Geochemical

Characterization
EMI 7135
Cause of ARD
 Cause of ARD

The chemical reaction representing pyrite oxidation requires three basic ingredients: pyrite,
oxygen, and water. The overall pyrite oxidation reaction generally is written as:
FeS2 + 7/2O2 + H2O = Fe2+ + 2SO42- + 2H+ [1]
 Cause of ARD
Common Sulphides Known or Inferred to Generate Acid when Oxidized
(Plumlee
Pl l , 1999)
Plumlee,
Mineral Formula
Common sulphides known (inferred) to generate
acid with oxygen as the oxidant:
Pyrite, marcasite FeS2
Pyrrhotite Fe1-xS
Bornite Cu5FeS4
Arsenopyrite FeAsS
Enargite/famatinite Cu3AsS4/Cu3SbS4
Tennantite/tetrahedrite (Cu,Fe,Zn)12As4S13/(
Cu Fe Zn)12Sb4S13
Cu,Fe,Zn)
Realgar AsS
Orpiment As2S3
Stibnite Sb2S3
Common sulphides that may generate acid with
ferric iron as the oxidant:
All of the above plus:
Sphalerite ZnS
Galena PbS
Chalcopyrite CuFeS2
Covellite CuS
Cinnabar HgS
Millerite NiS
Pentlandite (Fe,Ni)9S8
Greenockite CdS
 Cause of ARD
Diagram Showing ARD
ARD,, NMD,
NMD, and SD as a Function of Sulphate
Concentrations
 Cause of ARD
Fi kli Diagram
Ficklin Di Sh
Showingi S Selected
l t dP Principles
i i l th thatt G
Govern Mi
Mine W
Water
t Q Quality
lit ((adapted
d t d
from Plumlee et al., 1999)
Cause of ARD - Neutralization
Group Formula Buffer pH Neutralization
Potential Range
(kg CaCO3/tonne))
Carbonates 500-1,350
calcite, aragonite CaCO3 5.5 – 6.9
siderite FeCO3 5.1 – 6.0
malachite Cu2CO3(OH)2 5.1 – 6.0
Oxides
gibbsite Al(OH)3 3.7
3 7 – 4.3
43
limonite/goethite FeOOH 3.0 – 3.7
ferrihydrite Fe(OH)3 2.8 – 3.0
Jarosite KFe3(SO4)2(OH)6 1.7 – 2.0
Aluminosilicates 0.5 – 1.5
Feldspar Group
K feldspar
K-feldspar (K,Na)AlSi
(K Na)AlSi3O8 0.5-1.4
0 514
albite NaAlSi3O8 0.5-2.6
(Ab100-Ab50)
anorthite CaAl2Si2O8 5.3-12.5
(An51-An100)
Pyroxene Group (Me)(Si,Al)2O6 0.5-9.5
Amphibole Group (Me)7-8((Si,Al)4O11)(OH)2 0.2-8.1
Mi G
Mica Group
muscovite KAl2(AlSi3O10)(OH)2 0.3
biotite K(Mg,Fe)3(AlSi3O10)(OH)2 2.7-8.8
Chlorite Group (Mg,Fe,Al)6(Al,Si)4O10(OH)8 0.8-21.6
Clay Group (Me)(Si,Al)4O10(OH)2 -2.7-29.0
Garnet Group (Ca,Mg,Fe,Mn)3(Al,Fe,Cr)2(SiO4)3 1.3-6.3
p
Apatite Group p Ca5((PO4)3((F,Cl,OH)
, , ) 2.7-11.3
Miscellaneous
talc Mg3Si4O10(OH)2 1.7
serpentine Mg6Si4O10(OH)8 15.1-87.6
epidote Ca2(Al,Fe)3Si3O12(OH) 1.0-3.0
wollastonite CaSiO3 440
Geochemical Characterization
• Based in the International Network for Acid
Prevention Global Acid Rock Drainiage
(GARD
GARD)) Guide

1. Site Characterization
• Defining the problem
• Important to understand the overall components
and timing
g of a site
2. Prediction
• Data collection for prediction 5 relies on the
conceptual
t l models
d l discussed
di d iin P
Partt 1
 Site Characterization
• Is Acid Rock Drainage
g ((ARD
ARD)) Neutral Mine
Drainage (NMD
(NMD),
) or S
), Saline Drainage (S
(SD)) likely to
occur?

• What
Wh t are th
the sources off ARD?

• How much ARD will be generated and when?

