environment Canada, 1990).
The neutralization of acidity and the precipitation of metals were occurring primarily in the
anaerobic sediments beneath the wetland, in which the bacterial reduction of sulfate yielded
alkalinity and free sulfur ions as biochemical by-products (Kleinman, et al, 1986; Kleinman and
Girtis, 1986). The sulfur ions precipitate the metals as their very insoluble complexes, yielding
very low residual dissolved concentrations and very high removal efficiencies up to 99 percent.
Although wetlands have proved successful in treating ARD, several disadvantages have been
noted, which have limited their application. First, their effectiveness was limited in cold climates in
which the ground was frozen for extended periods of the year. Second, the wetlands did not
respond well to rapidly changing and elevated flows, which often occur in the spring in
mountainous regions, just as the plant and bacterial communities within the wetland are re-
establishing themselves. Third, the source of organic matter often became exhausted due to
ongoing bacterial activity, and required replacement from time to time. Fourth, the organic matter
or submerged anaerobic zone lost its metals removal capacity with time as its available sorptive
sites were occupied. Fifth, the metal removal efficiencies decreased with time due to short-
circuiting, which resulted in part from the continued precipitation of iron and aluminum
hydroxides within the submerged anaerobic zone.

The Biopass System
With the Biopass System many of the disadvantages of wetlands can be circumvented, while
taking advantage of the virtues of the bacterial and chemical processes that occur in an anoxic
environment. The performance of the Biopass System is not readily affected by temperature as it
is designed as an in-situ system in an area of moderate climate. Second, the flows that potentially
can enter the system are small and relatively constant. Third, sufficient organic matter or compost
can be placed in the system to accommodate the anticipated long-term flux of constituents in the
drainage, if it occurs. The fact that the organic layer will be placed well below a compacted fill
and vegetated surface promotes the necessary anoxic conditions. Fourth, since the heap leach
drainage is not acidic and does not contain elevated iron or aluminum levels, the problems
associated with precipitation of a large mass of metal hydroxides within the organic layer is
avoided.
The surface vegetation could be selected on the basis of specific metal uptake, as has been done
successfully in the rehabilitation of mine wastes (Morrey, 1993 and 1994). However, in the
current situation, the approach is to bacterially degrade the residual cyanide, while partially
reducing the residual nitrate and sulfate levels, and permanently fixing the precipitated the metals
within the subsurface organic layer. The fill and vegetative cover above the organic layer
promotes runoff and uptake of solution through capillary action. From a design perspective, the
primary concerns are associated with providing sufficient nutrients, moisture, and retention time
for stimulation of bacterial growth, acclimation, and degradation. During construction of the
system, the organic matter is wetted to promote anaerobic conditions, to supply the initial
moisture needed, and to encourage bacterial growth. The next section provides a discussion of
the basic biochemical processes that occur within the Biopass System.
2.2 Biological and Chemical Processes
The most important feature of the Biopass System is the organic layer into which the pad drainage
is directed, if it occurs. This layer contains the necessary nutrients and organic substrates to
support the growth of a diverse population of microorganisms, principally anaerobic and
facultative bacteria. Since the layer is placed many feet below the vegetated surface, anoxic or
anaerobic conditions are established along with a chemically reducing environment, as the organic
matter is degraded and the residual oxygen is depleted. The anaerobic and chemically reducing
environments promote the growth of the bacterial population capable of uptake, treatment,
sorption, and/or precipitation of cyanide, nitrate, sulfate, and metals, the primary constituents of
concern.
The initial chemical process that occurs as the drainage enters the Biopass System involves
physical sorption of a portion of the metals and complexed metal cyanides within the organic
layer, for example arsenic, copper cyanide, and mercury. The sorption of metals on both
inactivated and living biomass, even from solutions containing elevated total dissolved solids
levels, is well documented and forms the basis of several specialized treatment systems, such as
AlgaSORB and BIO-FIX, a treatment process being evaluated by the U.S. Bureau of Mines and
Department of Interior (Darnall and Gabel, 1989; Ferguson and Jeffers, 1991).

The Biopass System

The Biopass System
Figure 2: Biopass System Cross Section

The Biopass System
Figure 3: Biopass System Cell Detail

The Biopass System
The sulfate entering the organic layer, which contains the necessary organic substrate, nutrients,
and bacterial seeds, is slowly converted to sulfide by one of several strictly anaerobic and
chemoheterotrophic bacteria which utilize sulfate as a terminal electron acceptor and organic
matter as their carbon source. The genus and species of bacteria most commonly associated with
sulfate reduction are named Desulfovibrio and D. desulfuricans. The basic sulfate reduction
reaction is as follows (Lapakko and Eger, 1981; Dvorak and McIntine, 1992; Maree and
Strydom, 1985):
-2 -1
SO4 + 2 C3H4O3 (lactate) = (1)
-1 -2 -2
2 C2H4O2 (acetate) + 2 CO3 + S
The carbonate or bicarbonate produced buffers the solution pH and neutralizes acidity if present.
The short chain compounds needed as substrate and a source of carbon will be provided by the
organic material. In addition to sulfate reduction, the same organisms can through a similar
biochemical process reduce the oxidized forms of selenium (i.e., selenite and selenate) to the
elemental metal (Baldwin, et al, 1985; Levine, 1924). The removal of selenium through the use of
anaerobic bacterial reduction has been investigated by Times Limited and more recently by the
U.S. Bureau of Mines in Salt Lake City (Adams, et al, 1993; Altringer, et al, 1991). The sulfide
and carbonate produced can combine with free and complexed monovalent and divalent cations,
such as cadmium, lead, nickel, mercury, silver, and zinc, to form very insoluble compounds
-2 +2
S + M = MS(s) (2)
-2 +2
CO3 + M = MCO3(s) (3)
With the organic layer within the Biopass System being in an anoxic and chemically reducing
environment, the metal sulfides will remain stable and insoluble. In conjunction with the bacterial
reduction of sulfate, nitrate is converted to nitrogen gas or is taken up as a nutrient through the
microbially mediated process of denitrification according to the basic following reaction (Water
Pollution Control Federation, 1983; Metcalf and Eddy, 1979; U.S. Environmental Protection
Agency, 1975):
-1 +
NO3 + 1.08 CH4O (methanol) + H =
0.065 C5H7O2N (biomass) + 0.47 N2 + 0.76 CO2 + 2.44 H2O (4)
The genera of organisms principally responsible for denitrification include Pseudomonas,

Micrococcus, Achromobacter, and Bacillus. Although methanol is the preferred carbon source for
the engineered processes used in municipal wastewater treatment facilities, other organic
compounds found in composted manure, wastewater sludge, brewery wastes, and food processing
wastes can also be utilized by the microorganisms.
The other bacterially mediated reaction of importance is the anaerobic degradation of residual
cyanide. Although the aerobic oxidation of cyanide is well documented and forms the basis of full
scale heap leach decommissioning and mine water treatment facilities, for example at the
Homestake Mine in Lead, South Dakota, the degradation of cyanide under anoxic or anaerobic

The Biopass System
conditions is less common (Canby, 1993; Altringer, et al, 1992).
However, anaerobic degradation of free and complexed cyanide does occur in solutions and in
tailings, although at a slower rate, according to one of the following reactions:
HCN + 3H2 = CH4 (methane) + NH3 (5)
HCN + 2H2O = NH4COOH (ammonia formate) (6)
The genera of bacteria responsible for anaerobic degradation of cyanide include Pseudomonas,
and other strictly anaerobic and facultative microorganisms. Cyanide can be used as a sole carbon
source or can be degraded in the presence of a co-metabolite supplied by substrates contained in
the organic material present in the Biopass System.
2.3 Anticipated Process Performance and Limitations
As discussed in the previous section, the primary biochemical processes at work in the Biopass
System include bacterial sulfate reduction, denitrification, and cyanide attenuation, coupled with
chemical precipitation and physical sorption of the metals. All of these processes have been
examined in bench scale, continuous flow pilot plant evaluations, and full scale natural and
manmade wetlands. In the present system, only partial sulfate reduction is necessary to form
sulfide and carbonate, which in turn will precipitate the residual metals as insoluble compounds.
All of the biological processes would be classified and would function as fixed film or attached
growth systems, similar to the trickling filters used in domestic wastewater treatment plants. As a
result, the discussion of the design, performance, and limitations of these systems has been based
upon the principles affecting attached growth biological treatment processes.
A review of the sulfate reducing efficiency of twenty-five constructed wetlands, provided a mean
removal efficiency of 22 percent (Kleinman and Girtis, 1986). In a study conducted by the U.S.
Bureau of Mines, an average of 24 percent sulfate removal efficiency was obtained from two
separate continuous flow systems (Dvorak and McIntine, 1992). The lower percent reductions in
sulfate were related partially to the exhaustion of organic matter and short-circuiting through the
wetland. However, in a system designed especially to maximize sulfate reduction, removal
efficiencies as high as 88 percent have been reported using sludge from a domestic wastewater
treatment plant as the organic carbon source (Maree and Strydom, 1985). The untreated sulfate
levels employed in the various studies ranged from about 1,000-3,000 mg/l. In the case of most
heap leach operations, the sulfate levels in the barren solutions from the three heap leach pads
range from about 2,100-4,300 mg/l.
Assuming only a partial reduction in sulfate levels, sufficient sulfide is produced to precipitate the
residual metals present in the untreated barren solutions. Although the bacterial reduction in
sulfate requires a reaction time of hours, the initial growth and acclimation period requires many
days. In the studies reviewed, the initial startup, growth, and acclimation period ranged from
about 9-35 days to attain maximum sulfate removal.

The Biopass System
With respect to biological denitrification, the process is well defined and has been used in
municipal wastewater treatment applications for many years (Adams, et al, 1993; Altringer, et al,
1991; Water Pollution Control Federation, 1983). As with sulfate reduction, denitrification will
proceed at temperatures down to 10 degrees C, although a correction factor must be applied to
increase the capacity of the system to accommodate the slower growth and reaction rate of the
organisms. In order to achieve nitrate removals of 90 percent or greater, a mass loading rate for
denitrification in the range of about 400 lbs N/day/cu ft of reactor and a hydraulic loading rate in
the range of 2.0 gpd/sq ft would be employed at the lowest temperatures in an attached growth
biological system.
In the case of solids retention times (SRT) or startup periods for establishment and acclimation of
bacterial growth, the theoretical time required ranges from about 3-9 days, with the actual SRT's
ranging from 6-18 days using a safety factor of two. Nitrate removal efficiencies of about 75
percent or greater are anticipated producing treated levels below the MCL of 10 mg/l as N.
With respect to wad cyanide removal, the initial levels remaining in the pore solution are much
lower following draindown due to natural attenuation. Starting with an initial wad cyanide
concentration during leaching of >100 mg/l, the resultant solution wad cyanide level following
three months of natural attenuation assuming a pH of about 9.0, a conservative decay coefficient,
and a first order decay rate, would usually be well under 50 mg/l in temperate climates.
The anaerobic degradation of free and complexed cyanides up to 1,000 mg/l has been reported,
although cyanide levels of <100 mg/l have been more typically treated (Canby, 1993; Altringer, et
al, 1992). At initial wad cyanide levels of <50 mg/l, treated levels of <0.50 mg/l are achievable,
with treated levels of <0.20 mg/l being reported.
An initial growth and acclimation period of 10-15 days is usually needed, along with a
degradation period ranging from 10-15 days. The cyanide would be utilized for energy
production, as well as a source of carbon.
In the case of the removal of monovalent and divalent metal cations through sorption and sulfide
precipitation, an efficiency of 95 percent is reasonable based upon data gathered from bench,
pilot, and full scale sulfate reduction systems. Removal efficiencies of up to 99 percent have been
reported. A conservative removal efficiency of 50 percent is anticipated for selenium and sulfate,
although higher removal efficiencies up to 75 percent have been reported.
The levels of sulfate, nitrate, metals, and cyanide present in the drainage would be within ranges
that have been treated in bench, pilot, and full scale anaerobic systems, which involved the various
degradation reactions and bacteria in separate, but not necessarily combined systems. As a result,
it was necessary to verify the effectiveness and applicability of the Biopass System with respect to
its application for treating heap leach solutions. The next section provides a detailed discussion of
the materials and methods used in the laboratory evaluation of the system.

The Biopass System
3.0 METHODS AND MATERIALS
3.1 Introduction
The laboratory evaluation of the Biopass System involved continuous flow operation of six different
anaerobic columns, which differed either in the organic matter used, the retention period, or the
presence of an initial microbial seed. The purpose of the evaluation was to determine which organic
material was best suited for the Biopass System, appropriate retention and startup periods, and the
effectiveness of treatment under continuous and intermittent flow conditions. The results of the study
can then be used in the final design of the full scale Biopass Systems.
The length of the columns were chosen to reflect full scale depths of organic material. The different
organic materials evaluated were chosen on the basis of other laboratory and field demonstrations of
the in-situ anaerobic systems, similar to that of the Biopass System. The retention times and microbial
seeds were chosen on the basis of experience and the findings of the literature review.
3.2 Column Design and Construction
A total of six test columns were constructed using six inch (6") diameter clear schedule 40 PVC tubing
fitted with slip-on end caps. Each test column was eight feet (8’) long. The test columns were
designed to allow barren solution to flow upflow from bottom to top to maintain anaerobic conditions.
Solution entering each test column was distributed across the cross sectional area of the column
utilizing a four inch (4") thick lens of coarse (10-20 mesh) silica sand. A second four inch (4") thick
lens of silica sand was also located on the top of each column minimizing the migration of fines out of
the column, while providing a highly permeable exit region for solution. Each column was equipped
with two side sampling ports located two feet eight inches (2'8") and five feet four inches (5'4") from
the bottom of the column allowing for collection of liquid samples at points equivalent to 1/3 and 2/3
of the total column length or retention period. Each sampling port was comprised of a stainless steel
on/off plug valve and stainless steel side wall bore-through fitting connected via one-quarter inch (1/4")
nylon tubing that extended into the central interior portion of the test column.
Effluent collection cells were constructed for each test column using six inch (6") diameter clear
TM
Lexan tubing fitted with acrylic end plates. Each collection cell was approximately ten inches (10")
in height and had a collection capacity of about four liters. The cells were designed to enable the
collection of effluent from the test columns under anoxic conditions.
Each cell was equipped with an inlet to receive test column effluent and an outlet, comprised with an
on/off plug valve and one-quarter inch (1/4") nylon tubing extending to the bottom of the cell, to allow
periodic draining of the collection cell contents. During testing each cell was over pressured and
continuously purged with nitrogen to maintain an oxygen free environment within each test column
apparatus. A sturdy wooden frame was constructed to hold the test columns, solution delivery pumps,
and effluent collections cells throughout the duration of the test program. Photographs of the test
columns and effluent collection cells are presented in Figure 4.

The Biopass System
Figure 4: Photographs of the Laboratory Apparatus

The Biopass System
3.3 Test Solutions
A total of four different heap leach pad solutions were received from a Nevada project site. The
solutions were chosen on the basis of providing wad cyanide levels greater than 10 mg/l and residual
concentrations of metals, particularly arsenic, mercury, and selenium. The additional metals monitored
during the study included copper, molybdenum, silver, and zinc. The remainder of the metals were
generally at or below detectable concentrations.
3.4 Microbial Seed Material
It was decided to seed the organic material used in specific columns in order to determine if
enhancement of the initial microbial population would speed the process and effectiveness of treatment.
As is typical in microbial seeding, solution and solid samples were taken from various locations at he
mining operations where contact of solid surfaces or soils with solutions had occurred over time and
potential adapted microbial populations had developed. Below is a list of materials received from the
project site to be used in preparing a seeding solution with a high probability of containing a viable
population of sulfate reducing bacteria.
• 1-5 gallon bucket of crushed ore from the leach pad.

• 1 gallon plastic bag of scum-like material collected from the soil-air-water interface in the solution
ponds.
• 1 liter bottle of sludge from the solid/water interface in the solution ponds.
The microbial seed solution was prepared by mixing the components listed above in a 5-gallon bucket.
After settling, measured quantities of solution were decanted from the bucket and transferred to a two
gallon sprayer, which was used to apply the seed solution onto the organic material.
3.5 Test Column Organic Packing Materials
The composted media were selected based on the following criteria:
• Uniformity of product.
• Long-term availability of product.
• Suitability of product for study.
• Product cost.
The following is a list of the various materials used in performing this study:
• Straw.
• Premium 3 (Composted Cow Manure).
• Mushroom Compost.
• 2-Way Blend (50% composted cow manure/50% peat).
3.6 Operating Procedure

The Biopass System
A total of six column tests were conducted incorporating a variety of test conditions. A summary of
the testing parameters utilized for each of the six tests is contained in Table 1.
Table 1
Column Test IDs And Associated Test Conditions
Test I.D. Column Packing Material Seeded? Target

Retention
Time (days)
Test #1 Straw Only Y 30
Test #2 Premium 3 mixed with Straw N 30
Test #3 Premium 3 mixed with Straw Y 15
Test #4 Premium 3 mixed with Straw Y 30
Test #5 Mushroom Compost mixed with Straw Y 30
Test #6 2-Way (cow manure/peat) mixed with Y 30
Straw
Packing material mixtures were loaded into columns in several increments using a 5-gallon bucket.
Material was packed at periodic intervals using a 2x4 to achieve a uniform density throughout the
column length. A four inch (4") layer of coarse silica sand was placed in the bottom and top of each
column. Table 2 contains a summary of measurements determined on each packed test column.
After completion of the packing process each test column was mounted in the wooden frame. Solution
delivery to each column was accomplished using electronic metering pumps mounted at the base of
each column. The delivery rate of each metering pump could be individually controlled. Test solution
was fed from a common tank (30 gallon HDPE) to the inlet connection of each pump using one-
quarter inch (1/4") nylon tubing. The outlet of each pump was then connected to the bottom of each
test column. The flow rate of each individual pump was calibrated and adjusted to the estimated target
rate using D.I. water prior to test start up. All inlet lines and pump heads were purged and pruned with
test solution prior to test initiation.

The Biopass System
Table 2
Column Testing - Dimensions, Weights, Measures
Description Units Column Column Column Column Column Column

#1 #2 #3 #4 #5 #6
Packing I.D. ---- Straw Premium Premium Premium Mushroom 2-Way/
Only 3/ Straw 3/ Straw 3/ Straw / Straw Straw
Area Occupied by
Sample Material
- Diameter cm 15.2 15.2 15.2 15.2 15.2 15.2
- Height cm 223.5 223.5 223.5 223.5 223.5 223.5
- Volume cm3 46075 46075 46075 46075 46075 46075
Packing Material
Wet Weight gms 3675 26870 28300 25500 31500 25873

Moisture Content % wt 2.6 28.3 28.3 28.3 39.7 24.3
Dry Weight gms 3579 19266 20291 18284 18994 19586
Specific Gravity gms/cm3 0.90 1.86 1.86 1.86 1.84 2.10

Bulk Density (wet) gms/cm3 0.080 0.583 0.614 0.553 0.684 0.561
Bulk Density (dry) gms/cm3 0.078 0.418 0.440 0.397 0.412 0.425
Volume Occupied by: cm3

- dry packing cm3 3977 10358 11088 9830 10323 9327
material cm3 96 7604 8009 7217 12506 6287
- original moisture 2000 0 2650 3100 2000 3000
- seeding media cm3
40002 28113 24328 25928 21246 27461
Unoccupied volume cm3
42098 35717 34987 36245 35752 36748
Pore Volume
Effluent collection cells were mounted on the wooden frame near the top of each column. Effluent
lines were connected from the top of each column to the inlet port of each effluent collection cell. All
effluent collection cells were manifolded together with inlet and outlet nitrogen over pressure/purge
lines. A nitrogen purge outlet bubbler tube was constructed using a four feet (4') length of one inch
(1") diameter clear PVC tubing with a cap and check valve mounted on the bottom. The bubbler tube
was filled with about two feet (2') of water and mounted on the column frame so that the level of water
in the tube was above the height of the test column outlets. The outlet purge line from the last effluent
collection cell in the series (cell #6) was then connected to the bottom of the bubbler tube. A slow,
continuous purge of nitrogen gas was then initiated through all of the effluent collection cells. One
quarter (1/4") nylon tubing and stainless steel Swagelok fittings were used for all lines and connections
described above.

The Biopass System
The test solution used at start-up was Heap Leach Pad #2 - barren. No attempt was made to reduce or
limit the oxygen content of the test solution feed throughout the duration of testing. All test columns
were allowed to gradually fill with periodic monitoring of the system for leaks. Minor adjustments to
inlet pumping rates were made during column filling based on the observed level of liquid in each
column.
Once the feed solution, Pad #2 - barren, was depleted, the feed solution was switched to Pad #1 -
barren. A sodium cyanide spiking solution was added to the feed solution tank that theoretically should
have raised the WAD cyanide concentration in the Heap Leach Pad #1 - barren feed solution by 16
mg/L to 35 mg/L. A sample of the feed solution after spiking with cyanide was collected and
submitted for analysis for WAD cyanide.
Columns #1, #5, and #6 were shut down first. Column #2 was temporarily shut down at the same time
as Solumns #1, #5 and #6 and then allowed to sit idle for 14 days before restarting. Finally, Columns
#2, #3, and #4 were shut down four weeks after Columns #1, #5 and #6.
Effluent was drained from effluent collection cells on a regular basis (minimum once every 48 hours).
The quantity of effluent from each column was monitored on an ongoing basis by weighing the amount
of effluent recovered each time the effluent collection cells were drained. The date and time for each
effluent collection interval was also monitored and recorded. Specific intervals of effluent collected
from each column were retained for analytical testing.
General characteristics of test effluents was monitored throughout the course of the project. All
effluents from tests 2-6 were dark in color and exhibited a very strong H2S odor throughout the
duration of testing. The effluents from these tests were initially somewhat cloudy but became clearer
over time, however, they remained quite dark in color. The effluent generated from column #1 was
consistent over time, characterized by a light yellow color and a pungent straw or hay-like odor.
Unlike effluent from tests 2-6, test #1 effluent did not exhibit a strong H2S odor. Effluents from all
tests easily passed through a Whatman #1 filter paper but were difficult to filter through a 0.45um
membrane filter. Glass fiber pre-filters and a pressure filter press were required to 0.45um membrane
filter effluents in preparation for analysis. All filtered effluent samples contained precipitates after
preservation and exposure to air.
3.7 Analytical Testing
Effluent samples collected from column tests were analyzed for pH, Eh, alkalinity, WAD cyanide,
NO3-N, NO2-N, SO4, As, Cu, Hg, Mo, Se, and Ag.
Eh analysis on effluent samples was performed immediately following draining of the sample from the
column effluent collection cells. Analysis for remaining parameters was performed after 0.45 um
membrane filtration and appropriate preservation. All samples analyzed for metals via ICP were first
acid digested and then filtered prior to instrumental analysis.

The Biopass System
4.0 RESULTS AND DISCUSSION
The primary results of the study are presented in Tables 3 through 8. The numbers presented in
the tables in parentheses designate the analytical sample sent to ACZ Laboratories. With respect
to the qualitative testing for the presence of heterotrophic, sulfate reducing, and denitrifying
bacteria, all tests proved positive, with the exception of column #1, which contained straw only.
The heterotrophic plate counts reported in colony forming units (cfu) per ml indicated the
presence of large populations of bacteria. Large negative oxidation reduction potentials (ORP)
and Eh values were also initially noted for all the columns except column #1. These results
indicated that meaningful sulfate or nitrate reduction was not occurring initially in column #1 due
to the very slow growth of the bacteria and the low quantity of organic material. Although wad
cyanide removal was noted, the lack of sulfide production slowed the precipitation of the metals.
Although some variation in sulfate concentrations was noted, which may have been due to
sampling or analytical error, the large initial increase in sulfate production in column #5 was likely
due to the dissolution of gypsum which was a component of the organic material used in that
column. The removal of sulfate generally increased with time in all of the columns including #1.
However, the best removal of sulfate was noted in columns #2-#6, with effluent concentrations
well below 500 mg/l. Large quantities of hydrogen sulfide were produced as evidenced by the
continuous odor. Venting of the Biopass System is an essential feature of its full scale design.
In the case of nitrate removal, all of the columns, including #1, demonstrated excellent treatment
producing effluent concentrations routinely below 1.0 mg/l as N.
The alkalinity increased sharply during treatment thereby buffering the effluent solutions and
maintaining an acceptable pH, well within the range required by the State of Nevada. In the case
of wad cyanide, excellent removal was noted at both the initial and subsequently increased levels
of about 14 and 35 mg/l, respectively. In all cases, including column #1, the wad cyanide was
eventually reduced to <0.20 mg/l, and in many instances to below 0.10 mg/l.
With respect to the metals, the residual concentrations in the effluent samples were consistently at
or below their respective detection limits and/or drinking water standards, with the exception of
arsenic. In the case of arsenic the residual concentrations were slightly above its drinking water
standards. However, arsenic is strongly attenuated in soils of all types and effluent exiting the
Biopass System should not cause regulatory or environmental concerns with respect to this
parameter.
The microbial seeding of column #2 did not produce either more rapid or more complete
treatment of the barren solutions. In addition, no decrease in treatment efficiency was noted in
column #2, after startup of the column following a 14 day idle period, thereby demonstrating that
intermittent treatment and operation of the Biopass System is achievable.

The Biopass System
Table 3
Summary Of Column Effluent Collection
And Flow Rate Measurements For Selected Intervals
Column Test ID: #1 #2 #3 #4 #5 #6
units
Time Elapsed to Initial Effluent days 37.0 36.2 24.3 35.0 36.2 37.1
Effluent collection interval #1 (from initial effl through 2nd sample)
- Interval Range (see App. A) --- 1A-1P 2A-2Q 3A-3M 4A-4T 5A-5Q 6A-6R
- Total effluent Volume liters 24.53 18.17 18.19 23.55 15.93 21.18
- Time Duration days 21.3 22.1 13.8 23.3 22.1 21.3
- Flow Rate mls/min 0.798 0.571 0.917 0.702 0.501 0.692
- Empty Bed Contact Time days 40.1 56.1 34.9 45.6 63.9 46.2
Effluent collection interval #2 (from 2nd through 3rd sample)
- Interval Range (see App. A) --- ---- 2R-2AA 3N-3CC 4U-4CC ---- ----
- Total effluent Volume liters ---- 17.77 24.38 12.97 ---- ----
- Time Duration days ---- 15.3 20.3 15.9 ---- ----
- Flow Rate mls/min ---- 0.806 0.834 0.567 ---- ----
- Empty Bed Contact Time days ---- 39.7 38.4 56.4 ---- ----
Effluent collection interval #3 (from 3rd through 4th sample)
- Interval Range (see App. A) --- ---- ---- 3CC-3JJ 4DD-4JJ ---- ----
- Total effluent Volume liters ---- ---- 16.19 12.04 ---- ----
- Time Duration days ---- ---- 15.9 12.9 ---- ----
- Flow Rate mls/min ---- ---- 0.707 0.648 ---- ----
- Empty Bed Contact Time days ---- ---- 45.3 49.4 ---- ----
Effluent collection interval #4 (from 5th through 6th sample)
- Interval Range (see App. A) --- ---- ---- 3JJ-3QQ ---- ---- ----
- Total effluent Volume liters ---- ---- 16.46 ---- ---- ----
- Time Duration days ---- ---- 12.9 ---- ---- ----
- Flow Rate mls/min ---- ---- 0.886 ---- ---- ----
- Empty Bed Contact Time days ---- ---- 36.1 ---- ---- ----
* Empty Bed Contact Time = empty bed volume (in liters)/flow rate (in liters/day)

The Biopass System
Table 4
Column Effluent Test Results - Initial Sample, All Columns
Units "Head A" Column I.D.s

Parameter (Pad #2-
Barren)
(95010-2)
#1 #2 #3 #4 #5 #6
(95010-5) (95010-6) (95010-4) (95010-8) (95010-9) (95010-10)
Days Elapsed from Initial Effluent ---- 1.4 2.2 1.0 1.2 2.3 1.4
Eh mv ---- +198 -360 -349 -330 -229 -354

pH pH units 9.17 4.77 8.09 7.93 7.94 8.31 8.53
Alkalinity, Total mg/L (CaCO3) 143 288 8990 8940 7060 7970 10250
Sulfate mg/L 1850 2500 680 1700 680 13000 2900
6 6 6 6 8 9
Heterotrophic Plate Ct. cfu/ml ---- 4.0 x 10 1.2 x 10 1.4 x 10 1.2 x 10 2.1 x 10 1.5 x 10
SO4 reducing bacteria pos/neg ---- ---- ---- ---- ---- ---- pos
Denitrifying bacteria pos/neg ---- ---- ---- ---- ---- ---- pos
Wad Cyanide mg/L 14 2.9 <0.2 <0.1 <0.2 <0.2 <0.2

Thiocyanate mg/L 84 78 87 83 79 72 11
Nitrate mg/L (as N) 55.6 45.8 0.8 0.5 0.6 0.8 0.8
Nitrite mg/L (as N) 12.2 <0.1 0.4 0.6 0.4 0.4 4.2
Arsenic mg/L 0.45 0.29 0.11 0.09 0.11 <0.01 <0.02

Copper mg/L 10.3 3.99 0.11 0.13 <0.09 <0.09 0.44
Mercury mg/L 0.164 0.007 <0.0002 <0.002 <0.0002 <0.0002 <0.0002
Molybdenum mg/L 1.38 0.49 <0.09 <0.09 <0.09 <0.09 <0.09
Selenium mg/L 0.41 0.24 0.03 0.02 <0.001 0.01 <0.001
Silver mg/L 0.31 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
KEY
Column #1: 100% Straw (control), Seeded, Target Retention Time = 30 days
Column #2: Premium 3 (composted cow manure)/straw (5% by wt.), Unseeded, Target
Retention Time = 30 days
Column #3: Premium 3 (composted cow manure)/straw (5% by wt.), Seeded, Target Retention
Time = 15 days
Time = 30 days
Column #5: Mushroom Compost/straw (5% by wt.), Seeded, Target Retention Time = 30 days
Column #6: 2-Way (50% comp. cow manure, 50% Peat)/straw (5% by wt.), Seeded, Target Ret.
Time = 30 days

The Biopass System
Table 5
Column Effluent Test Results - Sample #2, All Columns
Parameter Units "Head A" Column I.D.s/Sample I.D.s

(Pad #2-
Barren)
(95010-2)
#1/#2 #2/#2 #3/#2 #4/#2 #5/#2 #6/#2

(95010-1) (95010-12) (95010-7) (95011-14) (95010-15) (95010-16)
Days Elapsed from Initial ---- 21.3 22.1 13.8 23.3 22.1 21.3
Effluent
Eh mv ---- +79 -319 -330 -367 -442 -402

pH pH units 9.17 4.63 7.93 7.94 7.91 8.04 7.53
Sulfate mg/L 1850 1600 500 700 <100 8600 1600
6 7 6 8 8 8
Heterotrophic Plate Ct. cfu/ml ---- 4.5 x 10 9.0 x 10 1.4 x 10 1.1 x 10 1.7 x 10 2.5 x 10
SO4 reducing bacteria pos/neg ---- neg pos pos pos pos pos
Denitrifying bacteria pos/neg ---- neg pos pos pos pos pos
Wad Cyanide mg/L 14 0.26 <0.1 <0.2 <0.1 <0.1 0.2

Thiocyanate mg/L 84 88 99 120 111 102 67
Nitrate mg/L (as N) 55.6 48.2 0.5 0.8 0.8 0.4 0.6
Nitrite mg/L (as N) 12.2 <0.4 0.3 0.2 0.3 0.5 1.4
Arsenic mg/L 0.45 0.18 0.05 0.06 0.04 0.02 0.02

Copper mg/L 10.3 4.44 <0.09 0.09 <0.09 <0.09 0.14
Mercury mg/L 0.164 0.011 <0.001 <0.0002 0.002 0.001 0.002
Molybdenum mg/L 1.38 0.53 <0.09 <0.09 <0.09 <0.09 <0.09
Selenium mg/L 0.41 <0.02 <0.006 0.02 <0.006 <0.006 0.006
Silver mg/L 0.31 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
KEY
Column #1: 100% Straw (control), Seeded, Target Retention Time = 30 days
Column #2: Premium 3 (composted cow manure)/straw (5% by wt.), Unseeded, Target
Retention Time = 30 days
Time = 15 days
Time = 30 days
Column #5: Mushroom Compost/straw (5% by wt.), Seeded, Target Retention Time = 30 days
Column #6: 2-Way (50% comp. cow manure, 50% Peat)/straw (5% by wt.), Seeded, Target Ret.
Time = 30 days

The Biopass System
Table 6
Column Effluent Test Results - Column #2
Parameter Units "Head A" "Head B" Column #2 - Effluent Sample I.D.s
(Pad #2- (Pad #1-
Barren) Barren)
(95010-2) (95010-1)
#1 #2 #3 #4
(95010-6) (95010-12) (95010-19) (95010-22)
Days Elapsed from Initial ---- ---- 2.2 22.1 40.4 51.2
Effluent
Eh mv ---- ---- -360 -319 ---- -345

pH pH units 9.17 9.43 8.09 7.93 8.02 7.76
Alkalinity, Total mg/L (CaCO3) 143 127 8990 7544 4810 5760
Sulfate mg/L 1850 1870 680 500 480 240
7
Heterotrophic Plate Ct. cfu/ml ---- ---- 9.0 x 10 ---- ----
SO4 reducing bacteria pos/neg ---- ---- ---- pos ---- ----
Denitrifying bacteria pos/neg ---- ---- ---- pos ---- ----
Wad Cyanide mg/L 14 16-35 <0.2 <0.1 0.1 <0.1

Thiocyanate mg/L 84 114 87 99 159 204
Nitrate mg/L (as N) 55.6 46.0 0.8 0.5 0.4 0.3
Nitrite mg/L (as N) 12.2 12.0 0.4 0.3 0.3 0.2
Arsenic mg/L 0.45 0.30 0.11 0.05 0.06 0.08

Copper mg/L 10.3 11.8 0.11 <0.09 <0.09 <0.01
Mercury mg/L 0.164 0.438 <0.0002 <0.001 0.003 <0.0002
Molybdenum mg/L 1.38 1.65 <0.09 <0.09 <0.09 <0.01
Selenium mg/L 0.41 0.38 0.03 <0.006 <0.01 0.009
Silver mg/L 0.31 0.46 <0.05 <0.05 <0.05 <0.05
* Column #2 was shut down after collecting the "day 22" sample and allowed to sit idle for
14 days. The column was then restarted with an "initial sample" (sample #3) collected 24
hours after start up.
NOTE: feed solution was switched from "Head A" to "Head B" on Day 5 after initial effluent
+ feed solution was spiked with additional cyanide on Day 24 after initial effluent

The Biopass System
Table 7
Column Effluent Test Results - Column #3
(Pad #2- (Pad #1-
Barren) Barren)
(95010-2) (95010-1)
#1 #2 #3 #4 #5
(95010-4) (95010-7) (95010-13) (95010-20) (95010-23)
Days Elapsed from Initial ---- ---- 1.0 13.8 34.1 50.0 62.9
Effluent
Eh mv ---- ---- -349 -330 -377 ---- -374

pH pH units 9.17 9.43 7.93 7.94 7.68 7.94 7.59
Sulfate mg/L 1850 1870 1700 700 200 100 120
6 7
Heterotrophic Plate Ct. cfu/ml ---- ---- ---- 1.4 x 10 1.3 x 10 ---- ----
SO4 reducing bacteria pos/neg ---- ---- ---- pos pos ---- ----
Denitrifying bacteria pos/neg ---- ---- ---- pos pos ---- ----
Wad Cyanide mg/L 14 16-35 <0.1 <0.2 0.2 0.2 <0.1

Thiocyanate mg/L 84 114 83 120 106 147 150
Nitrate mg/L (as N) 55.6 46.0 0.5 0.8 0.5 0.5 0.4
Nitrite mg/L (as N) 12.2 12.0 0.6 0.2 0.5 <0.1 <0.1
Arsenic mg/L 0.45 0.30 0.09 0.06 0.05 0.05 0.08

Copper mg/L 10.3 11.8 0.13 0.09 <0.09 <0.09 <0.1
Mercury mg/L 0.164 0.438 <0.002 <0.0002 0.002 0.003 <0.0002
Molybdenum mg/L 1.38 1.65 <0.09 <0.09 <0.09 <0.09 <0.1
Selenium mg/L 0.41 0.38 0.02 0.02 <0.006 <0.01 0.009
Silver mg/L 0.31 0.46 <0.05 <0.05 <0.05 <0.05 <0.05
NOTE: feed solution was switched from "Head A" to "Head B" on Day 17 after initial effluent
+ feed solution was spiked with additional cyanide on Day 36 after initial effluent

The Biopass System
Table 8: Column Effluent Test Results – Column #4
(Pad #2- (Pad #1-
Barren) Barren)
(95010-2) (95010-1)
#1 #2 #3 #4 #5 #6
(95010-8) (95010-14) (lower side port) (upper side port) (95010-21) (95010-24)
(95010-17) (95010-18)
Days Elapsed from Initial ---- ---- 1.2 23.3 24.2 24.2 39.2 52.1
Effluent
Eh mv ---- ---- -330 -367 -370 -357 ---- -365

PH pH units 9.17 9.43 7.94 7.91 7.78 8.27 8.30 7.81
Alkalinity, Total mg/L (CaCO3) 143 127 7060 3205 2750 2290 6440 4670
Sulfate mg/L 1850 1870 680 <100 170 300 320 130
8
Heterotrophic Plate Ct. cfu/ml ---- ---- 1.1 x 10 ---- ---- ---- ----
SO4 reducing bacteria pos/neg ---- ---- ---- pos ---- ---- ---- ----
Denitrifying bacteria pos/neg ---- ---- ---- pos ---- ---- ---- ----
Wad Cyanide mg/L 14 16-35 <0.2 <0.1 0.08 0.05 0.1 <0.1
Thiocyanate mg/L 84 114 79 111 103 103 174 153
Nitrate mg/L (as N) 55.6 46.0 0.6 0.8 <0.02 <0.02 0.3 0.3
Nitrite mg/L (as N) 12.2 12.0 0.4 0.3 0.27 0.03 0.2 0.2
Arsenic mg/L 0.45 0.30 0.11 0.04 <0.05 0.05 0.07 0.09
Copper mg/L 10.3 11.8 <0.09 <0.09 <0.09 <0.09 <0.09 <0.1
Mercury mg/L 0.164 0.438 <0.0002 0.002 0.002 0.002 0.002 <0.0002
Molybdenum mg/L 1.38 1.65 <0.09 <0.09 <0.09 <0.09 <0.09 <0.1
Selenium mg/L 0.41 0.38 <0.001 <0.006 <0.006 <0.006 <0.01 0.009
Silver mg/L 0.31 0.46 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
NOTE: feed solution was switched from "Head A" to "Head B" on Day 6 after initial effluent + feed solution was spiked
with additional cyanide on Day 25 after initial effluent

The Biopass System
The unexpected performance of column #1 indicated that a higher percentage of straw mixed with
composted cow manure or other organic material is warranted on the basis of economics. A large
increase in straw content is possible, as long as sufficient organic material in the form of
composted manure is present to convert the anticipated mass of sulfate entering the Biopass
System. The quantity of required organic material can be estimated on a semi-quantitative basis.
The results of effluent analysis from columns #3 and #4 indicated that treatment beyond one pore
volume of solution is acceptable. However, since the columns were not operated to
breakthrough, the extent of treatment is not known at the present time. Based upon the pore
volumes of columns #3 and #4, an additional 1 to 2 pore volumes of solution were effectively
treated following the initial filling of the columns. It would appear that additional pore volumes
of solution are treatable based upon these results, thereby allowing a reduction in the size of a
Biopass System depending upon the allowance for a discharge into the environment.
Due to the difficulty in determining pore volumes, the average retention periods did vary over a
range of about 35-50 days depending upon the column and feed period. In the case of column #4,
additional samples were collected from the two sampling ports located on the side of the column
at about one-third and two-thirds of its height. In the case of column #4 the cumulative empty
bed contact time over the entire test period was about 50 days. Using this retention period as a
basis, the retention time at sampling port one or two would have been about 16 to 33 days,
respectively.
The effluent quality associated with the two individual side port samples indicated excellent and
equivalent treatment with that observed at the much longer retention periods. Although it is still
recommended that the initial filling of the Biopass System be controlled to between 20 to 30 days
to initiate and promote sufficient biological activity, the actual retention period for treatment
could possibly be reduced to less than 20 days, pending the outcome of further laboratory studies.
The two controlling design constraints include the volume of organic material required and the
retention period. Based upon past experience, it appears that the retention period, and not the
volume of organic material, is the controlling process design variable. Shorter retention periods
are likely probable, based on results of other studies centered on the treatment of AMD.
5.0 BIOPASS DESIGN CONSIDERATIONS AND CONFIGURATIONS
Since the Biopass System is an enclosed system, the retention period for solution is on the order of
many days or a few weeks, providing maximum contact time for bacterial treatment and chemical
precipitation. There is no need to incorporate the volume of organic material into the Biopass System
to provide greater than a 30-day hydraulic retention period, but there remains a need to incorporate
sufficient organic material to complete the bacterial treatment without periodically replenishing the
carbon source. The organic material must be carefully selected on the basis of both efficiency and
economics. From an efficiency standpoint, the organic material must not only provide the appropriate
growth substrates for the individual bacteria needed, but also a suitable matrix for initial sorption of
cyanide and metals present in the incoming drainage.

