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Arsenic and Selenium Treatment Technology

Summary for Power Plant Wastewaters


1005365

Arsenic and Selenium Treatment Technology


Summary for Power Plant Wastewaters
1005365
Technical Update, November 2004

EPRI Project Manager


P. Chu

EPRI 3412 Hillview Avenue, Palo Alto, California 94304 PO Box 10412, Palo Alto, California 94303 USA
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CITATIONS
This document was prepared by
Water Systems Specialist, Inc.
5808 Princeton Ave. N.E
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Principal Investigators
C. Haussmann, P.E.
T. Wolfe
This document describes research sponsored by EPRI.
The publication is a corporate document that should be cited in the literature in the following
manner:
Arsenic and Selenium Treatment Technology Summary for Power Plant Wastewaters, EPRI,
Palo Alto, CA, 2004.1005365.

iii

ABSTRACT

This report summarizes the most suitable technologies available for the removal of arsenic and
selenium from power plant wastewaters. The information stems from literature searches and
the authors experience in wastewater treatment systems from generally non-power plant
sources since there are limited operating experiences for power plant applications. The report
lists existing and potential technologies that meet the treatment goals of reducing arsenic and
selenium to the levels set for EPA drinking water standards. The most suitable of the standalone technologies for the removal of the targeted pollutants are discussed in detail and
recommended for further evaluation as specifically tailored to power plant wastewaters.
The reader is also encouraged to review EPRI Report TR-107081, Power Plant Wastewater
Treatment Technology Review Report. This 1996 report summarizes information on treatment
process performance, economics, and applications for all key power plant wastewater
applications and target chemicals. Again, it is important on note the limited operating
experiences and the heavy reliance of applications in non-electric utility industries.

EXECUTIVE SUMMARY

Based on the authors years of experience in wastewater treatment system designs for power
plant and other industries and the extensive literature survey conducted, the most viable
technologies for the removal of arsenic and selenium from power plant wastewaters are
presented. The criteria used to identify suitable technologies were that the treatment be
capable of reducing the targeted pollutants to the EPA drinking water standards of 10 ppb for
arsenic and 50 ppb for selenium. Further requirements for the candidates were that their
application be economical, simple and result in a minimum waste residual (hazardous or nonhazardous). The feed water characteristics used as a basis for this evaluation were the ash
pond waters defined in the PISCES Report Metals Removal in Ash Ponds at PISCES Sites #4).
A wide spectrum of standard and new wastewater treatment technologies was reviewed and
evaluated. While many of these methodologies are capable of meeting the established pollutant
reduction criteria, many do so at high capital and operating costs and/or while generating
substantial volumes of process residuals, which must then be disposed of.
Of the technologies evaluated, fixed bed adsorption, especially using granular ferricoxyhydroxide media, appears to be the most promising approach. This simple and economical
process utilizes highly adsorptive, single use media that needs no pretreatment, suffers few
interferences and results in a small spent media residual that is land fillable. Biological
anaerobic treatment is another technology of interest. This technology has been successful in
treating mining operation wastewaters. Other techniques of potential interest are single use
alumina adsorption media and in-situ encapsulation using products that are made from the red
mud residual from aluminum production. Technologies, including coagulation/flocculation,
membrane separation and ion exchange are also viable approaches, but, based on their
economics and/or voluminous process residuals, are only reasonable methodologies if the
arsenic and/or selenium containing waters are co-treated as part of an already existing
treatment system.
Based on the findings of this report, recommendations for follow-on bench scale testing of the
most promising technologies, applied to actual power plant wastewaters, are presented and a
brief description for such screening tests outlined.

GLOSSARY OF TERMS

Term

Description

AA

Activated Alumina

AB

Applied Biosciences Corporation

ABMetTM

Biological Selenium Reduction Process (same as BSeRTM)

AMF

Active Mineral Filter

BDAT

Best Demonstrated Available Technology

BSeRTM

Biological Selenium Reduction Process (Applied Biosciences Co.)

TM

BasR

Biological Arsenic Reduction Process (Applied Biosciences Co.)

BV

Bed Volumes

ED

Electro-dialysis

EDR

Reverse electro-dialysis

EBCV

Empty Bed Contact Volumes

FOG

Fats, Oils and Grease

GFH

Granular Ferric Hydroxide

GFO

Granular Ferric Oxide

IX

Ion Exchange

ICOS

Iron Coated Sand

MDL

Minimum Detection Limit

MF

Micro-filtration

MCL

Maximum Contaminant Level

NF

Nano-filtration

PISCES

Power Plant Integrated System Chemical Emissions Study

PRB

Permeable Reactive Barrier

RO

Reverse Osmosis

SMI

Sulfur Modified Iron

TCLP

Toxicity Characteristic Leaching Procedure

TDS

Total Dissolved Solids

UF

Ultra-filtration

CONTENTS
SECTION
1

PAGE

INTRODUCTION ...................................................................................................................1
1.1

GENERAL ......................................................................................................................1

1.2

HEALTH EFFECTS ........................................................................................................2

1.2.1
ARSENIC
2
1.2.2
SELENIUM
2
1.3
OBJECTIVE AND APPROACH ......................................................................................2
1.4
2

PREFERENCE AND CRITERIA.....................................................................................3

WATER CHEMISTRY............................................................................................................4
2.1

ARSENIC........................................................................................................................4

2.2

SELENIUM .....................................................................................................................4

2.3

ASH POND WATER CHEMISTRY.................................................................................5

TECHNOLGY CATEGORIES AND REVIEW CRITERIA ......................................................7


3.1

TECHNOLOGIES ...........................................................................................................7

3.2

REVIEW CRITERIA........................................................................................................7

TECHNOLOGY CANDIDATES .............................................................................................9


4.1

SORPTION PROCESSES .............................................................................................9

4.1.1
GENERAL PROCESS DESCRIPTION
9
4.1.2
FERRIC OXIDE / HYDROXIDE MEDIA
10
4.1.2.1
Granular Ferric Hydroxide (GFHTM)................................................................11
4.1.2.2
Granular Ferric Oxide (GFO) .........................................................................12
4.1.2.3
GFHTM and GFO.............................................................................................12
4.1.3
ACTIVATED ALUMINA
14
4.1.3.1
Comparison of AA with Ferric-oxyhydroxide Media .......................................15
4.1.3.2
Activated Alumina TRAMFLOC AAFS50 ....................................................18
4.1.4
BASECONTM AND BAUXSOLTM TECHNOLOGIES
18
4.1.5
IRON OXIDE COATED SAND (ICOS)
20
4.1.6
GREEN SAND
21
4.1.7
SULFUR MODIFIED IRON (SMI)
21
4.1.8
IRON FILINGS
21
4.2
PRECIPITATION CHEMICAL TREATMENT ............................................................22
4.2.1

COAGULATION / FLOCCULATION

22

4.2.2
LIME SOFTENING
23
4.3
ION EXCHANGE ..........................................................................................................23
4.4

MEMBRANE SEPARATION.........................................................................................24

4.5

REVERSE OSMOSIS AND NANO-FILTRTIONS.........................................................24

4.5.1
RO AND NF PROCESS DESCRIPTION
24
4.5.2
RO AND NF TREATMENT RESULTS
25
4.6
ULTRA- AND MICRO-FILTRATION .............................................................................25
4.6.1
UF AND MF PROCESS DESCRIPTION
25
4.6.2
COAGULATION WITH MICRO-FILTERATION
26
4.6.3
ELECTRO-DIALYSIS (AND REVERSE ELECTRO-DIALYSIS)
27
4.7
BIOLOGICAL TREATMENTS ......................................................................................27
4.7.1
BIOFILM REACTORS
27
4.7.1.1
Applied Biosciences .......................................................................................28
4.7.2
CONSTRUCTED WETLANDS
29
4.8
EVAPORATION............................................................................................................29
5

DISCUSSION OF TECHNOLOGIES...................................................................................31
5.1

TECHNOLOGY OVERVIEW ........................................................................................31

5.2

VIABLE TREATMENT CONDIDATES .........................................................................31

5.2.1
5.2.2

SUITABLE TECHNOLOGY CANDIDATES


IN-SITU TREATMENT

31
33

CONCLUSIONS ..................................................................................................................34

RECOMMENDATIONS .......................................................................................................37
7.1

GENERAL RECOMMENDATIONS ..............................................................................37

7.2

CONCEPTUAL SCREENING TESTING ......................................................................37

BIBLIOGRAPHY .........................................................................................................................40

LIST OF TABLES
ITEM

PAGE

TABLE 2-1

Ash Pond Water Chemistry Characterization

TABLE 4-1

GFH vs. GFO Comparison

16

TABLE 4-2

Activated Alumina vs. GFO Comparison

19

TABLE 5-1

Arsenic and Selenium Removal Technology Summary

End

TABLE 5-2

Other Potential Arsenic And Selenium Removal Technologies

End

LIST OF FIGURES
Figure 2-1

Arsenic Redox Potential (Eh) vs. pH of Solution

Figure 2-2

Selenium Forms vs. pH of Solution

Figure 2-3:

Selenium Redox Potential (Eh) vs. pH of Solution

1 INTRODUCTION

1.1 GENERAL
Power plant wastewaters, including ash pond volumes and ash pond run-off or spillage, can
pose a serious threat to the surroundings by transferring contaminants to the environment.
Among the many pollutants contained in these waters, arsenic and selenium are of special
concern since they are harmful to humans even at very low doses.
Varying levels of both arsenic and selenium, typically in trace amounts, are present in coal and
crude oil. As the fuels are combusted these components are released and partially condense
on fly ash particulates. As the fly ash and other solids are captured and transferred to the ash
holding systems, arsenic and selenium are introduced to the ash ponds in either a solid or a
dissolved form. Other major sources for these pollutants can be from the plant makeup water.
The current USEPA drinking water limits for both arsenic and selenium are 50 ppb. Adopted in
2003 and mandated by January 23, 2006, the USEPA has lowered the arsenic level in drinking
water to 10 ppb.
With the ever-present risk of wastewater spills to the environment (from ash ponds or other
sources), it is imperative for the power industry to have a means of treating stored or discharged
wastewaters for arsenic and selenium. The goal of such a treatment is to reduce the level of
these contaminants to meet existing and future drinking water levels.
The objective of this technology summary report is to identify cost effective treatment processes
that are capable of reducing arsenic to 10 ppb and selenium to 50 ppb. With the capability of
meeting such treatment goals, the power industry could look forward to meeting future NPDES
requirements, which can be anticipated to become more stringent as the new drinking water
rules become effective.
Due to the extensive presence of arsenic in well water world wide and the chemicals
detrimental effect on human health, most of the literature references found in the search for
viable technologies were for the removal of arsenic from drinking waters. With the 50 ppb
arsenic in drinking water allowable in the US until the year 2006, it was further noted that most
small and larger treatment systems for arsenic are located abroad as are the new process
technologies that have recently been developed.
The traditional means of arsenic and selenium removal, used in large scale water treatment
plants, are by co-precipitation methods. This process has the obvious drawback of removing
other, untargeted constituents, thereby resulting in large-volume process residuals. Other
treatment methodologies include membrane separation and ion exchange, which are also nontargeted processes and leave large volumes of undesirable residuals. Recent advances in
sorption media have, however, been successfully applied to remove arsenic without resulting in
large volumes of process by-products. Selenium is also removed by this technology. Since
selenium is not commonly present in drinking water sources, there are little data describing
specific adsorption characteristics for selenium.

1.2 HEALTH EFFECTS


1.2.1 ARSENIC
Although arsenic has some medicinal value, exposure to this chemical can bring about
increased risk of various cancers, vascular and circulatory problems, anemia, high blood
pressure, heart disease, diabetes and nerve damage.
As described in detail later in this report, arsenic typically exists in the two oxidation states,
As+3 and As+5. Of these two states, As+3 is significantly more toxic than As+5.

1.2.2 SELENIUM
Low levels of selenium are essential in human diet as a necessary nutrient. Higher levels of
dietary selenium may, however, lead to heart problems, irregular breathing and
stomachaches. At even relatively short exposures to levels above the MCL, the EPA has
found selenium to potentially cause hair and fingernail changes or loss, damage to the
peripheral nervous system, flue-like symptoms, fatigue and irritability.
When Marco Polo made his legendary trip to China, his party passed through a region in
which most of his horses became very ill. The hooves of most severely affected horses
literally fell off! This was one of the first recorded instances of a disease now known as
"blind staggers", which is only encountered in areas where the soil is very rich in mineral
selenium.
Long-term selenium exposure to levels above the MCL carries the additional risk of causing
damage to the kidney and liver tissues as well as to the nervous and circulatory systems
and, in severe cases, respiratory failure and death. Selenium has not been found to be a
carcinogen and some studies have suggested that it may even play a cancer preventative
role.

1.3 OBJECTIVE AND APPROACH


The intent of this study was to identify potential technologies, either existing or promising,
that are capable of lowering arsenic and selenium to the existing and future EPA standards
set for drinking water. In addition to reducing these pollutants to the stated levels,
technologies were also evaluated for their economics and suitability for power plant
applications.
The focus of this study is on technologies that can be employed as targeted, stand-alone
treatments for arsenic and selenium.
Many of the processes commonly used in power plant wastewater treatment remove arsenic
and selenium to some degree as part of a general wastewater purification operation. The
technology sought in this study, however, was one that could remove these pollutants from
power plant wastewaters without subjecting the total wastewater stream to rigorous
purification of all pollutants. The study does also consider technologies that fall into the
general treatment arena, where wastewaters components are removed either as a
chemical category (metals or cations) or removed by physical/chemical principles.
Evaporation was not included as it was deemed too costly for this application.

