Sampling Analysis Testing Mine Wastes Geochemical Predictions Risk Assessment KMorin

Anlisis de Prcticas Actuales de Gestin de Aguas cidas
en Chile y en el Mundo
Sampling, Analysis, and Testing of

Mine Wastes for Geochemical
Predictions and Risk Assessment
Kevin A. Morin, Ph.D., P.Geo., L.Hydrogeo.

Minesite Drainage Assessment Group
www.mdag.com
Outline of This Presentation

3.1. Visin general, objetivos y alcances de la
caracterizacin de residuos mineros
3.2. Muestreos y anlisis
3.3. Tests de laboratorio
- Tests estticos
- Tests cinticos
3.4. Tests de campo

Each proposed, operating, and closed minesite may have different
sets of objectives for waste characterization. These objectives
often focus on the waters draining from a minesite and its
components, like mine walls, waste rock, low-grade ore, and
tailings.
Objectives can include:
-
predicting future drainage chemistry, including changes through time;

understanding current drainage chemistry for operating or closed
minesites;
estimating costs for preventing or controlling drainage-chemistry
problems;
choosing among prevention/control options based on their
effectiveness, risk, and cost;
evaluating whether wastes exceed sediment/toxicity levels and thus
must be physically confined.

The scope of studies to address these objectives can be
minimal to intensive. The scope depends on factors like
severity of environmental degradation, issues and
questions, available funds, and public concerns.
Although objectives and scopes may differ among minesites,

the same combination of geochemical tests can be used.
This combination of tests is discussed in Sections 3.3 and
3.4 of this presentation.

Each proposed, operating, and closed minesite may identify and
collect samples in different ways. The sizes, numbers, and types
of samples can differ, depending on objectives (Section 3.1).
For example:
one site may collect hundreds of samples from core, whereas others
-
may collect only dozens of samples from outcrop rock;

one site may collect 2 m sections of drill core, whereas others may
collect short, 10 cm sections;
one site may conduct detailed tests on tailings, whereas another may
not;
one site may collect on-site drainage waters, whereas another may not.
There is no one approach to sampling - it is unique to each minesite

and each objective. By showing the results of laboratory
analyses, the next section also illustrates the sampling programs
undertaken by mining companies and their consulting
companies.

For proposed minesites and proposed expansions, sampling can
coincide with mineral exploration, using the same core,
rejects, and pulps assayed earlier for ore. In this way, the
reliability of environmental predictions is tied closely to the
reliability of economic and resources estimates.
Once appropriate samples are collected, they should be

analyzed as explained in Sections 3.3 and 3.4 below.
3.3. Tests de laboratorio y 3.4. Tests de campo
The easiest way to explain the laboratory and on-site field tests
is by using the analogy of a wheel.
I call this the Wheel Approach for predicting, scaling, and
understanding mine-waste geochemistry and minesitedrainage chemistry.
Wheel Approach for Minesite-Drainage Chemistry

Acid Rock Drainage (ARD) is basically the result of a geochemical
battle within rock or soils containing sulphide minerals like pyrite.
Upon exposure to air and moisture, sulphide minerals like pyrite
oxidize, which releases acidity and leaches metals into nearby
water.
Frequently, there are also fast-acting acid-neutralizing minerals in
rock and soil that dissolve in response to the acid generation.
These neutralize and eliminate the acidity and, by raising the pH to
near-neutral values, minimize the leaching of metals into nearby
waters.
This geochemical battle continues until either:
(1) the sulphide minerals are depleted before the fast-acting neutralizing
minerals and thus there is no ARD or major leaching of metals, or
(2) the fast-acting neutralizing minerals are depleted first, leading to
significant ML/ARD.
This is a list of relevant references that can be downloaded for free from
www.mdag.com/presentations/iquique-2010.html
Ref. B0001, B0002, A1957

Metal leaching (ML) is the release of metals from rock or soil
into any water flowing over/through these materials. The
extent and degree of leaching are typically unique for each
metal, reflecting a sites unique combination of mineralogy,
water chemistry, water flow, and solid-liquid interactions.
In a general sense, the solubilities of several metals are

highest at acidic pH and lower around neutral pH, so that ML
is more severe with ARD. However, there are documented
cases where ML was more severe around neutral pH, so the
leaching of metals at a particular site must be examined even
when ARD is not present.
Ref. B0001, B0002, A1957

Because drainage-chemistry from mixed-mineral systems is
difficult to predict and understand, a suite of tests have been
developed and combined over the last century.
Each test has strengths and weaknesses, so no one test is
sufficient for drainage chemistry.
For simplicity, this suite of tests is depicted on the next slide
as a wheel with spokes. It is important to perform as many
of these types of tests as feasible.
The tests can be mostly divided into:
static tests performed only once to measure sample
composition
kinetic tests using repeating analyses to measure a samples
reactivity and leaching capacity
Ref. B0001, B0002, A1957

Kinetic; usually full scale
For a proposed minesite, full-scale

On-Site Monitoring Data may not
be available. Other Wheel tests
will lead to predictions of full-scale
drainage chemistry.
On-Site
Monitoring
Data
For a historical minesite, full-scale On-Site

Monitoring Data may be available. However,
to understand the origin of the full-scale
drainage chemistry, and to predict changes
through time, the other Wheel tests are
needed
Field
Kinetic Tests
Acid-Base
Accounting
Kinetic; usually medium scale
Static; usually small scale
Drainage Chemistry
Laboratory
Kinetic Tests
Kinetic; usually small scale
Total Elements &

Whole Rock
NAG Testing:
Single, Sequential,
Kinetic, and ABCC
Mineralogy
Retention/ Soluble-Mineral
Tests
~Static; usually small scale
Static and Kinetic; usually small scale
Ref. B0001, B0002, A1957

Summary Descriptions of Testwork under the Wheel Approach for
Predicting Minesite-Drainage Chemistry
Name
Description
Acid Base
Accounting
(ABA)
Bulk amounts of (1) acid-generating sulphide and non-acid-generating sulphate minerals

and (2) fast-neutralizing carbonate and slow-neutralizing minerals; overall net balances of
acid-generating and acid-neutralizing capacities
NAG Tests
Net acid generating capacity based on rapid oxidation with hydrogen peroxide
Total Element/
Whole Rock
Bulk solid-phase amounts of metals and other elements
Mineralogy
Identities and abundances of specific minerals
Retention/
Soluble Tests
Concentrations and amounts of readily soluble and leachable metals and other elements,
and of elements accumulated during past oxidation and reactions; check for equilibrium
Laboratory
Kinetic Tests
Primary rates of acid generation, acid neutralization, and metal leaching from relatively
small samples under controlled laboratory conditions; lag times to net acidity; site-specific
ABA criteria; check for equilibrium, especially in initial flushes
Field Kinetic
Tests
Secondary-mineral-distorted rates of acid generation, acid neutralization, and metal

leaching from relatively large samples with known volumes and weights under on-site
conditions; upscaling calibration of laboratory kinetic tests; check for equilibrium
On-Site
Monitoring
Secondary-mineral-distorted rates of acid generation, acid neutralization, and metal

leaching from an existing mined area, possibly of unknown volumes and weights, under
on-site conditions; check for equilibrium

Good explanations, strengths, and weaknesses of these
tests under the Wheel can be found in Price (2009).
Ref. A1957
Increasing Aqueous Concentration (mg/L)
Scale
Transition
Kinetic rates
apply in this
part of the
curve
Maximum equilibrium concentrations

apply in this part of the curve,
caused by thermodynamics,
metastability, emergence, etc.
At what scale, weight, time, ratio, etc., is the
Scale Transition met for a particular minesite
component and element?
full-scale minesite component

1-t leach pad
20-50-kg column
1-kg humidity cell
mesoscale
100-g shake flasks

a few grains of minerals
microscale
Most testwork and

modelling for
minesite-drainage
chemistry may extend
above and below the
Scale Transition.
This greatly
complicates the
interpretations of
testwork, and can
lead to errors.
geochemical modelling
Increasing Scale, Weight, Volume, Time, Solid:Liquid Ratio,
Reaction Rate, Residence Time, or Distance Along Flowpath
Ref. CS0026
Kinet
ic
Equilibrium
The smaller-scale kinetic tests of the

Wheel may measure only kinetic
conditions. Larger-scale kinetic tests
may measure only equilibrium
conditions. For a particular minesite
component, all kinetic tests may
measure only kinetic or only equilibrium
conditions.
The tests do not tell us which condition
applies. We have to determine that.
Increasing Size (Scale), Residence Time, or Distance Along Flowpath

