Minerals Engineering 80 (2015) 3336

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

A mineralogical approach to evaluating laboratory scale acid rock

drainage characterisation tests
M. Becker , N. Dyantyi, J.L. Broadhurst, Susan T.L. Harrison, J.-P. Franzidis
Minerals to Metals Initiative, Department of Chemical Engineering, University of Cape Town, Rondebosch, 7700, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: Effective management of the risks associated with acid rock drainage (ARD) requires the ability to iden-
Received 13 January 2015 tify material with a potential to generate ARD reliably. With the increasing prevalence of quantitative
Revised 22 June 2015 mineralogy (Quantitative XRD, auto-SEM), opportunity exists to use mineralogy at all stages in ARD char-
Accepted 23 June 2015
acterisation and prediction. This study uses a mineralogical approach across the head grade samples and
the residues obtained under leach conditions of several common ARD characterisation tests (Acid
Neutralising Capacity, Net Acid Generation), as well as the University of Cape Town (UCT) biokinetic test
Keywords:
to evaluate the extent to which acid-neutralising minerals react. The results show the contribution of the
Acid rock drainage
Mineralogy
carbonates to the acid neutralising capacity, as well as the partial dissolution of intermediate weathering
silicate minerals such as chlorite and mica.
2015 Elsevier Ltd. All rights reserved.

1. Introduction weathering). This has been described extensively by a number of

Acid rock drainage (ARD) is produced when sulfur-rich rocks are
oxidised. It is characterised by low pH waters with high sulfate
content and high concentrations of dissolved, often toxic elements.
The reactions occur in the presence of oxygen and water and are
accelerated by various naturally occurring Fe and S oxidising
microbial species (Blowes et al., 1998). Once running. the ARD
engine, as described by Lottermoser (2010), can continue for tens
to hundreds of years. The reactions can be offset by the inherent
neutralising capacity contained within many of the surrounding
rocks, known as the acid neutralisation capacity (ANC). The ANC
depends not only on the mineralogy of the surrounding rocks: dis-
solving carbonate minerals (e.g. calcite, dolomite), fast weathering
silicate minerals (e.g. anorthite, forsterite) and inert silicate miner-
als (e.g. quartz), but also the textural relationship of the acid form-
ing minerals to the acid neutralising minerals (mineral
association), as well as the textural characteristics of the individual
minerals themselves (liberation, morphology, degree of
Abbreviations: ANC, acid neutralising capacity; ARD, acid rock drainage; ARDI,
acid rock drainage index; MLA, mineral liberation analyzer; MPA, maximum
potential acidity; NAG, net acid generation; NAPP, net acid producing potential;
QEMSCAN, quantitative evaluation of minerals by scanning electron microscopy;
QXRD, quantitative X-ray diffraction; SEM, scanning electron microscope; TIMA,
Tescan integrated mineral analyzer; UCT, University of Cape Town.
Corresponding author.
E-mail address: megan.becker@uct.ac.za (M. Becker).
authors such as: Jambor et al. (2002), Lawrence and Wang
(1996), Moncur et al. (2009) and Smart et al. (2002).
Effective management of the risks associated with ARD requires
the ability to identify material with a potential to generate ARD
reliably so that appropriate measures can be put in place to either
mitigate the risk or remove it completely. Conventional ARD char-
acterisation and prediction entails the use of a suite of geochemical
tests which are designed to be simple, fast and inexpensive so that
they can be run on large numbers of samples (International
Network for Acid Prevention, 2009; Morin and Hutt, 1998; Smart
et al., 2002). Typically, only in cases where conicting results are
obtained between tests, is the role of mineralogy considered.
With the advent of X-ray diffraction (XRD) using Rietveld
renement (Young, 1995) and modern automated scanning elec-
tron microscope (SEM) systems such as QEMSCAN, MLA, TIMA
and Mineralogic providing quantitative detailed information on
bulk mineralogy and textural attributes of material at a range of
particle sizes down to the micron scale (Fandrich et al., 2007;
Gottlieb, 2008), opportunity exists to use mineralogy at all stages
of ARD characterisation and prediction to allow for more reliable
and effective characterisation (Brough et al., 2013). This would
include more regular use of mineralogical measurements for iden-
tifying material with a potential to generate ARD (e.g. Acid Rock
Drainage Index, developed by Parbhakar-Fox et al., 2011), as well
as using mineralogical information to interpret the results of rou-
tine geochemical ARD characterisation tests (Plante et al., 2012).