The Biopass System
The volume of organic matter required is dependent upon the total mass of sulfate and nitrate that
could be degraded over time. The anticipated total mass of these two constituents would be derived by
multiplying their concentrations in the drainage by the estimated volume of drainage exiting the pads.
By assuming a required mass of organic matter per unit mass of sulfate or nitrate reduced, a total
volume and weight of organic matter can be calculated for incorporation into the Biopass System
design. Calculation of the total mass of organic matter needed on the basis of the total mass of sulfate
alone in the drainage is conservative, since the sulfate concentration is typically in order of magnitude
or greater than that of nitrate and only a portion of the sulfate will be bacterially reduced over time.
The mass of organic matter required for sulfate reduction would be compared with the volume needed
to provide an appropriate treatment or retention period in days within the Biopass System. The
limiting factor of the two (i.e., mass versus retention period) would be used in the final process design.
As stated previously, the controlling design factor, using the current level of knowledge regarding the
Biopass System, is the retention period. Based upon the results of the laboratory study, the optimal
retention period for initial startup and semi-continuous treatment would be about 20-30 days. The
volume of the Biopass and required organic material would be determined by estimating the volume of
solution generated at the tail end of draindown and comparing that quantity with the volume of the
barren and pregnant solution ponds available.
Similar passive systems could be designed and built to accommodate leachate from a waste rock
disposal area and seepage from a tailings impoundment, depending upon the anticipated flows and
chemistry.
6.0 CONCLUSIONS
The Biopass System provides an effective approach to treatment of long-term draindown from heap
leach pads and greatly reduces the need for and expense of chemical treatment or detoxification of rinse
solutions.
The continuous flow laboratory studies have demonstrated that the removal efficiencies for cyanide,
sulfate, nitrate and metals were equal to or greater than anticipated based upon the literature, and were
generally below their respective detection limits or drinking water standards.
The results of the laboratory studies have indicated that a mixture of straw and composted manure can
provide the appropriate organic material, seeding of the mixture is not required, and an empty bed
contact time or hydraulic retention period of 20-30 days is adequate for treatment.
In addition to closure of a heap leach operation, the Biopass System will also find utility in the long-
term treatment of leachate from waste rock disposal areas and/or seepage from tailings impoundments.

The Biopass System
7.0 REFERENCES
Adams, D., Altringer, P., and Gould, W., “Bioreduction of Selenate and Selenite”, U.S. Bureau of
Mines, Salt Lake City, Utah, Proceedings from the International Biohydrometallurgy Symposium
1993, Jackson Hole, Wyoming, August, 1993.
Altringer, P., Lien, R., and Gardner, K., “Biological and Chemical Selenium Removal from
Precious Metal Solutions”, Proceedings of Environmental Management for the 1990’s, SME
Annual Meeting, Denver, Colorado, February, 1991.
Altringer, P., Lien, R., and Dinsdale, B., “Advances in Biological Cyanide Detoxification”,
Proceedings of the Randol Conference, p. 395, Vancouver, British Columbia, Canada, 1992.
Baldwin, R., Stauter, J., Kauffman, J., and Laughlin, W., “Process for the Removal and Recovery
of Selenium from Aqueous Solutions”, United States Patent, No. 4,519,913, May 28, 1985.
Canby, T., “Bacteria”, National Geographic, p. 36, August, 1993.
Darnall, D., and Gabel, A., “AlgaSORB: A New Technology for Removing and Recovering
Heavy metal Ions from groundwater and Industrial Wastewater”, Proceedings of the 1989 EPA
Symposium on Hazardous Waste Treatment: Biosystems for Pollution Control, Cincinnati, Ohio,
February, 1989.
Dvorak, D., and McIntine, P., “Treatment of Metal Contaminated Water Using Bacteria Sulfate
Reduction: Results from Pilot Scale Reactors”, Biotechnology and Bioengineering, Volume 40,
pp. 609-616, 1992.
Ferguson, C. and Jeffers, T., “Biosorption of Metal Contaminants from Acidic Mine Waters”,
U.S. Bureau of Mines, Salt Lake City, Utah, paper presented at the 1991 SME conference,
Denver, Colorado, February, 1991.
Kleinmann, R. and Girtis, M., “Constructed Wetlands for Treatment of Acid Mine Drainage: A
Preliminary Review”, 1986 Symposium on Mining, Hydrology, Sedimentology and Reclamation,
University of Kentucky, Lexington, Kentucky, December 8-0111, 1986.
Kleinman, R., Hedin, R., and Edenborn, H., “Biological Treatment of Mine Water - An
Overview”, U.S. Bureau of Mines, Pittsburgh Research Center, Pittsburgh, Pennsylvania, 15236,
1986.
Lapakko, K., and Eger, P., “Trace Metal Removal from Mining Stockpile Runoff Using Peat,
Wood Chips, ailings, Till and Zeolite”, Proceedings Symposium of Surface, Mining, Hydrology,
Sedimentology and Reclamation, University of Kentucky, Lexington, Kentucky, December 7-11,
1981.
Levine, V., “The Reducing Properties of Microorganisms With Special Reference to Selenium
Compounds”, Journal of Bacteriology, Volume X, No. 3, pp. 217-263, 1924.

The Biopass System
Maree, J., and Strydom, W., “Biological Sulphate Removal In An Upflow Packed Bed Reactor”,
The South African Institute of Mining and Metallurgy, MINTEK, Randburg South Africa, 1985.
Metcalf and Eddy, “Wastewater Engineering”, Second Edition, McGraw Hill Book Company,
1979.
Morrey, D., ”The Role of Biotechnology in the Rehabilitation of Toxic Mining Wastes”, Golder
Associates Inc., Lakewood, Colorado, 1993.
Morrey, D., “The Application of Toxicity and Stress Tolerant Plant Species to the Reclamation of
Mining Wastes,” Golder Associates Inc., Lakewood, Colorado, 1994.
Sencindiver, J., and Bhumbla, D., “Effects of Cattails on Metal Removal from Mine Drainage”,
Mine Drainage and Surface Mine Reclamation, Volume I, U.S. Bureau of Mines, IC9183,
Pittsburgh, Pennsylvania, pp. 359-369, 1988.
Smith, A., and Mudder, T., “The Chemistry and Treatment of Cyanidation Wastes”, Mining
U.S. Environmental Protection Agency, “Process Design Manual for Nitrogen Control,”
Technology Transfer, October, 1975.
Water Pollution Control Federation, “Nutrient Control”, Manual of Practice, FD-7, 1983.
ACKNOWLEDGEMENTS
The authors wish to thank Corona Gold, Inc., and Homestake Mining Company for supporting
this study and allowing the publication of these results, and Dr. Dirk Van Zyl, P.E. (Golder
Associates, Inc.) for his independent review of the paper.

THE BIOPASS SYSTEM
PHASE II: FULL SCALE DESIGN AND CONSTRUCTION
Prepared By:
Roy Cellan
Alan Cox
Ron Uhle
Doug Jenevein
Scott Miller
Terry Mudder, Ph.D.
Originally written in January 1997 and subsequently published in The Cyanide Monograph, First
Edition, Mining Journal Books, London, England, United Kingdom, June 1998
The Biopass System
Phase II: Full Scale System Design and Construction
1.0 INTRODUCTION
An in situ anaerobic biochemical system, termed the Biopass system, was designed and
constructed for passive treatment and discharge of residual drainage from a reclaimed cyanide
heap leach facility at the Homestake Mining Company’s Santa Fe Mine, in Mineral County,
Nevada. The Biopass system Phase I process and chemistry was first described by Mudder et.al.
(1995). The Biopass system consists of an anaerobic treatment cell constructed in an existing
process pond at the toe of the heap leach pad which receives draindown from the pad through.
The Biopass system was designed and constructed to handle draindown from the reclaimed leach
pad associated with the probable maximum precipitation event, as well as accommodate the
expected average flow rates. Additionally, the Biopass system was designed and constructed to
contain sufficient organic material to function for long-term treatment. These design requirements
resulted in construction of a large anaerobic cell which will maintain permeability and sufficient
treatment capacity. The significant design issues addressed for this innovative heap leach pad
closure include:
• Characterization of expected draindown quantity and quality.

• Sizing of organic substrate mass and treatment retention times.
• Design and placement of substrate layer to minimize consolidation and maintain permeability.
• Development of in situ field construction quality assurance procedures.
• Minimize construction/installation difficulties.
This paper summarizes the design issues and the construction sequence for the Biopass system.
2.0 DESIGN OF AN INSITU BIOCHEMICAL SYSTEM
To reduce construction costs and minimize environmental disturbance, the biochemical system is
designed utilizing the existing emptied barren pond as an in situ containment system. The barren
pond has bottom dimensions of approximately 100 feet by 100 feet, 3(H):1(V) side slopes, top
perimeter dimensions of approximately 200 feet by 200 feet, and a depth of approximately 16 feet.
The barren pond lining system consists of two geomembrane liners. The Biopass System is
designed as an in situ upflow passive treatment system in which the heap leach pad residual
drainage is piped to the bottom of the cell and flows upward through the organic substrate layer
where treatment occurs. Residual drainage (influent) from the heap leach pad is collected in a
perforated high density polyethylene (HDPE) pipe and routed to the bottom of the cell where the
flow is distributed into a 2 foot thick gravel layer. Influent entering the drainage layer at the base
of the cell migrates upward through a 9.5 foot thick substrate layer comprised of a gravel and
composted cow manure mixture for anaerobic treatment.
The treated solution (effluent) is collected within a collection system consisting of a 2 foot thick
gravel layer and piping. Effluent is routed via a HDPE pipe to a leach field where it is aerobically
treated. A schematic of the Biopass system is shown in Figure 1.
471 R. Cellan et al.

The Biopass System

The Biopass System
2.1 Design Approach
The first step in designing the Biopass system was to determine the chemical and metal
constituents of the residual drainage and to determine the long- and short-term flow rates and
volume of flow from the closed heap leach pad. Results of the first step of the design were used
to calculate the required mass of organic matter, retention time, hydraulic conductivity of the
substrate layer, and confirm the capacity of the existing barren pond. The last step of the design
was to determine the maximum consolidation settlement of the substrate layer so that the Biopass
system cover could be designed with an adequate slope. The Biopass system design and
construction are described below.
2.2 Chemical and Metal Constituents in the Drainage
The concentrations of the chemical and metal constituents of the closed heap leach pad drainage
were determined so that the required mass of organic matter could be calculated. A summary of
the closed leach pad solution chemistry is presented below.
Parameter Units Concentration
pH SU 8.59
Total Alkalinity as mg CaCO3/L 125
Bicarbonate mg/L 128
Carbonate mg/L 12
Total Dissolved Solids mg/L 5,860
Arsenic mg/L 0.87
Cadmium mg/L 0.006
Chloride mg/L 800
Fluoride mg/L 0.91
Manganese mg/L 0.11
Mercury mg/L 0.071
Nickel mg/L 0.079
Nitrate (as N) mg/L 126
Selenium mg/L 0.26
Silver mg/L 0.099
Sulfate mg/L 2,220
WAD Cyanide mg/L 0.86

The Biopass System
2.3 Flow Rate
Long-term seepage rates from the closed heap leach pad is a primary consideration in the design
of the Biopass system since calculation of the required mass of organic matter, hydraulic
conductivity of the substrate layer, piping size, and retention time are dependent on the flow rate.
Flow rates which were determined to be critical to the design included long-term post-closure
flow rates, peak storm events and associated flow rates, and short-term draindown volume. All
flow rates were calculated using the EPA Hydrologic Evaluation of Landfill Performance (HELP)
Model (U.S. Environmental Protection Agency, 1994).
Flow rates associated with peak storm events were determined by running the HELP model with
the 100-year 24-hour event replaced by events ranging from the 100-year 24-hour value to the
Probable Maximum Flood (PMP) estimate. Results indicated that only slightly higher flows of
greater duration were generated for precipitation events of a magnitude greater than the 100-year
24-hour event. The peak flow rate associated with the 100-year 24-hour event is approximately
-4
4.5 gpm. Given this rate and a set minimum hydraulic conductivity of the substrate layer of 5x10
centimeters per second (cm/sec), it was determined that the retention time will be approximately
88 days. The peak flow resulting from the PMP was predicted to be about 10.5 gpm. At a flow
rate of 10.5 gpm, the retention time would be on the order of 38 days. The probability of a storm
event resulting in flows which decrease the retention time to less than the target 20 days is
extremely small.
It was decided to maintain a large factor of safety for flow rates because of the uncertainty
involved with the decrease in hydraulic conductivity with time of the substrate material. Using the
set minimum hydraulic conductivity of the substrate layer, the maximum flow rate that the
Biopass system can achieve is 45.1 gpm. The calculated factor of safety for the 100 year 24-hour
and PMP events are 10 and 4.3, respectively.
In order to determine the life of the organic material, an estimate of the expected short-term
volume of solution passing through the Biopass system over time was calculated. The draindown
volume was calculated by estimating the volume of solution in the heap available for draindown at
the end of leaching and subtracting the volume of solution that will have drained from the heap in
approximately 1 year, between the cessation of rinsing and beginning to let solution flow through
the Biopass system. The volume that will pass through the Biopass system was calculated to be
approximately 6 million gallons due to residual draindown.

The Biopass System
2.4 Retention Time and Mass of Organic Matter
The Biopass system biological and chemical processes have been described in Mudder et. al.
(1995). The most important feature of the Biopass system is the organic layer into which the pad
drainage is conveyed. The chemical processes involved in the anaerobic treatment include
physical sorption and sulfate reduction. One of the limiting factors for the usable life of the
Biopass system is the quantity of organic substrate to initiate and complete treatment on a long-
term and cyclic basis. A second limiting factor is the retention time necessary to achieve the
required level of treatment. This was determined from an empirical laboratory evaluation as
summarized in Mudder et. al. (1995). The empirically determined retention times varied
depending upon constituents, but ranged from 10 to 30 days.
The required mass of organic matter was calculated on the basis of the anticipated sulfate load
requiring treatment. A predicted sulfate load was calculated using the average annual flow rates
totaled over a 20 year period with two 100 year 24-hour storm events and an average sulfate
concentration of 2,000 mg/l. The mass of organic substrate was determined assuming a
conservative ratio of volatile suspended solids that will be consumed per pound of sulfate.
2.5 Hydraulic Conductivity of the Substrate Layer
The hydraulic conductivity of the substrate layer must be designed to allow flow of the anticipated
peak discharge and provide a minimum hydraulic conductivity over the life of the system. If the
hydraulic conductivity is not sufficient, a blowout due to pressure buildup could occur or excess
drainage could backup and overflow from the lined area of the pad. Since the existing barren
pond was utilized in the design, both the cross sectional area and hydraulic gradient through the
cell are fixed. The only flow rate factor which can be adjusted is therefore the hydraulic
conductivity of the substrate layer. Darcy’s Law was used to estimate the minimum allowable
hydraulic conductivity of the substrate layer given a peak flow rate.
Laboratory hydraulic conductivity testing was performed on remolded samples of composted cow
manure and varying mixtures of gravel and composted cow manure to simulate the expected field
hydraulic conductivity of the substrate layer. Post-consolidated hydraulic conductivity of the
-4
composted cow manure with 5 percent straw was approximately 1.0x10 cm/sec at an effective
stress of 3 pounds per square inch (psi). Additional laboratory tests were performed to evaluate
amendment of the composted cow manure with gravel so as to increase the hydraulic
conductivity.
Materials used in the testing program consisted of composted cow manure, straw, and three
different gravels types. All mixes were prepared based on percentages of dry weight. The natural
moisture content of the composted cow manure was approximately 45 percent to 50 percent,
while the moisture contents of the straw and gravel materials were both below 3 percent by
weight.

The Biopass System
Hydraulic conductivity tests indicated that the straw creates structure which provides resistance to
compaction, and therefore, greater hydraulic conductivity. However, the straw will degrade over
time and result in a lowering of hydraulic conductivity. This process in an anaerobic environment
will take a period of years. To minimize the loss of hydraulic conductivity over time it was
decided to eliminate the straw and that a mixture by weight of 90 percent spent ore gravel and 10
percent composted cow manure (90/10 mix, dry weight basis) would provide the necessary
hydraulic conductivity for the consolidated materials.
The rigid-wall hydraulic conductivity test conducted on the 90/10 mix at an effective stress of 10
-2
psi indicated a hydraulic conductivity of 4.7x10 cm/sec. When the percentages by weight are
converted to volumetric percentages, the mix would be approximately 80 percent rock and 20
percent compost by volume. Based on the laboratory test results, it was decided that a minimum
-4
hydraulic conductivity of 5x10 cm/sec would be used for the substrate layer since biological and
mechanical processes would lower the hydraulic conductivity over time.
2.6 Consolidation Settlement of the Substrate Layer
Due to the large particle size of the substrate gravel (0 to 5 percent passing the 3/8-inch sieve),
traditional consolidation tests to predict settlement of the substrate layer could not be performed.
The method used to predict the amount of settlement was derived from the hydraulic conductivity
testing done on various substrate mixtures. The sample mixtures were tested in a 10-inch
diameter rigid wall permeameter. This device had the capability to apply a vertical consolidation
load to the sample. For each mix, a relationship of hydraulic conductivity versus load was
developed. Sample height was measured during each loading sequence to determine when the
majority of the consolidation due to the change in load had occurred. The expected maximum
effective stress in the biopass cell was approximately 7 psi. The measured strain of a 90/10 mix at
a load of 10 psi was approximately 9.9 percent. Therefore, the amount of settlement expected
was approximately 10 percent at the center of the Biopass cell. The Biopass cell topsoil layer was
designed with a 3 percent slope to maintain a slope after full consolidation settlement occurs.
3.0 CONSTRUCTION OF AN IN SITU BIOCHEMICAL SYSTEM
Construction of the Biopass system was accomplished in a two month period by Nielsons, Inc.
Third party (independent) construction quality assurance (CQA) surveying, testing, and
monitoring services were performed to provide assurance that the Biopass system was
constructed as specified in the design, thus minimizing environmental impacts and inadequate cell
performance as a result of substandard construction.
3.1 Substrate Test Fill Construction
Prior to constructing the Biopass System, a substrate test fill was constructed to establish a
method for moisture conditioning, mixing, hauling, placement, and compacting the substrate
materials such that the substrate would consist of a uniform compacted 90/10 mix with a
-4
hydraulic conductivity greater than or equal to 5x10 cm/sec.

The Biopass System
The substrate test fill consisted of several pads each approximately 40 feet wide and 75 feet long.
Prior to constructing the pads, the subgrade was moisture conditioned and 2 to 4 inches of gravel
was placed on the subgrade and wheel-rolled with a water wagon. Two ten cubic yard dump
trucks were used to haul gravel to the test fill pads. The dump trucks were weighed empty, then
filled with a front-end loader with two trimmed bucket loads of gravel, and then weighed again to
determine the weight of a gravel filled loader bucket and dump truck. Composted cow manure
was stockpiled in individual numbered stockpiles near the test fill pads as it was delivered to the
site. The wet weight, moisture content, and dry weight of each load of composted cow manure
and pile number were recorded and used to calculate the amount of gravel to be mixed with each
pile of composted cow manure. The gravel was placed on a pad and spread into a lift of constant
depth (typically between 10 and 11 inches) with a motor-grader. Composted cow manure was
then placed on top of the gravel lift with a front-end loader and spread over the gravel in a
uniform lift (typically between 3 and 4 inches) by a motor-grader. The substrate materials were
mixed together using a minimum of three one-way passes across the entire mixing pad by a soil
stabilizer. Water was added prior to and during mixing using six to twelve one-way passes of a
water wagon after field hydraulic conductivity testing indicated that the materials were
hydrophobic at moisture contents below approximately 4 percent.
To simulate picking up the substrate and placing it in the Biopass cell, the mixed substrate was
picked up by a front-end loader and placed on a test fill pad. A low ground pressure (LPG) dozer
(ground pressure less than 5 pounds per square inch) spread the materials into the desired lift
thickness and track-walked the loose lift surface with four to eight one-way passes. Field
moisture-density tests were conducted prior to track-walking, after four one-way passes, and after
eight one-way passes.
Field and laboratory tests were performed during construction of the test fill pads to determine the
construction compactive efforts, volatile organic content, and determine the acceptable moisture
content range for achievable hydraulic conductivity values. Moisture content, in-place density,
and hydraulic conductivity testing were conducted on the test fill pads and moisture content,
gradation, and organic content testing were performed at an on-site field laboratory to
characterize the substrate materials obtained from the test fill pads.
Laboratory organic content testing was conducted to determine the percentage of composted cow
manure in the substrate mixture. Organic content test results indicated that the volatile organics
ranged from 21.7 to 31.5 percent in the composted cow manure with an average of 31.3 percent
by dry weight. The percentage of composted cow manure in the substrate materials ranged from
9.2 to 19.7 percent with an average of 12.8 percent by dry weight.
All field moisture-density tests were conducted with a nuclear density gauge. At each test
location, a sample of the substrate from the nuclear density test location was obtained for
laboratory water content testing. Results of the laboratory moisture content tests were used to
recalculate the dry density values obtained with the nuclear density gauge. The nuclear density
gauge moisture content readings were on average 1.9 percent above the laboratory moisture
content. Laboratory moisture content testing was used as the true moisture content value since
organics can cause the nuclear density gauge to produce a higher moisture content value.

The Biopass System
The laboratory moisture contents of the compacted substrate materials ranged from 7.5 to 9.5
percent with an average of 8.2 percent. Based on the laboratory moisture contents, the dry
density ranged from 109.9 to 119.1 pcf with an average of 114.4 pcf after four one-way passes of
a LPG dozer. On average the dry density increased approximately 2.7 percent after four
additional one-way passes of the LPG dozer.
Field tests were conducted on each test fill lift to evaluate the in situ hydraulic conductivity of the
substrate materials. Initially, open stand pipe permeameter and standard Gulf permeameter
methods were used, but due to the hydrophobic nature of the drier substrate materials and
sidewall disturbance of the gravel portion of the substrate materials neither method proved to be
accurate. The field hydraulic conductivity tests were conducted using a 2 foot long by 20 inch
diameter steel pipe with an open top and highly permeable steel grate welded to the bottom. The
bottom 1 foot of the pipe inner wall was lined with an approximate 1 inch thick layer of hydrated
bentonite paste to prevent preferential side wall flow. The pipe was filled with moisture
conditioned substrate materials and placed in an excavated hole in the test fill with the top of the
pipe within 0.2 to 0.3 feet of the test fill surface. The substrate in the pipe was compacted with
eight one-way passes of a LPG dozer so that the sample density at a depth of 1 foot would be
similar to that at the surface after four one-way passes of a LPG dozer. The pipe was exhumed
and the substrate trimmed flush with the top of the pipe and a sand cone test performed to
determine the density and moisture content of the sample.
The top one foot of substrate sample was removed from the pipe leaving approximately 1 foot of
substrate sample in the bottom of the pipe. The pipe was placed in a tank and the annular space
between the pipe outer wall and the tank inner wall was gradually filled with water to the same
height as the surface of the 1 foot of substrate sample in the pipe. The substrate sample was
allowed to hydrate until the top surface of the sample became moist.
The permeameter reservoir was positioned so that a head of zero was equal to the top surface of
the substrate sample in the pipe. Water was added to the annular space to create an initial head in
the range of 2 to 5 centimeters and the permeameter reservoir was adjusted to maintain the same
initial head. Water volume readings were generally at 30 second or 1 minute intervals. Water
was drained from the surface of the substrate sample during the tests so that a constant head was
maintained across the sample.
-1 -2
The field test results indicated that the hydraulic conductivity ranged from 2.6x10 to 2.6x10
-2
cm/sec with an average of 6.7x10 cm/sec. Sand cone density tests conducted on the samples
indicated that the moisture contents ranged from 5.7 to 8.9 percent with an average of 7.8
percent. The dry density ranged from 105.7 to 108.9 pcf with an average of 107.5 pcf. This
permeameter method provided a relatively rapid and reliable hydraulic conductivity field test.

The Biopass System
Construction and evaluation of the substrate test fill provided an indication of expected
performance of the substrate layer in the Biopass system. The following conclusions can be made
from the results of the test fill:
• Quality of Substrate Layer. The results of field hydraulic conductivity testing indicate the
substrate materials and construction methods used during the test fill would produce a
-4
substrate layer with a hydraulic conductivity of greater than or equal to 5x10 cm/sec. It is
apparent from field test results that substrate materials with a moisture content less than 4
percent behave hydrophobicly and will not meet the specified hydraulic conductivity criteria.
• Quality Assurance of Substrate Materials. The discrete stockpiling of the composted cow
manure, care taken in measuring the dry weight of the gravel and composted cow manure, and
homogeneous nature of the mixed substrate material would aid in construction.
• Field Moisture-Density. From the field moisture density test data, it appears that in order to
-4
achieve a hydraulic conductivity of greater than or equal to 5x10 cm/sec, a placement dry
density of not more than 117 pcf must be maintained.
• Number of Dozer Passes. Field density test results indicate that a maximum of four one-way
passes with a LPG dozer is necessary to achieve a density of less than 117 pcf. Additional
passes with a dozer or other construction equipment is not recommended since an increase in
density will likely decrease the hydraulic conductivity.
• Lift Thickness. The results of the test fill program indicate that an acceptable hydraulic
conductivity can be achieved if a lift thickness of 1 to 3 feet is used.
3.2 Construction Sequence
Prior to constructing the Biopass system, the residual drainage from the closed cyanide heap leach
pad was temporarily diverted from the former barren pond to the surplus pond and two on-site
screening plants were set up to process on-site materials for use as influent, substrate, and effluent
gravel. Biopass system construction commenced with the placement of a geotextile cushion on
the cell floor and on the sideslopes where the influent gravel comes into contact with the cell
sideslopes. To allow construction equipment into the cell, a temporary access ramp was
constructed down the northwest corner of the cell using substrate materials. Trucks were used to
haul the influent gravel from the screening plant to the cell. The influent gravel was placed in the
cell with a front-end loader and spread in a single 2 foot thick lift with a LPG dozer.
Mixing of the substrate materials was performed adjacent to the cell using the method established
during the substrate test fill construction. Water was added prior to and during mixing using six
to twelve one-way passes of a water wagon. The mixed substrate was then picked up with a
front-end loader, placed in the cell, and spread with a LPG dozer in maximum 3-foot thick lifts.
A motor-grader was used to rip the temporary access ramp at the completion of each lift. Field
moisture-density tests indicated that the substrate layer was compacted to a dry density not
greater than 117 pcf and at a moisture content between 4 and 15 percent. Field hydraulic
-3 -2 -3
conductivity values ranged from 1.3x10 to 2.7x10 cm/sec with an average of 7.7x10 cm/sec.

The Biopass System
Prior to placing the effluent and upper gravel layers a geotextile cushion was placed on the cell
sideslopes where the gravel layers come into contact with the cell sideslopes. The effluent
material was then spread in a single 2 foot thick lift with a LPG dozer. Upper gravel layer
materials were spread in a single 2 to 3 foot thick lift over the effluent gravel with a LPG dozer.
The upper gravel layer was finish graded with a motor-grader. A 60 mil geomembrane cover
with pressure release vents was then placed over the geotextile cushion which covered the upper
gravel layer. Topsoil was spread in a minimum 2 to 4 foot thick lift over the geomembrane cover
with a LPG dozer. The topsoil was finish graded with a motor-grader.
Piping associated with the Biopass system was installed in trenches excavated with a front-end
loader. Laborers welded the pipe, end caps, tees, elbows, and reducers together and placed the
finished piping in the trenches. A LPG dozer was used to backfill the piping.
Results of the third party (independent) construction quality assurance (CQA) surveying, testing,
and monitoring performed during construction of the Biopass system indicated that the cell was
constructed in accordance with the project plans and specifications.
The authors wish to thank Homestake Mining Company of California for allowing the publication
of these results. In addition, the authors wish to acknowledge Nielsons, Inc. of Cortez, Colorado
for an innovative construction approach.
5.0 REFERENCES
Mudder, T., Miller, S., Cox, A., McWharter, D., and Russell, L. 1995. Lab Evaluation of an
Alternative Heap-Leach Pad Closure Method. Mining Engineering, November 1995, vol. 47(11),
pp 1007-1014.
U.S. Environmental Protection Agency Office of Research and Development, 1994. The
Hydrologic Evaluation of Landfill Performance (HELP) Model Engineering Documentation For
Version 3, EPA 600/R-94/168.

CHAPTER 5
Chemical and physical treatment
● An overview of cyanide treatment and recovery methods

● Mine water treatment with activated carbon
● Overview of water treatment methods for thiocyanate
removal
● Review of mine water nitrate removal technologies
● Process water management and treatment at the Golden
Cross mine
AN OVERVIEW OF CYANIDE TREATMENT
AND RECOVERY METHODS
Prepared By:

Terry Mudder, Ph.D.
Written for publication in The Cyanide Monograph, Second Edition, Mining Journal Books,
An Overview of Cyanide Treatment and Recovery Methods
1.0 INTRODUCTION
An integral and key component of many water management systems at mining sites is the
approach adopted to manage cyanide-containing solutions and slurries. Excluding the bulk
storage of cyanide reagents such as sodium cyanide, most cyanide present at mining sites will be
present in water solutions. Therefore, to a great extent the management of water and the
management of cyanide can be considered as one and the same and should be simultaneously
considered when developing water management and cyanide management plans.
All mining sites that utilize cyanide for metals recovery should have a comprehensive and well-
maintained cyanide management plan. A good cyanide management plan will include
descriptions of how cyanide-containing solutions and slurries are to be handled, stored, contained
and monitored, and in many cases the plan will also include a description of treatment plants
used to remove cyanide from solutions or slurries.
2.0 BACKGROUND
In the mining industry, cyanide is primarily used for extracting silver and gold from ores, but
cyanide is also used in low concentrations as a flotation reagent for the recovery of base metals
such as copper, lead and zinc. At these operations, cyanide treatment systems may be required to
address potential toxicity issues in regard to wildlife, waterfowl and/or aquatic life. This may
include the removal of cyanide from one or more of the following:
• Slurry tailings from milling operations

• Bleed solution from Merrill-Crowe operations
• Excess solution from heap or vat leaching operations
• Supernatant solution from tailings impoundments
• Seepage collected from ponds or tailings impoundments
The term ‘cyanide’ refers to one of three classifications of cyanide, and it is critical to define the
class of cyanide that is to be removed in a treatment plant. The three classes of cyanide are: (1)
total cyanide; (2) weak acid dissociable (WAD) cyanide; and (3) free cyanide as illustrated in
Figure 1.

Strong Metal-Cyanide Complexes of Fe
Weak and Moderately Strong

Total Metal-Cyanide Complexes of
Cyanide WAD Ag, Cd, Cu, Hg, Ni and Zn
Cyanide
Free CN-
Cyanide HCN
Figure 1
Classifications of Cyanides
The appropriate selection for most situations is WAD cyanide since this includes the
toxicologically important forms of cyanide, including free cyanide and moderately and weakly
complexed metal-cyanides. Total cyanide includes free cyanide, WAD cyanide plus the
relatively non-toxic iron-cyanide complexes.
Cyanide treatment processes are classified as either a destruction-based process or a recovery-

based process. In a destruction process, either chemical or biological reactions are utilized to
convert cyanide into another less toxic compound. Recovery processes are a recycling approach
in which cyanide is removed from the solution or slurry and then re-used in a metallurgical
circuit.
Selection of an appropriate cyanide treatment process involves the consideration of many factors,
but generally the number of candidate processes for a particular application can be narrowed
following an inspection of the untreated solution/slurry chemistry and the desired level of
treatment. In the following sections, several destruction and recovery processes are discussed
along with their typical areas of application. With all of these processes, laboratory and/or pilot
testing is required to confirm the level of treatment achievable and to evaluate the associated
reagent consumptions.

3.0 CYANIDE DESTRUCTION
Most cyanide destruction processes operate on the principle of converting cyanide into a less
toxic compound through an oxidation reaction. There are several destruction processes that are
well proven to produce treated solutions or slurries with low levels of cyanide as well as metals.
3.1 INCO Sulfur Dioxide/Air
The sulfur dioxide (SO2) and air process was developed by INCO Limited in the 1980’s and is
currently in operation at over thirty sites worldwide. The process utilizes SO2 and air in the
presence of a soluble copper catalyst to oxidize cyanide to the less toxic compound cyanate
(OCN-).
+2
SO2 + O2 + H2O + CN- Cu
 Catalyst
- -2
→ OCN + SO4 + 2H
+
The primary application of the sulfur dioxide and air process is with slurry tailings, but it is also
effective for the treatment of solutions for the oxidation of free and WAD cyanides. Iron
cyanides are removed in the process through precipitation of insoluble copper-iron-cyanide
complexes. A flow diagram for the process is provided in Figure 2.
The theoretical usage of SO2 in the process is 2.46 grams SO2 per gram of CN- oxidized, but in
practice the actual usage ranges from about 3.5 to 4.5 grams SO2 per gram of CN- oxidized. The
SO2 required in the reaction can be supplied either as liquid sulfur dioxide or as sodium
metabisulfite (Na2S2O5).
Oxygen (O2) is also required in the reaction and this is generally supplied by sparging
atmospheric air into the reaction vessels. The reaction is typically carried out at a pH of about
8.0 to 9.0 in one ore more agitated tanks, and lime is added to neutralize the acid (H+) formed in
the reaction to maintain the pH in this range. Lime usage is generally on the order of about 3.0
to 5.0 grams per gram of CN- oxidized. As indicated, copper (Cu+2) is required as a catalyst,
which is usually added as a solution of copper sulfate (CuSO4-5H20) to provide a copper
concentration in the range of about 10 to 50 mg/L. Upon completion of the indicated reaction,
metals previously complexed with cyanide, such as copper, nickel and zinc, are precipitated as
metal-hydroxide compounds.

Figure 2
Flow Diagram for the INCO SO2/Air Cyanide Destruction Process

Representative results for treatment of solution and slurry with the sulfur dioxide and air process
are shown in Table 1 (Ingles and Scott, 1987).
Table 1
Treatment Results Using the INCO Sulfur Dioxide/Air Process
Parameter Solution Slurry
(mg/L) Untreated Treated Untreated Treated
Total Cyanide 450 0.1 to 2.0 115 0.1 to 1.0
Copper 35 1 to 10 17 0.2 to 2.0
Iron 1.5 <0.5 0.7 0.02 to 0.3
Zinc 66 0.5 to 2.0 18 <0.01
This process is capable of achieving low levels of both cyanide and metals. Generally, the best
application of this process is with slurries containing low to moderately high initial levels of
cyanide when treated cyanide levels of less than about 1 to 5 mg/L are required. In some cases,
solutions treated with this process may be of suitable quality to permit their discharge.
3.2 Hydrogen Peroxide
The hydrogen peroxide treatment process chemistry is similar to that described for the INCO
process, but hydrogen peroxide is utilized rather than sulfur dioxide and air. With this process,
soluble copper is also required as a catalyst and the end product of the reaction is cyanate.
+2
H2O2 + CN- Cu
 Catalyst
-
→ OCN + H2O
The primary application of the hydrogen peroxide process is with solutions rather than slurries
due to the high consumption of hydrogen peroxide in slurry applications. The process is
typically applied to treat relatively low levels of cyanide to achieve cyanide levels that may be
suitable for discharge. The hydrogen peroxide process is effective for the treatment of solutions
for the oxidation of free and WAD cyanides, and iron cyanides are removed through
precipitation of insoluble copper-iron-cyanide complexes. As indicated in the above reaction,
hydrogen peroxide reacts to form cyanate and water, a process which limits the build-up of
dissolved solids in the solution being treated. A flow diagram for the process is provided in
Figure 3.
The theoretical usage of H2O2 in the process is 1.31 grams H2O2 per gram of CN- oxidized, but in
practice the actual usage ranges from about 2.0 to 8.0 grams H2O2 per gram of CN- oxidized.
The H2O2 used in the process is typically provided as a liquid in 50% strength.