Ref. CS0026
Not all tests under the

Wheel may be
applicable or feasible
for all minesite
components.
Ref. B0001, B0002, A1957

On-Site
Monitoring
Data
Field
Kinetic Tests
Acid-Base
Accounting
Drainage Chemistry
Laboratory
Kinetic Tests
Total Elements &

Whole Rock
NAG Testing:
Single, Sequential,
Kinetic, and ABCC
Mineralogy
Tests
Wheel Approach Acid-Base Accounting (ABA)

In more detail, expanded ABA can include:
paste pH in a mixture of pulverized rock and water,

total sulphur,
measured sulphide,
leachable sulphate (both HCl and carbonate leach techniques),
calculated sulphide by subtracting sulphate from total sulphur,
barium-bound sulphate calculated from barium analyses,
calculation of acid potentials based on sulphide levels plus any unaccounted-for sulphur
(Sulphide Acid Potential, SAP),
Sobek (U.S. EPA 600 compliant) neutralization potential (NP) by acid bath and base
titration,
inorganic carbonate for mathematical conversion to Carbonate NP (Inorg CaNP),
total carbon for mathematical conversion to Carbonate-equivalent NP (Total CaNP),
excess carbon calculated from the difference between total carbon and inorganic carbon,
CaNP calculated from calcium (Ca CaNP),
CaNP calculated from Ca + Mg (Ca+Mg CaNP),
various Net Neutralization Potential (NNP) balances of acid neutralizing capacities minus
various acid generating capacities, and
various Net Potential Ratio (NPR) balances of acid neutralizing capacities divided by
various acid generating capacities
Wheel Approach Acid-Base Accounting (ABA) - Criteria

Part of ABA includes measuring the pH of a mixture of powdered sample and water
(paste pH) and the calculation of Net Potential Ratio (NPR = Neutralization
Potential / Sulphide Acid Potential, or NP/SAP). These parameters can be used to
explain the current conditions and predict future ML/ARD using ABA Criteria.
Generic Non-Site-Specific ABA Criteria for Assessing or Predicting

the pH Range of Minesite Drainage Chemistry
(many exceptions are known, so site-specific criteria
must be developed to replace these)
Criteria
Prediction or Current Condition

Based on paste or rinse pH
Paste/rinse pH < 5-6.5
Currently acidic; future unknown
5-6.5 < Paste/rinse pH < 9-10
Currently near neutral; future unknown
Paste/rinse pH > 9-10
Currently alkaline; future unknown

Based on NPR or NNP
NPR < 1 or NNP < 0 kg/t
Eventually acidic after some lag time
1<NPR<2 or 0<NNP<+20 kg/t
Uncertain without further testwork
NPR > 2 or NNP > +20 kg/t
Indefinitely near neutral or alkaline
Wheel Approach Acid-Base Accounting (ABA) - NPR

Available
Acid Potential (Av AP)
The bad guys
trying to create ARD
through sulphide
oxidation
Available Neutralization
Potential (Av NP)
Net Potential Ratio

(NPR)
The good guys

trying to neutralize
the acidity from
sulphide oxidation
For NP to win the long-term geochemical battle and prevent ARD, there must be
more Available NP than Available AP. That is, NPR must be greater than 1.0,
often greater than 2.0. An NPR criterion of 2.0 is typical for minesites, but values
below 1.0 and above 4.0 have been reported.
ABA has implicit limitations, like it assumes all sulphide will generate acidity and all
NP can be measured within several hours of testing. If Available AP and/or
Available NP from ABA are wrong, then NPR-based predictions could be wrong.
Wheel Approach Acid-Base Accounting (ABA) - Sulphur

10
This is a scatterplot of
sulphide and total
sulphur from ABA at a
minesite, It showed
that most sulphur was
potentially acidgenerating sulphide.
0.1
Another part of the

Wheel, mineralogy,
was used to confirm
this sulphide was
primarily pyrite. Pyrite
is a common acidgenerating mineral
when exposed to air
and moisture.
:1
0.01
% S (Sulphide)
0.001
0.001
0.01
0.1
% S (Total)
10
Wheel Approach Acid-Base Accounting (ABA) - Sulphur

At this site, dozens of drillholes contained FeS2 (pyrite), often around 0.5-2%. This means
that a few ABA would not be sufficient to evaluate NPR reliably for thus site. Normally,
hundreds to thousands of ABA are required.
0
DDH 106
DDH 107
DDH 110
0 1 2 3 4
0 1 2 3 4
0 1 2 3 4
DDH 112
DDH 112
DDH 113
DDH 142
DDH 143
DDH 144
0 1 2 3 4
0 1 2 3 4
0 1 2 3 4
100
Drillhole Depth (m)
200
300
400
500
600
0 1 2 3 4
0 1 2 3 4
FeS2 (%)
0 1 2 3 4
Wheel Approach Acid-Base Accounting (ABA) - NP

One of the largest sources of errors, and misunderstood
concepts in minesite-drainage chemistry, is
Neutralization Potential (NP). Problems and errors
related to NP will be shown later in this presentation.
These problems and errors can be traced to three major

NP issues:
NP is an extrinsic rather than an intrinsic property
Several incompatible methods exist for measuring NP, but the
results of all are called NP
Available NP for NPR calculations is typically not equal to
measured NP
Ref. CS0032
NP is an extrinsic rather than intrinsic property

A sample of rock, overburden, tailings, or other minesite
material contains a specific amount of copper or sulphur or
other element in the Periodic Table, and has a certain mass.
These are called intrinsic properties. An intrinsic property can
be defined as a property that is specific to a sample or minesite
component, and wholly independent of any other object, action
or consequence.
Ref. CS0032

Extrinsic properties depend on, or are defined by, external conditions.
For example, two dry sponges have masses of 100 grams. If one
sponge is squeezed hard and the other softly, they both still have the
same mass, but different volumes. In this example, volume is an
extrinsic property that depends on the pressure (squeezing) applied
to the sponges.
As another example, two identical sponges are squeezed by the
same amount, but for different lengths of time. The one squeezed
longer will compress more through time, and thus have a smaller
volume at the end. So time also can affect extrinsic properties.
In these example, would you call one volume right and the other
volume wrong? This happens with NP methods.

NP for minesite materials is an extrinsic property that
depends on external conditions like pH, temperature, and
time.
The lower the pH in the NP test (more aggressive testing), the greater the
neutralization that may be obtained from some mixed-mineral samples. This
does not apply to all mixed-mineral samples.
The higher the pH endpoint of the NP test (additional neutralization, the
greater the neutralization that may be obtained from some mixed-mineral
samples. This does not apply to all mixed-mineral samples.
The higher the temperature of the NP test (faster reaction rates), the greater
the neutralization that may be obtained from some mixed-mineral samples.
This does not apply to all mixed-mineral samples.
The longer the time of the NP test (longer reaction times), the greater the
neutralization that may be obtained from some mixed-mineral samples. This
does not apply to all mixed-mineral samples.
Ref. CS0032

As an extrinsic property, NP is defined by the method to measure it.
This is the same for the aqueous parameters of alkalinity and acidity.
Confusingly, there are many methods to measure NP (see next
slides), each using different analytical conditions, but the results from
all methods are called NP. For any particular sample, three different
methods may yield three different NP values for that sample, but all
are called NP.
Some people and experts argue which NP method is right. None
are inherently right or wrong, but reflect the analytical conditions.
It is critical that a mining project or minesite select and use one NP
method consistently, so that all NP values can be compiled and
interpreted consistently and correctly for that site.
Ref. CS0032
REFERENCE:
Morin, K.A., and N.M. Hutt. 2009. On the Nonsense of Arguing the Superiority of an Analytical Method for Neutralization Potential.
MDAG Internet Case Study #32, www.mdag.com/case_studies/cs32.html
In response to comments on this case study, we saw value in expanding and elaborating some points in the following documents:
NP - Additional Discussion on Its Non-Intrinsic Nature
Ref. CS0032
NP - Arguments on NP-Method Superiority Translated into Varieties of Oranges
For any sample, the various NP methods may provide similar or notably
different values. Modified NP can be higher or lower than Sobek NP.
Comparison of Five NP Techniques for Acid-Base Accounting

Neutralization Potential (kg CaCO3 eq/tonne)
Sample (RK = rock;TL = tailings) RK1 RK2 RK3 RK4 TL1 TL2 TL3 TL4 TL5
TL6
Sobek NP
12
35
15
28
27
18
46
3.8
7.5
99
Modified NP
9.6
33
14
28
27
20
61
2.9
3.2
72
BC Research NP
7.7
11
25
33
30
25
82
15
20
58
Lapakko NP
3.0
2.8
3.3
28
24
16
30
3.8
15
55
Mineralogical NP
32
19
16
19
12
46
Carbonate CaNP
2.5
0.7
32
32
20
18
93
5.7
15
46
The problem with NP

methods is that not all
measured NP is
available, effective, and
reactive.
The International Static
Database is a
compilation of more than
19,000 ABA from
around the world. It
showed that, as NP
decreased, towards
zero, acidic pH values
were sometimes
encountered (left).
19,232 datapoints
Therefore, some
amount of measured NP
is unavailable for
neutralization.
Ref. M0002, M0015

Based on studies at various scales, Available NP for
NPR calculations can be estimated from:
Available NP =
Measured NP
- Unavailable NP
+ Slow-Reacting NP
COMPLICATIONS:
Measured NP is method specific.

