Estimating Mine Water Composition from

Acid Base Accounting and Weathering Tests; Applications from U. S. Coal Mines

Eric F. Perry(1)

Mine water quality for coal mines in the United States is estimated using whole rock
analysis for Acid/Base Accounting (ABA), or with simulated weathering tests. ABA
compares the quantity of acidity that can be generated from pyrite oxidation to the
amount of bases, mostly carbonates, that are available to neutralize acid. Studies of
surface mine drainage and overburden rocks in the Appalachian region show that the
quantity of acid neutralizers is the most important factor controlling mine water quality.
Mines producing net alkaline drainage (alkalinity >acidity) contain more than 2 to 3 %
neutralizers in overburden rocks, and had an excess of neutralization potential compared
to acid production potential. A ratio of about 2:1 or greater of neutralization potential to
potential acidity also produces net alkaline mine drainage. Most mines can be classified
as to potential to generate acid or alkaline waters. There is a small range of ABA
properties where both acid and alkaline waters occur, and interpretation from ABA alone
is uncertain. These relationships are consistent across different coalbeds and overburden
rocks. Similar ABA classifications have been proposed for base and precious metal
mines. Concentrations of metals or sulfate cannot be determined directly from Acid Base
Accounting, however.

Simulated weathering tests have the capacity to estimate mine water composition
including pH, and relative amounts of metals, sulfate, and trace elements. The relative
rates of acidity and alkalinity production can also be estimated from weathering tests.
Products of pyrite oxidation are soluble and are produced rapidly, while production of
alkalinity is limited by carbonate solubility. Weathering tests are especially useful where
ABA results are inconclusive, or the rocks contain sulfide minerals other than pyrite.
Different test protocols including columns, cells and soxhlet extractors are in use, so test
results must be evaluated against the specific test procedure. Rock to water ratio,
flushing frequency, pore gas composition and test length influence the results. A scaling
factor relating the laboratory results to mine site conditions is usually required, and
appears to be site specific.

Examples of mine drainage prediction and actual mine water quality are given for both
Acid Base Accounting and simulated weathering tests. Both overburden test methods
should be used in conjunction with other geologic, hydrologic and mine site data to
estimate post-mining water quality.

Eric Perry is a Hydrologist, U.S. Dept. of Interior, Office of Surface Mining, 3 Parkway
Center, Pittsburgh, PA, 15220, USA. Email eperry@osmre.gov
 Introduction
Mining of coal and minerals in the United States (U.S.) can sometimes produce acid
drainage and elevated concentrations of metals, dissolved solids, and sulfate in surface
and ground waters. To prevent water pollution by mining operations, testing of
overburden and waste rock is conducted in advance of mining. The purpose of testing is
to identify rocks with potential to generate acidic drainage, and determine which rocks
can neutralize acidity and generate alkalinity. Some mines also test rock and soil to select
materials that can be used for reclamation and plant growth.

Geochemical test methods are of two general types; static or whole rock analyses, and
kinetic or simulated weathering tests. Static tests include Acid Base Accounting(ABA),
X-ray diffraction for mineral identification, elemental analyses, exchangeable acidity,
cation exchange capacity and others. Acid Base Accounting compares the quantity of
acidity that can be generated from pyrite oxidation to the amount of bases, mostly
carbonates that are available to neutralize acid. It is the most common static test used for
testing overburden and waste rock at U.S. coal mines.

Kinetic or simulated weathering tests include various leaching protocols and batch
extract tests. Kinetic tests attempt to simulate chemical weathering of rocks in contact
with leach water. Mine water composition, including pH, metals, acidity, and alkalinity
is estimated from the leachate chemistry. Column leaching tests are the most frequently
used kinetic test method. Kinetic tests are especially useful where ABA results are
inconclusive, or the rocks contain more than one sulfide mineral. They are often used to
evaluate the acid drainage potential of waste rock and tailings from base and precious
metal mines.