Also sought were technologies for the in-situ treatment for arsenic and selenium in ash pond
waters by either pump-treat-return or by placing a treatment process directly into the pond
system.

1.4 PREFERENCE AND CRITERIA


Aside from the removal effectiveness, economics and simplicity of process and operations
were also important criteria for consideration. Obviously, a process that achieves the
removal goal, that is simple, cheap and requires minimal operation and maintenance is
much preferable compared to a treatment that requires a complicated process and then
leaves a large residual of hazardous arsenic and selenium concentrate.
The process and operating parameters that were deemed preferential included the following
attributes:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

High removal efficiency


Low capital and operating costs
Minimum residual volume and concentrations of pollutants
Process residuals categorized as non-hazardous, non-toxic wastes
Simple process
Simple operation
Simple controls and instrumentation
Minimum pre- and post-treatment requirements
Low maintenance
High reliability

2 WATER CHEMISTRY

2.1 ARSENIC
Arsenic can be in an organic or inorganic form with the latter being the most common in power
plant wastewater encounters. Inorganic arsenic occurs in two oxidation states:
Arsenite = As+3 (Reduced)
o Non-ionic at neutral pH (H3AsO4)
o Highly soluble
o More toxic than arsenate (As+5) for many organisms
o More difficult to remove compared to arsenate
o Arsenite consist of mainly H3AsO3 (arsenious acid)

Arsenate = As+5 (Oxidized)


o Ionic at a pH above 2.8, H2AsO4-1, HAsO4-2
o Less soluble than arsenite
o Strongly adsorbed
o Arsenate consists of mainly H3AsO4 (arsenic acid)

2.2 SELENIUM
Selenium is a metalloid element that is located just below sulfur in the periodic table. It
resembles sulfur and forms many of the same compounds. The solubilities of selenium are
similar to sulfur salts. Also, most selenate salts are more soluble than selenite salts.
Selenium can be in as many as five different oxidation states. Some are anions, some are
neutral and some are cations with the most common forms being:

Selenate
Selenite
Selenium (elemental)
Selenide

Se+6
Se+4
Se0
Se-2

SeO4-2
HSeO3-1
Se
HSe-1

Selenate and selenite are the most common in aqueous solutions. Selenium combines with
oxygen to form several other selenium compounds as well. In oxygenated environments,
selenium is typically present in the selenate form, while selenite should be predominant in
reducing conditions.

2.3 ASH POND WATER CHEMISTRY


The data source used for defining a typical ash pond water chemistry was taken from the
EPRIs PISCES ash pond characterization program Water Toxics Summary Report #4) and the
PISCES Plant Multimedia Toxics Characterization Data Base#5).
A listing of arsenic and selenium along with other general ash pond components is presented in
Table 2-1. The component concentrations, listed as median and range of the ash pond inand effluents, are the levels with no treatment other then pond residence and settling times. An
inspection of the ash pond influent and effluent levels indicates that, on average, some removal
of Se and As species occurs naturally in the ponds. This is most likely due to co-precipitation
with or adsorption onto the iron component of the pond chemistry. Note that iron is typically in
the range of 4 to 170 ppm entering and less than 0.5 ppm in the effluent. The ratio of iron to
selenium is over 500:1. Sufficient iron exists, therefore, to co-precipitate arsenic and selenium
as well as heavy metals.
It should also be noted that the difference between influent and effluent will, for the most part,
be found at the bottom of the ponds. Some gaseous selenium species exist (methyl selenium
C2H6Se, which is analogous to methyl sulfide) so it is possible that some selenium is being
discharged to the atmosphere.

TABLE 2-1
ASH POND WATER CHEMISTRY CHARACTERIZATION*)
Influent a (g/L)

Effluent b (g/L)

Median

Range d

Median

Range d

78,000

2,900 to 290,000

580

180 to 1,500

< D.L. (<1) to 30

10

3 to 31

Arsenic

340

25 to 1,500

60

6 to 160

Barium

1,200

93 to 7,800

110

70 to 130

15

1 to 49

0.2

0.1 to 0.9

1,200

430 to 5,500

1,100

270 to 7,800

Cadmium

1.5 to 23

0.3

0.1 to 3.6

Chromium

180

< D.L. (<10) to 380

2.5

1.0 to 12

Chromium VI

10

< D.L. (<10) to 55

1.4

0.05 to 11

Copper

310

< D.L. (<10) to 780

4.0

1.1 to 15

Iron

35,000

4,000 to 170,000

180

53 to 480

Lead

120

5 to 250

0.6

0.2 to 2.8

Mercury

0.3

0.05 to 4.0

.002

0.0006 to 0.01

Nickel

110

15 to 350

7.0

3 to 23

Selenium

51

8 to 210

35

5 to 100

Thallium

< D.L. (<2) to 33

1.1

0.3 to 9

Vanadium

600

30 to 1,400

59

6 to 100

Zinc

380

< D.L. (<100) to 890

7.0

2 to 44

pH

7.3

4.0 to 9.6

7.4

6.0 to 8.9

TDS (mg/l)

270

91 to 860

260

98 to 950

TSS (mg/l)

3,900

41 to 20,000

4 to 17

Aluminum
Antimony

Beryllium
Boron

This data is taken from Table 5-2 of the PISCES Report Metals Removal in Ash Ponds at PISCES Sites#4
Influent samples are 24 hour composite samples taken from water flowing through the ash deltas
Effluent samples were collected outside discharge structures so do not represent permitted outfalls or reflect pH
b
adjustment of some systems.
c
The apparent increase in antimony concentrations from influent to effluent is likely due to the quality of data in the
high-solids influent samples.
d
Range is 5th to 95th percentile
<D.L. = The result was below the method of detection limit (MDL) for conventional method achieved by the
conventional laboratory as defined in 40 CFR 136(22).
*)
a

3 TECHNOLGY CATEGORIES AND REVIEW CRITERIA

3.1 TECHNOLOGIES
This technology summary identifies several types of processes as potential treatment
candidates for the removal of arsenic and selenium from power plant wastewaters. They
are as follows:

Sorption / adsorption

Chemical treatment and precipitation

Ion exchange

Membrane separation (reverse osmosis, ultra- and micro-filtration, electro-dialysis)

Biological Removal

Evaporation

With the recent concern of arsenic levels in drinking water, most of the literature citations
encountered were focused on the removal of this component. Many of the same processes
are, however, also applicable and effective for the removal of selenium.
One factor that seems to be common to all inorganic arsenic treatment processes is that
As+5 is much more easily and effectively removed compared to As+3. While the more highly
oxidized As+5 is typically the predominant specie, the PISCES report of ash pond waters
indicates up to 5 percent of arsenic in a reduced state.
While the emphasis of this study was to identify proven, ready for use technologies, some
promising treatment processes that are still in the development stage are also cited. Until
such processes are commercially available, however, they cannot be considered real
candidates and are, therefore, not described in detail in this document.

3.2 REVIEW CRITERIA


The treatment candidates were evaluated and judged according to the criteria listed in the
previous section. Many of the described methodologies are standard wastewater
treatments that have been successfully used for removing organic and inorganic
constituents.
The requirements for viable technologies, established in this study, are that they must be
capably of reducing the relatively low arsenic and selenium concentrations in the feed to
extremely low levels in the effluent waters. While this can be achieved by many traditional
treatments the caveat is added that the processes be economical, simple and result in a
minimum waste residual, hazardous or non-hazardous.
A process that removes the pollutants to very low levels, but then leaves a 10, 5 or even 1
percent volume residual for disposal is not a desirable option since the volumes of
wastewaters to be treated may be high. Additionally, even a small residual volume of one

percent, that carries the removed arsenic and/or selenium in a concentrated form, may be
burdensome especially if the liquids and/or solids are of a hazardous nature.
While it is possible to deal with such residual concentrates through evaporation,
crystallization, precipitation or even reverse osmosis, these processes add to the complexity
and cost of the initial treatment. The goal for an optimal treatment technology is, therefore,
that it leaves a minimal residual volume, preferentially in a solid and non-hazardous form
that is suitable for a conventional landfill.

4 TECHNOLOGY CANDIDATES

Of the many different technologies reviewed, only some were deemed to reasonably meet the
selection criteria established for this study. The processes described in this section either meet
or have the potential promise to meet these criteria in power plant applications.

4.1 SORPTION PROCESSES


Sorption is a relatively simple fixed bed technology that uses media to adsorb contaminants
from the wastewater streams. Of the many sorption processes available, the following were
considered potential candidates for this application:
1.
2.
3.
4.
5.
6.
7.
8.

Granular Ferric Hydroxide (GFH)


Granular Ferric Oxide (GFO)
Activated Alumina (AA)
Green Sand Filtration
Iron Coated Sand (ICOS)
Sulfur Modified Iron (SMI)
Iron Filings
Ion Exchange (this technology is actually a sorption process, and is discussed in a
separate section)
9. Evaporation

4.1.1 GENERAL PROCESS DESCRIPTION


Sorption processes are typically carried out in fixed bed pressure vessel housings that are
similar to those used for multi-media filtration. The feed usually flows in a down-flow direction.
The vessels are equipped with piping and valving arrangements that allow the media bed to be
expanded and backwashed. Depending on the type of media used, provisions may also be
provided to facilitate periodic adsorbent regeneration.
In order to allow for a continuous operation, systems usually consist of at least two vessels that
may be arranged in a parallel or in a lead-lag alignment. The advantage of lead-lag is that
this minimizes the danger of break-through of contaminants when the media in the lead vessel
becomes exhausted. Parallel operation, on the other hand, provides for a higher feed
throughput, but requires more rigorous effluent monitoring. Other vessel arrangements, such as
dual train lead-lag, are also possible.
Adsorption is a complicated dynamic that is dependent on several media and adsorbed material
(adsorbate) properties. The critical parameters include media structure, surface area, surface
character, surface charge, pH and redox. The mass transfer mechanism of the adsorption
process consists of the following steps:

Bulk transport: The adsorbate is transported from the solvent to the boundary layer
surrounding the adsorbent.

External resistance: The adsorbate must overcome this resistance to reach the
adsorbent media.
Internal transport: The adsorbate moves through the pores to the adsorption sites.
Adsorption: The adsorbate is fixed to the adsorbent media surface.

4.1.2 FERRIC OXIDE / HYDROXIDE MEDIA


Two forms for ferric oxide / hydroxide media have shown to be effective for the removal of
arsenic and selenium to very low levels.
1. Granular Ferric Hydroxide (GFHTM): This material is in solution as Fe(OH)3, but exists as
a -ferric oxyhydroxide in its solid form.
2. Granular Ferric Oxide (GFO): This material exists as an -ferric oxyhydroxide or
Fe(OOH).
Both ferric-oxyhydroxide compounds are nearly identical chemically. They are known to occur
commonly as goethite (-FeOOH) and as the much less common akaganeite (-FeOOH) FN1.
Naturally occurring akaganite usually contains some nickel and chlorides so it is unsuitable for
use in treatment processes. The -FeOOH is typically produced by drying the precipitate of
ferric chloride and sodium hydroxide. Both compounds have been developed or exploited for the
removal of arsenic from drinking water. Due to the chemical nature of their adsorptive
properties, both are also an effective treatment for selenium. They both have affinity for As+3
and As+5, eliminating the need for oxidizing As+3 (if present) under most circumstances.
Both media are designed for single-use with subsequent disposal upon exhaustion. With the
tight bonds formed with the adsorbate, the spent media typically passes TCLP tests, allowing
disposal at conventional landfills. Although the adsorption is theoretically reversible, the oxide
bond between the iron and the arsenic and selenium is so strong that it would take concentrated
chemicals to regenerate the media. The strong adsorptive nature of the oxyhydroxide translates
to a treatment capacity of more than 130,000 to 150,000 bed volumes (BV) for drinking water
containing about 40 ppb arsenic in the feed and that there are no strongly competing
components. In both drinking and wastewater applications, higher levels of arsenic or selenium
or interfering contaminants (e.g. sulfates, nitrates) in the feed will decrease the BV capacity.
Both ferric media were developed in Europe where a 10 ppb arsenic limit in drinking water
already exists. With the drinking water standards in the U.S. only recently lowered to 10 ppb,
and this only effective as of 2006, there has not been a strong drive to develop or implement
new arsenic treatment processes until now. Most large treatment plants using GFO or GFHTM
are presently located in Europe.
Smaller applications of the same technologies are found in India and Bangladesh where the
focus has been mainly on small, point of use (POU) devices to deal with the significant arsenic
concentrations in drinking water sources there. Most ferric media applications in the U.S. are
presently in the pilot/demonstration phase to ensure that the technology will work once the
tighter arsenic limits are inaugurated in 2006. After extensive testing, the City of Phoenix placed
a 1.5 mgd GFHTM well water treatment plant into operation in June 2003. This facility is now the

ROSSO, K., RUSTAD, J, Structures and energies of AlOOH and FeOOH polymorphs from plane wave
pseudopotential calculations, American Mineralogist, Volume 86, pages 312317, 2001

largest arsenic treatment plant for drinking water in the U.S., taking 17 ppb arsenic well water to
10 ppb in the effluent.
Compared to other adsorption processes, like activated alumina or green sand filtration, GFHTM
and GFO are effective over a fairly wide pH range with good efficiencies up to a pH of about 8.0
to 8.5. This typically allows the treatment to be performed on the unconditioned influents and
eliminating the need for effluent pH control.
The ferric media removes arsenic, uranium, selenium, antimony, copper and phosphate. Other
components are also affected, but to a lesser degree. If significant levels of arsenite (As+3) are
present then an operation at a pH greater than 7.5 is typically advised to eliminate the need for
arsenite oxidation. Adsorption of selenate is also pH dependent.
Unlike activated alumina, interferences from moderate levels of other components like silica or
sulfates are not a problem. Phosphates will reduce the adsorptive capacity, however.
Suspended solids, including fly ash, precipitated iron and manganese, should be removed prior
to treatment due to the potential of media plugging by trapped solids.
Backwash of the vessels is required on a periodic basis (4-6 weeks of operation for well water)
to prevent compaction of the bed and to remove accumulated particulates. While applications
to ash pond or other stored waters may demand more rigorous backwashing, there should be
the benefit of a stable feed chemistry with little precipitation potential within the treatment
system.