Unavailable NP is discussed on the next slide
Slow-Reacting NP is dependent on factors like time,
scale, and mineralogy
Ref. CS0030, CS0031, CS0032

Unavailable NP (UNP) =
Analytical-method UNP + Sample-specific UNP +
Upscaling-effect UNP
UNP from:
- artifacts in analytical methods,
- sample-specific conditions, like siderite,
- upscaling emergent effects, like the encapsulation of reactive NP
rendering it unavailable at the existing grain size.
Ref. CS0030, CS0031, CS0032

Estimates of Unavailable NP can be obtained from ABA,
NAG (ABCC) testing, laboratory kinetic tests, and largerscale on-site kinetic tests.
The following slides show ABA results from actual
minesites and mining projects.
The objective of each was to estimate Unavailable NP,
relatively quickly and cheaply using only ABA (paste pH)
results. WARNING: This quick approach works only if
samples are well weathered and oxidized, and some have
become acidic. This approach does not work for fresh,
unoxidized samples.
Ref. B0001, B0002, A1957

10
Paste pH
But what about these

anomalous acidic samples
with NP > 10 kg/t?
Initial Estimate of
Unavailable NP =
10 kg/t at pH 5 and 6
2
-10
10
20
30
40
50
60
70
Neutralization Potential (kg CaCO3 eq/t)
80
90
100
Ref. CS0030

10
Paste pH
Rock Unit 1
Rock Unit 2 (excluding 2a)
Rock Unit 2a
Rock Unit 3
Rock Unit 4
Undifferentiated Waste Rock
Initial Estimate of
Unavailable NP =
3 kg/t
2
0
20
40
60
80
100
Ref. CS0030

10
8
Higher values of
NP truncated
Paste pH
6
Andesite
Argillite
Contact Zone
Rhyolite
Rhyolite Massive
Rhyolite Flow
2
Rhyolite Breccia
Initial Estimate of
Unavailable NP =
10 kg/t
Dacite
Ore
Mudstone
0
0
40
80
120
160
200
Ref. CS0030

9
U n availab le
N P = 5 kg /t
for Z o ne # 2
Paste pH
Z on e
O re Zo n e # 1
O re Zo n e # 2
O re Zo n e # 3
U n availab le
N P = 15 kg/t
fo r Z one #1
If d a ta w a s re p o rte d a s < d e te c tio n lim it

h a lf th e d e te c tio n lim it is s h o w n a n d w a s
u s e d in s u b s e q u e n t c a lc u la tio n s .
4
1
10
100
1000
Ref. CS0030

10
Three lime stone samples
w ith N P ~ 9 00 kg/t no t sh ow n
Paste pH
2
Initial Estimate of
Unavailable NP =
5 kg/t
0
-40
-20
20
40
Ref. CS0030

10
8
Rock Unit
BRK (Zone #1)
CBS (Zone #1)
Paste pH
MXZ (Zone #1)
OVB (Zone #1)

OXZ (Zone #1)
SPR (Zone #1)
SUL (Zone #1)
BRK (Zone #2)
CBS (Zone #2)
MXZ (Zone #2)

OVB (Zone #2)
Initial Estimate of
Unavailable NP =
10 kg/t at pH 6 and 5
OXZ (Zone #2)

SPR (Zone #2)
SUL (Zone #2)
2
0.1
10
100
1000
Ref. CS0030

The most common value for Unavailable NP is around 10
kg/t, but site-specific values from 0 to >50 kg/t have been
reported. UNP should be subtracted from all measured NP
values to obtain an Available NP for net-balance NPR
calculations.
In the past, there were rules of thumb, like only 1/3 of
measured NP should be used in ARD predictions.
Also, in the old days of NNP, the common criterion of +20
kg/t implicitly recognized up to 20 kg/t of NP would be
unavailable.
I have seen >95% ARD reports not subtracting Unavailable
NP (UNP), but using all the measured NP. With low-NP
samples, this can lead to major ARD errors. Such errors
have occurred, as shown later in this presentation.
10
Net acid
generating, not
yet acidic
Uncertain

Sulphide Net Potential Ratio
(SNPR) equals Neutralization
Potential divided by Sulphidebased Acid Potential.
Adjusted means Unavailable
NP has been subtracted before
the NPR calculation.
Net acid
neutralizing
In this example, 33% of these

230 samples are net acid
generating, based on generic
criteria. Many are not acidic at
this time. The lag time until
they become acidic is
determined from kinetic tests.
Net acid
generating,
already acidic
Uncertain
Paste pH
Theoretically not
possible
If S (Sulphide+del) <0.01 then
Adjusted SNPR = 200,
if (NP - 5) = < 0 then
Adjusted SNPR = 0.001.
2
0.001
0.01
0.1
Adjusted SNPR
10
100
1000
16% of the samples are

uncertain until further kinetic
testing. This testing will
provide the site-specific values
of SNPR and thus eliminate the
uncertain category.
% S (Sulphide)
=< 10

50% of the existing waste
rock has a sulphide content
of 0.3%S and less.
=< 1
=< 0.1
=< 100
=< 10
=< 0.01
20
40
60
80
% of Total Rock in Waste Rock Dump
100
Based on an SNPR criterion of 1.0,

32% of the waste rock is net acid
generating (55% with a criterion of
2.0). However, water-chemistry
monitoring shows this waste rock
does not affect pH or add sulphate to
the water, so it is not highly reactive.
SNPR
Net acid neutralizing
=< 1
Net acid generating

=< 0.1
=< 0.01
20
40
60
80
% of Total Rock in Waste Rock Dump
100

On-Site
Monitoring
Data
Field
Kinetic Tests
Acid-Base
Accounting
Drainage Chemistry
Laboratory
Kinetic Tests
Total Elements &

Whole Rock
NAG Testing:
Single, Sequential,
Kinetic, and ABCC
Mineralogy
Tests
Wheel Approach Total Element Analyses

Total-element analyses determine the total solid-phase levels of
metals and other elements in small-scale homogenized samples.
Such analyses include four-acid-digestion ICP-MS and x-rayfluorescence whole rock.
The purposes of such analyses include:
comparison to worldwide crustal abundances
comparison to environmental sediment-toxicity values
correlations among solid-phase elements, suggesting mineralogical
associations
correlations of aqueous leaching rates from kinetic tests with initial
solid-phase levels of sulphur or other elements
predicted times of solid-phase depletions of elements based on
aqueous leaching rates from kinetic tests
Ref. B0001, B0002, A1957

IMPORTANT: Solid-phase levels do not say whether
aqueous leaching rates will be high or low.
A high solid-phase level may create a high or low aqueous
leaching rate.
A high solid-phase level may be high, because it leaches
slowly.
Kinetic tests provide aqueous leaching rates, not solid-phase
static tests.
For some elements, some site-specific correlations are
sometimes seen between aqueous leaching rates and solidphase levels.
Ref. B0001, B0002, A1957

As examples for comparisons to crustal abundances or
sediment-toxicity criteria:
This showed that [this sites] rock samples were:
frequently elevated in silver, bismuth, copper, sulphur, and
selenium;
occasionally elevated in arsenic, mercury, molybdenum, and
antimony; and
rarely elevated in cadmium, chromium, cesium, indium,
phosphorus, lead, tungsten, and zinc.
At least one tailings composite was elevated in silver, arsenic,
bismuth, copper, sulphur, antimony, and selenium.
This showed that [this sites] samples were:

frequently elevated in silver, bismuth, copper, molybdenum,
sulphur, antimony, selenium, and tungsten; and,
occasionally to rarely elevated in arsenic, cadmium, cesium, lead,
and zinc.
Wheel Approach Total Elements