Figure 3
Flow Diagram for the Hydrogen Peroxide Cyanide Destruction Process

The reaction is typically carried out at a pH of about 9.0 to 9.5 for optimal removal of cyanide
and metals such as copper, nickel and zinc. However, if iron cyanide must also be removed to
low levels, then the pH is lowered somewhat to increase the precipitation of copper-iron-
cyanides at the expense of lowering the removal efficiencies of copper, nickel and zinc. As
indicated, copper (Cu+2) is required as a soluble catalyst, which is usually added as a solution of
copper sulfate (CuSO4-5H20) to provide a copper concentration in the range of about 10% to
20% of the initial WAD cyanide concentration. Upon completion of the indicated reaction,
metals previously complexed with cyanide, such as copper, nickel and zinc, are precipitated as
metal-hydroxide compounds.
Representative results for treatment of solution with the hydrogen peroxide process are shown in
Table 2 (Smith and Mudder, 1991).
Table 2
Treatment Results Using the Hydrogen Peroxide Process
Parameter Solution
(mg/L) Untreated Treated
Total Cyanide 19 0.7
WAD Cyanide 19 0.7
Copper 20 0.4
Iron <0.1 <0.1
application of this process is with solutions containing relatively low initial levels of cyanide
when treated cyanide levels of less than about 1 mg/L are required. Oftentimes, solutions treated
with this process may be of suitable quality to permit their discharge.
3.3 Caro’s Acid
Peroxymonosulfuric acid (H2SO5), also known as Caro’s acid, is a reagent used in a recently
developed cyanide treatment process that has found application at a few sites.
H2SO5 + CN- → OCN- + SO4-2 + 2H+
Caro’s acid used in the process must be produced on-site using sulfuric acid and hydrogen
peroxide since Caro’s acid decomposes rather quickly (Norcross, 1996). Caro’s acid is used in
slurry treatment applications where the addition of a copper catalyst is not desirable, which is
typically only in situations where the sulfur dioxide and air process is not suited. In solution
applications, other destruction processes, such as the hydrogen peroxide process, are preferred to
the Caro’s acid process. A flow diagram for the process is provided in Figure 4.

Hydrogen Peroxide Lime
Caro's Acid
Reactor
pH
M
Tailings Slurry Treated Slurry
Sulfuric Acid
Agitated Reaction Tank
Figure 4
Flow Diagram for the Caro’s Acid Cyanide Destruction Process

The theoretical usage of H2SO5 in the process is 4.39 grams H2SO5 per gram of cyanide
oxidized, but in practice 5.0 to 15.0 grams H2SO5 per gram of cyanide oxidized is required. Acid
produced in the reaction (H+) is typically neutralized with lime.
Full-scale results for treatment of mill tailings slurry with Caro’s acid were presented by
Castrantas et al. (1993, 1995a and 1995b) and are summarized in Table 3. Caro’s acid can also
be used to oxidize cyanide in clear solutions, but with clear solutions other treatment
technologies may be preferred based on economics (Castrantas and Manganaro, 1994).
Table 3
Slurry Treatment Results Using Caro’s Acid
Untreated Slurry Treated Slurry
Test Mole Ratio Caro’s Acid
WAD Cyanide WAD Cyanide
No. to WAD Cyanide
(mg/L) (mg/L)
1 1.12 44.5 8.5
2 2.90 37.5 4.2
3 0.57 46.0 14.0
4 2.80 39.8 4.0
5 0.66 115.0 27.1
6 1.07 113.1 16.3
7 0.78 101.5 18.7
3.4 Alkaline Chlorination
Alkaline chlorination at one time was the most widely applied of the cyanide treatment
processes, but it has gradually been replaced by other processes and is now only used
occasionally. Alkaline chlorination is effective at treating cyanide to low levels, but the process
can be relatively expensive to operate due to high reagent usages. The cyanide destruction
reaction is two-step, the first step in which cyanide is converted to cyanogen chloride (CNCl)
and the second step in which cyanogen chloride hydrolyzes to yield cyanate.
Cl2 + CN- → CNCl + Cl-
CNCl + H2O → OCN- + Cl- + 2H+
In the presence of a slight excess of chlorine, cyanate is further hydrolyzed to yield ammonia in a
catalytic type of reaction.
OCN- + 3H2O Cl

2 Catalyst

+ -
→ NH4 + HCO3 + OH
-
If sufficient excess chlorine is available, the reaction continues through ‘breakpoint chlorination’
in which ammonia is fully oxidized to nitrogen gas (N2).
3Cl2 + 2NH4+ → N2 + 6Cl- + 8H+

In addition to reacting with cyanide, cyanate and ammonia, the alkaline chlorination process will
oxidize thiocyanate, which in some cases can lead to excessively high consumptions of chlorine.
4Cl2 + SCN- + 5H2O → SO4-2 + OCN- + 8Cl- + 10H+
The primary application of the alkaline chlorination process is with solutions rather than slurries
due to the high consumption of chlorine in slurry applications. The process is typically applied
to treat low solutions flows initially containing low to high levels of cyanide to achieve cyanide
levels that may be suitable for discharge. The process is effective for the treatment of solutions
for the oxidation of free and WAD cyanides, but a lesser amount of iron cyanides are removed
depending on the levels of other base metals in the solution being treated. As can be seen in the
above reactions, a significant increase in the treated water dissolved solids concentration may
result, particularly with chloride.
The theoretical usage of Cl2 to oxidize cyanide to cyanate is 2.73 grams Cl2 per gram of CN-
oxidized, but in practice the actual usage ranges from about 3.0 to 8.0 grams Cl2 per gram of CN-
oxidized. The Cl2 used in the process can be provided as a liquid Cl2 or as a 12.5% solution of
sodium hypochlorite (NaOCl). Chlorine consumptions for the oxidation of ammonia and
thiocyanate can be calculated from the above reactions, which may significantly add to chlorine
required in the process. In addition, the above reactions generate varying amounts of acid (H+)
which is typically neutralized by adding lime or sodium hydroxide to the reaction vessels.
The reaction is carried out at a pH of greater than 10.0 to ensure cyanogen chloride is completely
hydrolyzed to cyanate. An advantage of the process is that copper is not required as a catalyst as
with the sulfur dioxide/air and hydrogen peroxide processes. Upon completion of the cyanide
oxidation reaction, metals previously complexed with cyanide, such as copper, nickel and zinc,
are precipitated as metal-hydroxide compounds.
Representative results for treatment of solution via alkaline chlorination are shown in Table 4
(Ingles and Scott, 1987).
Table 4
Treatment Results Using the Alkaline Chlorination Process
Parameter Solution
(mg/L)
Untreated Treated
Total Cyanide 2,000 8.3
WAD Cyanide 1,900 0.7
Copper 290 5.0
Iron 2.4 2.8
Zinc 740 3.9

application of this process is with low flows of solutions containing high to low initial levels of
cyanide when treated cyanide levels of less than about 1 mg/L are required. Oftentimes,
solutions treated with this process may be of suitable quality to permit their discharge.
3.5 Iron-Cyanide Precipitation
Free, WAD and total cyanides will all react with ferrous iron to yield a variety of soluble and
insoluble compounds, primarily hexacyanoferrate (III) (Fe(CN)6-3), Prussian blue
(Fe4[Fe(CN)6]3) and other insoluble metal-iron-cyanide (MXFeY(CN)6) compounds such as those
with copper or zinc (Adams, 1992).
Fe+2 + 6CN- + ¼O2 + H+ → Fe(CN)6-3 + ½H 2 O
4Fe+2 + 3Fe(CN)6-3 + ¼O2 + H+ → Fe4[Fe(CN)6]3 + ½H 2 O
The iron-cyanide precipitation process is limited in its suitability to situations where the
precipitation reactions can be controlled and the precipitated solids can be separated and properly
disposed. In the past, this process was widely used to convert free and WAD cyanides to less
toxic iron-cyanide compounds, but its present utility is primarily as a polishing process to reduce
total cyanide concentrations to less than about 1 to 5 mg/L.
The process is optimally carried out at a pH of about 5.0 to 6.0 and iron is added as ferrous
sulfate (FeSO4-7H2O). Ferrous sulfate usage ranges from about 0.5 to 5.0 moles Fe per mole of
CN- depending on the desired level of treatment (Adams, 1992 and Dzombak et al., 1996).
As indicated in Table 5, the iron-cyanide precipitation process is capable of achieving relatively

low levels of total cyanide at pH 7.0 and an Fe:CN molar ratio of about 4:1 (Dzombak et al.,
1996).
Table 5
Treatment Results Using the Iron-Cyanide Precipitation Process
Parameter Solution
Total Cyanide 8.8 0.89

3.6 Activated Carbon Polishing
Activated carbon has a relatively high affinity for many metal-cyanide compounds, including the
soluble cyanide compounds of copper, iron, nickel and zinc. Activated carbon is suitable for use
as a polishing treatment process to remove cyanide to relatively low levels. This is a simple and
effective process, convenient for installation at sites where activated carbon is used in
metallurgical processes for precious metals recovery.
Representative results for treatment of solution using activated carbon adsorption are shown in
Table 6 (Botz and Mudder, 1997).
Table 6
Treatment Results Using the Activated Carbon Adsorption Process
Parameter Solution
Total Cyanide 0.98 0.20
Copper 0.02 <0.02
Iron 0.22 0.02
Nickel 0.15 0.15
Zinc 0.02 <0.02
3.7 Biological Treatment
Biological treatment processes have recently become more widespread in the mining industry
due to the success of the plant installed at Homestake Lead, USA in the 1980’s (Mudder et al.,
1998a). In this plant, an aerobic attached growth biological treatment is used to remove cyanide,
thiocyanate, cyanate, ammonia and metals from tailings impoundment decant solution prior to
discharge into a trout fishery. The plant has been operating successfully for over fifteen years,
producing high-quality effluent.
A passive biological treatment plant was installed by Homestake Nickel Plate, Canada in the
mid-1990’s to treat tailings impoundment seepage (Given, 2001). This plant is a suspended
sludge system with both aerobic and anaerobic treatment sections to remove cyanide,
thiocyanate, cyanate, ammonia, nitrate and metals.
Another biological treatment process was developed for the Homestake Santa Fe, USA mine to
treat draindown from the decommissioned heap leach operation (Mudder et al., 1998b). This
process, known as the Biopass process, is suitable for solution flows of less than about 10
m3/hour for the removal of cyanide, thiocyanate, cyanate, ammonia, nitrate and metals.

The applicability of biological processes for the treatment of cyanide solutions in the mining
industry is somewhat limited, but in certain situations they are the optimal selection. Their
applicability is primarily in with continuous solution flows with temperatures above about 10oC.
Representative results from the above three biological treatment plants are presented in Table 7
(Given, 2001; Mudder et al., 1998a, Mudder et al., 1998b).
Table 7
Treatment Results Using Biological Processes
Parameter Lead Nickel Plate Santa Fe
(mg/L) Untreated Treated Untreated Treated Untreated Treated
Total Cyanide 3.39 0.37 1.04 0.44 -- --
WAD Cyanide 2.34 0.03 0.33 0.04 14 <0.2
Thiocyanate -- -- 379 0.08 -- --
Ammonia 5.31 0.27 25.3 0.15 -- --
Nitrate -- 21.9 2.8 0.13 55.6 0.8
Copper 0.49 0.04 0.02 0.005 10.3 <0.5
Iron 0.1 to 5.0 0.27 0.06 0.02 -- --
Nickel 0.01 to 0.04 0.03 -- -- -- --
Zinc 0.01 to 0.1 0.01 -- -- -- --
4.0 CYANIDE RECOVERY
A number of cyanide recovery processes have been investigated over the previous one hundred
years, but only two have found widespread application.
4.1 Stripping and Recovery
The stripping and recovery approach to recovering cyanide, also known as the acidification-
volatilization-reneutralization (AVR) and Cyanisorb processes, remove cyanide from solution as
hydrogen cyanide gas. At a pH of less than about 8.0, free cyanide and some WAD cyanide
compounds are converted to hydrogen cyanide gas, which can then be air-stripped from solution.
Once removed from solution as hydrogen cyanide gas, the hydrogen cyanide is easily absorbed
into an alkaline solution of sodium hydroxide.
The three main reactions involved with the cyanide recovery process are as follows.
(acidification) 2CN- + H2SO4 → 2HCN(aq) + 2SO4-2
(stripping) HCN(aq) → HCN(g)
(absorption) HCN(g) + NaOH → NaCN + H2O

This basic process has been used at about ten sites worldwide to affect WAD cyanide recoveries
ranging from about 70% to over 95% with both slurries and solutions (Moura, 2001; Goldstone
& Mudder, 1998; Botz et al., 1995 and Omofoma and Hampton, 1992). Its application is
primarily with solutions or slurries with moderate to high concentrations of cyanide under both
high and low-flow conditions. The presence of dissolved copper in untreated solution can cause
difficulties with conventional cyanide recovery processes, and in some cases pre-treatment of the
solution with sodium sulfide (Na2S) may be required to precipitate copper sulfide (Cu2S) prior to
cyanide recovery. A flow diagram for the process is provided in Figure 5.
Table 8 lists representative treatment results from several cyanide recovery processes (Moura,
2001; Goldstone & Mudder, 1998; Omofoma and Hampton, 1992).
Table 8
Treatment Results Using the Acidification & Stripping Cyanide Recovery Process
Plant WAD Cyanide (mg/L)
Untreated Treated % Recovery
Golden Cross, New Zealand
~250 <30 85% to 90%
(Slurry)
DeLamar, USA
~300 <25 >90%
(Solution)
Cerro Vanguardia, Argentina
~300 <30 >90%
(Solution)
4.2 Water Recycle
Cyanide can effectively be recovered and re-used by recycling cyanide-containing solutions

within a metallurgical circuit. This is commonly conducted using tailings thickeners or tailings
filters to separate solution from tailings solids, with the solution being recycled in the grinding
and/or leaching circuits. This approach to recovering cyanide should be evaluated for all
operations utilizing cyanide, and its performance can be determined by a simple mass balance
calculation.

Clean Gas
HCN Rich Gas
NaOH Feed
Two Two
Stripping Absorption
Towers Towers
Sulfuric Acid
pH
CIL Air
Tailings
Slurry Recovered NaCN
One Fan Per
One Acidification Tank Stripping Tower
Stripped Slurry
Lime
pH
Treated Slurry
To Tailings Impoundment
One Neutralisation Tank
Figure 5
Flow Diagram for the Cyanide Recovery Process

5.0 NATURAL CYANIDE ATTENUATION
It is well known that cyanide solutions placed in ponds or tailings impoundments undergo natural
attenuation reactions which result in the lowering of the cyanide concentration. These
attenuation reactions are dominated by natural volatilization of hydrogen cyanide, but other
reactions such as oxidation, hydrolysis, photolysis and precipitation also occur. Natural cyanide
attenuation occurs with all cyanide solutions exposed to the atmosphere, whether intended or not.
At several sites, ponds or tailings impoundments are intentionally designed to maximize the rate
of cyanide attenuation, and in some cases resultant solutions are suitable for discharge.
Two approaches have been developed to predict the rate of cyanide attenuation in ponds and
tailings impoundments. The first method is empirical in nature and uses experimentally derived
rate coefficients to estimate the rate of attenuation using a first order decay equation (Simovic et
al., 1985). This approach is relatively simple to apply, but its applicability at a given site must be
verified by conducting field testwork and the results may not be accurate under changing
weather, pond/impoundment geometry or chemistry conditions.
The second approach to modeling natural cyanide attenuation was developed by Botz and
Mudder (2000). This approach utilizes detailed solution chemical equilibria and kinetic
calculations to predict the rate of cyanide losses from ponds and impoundments through a variety
of reactions. This approach can be time-intensive to apply at a given site, but the results are
accurate under a wide variety of weather, pond/impoundment geometry and chemistry
conditions.
An example of the use of natural attenuation would be with a cyanide recovery facility where
solution or slurry with a cyanide concentration of about 20 mg/L is placed into a lined pond or
impoundment. The lined pond or impoundment could then be designed to maximize natural
attenuation such that the resultant cyanide concentration would be less than about 1 mg/L.
6.0 SUMMARY
As indicated in the previous discussion, there are over ten cyanide treatment processes that have
been successfully used worldwide for cyanide removal at mining operations. The key to
successful implementation of these processes is by considering the following:
• Site water and cyanide balances under both average and extreme climatic conditions
• The range of cyanide treatment processes available and their ability to be used individually
or in combination to achieve treatment objectives
• Proper testing, design, construction, maintenance and monitoring of both water

management and cyanide management facilities

By carefully considering these aspects of water and cyanide management before, during and after
mine operation, operators can reduce the potential for environmental impacts associated with the
use of cyanide.
Another aspect of cyanide treatment to be considered is the potential environmental impact of the
cyanide related compounds cyanate, thiocyanate, ammonia and nitrate. These compounds may
be present in mining solutions to varying extents and may require treatment if water is to be
discharged. Each of these cyanide related compounds is affected differently in the treatment
processes discussed and this should be considered when evaluating cyanide treatment
alternatives for a given site.
Table 9 provides a simplified summary of the general applications of various treatment

technologies for the removal of cyanide and its related compounds cyanate, thiocyanate,
ammonia and nitrate. This table represents a very simplified summary, but can be used as a
conceptual screening tool when evaluation cyanide treatment processes.
Table 9
Preliminary Selection Guide for Cyanide Treatment Processes
Iron WAD
Slurry Solution
Treatment Process Cyanide Cyanide
Application Application
Removal Removal
SO2/Air P P P P
Hydrogen Peroxide P P P
Caro’s Acid P P
Alkaline Chlorination P P P
Iron Precipitation P P P P
Activated Carbon P P P
Biological P P P
Cyanide Recovery P P P
Natural Attenuation P P P P

7.0 REFERENCES
Adams, M.D., “The Removal of Cyanide from Aqueous Solution by the Use of Ferrous
Sulphate”, Journal of the South African Institute Mining & Metallurgy, Vol. 92, No. 1, pp. 17-
25, January, 1992.
Botz, M.M. and Mudder, T.I., “Mine Water Treatment with Activated Carbon”, Proceedings
Randol Gold Forum, pp. 207-210, 1997.
Botz, M.M. and Mudder, T.I., “Modeling of Natural Cyanide Attenuation in Tailings
Impoundments”, Minerals and Metallurgical Processing, Vol. 17, No. 4, pp. 228-233, November,
2000.
Botz, M.M., Stevenson, J.A., Wilder, A.L., Richins, R.T., Mudder, T.I. and Burdett, B.,
“Cyanide Recovery & Destruction”, Engineering & Mining Journal, pp. 44-47, June, 1995.
Castrantas, H.M., Manganaro, J.L., Rautiola, C.W. and Carmichael, J., “The Caro’s Acid
Detoxification of Cyanide in a Gold Mine Tailings Pond – A Plant Demonstration” Proceedings
Randol Gold Forum, Beaver Creek, Colorado, pp. 337-342, 1993.
Castrantas, H.M. and Manganaro, J.L., “Hydrogen Peroxide and Caro’s Acid, Powerful Oxidants
for Cyanide Destruction, A Review and Case Study”, Proceedings Chemical Oxidation
Conference, Technologies for the Nineties, Vanderbilt University, Nashville, Tennessee,
February, 1994.
Castrantas, H.M., Manganaro, J.L., Mikida, R.J. and Carmichael, J., “Caro’s Acid the Low Cost
Oxidant for CN- Detoxification Attains Commercial Status”, Proceedings of the SME Annual
Meeting, Denver, Colorado, March, 1995a.
Castrantas, H.M., Manganaro, J.L., Rautiola, C.W. and Carmichael, J., “Treatment of Cyanides
in Effluents with Caro’s Acid”, U.S. Patent 5,397,482, 1995b.
Dzombak, D.A., Dobbs, C.L., Culleiton, C.J., Smith, J.R. and Krause, D., “Removal of Cyanide
from Spent Potlining Leachate by Iron Cyanide Precipitation”, Proceedings WEFTEC 69th
Annual Conference & Exposition, Dallas, Texas, 1996.
Given, B., Homestake Nickel Plate Mine, Private Communication, 2001.
Goldstone, A., and Mudder, T.I., “Cyanisorb Cyanide Recovery Process Design, Commissioning
and Early Performance”, In The Cyanide Monograph, Mining Journal Books Limited, London,
1998.
Ingles, J. and Scott, J.S., State-of-the-Art of Processes for the Treatment of Gold Mill Effluents,
Environment Canada, March, 1987.
Moura, W., AngloGold South America, Private Communication, 2001.

Mudder, T.I., Fox, F., Whitlock, J., Fero, T., Smith, G. Waterland, R. and Vietl, J., “Biological
Treatment of Cyanidation Wastewaters: Design, Startup, and Operation of a Full Scale Facility”,
In The Cyanide Monograph, Mining Journal Books Limited, London, 1998a.
Mudder, T.I., Miller, S., Cox, A., McWharter, D. and Russell, L., “The Biopass System: Phase I
Laboratory Evaluation”, In The Cyanide Monograph, Mining Journal Books Limited, London,
1998b.
Norcross, R., “New Developments in Caro’s Acid Technology for Cyanide Destruction”,
Proceedings of Randol Gold Forum, pp. 175-177, 1996.
Omofoma, M.A. and Hampton, A.P., “Cyanide Recovery in a CCD Merrill-Crowe Circuit: Pilot
Testwork of a Cyanisorb Process at the NERCO DeLamar Silver Mine”, Proceedings Randol
Gold Forum, pp. 359-365, 1992.
Simovic, L., Snodgrass, W., Murphy, K. and Schmidt, J. "Development of a Model to Describe
the Natural Attenuation of Cyanide in Gold Mill Effluents", Cyanide and the Environment Vol.
II, Colorado State University, pp. 413-432, 1985.
Smith, A.C.S. and Mudder, T.I., Chemistry and Treatment of Cyanidation Wastes, Mining
Journal Books Limited, London, 1991.

MINE WATER TREATMENT WITH ACTIVATED CARBON
Prepared By:

T. I. Mudder, Ph.D.
Originally presented at Randol Gold Forum, Monterey, California, May 18-21, 1997
Mine Water Treatment with Activated Carbon
1.0 INTRODUCTION
Discharge limitations for mine waters often require low concentrations for cyanide and metals,
and the trend is these limits to be lowered. In the event conventional treatment processes are not
sufficient to meet discharge regulations, advanced treatment technologies such as ion exchange
and reverse osmosis may be considered. Though these technologies can provide discharge quality
waters, they also require the disposal of a concentrated brine, are complex, and costly to operate.
At many mine sites, activated carbon can be included in the category of advanced treatment
technologies for polishing of effluents. Further, many mine sites currently using activated carbon
in precious metals recovery present the opportunity to economically operate an activated carbon
water treatment plant. This paper presents summaries of six (6) mining operations which have
evaluated or use activated carbon for treatment of water and which also use carbon in precious
metals recovery processes.
2.0 WHY ACTIVATED CARBON
At many gold and silver mining operations, granular activated carbon is used to adsorb precious
metals leached via cyanidation. The activated carbon systems at these operations consist of
carbon-in-pulp (CIP), carbon-in-leach (CIL) and/or carbon-in-column (CIC) circuits in which the
gold and/or silver pregnant solution is contacted with activated carbon to affect adsorption of
metal-cyanide species from the liquid phase. The resultant barren solution is recycled within the
mill or discharged into a tailings impoundment, while the carbon is processed for recovery of
adsorbed precious metals.
While most of the activated carbon is reused within the mill following regeneration, new carbon
must be periodically added to the circuit to make up for attrition losses. As a result of new
carbon purchases and regeneration of carbon on-site, a typical mill often handles many tons of
highly active carbon each day. This fresh carbon is ideal for use in polishing of mine waters which
require advanced treatment prior to discharge from the mine site. Following its use in treating
mine waters, the carbon can be returned to the mill for use in CIP, CIL and/or CIC circuits
without a loss of precious metals loading efficiency.
In addition to affecting excellent removal of many dissolved species, the use of activated carbon
to treat mine waters is particularly advantageous at mills containing CIP, CIL and/or CIC circuits
since:
1. These mills will contain complete facilities required for receiving, storing and regenerating
activated carbon, eliminating the need for off-site disposal or regeneration of carbon.
2. Use of an activated carbon treatment plant at these sites will not require unfamiliar or
complex equipment. The treatment equipment would be substantially identical to that
used in a CIP, CIL and/or CIC circuit and can easily be incorporated into the design and
operation of existing or proposed facilities.
Activated carbon can be used to remove cyanide and metals such as cadmium, copper, mercury,

and silver from these waters. The selectivity of carbon for these metal-cyanide species and the
percent removals are site specific and determined through laboratory or pilot tests. With activated
carbon, the presence of cyanide in the water increases metals removal due to the affinity of carbon
for metal-cyanide complexes.
3.0 CASE STUDIES
The following case studies provide performance summaries for laboratory, pilot and full-scale
operations which used activated carbon for removal of cyanide and metals from mine waters.
Site 1 In 1996 a gold and silver mine installed four (4) carbon columns to treat up to 500 gpm of
tailings impoundment decant water for removal of residual copper and weak acid dissociable
(WAD) cyanide. Further treatment of the water following cyanide destruction using hydrogen
peroxide is required to meet very stringent discharge regulations for the receiving water, which is
a trout fishery. Spent carbon from the treatment plant is returned to the CIL circuit, with no loss
in the adsorptive capacity of the carbon having been reported. A summary of carbon column
performance for four (4) months in 1996 for treatment of 400 to 480 gpm of water is presented in
Table 1.
Table 1
Treatment of Effluent from a
Hydrogen Peroxide Treatment Plant
Influent Effluent
Copper
0.15 0.02
(mg/L)
WAD Cyanide
0.12 0.04
(mg/L as CN)
The mass ratio of WAD cyanide to copper in the influent water is 0.80:1, nearly identical to the
-
theoretical ratio of 0.82:1 for the Cu(CN)2 complex. It is likely that the high removal of the
-
copper and cyanide is a result of the strong affinity of activated carbon to adsorb Cu(CN)2 .
In the treatment of mine waters containing both copper and cyanide, the cyanide concentration is
-
usually reduced to a point that the remaining copper and cyanide are present as Cu(CN)2 . This
complex can then be easily removed from solution with activated carbon to yield low
concentrations of both cyanide and copper in treated water. A similar process for removal of
cyanide from petroleum refinery waste water has been employed by adding copper chloride to
- 1
solution to form Cu(CN)2 prior to activated carbon treatment.
Site 2 In the mid-1980's a U.S. silver mine conducted laboratory tests with activated carbon to
determine the removal efficiencies of cyanide, copper, mercury, silver, selenium and zinc from
Merrill-Crowe barren solution. A summary of the test results is presented in Table 2.

Table 2
Treatment of Merrill-Crowe Barren Solution
Influent Effluent
Total Cyanide
1.7 0.05
(mg/L as CN)
Copper
0.39 0.02
(mg/L)
Mercury
0.014 <0.005
(mg/L)
Silver
0.90 0.04
(mg/L)
Zinc
0.09 0.09
(mg/L)
As indicated in Table 2, approximately 95% each of total cyanide, copper and silver were
removed from the water. In addition, mercury was removed to below the detection limit.
However, zinc removal was poor due to the very low initial concentration.
Site 3 In 1996 a U.S. gold and silver mine conducted laboratory tests using activated carbon to
remove iron-cyanide and mercury from tailings impoundment seepage water. Greater than 95%
of the cyanide in the water was present as iron-cyanide, therefore all cyanide analyses were
conducted for total cyanide. A summary of the test results is presented in Table 3 based on
average results from eighteen (18) tests with three (3) brands of carbon.
Table 3
Treatment of Tailings Impoundment Seepage Water
Influent Effluent
Total Cyanide
0.87 0.01
(mg/L as CN)
Mercury
0.27 <0.2
(µg/L)
The test results indicated that greater than 95% of iron-cyanide could be removed and that
mercury could consistently be reduced to less than 0.2 µg/L. In response to the anticipated need
to discharge the water from the site within approximately one (1) year and the positive laboratory
test results, the site constructed a plant in late-1996 to treat 350 gpm of tailings impoundment
seepage water. Spent carbon from the treatment plant will be directed to the existing CIP circuit
at the site for continued use and carbon regenerated in the mill will be used as feed carbon for the
water treatment plant.
Site 4 In 1982 a U.S. gold and silver mining operation conducted pilot tests with activated

carbon to determine removal efficiencies of cyanide, thiocyanate, iron, copper, nickel and zinc
from biologically treated tailings impoundment water. Results of the tests are summarized in
Table 4.
Table 4
Treatment of Biologically Treated
Tailings Impoundment Decant Solution
Influent Effluent
Total Cyanide
0.98 0.20
(mg/L as CN)
Free Cyanide
0.70 0.02
(mg/L as CN)
Thiocyanate
0.72 0.53
(mg/L)
Iron
0.22 0.02
(mg/L)
Copper
0.02 <0.02
(mg/L)
Nickel
0.15 0.15
(mg/L)
Zinc
0.02 <0.02
(mg/L)
As indicated in Table 4, approximately 80% of total cyanide, greater than 95% of free cyanide and
90% of iron were removed from the water. Due to the relatively low influent concentrations of
copper and zinc, the percent removals are difficult to quantify, however the removals likely
parallel that presented for Sites 1 and 2. Removals of thiocyanate and nickel were low indicating
that activated carbon would likely not be effective with these species.
Site 5 In 1996 a South American gold and silver mining operation proceeded with installation of
a CIC circuit to treat filtered CIL tailings pulp prior to discharge into a tailings impoundment.
The barren solution will be at a pH of approximately 5.0 as it exits the upstream cyanide recovery
plant and the improved recovery of gold at this pH prompted consideration of the CIC circuit. At
a pH of 5.0, the gold loading capacity of activated carbon is increased by approximately 20% and
2
the gold loading rate is increased by approximately 30% relative to a pH of 11.0. While the
primary purpose of the CIC circuit will be to remove residual copper from solution, it is
anticipated that up to 1,500 troy ounces of gold per year will be recovered as a result of operation
at the relatively low pH. Spent carbon from the CIC circuit will be directed to the existing CIL
circuit at the site for continued use.

Site 6 In 1994 a U.S. heap leach operation pilot tested the use of activated carbon to polish rinse
solution following treatment with hydrogen peroxide to remove cyanide. Treatment of the
solution was conducted to achieve less than 0.2 mg/L WAD cyanide and 1.0 mg/L copper prior to
land application. Results of the pilot test conducted at 3 gpm over five (5) days are summarized
in Table 5.
Table 5
Treatment of Heap Leach Rinse Solution
Pilot Tests
Influent Effluent
Copper
14.4 0.02
(mg/L)
WAD Cyanide
1.08 0.10
(mg/L as CN)
In response to the demonstrated effectiveness of activated carbon at the pilot stage, the site
purchased eight (8) carbon columns to treat approximately 1.6 million gallons of rinse solution.
Average results of the full-scale treatment operation which lasted approximately seven (7) weeks
are summarized in Table 6.
Table 6
Treatment of Heap Leach Rinse Solution
Full-Scale Operation
Influent Effluent
Copper
3.17 0.18
(mg/L)
WAD Cyanide
5.53 0.06
(mg/L as CN)
The full-scale carbon columns operated with an efficiency similar to that observed in the pilot
operation, though the effluent copper concentration was higher than expected in the full-scale.
The carbon columns were successfully operated and generated 1.6 million gallons of water
suitable for land application at the site.

4.0 COSTS
Operation of an activated carbon treatment plant at a mine site currently operating a CIP, CIL
and/or CIC circuit will not require a significant operations budget as the equipment is simple in
operation and existing inventories of carbon can be used. In the range of 50 to 500 gpm
treatment plant capacity, the constructed plant cost, including carbon columns, a heated structure
and piping, is approximately $30,000 for each 100 gpm to be treated. For example, the
constructed cost for a 350 gpm treatment plant would be approximately $105,000. However, due
to the high degree of variability in construction requirements from site to site, this estimate serves
only as an order-of-magnitude estimate to permit a quick preliminary economic evaluation of an
activated carbon treatment plant.
5.0 PROCESS DESIGN
Following a review of process conditions present at the six (6) sites, the following are
recommended for process design parameters. The recommendations apply to granular activated
carbon systems for removal of cyanide and metals.
Residence Time: The total hydraulic residence time in the carbon columns should be in the
range of 10 to 30 minutes. In calculating the required carbon column
volume, the space occupied by the carbon should not be ignored. For
static carbon beds, the void space (porosity) generally ranges from 25% to
30%, with the bulk density of carbon generally in the range of 25 to 35
pounds per cubic foot.
Carbon Type: Several types of granular carbon were employed in the testwork, though a
significant difference among manufacturers was not observed. Included in
one (1) test was sulfur impregnated carbon, which performed similarly to
standard carbons even in the removal of mercury. For consistency with
most mill operations, standard granular carbon in the size range of 6 to 20
mesh is recommended.
pH: The data for the six (6) sites corresponds to a feed water pH in the range of
7 to 10, with no significant change in pH occurring as the result of carbon
1,2,3
treatment. Previous publications note an increase in both loading and
the kinetics of adsorption at lower pH values. Operation at a pH of less
10.0 is recommended.
Vessel Sizing: Several vendors are available to provide both static carbon beds and those
operating in teeter conditions similar to mill operations. For static beds, an
upflow configuration is recommended. A minimum 24-inch depth of
carbon in a static bed of is recommended. If backwashing of static carbon
beds is anticipated due to suspended solids in the feed water, approximately
50% to 100% freeboard should be provided in the vessel.

The ability of activated carbon to remove cyanide and metals from water is dependent upon the
forms and concentrations of target species in feed water and required effluent concentrations.
Prior to operation of a full-scale carbon system for treatment of cyanide and/or metal-containing
water, laboratory or pilot tests should be conducted to estimate system performance. In addition,
the tests will permit estimation of the volume of carbon required to affect treatment.
6.0 REFERENCES
1. Cyanide Removal from Refinery Wastewater Using Powdered Activated Carbon, NTIS
Document PB80-211469, 1980.
2. Marsden, J., I. House, The Chemistry of Gold Extraction, Ellis Horwood, New York,
1993.
3. An Investigation of Techniques for Removal of Cyanide from Electroplating Wastes,

Water Pollution Control Research Series, USEPA Document 12010 EIE, 1971.

OVERVIEW OF WATER TREATMENT METHODS
FOR THIOCYANATE REMOVAL
Prepared By:

Originally presented at the Randol Gold & Silver Forum, Denver, Colorado, April 26-29, 1998
Overview of Water Treatment Methods for Thiocyanate Removal
1.0 INTRODUCTION
The formation of thiocyanate (SCN-) through the reaction of free cyanide with various sulfur
containing species present in precious metals ores and process solutions is common during
beneficiation. The formation of thiocyanate is considered a nuisance side reaction with adverse
impacts on the effectiveness of gold recovery and the consumption of cyanide. With respect to
toxicity and environmental issues, the presence of thiocyanate in treated effluents has not been of
regulatory concern.
In conjunction with the processing of refractory sulfide ores has been the emergence of
alternative lixiviants coupled with biological oxidation of reduced sulfides to initiate and
enhance the recovery of gold. The use of biological oxidation of sulfide containing or refractory
ores is a pre-treatment step often referred to as the "biox" process. It has been known for some
time that cyanide and thiocyanate are potentially toxic to the sulfur oxidizing bacteria
responsible for bio-oxidation and can interfere with the recovery of gold from carbonaceous ores
through a process known as "preg-robbing". Preg-robbing occurs through sorption of both gold
thiocyanate and cyanide complexes onto the natural carbonaceous matter within the ore matrix.
The toxicity of thiocyanate to these microorganisms has been noted at concentrations of only 5
mg/l or less (Hackl and Wright, 1989). Over time other researchers and metallurgists have also
reported toxic or inhibitory effects of thiocyanate on sulfur bacteria.
It may be advantageous in certain instances to remove both the residual thiocyanate and cyanide
from recycled process solutions associated with biological oxidation and carbonaceous ores.
Although the unit operations utilized for the destruction or recovery of cyanide are well known,
those available for removal of thiocyanate typically are not. The purpose of this paper is provide
a general overview of the various thiocyanate removal technologies with a limited discussion of
relative performance, ease of operation, reliability, and cost.
2.0 CHEMICAL TREATMENT ALTERNATIVES
There are only a few chemical, physical, and biological treatment processes capable of
simultaneous removal of thiocyanate and cyanide from process solutions. The traditional and
most widely employed chemical oxidation technologies based upon hydrogen peroxide, or sulfur
dioxide or sodium sulfite (i.e. the INCO process) do not completely destroy thiocyanate. Both
processes routinely remove between about 10-20% of the thiocyanate, with the INCO process
being able to achieve the higher removal percentage with some modification.
Interestingly, ozone actually creates cyanide from thiocyanate initially during oxidation (Soto, et.
al, 1995 and Layne, et. al, 1984). The production of cyanide during ozonation is a problem in
that it too is toxic to the sulfur bacteria and one must be careful to take ozonation to completion.
The formation of cyanide creates an additional demand for ozone, which is an expensive
chemical reagent generated from either atmospheric or pure oxygen.