4.1.2.1 Granular Ferric Hydroxide (GFHTM)


Granular Ferric Hydroxide GFHTM is a relatively new technology that employs a ferric based
media to adsorb arsenic and other pollutants, including heavy metals.
The GFHTM (also known in Europe as AdsorbAs) was developed at the Technical University of
Berlin, Germany. The material is approximately 50-60% by weight a mixture of -ferric
oxyhydroxide and Fe(OH)3 with the balance water FN2. In solution, it all converts to Fe(OH)3 or
ferric hydroxide. There are presently 17 operating plants, all located in Europe, with the largest
plant at 1 mgd. A large drinking water plant has recently been put on-line in Phoenix, Arizona
(see previous reference). US Filter is the licensee of the GFHTM technology in the U.S.
Typical feed concentrations for drinking water treatment with GFHTM are approximately 50 g/l
arsenic. At higher concentrations or in the presence of interfering constituents, the lifetime of
the media is decreased, which results in higher operating costs for media replacement,
maintenance labor and disposal.
The adsorptive capacity for arsenic is listed in the literature as high as 2.3% (in one test). US
Filter states that 1% is more realistic, however. The media must be kept wet (it is shipped wet)
in order to preserve its activity.
Arsenic removal down to 5 to 10 ppb in the effluent are cited in the literature and claimed by the
manufacturer.
2

Pal, BN, Granular Ferric Hydroxide for Elimination of Arsenic from Drinking Water, From BUET (BUETUNU, 2001), Technologies for Removal of Arsenic from Drinking Water, p 59-68.

4.1.2.2 Granular Ferric Oxide (GFO)


Bayer AG, the German chemical company, developed Granular Ferric Oxide (GFO), which is
marketed under the trade name of BayoxideE33. The product is a dry, robust, crystalline
granular ferric oxide, designed for a high arsenic and selenium adsorption capacity.
BayoxideE33 was developed specifically for the removal of arsenic from groundwater used for
drinking water sources.
The material is marketed in the US and worldwide by Severn Trent Services under an exclusive
agreement with Bayer. The arsenic removal system process (using BayoxideE33) is available
from Severn Trent Services under the trademark SORB 33TM .
Based on its sorptive capability, the material is suitable for wastewater applications, assuming
that there are no or only moderate levels of interfering components. With a high capacity for
arsenic, the media is long lasting. The exhausted material can be disposed of in local landfills.
Tests with GFO have shown arsenic effluent levels as low as 3 ppb.
According to the supplier, BayoxideE 33 has been used for the removal of arsenic in refineries
and chemical plant wastewaters. The treatment for selenium in industrial wastewaters is
presently being pilot tested by the manufacturer.
BayoxideE33 is shipped as a dry material.

4.1.2.3 GFHTM and GFO


A side-by-side comparison of GFO and GFHTM is presented in Table 4-1. Most data found for
the two ferric media types are from the literature reports of pilot demonstration tests.
Operating costs for both media are from the respective manufacturers and are stated as a
function of feed water quality, so that they vary with different applications. The treatment costs
presented in Table 4.1 are for drinking water containing moderate levels of arsenic and
assuming no interferences from competing ions.
Capital, maintenance and replacement costs should be similar for both media types. The
operating maintenance costs presented are based on manufacturer statements that did not
include the operating assumptions. The listed costs of the two media may, therefore, not be
based on the same premises. Attempts were made to clarify the GFHTM operating basis and
also to obtain the actual media costs, but the authors were unable to obtain this information. It
must be noted that GFO and GFHTM are supplied in dry and wet forms respectively, so that
media replacement costs, when available, must be normalized to the same basis.
While arsenic removal capacity is about equal for both media, no side-by-side media
comparisons for selenium capacities were found in the literature.

TABLE 4-1: GFH vs. GFO COMPARISON


GFHTM

PARAMETER

GFO

1.

Process type

Fixed bed adsorption


system

Fixed bed adsorption


system

2.

Capital costs for adsorption


systems

Similar

Similar

3.

Operating cost estimate for media


and maintenance (based on
manufacturers information)

$ 0.19 / 1000 gal


(assuming 50 ppb As)

$ 0.14 / 1000 gal


(assuming 40 ppb As)
$ 0.12 / 1000 gal
(assuming 25 ppb As)

4.

Adsorption effectiveness for


arsenic (As+3 & As+5)

About the same on a


volume basis.

About the same on a


volume basis.
About 2.5 times greater on
a weight basis

5.

Categorization of spent media for


disposal

Non-hazardous, passes
TCLP tests, i.e. land-fillable

Non-hazardous, passes
TCLP tests, i.e. land-fillable

6.

Categorization of other process


residuals.

Spent media is the only


process residual

Spent media is the only


process residual

7.

Technology Status

State-of-the-art for arsenic


removal from potable water.
Multiple installations in
Europe and India including
plants of 1 mgd

State-of-the-art for arsenic


removal from potable water.
Multiple installations in
Europe, including plants of
1 mgd

8.

Technology Source

US Filter / Wastewater
Group, Inc.

Severn Trent Services


Tampa, Florida

9.

Media Name
Media Source

GFHTM & AdsorpAs


Manufactured by Harbauer
GMBH (Germany), sole US
source via US Filter

BayoxideE33
Manufactured by Bayer AG
(Germany), sole source via
Severn Trent Services

10.

Chemical name

-ferric hydroxide
Fe(OH)3

-ferric oxyhydroxide
(FeOOH)

11.

Media Cost

$ 3.50 / lb

Not available from


manufacturer

12.

Grain size

0.3 2.0 mm

0.5 2.0 mm

Specific Surface Area

250-300 m2/g
(75% porosity)

140-180 m2/g

Loading capacity (Arsenic)


Loading capacity (Selenium)

2 % max

n/a

2 % max
1.2 % max

15.

Density
Bulk density

n/a
72 lbs/ft3

224.6 lbs/ft3 (3.6 g/cm3)


29 lbs/ft3

16.

Adsorber Loading rate

2 8 gpm/ft2

2 8 gpm/ft2

13.
14.

TABLE 4-1: GFH vs. GFO COMPARISON


GFHTM

PARAMETER

GFO

17.

Adsorber Backwash Rate

10-12 gpm/ft2 at 55 F

8 12 gpm/ft2

18.

Adsorber Max Bed Dept

63

63

19.

Adsorber Max differential pressure

7.3 psi

9.0 psi

20.

Typical EBCT

5 minutes

5 minutes

21.

Max Storage Temp

86 F

120 F

22.

Max Storage Period

12 months

36 months

23.

Media Delivery Form

Wet

Dry

4.1.3 ACTIVATED ALUMINA


Activated alumina (AA) is a general term for various granular, porous oxides and hydroxides of
aluminum that have been exposed to sodium hydroxide at high temperature. The adsorbent
media is effective for polishing already low levels of fluorides, arsenic, selenium, phosphates,
borates, silica and some organic complexes, to very low effluent concentrations. Although the
main application of activated alumina has been in the conditioning of potable waters (it is
identified as one of the technologies of choice for the removal of arsenic from drinking water).
AA may also be applied for specific pollutant reduction in wastewaters.
Activated alumina adsorption is typically applied in the fixed bed adsorption arrangement similar
to that previously described for the ferric media. Depending on the application, AA treatment
may include provisions for media regeneration.
In general, activated alumina can achieve an arsenic reduction rate of more than 90%,
depending on oxidation state, pH and the presence of competing components like iron. As+5 is
more readily removed than As+3 so that an oxidation pretreatment step is required if the water
contains significant amounts of As+3.
The AA adsorption preferences for wastewater constituents, in decreasing order, are as follows:
OH- > H2AsO4- > F > Si(OH)3O- > HSeO3- > TOC > H3AsO3- . While the presence of sulfates
and chlorides have only a slight impact, organics can significantly reduce the adsorption
effectiveness.
Adsorption of arsenic onto activated alumina is highly dependent on the pH of solution. This
because pH determines the surface charge of the media and affects the ionic type of arsenic
present in the water. The zero point of charge is identified at a pH of 8.2. The surface charge is
positive at pHs < 8.2 with a resulting electrostatic attraction to anionic species. Conversely, the
surface charge is negative at pHs > 8.2 and the media adsorbs cationic species.
A detrimental effect at higher pH values is that the more abundant OH- (the most highly
adsorbed) competes with arsenate for the available adsorption sites, which significantly affects

the adsorption rates and bed volume capacities. At more acidic pHs, on the other hand, the
activated alumina begins to dissolve. The optimum AA operating pH range is from 5.5 to 6.5.
Activated alumina is an effective means of removing selenium in its selenite (Se+4) rather than
its selenate (Se+6) form, this especially in the presence of sulfate ions. AA adsorption of
selenate is be significantly higher at low sulfate levels. The adsorption of selenite is pH
dependent, with an approximate three-fold decrease experienced when increasing the pH from
5 to 7.
Media regeneration is normally performed with a 1% to 4% sodium hydroxide solution. This is
followed by a 1% sulfuric acid solution rinse to recondition the alumina. Regeneration is carried
out in an up-flow manner to expand the bed, remove accumulated debris and to minimize
cementing,
During the regeneration procedure not all arsenic is eluted. Pilot tests, described in the
literature, indicate that that a 10% to 15% loss in adsorption capacity may be experienced with
each regeneration cycle.
While activated alumina is not widely used for water or wastewater treatment in general, it is a
proven technology that has been used for many years. The technology and equipment are
available from multiple sources.
The drawbacks of this technology include the need for pre-oxidation of As+3, the relatively
narrow pH operating range and the number of interferences from other components.
Furthermore, regeneration results in a waste stream that contains the removed arsenic,
selenium and other pollutants, which must be disposed of.
Media costs are approximately $ 1.00 to $ 1.30 per pound (density is 47 lbs/ft3). Spent media
can typically be disposed off as a non-hazardous material.

4.1.3.1 Comparison of AA with Ferric-oxyhydroxide Media


Granular ferric-oxyhydroxide media (GHFTM and GFO) have several significant advantages over
activated alumina. The following are some of the major advantages of the ferric based
materials over AA:

Ferric-oxyhydroxides are less affected by competing components.


They have significantly higher adsorption capacities, resulting in a longer bed life.
Due to the high adsorption capacities, single-use of the iron media is economically
feasible, eliminating the need for regeneration with dangerous chemicals and the
subsequent treatment/disposal issue associated with the spent regenerant encountered
with AA processes.
They are effective in removing moderate levels of As+3, eliminating the need for preoxidation to As+5.
They can be employed over a wider pH range, which typically eliminates the need for pH
control of the effluent.

A more detailed side-by-side comparison of ferric-oxyhydroxide vs. activated alumina media is


presented in Table 4-2.

TABLE 4-2: ACTIVATED ALUMINA vs. GFO COMPARISON


PARAMETER

AA

GFO **)

1.

Process type

Fixed bed adsorption


system

Fixed bed adsorption


system

2.

Capital costs for adsorption


systems

More costly than GFO/GFH


due to media regeneration
equipment.

Cheaper than AA

3.

Adsorption effectiveness for


arsenic (As+3 & As+5)

Poor adsorption for As+3


(requires oxidation to As+5)

About equal for As+3 and


As+5 at a pH > 7.5

4.

Effective bed volumes (BV) to


media exhaustion (assuming
moderate As levels of about 30-50
g/L)

2,000 to 5,000 BV (per


regeneration) . No
quantitative data for
selenium adsoprtion
available.
Adsorpitve capacity for
selenate (Se+6) is less than
for (Se+4).

> 100,000 BV
No quantitative data for
selenium adsoprtion
available.

5.

Selenium adsorption capacity

No quantitative data for


selenium adsoprtion
available. Adsorpitve
capacity for selenate (Se+6)
is less than for (Se+4).

No quantitative data for


selenium adsoprtion
available.

6.

Media Regeneration

Regeneration with NaOH,


followed by neutralization
with acid. Loss of
adsorption capacity with
each regeneration.

Single-use media - disposal


to landfill upon exhaustion

7.

Categorization of spent media for


disposal.