• What are the significant pathways and receptors?

• What are the anticipated environmental impacts?

• What can be done to prevent or mitigate/manage

ARD?
 Components of Site
Characterization Program
Characterization
Road Map
Conceptual Site Model
(CSM)
Objectives and Activities
by Mine Phase
Objectives and Activities
by Mine Phase
Characterization of Source, Pathway
and Receptor by Mine Phase
Characterization of Source
Material by Mine Phase
Summary of Sources and Pathways

• Applying the Conceptual Site Model to mine site

sources

• Consider
C id operations
ti and
d closure
l
Sources and Pathways in a Pit during
Operation and Closure
 Sources and Pathways in an
Underground Mine during Operation
and Closure
Sources and Pathways in a Waste
Rock Pile
Sources and Pathways in a Tailings
Impoundment
Pathways Summary
 Components of Site
Characterization
Characterization
• Geologic characterization/
characterization/Geoenvironmental
Geoenvironmental Models
• Conceptual model
• Testing
• Static testing
• Elemental analysis
• Mineralogy
• Short term leach testing
• Physical testing
• Kinetic testing
• Assessment
 Testing
Static Testing
• An
A analytical
l ti l ttechnique
h i applied
li d tto mine
i wastes t and d geologic
l i
materials that determines the potential acidity from sulfur
analysis versus the neutralization potential.
• It iis usedd tto predict
di t th
the potential
t ti l off th
thatt material
t i l tto b
be acid
id
producing or acid neutralizing.
• Acid generation Potential
• Acid Base Accounting
• Net Acid Generation Potential
Kinetic Testing
• Tests are designed to mimic weathering
• Humidity Cells
• Column tests
Physical Testing
• Grain size testing
 Testing
Elemental Analysis
• The primary purpose of determining chemical composition is the
identification of constituents of interest.
• Determining g chemical composition
p requires
q that a wide range
g of
metals be analyzed.
• Modern ICP-MS scans provide a large number of parameters at
relatively
y low costs.
• Mineralogy
l
 Tests
Mineralogy
• Mineralogical investigations provide valuable data that assist in
interpreting other laboratory tests. The purposes of a mineralogical
assessment include the following (Thompson et al., 2005):
• Confirm presence of minerals contributing to static and kinetic
laboratory test results
• Identify sulphide minerals that may contribute acidity and metals
and those that may not
• Determine presence of carbonates and silicates that may consume
acidity versus those that may not (e
(e.g.,
g calcite vs
vs. siderite)
• Assess relative distribution of acid producing and consuming
minerals in fractures and veins that could result in waste rock fines
p
of different composition form the whole rock
• Identify evidence of previous weathering and coatings
 Tests
• Although protocols for static (or short-term) leach
tests vary widely, all tests measure readily soluble
constituents of mine wastes and geologic materials
materials.
• The short-term nature of static leach tests provides a
p
snapshot in time of a material’s environmental
stability.
• Test results depend entirely on the present
disposition of the sample (e(e.g.,
g unoxidized vs.
vs
oxidized; oxidation products absent vs. oxidation
products present).
 Tests
• Laboratory selection is a primary consideration in successful
implementation of a monitoring program
• laboratory’s play a role in generation of an accurate and defensible
data set. Issues for consideration in laboratory selection include the
following:
• Location (shipping costs and sample delivery within holding times)
• Reporting limits (Reporting limits must be low enough to allow comparison
to applicable guidelines/standards.)
• Scope of services (water analyses, geochemical testing)
• QA/QC (laboratory SOPs, level of QA/QC reporting)
• Service (turn-around times, electronic reporting, report customization, and
responsiveness)
• Accreditation
• Cost
Components of Site Characterization
Over the Life of Mine
Sampling

• Once a conceptual model is

established
• Sample collection
• Baseline
B li line
li d data
t
• Water quality
• Hydrology
• Hydrogeology
Recommended Sample Numbers

Mine Phase Number of Testing

Samples
Exploration – 3 to 5 samples* Static testing
Prospect Testing
Exploration – 5 to 10 samples* Static testing
Resource Definition
Pre-Feasibility Several hundred Static testing
1 to 2 samples* Kinetic testing
Mine Planning, As required for As required
Feasibility,
y and block model
Design refinements

* Representative samples of each key material type

(i.e., lithology, alteration)
Recommended Sample Numbers

• Spatial distribution
• Vertical and horizontal
• Waste/ construction/ ore materials
• Material types
• Compositional representativeness
• Type & size of mine

