Tulisanku

TRITA-LWR PHD 1009
ISSN 1650-8602
ISRN KTH/LWR/PHD 1009-SE
ISBN 91-7283-607-5
GEOCHEMICAL MODELLING OF ACID
MINE DRAINAGE IN MILL TAILINGS:
QUANTIFICATION OF KINETIC PROCESSES FROM
LABORATORY TO FIELD SCALE
S. Ursula Salmon
November 2003
S. Ursula Salmon TRITA-LWR PHD 1009

ii
Geochemical modelling of acid mine drainage in mill tailings:
Quantification of kinetic processes from laboratory to field scale

iii

ABSTRACT
Assessment of the potentially acidic, heavy metalladen leachates that leave deposits of sulfide
ore mill tailings and evaluation of various possible options for mill tailing remediation are
scientific problems of increasing practical importance. High costs may be associated with the mill
tailing remediation, not least after recent changes in Swedish and European environmental
legislation. This thesis presents a methodology for studying and quantifying geochemical
processes that contribute to generation of so-called acid mine drainage (AMD). The methodology
builds from first principles regarding geochemical processes, and is based on geochemical
characterisation of the mill tailings combined with explicit model quantification of the effect of
factors, such as temperature, pH, and mineral (BET) surface area, that influence mineral
weathering rates. Application of the modelling methodology to a case study site, Impoundment 1,
Kristineberg, northern Sweden, including quantification of slow processes through literature rate
laws, successfully reproduced the pH and relative concentrations of major ions in the
impoundment groundwater. Absolute concentrations of most major ions, with the exception of
Zn, were 1-2 orders of magnitude higher in the model than in the field, which is consistent with
the commonly observed scale dependence of mineral weathering rates; however, application of a
single calibration factor, X
r
=10
-2
, to all weathering rate expressions, sufficed to account for this
apparent scale dependence.
Subsequent laboratory determination of mineral weathering rates in Impoundment 1 tailings
indicated that rates for the major minerals pyrite (FeS
2
) and aluminosilicates were in fact 1-2
orders of magnitude lower in the ~50-year-old tailings than rates reported in the literature.
Weathering rates of chalcopyrite (CuFeS
2
) and sphalerite (ZnS) were by contrast 1-3 orders of
magnitude greater than predicted by the literature rate laws that were used in the modelling study.
While the mechanism of Zn release requires further investigation for improved forward model
prediction, the underestimation of Zn concentration in Impoundment 1 by the model was
resolved. The laboratory study furthermore indicated that the weathering rates of most major
minerals exhibited the same dependence on pH, temperature and surface area as reported in the
literature, and thereby supported the use of literature rate laws for model assessment of dominant
geochemical processes in tailings deposits, once allowance is made for lower rates in older tailings
material.
Analysis of the dominant geochemical processes in the model of Impoundment 1 indicated that
slow weathering of aluminosilicate minerals provided the bulk of proton attenuation and, as a
result, considerably affected the rate of depletion of fast-reacting pH-buffering minerals.
Inclusion of the kinetics of aluminosilicate dissolution and of the feedbacks between slow and
fast processes is thus potentially crucial for prediction of pH and its long-term evolution. The
sensitivity of modelled groundwater composition and pH to iron redox reactions, such as may be
accelerated by acidophilic bacteria, indicated that, while iron redox cycling was low at the present
case study site, quantification of microbial mediation of these reactions may be necessary for
predicting AMD quality under other conditions. The laboratory studies also indicated that
application of common sterilisation techniques, such as is necessary for study of relative
contributions of abiotic and biotic weathering processes, had little effect on the long-term (>30
days) abiotic element release rates in the tailings.
This study suggests that within certain limits, which appear narrower than currently recognised in
industrial prediction practices, it is possible to predict the weathering behaviour of major
minerals, and hence proton release and attenuation, in base metal tailings under field conditions.