From a chemical oxidation standpoint, both alkaline chlorination and chlorine dioxide are
capable of completely destroying cyanide, thiocyanate, and other sulfur containing species at
initial concentrations of over 1,000 mg/l down to levels well below 5 mg/l (Wood, 1995; Smith
and Mudder, 1995; and White, 1986). If necessary, the traditional alkaline chlorination process
can be taken to the "breakpoint" to remove ammonia and other nitrogen species as well.
Alkaline chlorination is the oldest cyanide oxidation and destruction process, being applied
originally in the electroplating industry. The process is usually conducted in a series of complete
mix reactors operated at a pH of about 11.0 to avoid the accumulation of cyanogen chloride
(CNCl), which forms during the first step of alkaline chlorination as shown below:
1. NaCN + Cl2 = CNCl + NaCl
The intermediate cyanogen chloride is toxic but is rapidly hydrolyzed to cyanate at the elevated
pH according to the following reaction:
2. CNCl + 2NaOH = NaCNO + NaCl + H2O
The requirement for an elevated pH and the addition of base provides the basis for the name of
the process. The first stage of the process requires about 15 minutes. The second stage of the
process involves hydrolysis of the cyanate to ammonia and carbonate according to the following
reaction:
3. 2NaCNO + 4H2O = (NH4)2CO3 + Na2CO3
The hydrolysis requires about 1.0-1.5 hours, although reaction periods of several hours are
sometimes necessary. If excess oxidant is added the ammonia can be converted to nitrogen gas
through a modification of the process known as "breakpoint" chlorination according to the
following reaction:
4. (NH4)2CO3 + 3Cl2 + 6NaOH + Na2CO3 = N2 + 6NaCl + 2NaHCO3 + 6H2O
If ammonia removal is not needed alkaline chlorination would be restricted to the oxidation and
destruction of cyanide and thiocyanate according to the following overall equations:
5. NaCN + Cl2 + Ca(OH)2 = NaCNO + Ca(Cl)2 + H2O
6. 2NaSCN + 8Cl2 + 10Ca(OH)2 = 2NaCNO + 2CaSO4 + 8Ca(Cl)2 + 10H2O
It should be keep in mind that the addition of large quantities of lime needed during alkaline
chlorination of excess process or reclaim solution can lead to oversaturation of calcium sulfate
and resultant precipitation of large quantities of gypsum. As part of deriving a site water balance
and water management system, the impact of elevated calcium and sulfate levels in various
process solutions should be examined using a mass balance superimposed upon the hydrological
balance. The other major chemical disadvantage of alkaline chlorination is the production of
high residual chloride levels ranging into the hundreds of mg/l.

Based upon Equations 5 and 6, the theoretical quantity of chlorine needed to oxidize cyanide and
thiocyanate is 2.7 pounds per pound and 4.9 pounds per pound, respectively. The quantity of
lime (Ca) needed for cyanide and thiocyanate destruction is 2.2 pounds per pound and 5.0
pounds per pound, respectively.
The daily consumption of chlorine and lime required for destruction of cyanide and thiocyanate
is calculated using the following generic equation that converts millions of gallons per day into
the equivalent of pounds per day:
8. (millions of gallons per day of water treated)(8.34)(mg/l of chemical) = pounds per day
Other sulfur containing species, such as thiosulfate, can also be oxidized using this process. In
order to verify the effectiveness and chemical requirements of alkaline chlorination, a laboratory
bench scale study is needed. If this process is acceptable following more careful evaluation, then
a continuous flow pilot plant may be needed for the purposes of gathering the necessary design
information for a full scale system. There are several manufacturers of chlorination systems
capable of serving mining companies worldwide.
3.0 BIOLOGICAL TREATMENT ALTERNATIVES
Biological treatment has been shown effective in the treatment of varying levels of cyanide and
thiocyanate in full scale systems at two Homestake Mining Company (HMC) operations. At the
Homestake Mine in Lead, South Dakota an attached growth biological treatment facility
consisting of 48 rotating biological contactors has been continuously treating several million
gallons per day of wastewater and is capable of treating thiocyanate concentrations exceeding
100 mg/l (Mudder, et. al, 1998) At the HMC Nickel Plate Mine in British Columbia, the
existing CIL circuit was converted into a three stage combined aerobic/anaerobic activated
sludge process capable of treating about 200 gpm of tailings pond water with thiocyanate
concentrations exceeding 1,000 mg/l, along with ammonia and nitrate levels of several hundred
mg/l (Given, et. al, 1998). Both full scale biological treatment systems are producing effluent
thiocyanate concentrations well below 5 mg/l on a continuous basis.
The microorganisms involved in the biological treatment of cyanide and thiocyanate usually
include a heterogeneous mixture of commonly found, indigenous soil bacteria which have
through continuous long term exposure adapted to the treatment of these compounds over time.
In a simplified manner, the reactions associated with the biological treatment of cyanide and
thiocyanate are as follows:
10. NaCN + 2H2O + 1/2O2 = NaHCO3 + NH3
11. NaSCN + 2H20 + NaOH + 5/2O2 = NaHSO4 + NaHCO3 + NH3

Although cyanide is readily degraded by aerobic bacteria, thiocyanate is not readily removed
through anaerobic biological treatment. In addition, anaerobic biological treatment is slower and
more susceptible to toxic upsets resulting from exposure to other constituents present in the
solution being treated. As a result, the proper approach is to use an attached or suspended
growth aerobic biological treatment process for thiocyanate removal.
The most critical environmental factors associated with biological treatment include pH,
temperature, oxygen levels, and nutrient availability. In this particular application, the pH,
oxygen levels, and nutrient availability can be controlled in routine manners. However, the low
temperature of the reclaim solution needing treatment in the winter would likely result in an
unacceptable decrease in performance. As a rule of thumb, the solution temperature should be
above 50 degrees F to support adequate biological growth and treatment. The need to heat the
reclaim solution in a simple and economical manner is a challenge. It may be possible to use
some of the excess heat generated in other processes to increase the reclaim solution to the
desired temperature.
Typically the only limiting nutrient in solution is phosphate, which is conveniently added in
concentrations ranging from about 1-5 mg/l using concentrated phosphoric acid. As shown in
the equations, there is a need to add oxygen, which is accomplished through either natural or
artificial aeration of the solutions. The minimum dissolved oxygen needed is on the order of 2.0
mg/l. In addition to these environmental factors, the presence of toxic and/or inhibitory
substances reduce the effective rate of degradation below its optimal level. As a result, the
overall chemistry of the reclaim solution must be obtained and examined.
Due to the extreme chemical environment that the bacteria are exposed to, their growth is
typically slower than in other applications, such as in a conventional municipal sewage treatment
plant. Much longer reaction periods and retention times are therefore needed to achieve the
desired level of treatment.
There are a variety of attached and suspended growth processes available for the aerobic
biological treatment of cyanide and thiocyanate. These include rotating biological contactors,
packed beds, biological filters, sequencing batch reactors, facultative lagoons, and activated
sludge systems. In this particular application due to the low cyanide and thiocyanate levels,
there may not be sufficient biomass production to allow the use of suspended growth systems,
such as activated sludge. An attached growth system which is simpler to operate and less
susceptible to upsets would be the most suitable for the treatment of the lower levels of cyanide
and thiocyanate anticipated in the reclaim solution.

In order to evaluate the applicability and effectiveness of biological treatment, a two phase
program would be employed involving first a bench scale laboratory study followed by a
continuous flow pilot plant evaluation. A bench scale laboratory study of microbial degradation
is utilized to evaluate the feasibility of biological treatment and to obtain information for design
of subsequent pilot plant evaluations. The feasibility of biological treatment is typically
evaluated through a bench scale study using standard 4-liter static draw and fill reactors, also
known as chemostats. The reactors are operated using a 24-hour aeration period and are stirred
using filtered compressed air introduced through a diffuser. At the end of each 24-hour period
aeration is ceased and contents of the reactor are allowed to settle. The solution is removed and
samples taken for analysis. Fresh untreated reclaim solution is poured into the reactor and the
aeration process initiated again. Phosphoric acid and other nutrients are added as needed. Once
the degradation of cyanide and thiocyanate have been initiated shorter aeration periods can be
imposed to examine reaction kinetics.
The microbial seed used in the initial bench scale investigation is obtained from several potential
off-site and on-site sources. The microbial seed should be comprised of cultures obtained from
several sources to ensure that the largest population of bacteria exhibiting the widest range of
metabolic capabilities is employed in the bench scale studies. Unlike other microbial treatment
applications, mixed cultures of microorganisms provide better removal of cyanide and
thiocyanate than do single pure strains of bacteria. The off-site sources of microbial seed could
include other wastewater treatment facilities, commercial suppliers of microorganisms, and other
repositories of microorganisms such as the American Type Culture Collection. On-site sources
of microorganisms are found at various air/water/solid interfaces, such as the tailings beach, the
surface of heap leach pads, and the inside walls of process solution sumps and tanks. Samples of
solids and liquids at these interfaces are collected and placed into the draw and fill reactors along
with reclaim solution.
Once the draw and fill reactors are filled and under operation, an acclimation period follows
during which the various organisms contained in the mixture adapt and grow within the solution.
During this phase of the study, routine analyses are taken for cyanide, thiocyanate, dissolved
oxygen, total suspended solids, pH, temperature, alkalinity, phosphate, ammonia, nitrate, and
possibly other constituents.

Once biological degradation has been established in the draw and fill reactors, the second phase
of the evaluation is initiated, which involves a continuous flow pilot plant using microbial seed
taken from the bench scale reactors. The pilot plant evaluation could involve the two attached
growth systems, those being the rotating biological contactor (RBC) and a biological filter, or
activated sludge, a suspended growth process. The choice between attached and suspended
growth systems is usually based upon the influent SCN- levels. The pilot plant biological filter
or biofilter is typically constructed of six inch diameter clear plastic tubing and is about six feet
in height. The tubing is filled with crushed rock or a large surface area plastic media. The RBC
is a shaft onto which has been affixed multiple circular sheets of thin corrugated plastic, which is
rotated in the solution with about half of the surface area exposed to the air at any one time.
Both of these attached growth systems are similar in ease of operation and exhibit similar
performance. The biological filter is somewhat less complicated and requires somewhat less
maintenance. A small pilot plant RBC system can be rented from several vendors and
manufacturers of this equipment.
The initial bench scale study using the draw and fill reactors typically requires about two months
to complete. The second phase of the evaluation involving the continuous flow pilot plant
typically requires four months or longer to complete. Since each solution and application is
unique there is the possibility that some constituent or circumstance could prohibit biological
treatment.
4.0 PHYSICAL TREATMENT ALTERNATIVES
In the case of physical treatment technologies, there are granular activated carbon adsorption
(GAC), ion exchange, and the membrane process reverse osmosis. Although GAC is capable of
removing wad cyanide, the removal of thiocyanate is limited and breakthrough occurs rapidly.
Ion exchange is capable of removing thiocyanate to levels below 5 mg/l, but no full scale
operations have been commissioned. Although reverse osmosis has been shown capable of
removing thiocyanate to levels well below 5 mg/l, it has typically been applied in the treatment
of barren and/or reclaim solutions at low flows typically less than 100 gpm. The use of ion
exchange and reverse osmosis create unique treatment problems. First, neither of these
technologies are destructive in that they only remove and concentrate the constituents of concern
into a smaller volume of solution. As a result, a concentrated reject from reverse osmosis or the
resin backwash from ion exchange must be dealt with in a separate manner. The concentrated by-
product waste streams from these two treatment technologies could be classified as hazardous
wastes. Second, both of these technologies remove multiple constituents, not just thiocyanate or
cyanide. Third, these technologies are much more sophisticated than either alkaline chlorination
or biological treatment, and require highly trained and motivated operators for successful
continuous operation. Fourth, there is the issue of scaling again, which is more of an issue with
reverse osmosis. In many instances, the wastewater must first be softened prior to reverse
osmosis, which requires an additional set of pre-treatment steps. Fifth, ion-exchange and reverse
osmosis are more expensive to build and operate on a relative basis than are either alkaline
chlorination or biological treatment.

The preferred treatment alternatives for selective removal of thiocyanate would be alkaline
chlorination or biological treatment. On a relative basis, the capital cost of a biological treatment
system would be similar to that of the alkaline chlorination system. The capital cost for an ion
exchange or reverse osmosis process could be several-fold higher. The anticipated operating
costs of a biological treatment facility would be much lower than for an alkaline chlorination
system, while the operating costs for either an ion exchange or reverse osmosis system would be
several-fold higher than for alkaline chlorination. The choice of alkaline chlorination versus
biological treatment will be dictated by several factors, which must be evaluated on a case-by-
case site-specific basis at each mining operation at which the biological pre-oxidation of ore is
being considered. None of the technologies discussed are generally or directly suitable for
treatment of slurries and are confined to process, tailings, or reclaim solutions.
In order to identify the most efficient and economical water management and treatment system
for the removal of residual thiocyanate from potential BIOX solutions, it is recommended that a
comprehensive water balance be completed along with a corresponding mass balance.
Comparison and optimization of potential water and mass balances are accomplished using a
spreadsheet format. The mass balance is closed using a conservative constituent like calcium or
sulfate. Examination of the long term water and mass balances aids in the identification of
operational or environmental issues which only arise after several months or even years of
operation. Often the volume of solution requiring treatment can be reduced by several-fold
through indepth evaluations of the water balance and management systems.
6.0 REFERENCES
Given, B., Dixon, B., Douglas, G., Mihoc, R., and Mudder, T., "Combined Aerobic and
Anaerobic Biological Treatment of Tailings Solution at the Nickel Plate Mine", The Cyanide
Monograph, Edited by Terry Mudder, Mining Journal Books, London, England, UK, 1998.
Hackl, R., and Wright, F., "Scale-up Experiences in Biooxidation of Refractory Gold Ores and
Concentrates", Randol Sacramento '89, pp. 123-127, 1989.
Layne, M., Singer, P., and Lidwin, M., "Ozonation of Thiocyanate", Conference on Cyanide and
the Environment, Volumes II, pp. 433-455, Tucson, Arizona, December, 1984.
Mudder, T., Fox, F., Whitlock, J., Fero, T., Smith, G., Waterland, R., and Vietl, J., "Biological
Treatment of Cyanidation Wastewaters: Design, Startup, and Operation of a Full Scale Facility",
to appear in the The Cyanide Monograph, a collection of 25 papers assembled and edited by
Terry Mudder and published by Mining Journal Books, London, England, UK, 1998 (in press).
Smith, A., and Mudder, T., The Chemistry and Treatment of Cyanidation Wastes, First Edition,
Mining Journal Books, London, England, UK, 1995.

Soto, H., Nava, F., Leal, J., and Jara, J., "Regeneration of Cyanide by Ozone Oxidation of
Thiocyanate in Cyanidation Tailings", Minerals Engineering, Volume 8, Number 3, pp. 273-281,
1995.
White, C., The Handbook Of Chlorination, Second Edition, Van Nostrand Reinhold, New York
City, NY, 1986.
Wood, R., "Wastewater Treatment with Chlorine Dioxide", Third International Symposium,
Chlorine Dioxide: Drinking Water, Process Water and Wastewater Issues, New Orleans, LA,
(International Dioxcide, Inc. www.viscona.com/0627.htm), 1995.

REVIEW OF MINE WATER NITRATE
REMOVAL TECHNOLOGIES
Prepared By:
Gregory S. Kindt
James A. Stevenson, P.E.
Walt Hunt
Scott Miller
Presented at the 100th Annual Northwest Mining Association Meeting, Spokane, Washington,
November 1994
Review of Mine Water Nitrate Removal Technologies
1.0 INTRODUCTION
Sources of nitrates present in mine water include mine workings, open pits and waste rock
disposal areas. Drilling and blasting are part of normal mining operations. One of the commonly
used blasting agents is comprised of ammonium nitrate and fuel oil. A portion of the nitrates
present in water in the mine workings and open pits is due to residual ammonium nitrate. Another
source of the nitrates in the water is due to nitrates present in the waste rock.
Methods of controlling nitrates at the source include modification of blasting techniques to

improve housekeeping procedures and to minimize misfires. Water naturally seeps into mine
workings and open pits since they normally reside below the water table and must be constantly
removed to prevent flooding. Grouting of walls to prevent water infiltration and/or water
diversion to areas where blasting is not occurring are effective methods of controlling nitrates
entering the water system. Another method of control involves use of alternative blasting agents,
although this may be cost prohibitive.
Recently more emphasis has been placed on discharging mine water with high levels of nitrates.
Effluent nitrate limitations are typically being set at 10 mg/l as N, based on the allowable
maximum contaminant level (MCL) for potable use. Levels have been set lower in some instances
when local water non-degradation rules have been applied. Ingestion of nitrate in ground water
1
can cause health effects, including induction of methemoglobinemia in infants .
Methemoglobinemia occurs when nitrate is converted by bacteria to nitrite, which in turn converts
hemoglobin in the blood to methemoglobin, which fails to carry oxygen. Infants are especially
2
susceptible to the disease and, in more severe cases, anoxia and death can occur .
This paper presents a review of nitrate removal technologies which are currently available,
including a comparison of capital and operating costs.
2.0 NITRATE REMOVAL TECHNOLOGIES
Nitrate removal technologies reviewed include ion exchange, electrochemical ion exchange,
biological denitrification and combinations of the three.
519 G. Kindt et al.

2.1 Design Parameters
For the purpose of the removal technology review, the following design parameters were used:
• Water flow rate was assumed to be 100 gpm.

• Nitrate concentrations were assumed to be an average of 25 ppm and a maximum of 100 ppm.
• Sulfate concentrations were assumed to be a maximum of 500 ppm.
o
• Ambient temperatures were assumed to vary between –40vF and 100 F.
o o
• Water temperatures were assumed to vary between 33 F and 70 F.
• Mobility of the completed systems was evaluated and compared.
2.2 Ion Exchange
Ion exchange is the process by which soluble ions (either negatively or positively charged) are
removed from solution by replacement with ions of a different species. Ion exchange resins can
be either strong or weak base anionic (for exchange of negatively charged ions); or strong or
weak acid cationic (for exchange of positively charged ions). Strong acid or base resins work
effectively over the entire pH range while weak acid resins work effectively only above a pH of 7
2
s.u. A weak base resin is effective at a pH below 6 s.u. A more detailed explanation of ion
3
exchange technology can be found in the referenced material .
-
Nitrate (NO 3), the anion present in the water to be treated, has an affinity for strong base anionic
resins. Strong base resins are referred to as Type 1, anion exchange resins with quaternary
ammonium functionality. These resins also display an affinity for other ions present in water such
-2 - -
as sulfate (SO4 ), chloride (Cl ), and bicarbonate (HCO 3). Consideration must be given in design
of an ion exchange unit to allow for adsorption of these competing anions along with nitrate, since
it could lead to the requirement for a larger treatment system. Certain resins are available which
selectively adsorb specific ions. If interferences from other ions are anticipated, these specialty
resins may be used. Resins which are used for nitrate removal are usually in a chloride form
which exchange chloride for anions present in the water. A 0.5 to 2.0 N (3 to 12%) sodium
chloride solution is typically used to regenerate the resin once it has been exhausted.
A typical block form diagram for an ion exchange process is shown in Figure 1. Depending on
the concentration of total suspended solids (TSS), pretreatment ahead of the ion exchange unit
may be necessary. This pretreatment would probably consist of clarification and/or filtration,
depending on TSS concentrations. The ion exchange unit is typically a packed bed in which feed
water and regenerative brine flow from top to bottom. The process of ion exchange consists of
feeding water through the system until the resin has been exhausted, then regenerating the media
with a brine until the adsorbed ions from the water have been removed.
The length of time required between resin regenerations is dependent on the amount of resin
present in the exchange column or bed and the concentration and flow of ions entering the system.
The treated water can be discharged directly while the regenerative brine is typically further
treated.
520 G. Kindt et al.

Figure 1: Ion Exchange
Advantages of ion exchange include:
• It has a long history of use and is reliable to operate.

• It can be configured to be either manual or automatic operation.
• It can be operated effectively over a wide temperature range.
• It has been proven to be equally effective in small and large installations.
• The units can be modular and of sufficiently small size (4 foot diameter by 10 foot high)
vessels to allow potential mobility.
521 G. Kindt et al.

Disadvantages of ion exchange include:
• Regenerative solutions may be expensive to purchase.

• Brine produced during regeneration requires further treatment or disposal. For flows of 100
gpm and 100 ppm nitrate concentration, approximately 3,000 gallons per day of brine is
generated.
• The resins can be ruined by inexperienced operators and are expensive to replace.
• Manpower requirements and training may be higher than other types of nitrate removal
processes.
• Clarification of the water may be necessary before introduction to the system.
2.3 Electrochemical Ion Exchange
Electrochemical ion exchange (EIX), has been recently developed by Bradtec Ltd. for removal
4
and destruction of nitrates from wastewater and groundwater . The EIX process combines nitrate
removal by ion exchange with electrochemical treatment to move nitrate ions to an electrolytic
compartment where they are converted to nitrogen, oxygen and water. In addition to treating
water, the technology can also be used to treat ion exchange regenerants (i.e., brines), thus
allowing the regenerants to be recycled. A more detailed explanation of the process is presented
below, as summarized from a Bradtec Ltd. research paper.
Figure 2 shows a block flow diagram of the EIX process. An ion exchange resin is used as an
intermediate onto which nitrate is adsorbed prior to being moved into the anode compartment by
an electrical current. The resin is continuously regenerated as the nitrate migrates to the anode
compartment. The resin is contained between two anion selective membranes on one side of
which is the anode compartment and on the other side the cathode compartment.
522 G. Kindt et al.

Figure 2: Electrochemical Ion Exchange
As the inlet feed enters the top of the resin column, nitrate and other anions are exchanged onto
the resin sites. Electrical current in the cell is conducted from the cathode compartment to the
- -
anode compartment by anions. Either hydroxide (OH ) or carbonate (HCO 3) anions can be used
as conductors. While passing through the resin compartment the hydroxide or carbonate ions
exchange resin sites with the anions adsorbed from the water thus continually regenerating the
resin. The anions displaced from the resin sites then migrate to the anode compartment.
The catholyte chemistry controls the regenerating anion. The hydroxide ion appears to be the
most appropriate ion to use for nitrate removal. The hydroxide reactions are as follows:
+ -
Na + OH + electric field
+ -
⇒ Na   → OH migration (1)
membrane
+ - + -
Na + H2O + e ⇒ Na + OH
+ 1/2 H2(g) (2)
The catholyte is maintained by the dissociation of water, producing hydroxide ions for migration
while generating hydrogen gas which is released at the cathode.
523 G. Kindt et al.

The anolyte chemistry has two functions: determination of effluent stream nitrate concentration;
and affecting the selectivity of the migrating anions. These factors govern the overall efficiency of
the process. In an alkaline environment the use of sodium hydroxide as the anolyte gives the
following equation:
- + -
migration   → 4NO 3 + 4Na + 4OH
membrane
+ - -
⇒ 4Na + 4NO 3 + 2H2O + O2 (g) + 4e (3)
As previously mentioned, the electromigration of nitrate to the anode compartment is

- -2 -
accompanied by other anions (e.g., Cl , SO4 , HCO 3). These anions will build up in the anolyte
until they reach an equilibrium concentration with the anion concentration entering with the feed
stream. The effect of this equilibrium is that the anions will leave the resin chamber in the effluent
at the same concentration they enter with the feed. This process will occur with any anion,
including nitrate, unless it is removed from the anolyte. The selective removal of an anion from
the anolyte promotes the forward migration of that species in the EIX cell, thus leading to
selective treatment.
The selective destruction of nitrate is accomplished by the reduction to nitrogen or ammonia at a

cathode. The anolyte follows a tortuous route through a series of bipolar electrodes in the anode
compartment. The conversion of nitrate to nitrogen or ammonia is achieved through a series of
sequential reduction steps:
- - -
NO 3 + 3H2O + 5e → 1/2N2 (g) + 6OH (4)
- - -
NO 3 + 6H2O + 8e →NH3 (g) + 9OH (5)
As shown in Figure 2, both the catholyte and anolyte solutions are circulated from a reservoir to
their respective compartments. This serves as a mechanism for maintaining supply of the reacting
species, removing gas from the compartments and allowing chemical control and replenishment of
the electrodes in their respective reservoirs. Since water also moves through the membranes, the
volume of the solutions must be adjusted to prevent imbalances over extended periods.
Temperature is controlled in the EIX and destruction cell by flow of treated water and
recirculation of anolyte solution.
Advantages of the EIX process include:
• No brine is created which requires further treatment or disposal.

• It provides a versatile treatment for the removal of nitrate from groundwater and other
solutions.
• Nitrate in mine water can be concentrated and destroyed in a continuous operation.
• Regenerative streams from conventional ion exchange units can be treated to remove nitrate,
thus eliminating the need for spent regenerative solution disposal.
• The unit can be modular and of sufficiently small size to allow mobility.
524 G. Kindt et al.

525 G. Kindt et al.

Disadvantages of the EIX process include:
• Unproven on a large scale.

• As with conventional ion exchange, the potential exists for resin fouling.
• Multiple unit operations are involved in the process making it potentially more complicated to
operate.
• Off-gases from the process including hydrogen and ammonia may require control and venting
away from the process.
2.4 Biological Denitrification
Historically, one of the most common processes used for removal of nitrates from municipal
wastewater treatment plan effluent has been biological denitrification. This process consists of an
anaerobic (oxygen free) stage, occasionally with addition of a carbon source such as methanol, to
convert the nitrates to gaseous nitrogen and oxygen. Nitrate conversion is accomplished by
denitrifying bacteria present in the anaerobic stage.
For efficient conversion of nitrate at low organic carbon concentrations, methanol must be
supplied to the process at a stoichiometric ratio of between 2.5 and 3.0 mg/L per mg/L of nitrate.
5
theoretical methanol requirements can be calculated from the following McCarty equation .
CM = 2.47NO + 1.53N1 + 0.87DO (6)
where:
CM = amount of methanol required, mg/L

NO = nitrate-nitrogen concentration, mg/L
N1 = nitrite-nitrogen concentration, mg/L
DO = dissolved oxygen concentration, mg/L
Advantages of biological denitrification include:
• No brine is generated which must be disposed of off-site.

• Stability of operation has been widely demonstrated in municipal wastewater systems.
526 G. Kindt et al.

Disadvantages of biological denitrification include:
• An alternate carbon source such as methanol is required for efficient nitrate conversion.
• The degree of nitrate removal is highly variable depending on water chemistry factors.
• The rate of reaction is highly temperature dependent. For example, the biological
denitrification rate at 45°F has been reported as being approximately one-third of that at
5
55°F .
• Denitrifying bacteria may be inhibited or destroyed by exposure to toxicants (such as heavy
metals) present in the wastewater, rapid changes in pH and contamination by hydrocarbons.
A description of the different types of biological process equipment is presented in the following
text.
2.4.1 Submerged Rotating Biological Contactor
A rotating biological contactor (RBC) consists of large diameter corrugated plastic media
mounted on a horizontal shaft and placed in a concrete tank. Envirex Corporation is a leading
6
vendor of RBCs and has provided information used as the basis for this section of the report . A
block flow diagram of the system is shown in Figure 3.
The RBC can either be partially submerged in water to achieve aerobic conditions or fully
submerged (SRBC) to promote anaerobic conditions. After start up of the system, bacteria either
normally present in the wastewater or artificially seeded adhere to the rotating surfaces and
multiply. After about a week, the surface is covered with a thin film of biomass. As the biomass
grows, it continually sloughs off into the wastewater. The biomass will raise the suspended solids
concentration in the treated water effluent which may then require clarification, depending on
effluent suspended solids limitations.
527 G. Kindt et al.

Figure 3: Submerged Rotating Biological Contactor
Methanol requirements for the process can be a significant portion of the overall operating cost.
The following section of this report provides a summary of estimated operating costs for a typical
system. The methanol which provides the supplemental carbon source for nitrate conversion must
be carefully regulated. Excess methanol entering the system could lead to exceedance of
biological oxygen demand (BOD) effluent limitations.
Advantages of the SRBC system include:
• No brine is generated which must be further treated or disposed of off-site.

• Stability of operation has been widely demonstrated on a municipal scale.
• It does not require backwashing to remove accumulated excess biomass.
• Simple operation of facility.
528 G. Kindt et al.

Disadvantages of the SRBC system include:
• Clarification of effluent water may be required.
• The rate of reaction is highly temperature dependent.
• The unit is not typically mobile.
• Rotating driven equipment must be maintained at regular intervals and requires maintenance
personnel with appropriate training to be present on-site.
2.4.2 High Rate Fixed Film Biological Filters With Intermittent Backwash
The following discussion on high rate fixed film biological filters using intermittent backwashing is
based on discussions with and information provided by Tetra Technologies, Inc., regarding their
7
Denite system . The Denite system incorporates nozzleless deep-bed filtration technology to
act as a filter as well as a denitrification filter. A block flow diagram of the system is shown in
Figure 4. The systems typically employ a six foot deep bed of silica sand media contained in a
concrete or steel tank. Denitrifying bacteria grow on the media and in the media void spaces.
Specially sized and shaped media are selected to ensure a high surface area for bacterial growth,
maximum solids holding capacity, and effective backwashing capability with minimal media loss
or deterioration.
2
The system is normally operated in a downflow mode at a rate of 1 to 4 gpm/ft when inflow
nitrate concentrations are less than several hundred parts per million. When higher concentrations
of nitrates are present, an upflow configuration is used to promote self purging of byproduct
nitrogen gas. During normal downflow operations, nitrogen gas may accumulate in the media
which causes an increase in system head loss. The excess gas is removed by taking the filter out
2
of service and applying a backwash rate of 8 gpm/ft for several minutes. This process is referred
to as "bumping". Bumping releases the entrapped nitrogen gas to the atmosphere and reduces
system head loss. The frequency of bumping depends on the rate of denitrification occurring in
the filter.
Since the system has a high capacity for retaining solids in the media, it requires a heavy-duty
backwash to remove accumulated soils. Air and water are used simultaneously to create a
vigorous backwashing action while minimizing backwash water volumes. A final backwash
consisting of water only is used to remove entrained air before placing the filter back in service.
529 G. Kindt et al.

Figure 4: High Rate Fixed Film Biological Filter With Intermittent Backwash
Advantages of the intermittent backwash filter include:

• Stability of operation has been widely demonstrated in municipal wastewater systems.
• It can be used for both nitrate conversion and suspended solids removal.
Disadvantages of the intermittent backwash filter include:
• An alternate carbon source such as methanol will be required for efficient nitrate conversions.
• Requires disposal of backwash water.
• Backwashing requirements may become excessive depending on the suspended solids entering
the system.
• The unit may be too large to be easily mobile.
• Backwashing may disrupt the biomass layer if performed incorrectly.
530 G. Kindt et al.

2.4.3 High Rate Fixed Film Biological Filters With Continuous Backwash
The following discussion on high rate fixed film biological filters using continuous backwashing is
based on discussions with and information provided by Parkson Corporation (Parkson) regarding
8
their Dynasand filter denitrification system . The Dynasand filter is an upflow design with a
moving bed approximately 80 inches deep. It uses a simple airlift and washer system to
continuously clean the filter media, thus avoiding the need for a backwash control system and
eliminating the need for much of the piping associated with conventional intermittent backwash
sand filters. A block flow diagram of the system is shown in Figure 5. The media is normally
contained in either a circular steel tank or rectangular concrete tank for larger applications. The
Dynasand requires no backwash pump and only a small amount of compressed air (about 150 to
200 scfh) to operate the continuous backwash system when used for biological denitrification.
With this flow of air sand turnover rate in the filter is held to about 0.4 bed volumes per day. The
low bed turnover rate helps ensure a healthy colony of bacteria are present in the filter at all times.
The volume of wash water leaving the system is typically about 3% of the influent water total.
Figure 5: High Rate Fixed Film Biological Filter With Continuous Backwash
As with the Tetra Technologies Denite system, denitrifying bacteria grow on the media and in
the void spaces. Sand with an effective size of 1.7 mm is normally used in the Parkson units.
2
Filter loading rates have been found to vary between 1.4 and 4.6 gpm/ft depending on the
influent and desired effluent nitrate concentrations. Filter loading rates may require reduction
during colder winter months when the influent water temperature drops, thus causing a drop in
biological activity in the filter.
Since the system will also act as a filter, wastewater to be treated in the system should be clarified
to reduce TSS levels below the 20 to 30 ppm range to avoid a buildup of solids in the media
which could degrade system performance.
531 G. Kindt et al.

Advantages of the continuous backwash filter include:

• A minimal amount of media backwash water is created.
• Operation is simple and maintenance requirements are few since no moving parts are used in
the filter.
• The unit is modular and sufficiently small size (approximately 7 foot diameter by 14 foot high)
to allow for easy mobility.
Disadvantages of the continuous backwash filter include:
• The degree of nitrate removal is high variable depending on water chemistry factors.
2.4.4 Low Rate Fixed Film Biological Reactor
A low rate fixed film reactor is a large volume of coarse material, similar to a packed bed,
maintained in an anaerobic environment in which denitrification will occur. Figure 6 shows a
block flow diagram of an in-ground low rate fixed film reactor. This type of reactor is similar to a
high rate fixed film system with the exception of loading rates being much lower at 0.03 to 0.12
2
GPM/ft .
Figure 6: Low Rate Fixed Film Biological Reactor
532 G. Kindt et al.

The material or media used in the reactor should be greater than 1/2 inch, such as washed gravel,
to provide adequate void space to allow free flow of the biomass solids from top to bottom.
Wastewater entering the system should be free of suspended solids to prevent potential plugging
of the material. Impermeable liners should be provided around all sides of the reactor to prevent
lateral migration of the wastewater and to ensure oxygen does not enter the system. The reactor
is kept under anaerobic conditions by maintaining saturated conditions within the reactor at all
times.
The mechanism by which denitrification occurs is similar to a high rate fixed film reactor or
SRBC, as discussed above. Since organic carbon in the raw wastewater to be treated will be low,
a carbon source will be required for effective denitrification. Unlike the other biological
denitrification systems discussed previously, the rate with which the wastewater is fed through the
system is very low, thus the level of bacteria growth is kept to a minimum and the potential for
biomass sloughing and media clogging is minimized. As with the other types of biological
denitrification processes, a clarifier may be required to remove suspended solids from the effluent
stream before discharges.
Advantages of the low rate fixed film reactor include:
• Simplicity of construction and operation.

• Can be operated for extended periods of time with minimal maintenance requirements.
• Relative ease of operation and low maintenance requirements.
• The system is less susceptible to ambient temperature variations since it is buried in-ground
and effectively insulated.
Disadvantages of the low rate fixed film reactor include:
• Since this is a relatively new technology for treating nitrates it will require pilot testing before
full scale operation.
• Material present in the reactor may plug if high suspended solids are introduced to the system
or if denitrification is allowed to proceed at too high of rates.
2.5 Combined Technologies
To maximize the advantages of the various processes, it may be possible to combine technologies
to create a system that is more effective and efficient than the individual systems. A discussion of
533 G. Kindt et al.

combination technologies comprised of ion exchange and electrochemical ion exchange and ion
exchange and biological denitrification are presented in the following text.
2.5.1 Ion Exchange and Electrochemical Ion Exchange
A block flow diagram representing a combination ion exchange and electrochemical ion exchange
system is shown in Figure 7.
Figure 7: Ion Exchange and Electrochemical Ion Exchange
This system utilizes a conventional ion exchange system to remove nitrate from feed water and an
EIX system to destroy nitrate present in ion exchange regeneration brine. This system has several
advantages over the separate conventional ion exchange or EIX systems. These advantages
include:
• Waste brine is not generated eliminating a waste disposal concern.

• A majority of the brine is recycled, thereby eliminating the cost of purchasing makeup brine
for resin regeneration.
• Since only the brine for the ion exchange system is treated, the size of the EIX system is
considerably smaller than if it were used to treat the entire feed water stream.
• The unit will be modular and of sufficiently small size to allow easy mobility.
534 G. Kindt et al.

Disadvantages of the combination system include:
• Since a resin is used in both units, care must be taken to avoid fouling and subsequent resin
replacement.
• A trained operator will be needed to monitor the relatively complex system to ensure efficient
operation.
• Clarification of the water may be necessary before introduction to the ion exchange system.
• Unproven at large scale.
2.5.2 Ion Exchange and Biological Denitrification
A block flow diagram of a combination ion exchange and biological denitrification system is
shown in Figure 8.
Figure 8: Ion Exchange and Biological Denitrification
535 G. Kindt et al.

This system utilizes a conventional ion exchange system to remove nitrate from feed water and a
9
biological denitrification system to remove nitrate from the ion exchange resin regeneration brine .
This type of system has several advantages over the separate conventional ion exchange or
biological denitrification systems. These advantages include:
• The amount of waste brine generated is less than a conventional ion exchange system.
• A majority of the brine is recycled, thereby eliminating the cost of purchasing makeup brine
for resin regeneration.
• Since only the brine from the ion exchange system is treated, the size of the biological
denitrification unit is considerably smaller than if it was used to treat the entire feed water
stream.
Disadvantages of the combination system include:
• This technology has been tested only on a limited bench scale basis and has not been proven at
full-scale size.
• The unit may not be easily mobile.
• A portion of the regeneration brine would require off-site disposal due to anion accumulation,
other than nitrate, in the brine.
• Since a resin is used in ion exchange system, care must be taken to avoid fouling and
subsequent resin replacement.
• A trained operator would be needed to monitor the system to ensure efficient operation.
• Rate of reaction is highly temperature dependent.
• Clarification of the water may be necessary before introduction to the ion exchange system.
3.0 CAPITAL AND OPERATING COST COMPARISON
Capital and operating costs were estimated for each of the technologies based on the defined
design parameters. Table 1 presents a summary of the estimated capital and operating costs. The
cost estimates were generated by using conservative costs and reflect an accuracy of ± 30%. The
clarifier used in the cost estimate is a conventional clarifier. The final filter used in the estimate is
a Parkson Dynasand filter which may not be needed in all instances. Other cost savings may
also be realized during bench and pilot scale testing.
536 G. Kindt et al.