• Requires
• Coordination with site geologist
geologist-- consultant
• Understanding of samples available
• Geologic/geochemical
Geologic/geochemical characteristics
 Conclusions – Site Characterization
• Site characterization is the beginning of a viable
ARD Management Plan
• Site conceptual plan
• Understanding sources and pathways is important

• Characterization is relevant across the full mine

life--cycle
life
• Accurate and continuous testing and evaluation is
key to a successful characterization program
Geochemical
G h i l
Prediction
 General
• Predict drainage chemistry
• Site
Site--specific
• Two types:
• Qualitative
Q lit ti
• Straightforward
• High success rate
• Quantitative
• More complicated
• Greater uncertainty
 General
• Approaches
• Geo
Geo--environmental approach/analogue sites
• Characterization (geochemistry, mineralogy)
• Laboratory leach testing
• Field leach testing
• Geochemical modeling
• Expect most or all approaches to be used
during mine planning
Generic Program

• Flowchart
Flo chart “pillars”
• Project phase
• Objective
• ARD program stage
• ARD p program
g
activities
Generic Program
 Characterization
• Characterization and planning conducted during the early
phases, but frequently not followed through in operation to
closure
l
 Generic Flowchart

COPC – Contaminant of Potential Concern

 Generic Geochemical
Ch
Characterization
t i ti Program
P
 Methods
• Comprehensive table of methods (Table 5
5--1)
• Description
• Use in geochemical characterization and water
quality prediction
• Advantages Grain size
Chemical Composition
• Limitations Paste pH/EC
ABA
NAG
Mineralogical composition
Short term leach test
Long term leach test
Field test

Test Type Test Methods and Description
Sobek Method
AP commonly from total sulphur
Methods
NP by boiling, HCl to pH 0.8‐2.5
Modified Sobek (Lawrence Method)
AP from sulphide sulphur
NP at ambient temperature for 24 hours near
boiling, HCl to pH 2.0‐2.5
p
Lapakko
NP at ambient temperature up to 1 week,
H2SO4 to pH 6.0
BC Research Inc. (BCRI) Initial
NP at ambient temperature for 16‐24 hours,
H2SO4 to pH 3.5
Sobek Siderite Correction
as Sobek, but with H2O2
Net Carbonate Value (NCV),%CO2
NCV = ANP + AGP, where
AGP = ‐1.37[(total sulphur) ‐ (residual sulphur
Negative NCV indicates acid generation potential
after pyrolysis)]
Acid Base Accounting (ABA)
ANP = 3.67[(total carbon) ‐ (carb on after HCl
digestion)] (=see TIC)
Acid Buffering Characteristic Curve (ABCC)
Titration of sample with acid while
continuously monitoring pH
Use in Geochemical Characterization and Water
Advantages Limitations
Quality Prediction
All Methods: All Methods: All Methods:
Establish overall acid generating and acid Provide no information on relative
neutralizing capability of a material through Most techniques well established rates of acid generation and
independent determination neutralization
Id tifi ti off th
Identification the need
d ffor and
d samples
l that
th t A
Assume NP andd AG sulfur
lf or minerals
i l
Generally relatively fast and inexpensive
require kinetic testing are completely available for reaction
Provide operational screening criteria for Can over‐ or under‐estimate AG or NP
mine waste classification and management depending on method used
NPR cannot be calculated in the
absence of sulphur and sulphide
p
Acid addition dependent on a
subjective fizz test which can affect
accuracy
Prevent over‐estimation of NP or AP relative
to Sobek method
Widely used
ASTM draft method uses sulphuric acid
Requires no fizz test
Accounts for complete oxidation of soluble metals
Uses pH to determine acid addition
d i titration
during i i
requirements
Negative values indicate stored acid
Requires carbon‐sulphur
Developed by Newmont Standardized as ASTM E‐1915 sophisticated combustion‐infrared
instrumentation similar to Sobek
Results require conversion for
Negative ANP and positive AGP must be corrected Waste rock composites characterized with comparison against data from other
to zero metallurgical suite for ores ABA tests in order to differentiate
methods
Several options for sulphide confirmation
Metal carbonates overestimate ANP
depending on mineralogy
Confirm NCV classification using BC Research Does not account for silicate
Classification system limits uncertainty
Confirmation on zone composites buffering or stored acidity
Can be used to identify minerals responsible
Provides an indication of the portion of the NP that Only feasible to do on selected
for neutralization by comparing against
is readily available for neutralization samples due to long test time
ABCCs for reference minerals
Limited basis for comparison against
Well suited for measuring actual NP vs. total
Used principally in Australia results from more "traditional" ABA
NP
tests due to limited use to date
Represents a less conservative method of
Similar in nature to the BCRI Initial test
measuring NP