http://dx.doi.org/10.1016/j.mineng.2015.06.015
0892-6875/ 2015 Elsevier Ltd. All rights reserved.
34 M. Becker et al. / Minerals Engineering 80 (2015) 3336

The focus of this technical note is to demonstrate the use of a min-
eralogical approach to evaluating the nature and extent to which
the constituent minerals react in several common screening ARD
characterisation tests: acid neutralising capacity (ANC) tests, net
acid generation (NAG) tests, as well as the UCT biokinetic test
developed at the University of Cape Town (Broadhurst et al.,
2013; Hesketh et al., 2010).
2. Experimental details
A bulk sample of run of mine gold ore from an active South
African gold mine near Carletonville on the Witwatersrand in
South Africa was used. Following comminution (see Nwaila et al.,
2013 for further details), the 1 mm fraction was sub-sampled
for use in this study.
The sample was characterised mineralogically prior to the ARD
characterisation tests using QEMSCAN based on LEO 1450 SEM
platform at the University of Cape Town. Polished blocks of the
10, +10/38, +38/75 and +75/150 lm fractions were prepared
and run using the Particle Mineralogical Analysis routine (Goodall,
2008) to determine the bulk mineralogy and mineral associations
quantitatively. The integrity of the QEMSCAN data was determined
by comparing the bulk mineralogy with quantitative XRD, as well
as with chemical assays. Quantitative XRD analyses were con-
ducted on micronized samples using a Bruker D8 Advance diffrac-
tometer with Vantec detector with Co Ka radiation. The TOPAS
Rietveld renement software was used for phase quantication.
XRF major element analyses obtained on a Panalytical Axios
Wavelength dispersive XRF with Rh tube with natural element
standards (South African Reference Material, United States
Geological Survey) were used to compare the actual chemistry
with chemical assays calculated through the QEMSCAN iExplorer
software.
The acid neutralising capacity (ANC) was determined experi-
which were prepared as vertical sections to account for any parti-
cle settling due to size and density effects.
3. Results and discussion
3.1. Sample composition
Based on the bulk mineralogy measured with QEMSCAN and
relative mineral reactivities given in the literature e.g. Lawrence
and Wang (1996), the sample could be classied as containing just
over 4 wt.% acid forming suldes (pyrite + pyrrhotite) with
0.5 wt.% dissolving carbonate minerals. There were no fast weath-
ering silicate minerals such as anorthite. The majority of the sili-
cate neutralising capacity consisted of the intermediate
weathering chlorite (5.0 wt.%) and mica (12.8 wt.%). Slow weather-
ing minerals comprised the Fe-oxyhydroxides (1.6 wt.%), very slow
weathering minerals comprised K-feldspar (3.1 wt.%), inert miner-
als comprised quartz (70.7 wt.%) and sphene (0.8 wt.%). Accessory
uraninite and zircon were also present. The suldes were greater
than 90% liberated with unliberated suldes mostly associated to
quartz or mica. There was negligible association of the suldes to
the acid dissolving minerals. Mineralogical analysis of coarse parti-
cles by Dyantyi et al. (2013) showed that the sample had an acid
rock drainage index (Parbhakar-Fox et al., 2011) of 23 and was
potentially acid forming. The very low sulfate mineral content indi-
cated that the sample was relatively fresh.
3.2. Static and biokinetic test results
The results of all the ARD characterisation tests, as summarised
in Table 1, indicate that the sample was potentially acid forming.
Differences in the ANC (and subsequent calculated NAPP) were a
Table 1
ARD characteristics of the run of mine gold ore, Witwatersrand, South Africa.