Spent media should be


non-hazardous, typically
passes TCLP tests, i.e.
land-fillable

Spent media is nonhazardous, passes TCLP


tests, i.e. land-fillable

8.

Categorization of other process


residuals.

Caustic and acid residuals


from regeneration have to
be neutralized, but still have
arsenic and selenium (and
other) hazardous
components.

Single-use media
No regeneration.
Spent media is the only
process residual.

9.

Technology Status

State-of-the-art for arsenic


removal from potable water.
Multiple installations in the
US and world-wide, but
mainly smaller systems

State-of-the-art for arsenic


removal from potable water.
Multiple installations in
Europe, including plants of
1 mgd

10.

Technology Source

Available through many

Severn Trent Services

TABLE 4-2: ACTIVATED ALUMINA vs. GFO COMPARISON


water treatment companies

Tampa, Florida

11.

Media Name
Media Source

General term for various


granular, porous oxides and
hydroxides of aluminum

BayoxideE33
Manufactured by Bayer AG
(Germany), sole source via
Severn Trent Services

12.

Chemical name

Aluminum Oxide/Hydroxide

-ferric oxyhydroxide
(FeOOH)

13.

Media Cost

$ 1.00 to 1.30 / lb

Not available from


manufacturer

14.

Bulk density

47 lbs/ft3

29 lbs/ft3

**)

For simplicity AA is compared to only GFO. For AA comparison to GFH, consult GFO vs. GFH comparisons
shown in Table 4.1

4.1.3.2 Activated Alumina TRAMFLOC AAFS50


Tramfloc, Inc. (Tempe, AZ) offers the conventional activated alumina as well as an unique,
single-use, disposable AA product. The latter, sold under the trade name Tramfloc AAFS50, is
activated alumina that has been subjected to a proprietary process to enhance its arsenic
adsorption by up to 10 times. With the resultant increase in bed volume capacity (10X)
compared to conventional AA, AAFS50 is suitable for application as a single-use media. Based
on the strong arsenic bonding, the exhausted media typically passes TCLP criteria and is
usually suitable for direct landfill disposal.
According to the manufacturer, this adsorbent typically removes 95% of the arsenic in the feed
stream. As is the case for conventional AA, the affinity for As+5 is substantially greater than for
As+3.. Pre-oxidation is, therefore, required if significant amounts of As+3 are present.
The adsorption of arsenic is strongly influenced by competing ions. Depending on the
concentrations of interfering components, which are similar to those for conventional AA,
adsorption can vary by an order of magnitude.
AAFS50 is designed to be more pH stable than unpromoted activated alumina. According the
manufacturer, AAFS50 has a proprietary promoter in the formulation, which increases arsenic
adsorption and pH stability. (AAFS50 has a loss on ignition of approximately 15-20%.) Based
on the manufacturers information, the arsenic adsorption capacity of AAFS50 is greatest at an
operating pH of about 6.
As this media is fairly new, most applications are still in the pilot stage. The media cost is
approximately $ 1.00 per lb. Treatment costs are described in the Arizona Department of
Environmental Quality Arsenic Master Plan #14), which specifically analyzes the costing of
various alternatives for treatment as applied to Arizona drinking water sources.

4.1.4 BASECONTM AND BAUXSOLTM TECHNOLOGIES


BaseconTM Technologies, owned by Virotec International, Ltd. of Australia, has developed
adsorption/encapsulation processes that are based on chemically and physically modified red
mud residuals stemming from Bayer-Process aluminum production operations. The raw, red
mud material is blended with other additives, dried or slurried and packaged in a range of
products that are tailored to specific water treatment needs, including the enhanced adsorption,
precipitation, and co-precipitation of arsenic and other pollutants.
The BaseconTM Technologies were developed and refined during long-term testing on mine
tailings dams, mainly in Australia. According to Virotec claims, its reagents have shown the
capacity for significant arsenic and heavy metal reductions.
BauxsolTM, one of the BaseconTM products is typically used for the removal of arsenic. The test
results from one site showed arsenic (As+5) to be reduced from 175 to 11ppb. At a different site,
a reduction from 5.3 ppb to 2.8 ppb arsenic was experienced. While no data for selenium is
available, other metals like cadmium, nickel, lead and zinc were decrease from several
thousand to less than 50 ppb. Some metals were reduced to 5 ppb and even 1 ppb.

Again, As+5 is much more easily removed than As+3. Although As+3 can be directly reduced
using the BaseconTM reagent ViroMine, it is most effectively removed by pre-oxidation with
subsequent treatment using BauxsolTM.
Most of the BaseconTM product development has been carried out in Australia. As this continent
is selenium deficient, not much work has been done on its removal. Based on possible need in
the U.S. and Europe, there is presently an R&D project underway to determine the materials
effectiveness for selenium. Some earlier work on wastewaters indicated that selenium removal
of 60% is possible. Based on a more recent study, however, better adsorption rates can be
anticipated, especially in relation to a sulfide supplemented technology.
To date most applications of Virotec's reagents have been in the form of an in-situ treatment for
pond waters. Using the usual spray equipment and setup, the material is sprayed over the pond
surface. As the reagents settle through the water, they adsorb and firmly bind heavy metal
pollutants via a number of chemical mechanisms. Another characteristic of the reagents is that
they neutralize acidic solutions, typically buffering the water at a pH of approximately 8.5.
The manufacturer suggests spraying sufficient material to form a thin coating of a few
millimeters at the pond bottom. With time, the reagents have shown to stay active and bind
additional pollutants. TCLP tests of the settled material have demonstrated that the adsorbates
are firmly held and little or no leaching from the encapsulating product occurs. Specific pollutant
reduction data can be found in the Virotec Technology literature #31).
Fixed bed media systems have also shown to be effective for acid mine and acid rock drainage
wastes as well as for other industrial wastewater applications. For the pollutant laden mining
wastewaters, about 2 to 4 tons per million liters of reagent is required in these Active Mineral
Filters (AMF). This translates to a bed volume capacity of approximately 500. For relatively low
feed concentrations, as found in ash pond applications, the media capacity is expected to be
significantly higher. The AMFs presently tested by Virotec are of a gravity bed filter type.
Large-scale systems of the BaseconTM- AMF technology are being implemented or considered
for large mining operations Peru, Australia and Korea.
Other BaseconTM reagents are being developed in a pellet form to improve porosity and metals
binding capacity. This configuration has been successfully tested on mine and tannery
wastewaters.
BaseconTM reagents have also been employed in Permeable Reactive Barriers (PRB). PRBs
are constructed using porous pellets, blocks or by mixing the products with sand, soil or crushed
rock. The barriers are designed to provide the needed reaction time in relation to the
anticipated flow or overflow rates. PRBs have several benefits, including the fact that iron and
aluminum, typically present in larger concentrations, are mainly removed by crystal growth
rather than adsorption mechanisms. Crystal formation, including the precipitation of gypsum,
does not adversely affect the system permeability or exhaust adsorptive capacity. The barrier
bed also supports biological growth, which may aid in the remediation process.
As is typical for PRB systems, the bed must be replaced once the adsorbent capacity has been
exhausted. This technology may be of interest in areas where pond overflow issues are of
concern.

The BauxsolTM has been successfully demonstrated in a variety of large-scale mining


applications where arsenic and metals concentrations are typically several orders or magnitude
greater than those found for ash pond waters. The main interferences are from the presence of
oils and grease, which, like for other media applications, blind the binding sites. Other organic
or inorganic components are usually not found to be a problem.
According to the manufacturer, the costs for in-situ treatment equipment are dependent on the
dosing requirements and can vary widely. The manufacturer has provided a rough order of
magnitude estimate for equipment costs of approximately $50,000, based on a pond size of
about 1.5 million liters. Operating costs are a function of water quality and are price competitive
with other technologies.
BaseconTM Technology including BauxsolTM is available in the US through either the Hatch
Group in Toronto, Canada or through Virotec USA, Inc.

4.1.5 IRON OXIDE COATED SAND (ICOS)


The Iron Coated Sand (ICOS) process is an adsorptive filtration technology capable of reducing
heavy metals in wastewaters to very low levels. The treatment method is similar to that of other
fixed bed adsorption processes.
This technology, which is still in a development stage, has shown promise in achieving lower
heavy metal effluent levels than can be achieved with conventional alkaline iron precipitation,
iron co-precipitation or selective ion adsorption. The sludge volumes generated are 10 to 100
times less than those of precipitation technologies.
The ICOS treatment was initially developed by Dr. Mark Benjamin at the University of
Washington; Seattle, Washington. In the late 1990s, EPRI had sponsored some pilot testing of
the process at an East Coast power plant location. Due to inconclusive results, no further
testing was conducted by EPRI.
Testing has shown ICOS to be able to reduce arsenic to about 4 to 5 ppb. Similar to other
adsorption processes As+5 is better removed than As+3. While the presence of sulfates and
chlorides seem to have relatively little effect on the process, the presence of organics is more
detrimental. Adsorption is more efficient at lower pH values. Tests have shown that a pH
increase from 5.5 to 8.5 brings about a 30% reduction in effectiveness. The ICOS media has an
adsorptive capacity of approximately 175 to 200 g As/L.
ICOS requires regeneration with sodium hydroxide and subsequent neutralization with sulfuric
acid. This results in a troublesome disposal issue for the hazardous waste concentrate.
Regeneration typically results in loss of iron coating from the sand, especially at low pHs.
Some alternate versions of this technology are presently under development in the industry.
While there has been interest in this technology for point of use devices, especially in India and
Bangladesh, no references to commercially operating ICOS plants were found in the literature.

4.1.6 GREEN SAND


Green sand filters, a standard filtration and iron removal method, is also capable of removing
arsenic and selenium. The technology, which uses permanganate coated sand, is capable of
removing about 80% of arsenic in the water. The presence of iron aids in the removal
effectiveness. A significant benefit of this process is that the arsenic oxidation state is not
relevant since As+3 is inherently oxidized to As+5 on the green sand surface. Regeneration is by
use of potassium permanganate, which leaves a hazardous residual for post treatment or
disposal.
With the relatively low arsenic removal rate, approximately 80% is cited in the literature, and the
requirement for regeneration with hazardous chemicals, green sand filtration is not considered a
viable, stand-alone treatment process for arsenic and selenium.

4.1.7 SULFUR MODIFIED IRON (SMI)


Sulfur Modified Iron (SMI) is a patented adsorption process, which has the potential of removing
arsenic from wastewaters. The process utilizes raw granular iron in the presence of powdered
elemental sulfur to generate a granular media. To create SMI, iron and sulfur are mixed together
and wetted, which produces an exothermic reaction. The media is then allowed to mature until
no further heat is detectable, and is then air-dried and sieved.
Arsenic removal with the SMI process is via sorption onto the iron/sulfur matrix. It changes raw
iron from an extremely porous particle to one that is smoother and with a more homogeneous
structure. Due to the sorption onto the SMI particles, problems with rusting of the media,
cementing, clogging with fines, and formation of separated preferential flow paths have been
encountered during testing.
This technology is in the development stage and no references to commercially operating plants
were found.

4.1.8 IRON FILINGS


One approach that is frequently mentioned as a potential candidate for arsenic removal is the
use of a fixed bed containing sand and iron filings. Chemically speaking, this is a variation of
the iron-based technologies that have been proven in various forms.
Arsenic is removed by precipitation or co-precipitation in the presence of sulfate to result in
arseno-pyrite precipitate. The sulfur comes from reduction of the sulfate. Bench tests have
shown that arsenic concentrations of 2 and 20 mg/L in the feed can be reduced to 50 ppb. The
same tests have, however, not shown less than 25 ppb arsenic in the effluent water.
Furthermore, the arsenic reductions were only obtained by exposing the feed to very long
contact times, which translates to high empty bed contact volumes (EBCV) and consequently
large equipment size.
This technology is presently still in a demonstration phase. Also, since this effluent quality does
not meet the goals set for this study, this technology is not considered a viable candidate at this
time.

4.2 PRECIPITATION CHEMICAL TREATMENT


4.2.1 COAGULATION / FLOCCULATION
Coagulation / flocculation is one of the traditional arsenic treatments. This technology works
well for As+5, but is only marginally effective for As+3. If present, the latter must first be oxidized
using chlorine, hydrogen peroxide or other means in order to achieve the desired arsenic
reduction.
Ferric chloride is the typical iron salt used for coagulation. It works well over a wide pH range of
5 to 8. Alum can also be used, but it is effective only over a narrower pH range from 5 to 7.
The process is dosage dependent so that arsenic and/or selenium removal can be enhanced by
adding greater amounts of coagulant. The presence of sulfates has an adverse effect on the
process.
Coagulation / flocculation is an effective means of removing selenium as well. Since it is best
removed in its reduced state, additional processing may be required to reduce the selenium.
The chemical reaction for this process is as follows:
SeO4-2

Fe+3 + 3H2O Fe(OH)3(solid) + 3H+1


+ Fe(OH)3(solid) + 4H2O Fe(OH)3-SeO4-2 (solid) + 8H+1

This ferric-hydrite adsorption process (addition of a ferric coagulant) has been identified by the
EPA as a best available technology for selenium removal in mining wastes. The key points for
this technology for selenium applications are:

Se+4 is more effectively removed than Se+6


About 90% Se+4 removal can be expected in pH ranges from 4 to 6, decreasing to 80%
to 85% at a pH of 7 with a significant decline at higher pHs.
Due to its solubility, Se+6 is poorly removed at any pH.
Removal is affected by sulfate, bicarbonate and aqueous silica.
Se+4 adsorption is better on crystalline, compared to amorphous adsorption structures.
Lower selenium effluent levels are obtained when treating feeds of higher compared to
lower selenium concentrations.