There is more arsenic
than sulphide in this
region, so the arsenic
can occur in forms other
than FeAsS and AsS
In this example, a
correlation of sulphide
with arsenic
suggested the rate of
arsenic leaching may
depend on the rate of
sulphide oxidation.
As
S
Arsenic (%)
Fe
As
S
0.1
In that case, any

reduction in the rate of
sulphide oxidation will
also reduce arsenic
leaching.
0.01
All arsenic in this

region can exist as
FeAsS and AsS
0.001
0.001
0.01
0.1
% S(Sulphide)
10

This example showed that measured NP in most samples was, as a minimum,
carbonate based (lower left), but many samples contained some non-carbonate
NP.
1000
10000
If data was reported as < detection limit,

half the detection limit is shown and
was used in subsequent calculations.
Samples close to this line suggest most

of the measuredNP was composed
of carbonate. Most samples had
additional, non-carbonate NP.
100
Mitchell - Intrusive
Mitchell - Metasedimentary
Mitchell - Volcanic
Mitchell - Other/Unknown
Sulphurets - Intrusive
Sulphurets - Metasedimentary
Sulphurets - Volcanic
Sulphurets - Other/Unknown
Kerr - Intrusive
Kerr - Metasedimentary
Kerr - Volcanic
Kerr - Other/Unknown
10
If data was reported as < detection limit,

half the detection limit is shown and
was used in subsequent calculations.
Manganese (ppm)
Inorganic CaNP With a NP > 15 (kg CaCO3 equivalent/tonne)
Solid-phase manganese generally correlated with NP (lower right). Thus, a

significant portion of manganese was likely contained in carbonate minerals. In
turn, any acceleration of NP dissolution, such as by underwater disposal or acid
generation, could lead to accelerated leaching of manganese.
1000
Mitchell - Intrusive
Mitchell - Metasedimentary
Mitchell - Volcanic
Mitchell - Other/Unknown
Sulphurets - Intrusive
Sulphurets - Metasedimentary
Sulphurets - Volcanic
Sulphurets - Other/Unknown
Kerr - Intrusive
Kerr - Metasedimentary
Kerr - Volcanic
Kerr - Other/Unknown
100
10
10
100
Neutralization Potential (kg CaCO3 equivalent/tonne)
1000
10
100
Neutralization Potential (kg CaCO3 equivalent/tonne)
1000
Wheel Approach Large-Scale Three-Dimensional Modelling of

ABA/Total-Element Data
Modelos Geoestadsticos por Proyecto de Las Cristinas en Venezuela en
1995 (ABA = 2500)

The two approaches for three-dimensional modelling of acid-baseaccounting data at this site indicated 3.6-5.1% of the pit rock, by volume,
was net acid generating. This rock was not scattered throughout the pit
area, but occurred in distinct masses, within the black mesh zones below.
The much greater volume of rock was be net neutralizing.

Based on small-scale ABA samples, about 13% of samples

were net acid generating. This is greater than the 3.6-5.1%
from large-scale 3D modelling. Therefore, this modelling
showed that small-scale sample percentages overestimated the
large-scale 3D volume percentage.
In other cases, sample percentages can underestimate largescale volumes of net-acid-generating rock.

For open-pit mines before mining, ABA samples are collected in three dimensions
from drillholes (black straight lines below). Geostatistical modelling in three
dimensions highlights net-acid-generating zones (red areas below) within the
proposed pits (grey surfaces) that will become waste rock.
Wheel Approach Acid-Base Accounting and Total Elements
150 South Adit
150 North Adit
161 North Adit
D-66-088
D-68-036
D-66-001
D-66-109
D-68-051
D-66-083
D-66-007
D-66-119
Main Adit
D-68-055
D-66-080
N
D-66-012
D-66-124
D-68-060
D-66-075
D-66-130
D-68-066
D-66-026
D-66-067
D-66-015
D-68-071
D-66-062
D-68-075
D-66-022
D-66-054
D-68-081
D-68-046
D-66-034
D-68-090
D-68-041
D-66-040
D-68-097
D-68-021
D-66-046
D-68-102
Bowser
D-66-049
D-68-014
D-68-109
(Skeena
D-66-059
D-66-095
Sedimentary
D-68-142
D-66-099
Rock)
D-68-137
D-66-102
D-68-130
D-66-114
D-66-133
D-68-124
D-66-141
D-68-117
D-66-147
D-68-112
Hazelton Volcanics
D-66-145
(predominantly
tuffs)
D-68-144
D-68-156
D-66-155
D-68-001
D-68-164
D-68-155
D-68-005
D-68-176
D-68-236
D-68-010
D-68-242
D-68-188
D-68-024
D-68-200
D-68-248
D-68-215
D-68-030
D-68-258
Sampling Locations
D-68-232
Granodiorite
(ore zone)
161 South Adit

~500 ft
~150 m
Portal
For underground mines, ABA samples are not usually collected in three dimensions
as with open pits. This is because underground mines are often linear tunnels.
Thus, samples for ABA and total elements are collected in more linear patterns.

The resulting analyses, like solid-phase arsenic below, are
interpreted in a different manner than 3D open pits.
5.3
1
1.5
3.9
0.8
2.8
5.8
3.6
2.1
2.4
2.7
1
1.8
1.6
2.5
2.2
1.9
25.7
92.9
1.2
4
1.6
4.2
1.8
1.4
4.8
Main Adit
2.4
2
1.8
7.5
1.2
150 South Adit
150 North Adit
1.7
1.2
1.2
5.4
1.5
1.4
1.2
1.9
6.5
1.3
7.2
1.9
3.8
7.6
161 North Adit
2.5
1.9
4.9 1.7
Portal
7.5
3.2
3.5
1.2
2
2.1
2.2
3.5
3.8
2.7
2.3
64.7
1.5
Bowser
(Skeena
Sedimentary
Rock)
1.5
Hazelton Volcanics
(predominantly tuffs)
8
9.1
Arsenic
1.2
(ppm)
1.4
92.9 Red means As > 3

times crustal abundance
Granodiorite
(ore zone)
161 South Adit

~500 ft
~150 m
Adjusted Total-Sulphur-Based Net Potential Ratio

1000
100
Recent - Footwall
Historical - Footwall
Recent - Hanging Wall
Historical - Hanging Wall
Historical - Ore Zone
Historical - Location Unknown
10
Footwall
Samples below the line

are net acid generating
(Adj TNPR < 2.0)
0.1
0.01
0.001
Note: the ore zone is depicted here as

zero width, but has an apparent
thickness of 4-35 m according to
Western Keltic Mines in the
drillholes used here.
Hanging Wall
Based on drillhole distance

from the ore zone, net-acidgenerating samples in the
footwall were common at
least 40 m from the ore
zone.
Net-acid-generating
samples of the hanging wall
If % S(Total) < 0.01
were occasionally
then TNPR = 200
If % S(Total) > 0.01 and (NP-15) < = 0
encountered at distances
then TNPR = 0.001
These three samples with <0.12%S were up to approximately 20 m
from the adit, and their Adj TNPR values
from the ore zone, and less
would not rise above 2.0 unless
Unavailable NP was below 3 kg/t.
frequently at distances up to
134 m.
-200 -160 -120 -80 -40

0
40
80 120 160
Minimum Distance from Ore Zone along Drillhole (m)
200

Segregation of ARD Rock
Units during Mining
~7
~7
~7
pH
pH
pH
<3
<3
<3
~7
pH
<3
ARD Rock Units

Near neutral,
Low leaching
Near neutral,
High Leaching
Weak ARD
Moderate ARD
Strong ARD

No Segregation of ARD Rock
Units during Mining
Deposito de lastres
ARD Rock Units Occur in

Distinct Layers
Ao 9 y 10
Ao 7 y 8
Ao 5 y 6
Ao 3 y 4
Ao 1 y 2
La mina
7
pH
5
3
0
ARD Rock Units

Near neutral,
Low leaching
Near neutral,
High Leaching
Weak ARD
Aos
Moderate ARD
10
Strong ARD

No Segregation of ARD Rock
Units during Mining
Deposito de lastres
ARD Rock Units Do Not Occur in

Distinct Layers
La mina
pH
3
Meses, aos o dcadas?