iv

v

LIST OF PAPERS APPENDED.................................................................................................. VII
LIST OF PAPERS NOT APPENDED......................................................................................... IX
1 INTRODUCTION.................................................................................................................... 1
2 GENERATION OF ACID MINE DRAINAGE IN SULFIDIC MILL TAILINGS ...............5
2. 1 PROCESSES I N MI LL TAI LI NGS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2. 2 PREDICTI ON OF AMD ON FI ELD SCALE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3 MILL TAILINGS CASE STUDY: KRISTINEBERG IMPOUNDMENT 1.......................... 11
4 MODELLING OF PRE-REMEDIATION IMPOUNDMENT 1 ......................................... 15
4. 1 CONCEPTUAL MODEL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4. 2 PROCESS QUANTI FICATI ON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4. 3 MODEL RESULTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5 MODEL SENSITIVITY AND REMEDIATION IMPLICATIONS .................................... 21
5. 1 SENSI TI VI TY ANALYSI S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
5. 2 IMPLI CATI ONS FOR IMPOUNDMENT 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
6 QUANTIFICATION OF ELEMENT RELEASE RATES FROM BATCH
EXPERIMENTS ............................................................................................................................ 27
6. 1 MATERI ALS AND METHODS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
6. 2 EFFECT OF PH, TEMPERATURE, AND SURFACE AREA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
6. 3 EFFECT OF STERI LI SATI ON. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
7 MODELLING WEATHERING RATES ON BATCH, COLUMN, AND FIELD SCALE . 33
7. 1 MODEL I NTERPRETATI ON OF ELEMENT RELEASE RATES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
7. 2 MI NERAL WEATHERI NG RATES I N TAI LI NGS COMPARED TO MONOMI NERALIC
SAMPLES. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
7. 3 COMPARI SON: BATCH, COLUMN AND FI ELD RATES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7. 4 PREDI CTI ON OF FI ELD WEATHERI NG RATES FROM LABORATORY
EXPERI MENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
8 CONCLUSIONS AND IMPLICATIONS .............................................................................. 41
9 ACKNOWLEDGEMENTS..................................................................................................... 45
10 REFERENCES .................................................................................................................. 47


vi


vii
LIST OF PAPERS APPENDED

I. Salmon, S.U., Malmstrm, M.E., 2003. Geochemical processes in mill tailings deposits:
Modelling of groundwater composition. (Applied Geochemistry; in print)

II. Salmon, U.J., Malmstrm, M., 2000. Assessing geochemical processes in mill tailings
impoundments and the effect of remediation. In: Proc. ICAM 2000, 6
th
Int. Conf. on Applied
Mineralogy, Gttingen, Germany, July 13-21, 2000, pp. 671-673.

III. Salmon, S.U., Malmstrm, M.E., 2001. Quantification of mineral weathering rates in tailings
from Impoundment 1, Kristineberg, northern Sweden. In: Proc. Securing the Future, Int. Conf.
on Mining and the Environment, Skellefte, Sweden, June 25-July 1, 2001, pp. 747-756.

IV. Salmon, S.U., Malmstrm, M.E., 2003. Quantification of mineral weathering rates in mill
tailings: Effect of sterilisation method. In: Proc. ICARD 2003, 6
th
Int. Conf. on Acid Rock
Drainage, Cairns, Australia, July 14-17, 2003, p.1111-1116.

V: Salmon, S.U., Malmstrm, M.E., 2003. Mineral weathering rates in mill tailings from
laboratory to field scale: Effect of pH, temperature, mineral content, and surface area
(manuscript in preparation).

VI: Gleisner, M., Herbert, R., Salmon, S.U., Malmstrm, M.E., 2003. Comparison of sulfide
oxidation in unweathered pyritic mine tailings. In: Proc. ICARD 2003, 6
th
Int. Conf. on Acid
Rock Drainage, Cairns, Australia, July 14-17, 2003, p.1027-1030.

VII: Salmon, S.U., Destouni, G., 2001. National case studies: 3.Sweden. ERMITE Report: D1;
the European Commission Fifth Framework Programme, Energy, Environment and Sustainable
Development, Contract No EVK1-CT-2000-0078, University of Oviedo.

viii


ix
LIST OF PAPERS NOT APPENDED

Peer-reviewed publications:
Holmstrm, H., Salmon, U.J., Carlsson, E., Paraskev, P., hlander, B., 2001. Geochemical
investigations of sulfide-bearing tailings at Kristineberg, northern Sweden, a few years after
remediation. Sci. Tot. Environ., 273, 111-133.

Herbert, R.B.Jr., Malmstrm, M., Eben, G., Salmon, S.U., Ferrow, E., Fuchs M., 2003. Sterilisation
of mine tailings for the quantification of abiotic oxidation rates (in preparation).