Test Type Test Methods and Description
Sobek Method
AP commonly from total sulphur
Methods
NP by boiling, HCl to pH 0.8‐2.5
Use in Geochemical Characterization and Water
Test Methods and Description
Quality Prediction
Sobek Method All Methods:
Establish overall acid generating and acid
AP commonly from total sulphur neutralizing
Modified Sobek capability of a material through
(Lawrence Method)
independent determination
AP from sulphide sulphur
NP at ambient temperature for 24 hours near
boiling, HCl toIdentification
pH 2.0‐2.5 of the need for and samples that
NP by boiling, HCl to pH 0.8‐2.5 p
Lapakko
require kinetic testing
NP at ambient temperature up to 1 week,
H2SO4 to pH 6.0
BC Research Inc. (BCRI) Initial
NP at ambient temperature for 16‐24 hours,
H2SO4 to pH 3.5
Sobek Siderite Correction
as Sobek, but with H2O2
Net Carbonate Value (NCV),%CO2
NCV = ANP + AGP, where
AGP = ‐1.37[(total sulphur) ‐ (residual sulphur
Negative NCV indicates acid generation potential
after pyrolysis)]
Acid Base Accounting (ABA)
ANP = 3.67[(total carbon) ‐ (carb on after HCl
digestion)] (=see TIC)
Acid Buffering Characteristic Curve (ABCC)
Titration of sample with acid while
continuously monitoring pH
Use in Geochemical Characterization and Water
Advantages Limitations
Quality Prediction
All Methods: All Methods: All Methods:
Establish overall acid generating and acid Provide no information on relative
neutralizing capability of a material through Most techniques well established rates of acid generation and
independent determination neutralization
Id tifi ti off th
Identification the need
d ffor and
d samples
l that
th t A
Assume NP andd AG sulfur
lf or minerals
i l
Generally relatively fast and inexpensive
require kinetic testing are completely available for reaction
Provide operational screening criteria for Can over‐ or under‐estimate AG or NP
mine waste classification and management depending on method used
Advantages NPR cannot be calculated in the
Limitations
absence of sulphur and sulphide
All Methods: All Methods: p
Acid addition dependent on a
subjective fizz test which can affect
Provideaccuracy
no information on relative
Most techniquesPrevent over‐estimation of NP or AP relative
well established rates of acid generation and
to Sobek method
neutralization
Widely used
Assume NP and AG sulfur or minerals
Generally relatively fast and inexpensive
are completely available for reaction
Provide operational screening criteria for Can over‐ or under‐estimate AG or NP
mine waste classification and management depending on method used
ASTM draft method uses sulphuric acidNPR cannot be calculated in the
Accounts for complete oxidation of soluble metals
Requires no fizz test absence of sulphur and sulphide
Uses pH to determine acid addition Acid addition dependent on a
d i titration
during i i
requirements
Negative values indicate stored acid
subjective fizz test which can affect
Requires carbon‐sulphur
Developed by Newmont Standardized as ASTM E‐1915 sophisticated combustion‐infrared
instrumentation similar to Sobek
Results require conversion for
Negative ANP and positive AGP must be corrected Waste rock composites characterized with comparison against data from other
to zero metallurgical suite for ores ABA tests in order to differentiate
methods
Several options for sulphide confirmation
Metal carbonates overestimate ANP
depending on mineralogy
Confirm NCV classification using BC Research Does not account for silicate
Classification system limits uncertainty
Confirmation on zone composites buffering or stored acidity
Can be used to identify minerals responsible
Provides an indication of the portion of the NP that Only feasible to do on selected
for neutralization by comparing against
is readily available for neutralization samples due to long test time
ABCCs for reference minerals
Limited basis for comparison against
Well suited for measuring actual NP vs. total
Used principally in Australia results from more "traditional" ABA
NP
tests due to limited use to date
Represents a less conservative method of
Similar in nature to the BCRI Initial test
measuring NP
 Methods
• Static Tests
• Standard procedures
• Evaluate potential for ARD only
• Limited indication of on-
on-site drainageg q
quality
y
• No indication of when acidification will take place
• No indication of reaction rates
• Examples:
• Chemical composition
• Acid base accounting (ABA)
• Net acid generation (NAG)
• Mineralogical composition
• Short
Short--term leach testing (e.g.,
(e g SPLP,
SPLP MWMP)
• Wall washing
 Methods
• Kinetic Tests
• Provide an indication of reaction rates (oxidation, mineral dissolution)
• Provide an indication of drainage quality
• Provide an indication of lag time to acidification
• Examples:
• Humidity cell tests (HCT)
• Column tests
• Field cells
 Interperation