ARD Rock Units
Near neutral,
Low leaching
Near neutral,
High Leaching
Weak ARD
Moderate ARD
Strong ARD

Segregated ARD Rock Types
All ARD Rock Types
Mixed Together
~7
~7
pH
pH
<3
<3
~7
pH
<3
Months, Years, or Decades?
~7
~7
pH
pH
<3
<3
ARD Rock Units

Near neutral,
Low leaching
Near neutral,
High Leaching
Weak ARD
Moderate ARD
Strong ARD

On-Site
Monitoring
Data
Field
Kinetic Tests
Acid-Base
Accounting
Drainage Chemistry
Laboratory
Kinetic Tests
Total Elements &

Whole Rock
NAG Testing:
Single, Sequential,
Kinetic, and ABCC
Mineralogy
Tests
Ref. B0001, B0002, A1957
Wheel Approach Mineralogy

As part of the Wheel, mineralogy identifies the major and minor minerals
in a sample using optical, microscopic, laser, mass-spectroscopy, and xray techniques. Trace minerals, typically less than 0.1%, cannot typically
be identified this way.
Granite - Petrographics (ABA Sulphide = 0.02%S, NP = 5 kg/t)
Granite - Rietveld XRD
Epidote
1.5
K-feldspar
2
Plagioclase
Biotite
5
1
Calcite
0.3
Plagioclase
7.1
Muscovite
33.1
Sericite
40
Quartz
50
Kaolinite
0.8
Quartz
58.7

The Holy Grail Premise: Minerals create drainage chemistry.
So, if we know mineralogy accurately, we can predict aqueous
concentrations accurately.
This is incorrect. Minerals contain site-specific impurities and
non-idealities like solid solutions. These affect the site-specific
composition, reaction rates, and effects on water chemistry.
Question: Can we delineate mineralogy of a sample accurately
using everyday techniques?

In this sedimentary sample, visual observations indicated 15% plagioclase, whereas
Rietveld XRD reported no feldspar.
Rietveld detected the pyrite at a low level, whereas visually it was not reported.
The NP of 10.8 wt-% was similar to the visual 8 vol-% and the Rietveld sum of 17.0
vol-%, but the type of carbonate was not characterized visually.
Mudstone/Siltstone - Petrographics (ABA Sulphide = 0.25%S, NP = 108 kg/t)
Sub-opaque
10
Mudstone/Siltstone - Rietveld XRD

Siderite
4.2
Quartz
20
Ankerite-Dolomite
12.8
Carbonate
8
Pyrite
0.3
Chlorite
5
Kaolinite
10.7
Quartz
45.6
Plagioclase
15
VISUAL
XRD
Sericite
42
Muscovite
26.4

Some reasons for mineralogical discrepancies among
methods:
Different splits are analyzed. XRD is based on small, pulverized
samples, whereas petrographics require non-pulverized, larger
samples.
XRD cannot detected nearly/fully amorphous phases, like some
iron and aluminum oxyhydroxides. These can form large
portions of some samples associated with ARD. This lack of
detection by XRD will cause the percentages of detected
minerals by Rietveld to be higher.
Mineral names and ideal formulae can vary with country and
laboratory, so two different names for virtually the same
compound may appear.

Some reasons for mineralogical discrepancies among
methods:
Ideal formulae are just that, ideal. In reality, impurities and
elemental substitutions in minerals create broad spectrums and
solid-solution series. Selecting the right mineral name for a
naturally occurring mixture can be difficult. In this real-world
situation, peak matching used by XRD will not be reliable when
using ideal peaks in a database.
Detection limits are variable, but probably often between 0.1 and
1 vol-%. Petrographics has the option of including trace or
rare if requested to identify a few particles that may be
encountered by chance during observations. Rietveld detection
limits are sensitive to the grain size and spatial orientation of
grains.

On-Site
Monitoring
Data
Field
Kinetic Tests
Acid-Base
Accounting
Drainage Chemistry
Laboratory
Kinetic Tests
Total Elements &

Whole Rock
NAG Testing:
Single, Sequential,
Kinetic, and ABCC
Mineralogy
Tests
Ref. B0001, B0002, A1957
Wheel Approach Soluble/Retention Tests

The objectives of this testwork are to:
characterize the short-term leaching of soluble elements from fresh samples
characterize the leaching of soluble elements accumulated or retained on
weathered and oxidized samples
To interpret the results of soluble/retention tests correctly, it is important

to know:
the length of time since the sample was last rinsed well by water or rainfall
the solid:liquid ratio used in the testing (use several ratios to estimate
equilibrium levels)
the length of contact time between the solids and water (use longer times to
estimate equilibrium levels
The types of tests providing this information are:

the early weeks of humidity-cell testing (another test under the Wheel,
discussed later in this presentation)
shake flasks or similar sealed containers with water and solids that are
rolled or tumbled for a day or more

On-Site
Monitoring
Data
Field
Kinetic Tests
Acid-Base
Accounting
Drainage Chemistry
Laboratory
Kinetic Tests
Total Elements &

Whole Rock
NAG Testing:
Single, Sequential,
Kinetic, and ABCC
Mineralogy
Tests
Ref. A1957, B0001, B0002, CS0010
Wheel Approach NAG Testing

The hydrogen peroxide method was originally developed to
measure only sulphide in a sample. Section 3.2.11 of Sobek et
al. (1978) lists the technique. It required the removal of all
neutralizing minerals and leachable sulphate prior to testing, so
that sulphide could be measured through a titration with base.
This method was later changed so that no neutralizing minerals
or leachable sulphate had to be removed, and the remainder of
the method remained basically intact. The rationale was:
If the addition of hydrogen peroxide created acidic conditions, then that
sample would generate net acidity some day, and the pH from the test was
called the NAG pH (NAG pH < 4.5)
If acidic conditions developed, then the titration with base (part of the
original procedure) would indicate the strength of the net acid generation
and this was called the NAG capacity (NAG > 0 kg H2SO4/t)
If the addition of hydrogen peroxide did not create acidic conditions, then
that sample would never generate net acidity (NAG pH 4.5 & NAG = 0).
Ref. A1957, B0001, B0002, CS0010

As with all methods, there are weaknesses. For example,
Hydrogen peroxide is unstable in the presence of ferrous iron, and
pyrite and siderite are about one-half ferrous iron. Although ferrous
iron will be oxidized by hydrogen peroxide, which is a desired effect,
the iron can also apparently act as a catalyst for degrading the
peroxide. This has apparently led to the development of the
Sequential NAG test.
Not all acid-generating and acid-neutralizing minerals may react within
several hours of NAG testing. This has led to the development of the
Kinetic NAG test and subsequent columns.
Hydrogen peroxide solutions are often sold at acidic conditions (pH <
4.5), so the simple addition of the hydrogen peroxide to a sample can
lead to acidic NAG pH.
The NAG test does not provide any information on the neutralizing
capacity of a sample, or how much external acid addition it can
withstand. This led to the Acid Buffering Characteristic Curve (ABCC)
and the pre-test requirement of NAPP (basic ABA) results.
Due to the fast reactions and metal leaching, sulphide minerals can
become coated with precipitants and thus not react fully.
Ref. A1957, B0001, B0002, CS0010
As a example of using the Wheel approach, a minesite sample

was analyzed by NAG testing. The NAG results showed that
the NAG capacity was much less than that expected from
NAPP (basic ABA) testing based on total sulphur.
So the mineralogy of the sample was evaluated. This showed

that about half the sulphide minerals were non-acid-generating
(galena and sphalerite under certain conditions). Based on the
Wheel, we would say that only half the measured sulphide
should be included in NNP and NPR values for predictions.
This showed that

1. both methods could provide questionable results until mineralogy
was done, and
2. thus proved the value of the integrated Wheel approach

Today, NAG testing can involve elaborate and timeconsuming procedures, including the following.
The Single Addition NAG Test: For example, 250 mL of 15%
H2O2 is added to 2 g of sample, allowed to react overnight,
then gently heated to accelerate any remaining oxidation, then
boiled to decompose any remaining H2O2. The NAG pH and
NAG capacity are then measured after the solution cools.
NAG capacities can be defined at pH 4.5 and 7.0. This is
appropriate only for samples with less than ~1%S.
The Sequential NAG Test: For samples with elevated
sulphide or catalytic destruction of H2O2, the Single Addition
NAG Test is basically repeated until there is no more
oxidation. The NAG capacity is the sum of each tests NAG
capacity.
Ref. A1957, B0001, B0002, CS0010

The Kinetic NAG Test: The pH, temperature, and
electrical conductivity are recorded during a Single
Addition NAG Test. The pH trend gives an estimate of
relative reactivity and may be related to prediction of lag
times and oxidation rates similar to those measured in
leach columns. Qualitative lag times to net acidity
under on-site can be estimated.
The Acid Buffering Characteristic Curve (ABCC): The

ABCC test involves slow titration of a sample with acid
while continuously monitoring pH. This data will provide
an indication of the portions of Available and
Unavailable NP.
Ref. A1957, B0001, B0002, CS0010

Barren under NAG Testing is defined as Total %S < 0.1 and NP < 5 kg/t. WARNING: Such
samples can sometimes generate ARD and leach metals based on kinetic tests and case studies
4.5
Non Acid Forming (NAF)

= Net Acid Neutralizing
Uncertain
NAPP = 0
NAG pH
10.0
NAG pH = 4.5
Uncertain
Potentially Acid Forming (PAF)

= Net Acid Generating
1.0
-1000
+1000
NAPP (kg H2SO4/t)

For example, at this site, NAG testing indicated 56% were net acid
generating and 4% uncertain, which agreed well with ABA that
indicated 57% and 1%, respectively.