MiMi-reports:
Salmon, S., Malmstrm, M., 2002. Steady state, geochemical box model of a tailings impoundment:
Application to Impoundment 1, Kristineberg, Sweden, and prediction of effect of remediation.
MiMi 2002:2, Mitigation of the environmental impact from mining waste programme (MiMi),
Stockholm, Sweden.

Malmstrm, M., Werner, K., Salmon, U., Berglund, S., 2001. Hydrogeology and geochemistry of mill
tailings Impoundment 1, Kristineberg, Sweden: Compilation and interpretation of pre-
remediation data. MiMi 2001:4, Mitigation of the environmental impact from mining waste
programme (MiMi), Stockholm, Sweden.

Werner, K., Salmon, S., 2001. Mine waste deposits and mines in Kristineberg, Sweden: Summary of
remediation programme and identification of potentially critical assumptions. MiMi 2001:3,
Mitigation of the environmental impact from mining waste programme (MiMi), Stockholm,
Sweden.

Salmon, S.U., 1999. Overview of models for biogeochemical modelling of acid mine drainage. MiMi
1999:4, Mitigation of the environmental impact from mining waste programme (MiMi),
Stockholm, Sweden.

Herbert, R.B.Jr., Malmstrm, M., Eben, G., Ferrow, E., Salmon, S.U., Fuchs, M., 2003. Quantifying
the effects of mine tailings sterilization (in review).

Licentiate thesis:
Salmon S.U., 2000. Biogeochemical processes in mill tailings: Modelling and assessment of
remediation effects. Licentiate thesis TRITA-AMI LIC 2053, Water Resources Engineering, Dept.
Civil and Environmental Engineering, Royal Institute of Technology, Stockholm, Sweden.

International conference abstracts:
Eben, G., Ferrow, E., Fuchs, M., Herbert, R., Malmstrm, M.E., Salmon, S.U., 2003. A comparison
of methods for mine tailings sterilisation. In: Proc. ICARD 2003, 6
th
Int. Conf. on Acid Rock
Drainage, Cairns, Australia, July 14-17, 2003, p.1013.

Salmon, S.U., Malmstrm, M.E., 2001. Mineral weathering rates in mill tailings from Kristineberg,
northern Sweden. In Eleventh Annual V.M. Goldschmidt conference, Abstract #3375. LPI
Contribution No. 1088, Lunar and Planetary Institute, Houston (CD-ROM).

Salmon, S., Malmstrm, M., 1999. Importance of various sulfide oxidation processes in remediated
mill tailings impoundments. EUG-10, Strasbourg, 1999, J. Conf. Abst. 4(1):513.

x

1
1 INTRODUCTION
The history of mining in Sweden stretches
back over 1000 years; Swedish mines were
for many centuries one of the major
suppliers of steel, copper and silver to
central Europe (Gustafsson et al., 1999).
Although the number of operating mines
has decreased from approximately 500 in the
early 20
th
century to 16 in 1999, prospecting
has also increased after changes in
ownership laws in the early 1990s, indicating
that there is both the resource potential and
the will of the mining industry for new
mines to open (see also further discussion
on mining conditions in Sweden in Paper
VII and references therein).
Fine mill tailings and waste rock are waste
products from mining and ore enrichment
processes. Mining at the current level in
Sweden produces approximately half of all
waste in Sweden (SCB, 2000a); in 1996, over
two thirds of the mining waste produced, or
35Mt, was from mining of sulfide ores
(SEPA, 1998), such as chalcopyrite (CuFeS
2
)
and sphalerite (ZnS). As sulfide ore minerals
are generally associated with large quantities
of economically undesirable iron sulfides,
such as pyrite (FeS
2
), the iron sulfides often
comprise a large fraction of the waste, as do
the so-called gangue minerals that host the
ore, typically (alumino-)silicate and
carbonate minerals. Oxidation of the iron
sulfide minerals upon exposure to dissolved
molecular oxygen, e.g.,
+ + ) (
2
7
) (
2 2 2
aq O O H s FeS

