Research article
Mineralogical constraints on the
determination of neutralization
potential and prediction of acid
mine drainage
A.D. Paktunc
Abstract Acid-base accounting tests, commonly
used as a screening tool in acid mine drainage
(AMD) predictions, have limitations in (1) measur-
ing with confidence the amount of neutralizers
present in samples and (2) affording an interpreta-
tion of what the test results mean in terms of pre-
dicting the occurrence of acid mine drainage. Aside
from the analytical difficulties inherent to the con-
ventional methods, a potential source of error in
neutralization potential (NP) measurements is the
contribution from the dissolution of non-carbonate
minerals. Non-carbonate alkalinity measured dur-
ing static tests may or may not be available to neu-
tralize acidity produced in the field. In order to as-
sess the value-added of extending the NP with the
knowledge of mineralogical composition and evalu-
ate potential sources of errors in NP measurements,
a suite of samples were examined and characterized
in terms of their mineralogical and chemical com-
positions. The results indicate that although the
acid-base accounting tests work well for simple
compositions, the tests may result in overestima-
tion or underestimation of NP values for field sam-
ples. Mineralogical constraint diagrams relating NP
determinations to Ca, Mg and CO2 concentrations
were developed with the purpose to serve as sup-
plementary guides to conventional static tests in
identifying possible NP contributions from non-
carbonate minerals and checking the quality of the
chemical testing results. Mineralogical NP makes it
possible to interpret the meaning of NP results and
to assess the behaviour of samples over time by
predicting the onset of AMD and calculating NP
values for individual size fractions.
Key words Acid mine drainage 7 Acid rock
drainage 7 Neutralization 7 Acid-base accounting 7
Mineralogy 7 Tailings 7 Waste rock
Received: 1 June 1998 7 Accepted: 6 October 1998
A.D. Paktunc
CANMET, Mining and Mineral Sciences Laboratories, 555 Booth In summary, as stated by Lawrence and Wang (1997), re-
St, Ottawa, Ontario, K1A0G1, Canada
e-mail:dpaktunc6NRCan.gc.ca
Introduction
Acid-base accounting (ABA) tests, involving the determi-
nation of acid generating potential (AP) and neutraliza-
tion potential (NP) of samples, are commonly used as a
screening tool to predict the occurrence of acid mine
drainage (AMD). These tests are designed to examine the
balance between the acid-producing and acid-consuming
components of wastes (Coastec Research 1991). The tests
are static in nature and as such they do not predict drai-
nage quality from the wastes. Instead, the tests allow sim-
ple, rapid and low-cost screening of samples to make a
preliminary prediction for acceptable or unacceptable wa-
ter quality (Coastec Research 1991). The ABA tests have
limitations in terms of providing reliable measurements
of NP. Secondly, the meaning of measured NP in terms
of predicting the occurrence of AMD is often not clear.
Uncertainties or errors in NP measurements can arise
due to any or a combination of mineralogical composi-
tion, particle size, procedural limitations and human er-
ror. Among these, uncertainties due to particle size, pro-
cedural limitations and human error are inherent to the
techniques and as such they can be minimized by revis-
ing the procedures and by improving laboratory quality
control/assurance standards. Readers should refer to Nor-
ecol Environmental Consultants (1991), Lawrence and
Wang (1997), and Lapakko (1994) for an evaluation and
review of the conventional NP determinations.
Measured NP values do not necessarily indicate alkalinity
that is readily available to neutralize acidity produced by
the oxidation of sulfide minerals in mine wastes. One
limitation as noted by Coastec Research (1991) which in-
volves the inability of static tests in making a distinction
between the various acid consuming minerals and their
neutralization capacity, can lead to significant over or
underestimation of NP. Norecol Environmental Consul-
tants (1991) recommended that routine ABA tests include
a supporting mineralogical description to provide confi-
dence in the chemical results. In addition, Price and oth-
ers (1997) pointed out that existing static tests do not
identify minerals that contribute to effective field NP. In
cases where measured NP values reflect non-carbonate al-
kalinity, effective field NP is likely to be overestimated.
liable and confident determination of the practical NP
value of a waste cannot be achieved by a single static
Environmental Geology 39 (2) December 1999 7 Q Springer-Verlag 103
 Research article

test. It is clear that there is a need to make the static test
results more meaningful from the point of view of their
ability to better screen samples and to establish minera-
logical parameters prior to designing and conducting ki-
netic geochemical tests. Mineralogical composition is a
critical factor as it indicates the sources of NP and AP.
Provided that other conditions that cause and/or in-
fluence AMD are met, a static testing technique, based on
cast in terms of kg CaCO3 equivalent per tonne, the fol-
lowing consideration must be taken into consideration.
One important thing to consider is the fact that one or
two moles of CaCO3 are required to neutralize one mole
of sulfuric acid. This depends upon which one of the fol-
lowing reactions takes precedence during neutralization.
CaCO3cH2SO4 *Ca 2ccCO2cH2OcSO 2P (2)
4