The first ABCC curve shows
that available NP was 5 kg/t,
whereas measured NP was
11 kg/t. Therefore,
Unavailable NP was 6 kg/t, in
agreement with ABA-based
UNP of ~10 kg/t.
The second ABCC curve

shows that available NP was
4 kg/t greater than measured
NP, indicating there was
additional NP. This was
probably slow reacting NP,
that was not detected by
ABA.

The first Kinetic NAG test shows a lowNP, low-sulphur sample producing a
NAG pH below 4.5 in roughly 80
minutes.
This Kinetic NAG test shows a peak in

temperature due to the elevated sulphur
levels. The relatively low NP was
depleted within ~ 40 minutes.

8
A Sediments
B Sediments
C Sediments
Phaneritic Igneous
Aphanitic Igneous
NAG pH
Disagreement
Net Acid Neutralizing
At this site, NAG

pH from the NAG
test and Net
Potential Ratio
(NPR) from ABA
agreed well in their
predictions.
Net Acid Generating
Disagreement
The samples
marked
Disagreement
required further
testing to explain
the discrepancies.
0
0.001
0.01
0.1
TNPR
10
100
Ref. A1957, B0001, B0002, CS0010

On-Site
Monitoring
Data
Field
Kinetic Tests
Acid-Base
Accounting
Drainage Chemistry
Laboratory
Kinetic Tests
Total Elements &

Whole Rock
NAG Testing:
Single, Sequential,
Kinetic, and ABCC
Mineralogy
Tests
Ref. B0001, B0002, A1957
Wheel Approach Lab Kinetic Tests Humidity Cells

There are two basic types of humidity cells:
Traditional well-rinsed humidity cells
Recent trickle-leach humidity cells
Well-rinsed humidity cells have been in use for at least

50 years around the world. The following presentation
on cells applies only to well-rinsed cells.
Trickle-leach cells are similar in objectives to leach

columns, which are discussed next after humidity cells.
The basic objective of (well-rinsed) humidity cells is to

wash a sample regularly, usually weekly, with excess
water. Gentle stirring during rinsing improves rinsing of
all particle surfaces.
For at least the first six months, every cycle (week) of

rinse water should be analyzed for proper accuracy.
Reducing analyses to every second week or less
frequently can then be determined after six months.
Ref. B0001, B0002, A1957
The detailed objectives of humidity cells are:
Virtually all weekly reaction products are rinsed each week.

Analyses of the weekly rinse waters, combined with water
volume recovered, provide bulk reaction and leaching rates
for many elements and parameters. For example, mg of
copper/kg of sample/week.
Excess rinse water increases the probability that kinetic

conditions apply and that maximum equilibrium levels are not
reached in the weekly rinse water.
However, in some cells, the Scale Transition can be
surpassed and equilibrium conditions apply. For example,
this may happen during the initial weeks of rinsing any very
soluble, previously retained reaction products. When this
does happen, the equilibrium levels cannot be used as rates,
because they underestimate rates by ignoring secondary
minerals, etc.

The detailed objectives of humidity cells are:
The analyses of weekly rinse waters are not intended
to be direct predictions of drainage chemistry in mg/L,
but are intentionally diluted.
They become direct predictions only when the Scale

Transition is surpassed and equilibrium is reached.
Predictions of larger-scale, equilibrium chemistry can
require larger laboratory leach columns and on-site
larger-scale kinetic tests.

AIR
OUT
RINSE
WATER
IN
PLEXIGLASS
CONTAINER
MINEMATERIAL
SAMPLE
PERFORATED
SUPPORT
DRY AIR &
MOIST AIR IN
Ref. B0001, B0002, A1957
LEACHATE
OUT
The typical weekly

operation of a humidity
cell is:
1) three days of dry air
pumped through / over
a sample
2) three days of moist
air pumped through /
over a sample
3) one day for rinsewater addition, gentle
stirring, and rinse-water
draining.
Analysis of the rinse
water, combined with
the volume of water
recovered, provides
bulk reaction rates in
mg/kg/wk.
Production Rate (mg of parameter / kg of

sample / week) =
Measured rinse concentration (mg/L) *
Volume of rinse water recovered (L) /
[wt. of sample (kg) * No. of elapsed weeks
(wks)]
Ref. B0001, B0002, A1957
10
9
8
7
The following slides show some

examples of humidity-cell results.
This one shows that one cell became

acidic around Week 30. This a lag
time of 30 weeks.
5
4
3
MR 97-12
TH 98-09
2
0
10
20
30
40
50
60
70
Cycle (Week)
80
90
100
110
120

10
Humidity cells
provide rates of
metal leaching
through time.
Sb (mg/L)
Sometimes the
rates increase with
time, sometimes
decrease, and
sometimes remain
about the same.
0.1
0.01
0.001
0
Week

This well-rinsed humidity cell was sampled every week for 5.7 years. Acid-base
accounting (ABA) predicted the sample would eventually become acidic, and it did so
after 1.5 years, causing the metal leaching rate of copper to increase sharply. Kinetic
tests do not always have to operate until they become acidic, because the time can
often be calculated from earlier weeks of testing.
10
1000
Effluent pH
Sulphate Production Rate
Copper Production Rate
Effluent pH
10
0.1
4
Production Rate (mg/kg/wk)
100
0.01
0.001
0
100
Number of Weeks
200
300

This cell operated for about 9 years and did not show any major changes in
chemistry. Rates after the first year could be used to predict future rates that would
be accurate for at least 9 years into the future. This is not always the case, as
explained below.
Effluent pH
Copper Production Rate
Effluent pH
10
1000
100
10
1
8
0.1
0.01
12
0.001
0.0001
0
100
200
300
Number of Weeks
400
500

There are other samples which appear to be generally steady by the end of the first
year. However, after a year or more, a rate like molybdenum leaching (below) will
suddenly increase. There are no proven explanations for trends like this.
10
1000
Effluent pH
Molybdenum Production Rate
Effluent pH
10
0.1
4
100
0.01
0.001
0
50
100
150
Number of Weeks
200
250

There are other samples which appear to be generally steady by the end of the first
year. However, after two years or more, a rate like copper leaching (below) will
suddenly increase. There are no proven explanations for trends like this.
1000
100
6
10
Cu Rate
Rinse pH
SO4 Rate
0.1
2
0.01
0.001
0
0
40
80
Week
120
160

Cells showed that arsenic leaching at this minesite was not influenced
by pH (below left), but by the rate of sulphide oxidation (right). The
reason for this was the arsenic occurred in sulphide minerals, based
on mineralogy and total-element contents as part of the Wheel.
10
10
Acma/A4A Intrusive
Acma/A4A Sedimentary
Lewis Intrusive
Average As Rate (mg/kg/wk)
Average As Leaching Rate (mg/kg/wk)
Lewis Sedimentary
0.1
0.1
0.01
0.01
3
5
6
Average pH
0.1
10
Average SO4 Rate (mg/kg/wk)
100
1000

10
After 80 weeks of cell

testing for this site, only
three of the nine cells
expected eventually to
generate net acidity did so.
The three cells became

acidic within a few weeks
of testing, and latest pH
values were around 2.42.7.
For the near-neutral cells,

recent pH values were
around 7.2 to 8.2, with one
lower cell around pH 6.7.
Weekly pH
6
A
A
A
L
L
L
Intrusive
Greywacke
Sedimentary
Intrusive
Greywacke
Sedimentary
2
0
20
40
Week
60
80
100