The optimal removal pH for selenium differs from that best suited for arsenic. If both
components are to be treated in a single process step, compromises have to be made that
affect the effluent quality. In order to achieve the lowest levels of both arsenic and selenium, a
two-step process, operating at different pHs, may be required.
While coagulation / flocculation can be an effective process for removing arsenic and selenium,
it has the major drawback of producing a sludge residual that must be dealt with. The dried
sludge may be a hazardous waste, requiring either further treatment or resulting in high disposal
costs. Compared to other processes described in this summary, coagulation/flocculation is a
complicated, operator intensive operation. It also requires the handling of dangerous chemicals.
In a June 2001 EPA comparative study#18) of several different technologies for the removal of
selenium from mining wastes using a ferric chloride reagent (the system included pH control
and sludge dewater), the estimated the treatment costs were $ 13.90 per 1000 gallons. It must
be noted that the selenium levels in this feed water were several thousand ppb, which required
a ferric chloride addition dosage of more than 1,000 ppm (2000:1 Fe/Se). Since the coagulant

was a major portion of the above listed cost, treatment of less concentrated power plant wastes
are anticipated to be less.

4.2.2 LIME SOFTENING


Lime softening operations will also reduce arsenic. The arsenic removal rate with lime is > 90%
with higher removal rates for As+5 compared to As+3. While the presence of iron in the water
aids the arsenic removal process, sulfate and phosphate can have a detrimental effect. Since
lime softening occurs at elevated pH, removal of selenium is not very effective.
Due to the complexity of the process and the large volumes of sludge produced, lime softening
is not considered to be a good candidate as a stand-alone process for arsenic and/or selenium
removal. The generation of a potentially hazardous sludge is a further problem with this
process.

4.3 ION EXCHANGE


Ion exchange (IX), a widely used process in makeup and wastewater treatment, is an effective
means of removing arsenic and/or selenium. While there is no ion exchange resin designed
specifically for arsenic, the resins do have a relatively high affinity for this chemical.
Strong base IX resins are typically used for this application. The resins can be in the chloride
form. While regeneration with sodium chloride has the advantage of providing a process
without dangerous chemicals, the elevated chlorides in the effluent result in an increased
corrosion potential.
The order of ion exchange preference for the strong base resins is roughly as follows:
HCrO4-1 > CrO4-2 > ClO4-1 > SeO4-2 > SO4-2 > NO3-1 > Br-1 > (HPO4-2, HAsO4-2,
SeO3-2, CO3-2 ) > CN- > NO-2 > Cl-1 > (H2PO-4, H2AsO4-1, HCO3-1) > OH-1 > CH3COO-1 > F-1
Sulfates and nitrates, commonly present in wastewater, are preferentially adsorbed compared to
arsenate and arsenite. Ion exchange for the removal of arsenic is, therefore, typically used on
low TDS and low sulfate waters. In order to prevent breakthrough, columns are usually set up
in a lead-lag configuration, often with three vessels where one is in regeneration while the other
two are in service.
Use of a countercurrent operation can be helpful in enhancing the IX effluent quality. This
arrangement has the feed in the normal down-flow mode, while regeneration proceeds in an
upflow direction. With the downstream resin section thus most effectively rejuvenated by the
purest regenerant, the final effluent should be of the highest quality as it passes through the
most active resin just prior to discharge,
Iron (Fe+3) is an interfering component in the feed water since it can form a complex with
arsenic. This iron-arsenic complex is unaffected by the ion exchange and passes through the
resin bed unhindered.
Selective selenium removal has been described using a metal hydroxide loaded ion exchange
resin. This approach is particularly valuable in high salt streams like brines. Selenium can also
be selectively removed with chelating resins loaded with oxyanions. Weak base resins may be

able to remove selenate from acidic feed waters. Strong base resins are able to remove all
anions, including selenium.
There are several drawbacks to the use of ion exchange in this application. Since sulfate is a
competing component, IX is typically only useful if employed on waters of low TDS and low
sulfate concentration.
Resin fouling or scaling is an other potential problem. Although the spent regenerant in this
application may be used several times before discharge, it contains the removed pollutants
making it hazardous waste. Unless there is an on-site opportunity to co-treat this waste stream
with other wastewaters, such as in an evaporator or membrane separation system or chemical
precipitation, disposal of the regenerant may be problematic and expensive.

4.4 MEMBRANE SEPARATION


4.5 REVERSE OSMOSIS AND NANO-FILTRTIONS
4.5.1 RO AND NF PROCESS DESCRIPTION
Reverse osmosis (RO) and nano-filtration (NF) are membrane separation processes that are
effective for the removal of dissolved solids. RO is capable of the removal of up to 95% to 99%
while NF is typically limited to 60% of dissolved solids. In this type of cross-flow processing,
feed passes over the membrane surface while purified water permeates through the
membrane. Impurities, held back by the membrane (rejected), are continuously carried away in
the concentrate stream.
Membrane systems are non-selective in their separation, removing dissolved and suspended
components according to their rejection ratings. Based on the diffusion principles of RO and NF
operations, multi-valent ions are rejected to a higher degree compared to mono-valent ions.
Different membrane types have varying rejection characteristics for specific ions. Common to
all membranes is, however, that they reject a certain percentage of the feed stream
components. The higher the feed concentration of any specific component, the higher the
concentration in the effluent. Per example, a 95% removal for arsenic may, therefore, not be
sufficient to achieve the desired removal goals if the feed concentration is higher than 200 ppb.
Alternately, a membrane with 98% rejection may be able to achieve the 10 ppb arsenic goal
while treating a feed of 500 ppb. The percent rejection typically decreases with decreasing feed
concentrations.
Membranes are available in a variety of materials and configurations. The membrane modules
can be of spiral-wound, hollow-fiber, tubular, and flat sheet configurations. Due to their
relatively low cost and other process advantages, spiral wound elements are by far the most
common module configurations.
Depending on the application, feed quality, operator attendance and maintenance quality,
membrane life can vary from a few months to more than 7 years. RO and NF membrane
manufacturers typically offer three year, prorated guarantees for standard desalination
treatment. Due to the usually lower feed water quality, membrane life in wastewater may be
lower than in desalination applications.

Reverse osmosis and nano-filtration typically have identical equipment and process
arrangements. Both require pre-filtration for solids removal and possibly pH control of the feed.
With nano-filtration removing mainly multi-valent ions, the osmotic and hydraulic pressure
requirements are much lower compared to RO, allowing the NF process to be carried out at
much lower feed pressures.
Reverse osmosis and nano-filtration normally process the feed water in a single pass operation,
purifying 75 to 90% of the water while discharging the remaining flow as a concentrate that
contains the rejected components. Although not commonly used, batch and semi-batch
operation as well as two pass operations are sometimes employed to either further reduce the
concentrate stream volume (reject) or the improved permeate quality. The critical and limiting
parameters in membrane processing are the solubility limits of the dissolved components and
organic fouling. Both can normally be mitigated by use of inhibitors and membrane cleaners.
Unless a convenient means of dealing with a 10% to 25% residual concentrate stream is
available, membrane separation will be difficult to justify for this application as a stand-alone
process. This especially as the reject stream carries the arsenic, selenium and other pollutants
in concentrated form. If co-treatment of the reject with an already existing process is possible,
then the RO or NF approach may be worth considering.

4.5.2 RO AND NF TREATMENT RESULTS


Reverse osmosis membranes have shown the capacity to remove both arsenic and selenium to
a relatively high degree. Other than the standard RO pretreatment, no special preconditioning
is required. Arsenic is best rejected in its As +5 form, with rejections of greater than 96%. As +3
is reject to a lesser degree, with results showing 51 to 80% reductions.
Nano filters, commonly used in water softening operations, have shown high rejection capability
for As+5 but much lower rejection for As+3. If present in significant amounts, As+3 should be
oxidized to achieve the higher separation efficiency. It must be noted that most membranes
have a very low tolerance for oxidizing agents. Care must, therefore, be taken to prevent any
residual oxidizers from contacting the membranes.
The advantage of using NF rather than RO is that NF effectively removes the multi-valent
components like arsenic and selenium while retaining only about 50% of the mono-valent
components like sodium and chlorides. This provides a means of removing arsenic and
selenium, as well as hardness and sulfates, but not sodium and chlorides or silica.

4.6 ULTRA- AND MICRO-FILTRATION


4.6.1 UF AND MF PROCESS DESCRIPTION
Ultra- (UF) and micro-filtration (MF) are standard cross-flow separation treatments that are used
to remove suspended solids. The basic process and setup is similar to that of RO, except that,
with no osmotic pressure to contend with, the operation is carried out at much lower feed
(driving) pressures.

Membrane module configurations are similar to those of RO and NF, with tubular or hollow fiber
modules used for higher solids concentrations. Materials of construction can vary, and include
various polymers, ceramic and metal compositions.
Membranes are available in different porosities that can be selected to meet specific processing
needs. UF pore sizes are rated in molecular cut-off (or Daltons) that can range from a few
1,000 to several 100-thousands. UF pore sizes range from 0.001 to 0.2 microns while MF pore
sizes typically range from 0.1 to 1.0 microns.
Depending on the design, UF or MF systems deal with the rejected solids stream by different
means. Traditionally the rejected materials are flushed form the membrane and carried away in
the concentrate stream, which may be recycled in a batch mode or purged from the system.
Other designs allow the captured solids to build up on the membranes and are then periodically
purged by back-flushing or back pulsing. The latter design is more complex, but results in a
substantially smaller reject stream.
Since UF and MF processes are only capable of suspended solids removal, their use is limited
to the removal of particulate arsenic or selenium. These particulates may stem from source
waters or from chemical changes or may have resulted from prior coagulation or other chemical
treatment processes.

4.6.2 COAGULATION WITH MICRO-FILTERATION


The use of a combination of coagulation and micro- (or ultra-) filtration can be an effective
means of removing arsenic or selenium. This approach uses relatively small doses of ferric
chloride as a coagulant. The chemical is added to the feed stream, which is then subjected to
rapid agitation in a mixing chamber. Since the membrane process is capable of removing very
small particulates, no further treatment is needed once the solids are formed. With the absolute
filtration capacity of ultra- and micro-filters, essentially all of the suspended solids (inherent or
precipitated) are thus removed.
While UF and MF systems are designed to remove suspended solids, care must be taken to
select a system that is compatible with the process conditions produced by the ferric chloride
coagulant. Aside from material compatibility, the system must include appropriate membrane
flushing and chemical cleaning provisions. Flushing or backwash systems, offered by different
manufacturers, can consist of fast forward flushing, flow reversal, reverse flushing, air pulsation
and other means. The selection of the most suitable membrane type and system will be a
function of solids loading and process conditions.
Common to all of UF and MF operations is the generation of a slurry residual that contains the
rejected particles. The slurry may stem from the flushing operation or from a periodic purging of
the recirculating concentrate. Unless this process residual can be co-mingled with other
wastewaters, it is typically subjected to dewatering for volume reduction. Indications from other
ferric chloride treatments are that the dewatered material may pass the TCLP tests and may be
suitable for landfill disposal.
The advantages of this process are that very low levels of arsenic or selenium can be achieved
and the danger of overflow from the coagulation process is mitigated by the post-treatment
micro-filter. Furthermore, with the relatively low doses of coagulant needed, the amount of
suspended solids generated is commensurately low.

UF and MF systems are typically designed to operate with solids concentrations of 1% or more
in the recirculating concentrate. With only a few ppm generated in the treated feed, the solids
level in the recirculating concentration will remain low. Batch or semi-batch operating modes, or
dead-head filtration with periodic purging, minimize the reject blowdown stream.
The disadvantage of this process is the complexity of dealing with two integrated process
operations, one of which requires the use of dangerous chemicals. Arsenic and selenium can
only be removed to the extent that they are in solid form. This means that if As+3 is present, it
must be oxidized in order to convert it to the more treatable As+5 form. With the exception of
suspended solids carry-over, the shortcomings, previously described for the coagulation
process also apply.
The capital and operating costs for this technology are the sum of the coagulation plus the MF
processes.

4.6.3 ELECTRO-DIALYSIS (AND REVERSE ELECTRO-DIALYSIS)


Electro-dialysis (ED) and reverse electro-dialysis (EDR) are membrane separation processes
that use an electric potential as the driving force to draw the electrically charged impurities
through the separating membranes. This technology is commonly used in special wastewater
applications, usually in silica or otherwise saturated waters. The overriding shortcoming in this
application is that its arsenic and selenium removal efficiency is significantly lower than that of
reverse osmosis. As such, it is not deemed to be a viable process under the qualification
criteria established in this document.