the premise that bulk dissolution is complete and incor-

porating mineralogical composition, should provide a 2 CaCO3cH2SO4 *2 Ca 2cc2 HCO P
3 cSO 4
2P
(3)
reasonable estimate of the acid generating potential of NP can be recast in terms kg CaCO3 equivalent per tonne
rock and tailings samples (Paktunc 1999a). Recognizing by multiplying the Eq. 1 by 1.02 in the case of the reac-
these limitations, Lawrence and Scheske (1997) proposed tion in Eq. 2 and 2.04 in the case of the reaction in Eq. 3.
a new method to calculate NP based on mineralogy. This For pyrite, ni is 2 when the reaction 2 is applicable and 4
method involves the calculation of NP values for individ- in the case of the the reaction in Eq. 3. For pyrrhotite, ni
ual minerals based on their mineral abundances deter- is 1 when the reaction in Eq. 2 is considered and 2 for
mined through the use of CIPW norm calculations and the reaction in Eq. 3. ns is 2 for pyrite and 1 for pyrrho-
relative reactivity factors. As this approach can predict tite. Other parameters needed in the above NP equations
the presence of neutralizing minerals, not actually pres- are given in Table 1 for common carbonate species. NP
ent in the sample, its usefulness and applicability for the values for calcite can be written as:
intended purpose is questionable (Paktunc 1999b). Con-
sequently, the objectives of this study were to present mi- NPp9.8!Xi kg H2SO4 eq/t for reaction in Eq. 2 (4)
neralogical constraints as a guide to interpret the NP NPp4.9!Xi kg H2SO4 eq/t for reaction in Eq. 3 (5)
measurements and discuss the mineralogical NP method.
NPp10!Xi kg CaCO3 eq/t (6)
Although equal moles of calcite and dolomite are needed
to neutralize sulfuric acid, dolomites NP is 1.1 times
Mineralogical NP and AP greater than that of calcite. Siderite is initially a neutral-
izer; however, with continued dissolution, it produces
NP which is a measure of the amount of neutralizing acidity as ferrous iron is oxidized to ferric iron and ferric
bases present in a sample, is determined by various hydroxide precipitates. Thus, net contribution of siderite
chemical methods as outlined by Sobek and others to neutralization is considered to be zero. It is assumed
(1978), Lawrence and others (1989) and Coastec Research that Mn is not oxidizable; therefore, Mn in carbonates
(1991). Recognizing the difficulties involved in the meas- contributes to NP. If Mn is deemed to be oxidizable, then
urement and interpretation of NP values, Paktunc (1999a) the parameters for Mn-bearing carbonate species listed in
proposed a new approach to determining NP values Table 1 must be adjusted for the amount of non-oxidiza-
based on mineralogical composition. In this approach, ble cations.
NP of each mineral is calculated based on its abundance In conventional ABA tests, AP is calculated based on
in the sample and the stoichiometry of neutralization bulk sulfur concentrations. Although this is straightfor-
reactions. NP is expressed in terms of sulfuric acid equi-
valent or the conventional CaCO3 equivalent. In order to
take into account the presence of more than one type of Table 1
neutralizing mineral, a bulk NP is calculated Parameters used in the calculation of mineralogical NP.
w molecular weight; c number of non-oxidizable cations in one
98!10!Xi!ci!ns
k
formula unit
NPp A (1)
ip1 ni!vi
Mineral Formula w c
where NP is the mineralogical NP in kg sulfuric acid
Calcite CaCO3 100.0 1.0
equivalent per tonne, 98 is the molecular weight of Siderite FeCO3 116.0 0.0
H2SO4, 10 is the conversion factor for recasting in kg.t 1, Magnesite MgCO3 84.3 1.0
Xi is the amount of mineral i in wt%, ci is the number of Dolomite Mg0.5Ca0.5CO3 92.0 1.0
non-oxidizable cations in one formula unit of neutraliz- Ankerite Ca0.5Fe0.3Mg0.2CO3 101.7 0.7
ing mineral i, ns is the moles of sulfuric acid formed by Ankerite Ca0.5Fe0.1Mg0.4CO3 95.3 0.9
the oxidation of one mole of sulfide mineral s, ni is the Magnesian siderite Fe0.8Mg0.2CO3 109.5 0.2
moles of mineral required to consume ns moles of sulfur- Magnesian siderite Fe0.6Mg0.4CO3 103.2 0.4
Magnesian siderite Fe0.4Mg0.6CO3 96.9 0.6
ic acid produced by the oxidation of one mole of sulfide Magnesian siderite Fe0.2Mg0.8CO3 90.6 0.8
mineral s, vi is the molecular weight of neutralizing mi- Rhodochrosite MnCO3 114.9 1.0
neral i (g.mol 1) and k is the number of neutralizing mi- Kutnohorite Ca0.5Mn0.5CO3 107.5 1.0
nerals in the sample. If the mineralogical NP needs to be

104 Environmental Geology 39 (2) December 1999 7 Q Springer-Verlag