After any initial, soluble sulphate is rinsed from a cell, sulphate-production rates
represent the rates of sulphide oxidation and total-acid generation. For this site, the
acidic cells oxidized at rates roughly 10-100 times greater than the rates in the nearneutral cells (lower left).
100
2.63
7.94
7.96
7.8
7.97
10
7.2
8.268.04
7.81
8.15
8.13
7.9
6.64
8.15
0.1
One-half detection limit used for

any value below detection
0.01
A
A
A
L
L
L
0.1
1
Initial Solid-Phase Sulphide (%S)
Intrusive
Greywacke
Sedimentary
Intrusive
Greywacke
Sedimentary
10
Very High
1000
High
2.69
Three acidic cells
International Kinetic Database

543 cells from 72 minesites worldwide
100
10
Moderate
2.39
10000
Low
Last-five-week-average pH
shown next to datapoint
Very Low
Late-Average Sulphate Production Rate (mg SO4/kg/wk)
1000
Rate of Sulphate Production (mg SO4/kg of sample/week)
Compared with other minesites, sulphate-production rates were not unusual, but
typical to relatively low (lower right).
0.1
Cells to Week 82
0.01
0
Average pH
10
Some observations from sites that operated large numbers

of cells for long periods of time:
10 cells that operated for three to seven years indicated that
there was roughly a 50% chance that the oxidation rate of a
sample will stabilize geochemically (< factor of two
fluctuations) within the first year. There were no pre-test or
early indications of which cells would stabilize.
Seven batches of cells, with at least 12 cells each, indicated
that at least 12 cells were sufficient to show whether oxidation
rates were clustering around certain ranges. However, the
batches indicated more than 40 cells would be needed to
delineate a reliable statistical distribution such as lognormal or
normal.
Ref. M0017
Some observations from sites that operated large numbers

of cells for long periods of time:
Carbonate Molar Ratio (molar rate of NP consumption divided
by sulphate production) typically remained between 1.0 and
2.0, in near-neutral cells, even when rates fluctuate
significantly. This supports the typical NPR criteria for acidbase accounting between 1.0 and 2.0.
The CMR typically falls below 1.0 just before and during the
onset of net acidity.
If the sulphate rate falls below 5-30 mg/kg/wk, the CMR often
rises to values well above 2.0, indicating physical factors like
flow rate can affect or dominate the geochemical predictions of
acid drainage.
Ref. M0017

VALIDACIN GEOLGICA
Tipo de mineralizacin y su ocurrencia
Volumen y tipo de arcillas presentes
Volumen y tipo de carbonatos presentes
Volumen y tipo de sulfatos
Volumen y tipo de Oxi-hidrxidos
PETROCALCOGRAFA
200 Muestras de mano
RECUENTO PETROCALCOGRFICO
200 recuentos de cabeza
200 recuentos de ripios TCH
200 recuentos de ripios TCH Mod
200 recuentos de ripios TCF
Caracterizacin Geometalurgica de Detalle

Seleccin y mapeo de 200 muestras para pruebas
cinticas:
Test Celda Humeda TCH
Test Celda Hmeda Modificada TCH Mod
Test Celda Forzada TCF
Estudio de Extraccin Secuencial a cabezas y
ripios
Estudios de extraccin de Cu (QLT)

TEST CINTICOS
Test de Celda Hmeda (A)
21 Ciclos de 14 das a TAmbiente
3 das aire seco
3 das aire hmedo
3 das aire seco
4 das aire hmedo
1 da de inundacin con agua
destilada
Test Celda Hmeda Modificada (B)
21 Ciclos de 14 das a 40C
13 das aire hmedo
1 da de inundacin con agua
destilada
Test de Celda Forzada (C)
21 Ciclos de 7 das a 40C
6 das aire hmedo
1 da de inundacin con H2SO4 +
Frrico

TEST CINTICOS
Las soluciones obtenidas de cada ciclo sern caracterizadas por
la siguiente batera qumica:
pH
Acidez Alcalinidad
Conductividad
Sulfatos
CuT
As
Mo
Fe Total
Ferroso
ICP ptico de 27 elementos
Resultados Preliminares
pH A
10
9
8
7
6
5
4
3
2
1
0
pH B
1 2 3 4 5 6 7 8 9 10 11 12 13 14
Ciclos
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
1 3 5 7 9 11 13 15 17 19 21
pH
pH
pH
10
9
8
7
6
5
4
3
2
1
0
pH C
1 2 3 4 5 6 7 8 9 10 11 12 13 14
Ciclos
Ciclos
Wheel Approach Lab Kinetic Tests Leach Columns

Another type of laboratory kinetic test
is a leach column. Water can be
added to the top (or the bottom for
saturation) of a column in many ways.
So there is no one way to operate a
leach column.
Non-Recirculating
Leach Column
Reservoir for
Feed Water
Sample
Plexiglass
Tube
Perforated
Support
Sampling
Reservoir
Water
Out
Normally, water is dripped or

occasionally poured on the top of the
column sample. The water then flows
and trickles downward. This water
contacts some but not all particle
surfaces. The water then drains out
the bottom. This is one major way
columns differ from well-rinsed
humidity cells, but is similar to trickleleach humidity cells.
Ref. B0001, B0002, A1957

The objective is for the rinse water
NOT to contact all particle surfaces
(unless fully saturated) and NOT to
rinse off all weekly reaction particles.
Instead, some particles continue to
accumulate reaction products over the
test period.
Recirculating
Leach Column
Temporary
Reservoir (for
Initial Water;
one time only)
Sample
Plexiglass
Tube
Perforated
Support
Permanent
Reservoir (for
Recirculating
Water)
Water
Out
The solid:liquid ratio is much greater

than for well-rinsed cells, so there is a
greater potential that the Scale
Transition will be exceed. As a result,
aqueous concentrations in mg/L can
reflect full-scale, maximum equilibrium
concentrations. In this way, these
columns can provide predictions of
full-scale concentrations.
Ref. B0001, B0002, A1957
This is an example of laboratory

leach columns.
Each column is almost 3 m high.
Water within the columns can be
drawn out at water-sampling
ports along the sides of the
columns.

Leach-column tests can vary with:
variability in the sample, such as layers (left),
resulting in averaged or altered drainage
chemistry
degree of pre-test weathering of sample
particle size and mass
length and diameter of column
direction of flow and height of water table (e.g.,
saturated column with water forced into the
bottom)
internal conditions like temperature and oxygen
frequency of monitoring and number of internal
monitoring points

On-Site
Monitoring
Data
maana,
Da 2
Field
Kinetic Tests
Acid-Base
Accounting
Drainage Chemistry
Laboratory
Kinetic Tests
Total Elements &

Whole Rock
NAG Testing:
Single, Sequential,
Kinetic, and ABCC
Mineralogy
Tests
Ref. B0001, B0002, A1957
Wheel Approach Field Kinetic Tests
There are many types and forms of larger-scale onsite kinetic tests. As photographs on the following
slides show, they have many names, like leach
pads, barrels, cubes, and cribs.
Larger-scale on-site kinetic tests should be designed

and operated with specific objectives in mind.
Ref. B0001, B0002, A1957

These are the two types of
larger-scale on-site kinetic tests
that I often use:
barrels (to the left) and
cubes (below).
The major objective to have

greater height than lateral area,
with the intent to exceed the
Scale Transition.

At one site, these leach pads provide
unexpected, anomalously low
concentrations in the drainage. The
rock was moved into barrels, then
higher, typical concentrations were
obtained.

There are also various types of
leach pads elevated above ground.
At one site, the on-site leach pads
were draining ARD (pH ~3) with lots
of rusty iron-stained ARD. One day
the mining company called, very
excited. The iron staining and rust
had disappeared from the leach
pads. This must mean the ARD has
stopped after only a few years!
The actual explanation was that the
ARD draining from the pads had
become much worse (pH < 2). This
stronger acidity dissolved the solidphase iron and carried it away.

There are cribs that can hold 20
tonnes or more.
Some sites have other on-site kinetic
tests that contain hundreds to thousands
of tonnes. In effect, full-scale minesite
components with million to billion of
tonnes are also field kinetic tests.