Costs for engineering, construction management and start up assistance have not been included in
this summary, but are typically 15% of the total capital cost. A brief discussion of the costs
associated with each technology is presented below.
3.1 Ion Exchange
The complete ion exchange system as proposed includes the ion exchange unit, a 20 foot diameter
pretreatment clarifier to remove suspended solids, a storage 2,000 cubic foot storage silo for salt
and miscellaneous expenses associated with a building to house the ion exchange unit and controls
to operate the complete system. Costs as summarized in Table 1 are $100,000 for the ion
exchange unit, $150,000 for the clarifier, $50,000 for the salt storage silo and $100,000 for the
building, controls and other miscellaneous expenses. Total estimated capital cost for the complete
ion exchange system is $400,000.
Estimated operating cost for the ion exchange system as summarized in Table 1 includes the cost
of salt for the regeneration brine, manpower cost and other miscellaneous minor costs. U.S. Filter
Corporation provided both estimated capital cost for the ion exchange unit as well as estimated
salt required per day, approximately 2,000 pounds. Based on a delivered salt cost of $60 per ton,
approximately 4 hours of labor per day and minor miscellaneous expenses for power, the
estimated operating cost is $1.28 per 1,000 gallons of water treated excluding brine disposal and
storage costs. It was assumed that the bring, approximately 3,000 gallons per day, could be
disposed of in an on-site tailings pond or other impoundment and the cost for such disposal would
be minimal. In some instances this may not be a valid assumption.
3.2 Electrochemical Ion Exchange
The complete electrochemical ion exchange system as proposed includes the electrochemical ion
exchange unit, a 20 foot diameter pretreatment clarifier to remove suspended solids, and
miscellaneous expenses associated with a building to house the unit and controls to operate the
complete system. Costs as summarized in Table 1 are $340,000 for the ion exchange unit,
$150,000 for the clarifier and $100,000 for the building, controls and other miscellaneous
expenses. Total estimated capital cost for the complete electrochemical ion exchange system is
$590,000.
Estimated operating cost for the electrochemical ion exchange system as summarized in Table 1
includes the electrical cost to operate the unit, manpower cost and other miscellaneous minor
costs. Bradtec-US, Inc. provided both estimated capital cost for the electrochemical ion exchange
unit as well as the estimated operating cost of $0.57 per 1,000 gallons of water treated.
3.3 Biological Denitrification
Each of the biological denitrification technologies previously discussed were evaluated for capital
and operating cost. A brief discussion of the costs associated with each biological technology is
presented below. It was assumed that an equal amount of methanol, approximately 0.595 pounds
per 1,000 gallons, or a cost of $0.098 per 1,000 gallons, would be needed for each process.
Differences in operating costs were attributed to anticipated manpower and electrical
537 G. Kindt et al.

requirements.
3.3.1 Submerged Rotating Biological Contactor
The complete SRBC system as proposed includes the SRBC unit, a 20 foot diameter post-
treatment clarifier to remove excess suspended solids and miscellaneous expenses associated with
a building to house the unit and controls to operate the complete system. Costs as summarized in
Table 1 are $260,000 for the ion exchange unit, $150,000 for the clarifier and $50,000 for the
building, controls and other miscellaneous expenses. Total estimated capital cost for the complete
SRBC system is $460,000.
Estimated operating cost for the SRBC system as summarized in Table 1 includes the cost of
methanol needed for the unit, manpower cost and other miscellaneous minor costs. The estimated
operating cost for the unit is $0.95 per 1,000 gallons of water treated.
3.3.2 High Rate Fixed Film Biological Filters With Intermittent Backwash
The complete high rate fixed film biological filter using and intermittent backwash system as
proposed includes the biological filter unit, a 20 foot diameter pretreatment clarifier to remove
suspended solids, a post-treatment filter to remove excess suspended solids and miscellaneous
expenses associated with a building to house the unit and controls to operate the complete system.
Costs as summarized in Table 1 are $500,000 for the biological filter unit (as provided by Tetra
Technologies), $150,000 for the clarifier, $45,000 for the filter and $75,000 for the building,
controls and other miscellaneous expenses. Total estimated capital cost for the system is
$770,000.
Estimated operating cost for the system as summarized in Table 1 includes the cost of methanol
needed for the unit, manpower cost and other miscellaneous minor costs. The estimated
3.3.3 High Rate Fixed Film Biological Filters With Continuous Backwash
The complete high rate fixed film biological filter using and continuous backwash system as
proposed includes the biological filter unit, a 20 foot diameter pretreatment clarifier to remove
suspended solids, a post-treatment filter to remove excess suspended solids and miscellaneous
expenses associated with a building to house the unit and controls to operate the complete system.
Costs as summarized in Table 1 are $75,000 for the biological filter unit (as provided by Parkson
Company), $150,000 for the clarifier, $45,000 for the filter and $75,000 for the building, controls
and other miscellaneous expenses. Total estimated capital cost for the complete system is
$345,000.
538 G. Kindt et al.

3.3.4 Low Rate Fixed Film Biological Reactor
The complete low rate fixed biological filter using and continuous backwash system as proposed
includes the biological filter unit, a 20 foot diameter pretreatment clarifier to remove suspended
solids, a post-treatment filter to remove excess suspended solids and miscellaneous expenses
associated with a building to house the unit and controls to operate the complete system. Costs
as summarized in Table 1 are $150,000 for the biological filter unit (as estimated by UniField),
$150,000 for the clarifier, $45,000 for the filter and $50,000 for the building, controls and other
miscellaneous expenses. Total estimated capital cost for the complete system is $395,000.
3.4 Combination Technologies
Capital and operating cost summaries for the combination technologies previously evaluated are
presented below.
3.4.1 Ion Exchange and Electrochemical Ion Exchange
The complete combination ion exchange and electrochemical ion exchange system as proposed
includes the ion exchange and electrochemical ion exchange units, a 20 foot diameter
pretreatment clarifier to remove suspended solids, a 1,000 cubic foot storage silo for salt and
miscellaneous expenses associated with a building to house the unit and controls to operate the
complete system. Costs as summarized in Table 1 are $210,000 for the ion exchange and
electrochemical ion exchange units (as estimated by Bradtec-US, Inc.), $150,000 for the clarifier,
$25,000 for the salt storage silo and $100,000 for the building, controls and other miscellaneous
expenses. Total estimated capital cost for the complete combination system is $485,000.
Estimated operating cost for the system as summarized in Table 1 includes the electrical cost to
operate the unit, manpower cost and other miscellaneous minor costs. The estimated operating
cost as provided by Bradtec-US, Inc. for the unit is $0.52 per 1,000 gallons of water treated.
3.4.2 Ion Exchange and Biological Denitrification
The complete combination ion exchange and biological denitrification system as proposed
includes the ion exchange and biological units, a 20 foot diameter pretreatment clarifier to remove
suspended solids, a 1,000 cubic foot storage silo for salt and miscellaneous expenses associated
with a building to house the unit and controls to operate the complete system. Costs as
summarized in Table 1 are $400,000 for the ion exchange and electrochemical ion exchange units
(as estimated by Bradtec-US, Inc.), $150,000 for the clarifier, $25,000 for the salt storage silo
and $100,000 for the building, controls and other miscellaneous expenses. Total estimated capital
cost for the complete combination system is $675,000.
539 G. Kindt et al.

operating cost as provided by Bradtec-US, Inc. for the unit is $1.10 per 1,000 gallons of water
treated.
4.0 SUMMARY
This paper is intended to provide an overview of the technologies currently available for removal
of nitrates from wastewater. The majority of these technologies have been used in municipal
wastewater treatment applications but not in full-scale mining environments. In view of the
foregoing, it is recommended that a bench and pilot testing program be conducted to better
determine the feasibility of the technologies. Based on results of pilot testing, a single best
technology should be selected for the nitrate removal process. After the technology is selected,
preliminary engineering should be performed to more accurately determine the capital and
operating costs involved in a full-scale facility.
5.0 REFERENCES
1. American Water Works Association 1990, Water Quality and Treatment, McGraw-Hill,
Inc., New York, New York, 1990.
2. Sanks, Water Treatment Plant Design, Robert L. Sanks, Ann Arbor Science Publishers,
Inc., Ann Arbor, Michigan 48106, 1978.
3. Tchobanoglous and Schroeder, Water Quality Characteristics, Modeling, Modification,

George Tchobanoglous and Edward D. Schroeder, Addison-Wesley Publishing Company,
Reading, Massachusetts, 1985.
4. Bradtec-US, Removal and Destruction of Nitrates From Wastewater and Groundwater,

United Kingdom and Atlanta, Georgia.
5. Metcalf and Eddy, Wastewater Engineering, Treatment, Disposal and Reuse, Metcalf and
Eddy, Inc., McGraw Hill, Inc., New York, New York, 1991.
6. Envirex, Miscellaneous Articles, Waukesha, Wisconsin.
7. Tetra Technologies, Miscellaneous Articles, The Woodlands, Texas.
8. Parkson Corporation, Miscellaneous Articles, Fort Lauderdale, Florida.
9. Clifford, Dennis and Xiaosha Liu, Ion Exchange for Nitrate Removal.
540 G. Kindt et al.

Table 1
Nitrate Removal Technology Comparison
Nitrate
Removal Additional Total Operating
Description Unit Equipment Capital Cost Advantages Disadvantages
Capital Capital Cost Cost ($/1000
Cost gal.)
Ion Exchange $100,000 -Clarifier $400,000 $1.28 • Long history of use and • Regenerative solutions may be
$150,000 reliable operation. expensive.
• Either manual or automatic • Waste brine must be disposed of
-Salt Storage operation. off-site.
Silo $50,000 • Operable over a wide • Resins can be ruined by
temperature range. inexperienced operators.
-Misc. • Proven technology. • Manpower requirements may be
Building and • Unit will be modular and high.
Controls mobile. • Clarification of water may be
$100,000 necessary before nitrate
removal.
Electrochemical $340,000 -Clarifier $590,000 $0.57 • No waste brine is created. • Resins can be ruined by
Ion Exchange $150,000 • Provides a versitile treatment inexperienced operators.
technology. • Multiple unit operations are
-Misc. • Operable over a wide involved making it more
Building and temperature range. complicated to operate.
Controls • Nitrate can be destroyed in a • Off gases from the process need
$100,000 continuous operation. to be controlled and vented.
• Can be used to treat IX waste • Clarification of water may be
brine. necessary before nitrate
• Unit will be modular and removal.
mobile.
Table 1 (continued)
Nitrate
Cost gal.)
Biological $260,000 -Clarifier $460,000 $0.95 • No waste brine is created. • Carbon source required.
Denitrification $150,000 • Stability of operation has • Degree of nitrate removal is
- Submerged been widely demonstrated. highly variable with climatic
Rotating -Misc. • Does not require ackwashing. and water chemistry factors.
Biological Building and • Simple operation. • Denitrifying bacteria are
Contactor Controls susceptible to toxicants.
$50,000 • Equipment must be maintained
by experienced operators.
• A clarifier may be needed for
effluent suspended solids
removal.
• The unit may be too large for
easy mobility.
519 G. Kindt et al.

Table 1 (continued)
Nitrate
Cost gal.)
Denitrification $150,000 • Stability of operation has • Degree of nitrate removal is
- High Rate Fixed been widely demonstrated. highly variable with climatic
Film -Filter • Can be used for nitrate and water chemistry factors.
Biological Filter $45,000 conversion and suspended • Denitrifying bacteria are
- Intermittent solids removal. susceptible to toxicants.
Backwash -Misc. • Equipment must be maintained
Building and by experienced operators.
Controls • Requires disposal of backwash
$75,000 water.
• Backwashing may become
excessive with high suspended
solids loading.
• Backwashing may disrupt
biomass layer.
• Clarification of water may be
necessary before nitrate
removal.
• The unit may be too large for
easy mobility.
520 G. Kindt et al.

Table 1 (continued)
Nitrate
Cost gal.)
Denitrification $150,000 • A minimum amount of media • Relatively new technology, will
- High Rate Fixed wash water is used. require pilot
Film -Filter • Simple operation and testing.
Biological Filter $45,000 maintenance. • Degree of nitrate removal is
- Continuous • Unit will be modular and highly variable with climatic
Backwash -Misc. mobile. and water chemistry factors.
Building and • Denitrifying bacteria are
Controls susceptible to toxicants.
$75,000 • Clarification of water may be
removal.
Biological $150,000 -Clarifier $395,000 $0.80 • No waste brine is created. • Relatively new technology, will
Denitrification $150,000 • Can be operated for extended require pilot
- Low Rate Fixed periods of time with little testing.
Film -Filter maintenance. • Unit would not be mobile.
Biological $45,000 • Ease of operation and low • Carbon source required.
Reactor maintenance. • Degree of nitrate removal is
-Misc. • Less variable due to highly variable with water
Building and temperature than other types chemistry factors.
Controls of biological denitrification • Denitrifying bacteria are
$50,000 systems. susceptible to toxicants.
• Plugging may occur depending
on suspended Solids loading or
biomass sloughing rates.
• Clarification of water may be
removal.
521 G. Kindt et al.

Table 1 (continued)
Nitrate
Cost gal.)
Combined Ion $210,000 -Clarifier $485,000 $0.52 • No waste brine is created. • Potential for resin fouling exists.
Exchange and $150,000 • Regenerative brine is • Trained operator is needed for
Electrochemical recycled. efficient
Ion Exchange -Salt Storage • EIX system size is smaller operation.
Silo $25,000 than if used to treat entire • Clarification of water may be
water flow. necessary before nitrate
-Misc. • Unit will be modular and removal.
Building and mobile.
Controls
$100,000
Combined Ion $400,000 -Clarifier $675,000 $1.10 • Less waste brine is created • Potential for resin fouling exists.
Exchange and $150,000 than with IX alone. • Unproven technology.
Biological • Regenerative brine is • A portion of the regenerative
Denitrification -Salt Storage recycled. waste brine must be disposed of
Silo $25,000 • EIX system size is smaller off-site.
than if used to treat entire • Trained operator is needed for
-Misc. water flow. efficient
Buildign and • Unit will be modular and Operation.
Controls mobile. • Clarification of water may be
$100,000 necessary before nitrate
removal.
• Carbon source required.
• Rate of reaction highly
temperature dependent.
• Denitrifying bacteria are
susceptible to toxicants.
522 G. Kindt et al.

PROCESS WATER MANAGEMENT AND TREATMENT
AT THE GOLDEN CROSS MINE
Prepared By:
Mike Kindley, M.S.

Terry Mudder, Ph.D.
Tony O’Neill
Luke Russell
Originally published in The Cyanide Monograph, First Edition, Mining Journal Books, London,
England, United Kingdom, June 1998
Process Water Management and Treatment at the Golden Cross Mine
ABSTRACT
In order to provide long-term protection of surface water quality at the Golden Cross Mine,
initial process and engineering design were integrated with development of a comprehensive
water management strategy. The integrated strategy led to a sound permitting approach with
development of a modern cyanide recovery process, design of a water management system
capable of segregating flows and managing large water volumes, and construction of a process
water treatment plant capable of meeting very stringent effluent limitations. The effluent
limitations were based upon a set of site-specific instream water quality criteria developed for
protection of an important rainbow trout fishery. The process water treatment plant combined
numerous design features including state-of-the-art computerized control systems, process water
treatment steps for cyanide and metals removal, and an extensive instream biomonitoring
program. An effluent polishing system was subsequently installed using activated carbon
columns, which were capable of achieving very low residual cyanide and metals levels. The
treatment plant design was flexible and was modified during operations to allow for changing
influent characteristics, particularly iron cyanide. A nearly perfect compliance record has been
maintained. The intensive monitoring of the aquatic ecosystem within the receiving waters, has
demonstrated that treated effluent from a gold mining operation can be discharged into a trout
stream with no measurable adverse impacts to the sensitive ecosystem over a period of six years.
1.0 INTRODUCTION
The Golden Cross Mine is located in the southern end of the Coromandel mountain range near
the town of Waihi on the north island of New Zealand. The original project was commissioned
in 1991 under the initial direction and ownership of Cyprus Gold NZ, Ltd. The mine was sold to
Coeur Gold NZ, Ltd. in 1993, which presently manages the joint venture project with Viking
Mining Ltd.
The mine produced approximately 100,000 ounces of gold and 340,000 ounces of silver annually
prior to cessation of mining operations in April 1998. There have been important engineering
and environmental issues, including the development of both open pit and underground mines,
the disposal of tailings and acid-generating waste rock, the management of large volumes of
precipitation and runoff, and the discharge of excess treated water into the Waitekauri River.
The river is of cultural importance to the native people and supports an important rainbow trout
fishery. The project is situated in steep and rugged topography at an altitude of 400 meters,
exhibits an annual average rainfall of about three meters, and a catchment that adjoins a forest
park at the head of Waitekauri valley.
One of the most technically complex aspects of the project has been and remains the discharge of
treated site and process waters into the nearby aquatic ecosystem. Development of the water
management and treatment strategies began during the conception phase of the project, in
parallel with process and engineering feasibility and design. A nearly perfect compliance record
has been maintained, which coupled with intensive monitoring of the aquatic ecosystem within
the receiving waters, has demonstrated that treated effluent from a gold mining operation can be
discharged into a sensitive aquatic ecosystem over a six year period with no measurable adverse
524 Kindley et al.

impacts. As closure approaches, the water management and treatment systems will continue to
be used to treat excess site runoff for metals and suspended solids removal, as needed to
maintain compliance and to protect the river. This paper provides a discussion of the
development, design, and operation of the process water management and treatment systems
employed at the Golden Cross Mine.
2.0 SITE-SPECIFIC WATER QUALITY AND DISCHARGE CRITERIA
Treated water discharged from the site enters the Waitekauri River. The river is of cultural
importance to the native people of New Zealand and also contains a well-established reproducing
rainbow trout fishery. The water quality of the river is excellent and its protection has always
been the primary environmental concern.
In order to ensure long-term protection of the river a set of site-specific in-stream water quality
criteria were developed, using as a basis the Recalculation Procedure originally proposed by the
USEPA in its Water Quality Standards Handbook (USEPA, 1983). The ecological basis for
development of the criteria was to protect the most sensitive resident aquatic species and life
stages for each of the constituents of concern. In nearly all cases, the early life stage of the
rainbow trout was considered the most sensitive within the aquatic ecosystem of the river.
Protection of the early life stage of the rainbow trout would afford protection for the other
aquatic organisms living in the river, in particular the insects, which served as the primary food
source for the fish.
The primary constituents of concern included several metals, weak acid dissociable (WAD)
cyanide, and ammonia. The WAD cyanide analysis, which included its free and weakly metal
complexed forms, was shown to be of the most importance toxicologically. The derivation of
the site-specific aquatic life criteria took into account bioaccumulation, acute and chronic
toxicity, human consumption, and water quality (Mudder, 1987a and Kingett Mitchell and
Associates, 1987).
Through development of a water management system for the operation, it was determined that in
order to maintain the site water balance on an annual basis, the daily volume of the treated
discharge would ultimately account for about 20% of the flow of the river. The resultant
minimum dilution factor was 5/1 based upon the allowable percentage discharge flow. The
approach used in establishing a discharge point in the river, was to convey the treated effluent
downstream via a buried pipeline and release it through a diffuser. The flow in the river was
monitored using a gauging station, from which a continuous electronic signal was sent to the
treatment plant. This electronic signal information was used to control the volume of treated
discharge in a manner that maintained the 5/1 dilution in the river. Such an approach is termed a
hydraulically controlled release (HCR), and is sometimes referred to as a "staged" or "paced"
release system. This approach takes advantage of the variable flows that occur in the river over
time.
525 Kindley et al.

The effluent or discharge limitations, which were promulgated originally as Water Rights and
later as Consents, were calculated by multiplying the site-specific in-stream water quality criteria
by the allowable dilution ratio of 5/1. There are two sets of effluent or discharge limitations for
protection of the stream organisms against both acute and chronic toxicological effects. A
summary of the two sets of site-specific water quality criteria and effluent limitations are
presented in Table 1.
3.0 CYANIDE RECOVERY SYSTEM
During the design stages of the mine, it was determined that minimizing levels of cyanide stored
in the tailings impoundment would have several environmental benefits. First, by lowering the
levels of cyanide in the impoundment, the type and level of treatment needed prior to discharge
of this water would be reduced. Since the cyanide in the impoundment was lowered by an order
of magnitude using cyanide recovery, the quantity and associated cost of hydrogen peroxide
needed for cyanide destruction were reduced dramatically. The WAD cyanide levels averaged
13 g/m3 in the tailings impoundment with a maximum of 36 g/m3 during operations. Within one
year of ceasing operations the WAD cyanide within the tailings impoundment had naturally
attenuated to below the discharge standard.
Second, the resultant low levels of cyanide produced such low levels of ammonia through natural
attenuation, that there was no need to treat the residual ammonia levels produced using
additional processes, such as biological nitrification, breakpoint chlorination, or ion exchange.
Third, by lowering the cyanide levels entering the impoundment, the necessary level of
protection for birds, and in particular waterfowl was provided. Fourth, by lowering the cyanide
levels within the tailings, any seepage or drainage from the impoundment contained lower levels
of cyanide and metals, thereby eliminating the need for a natural or synthetic liner. It was
demonstrated that the low residual cyanide level would continue to attenuate as it percolated
through the tailings since the elevated pH conditions within the tailings would cause the free
metals, previously complexed with the cyanide, to precipitate.
In an attempt to realize the long-term benefits of reusing cyanide, an intensive research and
development program was initiated during project development to determine if the recovery
process could be applied to slurries as well as clarified barren solutions.
The research and development program involved extensive bench and continuous flow pilot
scale evaluations to address the fundamental aspects of recovering cyanide from tailings slurries.
Using information from these evaluations, various levels of cyanide were incorporated into a
detailed mathematical model of the water management system {Williams, 1989) to predict the
range of cyanide levels in the impoundment and those reporting to the water treatment plant. A
schematic of the Cyanisorb system is provided on Figure 1.
526 Kindley et al.

Table 1
Summary of In-Stream and Discharge Criteria
Parameter Discharge Permit Limitation River Site-Specific Criteria

4-Day Average Not to Exceed Chronic Acute
(maximum)
Arsenic 0.25 32.5 0.25 3.1
Cadmium (1) 0.015 0.045 0.002 0.007
Chromium 0.25 166 0.13 16.5
Copper (1) 0.081 0.209 0.013 0.035
Cyanide (WAD) 0.47 2.26 0.1 0.24
Iron 1 NS (2) 1 NS (2)
Lead (1) 0.029 0.716 0.005 0.116
Manganese 0.5 NS (2) 1 NS (2)
Mercury 0.0043 0.1 0.00086 0.01
Nickel (1) 1.04 36.408 0.183 6.407
Silver (1) 0.014 0.158 0.002 0.024
Selenium 0.05 20.44 0.023 2.1
Zinc (1) 0.355 3.085 0.060 0.484
Boron 1.7 1.7 NS (2) NS (2)
Ammonia (N) (3) 11 985 2.2 19.7
pH -- 6.5 – 9.5 -- --
All concentrations in mg/l.
Notes:
(1) Hardness related toxicity (for calculation the average discharge hardness was used; i.e.,
433 mg/l).
(2) NS = limits not set.
(3) Ammonia limits based on average river temperature and pH.
527 Kindley et al.

528 Kindley et al.

To aid in the prediction of the tailings seepage chemistry, a laboratory cyanide decay study was
conducted using anticipated levels of cyanide that would be achieved following recovery. This
body of research led to the design and construction of the first modern facility for the direct
recovery of cyanide from tailings slurry at the Golden Cross Mine (Mudder and Goldstone,
1989; and Mudder and Goldstone, 1992).
The cyanide recovery process combined four unit operations including acidification to convert
WAD cyanide to molecular HCN, stripping of the HCN from the tailings slurry in packed towers
using low pressure high volume air, recovery of the HCN gas in an alkaline solution, and finally
neutralization of the tailings. The benefits of the system included recovery of cyanide, large
reductions in water treatment costs, elimination of a tailings impoundment liner, reduced
potential for groundwater contamination, and protection of birds and other wildlife. Lower
cyanide concentrations in the interstitial pore water will reduce water treatment costs during
mine closure and may reduce the economic and environmental issues related to cyanide
byproducts, such as, ammonia {Smith and Mudder, 1991). The Coeur Corporation owns several
patents for the process, and has commercialized it under the name CYANISORB, for which a
modest licensing fee is required to utilize the technology.
4.0 THE OVERALL WATER MANAGEMENT SYSTEM
The priority task of the overall water management system is to ensure that the needs of the
mining and milling operations are met and that excess water is discharged from the site in
compliance with the various permit requirements.
The three main objectives of the system aimed at minimizing environmental impacts are to
maximize the diversion of runoff from undisturbed catchments, to maximize the segregation of
clean and contaminated water sources, and to maximize the recycle and reuse of water. The
original water management system was based upon division of site waters into three categories
including clean water, storm water, and process water (Goldstone and Peterson, 1991; and
Peterson, 1991). The layout of the water management system, including the primary site features
is provided on Figure 2.
The clean water management system is designed to minimize volumes of water on site requiring
treatment and to reduce inputs to the tailings dam water balance. Clean water not impacted by
the operations is diverted around the site for direct discharge into the Waitekauri River. The
storm water management system consists of a series of drains, pipes, sumps, culverts, silt dams,
and a treatment plant (WTP2) designed specifically for the removal of total suspended solids.
Site runoff and water containing sediment pumped from the open pit and underground workings
are directed to a sedimentation or silt dam prior to treatment at WTP2. Excess water from the
silt dam is treated in a series of tanks and ponds through pH adjustment with sodium hydroxide
and by the addition of the poly-aluminum chloride or PAC, a polymerized aluminum compound
designed to coagulate colloidal material dispersed in the water. After treatment and sampling to
ensure regulatory compliance, the water is discharged to the river via a permitted diffusion point,
which includes a fish access way.
529 Kindley et al.

530 Kindley et al.

Mine drainage and process solution, containing cyanide and metals, is directed to the main
treatment plant (WTP1). It is the design and operation of the process water treatment plant that
is the primary focus of this paper.
4.1 The Process Water Management System
This portion of the water management system incorporates the pipelines structures and controls
for conveying process water between the metallurgical process, the cyanide recovery plant, the
tailings impoundment, and WTP1. Three submersible pumps attached to a floating pontoon are
used to decant water from the tailings dam and pump it into a header tank, from which the water
flows by gravity to the mill makeup tank. This tank in turn supplies the process water pond and
a pipeline to WTP1 on a demand basis, based upon precipitation and the quantity of excess water
than can be stored. The decant pumps are operated from level controllers in the process pond
with the mill makeup tank demanding water from the header tank depending on the requirements
of the process water pond and WTP1.
If there is insufficient water for milling operations, water can be pumped back from WTP1 to the
makeup tank and into the process pond. If there is a surplus of water from WTP1, it can be
pumped from the makeup tank back to the header tank, and then overflow into the tailings dam.
The tailings dam underdrainage system discharges into the terminal well located at the toe of the
tailings dam. This source of water is comprised of groundwater plus seepage of pore water from
the tailings. The terminal well discharges into a pipeline, which conveys the water by gravity to
WTP1. A pumpback system is installed in the terminal well, which can pump the underdrainage
water back to the makeup tank. Both the metallurgical process and the cyanide recovery plant
areas are bunded and drained so that any overflow is directed into a holding pond, which is in
turn pumped into the process pond or tailings hopper using a automated level sensing system.
4.2 The Tailings Dam Water Balance
The most critical variable in the process water management system is the control of the volume
of water stored in the tailings impoundment. With limited available storage capacity in the
impoundment, it is important that tailings consolidation be optimized to ensure maximum
utilization of the available capacity.
The water balance is strongly positive, due to three meters of average annual rainfall that is
received at the site. Water must be continuously treated and discharged into the river. By
minimizing the stored water volume in the impoundment, WTP1 plays a vital role in the overall
operation, by allowing exposure and evaporative drying of the tailings through draining. The
end result is increased storage capacity for tailings and increased densities of the tailings
disposed of in the impoundment.
531 Kindley et al.

The water level and its volume in the impoundment are periodically obtained by survey methods,
but can also be calculated using a computer model originally developed specifically for the
Golden Cross Mine (M.P.A. Williams and Associates, 1994). The model was used in the
developmental and design stages of the project to allow the simulation of various anticipated
rainfall and treatment scenarios. These evaluations were critical in the selection and
optimization of the preferred treatment alternatives and approaches. The model has been
modified over time to reflect various changes that have occurred within the water management
system.
An automated and simplified model is still in use on a daily basis to determine the required
treatment rate to maintain sufficient tailings dam freeboard and to allow instantaneous
predictions of stored water volumes using an automated telemetry communication system linked
to a personal computer.
5.0 THE PROCESS WATER TREATMENT PLANT (WTP1)
Due to the importance of the water balance to the overall operation and the very stringent
numerical limitations in the discharge permit, a very sophisticated, but flexible water treatment
system, referred to as WTP1, was developed. A computer in the WTP1 control room monitors
the entire water management system, including the water supply to the process plant.
5.1 Computerized Control System
The computerized control system is an integral component of the whole water management
system and consists of a supervisory control and data acquisition (SCADA) package called
INTOUCH, which includes remote data access, telemetry out-stations, and a programmable logic
controller (PLC), as shown on Figure 3.
Telemetry out-stations, positioned at various remote sites, provide continuous monitoring of

critical water management components such as metallurgical process water requirements,
meteorological data, river flow data, pump flow rates, sump and pond levels, tailings dam
relative level (RL) and stored water volumes, and storm water treatment information from
WTP2.
Radio transmissions from the base unit, located in the main water treatment control room, to
individual out-stations, occur every 30 seconds on a staggered polling interval. Ten remote sites
receive and send transmission packets to the base unit over a 5-minute cycle, during which time
about 60 variables are updated or modified. Information from the base unit is transmitted to a
modem linked to software drivers that communicate with the INTOUCH package. Telemetry
out-stations in remote areas without electrical power, utilize solar panels.
532 Kindley et al.

533 Kindley et al.

A PLC monitors and controls several hundred operational variables in the process water
treatment plant. These variables or monitoring points consist of flows, pH values, turbidities,
pump operation, valve settings, and other instrument data needed to maintain compliance.
Communication with the INTOUCH package is achieved using modbus communication
protocol-linked directly to the PLC. The INTOUCH package monitors and controls all of the
incoming information from the PLC and all of the telemetry out-stations, using 24-hour historical
logging of several hundred operational variables, alarm monitoring, paging operations, historical
trending, data management, and operator display windows. This system is Microsoft Windows
NT based and uses Dynamic Data Exchange Protocol to communicate with other Windows
software, such as Microsoft Excel. The system has the capability of writing information directly
to spreadsheets for reporting purposes or process monitoring analysis.
Historical data logging enables operators to access historical plant performance data via trend
screens to continuously evaluate ongoing plant operations. Alarm monitoring is used throughout
the process water treatment plant and water management systems using various alarm set points
selected to achieve optimum performance of equipment and effluent quality.
Alarm paging is an added feature of the SCADA system that enables operators to carry out duties
around the mine site while still staying in touch with water treatment operations. Remote control
of and access to the water treatment and water management data can be carried out from any part
of the world, providing security clearance criteria have been met. Access to real time data
provides supervisors and/or managers current information when it is required for budgeting,
inventory control, and plant performance updates.
5.2 Treatment Plant Design and Layout
The treatment plant incorporates a cyanide oxidation treatment section and coagulation,
flocculation, and clarification sections for removal of metals and suspended solids. The plant
layout for WTP1 is shown on Figure 4. Control of segregated flows is accomplished at the head
of the plant to meet water management and proportional river discharge rate criteria (Mudder,
1987b).
Water containing cyanide is directed to the head of the plant in the oxidation section, while water
containing dissolved metals only is passed to the metals removal section, which is located in the
middle of the plant. The key to effective metals removal is to first oxidize and remove the
cyanide, freeing the metals for subsequent precipitation.
The oxidation section consists of complete mix reactor tanks, set in two parallel trains of three
tanks each. The chemical reagents, including hydrogen peroxide, copper sulfate, and lime, are
added via two rapid mix tanks placed in series in front of the oxidation tanks. The oxidation
reaction involves peroxide oxidation of free and weak acid dissociable (WAD) cyanide bound to
metals according to the following equations:
(1) CN- + H2O2 => OCN- + H2O
(2) M(CN)4-2 + 4H2O2 + 2OH- => M(OH)2 + 4OCN- + 4H2O
534 Kindley et al.

535 Kindley et al.

The metals released during oxidation are precipitated via co-precipitation and adsorption
mechanisms predominantly as hydroxides and carbonates in the subsequent metals treatment
section. This section incorporates two rapid mix tanks for addition of coagulant, precipitation
reagents, and lime, before entering one of two central feed clarifiers for flocculation and settling
of suspended solids and trace metals. Chemical reagents introduced in this section include the
coagulant ferric chloride, a synthetic anionic flocculating agent polyelectrolyte, lime, and a
proprietary organic precipitation reagent, known as trimercapto-s-triazine or TMT.
The two clarifiers have central, variable speed flocculation basins and double sided weirs set in
from the wall about one meter. Settled underflow from the clarifiers is recycled with excess
sludge pumped into the tailings impoundment for disposal following thickening in a separate
sludge conditioning tank.
Addition of sulfuric acid for pH adjustment and calcium chloride for hardness adjustment is
conducted at the end of the metals removal section. A Parshall flume at the end of the plant
monitors flow and also has online pH, conductivity, and turbidity meters.
The water treatment plant (WTP1) includes a number of features, including a large effluent
holding pond between the flume and the point of discharge to the river. The pond allows
sufficient time for analyses of the effluent to be reviewed prior to its discharge to the river. A
commercial regulatory-approved off-site laboratory completes all analyses.
In the event that the water fails to meet a required standard for a constituent, it is either retreated
through WTP1 or it is returned to the process pond via an emergency pump-back system. Other
safety features include chemical spillage containment systems, pager alarming systems, standby
power generation, duplication of key mechanical parts of the treatment plant, standby backup
pumping systems, and 24-hour monitoring of the plant (Peterson and Kindley, 1993). Extensive
training of the plant operators was conducted initially, is being continued, and is considered
essential in achieving long term compliance and optimal water treatment plant performance.
5.3 System Modifications
Fluctuations in constituents concentrations in the process water are considerable and result from
a complex interplay of chemical, physical, and biological reactions, including hydrolysis,
precipitation, adsorption, photolysis, volatilization, dilution, and microbial degradation. Table 2
provides the historical concentration ranges for the WTP1 effluent and the river.
The seasonal variation in concentrations affect the volume of process water treated at WTP1,
based upon the design mass loading criteria for the treatment plant and receiving water
environment. A critical variable affecting process water influent volumes to WTP1 is the
presence of iron cyanide, which can combine with copper to form a precipitate according to the
equation:
(3) 2Cu+2 + Fe(CN)6-4 => Cu2[Fe(CN)6 ] (solid)
536 Kindley et al.

Table 2
Summary of In-Stream and Discharge Data
WTP1 Discharge (1992-1998) Waitekauri River (1994-1998)

Parameter Average Maximum Minimum Average Maximum Minimum
Arsenic 0.06 0.1 <0.001 0.07 0.1 <0.001
Cadmium (1) 0.003 0.022 <0.001 0.002 0.003 <0.001
Chromium 0.01 0.044 <0.004 0.01 0.04 <0.004
Copper (1) 0.038 0.18 <0.001 0.004 0.022 <0.001
Cyanide (WAD) 0.07 0.8 <0.007 0.01 0.3 <0.007
Iron 0.17 0.98 <0.1 0.18 1.6 <0.02
Lead (1) 0.004 0.054 <0.008 0.003 0.008 <0.0001
Manganese 0.06 0.5 <0.1 0.10 0.5 <0.02
Mercury 0.0021 0.07 <0.0001 0.0001 0.0001 <0.000005
Nickel (1) 0.015 0.21 <0.003 0.009 0.01 <0.003
Silver (1) 0.004 0.03 <0.0001 0.001 0.001 <0.0001
Selenium 0.012 0.11 <0.001 0.002 0.005 <0.001
Zinc (1) 0.010 0.087 <0.004 0.009 0.089 <0.001
Boron 0.05 0.107 <0.005 0.09 1 <0.014
Ammonia (N) (3) 4.0 10.4 <0.1 0.6 3.2 0.1
Hardnesss 433 1,221 65 84 201 11
pH 7.8 9.6 6.5 7.1 8.6 5.8
Notes:
(1) Hardness related toxicity (for calculation the average discharge hardness was used; i.e.,
433 mg/l).
(2) NS = limits not set.
(3) Ammonia limits based on average river temperature and pH.
537 Kindley et al.

When iron cyanide is present in elevated concentrations, problems in achieving copper

compliance can arise. The operational problem occurs because the clarifiers are operated at a pH
of 10 to maximize the precipitation of the metal hydroxides, which have low solubilities at this
pH. Unfortunately, the cupro-ferrocyanide complex is much more soluble at this pH, resulting in
elevated copper concentrations.
This problem has been managed through a combination of source control and operational
changes. Source control was accomplished by enhancing the oxidation of iron in the
metallurgical circuit prior to the addition of cyanide. The excess free iron in the process
solutions arose from excessive deterioration of the grinding balls and natural increases in the ore.
To minimize the formation of iron cyanide in the process solutions additional air and lime were
added to the first leach tank to promote precipitation of iron hydroxide before the metal could
combine with cyanide.
Since the concentration of iron cyanide increases with depth in the tailings impoundment, a
floating decant system is used to pump decant water to the process pond. In spite of these
approaches to lower iron cyanide levels, wind induced circulation in the impoundment results in
elevated suspended solids containing total cyanides being sucked into decant pumps.
As a result of this problem, the original plant design was modified to include a pre-treatment step
for process water. Process water influent was re-routed directly into the first clarifier, with the
addition of ferric chloride, sulfuric acid, and low pH mine water. The water in the clarifier turns
a dark Prussian blue color, characteristic of precipitated iron cyanide, allowing the precipitated
solids to coagulate, flocculate, and settle. The use of otherwise unwanted low pH mine waters as
a coagulant has been successful, provides a free source of ferric ions, and improves clarifier
performance. The clarifier underflow pumps remove the blue/brown sludge containing the
precipitated iron cyanide directly to the tailings hopper, while the overflow from the clarifier is
pumped to head of the oxidation section of the treatment plant. This innovative modification has
resulted in excellent removal efficiencies for suspended solids and iron cyanides and in increased
volumes of process water being treated at WTP1.
The average total suspended solids levels entering and exiting the clarifiers were 1,473 mg/1 and
10 mg/l, respectively. Following modification of the clarifiers to enhance the removal of iron
cyanide through precipitation, the total cyanide was lowered from an average of 38 mg/1 to 25
mg/l.
5.4 Activated Carbon Effluent Polishing System
Another system modification has been the installation of activated carbon columns for the
purpose of polishing the effluent to remove low residual levels of metals, such as copper. The
original water treatment strategy envisioned that the activated carbon polishing system could be
used in the future if needed. In this application, treated effluent from the flume is pumped up-
flow through four activated carbon columns operated in parallel.
538 Kindley et al.