+ +
+ + H SO Fe 2 2
2
4
2
(1),
by abiotic or microbially mediated processes,
combined with reactions of the other
minerals in the waste, can lead to release of
acidic leachate with high concentrations in
metals and sulfate (referred to as acid mine
drainage, AMD) over hundreds to thousands
of years (SEPA, 1986).
The largest Swedish environmental concern
associated with mining, according the
Swedish Environmental Protection Agency
(here referred to as SEPA), is oxidation of
sulfidic wastes after closure of the mines,
and in particular, discharge of Hg, Cd, Pb,
Cu, Zn, As, Fe, Al, and acidity (SEPA,
1995). In 1995, it was estimated that over
60% of all Pb, Cd, Zn and Cu discharge to
Swedish waters came from mining and
mining waste, with the majority originating
from waste (SCB 2000b). The main
environmental impact of AMD is generally
considered to be associated with the heavy
metal content, with effects such as acute and
chronic toxicity and bioaccumulation, where
the low pH of the mine waste leachate
enhances metal mobility (SEPA, 1995).
However, AMD is also often characterised
by high concentrations of Fe(II), aluminium,
and sulfate, where these components are
mobile even under non-acidic conditions
(e.g., Smith and Huyck, 1999). Oxidation of
Fe(II) upon exposure to oxygen and
precipitation of characteristically yellow-red
Fe(III) phases, as well as precipitation of
Al
3+
phases, both release further acidity and
may physically impair biological function
(e.g., Pentreath, 1994). Also dissolved Al
3+

may be harmful at high concentrations (e.g.,
Wachtmeister and Sundstsrm, 1986;
Pentreath, 1994). In addition, in countries
where water is in short supply, even high
concentrations of sulfate may be critically
detrimental to water resources (Pulles, 2003).
The focus of regulation of water polluting
activities in Sweden and the E.U. has
recently changed, from placement of limits
on individual discharges, to regulation of the
integrated impact of many different
pollution sources within a catchment on the
receiving water body (see also more detailed
legislation discussion in Paper VII).
Relatively new Swedish and EU legislation
has introduced concepts such as
Environmental Quality Standards, which will
specify limits, for example, of concentrations
of metals that may not be exceeded in
surface or ground water bodies. Inability to
fulfil these criteria, or to demonstrate the
capability to do so, may thus have serious
consequences for the future of the mining
industry; while the impact of the new
legislation on AMD regulation is largely
untried, the Swedish mining industry is

2
concerned for its viability (Paper VII). At
the same time, societies will for the
foreseeable future continue to depend upon
mining to meet resource needs (Plumlee and
Logsdon, 1999). Sustainable regulatory
decisions on mining require means to
accurately assess the long-term
environmental impact of mining, the
associated waste material, and the outcome
of any remedial measures.
Remediation measures are commonly
applied with the intention of limiting
generation of AMD through reduction of
oxygen availability, for example through
application of water or soil covers. The large
quantities of generated mining waste leads to
such remediation being a costly undertaking
(e.g., SEPA, 1998). Despite the considerable
financial burden of remediation, remediation
measures are often based on reproducing at
any mine waste site similar practices as have
applied elsewhere, rather than linked to the
actual, site-specific downstream effect of the
remediation measure (OKane and Wels,
2003). In order to quantify and predict such
downstream effects, accurate source term
quantification and prediction is necessary.
Such quantification and prediction is also
necessary for optimisation of remediation
measures with respect to individual mine
waste sites (OKane and Wels, 2003), or the
total number of mine waste sites within a
water catchment (Baresel et al., 2003);
optimisation is required for economic
efficiency in environmental preservation and
reduced costs to the mining industry and to
society as a whole.
Methods that have been used for prediction
of AMD generation in tailings are both
laboratory and model based, with
standardised methods of static and kinetic
laboratory testing being often applied (e.g.,
White et al., 1999; MEND, 2000). However,
static tests can at best only predict whether
leachate pH will become acidic at some
(unknown) point in time (Parker and
Robertson, 1999), and typical application of
kinetic laboratory testing to prediction of
field scale leachate quality is associated with
a high degree of uncertainty (Salomons,
1995). Furthermore, these methods assume
geochemical control of AMD quality
(Salomons, 1995), and thereby largely
neglect the crucial interaction with oxygen
availability.
A number of modelling studies of AMD
generation from mill tailings exist in the
literature (e.g., Scharer et al., 1994;
Wunderley et al., 1996; see also review in
Alpers and Nordstrom, 1999) where models
have been produced as tools to examine
effects of dominant processes and compare
different tailings remediation measures.
However, the predictive capability of many
of these models is limited (MEND, 2000;
Parker and Robertson, 1999), due to, for
example, oversimplification or neglect of
some important geochemical processes.
Recent model developments open for better
consideration of kinetic processes (Lichtner,
1996; Mayer et al., 2003), with application of
such models to field data including model
calibration to field observations (Mayer et
al., 2003).
In parallel lines of investigation, focussed on
weathering of aluminosilicate minerals,
independently determined weathering rate
laws for monomineralic samples on
laboratory scale have been applied to field-
scale prediction of, for instance, acidification
and mineral weathering impact on global
climate (White and Brantley, 1995), or AMD
generation in waste rock (Strmberg and
Banwart, 1994). It is then commonly
observed that weathering rates determined
on the laboratory scale overestimate
apparent field rates by orders of magnitude
(e.g., Schnoor, 1990; White and Peterson,
1990; Strmberg and Banwart, 1994). The
study by Malmstrm et al. (2000) indicates
that such discrepancies between apparent
field and laboratory rates may be resolved
through relevant, explicit consideration of
the influence of factors, such as temperature,
pH, and water flow conditions, which may
be quite different on different scales.
This thesis presents a modelling
methodology that is based on fundamental
geochemical principles and is adapted to
field conditions of a mill tailings
impoundment case study, Impoundment 1,
Kristineberg, northern Sweden, in analogy