mentally using the AMIRA modications of the standard Skousen, Parameter (units) Amount
and Lawrence and Wang geochemical test methods (Smart et al., Total S (wt.%) 1.3 0.9
2002). All experiments were conducted in triplicate. The ANC Sulde S (wt.%) 1.3 0.04
was also determined mineralogically from QEMSCAN results using ARDI (mineralogy) 23
the method of Paktunc which considers the contribution from the MPA (chemical) (kg H2SO4/t) 40.7 1.3
ANC (Skousen) (kg H2SO4/t) 17.4 0.002
fast dissolving carbonates (Paktunc, 1999). The maximum poten-
ANC (Lawrence & Wang) (kg H2SO4/t) 4.2 0.6
tial acidity (MPA) was calculated from the sulde sulfur content ANC (mineralogy) (kg H2SO4/t) 4.9
obtained using the Chromium Reducible Sulfur method (Ahern NAPP (Skousen) (kg H2SO4/t) 23.3 0.65
et al., 2004) by applying a stoichiometric factor of 30.6. The net NAPP (Lawrence & Wang) (kg H2SO4/t) 36.5 0.46
Single-addition NAG pH 2.5 0.03
acid producing potential (NAPP) was calculated based on the dif-
Cumulative sequential NAG (kg H2SO4/t) 51.6 2.8
ference between the ANC and MPA. Biokinetic test pH at day 63 2.1 0.03
The net acid generation (NAG) was determined according to the Classication Potentially acid forming
method of Smart et al. (2002), using a series of sequential NAG
tests until the pH stabilised at 4.5. These tests were performed in
triplicate.
Biokinetic tests were conducted to provide a time related indi-
cation of the acid neutralising and acid generating behaviour of the
material under microbial conditions. The methodology given in
Broadhurst et al. (2013) and Hesketh et al. (2010) was used. Two
sets of experiments were performed in ve replicates on
150 lm material: pH controlled at 2 and without pH control.
7.5 g of sample was inoculated with 7.5 ml of a mixed culture
(1.0  106 cells Acidithiobacillus ferrooxidans, Leptospirillum fer-
riphilum, Acidithiobacillus caldus and Sulfobacillus benefaciens), in
150 ml of an autotrophic basal salt medium. The asks were main-
tained at 37 C on an orbital shaker for 63 days.
The solid residues obtained under the leach conditions of all the
ARD characterisation tests were further characterised using
QEMSCAN, QXRD and XRF. QEMSCAN analyses of residues were Fig. 1. pH prole for the biokinetic tests: pH controlled at 2, and without pH
conducted on un-sized samples (given the low mass available) control. Error bars represent the standard deviation.
 M. Becker et al. / Minerals Engineering 80 (2015) 3336
Table 2
Extent of mineral leaching of run of mine gold ore in the various ARD characterisation tests, as calculated using Eq. (1).
Type of test mineral ANC tests
Lawrence & Wang (%) Skousen (%)
Suldes 130 130
Carbonates >90 >90
Quartz 0 0
K-feldspar 0 0
Mica 0 130
Chlorite 3160 3160
Fe-oxyhydroxides 130 130
Sulfates <0 <0
result of the inherent assumptions and chemical conditions of the
method used in determining the ANC. The mineralogical ANC (cal-
culated on the% calcite present, 4.9 kg H2SO4/t) was similar to the
Lawrence and Wang ANC (4.2 0.6 kg H2SO4/t), both of which
were signicantly lower than the Skousen ANC (17.4 0.002 kg
H2SO4/t). This is due to the more aggressive experimental condi-
tions used to determine the Skousen ANC experimentally com-
pared to Lawrence and Wang ANC: rapid boiling step for the
dissolution of carbonates, and fast and intermediate weathering
silicates versus dissolution at ambient temperature for 24 h for
the dissolution of carbonates and fast weathering silicates (Smart
et al., 2002). The single addition NAG pH was 2.5 0.003, with a
sequential NAG of 51.6 2.8 kg H2SO4/t, similarly indicating that
the sample was potentially acid forming.
The time related pH prole of the biokinetic test performed
without pH control illustrated in Fig. 1 shows that the acid neutral-
ising reactions dominated in the rst few days (dissolution of car-
bonate, days 14), whereafter the system moved into a regime
where sulde oxidation dominated (days 514), followed by a
phase of competing sulde oxidation and release of less readily
available neutralising capacity (days 1534), until there were no
suldes left to react and the pH stabilised (days 3563). In this