The treated effluent moves upward through the columns, creating a fluidized bed of activated
carbon that adsorbs low levels of metal cyanide complexes. The water then flows from the top
of the columns through screens and into a launder, which discharges directly into the effluent
holding pond. Each column contains three tons of activated carbon, which at a flow rate of 200
m3/hr provide a retention time of 3.6 minutes.
The carbon columns are changed-out on a rotational basis with fresh carbon, with the spent
carbon being recycled in the CIP circuit at the mill. The metal complexed cyanides adsorbed
onto the carbon have had no detrimental effect on the cyanidation and gold recovery circuits.
Excellent removal efficiencies for copper and WAD cyanide have been achieved. An added
benefit of the system is that the low levels of gold present in the treated effluent are also sorbed
onto the carbon. Several kilograms of gold have been recovered each year in this way, the value
of which offset a portion of the overall water treatment costs.
The average copper and WAD cyanide concentrations entering the activated carbon columns
were 0.17 g/m3 and 0.13 g/m3, respectively. Following treatment, the copper and WAD cyanide
were lowered to 0.006 g/m3 and 0.03 g/m3, respectively. Even when the copper and WAD
cyanide reached levels approaching 0.50 g/m3 in the effluent, removal efficiencies through the
granular activated carbon were sufficient to meet discharge criteria.
6.0 EFFLUENT BIOMONITORING SYSTEM
Effluent and in-stream biomonitoring programs were established in addition to the water
treatment process and water quality monitoring systems, which include extensive computerized
on-line monitoring systems and daily chemical analysis of the effluent. The allowable effluent
limitations contained in the discharge permit were based upon the site- specific in-stream water
quality standards developed in accordance with the USEPA Recalculation Procedure.
The overall environmental goal was and is to protect the sensitive aquatic ecosystem present in
the river below the mine. The approach involved identification of the most sensitive species and
life stage for each constituent, followed by derivation of a site-specific standard using the
USEPA Recalculation Procedure. The most sensitive species for nearly all of the constituents,
with the exception of nickel, was determined to be the juvenile rainbow trout (Oncorhynchus
mykiss).
Accordingly, an effluent biomonitoring system using this species as a sensor was established. A
series of flow through aquaria were installed in the WTP1 laboratory, each with a volume of 60
liters and a flow rate of 200 L/hr. The tanks had two in-flows, which were manually controlled
by valves and included either river water, gravity feed up-stream from the nearby Waitekauri
River, or treated WTP1 water pumped from the effluent holding pond. Juvenile rainbow trout at
the alvein stage were obtained from a local hatchery and allowed to acclimate in river water until
they had reached the swim up fry stage.
539 Kindley et al.

Ten fish were placed into each of the test tanks and the remainder placed into a stock tank.
Effluent water flows were controlled so that the first tank contained 100% river water (control
tank), tank two contained 20% WTP1 discharge water and 80% river water (the maximum
allowable discharge mixture), and tank three contained 100% WTP1 water. Fish behavior was
closely monitored, and if unusual behavior and/or mortality were noticed, the discharge to the
river was ceased, the water re-treated and re-analyzed. The bioassay setup and test procedures
followed the recommendations of Environment Canada (Environment Canada, 1990).
During the 90-day experimental period, there was no mortality and no discernable sub-lethal
toxic effects on the fish in the tank containing the maximum allowable (20% effluent/80% river
water) discharge mixture. The fish exhibited positive rheotaxis throughout their exposure and
general behavior appeared similar in all three tanks. Respiratory and cough rates for each group
of fish were similar. No retracted gill opercula were evident, the dorsal fins were not eroded, and
there was no sign of mucous trailing from their gills. Body markings and coloring were normal,
and no fin erosion or external lesions were evident. There was no sign of any external
pathogens, and gill filaments were not eroded and their color was good. When the fish became
too large for their tanks, they were liberated into holding ponds and the experiment was restarted
when stock was available.
The use of effluent biological monitoring systems to provide feedback for water quality
monitoring and operational process control was used for the first time on a continuous basis in
New Zealand at the Golden Cross Mine. Regular observations of fish behavior, coupled with
analysis of fish weights and lengths, have shown that there were no discernable differences
between treatments.
The effluent biological monitoring system has been very successful, and has provided a clear
visual demonstration of the excellent water qualify being discharged, and can be used to
minimize the effects from any unplanned events or possible synergistic toxic effects. The
effluent biological monitoring system has been in place since 1993, and will continue to be used
during the closure and rehabilitation phase of the project. Despite all of the strict operating
controls, the quality assurance system in place, and the near perfect compliance record, the
ultimate test of the water treatment system are the effects of the treated effluent on the in-stream
ecological system following discharge into the river.
540 Kindley et al.

7.0 INSTREAM BIOMONITORING PROGRAM
In addition to the point of discharge monitoring, there is also a requirement in the discharge
permit for in-stream monitoring of water quality, as well as fisheries, periphyton, and
invertebrate surveys and bioaccumulation studies. Water quality samples are taken in the river
above and below the discharge on a daily and weekly basis. The data has shown that the river
analyses below the discharge point have remained below the in-river site-specific criteria (Table
5). Based on the results of the latest in-stream biological surveys, and comparison of those with
the results of previous annual surveys, the discharge of treated water has no measurable effects
on the fish or other fauna within the river (Kingett, Mitchell and Associates, 1996 and 1997).
There has also been a marked increase in the number of medium and large trout observed in the
river during the 1996 survey. The trout were all in very good condition, with their ongoing
presence being a major indicator that the water quality in the river has not been impaired.
The bioaccumulation studies used flesh samples taken from the trout's lateral swimming muscles.
These samples were digested and copper analyses were carried out using standard ICP-MS
techniques. A comparison of the copper concentrations in the fish below the discharge with
those of other investigations shows generally lower concentrations than those found previously
(Kingett Mitchell and Associates, 1996).
It was concluded that the copper in the WTP1 discharge was having no measurable effect on the
accumulation of this metal in the muscle tissue of trout. The copper concentrations in the flesh
of the trout sampled were well below acceptable levels.
8.0 REFERENCES
Environment Canada, "Environmental Protection Series Report EPS 1/RM/9", Canada, 1990.
Goldstone, A. and Peterson, D., "Development of Treatment and Discharge Strategies for the
Golden Cross Mine", Proceedings of the IPENZ Conference, Auckland, NZ, 1991.
Kingett Mitchell and Associates (formally Kingett and Associates), "Receiving Water
Objective", Report to Cyprus Minerals NZ, Ltd., Waihi, New Zealand, December, 1987.
Kingett Mitchell and Associates, "Waitekauri River Fisheries Survey and Biomonitoring
Evaluation", Report to Coeur Gold NZ Ltd., March 1996.
Kingett Mitchell and Associates, "Waitekauri River Fisheries Survey and Biomonitoring
Evaluation", Report to Coeur Gold NZ Ltd., 1997.
M.P.A. Williams and Associates, "Tailings Monitoring and Water Balance Modeling", Report to
Coeur Gold NZ Ltd., Waihi, New Zealand, 1994.
541 Kindley et al.

Mudder, T., "Development of Site-specific Water Quality Criteria for Cyanide", Report to
Cyprus Minerals NZ, Ltd., prepared by Industrial Waste Management, Ltd., Waihi, New
Zealand, 1987a.
Mudder, T., “Review and Selection of Preferred Wastewater Treatment Technologies for Cyprus
Minerals”, Water Right Application Technical Support Document, Report to Cyprus Minerals
NZ, Ltd., Prepared by Industrial Waste Management, Ltd., September 1, 1987b.
Mudder, T. and Goldstone, A., “The Recovery of Cyanide from Slurries”, Proceedings of the
International Gold Expo Conference, Reno, Nevada, September, 1989.
Mudder, T. and Goldstone, A., “Cyanisorb Cyanide Recovery Process: Design, Commissioning
and Early Performance”, Written for and Presented at the Northwest Mining Association Annual
Conference, Spokane, Washington, December, 1992.
Peterson, D., “Water Management and Wastewater Treatment for the Golden Cross Mine”,
Water and Wastes in New Zealand, September, 1991.
Peterson, D. and Kindley, M., "Contaminated Water Management for the Golden Cross Mine",
paper presented at the 27th Annual Conference of the New Zealand Branch of the Australasian
Institute of Mining and Metallurgy, Wellington, 1993.
Smith, A. and Mudder, T., The Chemistry and Treatment of Cyanidation Wastes, Mining Journal
Books, 1991.
USEPA, The Water Quality Standards Handbook, Office of Water, Washington, D.C.,
December, 1983.
542 Kindley et al.

CHAPTER 6
Heap leach decommissioning and closure
● Closure concepts
● Solution management and closure alternatives for precious
metals heap leach facilities
● Solution management during decommissioning of heap
leach operations
● Geochemical study of leach pad cyanide neutralization at
Brohm Mining Corporation, South Dakota
CLOSURE CONCEPTS
Prepared By:
Terry Mudder, Ph.D.

Kevin Harvey
Published in Mining Environmental Management, Mining Journal Limited, London, England,

United Kingdom, November, 1998
The State of Mine Closure:
Concepts, Commitments, and Cooperation
1.1 INTRODUCTION
The objectives for closure of a typical hard rock mine include minimizing long term
environmental liability, attaining regulatory compliance, and maintaining geotechnical stability,
while closing as quickly and cost effectively as possible in a manner that returns the land to a
safe and stable configuration for post-mining uses. Some of the key features that must be
considered during decommissioning and closure of a mine could include any underground
workings, a tailings impoundment, an open pit, surface waste rock piles, and spent leach pads.
The environmental concerns surrounding each of these features have changed dramatically over
the years with varying economic consequences to mine closure. Of particular interest is the heap
leach operation and the related features of an open pit, waste rock piles, and the spent leach pads.
The open pit has become a center of controversy due to its physical aspects and the potential for
becoming a temporary or permanent water impoundment. The resultant quality of the pit lake
and its subsequent classification becomes important as to "waters of the state.” The primary
concern with waste rock piles is the potential for oxidation of reduced sulfides and the release of
acid and metals contained in the drainage. Lastly, there is the spent leach pad and its draindown
solution which contains cyanide, metals, and other inorganic constituents. Although the fear of
cyanide prompted the initial regulations related to rinsing of spent leach pads, it is the potential
release of metals and other inorganic constituents that have become the major regulatory focus
over the years. The environmental issues related to closure of underground workings, tailings
impoundments, and conventional milling operations present similar challenges but appear to be
less of an issue to the public and the regulatory agencies.
Proper planning for closure should come during the feasibility study, design and permitting
phases of a mine, and during operations as upgrades. This approach has become the standard or
is a required practice today. The lack of a proper or updated closure plan for a mine can result in
severe environmental and economic consequences. Inadequate closure activities, water
management, and waste rock disposal plans have prompted unexpected and, in some instances,
unwarranted secondary environmental impact statements or assessments.
In other cases, the lack of proper planning for closure has resulted in major changes to the
required reclamation bonding for a mine. More emphasis is being placed upon the initial and
ongoing bonding of mining operations due to concerns arising from the financial status of a
company and the potential for long term environmental damage from acid mine drainage. The
examples of improper management and the related consequences are well documented and are
too numerous.
544 T. Mudder & K. Harvey

Beyond the direct economic aspects of inadequate closure plans and bonding, are the indirect
impacts being felt by the mining industry. For example, the State of Wisconsin recently passed
legislation that stopped further hard rock mining until an example could be identified that had
operated for ten years and had been closed for ten years without any environmental impacts to
ground or surface waters. In the State of Montana various referenda have been put forth over the
last two years, with the most recent one calling for a ban on further open pit mines that use
cyanide. A few years ago there was a referendum in South Dakota calling for complete backfill
of open pits to original contours. These types of legislation are not generally prompted by
concerns over improper mine permitting or operation; they are the direct result of issues related
to improper mine closure and abandonment.
Proper mine closure is the result of a combination of innovative concepts, long term
commitments, and multi-party cooperation. Public education, in addition to participation, is a
major factor because in the absence of knowledge, fear resides. The purpose of this paper is to
discuss concepts, commitments, and cooperation which can be blended into an effective and
implementable closure plan.
2.0 CONCEPTS
There are many different words used to describe closure including decommissioning,
reclamation, rehabilitation, and post-closure. In this paper, decommissioning is referred to as the
transitional period between cessation of operations and final closure. Reclamation refers to the
physical aspects of earth moving, regrading, and revegetation. Rehabilitation is another word for
closure used primarily in countries other than the United States, for example Australia. Closure
is a term reserved for the point in time at which revegetation has been completed, excess
solutions have been eliminated to the extent practical, the maximum degree of passive
management has been implemented, and a final surface and/or ground water monitoring program
has been initiated. The ability to "walk away" from a mine site at closure is dependent upon the
degree of passive management that can be implemented, as compared with long term operation
of a mechanical water treatment plant. Post-closure, a term often used improperly, is the point in
time beyond which no further monitoring or passive management is needed or required. The
same basic concepts and terms apply to the different types of mining operations at any location.
The inability to "walk away" from a mine site at closure has related primarily to the two issues of
water management and waste rock disposal. The environmental and economic aspects of water
management and waste rock disposal during decommissioning and following closure of a hard
rock mine have not always received the level of attention warranted during project development
and operation. Historically, the focus of decommissioning and closure has been on physical
reclamation and revegetation.

In coal mining, these issues are of less concern than for hard rock mines, due to the practice of
continuous reclamation. Both open pit and underground hard rock mines have incurred
unexpected and increased levels of expenditures and environmental liability at the end of active
operations, at a time when revenues can be declining. The single most important issue which
directly affects all other aspects of closure is water management. Often a mining operation, and
in particular an open pit heap leach facility, can operate with a "zero" water balance due to
evaporative losses and the wetting of ore. As a result, there is initially no need for a discharge
permit and a major regulatory issue is circumvented. But as decommissioning and closure
approach, the site water balance remains as before, but the entire water management system is
replaced by the need to eliminate large stored inventories. A common misconception regarding
the mine site water balance stems from the belief that water management is automatically
successful if annual evaporation exceeds precipitation.
In wetter climates, the management and elimination of the relatively large solution inventories
present a number of challenges due to the continued accumulation of runoff within underground
workings, open pits, and tailings impoundments; infiltration through surface waste rock; and
long-term draindown from spent leach pads. Although the historical approaches of continuous
fresh water rinsing or recycle of treated water through a spent leach pad adequately addressed the
standards associated with WAD cyanide or pH, they did not always satisfy the regulatory
requirements for metals or other inorganic constituents. Each open pit heap leach mining
operation presents a unique set of circumstances for consideration during decommissioning and
closure. Based upon a thorough understanding of the quantity and quality of remaining solutions
and application of proven water management and treatment concepts, a suitable closure scenario
can be designed and implemented. The water management and treatment concepts range from
enhanced evaporation, to land application, to passive and mechanical treatment. An excellent
handbook for minesite water management has been recently published in Australia (Minerals
Council of Australia, 1997). Of equal importance and concern is the water balance situation
created at temporarily shutdown mines.
In addition to solution and water management, long-term commitments are needed with respect
to reducing infiltration through surface waste rock piles, spent heap leach pads, and tailings
impoundments through design and construction of appropriate synthetic or natural barriers and
revegetative covers. Depending upon the site water balance and the management of sulfide
containing waste rock during operations, unnecessary and expensive long-term commitments to
water treatment may occur during decommissioning and following closure.
The direct impacts of treating acid mine drainage and indirect negative publicity associated with
it are substantial. In a recent report prepared by the Office of the Supervising Scientist and the
Australian Centre for Minesite Rehabilitation Research, an in-depth evaluation of the anticipated
cost of treating acid mine drainage was presented. The total economic liability could reach
$A80,000,000 per year with an overall liability to the industry nationwide of about
$A1,000,000,000 over the next fifteen years (Harries, 1997). The economic estimate to deal
with acid mine drainage for the Canadian mining industry has been placed at $C2,000,000,000-
$C5,000,000,000 (Feasby and Jones, 1994; MEND, 1995; and MEND, 1996).

Although comparable values are not available for the United States, the Bureau of Mines
estimated that several thousand miles of surface waters had been impacted by acid mine
drainage, the treatment of which was costing the mining industry over $US1,000,000 per day
nationwide (Kleinmann, 1991). This cost of treatment translates into $US365,000,000 per year,
or nearly $US4,000,000,000 over the last decade of this century.
From a short term perspective, the prediction and evaluation of pit lake chemistry and the
associated risks has resulted in substantial and unexpected expenditures ranging from several
hundreds of thousands of dollars to over a million dollars. The concern over pit lake chemistry
stems from the need to define its ultimate beneficial use and corresponding standards. In many
instances the regulatory requirements are not well defined.
The traditional approach to closure of spent heap leach pads has been to rinse continuously with
fresh water. Unfortunately, this approach has worked acceptably for run-of-mine (ROM)
materials, but not so well for agglomerated pads. The cost of pumping and recirculation of
solution onto the pad has become excessive as many more pore volumes of rinsing are required
than anticipated to achieve standards for constituents other than WAD cyanide and pH.
Another approach involves the recirculation of treated solution to minimize pumping costs, but it
has become apparent that WAD cyanide and pH are not the only constituents of concern, and
that metals standards are difficult to achieve with recirculation of treated solution alone. In order
to reduce the solution inventory for closure, enhanced evaporation has been a favored approach
coupled with land application and passive in-situ treatment.
A variety of technical concepts are available to aid in the efficient and cost-effective closure of a
heap leach facility. A summary of the basic closure approach for heap leach facilities is
presented in a literature publication (Mudder and Miller, 1998). The major point to be noted
relates to the unique and varying situations that exist at different mining operations and the fact
that environmental concerns change with time. As a result, closure concepts must be modified
periodically to reflect technological advancements, to account for current regulatory
requirements, and to allow development of the most cost-effective closure plan.

3.0 COMMITMENT
Although consideration of closure in association with mine design and permitting is often
required today, there are some existing operations that do not even have a conceptual closure
plan, let alone a plan that can be reviewed and updated on a periodic basis. Without a closure
plan, a new environmental assessment or the promulgation of a discharge permit may be
initiated. It is in the best interest of an active mining operation to develop and periodically
review and update the closure plan and to modify its internal accrual process so that unexpected
economic surprises do not occur at the beginning of decommissioning. More emphasis is being
placed on not only the internal accrual process but the external bonding requirements. In order
to circumvent further public intervention into the accrual and bonding aspects of a mining
operation, there needs to be a commitment to conduct these periodic assessments in a realistic
manner. Commitments to an outdated closure concept may actually cost the operation more than
necessary.
Commitments must also be kept with respect to ongoing reclamation projects and waste rock
management programs during operations in order to minimize long term environmental and
economic liability. Deviations from waste rock management programs over time, with less solid
sampling and acid/base accounting, inadequate field classification systems, and reduced in-place
disposal methods can result in increased costs at closure. There needs to be a commitment not
only to the overall closure approach or concept, but also the individual components of that
approach, some of which involve ongoing programs during operations.
With respect to physical reclamation there needs to be ongoing revegetation studies and a
commitment to maintain topsoil stockpiles, and not inadvertent use of this material for other
purposes. There must be a commitment to continued evaluation of closure alternatives and
continued education of environmental personnel regarding the potentially changing closure
requirements. In some instances, different phases of a single mining operation can be permitted
under different sets of regulations. The industry as a whole must be open-minded to new ideas,
because without innovation there will be stagnation.
From experience, the overall cost of closure based upon total disturbed surface area of a mine
site typically ranges from about $US5,000-$US15,000 per acre. At coal mines the ongoing
reclamation costs generally range between about $US10,000-$US15,000 per acre. At hard rock
mines, the lower range of closure costs is usually associated with arid sites with rainfalls of only
a few inches per year and minimal waste rock issues. Depending upon the level of water
management and treatment required, along with waste rock encapsulation and generation of acid
mine drainage, the overall closure costs raise toward the upper range.

In an annual company environment, health, and safety report published by Homestake Mining
Company, the average company-wide reclamation costs were reported to be about $US13,600
per acre (Homestake Mining Company, 1996). A total of 136 abandoned coal mine sites were
reclaimed in Pennsylvania between 1980 and 1992 at a cost of about $US9,500 acre (Bogovich,
1992). An in-depth study conducted in Australia revealed that the cost of managing sulfide
wastes at historical mine sites was easily double the cost compared to if managed during
operations. Based upon the Summitville experience, leaving the cleanup of historical mine sites
to the government may not be the most economical approach. In the absence of ongoing
commitment, there will likely be additional costs.
The best approach toward maintaining a commitment to closure, accrual, and bonding is through
the use of the environmental audit. Most companies have some form of audit program, with
some being quite outstanding by involving both internal and external technical and legal experts.
There is a need to commit to ongoing air and water quality monitoring programs at a mining
operation without the tendency to modify the monitoring programs for the sake of reducing
costs. Monitoring plans should be conducted for the purpose of gathering the information
necessary to make long-term predictions. Monitoring requirements may change over time, for
example when analytical detection limits get lower and lower.
If the mining industry does not commit to the conceptual and cash requirements of closure, some
other entity will likely do it through either litigation and/or regulation, with the potential
promulgation of more stringent bonding requirements. This commitment must be accompanied
by the continued education of the public, replacing fear with knowledge. Unfortunately, fear is
often more marketable than knowledge. In conjunction with the closure of the Golden Cross
Mine in New Zealand, Coeur is publishing periodic updates to help the public understand the
rehabilitation process (Coeur Gold NZ Ltd., 1998). The mining company publication aids the
decommissioning process during a time when employees and local business people have
legitimate economic concerns about their future. Often the resulting anxiety and stress expresses
itself as anger and resentfulness. Often, the economic and emotional states of people are
overlooked as environmental issues are emphasized.
4.0 COOPERATION
Above all, there must be both internal and external cooperation and understanding between
participating stakeholders in the closure process. Consistent cooperation, coordination, and
communication results in good corporations. There must be internal understanding of concerns
and cooperation between the daily operational staff and the corporate personnel. There also must
be coordination and cooperation among the mining, metallurgical, health and safety, and
environmental staff within the individual operation. When there is a lack of communication
between management and the workers, then the sag mill is replaced by the rumor mill, with a
reduction in productivity.

As decommissioning and closure of a mine approaches after years of operation, the emotional
aspects become as important as both the economic and environmental issues. Through a
combination of cooperation, communication, and coordination, a transitional team should be
assembled to accommodate all aspects of decommissioning and closure. Being humans, we tend
to be more comfortable with stability and routine; we have difficulty during transitional periods.
From an external viewpoint, there must be cooperation among the mining operation, the
community, and the regulatory agencies. Permitting, operations, and closure often becomes
time-consuming due to mistrust, inflexibility, misinterpretation, and a lack of closure concepts
and goals. The regulatory process has not kept pace with the changing times. When cooperation
fails, litigation can prevail. Prolonged legal confrontations are not productive and do not serve
the purpose of protecting the environment. Although lawsuits may benefit certain personal
agendas, they usually do not resolve the long-term issues, and the environment and most
everyone else involved suffers as a result. There is a tendency in the mining industry to not
upgrade or modernize a closure plan, since the need for a simple technical revision has often
resulted in a full scale environmental impact assessment or statement. Such a situation recently
occurred at a mining operation regarding its management plan for sulfide waste rock. In
addition, there is the impact of other regulatory requirements (for example, from Biological
Opinions which are prepared regarding endangered species at minesites).
Over the next decade, scores of mining operations throughout North America and the world will
begin the decommissioning and closure processes. It is important for politicians and the
regulatory agencies to consider the consequences of rigid and prescriptive regulations. A
cornerstone of our modern society has been accepting and reducing risks through innovation and
imagination.
There is frustration within many different groups of stakeholders and stockholders regarding the
mining industry as a whole. A conflict has arisen between the need for the industry and the
desire for its products. Each year there is a growing demand for the products of mining, with
more reliance on foreign suppliers of those products as the industry in the United States declines.
There is an economic, environmental, and emotional price to pay for increasing our reliance on
foreign metals and minerals.
The consulting industry must do a better job of responding to the future needs of the industry
through development and implementation of innovative approaches. There is no single approach
that can resolve all of the closure issues. Consulting must go beyond simply responding to the
Request for Proposal (RFP) and the mining industry must go beyond thinking of closure as
merely engineering and earth-moving. There are many interrelated issues that must be integrated
into a comprehensive closure plan.

It is recommended that about three years before decommissioning begins, a closure strategy
team, comprised of both internal and external personnel, be formed. The closure strategy team
should then meet on an annual basis to identify issues early in the process with sufficient time for
resolution to avoid crisis management. Initially, a closure audit should be conducted to
determine the status and success of the ongoing operational environmental management systems.
About a year before the decommissioning process begins, a final or revised closure plan should
be submitted to all involved entities.
These time frames are variable due to the regulatory requirements that exist from state to state.
An educational program should be initiated for the public and the mine personnel as the
transition period approaches. From a cooperation, coordination, and communication standpoint,
there is a need for the global mining community to share ideas and closure plans. In this era of
electronic and instantaneous communications, there is no excuse for the lack of information
exchange. In addition, there is a need for a major mining closure conference to discuss current
thinking and present the state-of-the-art information.
The success and future of mining will not be tied to the promises made during permitting or to
the actual environmental, health, and safety record compiled during operations; however, it will
be tied to the condition of the mining site after closure.
5.0 REFERENCES
Bogovich, W., "Twelve Years of Abandoned Mineland Reclamation Activities by the U.S. Dept.
of Agriculture and Soil Conservation Service in Southwest Pennsylvania", Land Reclamation:
Advances in Research and Technology, American Society of Agricultural Engineers Publication
14-92, 1992.
Coeur The Precious Metal Company, " Golden Cross REHAB. News", Edition 1, Waihi, New
Zealand, April, 1998.
Feasby D. and Jones, R., Report of Results of a Workshop on Mine Reclamation, Canadian
Centre for Mineral and Energy Technology, Ottawa, Ontario, March 10-11, 1994.
Harries, J., Acid Mine Drainage in Australia: Its Extent and Potential Future Liability,
Supervising Scientist Report 125, Office of the Supervising Scientist, Environment Australia,
and Australian Centre for Minesite Rehabilitation Research (ACMRR), Canberra, Australia,
1997.
Homestake Mining Company, Environment, Health, and Safety Report, San Francisco,
California, 1996.
Kleinmann, R., "Acid Mine Drainage: An Overview", Proceedings of a Specialty Conference

Sponsored by the Energy Division of the American Society of Civil Engineers, American
Society of Civil Engineers, Pittsburgh, Pennsylvania, March 10-13, 1991.

MEND, Economic Evaluation of Acid Mine Drainage Technologies, MEND Report 5.8.1,
Energy Mines and Resources Canada, Ottawa, Ontario, Canada, January, 1995.
MEND, "What is MEND? Mine Environment Neutral Drainage", Natural Resources Canada,
www.nrcan.gc/mets/mend, September 6, 1996.
Minerals Council of Australia, Minesite Water Management Handbook, ISBN 0909276730, 125
pp., 1997.
Mudder, T. and Miller, S., "Closure Alternatives for Heap-Leach Facilities", Mining
Environmental Management, Volume 6, Number 1, January, 1998.

SOLUTION MANAGEMENT AND CLOSURE ALTERNATIVES
FOR PRECIOUS METALS HEAP LEACH FACILITIES
Prepared By:
Terry Mudder, Ph.D.

Scott Miller
Published in Mining Environmental Management, Mining Journal Limited, London, England,

United Kingdom, January, 1998
Solution Management And Closure Alternatives
For Precious Metals Heap Leach Facilities
1.0 INTRODUCTION
1.1 Issues
Cyanide heap leaching for the recovery of precious metals from low-grade ores emerged as a cost
effective and efficient process, and has been widely implemented in a variety of climates and
environmental conditions. The recovery process involves mining, stacking ore on engineered
leach pads with or without crushing and/or agglomeration, followed by application of a low
concentration sodium cyanide solution as a lixiavant. The metal bearing leach solution is collected
and processed using zinc precipitation or activated carbon absorption to extract the precious
metals. Barren solutions are then recycled following pH adjustment and addition of sodium
cyanide for re-application.
Heap leach facilities are generally constructed as permanent structures, built sequentially in
vertical lifts and lateral expansions. Heap leach operations may also involve reusable pads for ore
with consistent and rapid leaching rates. Given the relatively low-grades of the ore, heap leach
operations are generally large scale requiring large surface areas for leach pad construction, and
use of significant quantities of process water and cyanide. The leaching process continues until all
economic metal values are removed at which time the spent ore and remaining solution inventory
in the process circuit requires removal and final closure. The management and reduction of the
remaining solution inventory in the process circuit presents a number of challenges given the
volumes, chemical composition, and likelihood of continued generation of solution due to
infiltration of precipitation and long-term draindown.
The environmental and economic aspects of heap leach facility solution management at closure
has not received the level of attention warranted during project planning and operation. As a
result, many operations have recognized increased and unexpected levels of expenditure and
associated environmental liability at the end of active leaching, when operating revenues and
cashflow are minimal or have ceased. Many of the solution management and inventory reduction
challenges can be effectively addressed and dealt with during project planning and active
operation. This paper summarizes the alternatives available for the management of process
solutions in terms of both quality and quantity, and implications for spent ore management during
operations, closure, and post-closure. This paper updates the issues and approach developed
previously by Mudder and Smith (1992).
572 T. Mudder & S. Miller

1.2 Objectives
The objectives for heap leach facilities closure generally includes the following:
• Minimize potential long-term environmental liability
• Meet all applicable federal and local regulatory requirements
• Close the facility as quickly and cost effectively as possible
• Return land to a safe and stable configuration
• Return land to a suitable post-mining use
Applicable standards for heap leach facility closure varies from state to state and country to
country in terms of numeric criteria, parameters regulated, and duration and type of post-closure
monitoring. As most heap leach facilities are designed and operated as zero discharge systems,
frequently closure and post-closure discharge criteria have not been established and tend to
default to receiving water quality or drinking water standards. Criteria generally applied to closed
and reclaimed heap leach facilities include:
• Numeric water quality standards for seepage discharges
• Monitoring of surface and groundwater with non-degradation requirements
• Verification of spent ore solids leachability behavior and prediction of long-term

potential for acid generation
• Establishment of safe and stable slopes
• Establish vegetation and minimize erosion
• Post-closure monitoring of seepage quality and quantity and success of reclamation
Weak acid dissociable (WAD) cyanide is widely accepted as the most appropriate cyanide species
for environmental monitoring and compliance due to its geochemical behavior in the environment
and relatively accurate analytical methods for measurement (Smith and Mudder 1991). Free
cyanide is generally unstable in the environment and is difficult to measure at the regulatory levels.
Total cyanide is also subject to analytical error, although to a lessor degree, but measures forms
which are considerably less harmful from a environmental perspective.

1.3 Historical Closure Approach
The focus of this article is on the chemical and physical aspects of the heap leach pad during the
last phase of operation, closure, and post-closure. There are three factors which must be
considered during the selection and design of heap leach facility closure options. Foremost is the
site water balance, and prediction of the quantity of precipitation that will eventually percolate
through the heap. The quantity of seepage ultimately discharging from the closed heap leach pad
must be managed long-term and will affect the selection of the final reclamation cover for the
facility.
A second factor is the geochemistry of the spent ore which controls the composition of the
draindown solution and long-term seepage. The effects of ore agglomeration and/or the presence
of sulfides on the geochemistry of the seepage must be taken into account during closure
planning. The third factor includes the regulatory requirements, which affect the manner in which
the excess process solutions and seepage are treated and/or released to the environment.
The traditional approach to closure of heap leach pads was to rinse them continuously with fresh
water until a required chemistry was attained that allowed discharge of the solution and seepage.
The solution chemistry requirements generally focused on pH and cyanide. The rinsate standards
were typically less than 0.20 mg/l WAD cyanide and a pH of less than 9.5.
Although the WAD cyanide and pH standards could be met in most situations, it was common for
residual cyanide levels to spike over time as cyanide sorbed in the fines at the bottom fracture of
the heap was periodically released as water moved through the rinsed ore. The addition of
cement during agglomeration made the process of lowering pH from operational levels very
difficult due to the presence of excessive quantities of lime. Agglomeration also had the potential
of promoting scaling and armoring within the heap, that hindered the rinsing of the spent ore with
recycled solutions. Since the elimination of cyanide through natural attenuation requires pH
values generally below 9.0, the elevated pH associated with agglomerated heaps greatly reduces
the effectiveness of this process.
The traditional heap leach closure approach involved a fresh water rinse but, had many
drawbacks. First it required tremendous quantities of water. Secondly, rinsing generated
contaminated water requiring treatment and disposal. Thirdly, it was eventually recognized by
operators and regulators that cyanide and pH were not the only chemical constituents of concern
in the heap draindown and seepage. It is typical that many metals and inorganic compounds were
present in elevated concentrations is spent ore heaps. These other constituents were not as
readily rinsed from the spent ore and required many more pore volumes of rinse solution to
achieve acceptable discharge concentrations. Although the rinsing of the cyanide from the spent
ore typically required 3 to 5 pore volumes of fresh water, the removal of one or more of the
metals often required 10 pore volumes or more. In some cases, the residual levels of a particular
metal or other parameter, such as TDS or nitrate, could not be reduced to acceptable levels
through fresh water rinsing alone.

In order to reduce the volume of contaminated rinse solution and the management issues
associated with its disposal, the focus turned towards recycling treated rinse solution. This
approach allowed removal of constituents which were otherwise difficult to remove through
rinsing alone, while minimizing the total volume of solution. Water treatment involved the
implementation of various chemical, physical, and biological unit processes for the oxidation of
cyanide and the precipitation and/or sorption of metals and other by-products of gold extraction
as discussed below.
With experience it was noted that free and WAD cyanide naturally attenuated rapidly, if the pH of
the rinse solutions or pore water was below 9.0. The attenuation process was accelerated if the
rinse solutions were sprayed into the air to promote volatilization of free cyanide. Since air could
move naturally through the spent ore between rinsing cycles, it was found the cyanide attenuation
occurred even in the absence of rinsing and/or spraying.
Over time the preferred closure method evolved into a sequence of recycling the untreated or
treated process leach solution and evaporating or land applying it until the volume was been
reduced to a manageable volume.
2.0 HEAP LEACH SOLUTION / SOLIDS
2.1 Chemistry
In addition to the preferential formation of a strong complex between gold and cyanide, other
reactions take place between the ore and the process solution during leaching. These include the
formation of other metallo-cyanide complexes and the solution of other inorganic compounds
soluble under high pH conditions. The net result of the chemical interactions in the heap leach
circuit, as described in detail in Smith and Mudder (1991), is to produce a post-leach solution
with the following chemical characteristics:
• A high pH generally in the range of 9.5 to 11.0
• Moderate to high total dissolved solids, mainly sodium, calcium (from lime use in pH
control), sulfate, nitrate, thiocyanate, and cyanide complexes
• Potentially elevated levels of constituents which form anionic complexes at high pH

such as arsenic, molybdenum, and selenium
• Potentially elevated levels of metals which form soluble metallo-cyanide complexes,

such as iron, copper, mercury, cadmium, nickel, and zinc

The actual chemistry of the process or leach solutions will vary throughout the leach and recovery
circuit and will vary from project to project, depending on the ore composition and leaching
practices. Some examples of leach solution chemistry for operations in closure are presented as
Table 1. It is this solution composition which requires management to meet applicable water
quality discharge criteria prior to release to the environment. Post-closure seepage chemistry will
depend upon the volume of precipitation moving through the heap, the degree to which the heap
has been rinsed, and the composition of ore particularly as it relates to the presence of cement or
sulfides.
2.2 Solution Volumes / Water Balance
2.2.1 Operation Volumes
During operation of a heap leach facility the system water balance involves two components: 1)
the process circuit and 2) the climatic conditions. The design of a heap leach facility water
balance is presented in Van Zyl et al. (1988). In general the heap leach water balance consists of:
Change in Storage = Precipitation - Evaporation - Ore Uptake + Process Water
The process circuit applies NaCN solution to the heap at a slow rate (generally in the range of 10
2
liters per hour/m ) to promote leaching. The process circuit loses water to moisture uptake as
newly mined ore at a natural moisture content is wetted to field capacity. The field capacity is the
maximum moisture content the ore can maintain prior to gravity flow of solution. During
leaching the volume of water applied to bring the ore moisture from natural moisture content to
field capacity is lost. Normal operating solution application rates are slightly higher than field
capacity to promote solution circulation. This volume of circulating solution in the process circuit
can be a very significant volume of solution. Example ore moisture contents are summarized
below:
Natural Moisture Content of Ore (by weight): 4-6 percent

Field Capacity of Ore: 10-12 percent
Leaching Moisture Content: 12-14 percent
For this example, each ton of ore requires 53 liters (14 US gallons) of water to reach field
capacity, with a circulating volume of approximately 38 liters (10 US gallons). Assuming a
leaching volume of 1.2 million tons of ore (one 4 m lift at an application rate of 250 liters per
hour) there could be approximately 45 million liters in circulation. As the heap leach facility
grows in the number of stacked lifts and area circulating volumes can reach hundreds of millions
of liters. Management of this volume of solution is achieved through construction of pond
storage, in-heap solution storage, and circulation of solution through the heap. At the end of
economic metals recovery this volume of solution must managed in accordance with
environmental constraints.