The purpose of this paper is to review the use, assumptions and limitations of static and
kinetic test methods for predicting mine drainage quality. Examples of mine drainage
prediction and actual mine water quality are given for both Acid Base Accounting and
simulated weathering tests. Both overburden test methods should be used in conjunction
with other geologic, hydrologic and mine site data to estimate post-mining water quality.

The U.S. has major coal deposits ranging from lignite to anthracite grade in several
fields. Most coal mined is either subituminous or bituminous. Figure 1 shows the
location of major U.S. coal deposits and the approximate percentage of mines in each
field encountering acid forming materials. The most severe acid drainage associated with
coal mining occurs in northern Appalachian and the Eastern Interior region. Rocks in
these regions are Upper Pennsylvanian age, consisting of cyclothems of coal, shale,
limestone and sandstone. The rocks generally contain moderate amounts of pyrite and
carbonates. Annual precipitation is about 1000 to 1500 millimeters per year in these
areas, and the climate is humid continental. The southern Appalachian region, which has
less acid drainage, contains Lower Pennsylvanian age rocks, which generally contain low
concentrations of pyrite and carbonates. The Powder River Basin is semi-arid and
receives about 250 to 375 millimeters of precipitation per year. Coal bearing rocks are
Cretaceous age, and generally contain low amounts of pyrite and moderate concentrations
of carbonates.
 44%
23%
0%

12%
17%

Figure 1. Extent of Acid Drainage From U.S. Coal Mines.

Most active base and precious metal mining is concentrated in the western U.S. Acid
drainage from old metal mining occurs in Colorado, Montana, California and several
other states. Geologic, geochemical, and hydrologic conditions largely determine the
potential for acid drainage form coal and metal mines.

Static Test Methods

Origin of Acid Base Accounting

Acid Base Accounting is the most frequently used static test for estimating acid drainage
potential. ABA was developed at West Virginia University by soil scientists interested in
reclamation (Skousen et al., 1990). The approach came from early attempts at classifying
mine spoils for revegetation potential, based on acidity or alkalinity, and rock type. From
these classifications, they could determine if plants could grow on the mine spoil, and
whether lime should be applied.
In 1971, West Virginia University began to formally develop a system of balancing the
acid and alkaline producing potential of rocks. This work included coal overburden rocks
throughout the Appalachian and Interior coal basins. The importance of acid neutralizing
minerals was recognized and quantified, and the term "neutralization potential" (NP) was
introduced. This work was published in a series of reports, including a manual of
recommended field and laboratory procedures (Sobek et al.,1978).
ABA, as originally developed, consists of measuring the acid generating and acid
neutralizing potentials of a rock sample. These measurements of Maximum Potential
Acidity (MPA) and Neutralization Potential (NP) are compared to obtain a Net
Neutralization Potential (NNP), or net Acid-Base balance for the rock as follows:

Net Neutralization Potential (NNP) = NP – MPA (1)

The measurements are usually reported in tons per thousand tons of overburden or parts
per thousand(ppt). The units designation reflects the agricultural origins of ABA. One
acre (0.40 hectatres) of plowed agricultural soil weighs about 1000 tons (907 kilograms).
Liming requirements are usually expressed in tons per acre (kg/hectare). The units of
measure for ABA are therefore comparable to lime requirement designations for
agricultural lands.

Maximum Potential Acidity(MPA)