4.7 BIOLOGICAL TREATMENTS


4.7.1 BIOFILM REACTORS
Biofilm reactors have been demonstrated to be an effective and economical means for treating
both selenium and arsenic as well as other metals and pollutants in wastewaters. Most of the
work published in this area describes the treatment of metals from mining wastes where the
concentrations of arsenic and selenium and other pollutants are higher than those found in most
power plant wastewaters.
Bioreactors for this application are typically anaerobic processes that are designed using
specialized microbes and are controlled by the metered addition of nutrients to sustain the
biomass. The biofilm is formed on a substrate within the reactor vessels where a stable
biomass is then established. The nutrient supplements added to the process consist of
organics like ethanol, acetic acid or biosolids.
Due to the variable nature of feed waters, site specific selections of microbes, nutrient cocktail
supplements and biomass arrangements are required to optimize a treatment system.
Since the microbes are typically selected to target specific pollutants, the treatment systems
usually consist of two or more reactor vessels per targeted pollutant. A wastewater containing
both arsenic and selenium may, therefore, consist of a reactor train each for arsenic and

selenium, with each train containing two or more vessels. All trains and vessels would be
arranged in series.
Using pollutant targeted and controlled systems, biofilm reactors have been demonstrated to be
effective for removing both arsenic and selenium to below detection limits on a consistent basis.
The reactors are able to remove selenium and arsenic in either of their respective, common
oxidation states.

4.7.1.1 Applied Biosciences


Applied Biosciences of Salt Lake City, Utah has developed a specialized biofilm technology for
the reduction of pollutants, including arsenic and selenium. The technology, offered as
ABMetTM for metals (and ABMetTM DN for nitrate, -CN for cyanide and NH3 for ammonia) has
been successfully demonstrated in mining operations treating 150 gpm to 300 gpm of arsenic
and selenium laden wastewater streams.
Applied Biosciences uses specialized microbes that are attached to activated carbon
substrates. Molasses based nutrient cocktails, tailored to the process microbe needs, are
metered to the biomass reactors. The systems are designed to allow periodic (but infrequent)
backwashing to remove the removed pollutants. Selenium is reduced to and removed in its
elemental form. Arsenic is removed in its arsenic sulfite form. With the biomass staying
essentially in tact during this operation, the main treatment residuals are in the form of the
removed pollutants. Since the concentrations of arsenic or selenium in the feed water are
normally low, the residual volume should be correspondingly small. According to the
manufacturer, backwashing is usually required only once per year.
The rate of biofilm activity is strongly influenced by temperature, translating to varying contact
times. Per example, an operation at 2C (35F) requires a 12 hour contact time while an
operation at 24C (75F) requires only 2 hours. Systems are normally sized for the coldest
temperature conditions expected.
According to the manufacturer, the ABMetTM systems use standard water treatment techniques
to control the process, including the proper and optimal feeding rate of the biomass nutrients.
Using this approach, the biofilm reactors are able to maintain a consistently high effluent quality.
Operational data from the manufacturers and EPAs literature shows that, once stabilized after
startup, the reactors have been able to consistently reduce arsenic and selenium to below the 5
ppb detection limits.
The Applied Bioscience biofilm process has been successfully demonstrated in pilot tests at
several different mining operations in the U.S. and Canada. A large scale pilot test for the
removal of selenium was conducted at the Kennecott Utah Corporations Garfield WetlandsKessler Spring site (where the selenium contamination stems from an artesian well source).
This demonstration program was carried out for the EPAs National Risk Research Laboratory
and the Federal Energy Technology Center of the US Department of Energy #18).
The ABMetTM process (referred to as BSeRTM in the EPA report) was conducted in parallel with
and in comparison to two other selenium reduction technologies:
1) Ferrihydrite precipitation/adsorption (precipitation with ferric chloride or sulfate) and
2) Catalyzed cementation (variation on iron/lime treatment).

The EPA identified both of these chemical treatments as best available technologies in mining
applications. (Ferric hydrite precipitation/adsorption i.e. precipitation with ferric chloride or
sulfate, is discussed earlier in this document.)
The EPA sponsored ABMetTM (BSeRTM ) test was conducted for 187 days on feed water that
contained 1,500 to 2,000 ppb selenium and about 70 ppb arsenic. Both selenium and arsenic,
as well as some other heavy metal components were consistently removed to the drinking water
limits, with most effluent samples showing selenium and arsenic below detection limits. The
bioreactor contact times to achieve these results were typically 5.5 hours.
The demonstration program showed that all three technologies tested were able to meet the
selenium reduction goals under their best operating conditions. The ABMetTM (BSeRTM )
process was the only one to meet the reduction goals consistently, however. The cost
comparisons between the three technologies for this application, showed that the capital costs
for the ABMetTM (BSeRTM ) system were less than one tenth the cost of the other two
technologies and that the operating costs, including nutrients, was $ 0.58 per 1,000 gallons.
Capital costs were estimated to be $ 1.32 per 1,000 gallons treated.
In a more recent publication, the manufacturer claims that the operations and maintenance
costs for their systems are about $ 0.20 per 1000 gallons treated, with the majority of this
amount for the nutrient supplement. Both operating and capital costs vary depending on the
application, feed concentrations and reactor sizing.
For the removal of arsenic and selenium, the manufacturer recommends a three stage system,
consisting of one multi-vessel reactor anaerobic train for arsenic and one for selenium, followed
by an aerobic reactor train to remove undesirable process residuals like ammonia or other
pollutants either intrinsic in the feed water or generated in the anaerobic process.

4.7.2 CONSTRUCTED WETLANDS


Constructed wetlands have been used to remove pollutants, including arsenic and selenium
from wastewaters. While viable and reasonably effective, this technology is not considered to
be cost effective as a stand-alone process for selenium and arsenic. If wetlands are used as an
overall means of treating the wastewaters from a power plant, then this technology may be a
reasonable choice for co-treatment.
A negative implication for using constructed wetlands to remove arsenic and selenium is the
potential of creating a toxic hazard for fish and wildlife. Removed and retained arsenic and
selenium can strongly bio-accumulate, increasing its concentration in the aquatic food chain
many times over #21).

4.8 EVAPORATION
Evaporation would be an effective means of removing arsenic and/or selenium. While many
power plants have vapor compression or other evaporators as part of their wastewater
management, these units are typically specifically sized for a final volume reduction stage prior
to discharge to evaporation ponds or crystallizers.

Since evaporation processes are non-targeted processes and are typically very high in both
capital and operating costs, they do not meet the selection criteria established for this study and
are, therefore, not further discussed.

5 DISCUSSION OF TECHNOLOGIES

5.1 TECHNOLOGY OVERVIEW


A tabulation summary of different treatment technologies, along with their advantages,
disadvantages and applicability to arsenic and selenium removal from power plant wastewaters
is presented in Table 5-1. Listed are all the technologies discussed in Section 4. Other
processes that are of general interest, but were not considered to be viable candidates are
summarized in Table 5-2.

5.2 VIABLE TREATMENT CANDIDATES


As described in Section 4 and summarized in Table 5-1, there are numerous technologies that
can be employed to treat power plant wastewaters for arsenic and selenium. Presented in this
report are treatments that are traditional or have recently been developed for this application.
The viable technology candidates that met the established selection criteria are discussed at
length. In order to present a comprehensive overview of treatment processes in general,
however, brief summaries of standard technologies that did not meet the criteria or new
technologies that are still in the development stage are also briefly discussed in Section 4 and
Table 5-1.
As previously described, much of the arsenic and selenium technology information is relatively
new so that there is only limited data available for some of the processes described in this
paper. Some of the technical and economic data was obtained from product bulletins or by
direct contact with the various manufacturers. In order to alert the reader of the source,
whenever the information presented is based manufacturers claims, it is so referenced.

5.2.1 SUITABLE TECHNOLOGY CANDIDATES


Listed below are technologies that are fully operational or have been successfully demonstrated
beyond the pilot test stage as viable and effective processes. All of them are capable of
meeting the required 10 ppb arsenic and 50 ppb selenium effluent standards:
1. Adsorption
Granular Ferric Oxide (GFO)
Granular Ferric Hydroxide (GFHTM)
Activated alumina (AA)
Single-use (promoted) activated alumina
BaseconTM and BauxsolTM
2. Ion Exchange
Strong base ion exchange resins
Chelating ion exchange resins
3. Chemical Flocculation/Precipitation

Flocculation with alum or ferric chloride

4. Membrane Separation
Reverse osmosis and nano-filtration
Flocculation followed by micro-filtration
5. Biological treatment
Anaerobic Biofilm Reactors
The selection of the most suitable and cost effective technology is usually dependent on the
specific application, including wastewater quality (concentration and composition), the
percentage of As+3 vs. As+5 and/or Se+4 vs. Se+6 present, the levels of interfering inorganic and
organic components as well as liquid volumes (pond volumes) or flow rates to be treated. The
presence of existing treatment systems on site, that may allow co-treatment with other
wastewaters, may also be a decisive factor.
In situations where the ash pond or other arsenic and/or selenium containing wastewaters are to
be addressed on a stand-alone basis, the selection of the most suitable technology narrows. If
only arsenic and/or selenium and perhaps some other heavy metals are to be targeted, then a
process that removes large quantities of peripheral components is of less interest, especially if
this results in significant costs for treatment and the disposal of residuals.
Chemical precipitation, ion exchange and reverse osmosis processes fall into the category of
co-removing non-targeted components at the expense of generating large process residuals.
Iron and alumina adsorption, on the other hand, target mainly heavy metals, including arsenic
and selenium. Since the concentrations of heavy metals in power plant wastewaters are usually
relatively low, their co-removal along with arsenic and selenium should be acceptable, as long
as arsenic and selenium are reduced to the desired limits. Anaerobic bioreactors also represent
a focused treatment since specialized bugs are needed to remove specific components.
Although the BauxsolTM technology does adsorb components other than heavy metals,
according to the manufacturer it does so at low media costs. If the technology is used for in-situ
encapsulation of pollutants, then excess process residuals are not an issue.
Both granular ferric-oxyhydroxide (GFO and GFHTM) and activated alumina adsorption are
capable of lowering arsenic and selenium to the target levels. Single-use media of both ferricoxyhydroxide and special formulations of AA offer a simple and cost effective means for
treatment. Since, however, the presence of trivalent arsenic typically requires a pre-oxidation
step, activated alumina treatment represents a more complex process to achieve the same
ends. The standard application of activated alumina with sodium hydroxide regeneration has
the drawback of a relatively low bed volume capacity and the degeneration of active media sites
with each regeneration. Compared to the ferric-oxyhydroxides, activated alumina (including the
single-use version) operate within a lower pH range and are more adversely affected by
interfering components.
In selecting the most suitable technology for arsenic and selenium removal, other factors may
also come into play. Some of adsorptive media described is impacted by the presence of
interfering components, both organic and inorganic. A problem for all media processes is the
presence of organics such as oils (FOG), which blind adsorption sites. Reverse osmosis and
ion exchange are also adversely affected by FOG as it fouls the active process surfaces.

Suspended solids may be problematic for the above technologies, as they can lead to plugging
and fouling, which then requires increased backwashing and cleaning cycles.
Bio-treatments in the form of anaerobic biofilm reactors are also an effective means of
addressing arsenic and/or selenium. This technology, developed mainly for the mining industry,
is capable of consistently and economically removing both arsenic and selenium to the
detection limits (5 ppb) while leaving only a very small process residual. Biofilm reactors, which
are typically designed and optimized for specific applications and pollutants, can treat arsenic
and selenium in either of their common oxidation states. According to literature references, the
technology to date has been applied mainly in large pilot systems. There are, however, two
operational installations of 300 gpm, treating mining wastewaters in Canada. One 150 gpm
arsenic removal plant is presently under constructions for a gold mining operation.

5.2.2 IN-SITU TREATMENT


The only effective in-situ treatment, capable of meeting the established reduction standards of
this report, is the encapsulation of arsenic and selenium using BauxsolTM. This process
removes the pollutants by chemically binding and trapping them at the bottom of the pond.
Use of iron filings is another in-situ processes described. While effective in removing arsenic
and selenium to some degree, this passive treatment typically is unable to meet the established
reduction goals.
All of the technologies listed in this report can be used as a pump-treat-return treatment for
pond remediation. A concern for such an approach is that many processes become less
effective as feed concentrations decrease. As the pollutant levels in the pond are reduced and
approach the 10 ppb arsenic and 50 ppb selenium goals, the treatment efficiency may drop
making it difficult to meet the end point concentrations.
In an active ash pond, in-situ processing to meet the set reduction goals would be difficult in any
case since pollutants are continually added. Periodic remediation with BauxsolTM or other
means, however, could be applied to keep the concentrations at some acceptable level.