Table 1
Typical Range of Heap Leach Pad Solution Chemistry at Closure
Parameter Units Heap Solution 1 Heap Solution 2
pH pH units 9.43 7.2

Conductivity umbos/cm 5650 5410 umho
Total Diss. Solids mg/L 4720 NA
Alkalinity, Total mg/L as CaCO3 127 45
Chloride mg/L 580 301
Sulfate mg/L 1870 2500
Fluoride mg/L 0.6 0.34
Calcium mg/L 543 788
Magnesium mg/L 8 17.5
Sodium mg/L 774 851
Potassium mg/L 23 18.2
Wad Cyanide mg/L 16 0.062
Cyanate mg/L 32 NA
Nitrate mg/L as N 46 177
Nitrite mg/L as N 12 3.1
Nitrate/Nitrite mg/L as N 58 NA
Phosphorous, Total mg/L <0.01 NA
Aluminum mg/L <0.05 0.28
Antimony mg/L 0.2 NA
Arsenic mg/L 0.3 0.062
Barium mg/L 0.02 <0.05
Beryllium mg/L <0.01 NA
Cadmium mg/L <0.01 <0.005
Chromium mg/L <0.01 <0.05
Cobalt mg/L 1.02 NA
Copper mg/L 11.8 0.03
Iron mg/L 0.23 0.09
Lead mg/L <0.02 <0.05
Manganese mg/L <0.01 0.09
Mercury mg/L 0.438 0.0015
Molybdenum mg/L 1.65 NA
Nickel mg/L 0.58 <0.02
Silver mg/L 0.46 0.025
Selenium mg/L 0.38 0.181
Strontium mg/L 4.63 NA
Thallium mg/L <0.2 NA
Vanadium mg/L <0.01 NA
Zinc mg/L <0.02 0.026
NA = Not Analyzed

2.2.2 Closure and Post Closure Water Volumes
Closure of heap leach facilities historically has involved chemical detoxification and reduction of
the operational volumes of solution. Depending on the size of the heap leach facility this
operational volume can be significant. During leaching and metals recovery pumping large
volumes of solution are required. At the time of closure solution management becomes a different
matter due to the expense of pumping and the disposal of the solution through evaporation, land
application, or treated discharge. Closure solution management has to be coordinated with
chemical detoxification of the ore and reclamation of the heap surface. In wet climates the
solution inventory at closure can further increase due to precipitation gains.
Management of solution volumes during later stages of the operation to reduce the inventory can
greatly reduce solution volumes at the time of closure. Continued recovery of precious metals
during the closure phase through the use of small carbon columns is a common practice for
management of small volumes of solution. Management of precipitation during closure also can
be a significant issue in wetter climates and must be incorporated into the overall water balance.
Solution management alternatives during closure are presented below.
Post-closure solution management at heap leach facilities is common where the seepage quality
does not meet discharge limitations. Post-closure seepage from reclaimed heap leach pads occurs
due to infiltration of precipitation and residual draindown of process solution as the ore returns to
a residual moisture content. Volumes of seepage during post-closure depend upon the type and
effectiveness of the reclamation cover, volume of precipitation, area and extent of the pad and
liner, and the volume and moisture content of the ore. Predictions of long-term seepage rates can
be developed using a variety of unsaturated numeric flow models or using more simplistic water
balance methods. Quality of the post-closure seepage is dependent upon the operating history,
rinsing history, chemistry of the ore, and presence of cement or sulfides within the ore. Seepage
management alternatives are presented below.
Efficient management of heap leach facility during closure and post-closure is generally best
achieved through development of an integrated strategy. This strategy should be initiated during
operations to promote timely elimination of process solution during decommissioning and
placement of an appropriate reclamation cover for post-closure.

2.3 Solution Management Alternatives During Closure and Post-Closure
This section presents a summary of the closure and post-closure solution management
alternatives. Due to variable climatic conditions and differing ore geochemistry not all of these
alternatives will apply to every site. The alternatives for solution management include:
• Rinsing to Achieve Chemical Stability
• Evaporation
• Land Application
• Water Treatment (both active and passive)
• Natural Attenuation / Enhanced Biodegradation of Cyanide
• Heap Encapsulation / Reclamation
2.3.1 Rinsing
Rinsing of the spent ore using fresh water or recycled treated water to achieve chemical stability is
the traditional approach to heap leach facility closure. This method has been demonstrated to be
effective for cyanide attenuation at a number of facilities. As discussed in Mudder and Smith
(1992), 3 to 10 pore volumes of solution may be required to achieve compliance with rinse
solution standards. The successful implementation of rinsing is dependent upon the volume of
ore, chemistry of the ore, and cost associated with treatment or disposal of rinse water. Given
that a single pore volume of a heap leach facility represents approximately 35 percent of the total
volume of the heap, 3 to 10 pore volumes can represent billions of liters of water (e.g., a 50
million ton heap has a 7.6 billion liter pore volume). There are a number of other potential
disadvantages to rinsing which include:
• Difficulty in achieving complete rinsing of the spent ore due to preferential pathways
• Potential high cost and long duration necessary to achieve compliance standards to
pumping cost, ongoing site management, and compliance monitoring
• Numeric standards for certain metals or inorganic compounds may not be attainable on
either a short- or long-term or basis
Given the potential problems associated with rinsing, careful analysis of the costs, duration, and
attainability of the discharge limitations should be conducted prior to selecting this approach.

2.3.2 Evaporation
In many mining districts around the world, evaporation exceeds precipitation on an average
annual basis and in many cases for all months of the year. Evaporation of heap leach process
solutions during closure by converting the drip system to elevated sprays can be an effective tool
to reduce inventory. Additionally, in this type of climate, infiltration into the heap will be
relatively minor resulting in minimal seepage after complete draindown of process solutions.
Evaporation of process solutions on the heap leach pad and pond areas has several advantages,
most notably no discharges to surrounding surface or groundwater are required, and the precious
metal extraction can continue throughout the process. However, there are several disadvantages
including:
• Generally not an effective method when total precipitation exceeds evaporation
• Can result in a significant chemical load returning to the pad due to precipitation of
metals and inorganic compounds as solution evaporates
• Can require long duration and can be subject to high maintenance costs
Evaporation has been proposed as a management tool for long-term seepage from reclaimed
facilities. Given the correct climatic conditions this is a viable alternative. However, evaporation
systems require maintenance and would likely require protection for wildlife.
2.3.3 Land Application
In areas of net precipitation, process solution must be bled out of the heap leach circuit to
maintain adequate solution storage capacity. Bleed solution is generally treated, and discharged
to land or surface water. Land application can be used as a means to dispose of treated process
solution during closure. Environmental studies to support the design of the land application
program may include solution treatability, soil attenuation for constituents of concern, receiving
water quality and quantity, soil percolation rates, and review of potential ecological risk to plants
and animals.
Land application as a means to manage post-closure seepage is a viable alternative, but does
require long-term maintenance, and depending on solution volumes and quality, may require
extensive land application areas over time.

2.4 Active Water Treatment
Water treatment and discharge of process solutions during closure have been implemented at a
number of projects and can be a cost effective approach to rapidly reducing solution volume and
duration of closure. There are several chemical, physical, and biological process options available
for the treatment of leach solution during closure and post-closure. For an overview of cyanide
treatment and recovery options the reader is referred to Mining Environmental Management, June
1995. The preferred chemical oxidation processes include copper catalyzed hydrogen peroxide,
sulfur dioxide/air, and alkaline chlorination. All of these processes are suitable for batch or
continuous treatment and are capable in many cases of attaining an effluent WAD cyanide less
than 0.2 mg/l. If required, additional treatment steps can be implemented beyond cyanide
destruction to enhance the removal metals. Typical process solution influent and treated effluent
quality is presented in Table 2. The preferred metals removal processes include pH adjustment,
coagulation/flocculation, sulfide precipitation, and activated carbon adsorption. A major
disadvantage of active water treatment is the potential high capital and operating costs.
Temporary skid mounted treatment equipment may be a potential alternative available for
treatment of the solution inventory prior to reclamation.
An alternative approach to treatment plants involves a simplified system using existing process
ponds as reaction cells with chemical feed systems. The ponds can be configured to be employed
as equalization basins, reactors, and settling basins. Either of the two chemical oxidation systems
can be sized to treat flows ranging from a few to several hundred gallons per minute.
Another proven treatment option for treatment of cyanide and metals involves biological
processes similar to that employed in the microbial treatment facility at the Homestake Mine near
Lead, South Dakota (Mudder and Whitlock 1984). This process has been adapted to heap leach
solution treatment to enhance the natural breakdown of residual cyanide (Thompson et al. 1995).
Use of granular activated carbon for removal of low levels of metals and WAD cyanide is a
physical treatment system successfully employed. The carbon is effective in removing cyanide and
the complexed trace metals including cadmium, mercury, copper, silver, and gold.

Table 2
Summary of Treatment Values for Key Parameters – Heap Leach Solution
Parameter Units Influent Effluent
Total Cyanide mg/L 133 2.75

WAD Cyanide mg/L 124 0.28
Thiocyanate mg/L 10 0.1
Cyanate mg/L 240 150
Ammonia (NH3-N) mg/L 89 73
Nitrate + Nitrite (NO3 + NO2 - N) mg/L 1.57 0.39
Aluminum (Al) mg/L 0.54 0.2
Antimony (Sb) mg/L 0.045 0.044
Arsenic (As) mg/L 1.23 0.1
Barium (Ba) mg/L 0.004 0.007
Beryllium (Be) mg/L <0.001 <0.001
Boron (Bo) mg/L 0.41 <0.05
Cadmium (Cd) mg/L 0.029 0.011
Chromium (Cr) mg/L 0.02 0.02
Cobalt (Co) mg/L 0.75 0.55
Copper (Cu) mg/L 2.93 0.02
Iron (Fe) mg/L 0.97 1.58
Lead (Pb) mg/L <0.002 <0.002
Manganese (Mn) mg/L 0.002 0.002
Mercury (Hg) mg/L 0.0069 0.0002
Molybdenum (Mo) mg/L 0.97 0.9
Nickel (Ni) mg/L 0.042 <0.005
Selenium (Se) mg/L 0.026 0.02
Silver (Ag) mg/L 0.04 <0.0005
Thallium (Tl) mg/L <0.003 <0.003
Vanadium (v) mg/L <0.05 <0.05
Zinc (Zn) mg/L 26.2 0.21
2.5 Passive Treatment Systems
Passive treatment of residual draindown and long-term post-closure heap seepage is an emerging
technology which provides relatively low capital costs and little to no long-term maintenance.
Due to flow limitation of the passive treatment system it is unlikely that this approach will be
effective in treating process solution volumes during closure. The general approach involving
passive treatment for closure of heap leach facilities has been outlined in Mudder et al. (1995).
The treatment system has been termed the Biopass, and consists of an anaerobic upflow cell
which is capable of collecting and treating residual heap leach solution on an as-needed basis. The
treatment cell includes an influent piping system, substrate layer comprised of composed manure
and gravel, an effluent piping system, and an septic like infiltration cell. The system uses sulfate
reducing and denitrifying bacteria to treat heap solutions prior to discharge to groundwater.

Cyanide complexes are detoxified, metals precipitate as sulfate, sulfide is reduced, and nitrate is
biologically denitrified. The Biopass offers an alternative means to manage post-closure seepage
from heap leach facilities without costly rinsing of the spent ore. Full scale operation of these
systems in Nevada is ongoing. Figure 1 presents a conceptual cross-section of the system.
Figure 1: Biopass System
2.5.1 Natural Attenuation / Enhanced Biodegradation
Natural attenuation of cyanide complexes is a proven methodology for reduction of cyanide to

relatively low concentrations. This process is primarily pH controlled and as discussed in Mudder
and Smith (1992) can occur while the heap leach facility is under active rinsing or while dormant.
The duration of natural attenuation can take many months to achieve the low discharge levels
usually required. To improve the efficiency of cyanide attenuation, enhanced biodegradation has
received some attention (Thompson et al. 1995). This is achieved by stimulating cyanide
degrading bacteria already present in the heap leach pad and by nutrients and/or introducing
bacterial seeds to the rinse circuit. Biological processes introducing for cyanide detoxification of
heap leach solutions has several potential advantages as it lowers treatment costs, can be
performed in situ, and can shorten the duration of detoxification. However, a potential
disadvantage includes the process may not achieve compliance with metals and inorganic
compounds discharge limitations, and produces other unreusable by-products such as ammonia
and nitrate.

2.6 Facility Reclamation / Covers
Physical reclamation of heap leach facilities can play an important role in the post-closure solution
management by reducing the volume of infiltration entering the spent ore. Reclamation cover
alternatives include direct revegetation of the spent ore, compaction of the spent ore surface,
placement of soil cover and revegetation, and placement of low permeability barriers made of
synthetic or natural materials. Evaluation and selection of a cover type for reclamation of a heap
leach pad is dependent upon site specific climatic and environmental conditions. Selection of the
type of the reclamation cover should be based on an integrated evaluation including the quality
and quantity of heap leach seepage after reclamation and potential seepage management
strategies.
3.0 EVALUATION OF ALTERNATIVES
3.1 Approach
This section presents an overview of an approach to heap leach facility closure planning,
alternative development, evaluation, and selection. This approach provides a framework to define
objectives, identify and quantify risk, evaluate alternatives for effectiveness, cost, constructability,
and adherence to the corporate objectives. Often this process is iterative in nature, and will allow
selection of the closure alternatives which best meet the cost, operations and maintenance (O&M)
objectives, and regulatory requirements.
• Define Objectives (Corporate, Regulatory, Stakeholders)
♦ Physical Stability
♦ Chemical Stability
♦ Return Land to Beneficial Use
♦ Type of Closure: walk-away, passive care, active care
• Identify and Rank Closure Issues
♦ Stability/Safety
♦ Eliminate Process Solution
♦ Short and Long-Term Chemistry of Spent Ore
♦ Control of Infiltration and Seepage

• Develop/Evaluate Closure Alternatives
♦ Cost
♦ Effectiveness
♦ Regulatory/Public Acceptance
♦ Ease of Construction
• Selection of Alternative
♦ Performance Indicators
♦ Risk Analysis
♦ Decision Analysis
♦ Conduct Additional Studies as needed to reduce Uncertainty
• Design and Implement Final Closure and Post Closure Strategy
Selection of closure options (i.e., walk-away, passive care, or active care) should be balanced so
closure costs reflect actual reduction of liability. For example, heap leach pad rinsing which has
been implemented at significant cost at numerous facilities may not reduce the liability associated
with chemistry of the heap seepage. Figure 2 presents a flowsheet for the evaluation and selection
of heap leach facility closure and post-closure strategies.
3.2 Water Balance
The site water balance is the single most important evaluation tool for determining the project
closure issues and long-term environmental liabilities at the site. The short-term water
management issues at heap leach facilities include characterization of the transition from operating
solution management to closure solution management. During operations consumption of water
is high and cash flow allows expenditures associated with water management activities. At
closure process water consumption is eliminated and a new site water balance is required. Cost
effective short-term water management can only be achieved by anticipating the changes from
operations to closure.
The long-term water management issues at heap leach facilities include prediction of post-closure
seepage quantities. This is generally approached using numeric unsaturated flow models
calibrated with site specific ore moisture release characteristics and draindown data.

Figure 2: Flowsheet for Heap Leach Facility Closure and Post-Closure Process

3.3 Geochemistry
Characterization of the short- and long-term geochemical behavior of the spent ore is critical to
sites where climatic conditions dictate water discharge from the site. Logsdon and Mudder
(1995) present an evaluation approach for geochemical characterization of spent ore and the
associated water treatment issues. Spent ore characterization included acid base accounting, US
EPA Method 1312 leaching, and sequential leach testing of bulk samples. The sequential leach
test can be designed to simulate a geochemical response given the proposed heap infiltration and
post-closure monitoring period. Treatability studies to evaluate cyanide and metals removal are
also conducted. These data allowed prediction of short-term chemistry associated with the
treatment and discharge of process solution, the potential effectiveness of rinsing, and the long-
term potential for acid generation if sulfides are present in the spent ore.
4.0 SUMMARY
This paper reviewed the principal elements associated with the solution management and closure
planning for heap leach facilities. Decommissioning of heap leach facilities is characterized by
both short-term and long-term solution management and geochemical issues. Each facility is
unique given the site specific climatic conditions, ore chemistry, volumes and layout of the
operation, and the sensitivity of the receiving environment. Although unique, each facility must
develop site water balances, eliminate process solution, develop reclamation strategy, and
evaluate post-closure seepage quantity and quality.

5.0 REFERENCES
Logsdon, M. and Mudder, T.I., 1995. Geochemistry of Spent Ore and Water Treatment Issues.
In: Colorado Geological Survey, Special Publication 38, Proceedings: Summitville Forum 95,
Eds. Posey, Pendleton, and Van Zyl. pp 146-151.
Mudder, T.I., Miller, S.H., Cox, A., McWharter, D., and Russell, L., 1995. Lab Evaluation of An
Alternative Heap Leach Pad Closure Method. Mining Engineering. November 1995, pp 1007-
1014.
Mudder, T. I., and Smith, A., 1992. Solution Management During Decommissioning of Heap
Leach Operations. Presented and published at AIME/SME Annual Conference, Phoenix,
Arizona, February 24-27, 1992. 18 pp.
Mudder, T.I. and Whitlock, J.L., 1984. Biological Treatment of Cyanidation Wastewaters. Paper
presented at the 38th. Industrial Wastewater Conference, Purdue University., Lafayette, Ind.
August 1984.
Smith, A. and Mudder, T.I, 1991. Chemistry and Treatment of Cyanidation Wastes. Mining
Journal Books Limited, London. 345 pp.
Thompson, L.C., Fischer, R., Seep, A.E., Beckman, S.W., Williams, L., and Hubbard, J., 1995.
Biotreatment Processes for Spent Ore Detox at the Summitville Mine. In: Colorado Geological
Survey, Special Publication 38, Proceedings: Summitville Forum 95, Eds. Posey, Pendleton,
and Van Zyl. pp 146-151.
Van Zyl, D., Hutchison, I., Kiel, J., (editors) 1988. Introduction to Evaluation, Design and
Operation of Precious Metal Heap Leaching Projects. Society of Mining Engineers, Inc.
Littleton, Colorado. 372 pp.

SOLUTION MANAGEMENT DURING
DECOMMISSIONING OF HEAP LEACH OPERATIONS
Prepared By:
Terry Mudder, Ph.D.

Adrian Smith, Ph.D.
Published in Proceedings of the 121st Annual SME Meeting and Exhibit, The Society of Mining,
Metallurgy, and Exploration, Inc. (SME), Phoenix, Arizona, February, 1992
8307 Shaffer Parkway, Littleton, Colorado 80127-5002
Solution Management During
Decommissioning Of Heap Leach Operations
1.0 INTRODUCTION AND OBJECTIVES
Heap leaching has become one of the prime technologies used for the recovery of precious metals
from low-grade ores over the past ten years. The recovery process involves mining and stacking
the ore on engineered leach pads, with or without crushing and/or agglomeration, followed by
leaching with a low concentration sodium cyanide solution. The metal-bearing, pregnant solution
is then processed by zinc precipitation or activated carbon absorption to extract the precious
metals.
The leaching process continues until all economic metal values are removed at which time the
spent heap leach pads, the leached materials and excess process solutions require
decommissioning. The management of these solutions may present a potential challenge for
successful and environmentally sound decommissioning due to their composition, volume or
continuity of generation from the spent ore even though active leaching has been terminated.
The principal objectives of solution management in decommissioning spent heap leach pads are to
meet all operative environmental regulations in a cost-effective manner and to leave the pads in a
condition where they do not present a long-term liability either to the operator or to the
environment. This involves the reduction in volume of the residual process solutions and/or
treatment of these solutions to where they meet applicable water quality criteria.
In the past, the environmental and economic aspects of decommissioning and solution
management have been overlooked or under estimated during the planning of mining operations.
As a result, there is a potential for long-term liabilities and costs to be recognized only at the end
of active leaching, a time at which operating revenues and cashflow are minimal. Therefore, the
decommissioning process requires addressing at the mine planning stage and agencies now require
that a plan for solution management after the cessation of operations be submitted prior to
initiation of mining.
This paper discusses aspects of process solution management during decommissioning, both in
terms of quantity and quality, and how potential issues may be recognized and planned for in the
initial stages of heap leach design.
2.0 LEACH AND PROCESS SOLUTION CHEMISTRY
2.1 Chemistry
While solution management encompasses consideration of aspects of process solution quantity

and quality, it is advantageous to have a general appreciation of process solution quality prior to
consideration of overall management strategies and approaches, as it is the quality of the process
solutions which ultimately determine their disposition.
554 T. Mudder & A. Smith

2.2 Leach Process Chemistry
Gold solution by sodium cyanide (NaCN) involves a two-stage process which can be summarized
as:
(1) 4Au + 8NaCN + O2 + 2H2O → 4NaAu(CN)2 + 4NaOH
In theory, at an optimum pH value of 10.3, relatively weak cyanide solutions can be used for the
process (about 100 ppm NaCN), because of the strong complex which forms between the gold
and cyanide. In practice, leach solutions generally carry between 200 ppm and 500 ppm NaCN in
the range of pH 10.5 to 11, to obtain optimal recovery of gold.
-
The high pH value is necessary in order to keep the cyanide in the ionic state as CN ions. At
lower pH values cyanide will be lost by volatilization as hydrogen cyanide, a gas at ambient
conditions, is formed.
2.3 Process Solution Chemistry
Irrespective of the preferential formation of a strong complex between gold and cyanide, other
reactions taken place between the ore and the process solution during leaching. These include the
formation of other metallo-cyanide complexes and the solution of other species from the ore
soluble under high pH conditions.
The net result of the chemical interactions in the heap leached ore, described in detail by Smith
and Mudder (1991), is to produce a post-leach process solution with the following general
chemical characteristics:
• A high pH value in the range of pH 9.5-11.

• Moderate to high dissolved species, mainly sodium, calcium (from lime use in pH control),
cyanide, and sulphate.
• Potentially elevated levels of species which form anionic complexes at high pH values, such as
arsenic, molybdenum, and selenium.
• Potentially elevated levels of metals which form soluble metallo-cyanide complexes, such as
iron, copper mercury, cadmium, and zinc.
The actual chemistry of the process or leach solutions will vary throughout the leach and recovery
circuit and will vary from project to project, depending on the ore composition and the leaching
parameters used.
Some examples of leach solution composition are given in Table 1 to illustrate this range and
variation. Once the ore leaching process is complete it is this solution composition which requires
treatment to meet applicable water quality criteria should it need to be released to the
environment.

Table 1
Examples Of Leach Solution Composition
Project Project Project
Parameter* A B C
pH (units) 9.5 - 10 9.5 - 10.5 10 - 10.5
Total Dissolved Solids ND >1,800** 2,500
Total Cyanide 130 180 - 200 100

Wad Cyanide 80 - 110 120 - 170 90
Free Cyanide 60 120 - 150 75
Arsenic 2 <1 1.0

Cadmium <1 <1 <0.10
Copper 2 - 10 5 - 10 10
Iron ND 15 - 20 2-5
Mercury ND ND 4-5
Molybdenum ND <1 ND
Selenium ND <1 0.10 - 1.0
Zinc 2 - 10 <5 - 10 1-5
Notes:
* All values in mg/l unless stated otherwise.
** Based on solution conductivity values.
ND Not determined.

3.0 DECOMMISSIONING OBJECTIVES AND CRITERIA
3.1 General Objectives
In order to attain the goal of decommissioning a state agency usually has numerical or narrative
standards which must be attained to protect the beneficial uses associated with the surface and
groundwaters. The beneficial use classifications may include potable water, agriculture, stock
watering, aquatic life, industrial, or recreation. The standards vary widely from state to state as
do the controlling agency or agencies. Since the regulations are changing rapidly the first step in
the decommissioning process is to contact the appropriate state agency and personnel and obtain
a current set of water quality and mining regulations.
After formulating an approach to decommissioning including a water management plan, if it

becomes apparent that the established standards can be not attained, an alternative approach must
be sought. In certain states, a risk or fate analysis can be prepared to demonstrate quantitatively
that release of partially treated solutions into the environment will not result in either short or
long-term adverse impacts.
3.2 Applicable Standards
Decommissioning standards for heap leach pads vary between jurisdictions and from state to
state, both in terms of the parameters regulated and the numeric standards used. Such regulation
can be generic, e.g., state-wide or set on a site-specific basis.
Numeric standards used by individual agencies and which can apply to both spent heap leach
solids and process solutions, either generically or specifically depending on the jurisdiction, have
been variously collated and detailed; for example, Smith and Struhsacker (1987), Van Zyl et al
(1988).
Normally regulations are set and standards prescribed for pH value, a range of metal species and
cyanide. While historically cyanide was regulated as "free" cyanide, which has been shown to be
analytically inexact at the desired regulatory levels, newer standards are specified as weak acid
dissociable (wad) cyanide. Wad cyanide values are more easily determined at the sub part per
million level, as well as making more sense from a potential environmental perspective.

4.0 SOLUTION MANAGEMENT OPTIONS
4.1 Management Alternatives
There are five primary alternatives for attaining regulatory compliance and handling post-
operational process solutions from a spent heap leach facility, although not all may be available
for consideration at one particular site:
• Natural attenuation.
• Fresh or treated water rinsing.
• Transfer of solution to another facility or into a tailings impoundment.
• Evaporation of excess solution.
• Treatment and discharge of rinse solutions to meet applicable water quality criteria.
Each of these alternatives is discussed briefly below. In addition, after partial treatment by either
natural leaching or conventional process technology, solutions can be applied to land in certain
circumstances as a final "polishing" step.
4.2 Natural Attenuation
The natural degradation of cyanide, a time-dependent process, is well established. It is not

unreasonable, therefore, to leave the spent ore on the pad exposed to the forces of nature so that
natural degradation can take place. In areas or climates where cyanide degradation is enhanced,
for example high temperatures and altitudes, as in Smith et al (1985), this could be an appropriate
strategy.
However the time dependency of the process means that the control of the process is out of the
operator's hands. The operator is forced to monitor the system and collect any runoff or seepage
from the spent ore which fails to meet regulatory discharge criteria, then wait until the heap leach
can be decommissioned. Both the time monitoring requirement and the possibility of handling/
treating large volumes of non-dischargeable runoff can be fiscal and practical disincentives to the
use of natural degradation.

The effectiveness of natural degradation of cyanide has been documented by Englehardt (1985) as
shown on Figure 1. While the method of cyanide degradation was not determined, this study
gave the careful quantification and monitoring of a heap system. The data indicated destruction
of cyanide approximates a first order chemical reaction, proportional to the concentration of the
cyanide. At the observed rate of degradation, it would take approximately four years to attain
about 1 mg of cyanide per kilogram of leachate.
This degradation and its nature, as described by Englehardt, is essentially consistent with data
developed by others; for example, data by Hendrix (1987) on cyanide decay in vat leached
tailings, and degradation in effluents by Schmidt et al (1981).
4.3 Fresh or Treated Water Rinsing
The natural attenuation process may be comparatively slow, but can be enhanced by "speeding
up" the forces of nature. The most expedient method of achieving such acceleration, without
resorting to chemical treatment, is cycling rainwater or similar water through the spent ore.
Rainwater normally has a pH value less than 7 meaning it is neutral to acidic, although the pH
value is regionally variable. For example, a rainfall pH of 4 to 4.5 is not uncommon on the east
coast of the United States while values approaching pH of 5 to 5.5 are more typical in the arid,
southwestern states of Arizona and New Mexico. Although rainwater has a low neutralization
capacity, when compared with the buffering capacity of the pore water in typical spent ore (pH
10.5), circulation of rainwater through the spent ore can depress the pH enough to convert free
cyanide to hydrogen cyanide, which is then lost to the atmosphere by volatilization (Huiatt, et al,
1982).
Data on cyanide degradation by water leaching have been developed by Wharf Resources, Lead,
South Dakota. Their data were reported by Smith and Brown (1986), and served as an
illustration of the process as discussed below.
Wharf degradation testing resulted in data on both total and wad cyanide (Method "C", ASTM)
with respect to pore volumes of discharge effluent. From an initial total cyanide value of 133 ppm
CN in the spent ore pore fluid, the total cyanide levels were reduced to below 1 ppm before 3
pore volumes of water had passed through the material (Figure 2).
Perhaps the major potential concern with water leaching for spent ore detoxification is the
possibility of generating large volumes of partially contaminated waste solutions. These solutions
may be unacceptable for discharge to the environment and/or unamendable to further treatment.
Should this be the case, chemical treatment for detoxification becomes more attractive.
It may be advantageous to combine evaporative and treatment strategies; for example, eliminating
the bulk of the process solution by evaporation and treating the residual so that the time to
complete the decommissioning of the heap leaching is not unduly extended.
A potential downside of using evaporation as a method of solution disposal is that the evaporated
solids from the solutions are left within the matrix of the spent ore on the pad. As such, these
solids will likely be highly soluble and report to the fluid phase in any test to determine
compliance with spent ore solid material decommissioning criteria. While the mass of solids so
formed may only become significant when there is a large solution inventory to be evaporated,

compliance with solids criteria may become more difficult.
Figure 1: Concentration of Cyanide in Moisture in Abandoned Heap

Figure 2: Plot of Cyanide Attenuation vs. Number of Pore Volumes for Rinsing

4.4 Transfer of Process Solution
In the case where a heap leach operation utilizes a number of pads either on a once through basis
or load/unload, the transfer of process solution represents a temporary expedient as, on final
decommissioning, the disposal solutions will need addressing ultimately. However, judicious
transfer of process solution within the operation can have the effect on minimizing the total
amount of fluid the operation requires, leading to a smaller ultimate management concern.
However, where heap leaching and milling are operated concurrently, there is an opportunity to
transfer the final heap leach process solution to the mill tailings impoundment. The process
solution can be incorporated in the tailings, evaporated from the tailings pool or reclaimed to be
used at least partially consumptively in subsequent tailings slurrying. This may allow the leach
pads to be decommissioned more rapidly and potentially cost effectively than if the solutions were
to be evaporated or treated at their source.
4.5 Evaporation of Excess Solution
Intuitively and probably economically, the evaporation alternative is normally preferred where
natural attenuation is unlikely or feasible and there are no other mine facilities, such as other
operational pads or tailings impoundments, which can accept the redundant process solutions.
However, such an approach is only feasible normally where the climate is conducive: i.e., when
natural evaporation exceeds precipitation. However, small inventories of process solution may be
evaporated where precipitation/evaporation are antipathetic and highly seasonal, utilizing
enhanced evaporation methods.
In addition, natural evaporation can be enhanced through modification of the sprinkler system
used for leaching. During leaching the approach is to minimize evaporation and loss of solution.
By using more spray nozzles and/or elevated nozzles which produce finer droplets, the
evaporation rate can be increased in certain instances by several percent in the summer months.
However, concerns with solution drift and cost for nozzle replacement must be evaluated.
4.6 Treatment and Discharge of Rinse Solutions
In the event fresh water rinsing and/or natural attenuation are not successful in attaining a desired
effluent quality, treatment of the solutions may be required. The goal of rinse solution treatment
is to reduce the pH, metals, and/or wad cyanide to levels acceptable for discharge into surface
water or land application.
If treatment is required, the identical processes are available as would be applied in either
discharge option. Wad cyanide will be parameter of primary concern due to potential for impacts
to wildlife. However, the levels of wad cyanide are readily reduced through rinsing, natural
attenuation, or treatment to acceptable levels.
With respect to surface water discharges, a NPDES permit would be required. The narrative or
numerical standards that must be attained would be very stringent in the event aquatic life
protection is necessary. Initially the applicable beneficial use classifications and standards must be
identified.

With respect to land application, the two issues include adsorption by soils and potential for
groundwater impacts. To resolve these issues a quantitative risk or fate analysis would be
required to demonstrate that discharge of treated or potential untreated solutions would not
exceed the accumulative capacity of the soils and ultimately adversely impact the vegetation or
existing groundwater quality. A detailed laboratory study may be required to evaluate the
adsorptive capacity of the soils, while a detailed modelling study may be required to evaluate the
hydrological aspects of land application.
There are several chemical, physical, and biological processes options available for treatment of
excess leach or process solutions. The preferred chemical oxidation processes include copper
catalyzed hydrogen peroxide, sulfur dioxide/air, and alkaline chlorination. All of these processes
are suitable for batch or continuous treatment and are capable in many cases of attaining an
effluent wad cyanide <0.20 mg/l.
If required, additional treatment steps can be implemented beyond cyanide destruction to enhance
the removal of metals. The preferred metals removal processes include pH adjustment,
coagulation/ flocculation, and/or sulfide precipitation.
A major disadvantage of these processes relates to the potential for excessive capital and
operational costs. If a permanent or semi-mobile system is constructed for chemical oxidation the
design would include a series of usually four complete mix reactors, rapid mix chambers for
chemical addition, and skid mounted chemical feed systems. A schematic of a semi-mobile
hydrogen peroxide system is shown on Figure 3.
An alternative approach involves a more simplified system which is applicable to many heap leach
operations and in instances where significant metals removal is not required. In this simplified
design the existing barren and pregnant ponds located at the base of a spent leach pad would be
operated in series in conjunction with a simplified chemical feed system.
The ponds can be configured to be employed as equalization basins, reactors, and/or settling
basins through the addition of floating baffles or weirs. Either of the two chemical oxidation
systems can be sized to treat flows ranging from a few to several hundred gallons per minute.
Another chemical treatment option employed at less frequently involves addition of ferrous sulfate
to either barren or rinse solutions to precipitate cyanide and to form a relatively stable iron
cyanide. The addition of ferrous sulfate to a solution with a pH below about 8.5 would
quantitatively precipitate the free cyanide from solution. The process does not remove iron or
other metal complexed cyanides which report as wad cyanide. As a result, the process is not
usually effective in attaining a required wad cyanide effluent standard. In the event that the pH of
the solution containing precipitated iron cyanide raises above 8.5, it is probable that
resolubilization of the iron cyanide would occur. Furthermore, ferrous sulfate is an acid and can
contribute to the promotion of acid generation and drainage in the presence of reduced sulfide
materials.

Figure 3: Typical Treatment System

Another proven option for treatment of cyanide and metals involves biological processes, in a
manner similar to that employed in the microbial treatment facility located at the Homestake Mine
in Lead, South Dakota (Mudder and Whitlock, 1984). However, the process has not been
adapted to applications involving decommissioning of spent leach pads, although researchers are
investigating the possibility. As with chemical treatment, there are two approaches which are
applicable to treatment of rinse solutions and residual wad cyanide.
The first approach involves a standard engineered attached or suspended growth treatment system
utilizing either biofilters, rotating biological contactors, or activated sludge. These systems would
be constructed on a permanent or semi-mobile basis and would be located at the base of a spent
leach pad.
The second more simplified system would involve addition of either phosphate and/or bacterial
seeds to the rinse solution prior to its recycle onto the pad. Although a significant reduction in
both rinsing time and costs are probable, the approach has not been investigated in detail in the
field. The preferred configuration would involve introduction of nutrients and bacterial seeds into
an aerated pond containing rinse solution. A minimal increase in operational costs in comparison
to rinsing alone would be anticipated.
From experience with biological treatment, the standard engineered systems do not appear cost
competitive when compared with chemical treatment, due to the capital investment required and
lead time needed for installation and startup of the system. As a result, natural attenuation
combined with rinsing and/or chemical treatment remain the preferred treatment and
decommissioning approaches.
One physical treatment system worthy of mention involves the use of granular activated carbon or
GAC for removal of low levels of metals and wad cyanide below about 1-2 mg/l. Since the
cyanide is bound to trace metals in solution, not only is cyanide removed but also cadmium,
mercury, copper, silver, and gold. In the event the residual wad cyanide in a rinse solution is very
low and recoverable metals are present, GAC presents a potential treatment option for smaller,
fixed volumes of solution like those contained in a barren or pregnant pond.
5.0 SITE WATER BALANCE AND MANAGEMENT PLAN
There are two fundamental aspects associated with decommissioning of a spent leach pad. The
first involves chemical reclamation during which the constituent concentrations in solution are
reduced to acceptable levels either through continuous rinsing with fresh or treated solution,
either alone or in combination with natural attenuation.
The second aspect of decommissioning involves physical reclamation which includes an evaluation
of the need for capping a spent pad and the options available for reducing the generation of
solution entering and exiting the pad. The capping options include compaction alone, compaction
with addition of low permeability natural materials, and synthetic covers.

The degree and sophistication of capping required is dependent upon the success of rinsing and
the potential for generation of acidic drainage through sulfide oxidation. Although the generation
of acidic drainage may not occur during operation due to the presence of elevated buffering
capacity, the flushing and neutralization occurring within the pad may reduce the pH over time.
As the ratio of reactive sulfide to base increases so does the potential for acid generation.
The decommissioning process should be addressed in conjunction with mine development and
permitting. Although this approach has not been followed extensively in the past, most States
now require its consideration during the mine permitting phase. As a result, the water
management plan and site water balance associated with closure should be addressed along with
development of the operating water management plan. A schematic of the pad water management
system is shown on Figure 4, taken from an excellent review of the heap leach process by Van Zyl
et al (1988).
The two primary methods for elimination of solution include evaporation, discharge into a surface
water, tailings impoundment, open pit, or land application. If the receiving system involves
surface or groundwater, then Federal and/or State standards must be maintained. Discharge into
a tailings impoundment or open pit poses further long-term water quality issues which must be
considered. In both cases a periodic or continuous discharge may occur to surface or
groundwaters.
Often the conventional treatment options which are effective in removing wad cyanide are not
effective in lowering either residual metals or solution pH to acceptable levels for discharge. The
problem with removal of low metals levels is their complexation with cyanide which transforms
the metals into species not amenable to conventional removal processes. The elevated pH levels
encountered are usually associated with agglomerated pads in which considerable quantities of
lime and/or cement have been applied.
If conventional or advanced treatment processes are not effective in achieving required effluent
standards prior to discharge then an alternative disposal plan must be formulated. One such
option is to conduct a fate transport analysis (FTA) or environmental risk assessment (ERS) to
demonstrate through hydrological and geochemical considerations that discharge of a limited
volume of solution released from a spent leach pad would not result in adverse environmental
impacts to either surface or groundwaters. Such an approach has been proposed in the states of
South Dakota, Montana, and Nevada. A summary of the decommissioning process is depicted in
schematic form on Figure 5.