3
with earlier modelling of mining waste rock
deposits (Strmberg and Banwart, 1994). In
particular, this thesis addresses the
importance of aluminosilicate weathering
and iron redox cycling for the groundwater
composition and pH in mill tailings deposits.
Furthermore, laboratory studies are
performed to test model assumptions made
in the application of literature rate laws to
the modelling of field-scale AMD
generation. These laboratory studies
investigate the dependence of mineral
weathering rates on pH, temperature, and
BET surface area under conditions relevant
for mill tailings. In addition, the laboratory
studies include investigation of sterilisation
techniques that are required to investigate
abiotic vs biotic weathering processes.
Specific objectives of this thesis can be
summarised as:
1. To develop a modelling
methodology for quantifying
leachate composition and pH in
pyritic base metal tailings
impoundments, which include
kinetic reactions and their feedbacks
with equilibrium processes.
2. To apply this modelling
methodology to a specific case study,
Impoundment 1, Kristineberg, using
independently reported mineral
weathering rate laws, and particularly
investigate the site-specific
importance of slow aluminosilicate
dissolution and iron redox cycling
coupled with fast geochemical
processes and oxygen availability.
3. To test various model assumptions
through systematic laboratory studies
of site-specific tailings material from
Impoundment 1 and separated
sulfide phases, and through
comparison of weathering rates
determined on different
experimental/observation scales.


4


5
2 GENERATION OF ACID MINE DRAINAGE IN SULFIDIC MILL TAILINGS

Mill tailings are the finely ground waste product from ore enrichment by flotation. As mentioned
in the introduction, common minerals in base metal pyritic mill tailings are iron sulfides and
gangue minerals from the ore body host rock, such as aluminosilicate and carbonate minerals, as
well as lesser amounts of ore minerals. The focus of this work is geochemical processes
contributing to the major ion composition and pH in tailings impoundment groundwater. Below
is an overview of major physical and geochemical processes (see also detailed reviews in
Evangelou and Zhang, 1995; Nordstrom and Southam, 1997; Nordstrom and Alpers, 1999) and
general means of quantification of kinetic geochemical processes, such as is applied in the
modelling study in Chapter 3. In Chapter 2.2, earlier approaches to modelling the aqueous
geochemistry of AMD are briefly reviewed.