The acid generating potential, MPA, is calculated from a measurement of the total sulfur
content of the rock by combustion in a sulfur furnace. It is assumed that sulfur is present
in the form of pyrite (FeS2). For most coal overburden rocks, this is a good
approximation, and potential acidity calculations are valid. If the rocks have undergone
significant chemical weathering and contain some sulfate minerals such as gypsum
(CaSO4* 2 H2O ) melanterite (FeSO4* 7 H2O) and others, total sulfur content may not
accurately reflect potential acidity. Alkaline earth sulfate salts like gypsum are nonacid
formers. Metal sulfate salts, however, are intermediate products of pyrite oxidation, and
represent "stored acidity". These minerals can undergo dissolution and hydrolysis with
acid generation. Sulfate sulfur cannot be ruled out as a potential acid source unless the
mineralogy is known, and the common lab procedures for sulfur fractionation do not
identify the specific minerals present.
If samples are suspected of containing significant amounts of sulfate or organic forms of
sulfur, sequential extractions can be used to separate the components (Sobek et al, 1978).
Organically bound sulfur is generally considered to be to nonacid forming and is found in
coals, carbon rich shales, partings, "bone coal", etc. In these cases, a revised calculation
of potential acidity is made based on the pyritic sulfur content.
Ore bodies and waste rock at metal mines usually contain different sulfide minerals such
as sphalerite (ZnS), galena (PbS), and others, in addition to pyrite. Not all sulfide produce
acidity when oxidized, so a measure of total sulfur will probably over estimate potential
acidity. For these mines, identification of specific sulfide minerals is helpful, using X-ray
diffraction (XRD) and x-ray florescence (XRF) or optical techniques. The samples may
also be tested using kinetic methods.
Neutralization Potential(NP)
The neutralization potential, NP, is determined by reacting the sample with a known
quantity and strength of HCl, and measuring the amount of acid consumed by back
titration. It is a modification of a test method designed to measure the calcium carbonate
content of agricultural lime. The value reported for NP is assumed to represent mostly
carbonates, exchangeable bases and readily soluble silicate minerals.
The iron carbonate, siderite (FeCO3) can interfere with the determination of
neutralization potential. Siderite will initially neutralize acid because it is a carbonate.
However, iron hydrolysis of the iron that is released will produce acid will produce a net
neutralization of zero as shown below.
FeCO3 + 2 H+ → Fe2+ + CO2↑ + H2O (2)

Fe2+ + 0.25 O2 + H2 O + H+ → Fe3+ + 1.5 H2O (3)

Fe3+ + 3H2 O → Fe(OH)3 + 3H+ (4)

------------------------------------------------------------------------------
FeCO3 + 1/4 O2 + 3/2 H2O → Fe(OH)3 + CO2 ↑ Summary reaction (5)

Skousen et al (1997) tested rocks of known mineralogy with four variations of the
neutralization potential test. Some of the rocks contained significant amounts of siderite.
They found that interference from siderite was reduced if hydrogen peroxide was
included in the test protocol. This modified test procedure is now being used by some
U.S. laboratories.

Net Neutralization Potential(NNP)

The measurements and calculations of NP, MPA, and NNP are based on the following
assumed stoichiometry of pyrite oxidation and followed by calcite neutralization
(Cravotta et al., 1990):

FeS2 + 2 CaCO3 + 3.75 O2 + 1.5 H2O → 2 SO42- + Fe(OH)3 + 2 Ca2+ + 2 CO2 ↑ (6)

For each mole of pyrite reacted, 4 moles of acidity are produced by sulfur oxidation and
iron hydrolysis. Two moles of calcite are required to neutralize the acidity. On a mass
basis, 200 grams of calcium carbonate are required for each 64 grams of pyritic sulfur, or
a ratio of 3.125. If the Acid Base Accounting data is expressed in parts per thousand, the
mass ratio is 31.25. This factor is used to convert sulfur content into potential acidity as
calcium carbonate equivalent.
The components of ABA measurements are sometimes referred to by other terms, as they
have been adapted for use in metal mining and other applications (Miller and Murray,
1988, British Columbia Acid Mine Drainage Task Force, 1989). In Australia and
Canada, the term "Acid Production Potential" (APP) is equivalent to MPA, "Acid
Neutralizing Capacity" (ANC) is equivalent to NP; and "Net Acid Producing Potential"
or NAPP is the same as NNP.
Estimating Water Quality from Acid Base Accounting
Sobek et al(1978) suggested that an NNP value of less than -5 parts per thousand(ppt),
could be used to identify materials unsuited for use in reclamation. It was soon realized
that ABA could also be used to identify rocks likely to generate acid drainage and
develop some estimate of mine drainage quality before mining actually began. The
question was how to use ABA results to classify rocks as acid producers or acid
neutralizers?
There have been numerous attempts to define numerical criteria or levels of significance
for classifying ABA results and expected rock behavior. These numeric criteria have
taken the form of (1) boundaries on NNP values; (2) ratios of NP to MPA; and (3)
boundaries on values for NP or MPA. Some of these criteria, and their geologic and
geographic applications, are presented in Table 1. Values in the table refer to
characteristics of individual rock samples. Variation exists in the reported values, which
are drawn from diverse geologic settings and climates. Some general conclusions are
summarized as follows:

ΠA deficit of carbonate material or NP increases the likelihood of acid drainage. These

include rocks with less than about 20 ppt NP and rocks with NNP less than zero, or
ratio of NP to MPA of less than 1.
ΠConversely, excess carbonate lessens the potential for acid drainage. These include
rocks containing more than about 30 ppt NP and rocks with NNP greater than about
10 ppt, or ratio of NP to MPA greater than 2
ΠA range of ABA values exists where drainage quality is variable. Both acid and
alkaline waters can occur within a small range of Acid Base Accounting properties.
Ratios of NP to MPA between 0 and 1 are often classified as variable.
ΠA universal ABA criteria for separating acid and alkaline producing rocks on all types
of mines does not exist.

The lack of universal criteria is not surprising since mine drainage quality is a product of
the interaction of many geologic, hydrologic, climatic, and mining factors.

Acid-Base Accounting and Coal Mine Drainage Studies in Appalachia

ABA and mine drainage quality relations have been evaluated in Pennsylvania and
northern Appalachia in four studies, including projects by the Pennsylvania Department
of Environmental Protection, West Virginia University, and the U.S. Bureau of Mines.
These studies have shown that carbonate content of the overburden (neutralization
potential) is a very important factor controlling mine drainage quality. In each study, net
alkalinity (alkalinity minus acidity) was used as the primary index of postmining drainage
quality. The parameters acidity, alkalinity, and net alkalinity are measures of the
 complete acidity or alkalinity generating capacity of a water. They are also the aqueous
analogues of the ABA rock parameters of MPA, NP, and NNP. In this paper, I discuss

Table 1
Summary of Suggested Criteria for Interpreting Acid-Base Accounting (1)
CRITERIA APPLICATION REFERENCE
Rocks with NNP less than Coal overburden rocks in northern Smith et al., 1974, 1976;
-5 ppt CaCO3 are considered Appalachian basin for root zone Surface Mine Drainage Task
potentially toxic. media in reclamation; mine Force, 1979; Skousen et al.,
drainage quality. 1987
Rocks with paste pH less than 4.0 Coal overburden rocks in northern Smith et al., 1974, 1976;
are considered acid toxic. Appalachian basin for root zone Surface Mine Drainage Task
media, mine drainage quality. Force, 1979
Base and precious metal mine
waste rock in Australia and Miller and Murray, 1988
southeast Asia.
Rocks with greater than 0.5% Coal overburden rocks in northern Brady and Hornberger, 1990
sulfur may generate significant Appalachian basin, mine drainage
acidity. quality.
Base and precious metal mine Miller and Murray, 1988
waste rock in Australia and
southeast Asia.
Rocks with NP greater than 30 Coal overburden rocks in northern Brady and Hornberger, 1990
ppt CaCO3 and "fizz" are Appalachian basin, mine drainage
significant sources of alkalinity. quality.
Rocks with NNP greater than 20 Coal overburden rocks in northern Skousen et al., 1987;
ppt CaCO3 produce alkaline Appalachian basin. Base and British Columbia Acid Mine
drainage. precious metal mine waste rock and Drainage Task Force, 1989;
tailings in Canada. Ferguson and Morin, 1991
Rocks with NNP less than Base and precious metal mine British Columbia Acid Mine
-20 ppt CaCO3 produce acid waste rock and tailings in Canada. Drainage Task Force, 1989;
drainage. Ferguson and Morin, 1991
Rocks with NNP greater than 0 Base and precious metal mine Patterson and Ferguson, 1994;
ppt CaCO3 do not produce acid. waste rock and tailings in Canada. Ferguson and Morin, 1991
Tailings with NNP less than 0 ppt
CaCO3 produce acid drainage.
NP/MPA ratio less than 1 likely Base and precious metal mine Patterson and Ferguson, 1994;
results in acid drainage. waste rock and tailings in Canada. Ferguson and Morin, 1991
NP/MPA ratio is classified as less Base and precious metal mine Ferguson and Robertson, 1994
than 1, between 1 and 2, and waste rock and tailings in Canada.
greater than 2.
Theoretical NP/MPA ratio of 2 is Coal overburden rocks in northern Cravotta et al., 1990
needed for complete acid Appalachian basin, mine drainage
neutralization. quality.
Use actual NP and MPA values Base metal mine waste rock, Filipek et al., 1991
as well as ratios to account for United States.
buffering capacity of the system.
(1) Criteria in this table were developed for classification of individual rock samples
the results of a study that included about 40 surface mines from Pennsylvania's
bituminous coal field (Brady et al., 1994, and Perry and Brady, 1995).
Each mine had two or more ABA drill holes and multiple postmining water quality
samples from seeps, springs, or monitoring wells. Raw ABA data were processed into a
summary value for the entire mine using mass weighting procedures described by Smith
and Brady (1990). Summary ABA data were compared to median water quality values.