6 CONCLUSIONS

There are several traditional and new technologies available to remove arsenic and selenium
from power plant wastewaters. These treatment processes, which all appear to be capable of
meeting the contaminant reduction goals, established for this evaluation, are listed in the
previous discussion section. Some of these technologies are targeted while others are general
water purification processes. Due to the variation of wastewaters encountered in power plant
operations, the choice of the most suitable treatment option will be a function of the specific
situation encountered.
In general, however, the removal of arsenic and selenium from power plant wastewaters seems
to be most effective and economical using single-use adsorptive media in the form of granular
ferric-oxyhydroxide, single use activated alumina media, BauxsolTM or anaerobic biofilm
reactors. While ion exchange, membrane separation, coagulation/flocculation or chemical
precipitation are also effective, these methodologies should be mainly considered if the arsenic
and/or selenium laden waters can be co-treated with other wastewaters in already existing
systems.
Metal oxide and hydroxide, fixed bed media systems are low in capital, operating and
maintenance costs and are effective for the removal of both arsenic and selenium. Additionally,
they have the advantage of leaving only a solid process residual that can be land filled.
Of the metal adsorption media options, the granular iron based materials appear to have better
process characteristics compared to activated alumina by having affinity for both common
oxidation states of arsenic and having a significantly higher adsorption capacity.
While there are several forms of granular ferric media available, granular ferric-oxyhydroxide,
GFO and GFHTM, seem to have the most extensive operational histories. Since the arsenic
limits in Europe are lower than in the US at this time, all of the large scale operational plants are
presently located there. Smaller scale units for both media types are currently operating in the
U.S. as demonstration plants. One large arsenic treating GFHTM plant has recently become
operational in Phoenix, Arizona.
While capable of operating on more concentrated feed waters, GFO and GFHTM are typically
employed for low pollutant levels of < 1,000 ppb arsenic and < 5,000 ppb selenium, which fall
well within the concentrations encountered in power plant wastewaters. At higher
concentrations, such as found in mining wastewaters, the economics of single use media may
yield their advantage to other technologies.
The BauxsolTM adsorption process, used for in-situ encapsulation and fixation of pollutants in
pond waters, has proven to be effective in mining applications. Use of related materials in
Active Mineral Filtration (gravity filtration) and Permeable Reactive Barriers filtration has also
shown promise. Data from mining wastewater operations, as well as test data from other areas,
have shown the technology in either of the three application methods to be effective for the
removal of arsenic and other metals. As the BauxsolTM processes were developed in Australia,
where selenium is generally not an issue, the majority of the data available is focused on

arsenic. Recent testing with selenium waters indicates, however, that the treatment may be
effective for this chemical as well.
Based on the treatment results from mining operations, anaerobic biofilm reactors, like
ABMetTM, are capable of treating both arsenic and selenium waters effectively and
economically. In most cases the pollutants are removed to below detection limits. While
biological treatment is not common in power plant operations, this relatively compact anaerobic
biomass technology may offer an effective, stand-alone alternative for the removal of arsenic
and selenium.
In summary, based on the information found in the literature, the stand-alone treatment
technologies identified in this report appear to be capable of removing both arsenic and
selenium to the levels of the EPA drinking water standards. While most arsenic references
found were for drinking water, most selenium references were for mining waste applications.
No references for the viable, stand-alone technologies, identified in this report, were found for.
No references for arsenic and selenium removal from power plant wastewaters using the
identified viable, stand-alone technologies were found in the literature search. Since power
plant wastewaters, such as ash pond or cooling tower (concentrated makeup) waters, typically
have unique compositions with respect to arsenic and selenium concentrations, oxidation
states, co-precipitation opportunities, residence times, TDS levels, pH and/or interfering
components, it is not a given that the identified viable, stand-alone technologies will work in
the same fashion as the referenced drinking or mining waters indicate. It would, therefore, be
prudent to review and corroborate the applicability of the most promising technologies in actual
power plant environments.

7 RECOMMENDATIONS

7.1 GENERAL RECOMMENDATIONS


The effectiveness of standard treatment processes like chemical precipitation, ion exchange or
membrane separation are well established and ample data is available to provide arsenic and
selenium removal assurances, assuming properly designed and operated systems.
Most data for the ferric (oxyhydroxide) media - fixed bed processes is for drinking water while
references for the other technologies described are mainly for mining operations. Arsenic and
selenium laden waters in power plants are, for the most part from ash pond sources, where the
pollutants present have experienced long residence times. As indicated in the PISCES report, a
good portion of the arsenic and selenium is reduced due to co-precipitate or adsorption to other
materials in the ponds. The relatively low levels of residual arsenic and selenium may,
therefore, be of a refractory nature and may have different adsorption dynamics compared to
what is described in the drinking water or mining operations literature.
Based on the above concerns and the fact that the referenced literature does not address power
plant applications, it is recommended that a bench scale demonstration program be set up to
verify the most appealing technologies effectiveness, economics and applicability to power
plant wastewaters.
It is suggested that an initial screening test be set up for GFO, GFHTM, Tramfloc AAFS50 and
BauxsolTM to cull the most effective of these adsorptive media options. It is further
recommended that anaerobic bio-treatment be part of the initial screening test. A more detailed
description of the envisioned screening is presented in the next section.
With the most suitable technologies identified, the screening test should be followed by a
longer-term demonstration of the best one or two treatment processes, to be conducted at
several different power plant sites. This longer duration testing could be set up as a pump and
return operation.
With the relative simplicity of fixed bed media processing, an automated test unit could be used
for a long-term operation that requires only minimal supervision. Monitoring and data recording
could be done remotely, and sampling could be via long duration composite samplers. The goal
of this test would be to establish media performance with respect to removal effectiveness,
adsorptive capacity (i.e. bed volumes), spent media characteristics and general operating
parameters. Anaerobic bioreactor testing could be set up in a similar fashion.

7.2 CONCEPTUAL SCREENING TESTING


This report identifies adsorption processes and anaerobic bio-treatment as the most promising
stand-alone approaches to remove arsenic and selenium from power plant wastewaters. Since
none of the literature sources reviewed dealt with power plant applications, and the technical
and economic data presented in the literature did not offer sufficient side-by-side and apples-forapples comparisons, it is recommended that a comparative screening of the highlighted

technologies be performed. This evaluation should be specifically tailored to power plant


applications.
It is envisioned that the screening test be set up to allow for parallel testing of GFO, GFHTM,
Tramfloc AAFS50 and BauxsolTM media as well as the anaerobic bioreactor option. In order to
obtain comparative results it would be important to run the tests concurrently to make sure that
the feed water and operating conditions be identical. This is especially important since the
physical quantities of media, run times and process samples involved would be relatively small,
so that minimizing process variables and fluctuations would be crucial.
To facilitate this approach, a test apparatus consisting of four 1 x 30 inch columns
(approximate), filled with different test media, should be assembled. The four columns should
be designed to allow feeding through a common header. Each column outlet would contain a
control valve to allow accurate regulation and balancing of the throughput. Each column
effluent would be collected in individual containers so that composite samples could be taken at
the conclusion of each run. The common feed would be supplied and controlled using a
metering pump. Depending on the feed characteristics, preconditioning like arsenic oxidation
for the AAFS50 would have to be dealt with on an in-line basis. If necessary, the apparatus
could consist of additional columns to allow other media to be tested as well.
The test for the encapsulating material BauxsolTM would be conducted on the same feed source,
but using a larger container where the material would be mixed and allowed to settle. It may be
possible to use a conical shaped container, like an inverted Nalgene bottle, where the settled
solids could concentrate in the neck area while the clarate is drawn off. This may allow several
batches to be run, so that sufficient settled material could be generated to allow it to be
analyzed and characterized.
The anaerobic testing would be carried out in a bench scale apparatus that could be obtained
from the manufacturer. Since the microbes of the bioreactor are typically pollutant specific, two
separate but parallel bio-tests would have to be conducted to test the removal ability of arsenic
and selenium.
It is anticipated that several samples from each run be collected for analysis: one feed and one
effluent composite as well as one effluent at the beginning and one at the end of each run. All
testing would be carried out based on manufacturers recommendations for the proper
arrangements and operation of their respective media and technologies.
With the relatively simple apparatus described above, it is envisioned that the screening tests
could be conducted at several sites. Depending on funding and finding willing site hosts, it
would be best to perform the evaluations at several ash ponds of diverse water characteristics.
If possible, non-ash pond waters, i.e. cooling tower blowdown or other power plant wastewaters
containing arsenic and or selenium, should also be included. Testing of synthetic wastewaters
is not recommended as it may not be representative of the refractory arsenic or selenium
components found in ash pond waters (see previous section).
The trade-off of conducting the screening test on site vs. having the water shipped to a central
testing location should be evaluated before establishing a test plan. It is anticipated that more
reliable results would be obtained from on-site testing. Due to the more complex testing
required by the bio-treatment, it may be advantageous to conduct the bioreactor screening by
the manufacturer in his facilities.

The major expenses of the recommended screening tests would be for travel, man-hours on site
and chemical analyses.
It is envisioned that the test would consists of the following major tasks:
1. Identify hosting sites
2. Obtain specific recommendations from the manufacturer for best treatment
parameters
3. Assemble test apparatus
4. Receive water samples from identified host sites for analysis
5. Conduct tests at selected sites
6. Analyze samples and interpret results
7. Prepare report and presentation to EPRI
The goal of the screening test(s) would be to identify the most suitable technology(ies) for the
applications tested. Care would have to be taken to ensure that the treatment effectiveness be
matched to the application and not to eliminate a technology that may have failed in one
application, but performed well in others.
The results of the screening would be used as a basis for a longer-term pilot demonstration test
of the technology(ies) deemed most suitable and promising.

BIBLIOGRAPHY
1. EPRI Toxics Release Inventory: Chemical Profile Arsenic
2. EPRI Toxics Release Inventory: Chemical Profile Selenium
3. An EPRI Perspective on USEPAs Arsenic MCL for Drinking Water
4. Water Toxics Summary Report: Summary of Research on Metals in Liquid and Solid Streams,
EPRI Document No. 1005409. Final Report January 2003.
5. EPRI Product Brief: PISCES Plant Multimedia Toxics Characterization Data Base
pisces.epri.com/pls/pisces/epri.data_qual
pisces.epri.com/pls/pisces/epri.t_frames
6. Power Plant Wastewater Treatment Technology Review Report, EPRI, TR-107081, November
1996
7.

Technologies and Costs for Removal of Arsenic from Drinking Water; USEPA, Office of Water,
EPA 815-R-00-028, December 2000

8. Technologies and Costs for Removal of Arsenic from Drinking Water; USEPA, Office of Water,
EPA 815-P-01-001, April 1999
9. Arsenic, Part 2 of 2: Removing Arsenic from Drinking Water, The Importance of pH, Background
Contaminants and Oxidation, Dennis Clifford, Ph.D., P.E., WCP Online
10. Regulations on the Disposal of Arsenic Residuals from Drinking Water Treatment Plants,
Science Application International Corporation, EPA/600/R-00/025/May 2000, National Risk
Management Research Laboratory, Office of Research and Development, USEPA, Cincinnati,
Ohio 45268
11. Technologies and Costs of Removal of Arsenic from Drinking Water; EPA 815-R-00-028, Dec
2000; www.epa.gov/safewater
12. An Overview of Arsenic Removal Technologies in Bangladesh and India, M. Feroze Ahmed,
Department of Civil Engineering, Bangladesh University of Engineering and Technology, Dhaka1000, Bangladesh
13. Wastewater Technology Fact Sheet, Chemical Precipitation, EPA-832-F-00-018, September
2000
14. Arizona Arsenic Master Plan: Part 3 - Compliance Options, Final Report, Arizona Department
of Environmental Quality, Water Infrastructure Finance Authority of Arizona, January 2003
15. An Overview of Arsenic Treatment in Drinking Water, Phil Bandhuber, Ph.D., McGuire
Environmental Consultants, Presented at the RMSAWWS 2000 Annual Conference
16. Arsenic in Drinking Water: Treatment Technologies: Removal
www.epa.gov/ogwdw000/ars/treat.html
17. Rapid Small-Scale Column Testing for Arsenic Adsorption Media, Aragon and Bruce
Thompson, University of New Mexico, Albuquerque, NM, Joe Chwirka, CH2M-Hill

18. Selenium Treatment/Removal Alternatives Demonstration Project, Mine Waste Technology


Program Activity III, Project 20, MSE Technology Applications, Inc., Butte, Montana 59702, IAG
DW89938870-01-0, National Risk Management Research Laboratory, Office of Research and
Development, USEPA, Cincinnati, Ohio 45268
19. Success Stories: Investigation of the Removal of Selenium from Wastewater Using Ferrous
Iron, E.M. Trujillo et al, Department of Chemical and Fuels Engineering, University of Utah.
20. Technologies and Potential Technologies for Removal of Selenium from Process and Mine
Wastewaters, L.G. Twidwell, Montana Tech of The University of Montana, and J. McCloskey, P.
Miranda, M. Gale, MSE Technology Applications, Inc.
21. Regulatory Implications of Using Constructed Wetlands to Treat Selenium Laden Wastewaters,
A. Dennis Lemly and Harry Ohlendorf, Ecotoxicology and Environmental Safety, 52, -46 56
(2002)
22. Green Rust Able to Convert Toxic Selenium to Safer From, Lynn Yarris, January 27,1998
Berkley Lab: Research News
23. Granular Ferric Hydroxide: An Efficient, Innovative Sorbent for Arsenic Removal From Ground
Water, Kashi Banerjee, Charles D. Blumenschein, Mike Selbie, Vivendi Water/U.S. Filter
24. US Filter Bulletin: Granular Ferric Hydroxide (GFH) Arsenic Removal System, April 2001
25. Granular Ferric Hydroxide for Elimination of Arsenic from Drinking Water, B.N. Pal, M/S Pal
Trockner Ltd.
26. Sorb 33TM System Economics, Typical As Application, Severn Trent Services, Filtration
Products
27. Part III Geochemical Engineering Experts Report: Description and Overview of the BauxsolTM
Technology, Prof. David McConchie, 3.July 2001
28. Polluted Mine Drainage Cleanup, Dr. David McConchie, www.eco-web.com/editorial/06054.html
29. AWM Consulting: BauxsolTM Technology,
www.atmconsulting.com/environmental/Bauxsoltechnology.html
30. BauxsolTM Technology, Water for Life, www.waterforlifelimited.com
31. The Use of Bauxsol Technology to Treat Acid Rock Drainage Mining Environmental
Management, July 2002
32. Removal of Dissolved Heavy Metals from Pre-settled Stormwater Runoff by Iron-oxide Coated
Sand (ICOS), Jens Moeller, et al.
33. Sorption and Filtration of Metals Using Iron-oxide Coated Sand, Benjamin, M.M. et al (1996),
Water Science Technology, 30,2609-2620
34. An Evaluation of Sulfur Modified Iron (SMI) for Removing Arsenic from Drinking Water,
Demonstration Project Summary, March 2001, Montana University System Water Center
35. Tonka Technical Bulletin: Arsenic Removal from Potable Water, Tonka Equipment Company,
Plymouth, MN, www.tonkawater.com.