• Classification and p
prediction depend
p on:
• Objectives
• Characterization data
December 3, 2008 NWMA - Reno, NV 48
ARD Classification
 Modeling
• Powerful tools

• Computational abilities
exceed abilityy to represent
p
system complexity

• Model types:
• Geochemical
• Hydrological
• Hydrogeological
• Gas transport
• Geo-
Geo-environmental
 Modeling
• Benefits:
• Provide insight in future conditions
• Determine which variables are most important
• Assess effects of alternative approaches to ARD management
• Assess effects of uncertain parameters
• Establish objectives and conditions for field and laboratory
studies
• Integrate available information
• Limitations
• Insufficient input data
• Challenging
• Results can be misinterpreted
• Uncertain, variable, and non-
non-unique results
• Difference between modeled and actual field conditions
Mine Water Q
Quality
y Prediction
• Sophisticated tools + many samples ≠ increased
accuracy/precision
• What is the expected concentration of constituent X? –
not useful

• Instead: nature and sophistication should vary

d
depending
di on d desired
i d outcome
t
• Is a certain water quality threshold for constituent X
likely to be exceeded? - useful
• Do we need waste rock segregation?
• Do we need to capture seepage?
• Do we need a treatment plant?
Mine Water Q
Quality
y Prediction
• Tools selected to suit the need of a particular
application
• Regulatory expectations more realistic
• Large
L sampling
li and d ttesting
ti campaigns
i coupled
l d
with sophisticated (= expensive, extensive,
opaque) prediction methods no guarantee for
more precise/accurate water quality predictions
• May provide false sense of security
• Simpler, robust approaches may be
appropriate and reliable for decision making
Mine Water Q
Quality
y Prediction

• Example: Large range of estimates for

sea level rise due to global warming
• USGS: 7373--meter rise
• Lawrence Weinstein (Old Dominion U):
30
30--meter rise
• Weinstein: “I don’t need to refine that
number
number. I’m
I m in Virginia Beach
Beach. Either
way, I’m under water.” (National Geographic,
April 2009)
Geo--Environmental Models
Geo
• Economic geologists have long recognized
unifying
y gp principles
p between various ore deposit
p
types

• Provide
P id basis
b i for
f exploration
l ti geochemistry,
h i t b
butt
more recently also for prediction of
environmental behavior
 Recommendation
• Increased appreciation of geo-
geo-environmental
models
• Improve discovery, permitting, development and
closure of ore deposits
p
• Identify potential environmental challenges
• Improved focus
• Confirmatory characterization
program instead of de novo
testing
• More effective waste
g
management and mine
closure
 Conclusions
• Prediction is dependent on characterization

• A range of accepted techniques are available, a

systematic
y approach is needed for a site

• Regulatory frameworks and global guidelines

available
il bl

• Use of a range of state of the art methods

results in defensible predictions achievable by
knowledgeable practitioners
 Not everyone
y agrees….
g
• Predicting Water Quality Problems at Hardrock
Mines – a Failure of Science, Oversight, and
Good Practice (Earthworks, December 2006)

• “Do predicted water quality impacts match reality? The

answer, in short, is no.
no..”
no.”
• “The science of mine water quality prediction is
imperfect”
• “The
The science of mine water quality prediction is
imperfectly applied”
• “… consultants are rewarded for having favorable
predictions [[…]] …consultants
predictions. consultants that predict poor water
quality often are not rehired. This perverse incentive is
contrary to the spirit of unbiased science…”
 In Reality
Reality…
• Prediction and prevention of environmental impacts
significantly improved in last decades

• Understanding of geologic materials

materials, mine wastes
wastes, and
hydrogeochemical controls on mine water quality
continues to advance

• Necessary tools for geochemical, hydrological, and

hydrogeological characterization and modeling are
available

• Global guidance on best practices, including the GARD

Guide
Best Practice Methods
Best Practice Methods
Best Practice Methods