Results of Pennsylvania Acid Base Accounting Study

Mines with neutralization potential (NP) greater than about 21 ppt produced net alkaline
water (Figure 2). Eight of eleven sites with NP less than 10 ppt had negative net alkaline
(net acid) water. NP values between 10 and 21 tons/1000 tons included both net acid and
net alkaline sites (variable water quality). Ten of 17 mines (58%) in this category
produced alkaline water. Two low NP sites with net alkaline water were anomalous. The
anomalies could result from nonrepresentative overburden sampling, an influx of alkaline
ground water from offsite, or alkalinity production from noncarbonate sources.

PLOT OF NET ALKALINITY vs NEUTRALIZATION POTENTIAL

400
Acid
Net Alaklainity (mg/L

200
Water
0
CaCO3 Eq)

Alkaline Water
-200
Variable
-400

-600

-800

-1000
0 10 20 30 40 50 60 70 80
Neutralization Potential (ppt)

Figure 2. Plot of Overburden Neutralization Potential and Mine Drainage Net Alkalinity.

Figure 3 is a plot of Net Neutralization Potential and mine drainage alkalinity for the
same mines. For NNP, all sites with NNP greater than about 12 ppt produced net alkaline
water. Seven of nine sites with NNP less than 0 produced net acid water, and variable
results were obtained between NNP 0 and 10 ppt. Twelve of 19 sites (63%) of mines in
this category produced alkaline water.
 Net Alkalinity (mg/L CaCO3 E Plot of Net Alkalinity vs Net Neutralization Potential

400
Variable
200
0 Alkaline Water
-200 Acid
Water
-400
-600
-800
-1000
-20 0 20 40 60 80
Net Neutralization Potential (ppt)

Figure 3. Plot of Net Neutralization Potential and Mine Drainage Net Alkalinity

Figure 4 is a plot of the sum of the metals iron, manganese and aluminum in mine
drainage and overburden neutralization potential. All mines that produced alkaline water
contain low concentrations of metals, usually less than 0.5 mmoles. Acid waters, however
contain low (less than 1 mmole) to high concentrations (greater than 5 mmoles) of
metals, with overall worse water quality. Most of the mines classified in the “variable”
category contain less than 1 mmole of metals. Thus highest metal concentrations are in
mines with little neutralization potential, while mines with more neutralization potential
and alkaline waters usually contain the least amount of metals. Even in alkaline waters
however, metal concentrations may not meet all water quality standards without some

Plot of Total Metals vs. Neutraliztion Potential

7.0
Total Metals (mmoles

6.0
5.0
Acid Variable
4.0 Water
3.0
2.0
Alkaline Water
1.0
0.0
0 10 20 30 40 50 60 70 80
Neutralization Potential (ppt)

Figure 4. Plot of Overburden Neutralization Potential and Metals, Iron, Manganese and
Aluminum.
additional treatment. Median water quality values, classified by Acid Base Accounting
data for pH, alkalinity, metals and sulfate are summarized in Table 2 .