36. An Elemental Iron Reactor for Arsenic Removal From Ground Water, Demitrious Vlassopoulos,
et al,
37. Structures and Energies of AlOOH and FeOOH Polymorphs From Plain Waive Pseudopotential
Calculations, Kelvin M. Rosso and James R. Rustad, W.R. Whiley Environmental Molecular
Science Laboratory, Pacific Northwest National Laboratory, Richland, WA
38. Environmental Technology Verification Program, Reverse Osmosis Membrane Filtration used in
Packaged Drinking Water Treatment Systems , Removal of Arsenic in Drinking Water at Park
City, Utah Hydranautics, Oceanside, CA www.membranes.com
39. As Removal Using Ion Exchange With Spent Brine Recycling, Dennis a. Clifford, et al, 95:6
Journal AWWS, June 2003
40. Membrane Systems Design and Fundamentals Philip Brandhuber, Ph.D., McGuire
Environmental Consultants, 2001 Water Quality Technology Conference
41. Selenium Removal: Bioremediation of Selenium in Waters, Applied Biosciences,
www.bioprocess.com
42. Biological Arsenic Removal (BAsRTM) Process, Applied Biosciences, www.bioprocess.com
43. Effective Biological Water Treatment Through Biological Process Control, Brad Wahlquist and
Tom Pickett, Applied Biosciences Corporation
44. Anaerobic Biorreactor Technologies, Applied Biosciences Corporation
45. Effects pf CO3-2/bicarbonate, Si and PO4-3 on Arsenic Sorption to HFO, April 2002, Journal
AWWA, 94:4, Peer Reviewed, HOLM
46. "Mechanisms of selenate adsorption on iron oxides and hydroxides." Peak, J. D. and D.L. Sparks.
2002, Environ. Sci. Tech.36: 1460-1466
47. www.dow.com/liquidseps/pe/pt/se.htm
48. www.virotec.com; www.hatch.ca
49. www.severntrentservices.com
50. www.usfilter.com
51. www.tramfloc.com
52. www.applied-biosciences.com

TABLE 5-1
ARSENIC AND SELENIUM REMOVAL TECHNOLOGY SUMMARY
METHOD

ADVANATAGES

DISADVANTAGES

SORPTION PROCESSES
Granular Ferric Hydroxide
(GFH)

Newly developed for arsenic removal. Single use media. High


adsorptive capacity. Effective for As+3 & As+5 & selenium.
Effective up to a pH of 8.5. Not affected by interferences as
other sorption processes. Uses standard filtration equipment.
Spent media passes TCLP tests.

Single supplier (US Filter)


Media is shipped wet, i.e. higher shipping
costs compared to GFO.

Similar properties and operation to GFO.


Granular Ferric Oxide
(GFO)

Newly developed for arsenic removal. Single use media. High


adsorptive capacity. Effective for As+3 & As+5 & selenium.
Effective up to a pH of 8.5. Not affected by interferences as
other sorption processes. Uses standard filtration equipment.
Spent media passes TCLP tests.

Single supplier (Severn Trent Services)

Similar properties and operation to GFH.


Activated Alumina

Standard technology. Adsorption media available from several


sources. Some regeneration possible (but with loss of media
activity). Discarded media should pass TLCP test.

May require lowering of pH. Adsorption


capacity (BV) relatively low. Not effective for
As+3, must be oxidized to As+5. Regeneration
produces hazardous chemical residue.

Activated Alumina
Tramfloc AAFS50

Same principles as with standard AA, but with 10X adsorption


capacity. Can use as single use media.

Same disadvantages as standard AA. Single


supplier (Tramfloc).

BaseconTM & BauxsolTM


Technologies

Proven high removal/encapsulation efficiency for arsenic. May


be used as in-situ pond treatment or fixed bed technology.
Strong affinity and binding of arsenic.

Little data for selenium, but should also be


effective for this. Single media source.

Standard water treatment technology. Depending on iron in the


feed, may require iron dosing to co-precipitate As.

Requires regeneration with permanganate.


Does not meet removal goal of 10 ppb As.

Green Sand Filtration

Single supplier (Virotec USA, Inc.)

TABLE 5-1
ARSENIC AND SELENIUM REMOVAL TECHNOLOGY SUMMARY
METHOD

ADVANATAGES

DISADVANTAGES

Iron Coated Sand (ICOS)

Promising technology. Media is regenerable. Technology


should be cost effective.

Still under development.


Some difficulties making the coated sand
media. No operational systems.

Sulfur Modified Iron (SMI)

Promising technology.

Still under development.


Problem with media cementing and clogging.

Iron Filings & Iron Filings


with Sand

Fixed bed media or potential in-situ treatment with filings.


Arsenic adsorbed on iron. May pass TCLP test. Should not
need oxidation of As+3.

Needs testing at each site to evaluate amount


needed. Sensitive to pH. No full scale,
operational systems.

Iron CoagulationFlocculation

Use of common chemicals. Standard water treatment


technology. Effective for arsenic and selenium. More efficient
than alum on weigh basis.

Medium removal of As+3. Sludge residual,


may be of hazardous nature.

Alum CoagulationFlocculation

Use of common chemicals. Standard water treatment


technology. Effective for arsenic and selenium.

Efficient pre-oxidation is a must if As+3 is


present. Sludge residual, may be of
hazardous nature.

Lime Softening

Use of common chemicals. Standard water treatment


technology.

Not as efficient for As or Se removal. Does


not meet treatment goals. Large sludge
residual, may be of hazardous nature.

PRECIPITATION
CHEMICAL TREATMENT

ION EXCHANGE

TABLE 5-1
ARSENIC AND SELENIUM REMOVAL TECHNOLOGY SUMMARY
METHOD
IX Processes

ADVANATAGES

High removal efficiency for both As and Se. Standard water


treatment technology. Use of strong base or chelating resins.
Reasonable technology if used as a co-treatment with other
wastes.

DISADVANTAGES
High equipment cost.
Sulfate interference major problem.
Regeneration creates liquid or sludge
disposal problem.
Prefiltration to minimize resin fouling.

MEMBRANE SEPARATION
Reverse Osmosis and
Nano-filtration Processes

High removal efficiency for both As and Se. Standard water


treatment technology. Reasonable technology if used as a
co-treatment with other wastes.
Effluent quality guarantee with membranes being a high
efficiency barrier for di- and tri valent ions.

Ultra- and Micro-filtration


Processes.

High efficiency for particulate removal. Standard water


treatment technology. Reasonable technology if pollutants
are in suspended solids form only. Application is the most
reasonable if used as a co-treatment with other wastes.
Effluent quality guarantee with membranes being an absolute
filter for suspended solids.

Coagulation with Microfiltration

High removal efficiency. Lower dosage requirements than


coagulation/flocculation. Standard water treatment
technologies.
Effluent quality guarantee with MF membranes being an
absolute filter for suspended solids.

ED & EDR

Standard water treatment technology.

Prefiltration and possible pH control to


condition feed water.
Membranes do not withstand oxidizing
agents.
Large brine volume disposal problem.
Most membranes do not withstand oxidizing
agents.
Concentrate disposal problem
Not effective for the removal of dissolved
components.
Most membranes do not withstand oxidizing
agents.
Concentrate disposal problem
Requires two process operations.

Membrane does not withstand oxidizing


agents. Does not meet As and Se removal

TABLE 5-1
ARSENIC AND SELENIUM REMOVAL TECHNOLOGY SUMMARY
METHOD

ADVANATAGES

DISADVANTAGES
goals.

BIOLOGICAL TREATMENTS
Biofilm Reactors

Anaerobic reactors have shown high removal efficiency. Low


equipment and operating costs. Can treat arsenic and selenium
in either of their common oxidations states. Anaerobic reactors
are standard water treatment technology.

Operating a bioprocess in power plant


environment where most technologies are
physical/chemical. Temperature sensitivity.

Applied Biosciences Biofilm


Reactors

Extensive and successful pilot testing on mine wastewaters with


high levels of As & Se. Systems use monitoring and control
principles to optimize treatment efficiency. Very small residual,
consisting of mostly removed components in elemental or
concentrated form.

Operating a bioprocess in power plant


environment where most technologies are
physical/chemical. Temperature sensitivity.

Constructed Wetlands

Standard technology.

May not meet As and Se removal goals.


Not a positive control process.
Potential of bioaccumulation of contaminants
in settled material. Potential danger to fish
and wildlife.

TABLE 5-2
OTHER POTENTIAL ARSENIC AND SELENIUM REMOVAL TECHNOLOGIES
METHOD

GENERAL DESCRIPTION

DEVELOPMENT/SOURCES

Ferric Oxyhydroxide
FeO(OH) + Settling

Uses co-precipitation method. Applied in rural areas for potable


water treatment. Effluents, if carefully filtered, are very low ion
As ~1 ppb. Sludge disposal an issue.

Auckland University of Technology / Rajshahi


University under the New ZealandBangladesh Bilateral Development Program,
New Zealand Ministry of Foreign Affairs

UV FeOx

This process, first described by an Australian team in a 1997


patented invention, removes arsenite (As+3) and other dissolved
species, such as iron, phosphorus and sulfur, from solution by
supplying an oxidant and a photoabsorber, irradiating the
resultant solution with ultraviolet (UV) radiation, and removing
the arsenic, (iron, etc.) by coagulation/precipitation and
sedimentation. The oxidant can be oxygen in the form of air or
pure oxygen; the photoabsorber can be Fe+2, Fe+3, Cu+2; UV
radiation can be from sunlight. The reactions can occur at room
temperature and at low pressure, hence do not need expensive
or complex equipment.

Australian Cooperative Research Centre for


Waste Management and Pollution Control
(CRC WMPC), in collaboration with the
Australian Nuclear Science and Technology
Organization (ANSTO)

FMC's OxyPure H2O2

Uses hydrogen peroxide plus FeCl2 to generate Fe(OH)3 in-situ


plus As+3 to As+5 for adsorption and filtration

11/1992 Water Environment & Technology,


"Applications of Chemical Oxidation and
Electrochemical Iron Generation for
Removing Arsenic and Heavy Metals from
Water"

Ligand Reaction Based


Ceramic Arsenic Removal
Technology

The process uses a chemically and biologically stable ceramic


media with a high affinity for soluble arsenic species. The
mechanism of As removal is thought to be a ligand reaction
between the arsenite species and the media. The media will
react strongly with other ionized species such as chromate, but
has little or no affinity for chloride, sulfate, bicarbonate ions, etc.
About 0.3 to 1.5% As by weight in media at breakthrough.

EDA Inc. and Luxor Group

TABLE 5-2
OTHER POTENTIAL ARSENIC AND SELENIUM REMOVAL TECHNOLOGIES
METHOD

GENERAL DESCRIPTION

DEVELOPMENT/SOURCES

Biological Filtration for


Arsenic Removal

Uses a biological sand filter much like conventional gravity


filters. Needs natural iron or iron added as Fe+2 to solution. Iron
oxidizing bacteria growing on the sand also oxidize the As+3 to
As+5, allowing As removal with iron in the filter.

SAUR - United Kingdom

Sulfur and Iron Removal

Iron filings with high surface sponge iron are slurried with
elemental sulfur. Sulfur and iron work together to remove As as
elemental As, which is filtered out. Technology is being applied
in California locations

US patent 6,093,328

Adsorption with Molybdate


Impregnated Chitosan Gel
Beads (MICB)

Chitosan beads (average diameter: 2.2 mm) impregnated with


molybdate ions can be packed into a single column in a flowthrough system to remove As+3 and As+5. The impregnation
with molybdate allows the sorbent to be very selective even in
the presence of high concentrations of salts and heavy metals.
The adsorption of arsenic species is at a maximum between pH
2.5 and 4.0. The presence of phosphate ions and reducing
agents in solution affects performance efficiency. Greater than
10 absorption-desorption cycles can be carried out with the
same sorbent. The spent sorbent can be reused for many
adsorption-desorption cycles. The major limiting factor of the
adsorption-desorption cycles is the release of molybdate ions
during the arsenic sorption step, the release ranging from 0.5 to
1%

Ecole des Mines d'Ales --Laboratoire Genie


de l'Environment Industriel 6, Avenue de
Clavieres - F-30319 Ales cedex, France

Microfloc Water Boy

US Filter packaged unit to purify drinking water for various


pollutants, including arsenic. The system provides coagulation,
flocculation, mixed media filtration, and semi-hex tube settler
clarification

System is designed to remove many


components that are not an issue for power
plant applications. May, however, be suited
for some specialized applications. Packed
unit flow rates from 10 100 gpm.

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