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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- Acid-base accounting (ABA) tests, involving the determi-
ing with confidence the amount of neutralizers nation of acid generating potential (AP) and neutraliza-
present in samples and (2) affording an interpreta- tion potential (NP) of samples, are commonly used as a
tion of what the test results mean in terms of pre- screening tool to predict the occurrence of acid mine
dicting the occurrence of acid mine drainage. Aside drainage (AMD). These tests are designed to examine the
from the analytical difficulties inherent to the con- balance between the acid-producing and acid-consuming
ventional methods, a potential source of error in components of wastes (Coastec Research 1991). The tests
neutralization potential (NP) measurements is the are static in nature and as such they do not predict drai-
contribution from the dissolution of non-carbonate nage quality from the wastes. Instead, the tests allow sim-
minerals. Non-carbonate alkalinity measured dur- ple, rapid and low-cost screening of samples to make a
ing static tests may or may not be available to neu- preliminary prediction for acceptable or unacceptable wa-
tralize acidity produced in the field. In order to as- ter quality (Coastec Research 1991). The ABA tests have
sess the value-added of extending the NP with the limitations in terms of providing reliable measurements
knowledge of mineralogical composition and evalu- of NP. Secondly, the meaning of measured NP in terms
ate potential sources of errors in NP measurements, of predicting the occurrence of AMD is often not clear.
a suite of samples were examined and characterized Uncertainties or errors in NP measurements can arise
in terms of their mineralogical and chemical com- due to any or a combination of mineralogical composi-
positions. The results indicate that although the tion, particle size, procedural limitations and human er-
acid-base accounting tests work well for simple ror. Among these, uncertainties due to particle size, pro-
compositions, the tests may result in overestima- cedural limitations and human error are inherent to the
tion or underestimation of NP values for field sam- techniques and as such they can be minimized by revis-
ples. Mineralogical constraint diagrams relating NP ing the procedures and by improving laboratory quality
determinations to Ca, Mg and CO2 concentrations control/assurance standards. Readers should refer to Nor-
were developed with the purpose to serve as sup- ecol Environmental Consultants (1991), Lawrence and
plementary guides to conventional static tests in Wang (1997), and Lapakko (1994) for an evaluation and
identifying possible NP contributions from non- review of the conventional NP determinations.
carbonate minerals and checking the quality of the Measured NP values do not necessarily indicate alkalinity
chemical testing results. Mineralogical NP makes it that is readily available to neutralize acidity produced by
possible to interpret the meaning of NP results and the oxidation of sulfide minerals in mine wastes. One
to assess the behaviour of samples over time by limitation as noted by Coastec Research (1991) which in-
predicting the onset of AMD and calculating NP volves the inability of static tests in making a distinction
values for individual size fractions. between the various acid consuming minerals and their
neutralization capacity, can lead to significant over or
Key words Acid mine drainage 7 Acid rock underestimation of NP. Norecol Environmental Consul-
drainage 7 Neutralization 7 Acid-base accounting 7 tants (1991) recommended that routine ABA tests include
Mineralogy 7 Tailings 7 Waste rock 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
Received: 1 June 1998 7 Accepted: 6 October 1998 cases where measured NP values reflect non-carbonate al-
A.D. Paktunc kalinity, effective field NP is likely to be overestimated.
CANMET, Mining and Mineral Sciences Laboratories, 555 Booth In summary, as stated by Lawrence and Wang (1997), re-
St, Ottawa, Ontario, K1A0G1, Canada 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 cast in terms of kg CaCO3 equivalent per tonne, the fol-
results more meaningful from the point of view of their lowing consideration must be taken into consideration.
ability to better screen samples and to establish minera- One important thing to consider is the fact that one or
logical parameters prior to designing and conducting ki- two moles of CaCO3 are required to neutralize one mole
netic geochemical tests. Mineralogical composition is a of sulfuric acid. This depends upon which one of the fol-
critical factor as it indicates the sources of NP and AP. lowing reactions takes precedence during neutralization.
Provided that other conditions that cause and/or in-
CaCO3cH2SO4 *Ca 2ccCO2cH2OcSO 2P (2)
fluence AMD are met, a static testing technique, based on 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
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
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