Table 2
Median Water Quality for Mines Classified by Acid Base Accounting Analysis (1)
Water Alkalinity Mn SO4
ABA Data pH Fe (mg/L)
Quality (mg/L) (mg/L) (mg/L)
Net
NP >21 7.0 135 2.15 5.1 344
Alkaline
10<NP<21 Variable 6.0 79 1.97 7.1 408
NP<10 Acid 4.1 0 15.55 19 756
Net
NNP> 12 7.07 194 2.08 4.7 358
Alkaline
0<NNP<12 Variable 6.0 56 1.73 8.3 413
NNP<0 Acid 4.1 0 61.7 30.1 971
(1) ABA data in ppt, pH in standard units, all others in mg/L

Table 2 shows trends similar to figure 4. The highest median concentrations of metals
and sulfate are from mines containing little neutralizing capability. Sulfate concentrations
are 2 to 3 times greater in acid waters compared to alkaline waters. Iron and manganese
concentrations are 4 to 7 times greater in acid waters compared to alkaline waters. Thus
the worst water quality can be expected to form on mines lacking adequate neutralizers.

Table 2 also shows that postmining sulfate concentrations decrease as NP increases.

These data are interpreted as showing that pyrite oxidation is inhibited by the presence of
carbonate minerals in amounts as low as 1 to 3 percent (10 to 30 ppt NP).

Carbonates, with the exception of siderite, have at least three different inhibiting effects
on pyrite oxidation and acid generation. 1) Carbonates are acid reactive, with their
dissolution rate a function of H+ activity (pH) and the partial pressure of CO2 (Plummer
et.al,1978). As acidity increases, the rate of carbonate dissolution increases. Conversely,
under alkaline conditions, carbonate dissolution slows until equilibrium is reached.

2) Alkaline conditions created by carbonate dissolution are not conducive to bacterial

catalysis of ferrous iron oxidation. Singer and Stumm (1970) showed that the activity of
Thiobacillus species could increase the rate of ferrous to ferric iron conversion by six
orders of magnitude. These bacteria are most active in the pH range of about 2 to 4.
Ferrous to ferric iron conversion is the "rate determining step" in the overall sequence of
acid generation from pyrite (Singer and Stumm, 1970). Thus, inhibiting bacterial activity
slows pyrite oxidation.

3) Alkaline conditions greatly limit the activity of dissolved ferric iron. Removal of
dissolved ferric iron by alkaline conditions is important since it interrupts the self
propagating acid cycle. Dissolved ferric iron is capable of rapidly oxidizing pyrite as
follows:
FeS2 + 14 Fe3+ + 8 H2O → 15 Fe2+ + 2 SO2-4 + 16 H+ (7)

We also determined if active carbonate dissolution is occurring, by examining mineral

saturation indices for waters with sufficiently detailed analyses. All waters were
undersaturated with respect to calcite; that is calcium carbonate will dissolve.
Equilibrium calculations determined from PHREEQC (Parkhurst and Appelo,1999) are
expressed as a logarithm of the ratio of ion activity product to equilibrium constant.
Values less than zero indicate undersaturation (mineral is expected to dissolve), values of
zero indicate saturated conditions (equilibrium), while values greater than zero indicate
oversaturation (mineral could precipitate). The highest saturation index obtained on any
water was -0.13 or about 73% of saturation. Most waters were one or more orders of
magnitude below saturation. Calcite saturation indices are shown in figure 5.