2.1 Processes in mill tailings
2.1.1 Oxygen availability and solute transport
Fine tailings are often deposited as a slurry
in a containing dam and allowed to
sediment. Tailings impoundment dams can
contain vast volumes of material, for
example, the tailings dam at the Aitik open
cut porphyry copper mine in northern
Sweden, which has been in operation for
approximately 35 years, covers up to 11 km
2
,
and is up to 40 m in depth (Lindvall and
Eriksson, 2003). As diffusion of oxygen in
air is approximately 4 times greater than in
water (e.g., Nicholson et al., 1998), ingress of
oxygen into tailings is relatively slow under
water-saturated conditions. After closure of
an impoundment, or even during use,
decrease in the water level may lead to
formation of an unsaturated zone, thereby
opening the way for oxygen diffusion in
pore spaces, and hence faster oxidation
processes such as in Equation 1.
The dependence the overall reaction rate on
the availability of oxygen implies that
oxidation, and hence proton production, will
predominantly occur in the unsaturated zone
of tailings deposits. This is consistent with
the commonly reported field observations of
depletion of sulfides above the water table in
tailings deposits (e.g., Holmstrm et al.,
2001). The partial pressure of oxygen, Po
2
,
in the impoundment is a result of the
balance between the rate of transport into
pore spaces, by diffusion and advection, and
the rate of oxygen consumption. If the rate
of transport is relatively fast, the overall
reaction rate is controlled by the surface
reaction, and the Po
2
will be equal to the
atmospheric Po
2
(0.2 atm). If the rate of
transport is of a similar order of magnitude
as the rate of consumption, or slower, the
overall reaction rate will be mixed kinetic or
transport controlled, and Po
2
will decrease.
Transport of reaction products from the
reaction site to downstream environment
depends upon inflow of precipitation,
groundwater and/or surface water. The
aqueous composition and pH of the
groundwater in tailings deposits thus
depends upon the relative rates of
geochemical processes occurring in the
tailings, as well as physical processes such as
gas and solute transport, and feedbacks
between these processes.
2.1.2 Oxidation processes
The slow oxidation of sulfide minerals leads
to release of sulfate, Fe(II), protons and
heavy metals and metalloids, as exemplified
by Equations 1-6 in Table 1 (see also, e.g.,
reviews Nordstrom and Southam, 1997, and
Nordstrom and Alpers, 1999). Under most
conditions in the presence of dissolved
molecular oxygen, Fe(III) is the
thermodynamically more stable specie of the
iron redox couple; however, kinetic
limitation on the oxidation of Fe(II) results
in a relatively slow abiotic rate of oxidation
to Fe(III) (Equation 10 in Table 1),
particularly at low pH. The produced Fe(III)

6

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7
is also a powerful oxidant for sulfides
(Equations 2, 4, and 6 in Table 1) and is
itself reduced to Fe(II), leading to iron redox
cycling (Fig. 1). The availability of aqueous
Fe(III) for reaction is potentially limited by
relatively fast precipitation of secondary
Fe(III) phases, such as amorphous ferric
hydroxide:
+ +
+ + H s OH Fe O H Fe 3 ) ( ) ( 3
3 2
3
(2)
where the final position of equilibrium is a
function of, and may also affect, solution
pH. Availability of ferrous and ferric iron for
slow reactions and equilibria, such as
Equation 2, will also depend upon aqueous
speciation of these components and
amounts of complexing agents present.
Table 3 in Paper I gives examples of
aqueous speciation reactions for
components released by reactions such as
those in Table 1. Modelling of pH and
aqueous component concentrations thus
clearly requires consideration of coupling
between slow kinetic and fast equilibrium
processes.
The slow oxidation of sulfide minerals is
accelerated by mediation by acidophilic
bacteria. Optimal conditions for microbial
mediation have been reported to be
~30 C, Po
2
=0.2 atm, acidic pH, and with
nutrients such as phosphate, nitrate, and
carbon readily available (e.g., Ehrlich, 1996).
In laboratory studies under such favourable
conditions, pyrite oxidation by oxygen has
been reported to be up to a factor 35 greater
in microbial experiments than in abiotic
controls (Olson, 1991; Fowler et al., 2001,
Yu et al., 2001). The acceleration of sulfide
oxidation by microorganisms is even utilised
in industrial hydrometallurgical metal
extraction (e.g., Rossi, 1990). Observations
made on the field (Elberling et al., 2000) and
near-field (large columns; Strmberg and
Banwart, 1999) scales at low temperature
also indicate higher rates of oxidation, by a
factor 1.5-5, prior to addition of bactericides.
The rate of oxidation of Fe(II) is also
increased by microbial mediation, by up to 4
orders of magnitude or more (Lacey and
Lawson, 1970; Singer and Stumm, 1970;
Nemati and Webb, 1997; see also reviews by
3
pyrite
Fe(II)
Fe(III)
O
2
O
2
Fe(OH)
3
(s)
1
2
4
3
pyrite
Fe(II)
Fe(III)
O
2
O
2
Fe(OH)
3
(s)
1
2
4