Figure 4: Typical Heap Leach Operation Water Balance Flowsheet

Figure 5: Flowsheet for the Decommissioning Process

6.0 SUMMARY
Solution management planning and the requirement to produce such a plan as a prerequisite for a
mining permit are now a fact of life in the mining industry. The potential operator must be in a
position to make a rational prediction of the likely methods and potential cost to decommission
the heap leach system, including spent ore.
It is fortunate that a body of data exists, both published material and practical experience over the
past ten years, which allow an operator to anticipate the likely response of future spent ore to
various decommissioning alternatives. In making such an evaluation, these data can be combined
with project-specific bench or pilot plant results, (for example, rinsing test on extracted
metallurgical columns), to increase the likelihood of their applicability.
The formulation of a solution management plan requires a logical approach to decision making,
which should be based on a knowledge of management alternatives, their applicability, and
economics as demonstrated in this present paper.
7.0 REFERENCES
Englehardt, P., "Long-term Degradation of Cyanide in an Inactive Leach Heap," Cyanide and the
Environment, Van Zyl (Ed), Pub., CSU, Fort Collins, CO, Vol. 2, pp. 539-547, 1985.
Hendrix, J. Nelson, J., and Ahmadiantehrani, M., "Cyanide in Precious Metals Mill Tailings
Impoundments," AIME Annual Meeting, 1987.
Huiatt, J.L., Kerrigan, J.E., Olson, F.A., and Potter, G.L., Cyanide from Mineral Processing, Salt
Lake City, Utah, U.S. Bureau of Mines and Utah Mining and Mineral Resources Research
Institute, February 2-3, 1982.
Mudder, T.I. and Whitlock, J.L., "Biological Treatment of Cyanidation Wastewaters," paper
presented at the 38th Industrial Wastewater Conference, Purdue Univ., Lafayette, Ind., August,
1984.
Schmidt, J.W., Simovic, L., and Shannon, E., "Natural Degradation of Cyanides in Gold Milling
Effluents," Proc. Sem. Cyanide and Gold Mining Industry Seminar; Environment Canada, Ottawa,
Ontario, Jan. 22-23, 1981.
Smith, Adrian and Brown, A., "The Potential for Cyanide Migration from the Annie Creek
Process Facility," Rept. No. 1086/2 to Wharf Resources (USA), Inc., SRK, Lakewood, CO,
November, 1986.
Smith, A. and Mudder, T.I., Chemistry and Treatment of Cyanidation Wastes, Pub. Mining
Journal Press, London, UK, 366 pp (1991-in press).
Smith, A and Struhsacker, D.W., "Cyanide Geochemistry in an Abandoned Heap Leach System
and Regulations for Cyanide Detoxification," Introduction to Evaluation, Design and Operation of
Precious Metal Heap Leaching Projects, Chapter 12, Van Zyl, Hutchinson, and Kiel (eds), Soc.
Mining Eng./AIMME, 1988.

Smith, A., Dehrmann, A., and Pullen, R., "The Effects of Cyanide-Bearing, Gold Tailings
Disposal on Water Quality in Witwaterstand, South Africa," Cyanide and the Environment, Van
Zyl (ed.), Pub., CSU, Fort Collins, CO, pp 221-229m 1985.
Van Zyl, D.J.A., Hutchinson, I.P.G., and Kiel, J. (ed), Introduction to Evaluation, Design and
Operation of Precious Metal Heap Leaching Projects, Pub. Soc. Mining Eng./AIMME, 1988.

GEOCHEMICAL STUDY OF LEACH PAD CYANIDE NEUTRALIZATION
AT BROHM MINING CORPORATION, SOUTH DAKOTA
Prepared By:
Laura Damon
Adrian Smith, Ph.D.
Terry Mudder, Ph.D.
Published in Proceedings of the 121st Annual SME Meeting and Exhibit, The Society of Mining,
Metallurgy, and Exploration, Inc. (SME), Phoenix, Arizona, February 1992.
8307 Shaffer Parkway, Littleton, Colorado 80127-5002
Geochemical Study Of Leach Pad Cyanide Neutralization
At Brohm Mining Corporation, South Dakota
ABSTRACT
A geochemical study of cyanide neutralization processes was conducted at Brohm Mining

Corporation to gain a better understanding of the leach pad behavior and to develop a simplified
procedure to quantify the attainment of compliance with permitted cyanide neutralization criteria.
Such attainment is a prerequisite for off-loading spent ore from the leach pad at the "load/unload"
gold heap leach operation.
The geochemical study program consisted of size fraction analyses and weak acid dissociable
(WAD) cyanide analyses for various sections of the spent ore from the actual leach pad. Further
test work included size fraction analyses and WAD cyanide analyses on the ore from four 29 foot
laboratory test columns which were leached and neutralized with different neutralization
treatments in parallel with an actual active leach pad. WAD cyanide was analyzed daily on the
neutralizing columns and various parameters were monitored weekly on the influents and effluents
during the leach cycle and neutralization period. A comparison was made of neutralized effluent
chemistry and porewater extraction fluids, as well as an analysis of the selective adsorption of
cyanide on various particle size fractions.
1.0 INTRODUCTION
1
In a "load/unload" gold heap leach operation, the time that a heap is on the reusable leach pad is
of critical economic importance. The turnover of heaps must flow in a consistent and cyclic
manner in order to leach the gold bearing ore in an economically feasible manner. The process
cycle is time dependent on two main stages, leaching and neutralizing. During the leaching stage,
an alkaline solution containing cyanide is sprayed over a heap to extract the precious metals from
the ore. After the precious metals have been extracted from the ore, the remaining cyanide must
be rinsed from the heap in a neutralization phase. The cyanide is rinsed from the ore and
detoxified with hydrogen peroxide using copper sulfate as a catalyst for the reaction. A
prolonged neutralization stage interrupts the continuity of the process cycle and becomes the
limiting factor in heap turnover time. Therefore, an understanding of the neutralization processes
can be beneficial in expediting neutralization, while ensuring an environmentally safe level of weak
acid dissociable (WAD) cyanide prior to the unloading of spent ore.
The South Dakota treatment standard for off-loading a heap requires <0.5 mg/l WAD cyanide in
2
the heap effluent. Other species are regulated using a solid sample extraction test on the spent
ore. During the testing to assess the effectiveness of rinsing the spent ore, it was found that
3
compliance for WAD cyanide was met more rapidly in the porewater from the spent ore than in
the heap effluent.
(1) A Brohm heap contains approximately 65,000 tons of ore
(2) Heap effluent: solution collected from the toe of the heap
(3) Porewater (synonym: pore fluid): the water that exists in the voids between the rock particles in the spent ore,
i.e., the interstitial water
590 L. Damon et al.

The neutralization period required to meet the treatment standard in the heap effluent required an
average 80 days per heap, close to the time allotted for the entire process cycle. Compliance for
WAD cyanide was achieved in the porewater after about 30 days. Because of the difficulty in
meeting the process cycle time requirement and due to the observations from the solid sample
testing, Brohm Mining Corporation (BMC) requested a Technical Revision from the South
Dakota Department of Water and Natural Resources (DWNR) to off-load spent ore using the
porewater test.
After review of the existing data, the DWNR allowed the off-loading of spent ore at a heap
effluent WAD cyanide level of 2 mg/l providing the spent ore porewater sampling met the unload
criteria of <0.5 mg/l WAD cyanide. Spent ore could be off-loaded using this criteria for an
interim period. During this time BMC agreed to conduct an Interim Neutralization Study to gain
a better understanding of the leach pad behavior. The program consisted of size fraction analyses
and WAD cyanide analyses for various sections of the spent ore from the actual leach pad.
Further test work included size fraction analyses and WAD cyanide analyses on the ore from four
29 foot laboratory test columns which were leached and neutralized with different neutralization
treatments. A comparison was made of neutralized effluent chemistry and porewater extraction
fluids, as well as an analysis of the selective adsorption of cyanide on various particle size
fractions.
2.0 METHODS AND MATERIALS
2.1 Leach Pad Heap Tests
During the off-loading of an actual leach pad, spent ore samples were collected from 5 foot
sections extending from 5 to 30 feet, and from 1 foot sections extending from the base of the heap
up to 5 feet. The five uppermost samples were collected by first exposing a 5 foot bench in the
spent ore and then removing a vertical composite from the exposed bench. Vertical control was
maintained by using a level and tape. The bottom 5 foot section of the heap was sampled by first
exposing the 5 foot bench and then collecting successive 1 foot thick shelves of material. Care
was taken not to allow slumping material from the already sampled sections to mix with samples
being collected. The bottommost sample (0-1 foot) included the material directly on top of the
asphalt surface underlying the heap. All samples contained over 250 pounds (114 kg) of spent
ore, were placed in plastic lined 55 gallon barrels and were immediately closed and sealed, leaving
minimal air retention.
The samples were prepared for analyses by mixing the sample which was then coned and
quartered. In addition to the above sample preparation procedure, subsampling was conducted on
the samples from 25-30 feet, 10-15 feet, and 1-2 feet, as a quality assurance measure on WAD
cyanide volatilization during mixing.
The sample to be analyzed for size gradation and moisture was placed in a tared container,
weighed, and dried at 100C. After drying, the sample was again weighed and the moisture
content calculated. The dried sample was screened yielding size fractions of plus 2 1/2, 2, 1 1/2,
1, 3/4, 1/2, 1/4, and minus 1/4 inch. The "fines" were washed off the individual size fractions and
591 L. Damon et al.

combined with the minus 1/4 inch material.
The individual size fractions were re-dried and weighed. The minus 1/4 inch material was wet
screened yielding plus 4, 8, 14, 28, 48, 100, 200, and minus 200 mesh (Tyler) sieve fractions. The
individual sieve fractions were filtered through a pressure filter pot, dried and weighed.
4
Batch tests were run on samples from each section of the heap as well as on the various
subsamples. The batch tests were run as a 2:1 solution to dry ore weight ratio, using USEPA
5
Method 1312 Extraction Solution #1 for the liquid phase. The solution and ore were placed in a
bottle with zero headspace, rolled on a bottle rolling device for 23 3/4 hours, and allowed to settle
for 15 minutes. The solution was decanted into a pressure filter pot and filtered. The solid
6
sample equilibrated solution was collected and immediately tested for sulfides and oxidants. Two
splits were made from the filtered solution. One split was refrigerated, nonpreserved, and
analyzed within 24 hours for WAD cyanide and thiocyanate (SCN). The second split was
preserved with 5 molar (M) sodium hydroxide (NaOH), refrigerated, and analyzed within a week
of collection for WAD cyanide.
2.2 Column Tests
Four 29 foot (8.839 m) long, 10 inch (0.254 m) diameter columns were constructed from white
PVC pipe and connected with 12 bolt PVC flanges with rubber gaskets. The bottom section had
a 12 inch sight glass and two screens on the bottom, a 1 inch heavy screen covered with a 40
mesh screen. The columns sat on a metal plate, six inches off the floor. A 1 inch black steel pipe,
with a 3/8 inch reducer and ball valve, extended from the bottom of the column. Tygon tubing
connected the pipe to a 7 gallon (26.5 L) covered collection vessel. The collection vessel held a
bottle for the assay sample collection. The influent solutions were delivered by metering pumps.
A 125 gallon storage tank, with continuous feed from the process plant barren line, was used for
the leach cycle influent. An 1100 gallon tank was used for neutralization solution collection and
storage during the neutralization period.
Approximately 12 tons of ore was collected by random sampling of the crushed ore stockpile.
The ore was collected in the bucket of a front-end loader and transferred to the crusher bin. The
ore was passed through the crusher to ensure 80-90 percent less than 1 inch material and to blend
the ore into a homogeneous sample.
The columns were loaded with ore sequentially by 5 foot sections. The ore was loaded by
random shoveling of the "stockpile" into a tared funnel bucket containing a slide gate. The loaded
funnel bucket was weighed and hoisted above the column section and the material was allowed to
fall into the section. The top two sections were loaded by tared and weighed 5 gallon buckets.
(4) Batch test: bottle roll for solid sample extraction
(5) EPA Method 1312 Extraction Solution #1: deionized water pH adjusted to 4.2 with a 60:40% mixture of
sulfuric and nitric acids
(6) Solid sample equilibrated solution: the liquid portion derived from a solid sample extraction or leaching test
592 L. Damon et al.

The ore density was calculated for each column. The loaded columns were then filled with water.
The water was allowed to saturate the ore and the columns were drained slowly. The amount of
7
drained water was measured for each column, giving the pore volume.
The ore in each column was leached for 60 days, the average of actual operating conditions, with
0.5 pound per ton sodium cyanide (NaCN) barren solution at an application rate of 0.00409 gpm
per square foot (0.159 L per min per sq m), to mimic field conditions. The columns were run
concurrently with Cell #5, a heap containing the same ore type as the columns. A 15 inch phreatic
head was maintained in the base of the leaching ore simulating actual heap conditions. The
effluent was collected daily in the collection vessel. Tygon tubing went to the bottom of the
collection bottle and as the bottle filled it displaced the solution making it overflow into the tank
resulting in a positive discharge system. The column effluent was weighed daily. Gold (Au),
silver (Ag), NaCN and pH were analyzed daily on the column effluents, Cell #5 effluent and the
barren solution. Iron (Fe), copper (Cu), zinc (Zn), total hardness, alkalinity, conductivity, WAD
cyanide and thiocyanate (SCN) were analyzed on a weekly basis for the above solutions.
After leaching and a two day drain period were completed, the columns were neutralized at an
application rate of 0.0043 gpm per square foot (0.171 L per min per sq m), equivalent to the
average of actual operating conditions. The process neutralization solution contained 0.2 mg/l
WAD cyanide. Each of the four columns had a different neutralization treatment. Column A was
neutralized with neutralization solution to a WAD cyanide value of 2 mg/l as was Cell #5.
Column B was neutralized with neutralization solution until a WAD cyanide equilibrium was
reached. Column C was neutralized with neutralization solution to 2 mg/l WAD cyanide followed
by one pore volume groundwater rinse. Column D was neutralized with neutralization solution to
2 mg/l WAD cyanide followed by one pore volume deionized water rinse. A 15 inch phreatic
head was maintained in the base of the neutralizing ore. Effluent sample collection was the same
as in the leach cycle. WAD cyanide was analyzed daily on the column effluents and Cell #5
effluent. Cu, Fe, Zn, manganese (Mn), nickel (Ni), calcium (Ca), magnesium (Mg), sodium (Na),
chloride (Cl), sulfate (SO4), ammonia (NH3), SCN, total hardness, conductivity, alkalinity and pH
were analyzed on a weekly basis. The neutralization solution, groundwater and deionized water
were analyzed on collection and at the end of their use. All samples were refrigerated, analyzed
within 48 hours of collection, and not preserved, excluding the samples analyzed for dissolved
metals. These samples were preserved with nitric acid to pH <2. Ten percent of all samples
generated were sent to outside laboratories for quality assurance purposes.
The columns were allowed to drain for three days at the end of the neutralization period and then
were unloaded a section at a time. Samples were removed from each section with a post hole
digger and collected in plastic lined 5 gallon buckets. For sections 2-6, the second bucket of
material (from the top of each section) was removed and saved for size fraction and moisture
analyses. The third bucket of material was removed and saved for batch test analyses. The
second and fourth buckets of material were saved for size fraction and moisture analyses from
section 1 and the first, third and fifth buckets of material were saved for batch test analyses.
(7) Pore volume: the volume of solution that will just saturate a fully drained (under gravity) volume of rock
593 L. Damon et al.

The samples collected for size gradation were prepared by dumping the material from the bucket
onto a clean tarp and rolling the ore until uniform. The sample was then coned and quartered and
two opposite quarters analyzed for size gradation and moisture content in the same manner as the
"Leach Pad Heap Tests".
Batch testing was done on the various sections collected from the column spent ore. Column A
and Column D batch tests were run at a 1:1, 2:1 and 4:1 solution to dry ore weight ratio to
compare the WAD cyanide concentrations to the various ratios. Column B and Column C batch
tests were run at a 2:1 ratio. If WAD cyanide was detected in the 2:1 ratio batch test then 1:1 and
4:1 batch tests were run using USEPA Method 1312 Extraction Solution #1 for the liquid phase.
The batch testing was conducted in the same manner as the "Leach Pad Heap Tests" procedure
except no preserved splits were made. The solid sample equilibrated solution was analyzed within
48 hours for WAD cyanide and SCN. Ten percent of all samples generated were sent to outside
laboratories as a quality assurance measure.
Cell #5 was off-loaded using the same criteria set forth in the sampling of the actual leach pad
heap in the "Leach Pad Heap Tests". Cell #5 had a HDPE liner instead of asphalt on the bottom
of the cell. To protect the liner, a one foot layer of fines (minus 1/4 inch material) was put
directly on top of a geotextile covering (0-1 ft). A one foot layer of coarse material (plus 1/4
inch) covered the layer of fines (1-2 ft). This was the only difference between this heap and the
heap in the "Leach Pad Heap Tests". Size gradation and batch tests were done in the same way as
the "Leach Pad Heap Tests". In addition, batch tests were run at a 1:1 and 4:1 ratio if WAD
cyanide was detected in the 2:1 batch test.
3.0 RESULTS AND DISCUSSION
3.1 Leach Cycle
Table 1 shows the comparison between operating parameters during the leach cycle. Each
column and Cell #5 were leached for 61 days at a constant flow rate. The pH of the columns was
consistently lower than that of Cell #5 presumably due to the amount of lime in the original
crushed ore. The NaCN (lb per ton) levels also stayed consistently lower for the columns
compared to Cell #5 probably due to increased cyanide volatilization.
Table 1: Leach Cycle Data Comparison
Column Column Column Column Cell

Sample I.D. A B C D #5
Days on Leach 61 61 61 61 61
Avg. gpm/sq ft 246 249 243 249 222
Final pH 8.25 8.31 8.18 8.12 10.4
Final MaCN lb/ton 0.28 0.29 0.28 0.28 0.45
Final Wad Cyanide (mg/l) 207 210 210 210 200
594 L. Damon et al.

3.2 Neutralization Period
Table 2 shows various data comparisons during the neutralization period. The flow rates were
relatively constant for all of the columns and Cell #5. All columns took about the same amount of
time to reach 2 mg/l WAD cyanide. Cell #5 took approximately twice as long to reach this same
WAD cyanide concentrations. Column C and Column D both had water rinses after the 2 mg/l
WAD cyanide level was reached. These columns took about the same amount of time to go from
2 mg/l to 0.5 mg/l WAD cyanide. Column B had continued neutralization solution application,
shown in Table 2, and lagged behind Column C and D.
Column A and Cell #5 were both neutralized to 2 mg/l WAD cyanide with neutralization solution
and unloaded. Figure 1 shows that the rinse of Column A was more efficient than the rinse of
Cell #5. Cell #5 took about twice the amount of solution to ore ratio as Column A.
Table 2: Neutralization Period Data Comparison
Column Column Column Column Cell

Sample I.D. A B C D #5
Days to -2 mg/l Wad Cyanide 20 23 22 22 42
Actual Wad Cyanide Value (2.00 mg/l) (1.68 mg/l) (1.85 mg/l) (1.60 mg/l) (2.00 mg/l)
Avg. gpm/sq ft 280 287 280 283 287
Days to 0.5 mg/l Wad Cyanide 0 34 31 30 0
Column C and Column D were neutralized to 2 mg/l WAD cyanide with neutralization solution
and then given one pore volume water rinses. Column C had a local groundwater rinse to
determine if the removal of WAD cyanide from 2 mg/l to 0.5 mg/l would improve significantly
with the fresh water rinse. Column D had a deionized water rinse to compare the WAD cyanide
extraction efficiency between the groundwater and deionized water. As seen in Figure 2, the
columns track almost identically to 2 mg/l WAD cyanide. The columns also show the same slope
from 2 mg/l to the end of rinsing indicating that both rinsing methods behave in the same manner.
Column B was rinsed with neutralization solution for its entire duration under neutralization.
Figure 3 shows a comparison between Column C, having a groundwater rinse once it reached 2
mg/l WAD cyanide, and Column B. Again the two columns track almost identically to 2 mg/l
WAD cyanide. However, comparing the slopes as the WAD cyanide concentration decreases
from 2 mg/l, it can be seen that Column C has a steeper slope than Column B indicating that the
neutralization solution rinse is less efficient than the groundwater rinse at lower concentrations of
WAD cyanide. The concentration gradient between the neutralization solution (0.16 mg/l WAD
cyanide) and the column effluent is less than the concentration gradient between the groundwater
(<0.1 mg/l WAD cyanide) and the column effluent. This may contribute to the neutralization
solution rinse being less efficient than the groundwater rinse. The lower pH in the groundwater
(pH = 5.6) versus the neutralization solution (pH = 8.6) may also be a factor in the differences
between the two rinse procedures as cyanide volatilization will be enhanced at the lower pH.
595 L. Damon et al.

A kilogram of solution (equivalent to 1 liter) per kilogram of ore ratio has been used for
comparison to the WAD cyanide concentration. This ratio has been used in the past at BMC to
track the neutralization progress of heaps. A definite trend was observed from heap to heap. The
consistency in the amount of solution per amount of ore between the heaps enabled the prediction
of the readiness of heaps, within a few days, for compliance testing.
From Figures 1-3 it appears that about five days (fifth character on the illustration) are required to
reach equilibrium. Table 3 shows the linear regression equations and correlation coefficients for
each column and Cell #5 from Day 5 to 2 mg/l WAD cyanide. The data for the four columns fit
an equation of the form logC=mlogV+constant where C is the WAD cyanide concentration, V is
the cumulative volume of effluent, in liters, and m is the slope, or (C = 10^(mlogV+constant))
2
with the coefficient of correlation (r ) >0.996.
2
Cell #5 shows a similar fit, but at a lower r value of 0.958 which may be due to its not being as
controlled in the experiment, i.e., the amount of effluent was not measured exactly, the tons of ore
on the cell were measured by truck loads, and there is more variance in sample collection.
596 L. Damon et al.

Figure 1: Wad Cyanide Concentration vs. Kg Solutions per Kg Ore for Cell #5
And Column A (both neutralized to 2 mg/l wad cyanide with neutralization solution).
Figure 2: Wad Cyanide Concentration vs. Kg Solution per Kg Ore for Column C and
Column D (both neutralized to 2 mg/l wad cyanide with neutralization
solution and Given 1 pore volume water rinses).
597 L. Damon et al.

Figure 3: Wad Cyanide Concentration vs. Kg Solution per Kg Ore for Column B and
Column C (both neutralized to 2 mg/l wad cyanide with neutralization solution, Column
B continued neutralization solution rinse and Column C local groundwater rinse).
Table 3: Linear Regression Equation and Correlation Coefficient

for Wad Cyanide Concentration vs. Cumulative Effluent
Day 5 to 2 mg/l Wad Cyanide

Linear Regression Equation Correlation Coefficient
Call #5 C = 10^(-1.504594+-log (Veff) + 12.171820) 0.957563
Column A C = 10^(-2.23648+-log (Veff) + 5.559605) 0.998542
Column B C = 10^(-1.997499+-log (Veff) + 5.090031) 0.995512
Column C C = 10^(-2.089519+-log (Veff) + 5.261638) 0.996854
Column D C = 10^(-2.089597+-log (Veff) + 5.257948) 0.996905
598 L. Damon et al.

3.3 Displacement, Dilution, and Diffusion
Displacement appears to play a part in the rinsing of a heap or column. If the mechanism of
rinsing were strict displacement, the cyanide concentration in the effluent would remain constant
until the cyanide was displaced and the concentration decreased to zero. However, the cyanide
concentration decreases steadily from the beginning of the neutralization period, indicating that
dilution is taking place.
The decrease in cyanide concentration occurs more slowly during the first four or five days of the
neutralization period than in the subsequent days. Dilution seems to be the main controlling
factor in the decrease of cyanide from the beginning of the neutralization period. However, the
cyanide concentration decrease is slower than what can be accounted for by strict dilution. For
example, the WAD cyanide concentration for Column A at 0.01 kg solution per kg ore is 200
mg/l. At 0.1 kg solution per kg ore, the WAD cyanide concentration is about 40 mg/l. If the
cyanide removal mechanisms were strict dilution, then at ten times the amount of solution, i.e. 0.1
kg solution ore, the WAD cyanide concentration should be ten times less, i.e. 20 mg/l. This is not
the case. Therefore, the neutralization processes in the columns seem to be a combination of
displacement and dilution. The WAD cyanide concentration for Cell #5 decreases more slowly
than the columns. The heap could be showing lateral displacement due to the construction of the
heap itself while there is probably an edge effect in the columns where the solution is confined by
the walls, giving a more efficient use of the neutralization solution.
Along with displacement and dilution, diffusion could also play a part in the rinse processes.
Cyanide held in the pore space in the spent ore could diffuse into solution more slowly than by
dilution. The slope from the Column B data does not support this theory since the slope of the
rinse curve is steeper from 2 mg/l WAD cyanide to <0.5 mg/l than at the higher concentrations. It
would appear that if diffusion played a part in the neutralization of the columns, it would be more
pronounced at the lower concentrations. However, channeling of solution in the actual heaps,
due to the flow characteristics of the ore, could create a diffusion effect in the heaps. A higher
concentration of cyanide in the less effectively rinsed nonchanneled areas may be diffusing into the
stream of channeling solution.
The neutralization history of the actual heaps showed that it took almost as long to get from 2
mg/l to 0.5 mg/l WAD cyanide from Day 1 to 2 mg/l WAD cyanide. Cell #5 took 42 days to
reach 2 mg/l WAD cyanide. At twice the time, neutralization would take 84 days to reach 0.5
mg/l WAD cyanide for Cell #5. This is in agreement with the average time (80 days) of rinsing
required to reach 0.5 mg/l WAD cyanide before the Interim Neutralization Study was started.
Table 4 shows the WAD cyanide concentrations during drain down of the columns and Cell #5
and the amount of drain effluent from each drain down day for the columns. Generally the
cyanide concentration increases slightly as the solution volume decreases, indicating that the
mechanism of cyanide removal is dilution.
599 L. Damon et al.

Table 4: Neutralization Period Data Comparison During Draindown
Column Column Column C Column D Cell

Sample I.D. A B 1st 2nd 1st 2nd #5
Final Wad Cyanide Level in Effluent 2 0.12 1.85 0.10 1.60 0.20 1.8
Draindown Day 1
Effluent Return (Liter 10 9 10 6 10 11 0
Wad Cyanide (mg/l) 1.9 0.1 1.8 0.05 1.5 0.21 1.9
Day 2
Effluent Return (Liter) 9 3 9 9 9 4 0
Wad Cyanide (mg/l) 2 0.13 1.6 0.1 1.3 0.53 3
Day 3
Effluent Return (Liter) 2 8 3 2 2 8 0
Wad Cyanide (mg/l) 2.2 0.1 2.1 0.18 2.9 0.57 3.9
3.3 Screen Analysis and Batch Tests
Figure 4 illustrates the size gradation distributions for the Leach Pad Heap, Column A, and Cell
#5. While the heaps do not have the same mean particle size (d50), nonetheless they are
distributed similarly around the mean as evidenced by the similar slopes. Column A shows a
different distribution although the overall mean particle size is very similar to the heaps.
Table 5 shows a summary of the batch test results. There is no appreciable amount of residual
WAD cyanide in the ore from the upper sections (10-30 ft) of the heaps. Cell #5 shows no
appreciable amount of WAD cyanide in any ore above the very bottom section (0-1 ft). At the 0-
1 foot section from Cell #5, the WAD cyanide concentration is 2.8 mg/l. The "Leach Pad Heap"
shows a WAD cyanide concentration of 0.5 mg/l in the 5-10 foot section. There is an average of
1.7 mg/l WAD cyanide in the bottom 5 feet of the heap. The difference in the heaps can be
explained from the difference in their neutralization treatments. The "Leach Pad Heap" was
neutralized in the winter months with spray wobblers covered with cups. The cups cause direct
channeling into the heap and do not allow even coverage of the surface of the heap. Cell #5 was
neutralized in the summer months having no such cups on the wobblers. The heap was more
efficiently covered with neutralization solution and therefore more thoroughly rinsed. There is no
appreciable amount of residual WAD cyanide in the column ore in any section.
600 L. Damon et al.

Figure 4: Size Gradation Distribution for Leach Pad Heap, Column A and Cell #5
601 L. Damon et al.

Table 5: Batch Test Summary - Columns A-D, Cell #5, and Leach Pad Heap
Column Column Column Column Cell Leach Pad

Section Depth A B C D #5 Heap
25' - 30' 0.02 0.02 0.01 0.04 0.01 0.04
20' - 25' 0.08 0.08 0.01 0.01 0.01 0.11
15' - 20' 0.02 0.01 0.01 0.01 0.02 0.03
10' - 15' 0.03 0.02 0.01 0.05 0.01 0.02
5' - 10' 0.01 0.01 0.01 0.01 0.01 0.48
4' - 5' 0.01 0.01 0.01 0.01 0.01 1.52
3' - 4' 0 0 0 0 0.01 1.92
2' - 3' 0.01 0.01 0.02 0.01 0.01 2.26
1' - 2' 0 0 0 0 0.01 1.47
0' - 1' 0.02 0.01 0.01 0.02 2.58 1.15
In addition to the batch tests using USEPA Method 1312 Solution #1, two batch test samples
were run using extraction solution with the pH adjusted to pH >12 with 1.25 M NaOH. This
was requested by the DWNR to assess whether the pH of the extraction solution affected the
final WAD cyanide results.
The results were as follows:
Sample #1: 1312, pH 4.2 solution 0.01 mg/l WAD cyanide

NaOH, pH >12 solution 0.02 mg/l WAD cyanide
Sample #2: 1312, pH 4.2 solution 2.58 mg/l WAD cyanide

NaOH, pH >12 solution 2.60 mg/l WAD cyanide
The USEPA Method 1312 Solution #1 is a poorly buffered fluid. When it encounters the ore, the
solution is buffered by the spent ore itself at a higher pH (in this case, pH values about 9). As the
above data indicates, the initial pH of the extraction solution for the Brohm spent ore is essentially
irrelevant to the final WAD cyanide result.
WAD cyanide is detected in the material on the geotextile filters that covered the screens at the
bottom of the columns to avoid the loss of fine particulate material during the leach and
neutralization cycles. Approximately 20 grams of fines adhered to each of the saturated filters.
The filters were bottle rolled in the same manner as the batch test procedure using 1 liter USEPA
Method 1312 Extraction #1.
Table 6 shows the amount of WAD cyanide in each of the filters. Column A, having the least
amount of wash solution, shows the highest WAD cyanide level. Column B, having the greatest
amount of wash solution, shows the lowest WAD cyanide level. Column C and Column D,
having one pore volume water rinses, fall in between Column A and Column B.
602 L. Damon et al.

Also shown in Table 6 are the dissolved trace metals associated with WAD cyanide for each of
the column filters and the various sections from Cell #5. The cyanide appears to be in the form of
WAD copper cyanide complexes. Cell #5 shows WAD cyanide enrichment only in the lowest (0'-
1'), fines-bearing layer.
Table 6:
Wad Cyanide and Metals Comparison from Column Filters and Cell #5 Batch Tests
Column A* Column B* Column C* Column D* Cell #5**
Sample I.D. Filter Filter Filter Filter 1'-25' 0'-1'
Wad Caynide (mg/l) 8.8 0.36 2.05 1.60 <.01 2.3
Copper (mg/l) >6.6 0.31 1.3 0.47 <.05 2.5
Iron (mg/l) 0.2 0.2 1.1 2.3 <.01 0.2
Manganese (mg/l) 0.04 0.03 0.04 0.03 <.05 <.05
Nickel (mg/l) 0.03 0.02 0.04 0.04 <.05 <.05
Zinc (mg/l 0.03 0.01 <.01 0.01 <.05 <.05
(Dissolved metals)
* +-20g filter solids in 1 liter of extractant (50:1 liquid to solid ratio)

** 2:1 liquid to solid ratio
Even though migration of fines does not appear to be an appreciable factor from the screen
gradation data, the fines in the very lowest part of the column or heap appear to be contributing to
the elevated WAD cyanide values in the effluent. The filter and trace metal data indicating that
fines are collecting at the base of the columns (and most likely the heaps) and holding the
enhanced levels of WAD cyanide.
Table 7 shows a comparison of the various liquid to solid ratios used in the batch tests for Cell #5
- section 10. There is no effect in the variation of liquid to solid ratio indicating that there is a
linear relationship between the ratios tested. The 4:1 ratio is 25% of the 1:1 ratio and 2:1 ratio is
50% of the 1:1 ratio for WAD cyanide in mg/l. Also shown is the calculated concentration in mg
WAD cyanide per kg ore. This shows that basically the same amount of WAD cyanide is leached
out of the ore whether a 4:1 or 1:1 liquid to solid ratio is used.
603 L. Damon et al.

Table 7: Liquid to Solid Ratio Comparison for Cell #5 - Section 10
Liquid to Wad Cyanide mg Wad Cyanide

Sample I.D. Solid Ratio mg/l kg Ore
(10) 0'-1' Sample #2 2:1 2.58 1.4
(10) 0'-1' Subsample A 2:1 2.39 1.3
(10) 0'-1' Subsample B 2:1 2.23 1.2
(10) 0'-1' Sample #2 1:1 4.75 1.5

(10) 0'-1' Sample #2 2:1 2.28 1.2
(10) 0'-1' Sample #2 4:1 1.18 1.2
(10) 0'-1' Subsample A 1:1 4.67 1.5

(10) 0'-1' Subsample A 2:1 2.23 1.2
(10) 0'-1' Subsample A 4:1 1.14 1.1
(10) 0'-1' Subsample B 1:1 4.39 1.4

(10) 0'-1' Subsample B 2:1 2.21 1.2
(10) 0'-1' Subsample B 4:1 1.08 1.1
Solid sampling is more indicative of heap neutralization than effluent sampling at BMC. The
bottom layer of ore, in the case of the columns of the geotextile filter, is continuously saturated
with relatively high concentrations of cyanide bearing solution. It appears that fines collect in this
bottom layer. Having continuous contact with the cyanide solution, the fines may indeed adsorb
cyanide on their high surface area. The cyanide slowly diffuses from this saturated zone, never
being thoroughly flushed, and causes elevated cyanide levels in the effluent, but is not indicative of
the porewater in the neutralized spent ore above this layer. The enhanced cyanide levels during
drain down appear to be coming from these cyanide enriched fines, the cyanide being in the form
of WAD copper cyanide complexes.
Neutralization seems to be dependent on a combination of displacement, dilution and possibly

diffusion mechanisms. It takes longer to rinse WAD cyanide from leach pad heaps then from
column ore presumably due to different flow characteristics within the heap and the columns. A
water rinse after initial neutralization does decrease the amount of time to rinse ore from 2 mg/l to
0.5 mg/l WAD cyanide but not significantly. Groundwater and deionized water rinses behave in
the same manner.
Batch tests on spent ore solids are an acceptable simplified procedure to quantify the attainment
of compliance with permitted neutralization criteria. As shown from the subsampling protocol, no
cyanide volatilization occurs during mixing of the samples for homogeneity. The pH of the
extraction solution, as applied to Brohm spent ore, does not influence the final WAD cyanide
result.
604 L. Damon et al.

It has been shown that the spent ore above the bottom one foot layer is sufficiently rinsed at BMC
to remove most cyanide species. The bottom three feet of ore is left in place when off-loading the
spent ore to protect the liner. Therefore, as shown in this Interim Neutralization Study, the spent
ore at Brohm Mining Corporation passes state compliance (WAD cyanide <0.5 mg/l) when the
heap effluent is at 2 mg/l WAD cyanide.
605 L. Damon et al.

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The Cyanide Monograph

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The Cyanide Monograph

Terry I. Mudder, Ph.D.

MINING JOURNAL BOOKS LIMITED

Terry I. Mudder, Ph.D. Michael M. Botz, M.S., P.E.

THE CYANIDE MONOGRAPH

SECTION 1: CHEMISTRY, FATE AND ANALYSIS

Making Sense of Cyanide ........................................................................................................... 1

SECTION 2: TOXICOLOGICAL PROPERTIES

The Ecotoxicological Properties of Cyanide.............................................................................. 63

SECTION 3: RECOVERY AND REUSE

The Recovery of Cyanide from Slurries .................................................................................. 202

i Mudder & Botz

THE CYANIDE MONOGRAPH

TABLE OF CONTENTS (Continued)

SECTION 4: ACTIVE AND PASSIVE BIOLOGICAL TREATMENT

Microbial Treatment of Industrial and Hazardous Wastes ....................................................... 326

SECTION 5: CHEMICAL AND PHYSICAL TREATMENT

An Overview of Cyanide Treatment and Recovery Methods ................................................... 481

SECTION 6: HEAP LEACH DECOMMISSIONING AND CLOSURE

Closure Concepts .................................................................................................................... 543

ii Mudder & Botz

Chemistry, fate and analysis

● Making sense of cyanide

Terry Mudder, Ph.D.

Originally published as a booklet by The Gold Institute in August 1999

2.0 CYANIDE SOURCES AND USES

3.0 CYANIDE TOXICITY, EXPOSURE, AND RISK

Cyanide is generally considered a short-term or acute toxicant. Cyanide is neither carcinogenic,

4.0 CYANIDE CHEMISTRY, ANALYSIS, AND TREATMENT

5.0 CYANIDE RELATED COMPOUNDS

Terry Mudder, Ph.D.

1.0 HISTORY, SOURCES AND USES OF CYANIDE

12 T. Mudder & M. Botz

Figure 2. Industrial Uses of Hydrogen Cyanide

13 T. Mudder & M. Botz

2.0 THE RISK AND EXPOSURE OF CYANIDE TO HUMANS

14 T. Mudder & M. Botz

3.0 THE TOXICIY OF CYANIDE TO WILDLIFE

15 T. Mudder & M. Botz

4.0 CYANIDE CHEMISTRY, ANALYSIS AND TREATMENT

16 T. Mudder & M. Botz

17 T. Mudder & M. Botz

5.0 ENVIRONMENTAL INCIDENTS RELATED TO CYANIDE AND MINING

To begin a discussion regarding development of a global code of practice for cyanide

18 T. Mudder & M. Botz

19 T. Mudder & M. Botz

By Mine Type Involving Cyanide

Base Metals Cyanide Not

Figure 3. Summary of Major Mining-Related Environmental Incidents Since 1975

20 T. Mudder & M. Botz

21 T. Mudder & M. Botz

6.0 CYANIDE REGULATIONS, MANAGEMENT AND CODES

22 T. Mudder & M. Botz

7.0 CONCLUDING REMARKS

23 T. Mudder & M. Botz

Botz, M. and T. Mudder, 1999, “Modeling of Cyanide Degradation in Tailings Impoundments”,

Chemical Market Reporter, November 23, 1998.

Chemical Market Reporter, February 15, 1999.

Duffield, J. and P. May, Cyanide Management, Best Practice Environmental Management in

24 T. Mudder & M. Botz

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