Calcite Saturation Indices For Some Mine Waters

2
1
Calcite Saturation Index

0
-1
-2
-3
-4
-5
-6

Figure 5. Calcite Saturation Indices for Selected Mine Waters, Pennsylvania Study.

Kinetic Testing

Kinetic tests, also called simulated weathering can be useful for estimating mine water
composition where Acid Base Accounting is inconclusive, or multiple sulfide minerals
are present in the rock. One advantage of kinetic tests is that they produce an effluent of
simulated mine drainage quality. The effluent may be tested for the same water quality
parameters that will be applied to the mine. For U.S. mines, these parameters usually
include pH, acidity, alkalinity, sulfate, iron, manganese and aluminum. Other analyses
for major and trace elements can also be included as needed.

A limitation of kinetic tests is the interpretation of the results and extrapolation to the
actual conditions of the proposed mine. There is no single standard test protocol for
kinetic testing. The results are therefore somewhat dependent on the chosen test method.
Some of the physical and chemical variables that influence kinetic testing include:
particle size distribution of the sample, degree of saturation of the sample (immersed,
capillary fringe, unsaturated), solid to liquid ratio, leaching frequency, mineralogy of the
rock; reaction kinetics and solubility controls on the acidity- and alkalinity-generating
processes, and the composition of gaseous phases (e.g. partial pressures of oxygen and
carbon dioxide). A complete discussion of these factors is beyond the scope of this paper
but is discussed elsewhere (Hornberger and Brady, 1998; Kleinmann et al, 2000). The
influence of gas composition is illustrated with a simple example, however.
The influence of gas composition on leachate chemistry is shown in Figure 6. The graph
displays alkalinity and sulfate concentrations for a rock sample containing about 20%
carbonate. The sample was tested under two conditions, atmospheric (CO2 =0.03%), and
10% CO2. The increased CO2 concentration was selected to simulate subsurface
conditions often found in waste rock piles and ground waters. Alkalinity concentration
under atmospheric conditions quickly drops to about 60 mg/L, representing the maximum
solubility of calcite under these conditions. Calcite solubility and concentration of
alkalinity increase as partial pressure of CO2 increases (Langmuir, 1997; Appelo and
Postma, 1992) and alkalinity quickly increases to about 200 to 300 mg/L under 10% CO2.
Sulfate production from pyrite oxidation is not influenced by carbon dioxide
concentration. Values are virtually the same for both treatments. For samples containing
abundant carbonate, the choice of atmospheric composition during the test could
influence expected alkalinity production.

Influence of Atmosphere on Leachate Quality

1000
900
800
Concentration (mg/L

700
Alkalinity,10%CO2
600
Sulfate,10%CO2
500
Alkalinity, air
400
Sulfate, air
300
200
100
0
0 2 4 6 8 10 12
Leaching Cycles

Figure 6. Influence of Atmospheric Composition on Leachate Production of Alkalinity

and Sulfate.

Kinetic Test Data and Mine Water Case Study

A coal mine site in West Virginia included a disposal area for waste rock from coal
cleaning. The waste rock contains abundant pyrite, and little neutralization potential. An
Acid Base Accounting test showed the waste rock had a net neutralization potential
(NNP) of – 82.5 ppt. Therefore the waste rock was expected to be acid producing. The
mining company conducted column leaching tests to estimate the composition of
drainage from the pile. Five leaching cycles were conducted by passing distilled water
through a column packed with waste rock sample. The quantity of water added to the
column during testing was equal to about one year of precipitation. Results of the
leaching cycles and composition of two ground water samples collected at the waste rock
pile are shown in table 3.

Leachate from 5 five cycles of testing produced strongly acid drainage, as expected.
Concentrations of all parameters were high in the first cycle, then began to decline, but
increased again at the end of the test cycle. More leaching cycles are needed to determine
if water quality would continue to decline or improve. Comparing the leaching data to the
actual ground water analyses, concentrations of manganese, sulfate and aluminum are
similar for the test data and field conditions.