case, the pH stabilised at 2.1 0.03 at day 63.
3.3. Determining the extent of element and mineral reaction
In order to evaluate the extent of reaction taking place during
the various tests, the residues obtained under typical leach condi-
tions were analysed mineralogically and chemically. The absolute
extent of element and mineral reaction was thereafter calculated
using Eq. (1) with the QEMSCAN, XRD and XRF results.
%mineral; element reacted
mass mineral; element in residue
100  100 
mass mineral; element in feed
For a clear comparative evaluation of the extent of leaching in the
various ARD characterisation tests using three different datasets
(QEMSCAN, XRD, XRF), the results needed to be interrogated with
user dened categories as follows: <0% reacted (i.e. precipitated),
0% reacted (i.e. unreacted), 130% reacted, 3160% reacted, 60
90% reacted, >90% reacted (i.e. completed reacted) see Table 2.
Minerals present in minor to trace quantities such as sphene, urani-
nite and zircon were not included in the interpretation due to the
low level of condence in the results.
The results given in Table 2 show near complete reaction of all
the dissolving carbonate minerals (>90% reacted) in the ARD char-
acterisation tests, as would be expected. Similarly, the results show
near complete reaction of the sulde minerals (>90% reacted), but
only in the tests designed to promote sulde oxidation i.e. NAG and
the UCT biokinetic test (Hesketh et al., 2010; Smart et al., 2002).
Sulfates precipitated in all the tests (conrmed with QXRD and
characteristic yellow precipitate in biokinetic shake ask at day
35
NAG UCT biokinetic test
Sequential NAG (%) Without pH control (%) pH controlled (%)
>90 >90 >90
>90 >90 >90
0 0 0
130 <0 130
130 0 <0
130 3160 3160
<0 130 <0
<0 <0 <0
14). The inert quartz and very slow reacting K-feldspar were gen-
erally unreacted in all tests. Of particular interest is the behaviour
of the intermediate weathering silicates chlorite and mica: (i) the
more aggressive Skousen ANC shows a greater extent of mineral
leaching than the less aggressive Lawrence and Wang ANC which
is consistent with the experimentally derived ANC values in
Table 1; and (ii) evidence that intermediate aluminosilicate miner-
als (chlorite mica) actively contribute to acid neutralising capac-
ity in ARD characterisation tests (c.f. Jambor et al., 2002; Plante
et al., 2012; Tan et al., 2012) and should not be discounted as a
source of long term acid neutralising capacity should the appropri-
ate environmental conditions prevail.
4. Conclusions
 Mineralogical and chemical techniques were used in conjunc-
tion with one another to evaluate the extent of reaction of the
acid forming and acid neutralising minerals under various
ARD characterisation test conditions.
 The extent of reaction in the various tests is broadly consistent
as expected: near complete reaction of dissolving carbonates,
near complete reaction of suldes (NAG and biokinetic test
only), precipitation of sulfates, slight to moderate leaching of
intermediate weathering silicates (chlorite, mica), and generally
no reaction of quartz and K-feldspar. The results afrmed that
acid neutralising capacity can be provided by the aluminosili-
cate minerals (mica, chlorite).
 The ANC tests provide characterisation of the leaching of neu-
tralising capacity only, the MPA the total acid formation poten-
tial, while the NAG and UCT biokinetic tests showed their
combined removal.
1
Acknowledgements
The contribution of colleagues in the Department of Chemical
Engineering is acknowledged for support with analytical measure-
ments. This work is also based on the research supported in part by
the National Research Foundation of South Africa (Grant Numbers
80599 and 86054), and on research supported by the South African
Research Chairs Initiative (SARChI Chair in Minerals Beneciation,
held by J-PF) of the Department of Science and Technology and
National Research Foundation of South Africa. Any opinion, nding,
conclusion or recommendation expressed in this material is that of
the authors and the NRF does not accept any liability in this regard.
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