Large-scale containers for heap-leach testwork can also be used for field
kinetic testing.
For one project, we used an airstrip at the site as an on-site kinetic test,
monitoring its drainage for upscaled predictions.
Scaling of Minesite-Drainage Chemistry

Below the Scale Transition,
kinetic conditions apply.
Scale
Transition
Maximum equilibrium concentrations

apply in this part of the curve,
caused by thermodynamics,
metastability, emergence, etc.
At what scale, weight,
time, ratio, etc., is the
Scale Transition met
for a particular
minesite component
and element?
Kinetic rates
apply in this
part of the
curve
Components of Scale:
- grain: resolution or minimum
homogeneous unit
- extent: study area or time duration
- coverage: sampling density
- spacing: sampling interval
Increasing Scale, Weight, Volume, Time, Solid:Liquid Ratio,

Reaction Rate, Residence Time, or Distance Along Flowpath
Above the Scale Transition,

equilibrium conditions apply.
This does not mean reactions
stop, but that secondary-mineral
precipitation and accumulation
increase. Aqueous
concentrations stabilize around
average values.
In my work, I find equilibrium
conditions exist at full scale for
most minesites (not all) for most
elements (not all). Full-scale
equilibrium is discussed here,
while full-scale kinetics are
discussed later.
Ref. CS26
Full-Scale Drainage-Chemistry Equilibrium

To identify equilibrium in full-scale minesite-drainage chemistry, annual
statistics and histograms are helpful. Histograms (below) of thousands of pH
measurements, over years and decades of monitoring, from all components
at a minesite, show a bimodal distribution. The near-neutral and acidic pH
cluster together at certain values at a minesite, but the preferred pH
Ref. CS033, CS0034
values vary from minesite to minesite.
1000
Best-Fit Equation for pH <3.0,

and Cu-D > 10 mg/L:
log(Cu-D) = -1.17265*pH + 5.37432
Log standard deviation = 0.37011
Count = 137
Sum of prediction errors = +1.0E-06
Dissolved Copper (mg/L)
100
10
Best-Fit Equation for 3.0=>pH =>5.5,

and Cu-D > 1 mg/L:
log(Cu-D) = -0.48982*pH + 3.32581
Count = 499
Sum of prediction errors = -1.0E-06
0.1
0.01
Tailings and Related Dams

Rock Dumps and Related
Surficial Pit Lake
Groundwater
Two erroneous
datapoints
ignored
If data was reported as < detection limit

half the detection limit is shown.
Best-Fit Equation for pH>5.5:

log(Cu-D) = -1.04518*pH + 6.38030
Count = 4757
0.001
Readily apparent errors in data

have been corrected or deleted.
When lab data was available it is
shown, otherewise, field was used.
0.0001
0
Lab/Field pH
12
120
60
20
80
Number of Values
Number of Values
40
1200
Best-Fit Equation for 3.0=>pH =>5.5,

and Cu-D > 1 mg/L:
log(Cu-D) = -0.48982*pH + 3.32581
Count = 499
Best-Fit Equation for pH <3.0,

ignoring Cu-D < 10 mg/L:
log(Cu-D) = -1.17265*pH + 5.37432
Count = 137
Number of Values
This minesite has more than

5000 analyses over ~30 years,
including pit, waste rock, and
tailings. Dissolved copper
correlated well with pH, but in
three pH-dependent
segments.
0
-2 -1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
0.2 0.4 0.6 0.8
Measured Minus Predicted Values

Above (+) or Below (-) the Best-Fit Line
800
400
40
Best-Fit Equation for pH>5.5:

log(Cu-D) = -1.04518*pH + 6.38030
Count = 4757
0
-2
-1.5
-1
-0.5
0.5

1.5
-4
-3
-2
-1


Another example showing a best-fit equation, but with sulphate
rather than pH, and associated standard deviation.
1200
10000
Hardness (mg/L)
1000
Tailings and Related Dams

Rock Dumps and Related
Surficial Pit Lake
Groundwater
100
Number of Values
Best-Fit Equation for Sulphate > 100 mg/L:

log(Hardness) = +0.98380*log(SO4) - 0.00500026
Count = 2482
Best-Fit Equation for Sulphate > 100 mg/L:

log(Hardness) = +0.98380*log(SO4) - 0.00500026
Count = 2482
800
400
If data was reported as < detection limit

half the detection limit is shown.
Readily apparent errors in data
have been corrected or deleted.
When lab data was available it is
shown, otherewise, field was used.
10
1
10
100
1000
Dissolved/Total Sulphate (mg/L)
10000
100000
0
-2
-1.6
-1.2
-0.8
-0.4
0.4
0.8
1.2

Ref. CS0033, CS0034, M0008, M00101, M0012, M0018, M0032, M0053, M0058, M0061, M0066
1.6
CONCLUSION
Each proposed, operating, and closed minesite may have

different sets of objectives for waste characterization. These
objectives often focus on the waters draining from a minesite
and its components, like mine walls, waste rock, low-grade
ore, and tailings.
Each proposed, operating, and closed minesite may identify
and collect samples in different ways. The sizes, numbers,
and types of samples can differ, depending on objectives.
There is no one approach to sampling - it is unique to each
minesite and each objective.
The easiest way to explain the laboratory and on-site field
tests is by using the analogy of a wheel. I call this the
Wheel Approach for predicting, scaling, and understanding
mine-waste geochemistry and minesite-drainage chemistry.

Most of these tests were described
and illustrated. These were
primarily smaller-scale tests. The
larger-scale on-site field kinetic
tests and on-site monitoring data
will be discussed tomorrow.
On-Site
Monitoring
Data
Field
Kinetic Tests
Acid-Base
Accounting
Drainage Chemistry
Laboratory
Kinetic Tests
Total Elements &

Whole Rock
NAG Testing:
Single, Sequential,
Kinetic, and ABCC
Mineralogy
Tests
Ref. B0001, B0002, A1957
THE END

Sampling Analysis Testing Mine Wastes Geochemical Predictions Risk Assessment KMorin

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Anlisis de Prcticas Actuales de Gestin de Aguas cidas

Sampling, Analysis, and Testing of

Kevin A. Morin, Ph.D., P.Geo., L.Hydrogeo.

Outline of This Presentation

3.1. Visin general, objetivos y alcances de la

predicting future drainage chemistry, including changes through time;

3.1. Visin general, objetivos y alcances de la

Although objectives and scopes may differ among minesites,

3.2. Muestreos y anlisis

may collect only dozens of samples from outcrop rock;

There is no one approach to sampling - it is unique to each minesite

3.2. Muestreos y anlisis

Once appropriate samples are collected, they should be

3.3. Tests de laboratorio y 3.4. Tests de campo

Wheel Approach for Minesite-Drainage Chemistry

Ref. B0001, B0002, A1957

Wheel Approach for Minesite-Drainage Chemistry

In a general sense, the solubilities of several metals are

Ref. B0001, B0002, A1957

Wheel Approach for Minesite-Drainage Chemistry

Wheel Approach for Minesite-Drainage Chemistry

For a proposed minesite, full-scale

For a historical minesite, full-scale On-Site

Kinetic; usually medium scale

Static; usually small scale

Total Elements &

Static; usually small scale

Static and Kinetic; usually small scale

Ref. B0001, B0002, A1957

Wheel Approach for Minesite-Drainage Chemistry

Bulk amounts of (1) acid-generating sulphide and non-acid-generating sulphate minerals

Bulk solid-phase amounts of metals and other elements

Identities and abundances of specific minerals

Secondary-mineral-distorted rates of acid generation, acid neutralization, and metal

Secondary-mineral-distorted rates of acid generation, acid neutralization, and metal

Wheel Approach for Minesite-Drainage Chemistry

Wheel Approach for Minesite-Drainage Chemistry

Increasing Aqueous Concentration (mg/L)

Maximum equilibrium concentrations

full-scale minesite component

100-g shake flasks

Most testwork and

Wheel Approach for Minesite-Drainage Chemistry

Increasing Aqueous Concentration (mg/L)

The smaller-scale kinetic tests of the

Increasing Size (Scale), Residence Time, or Distance Along Flowpath

Wheel Approach for Minesite-Drainage Chemistry

Not all tests under the

Ref. B0001, B0002, A1957

Wheel Approach for Minesite-Drainage Chemistry

Kinetic; usually medium scale

Static; usually small scale

Total Elements &

Static; usually small scale

Static and Kinetic; usually small scale

Wheel Approach Acid-Base Accounting (ABA)

paste pH in a mixture of pulverized rock and water,

Wheel Approach Acid-Base Accounting (ABA) - Criteria

Generic Non-Site-Specific ABA Criteria for Assessing or Predicting

Prediction or Current Condition

Paste/rinse pH < 5-6.5

Currently acidic; future unknown

5-6.5 < Paste/rinse pH < 9-10

Currently near neutral; future unknown