Iron, and consequently acidity are predicted to be much higher in the leaching column
than actually exists in the ground water. Iron and acidity are overestimated by a factor of
about 4 to 10 times actual field conditions, and laboratory pH is one unit or more lower
than in the ground water. The results can be interpreted in one of two ways. First is to
conclude that column leaching test is a more severe chemical weathering environment
than actually exists on the mine, and that the test will over predict iron and acidity
concentrations. Second, is to conclude that the ground water has already undergone some
in-situ neutralization, reducing acidity and iron levels. The ground water sampling sites
were located at the pile, where the flow path would only contact the waste rock.
Therefore it seems unlikely that much in-situ neutralization could have taken place, and a
scaling factor is needed to relate the lab and field data. Hood(1984), using a different
column leaching technique, concluded that his lab results needed a scaling factor of about
4.5 to simulate actual mine drainage quality. He also concluded that one cycle of his test
was equivalent to about 3 years of natural weathering.

Table 3
Example Comparison of Kinetic Test Cycles to Actual Mine Water Quality(1)
Sp.
Cycle pH Acidity Fe Mn SO4 Al Cu Ni Zn
Cond.
1 2.6 4960 2030 564 7.1 1695 68.5 1.21 1.22 2.96
2 2.9 3750 835 200 6.7 1026 40.4
3 2.7 3600 994 256 5.37 902 35.8 0.76 0.04 1.74
4 2.4 4300 1610 438 4.91 1445 41.3
5 2.5 6460 2492 750 6.83 2240 56.5 0.92 0.04 1.53
Sample
GW-13 3.79 2000 431.7 71.7 17.7 1852 35.7 0.01 0.37 0.53
GW-15 3.69 2900 414.5 48.3 5.16 2603 47.8 0.38 0.82 0.74
(1) pH in standard units, Specific Conductance in umhsos/cm, acidity in mg/L CaCO3
Eq., all others in mg/L.
 Summary
Mine water quality can be estimated using static tests like Acid-Base Accounting, or
kinetic test methods. Acid Base Accounting compares the acid producing potential
against the acid neutralizing potential, to arrive at a net balance for the rock. These data
are interpreted to indicate whether the rock will produce alkaline or acidic drainage. The
method has been in used for over 25 years at mines in the United States and elsewhere.
Test methods are relatively simple and reproducible. Acid Base Accounting does not
predict mine water concentrations of metals or sulfate, however.

Several studies comparing Acid Base Accounting and postmining water quality have
been conducted on Appalachian coal mines. These studies have shown that carbonate
content, or neutralization potential is a very important control on the quality of mine
drainage. Similar results have been reported for metal mines (Ferguson and Morin 1991).
NP contents of as little as 20 to 30 ppt CaCO3 equivalent, or 2 to 3 % of the rock mass,
are effective in producing alkaline drainage. Pyrite must obviously be present for acid
generation to occur. However, potential acidity of the rock is unrelated to water quality
parameters, except in the absence of carbonate. By itself, potential acidity is a poor
predictor of mine drainage. Carbonate dissolution consumes (neutralizes) acidity and
inhibits pyrite oxidation. Alkaline conditions suppress two key components of the acid
generating process. Bacterial catalysis of ferrous iron oxidation is inhibited and ferric
iron activity is also greatly reduced.

Kinetic tests are useful for samples where Acid Base Accounting data are inconclusive,
or where more than one sulfide mineral is present in the rock. Relative, if not absolute,
mine water composition, and rate of chemical weathering can be estimated from kinetic
test data. A scaling factor may be needed to relate laboratory and field data, and the factor
may be site specific. Different kinetic test protocols are used, and the leachate results are
somewhat dependent on the test method. Production of alkalinity is sensitive to
composition of the gas phase (Kleinmann et al, 2000; Hornberger et al, 2004) in rocks
containing significant carbonate.

Static and kinetic geochemical test methods should be used along with information on
geology, hydrology, mining method, and reclamation practices to estimate mine water
quality.
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