Figure 1. Iron redox cycling. Pyrite oxidation
by 1) dissolved molecular oxygen and 2)
aqueous ferric iron; 3) Oxidation of aqueous
ferrous iron by oxygen. Reaction
stoichiometry and abiotic rate laws are given
in Table 1. 4) Solubility equilibrium between
aqueous solution and Fe(OH)3(s), as
represented in Equation 2.
Nordstrom and Southam, 1997; and Nemati
et al., 1998), particularly at low pH where the
abiotic oxidation rate is relatively low. It has
even been suggested that the overall rate of
pyrite oxidation is limited by the rate of
generation of ferric iron (e.g., Singer and
Stumm, 1970); particularly in microbial
studies, this is still a topic of debate and
investigation (Fowler et al., 2001, Yu et al.,
2001; Sand et al., 2001). Oxidation of
aqueous Fe(II) and sulfide minerals may also
be increased by abiotic factors; for example,
acceleration of aqueous Fe(II) oxidation has
been reported subsequent to adsorption of
Fe(II) on to surfaces of iron oxy-hydroxides
(Tamura et al., 1976; Wehrli, 1990), and
contact between two sulfide minerals can
lead to accelerated dissolution of the sulfide
with lower electrochemical rest potential
(e.g., Kwong, 1993, 2001).
Rate laws quantifying the dependence of
reaction rates, r, upon various key factors are
given in Table 1 for slow, abiotic reactions
of common minerals in mill tailings and
aqueous Fe(II). The rate laws are selected,
where available, from studies reported in the
literature, where they have been determined
from systematic laboratory experiments. As
can be seen, reaction rates [mol s
-1
] depend

8
on factors such as the value of the
temperature-dependent rate constant, the
availability of oxidant and protons, and
mineral surface area.
Although acceleration of oxidation reactions
in Table 1 by various mechanisms as
described above is widely reported in the
literature, these alternative reaction pathways
are seldom quantified in a way that is useful
for modelling (e.g., Edwards et al., 2000);
additionally, there is no consensus as to
which of the few rates laws that are available
is best (Kirby et al., 1999). In the modelling
study presented in Papers I and II (see also
Chapters 4-5), abiotic rate laws are applied
and the sensitivity of model results to
acceleration of rates is tested. Furthermore,
systematic study of the relative contribution
of abiotic and biotic processes in tailings,
such as is required for determination of rate
laws, requires sterilisation. However, the
effect on mineral weathering rates of
exposure to extreme chemical or physical
conditions usually associated with
sterilisation has not been reported; this is
investigated in Paper IV.

2.1.3 pH-buffering processes
As described above, processes such as
oxidation of sulfides and precipitation of
Fe(III) phases leads to release of protons in
tailings impoundments. Natural attenuation
of the released protons and, thus, the final
pH in the tailings impoundment
groundwater, is dependent upon the
reactions of minerals that dissolve and
consume protons, which in turn depend on
the quantity of the mineral available for
reaction and the reaction rate. Acid-
neutralising process rates are expected to be
higher in the unsaturated zone, where the
rate of protons production is higher, as a
result of greater oxygen availability (e.g.,
Banwart and Malmstrm, 2001; Banwart et
al., 2002).
Carbonate minerals, such as calcite, are
generally considered to dissolve sufficiently
quickly to maintain solubility equilibrium
with aqueous solution and buffer pH at
around neutral, e.g.:
CaCO
3(s)
+ H
+
Ca
2+
+ HCO
3
-
(3).
Maintenance of pH at high levels, combined
with release of components such as iron and
aluminium, leads to precipitation of
secondary carbonates and hydroxides such
as amorphous Fe(OH)
3(s)
and Al(OH)
3(s)
.
After depletion of calcite, pH is buffered at
successively lower levels by the dissolution
sequence of the secondary minerals (Blowes
and Ptacek, 1994). Acid neutralisation by
dissolution of aluminosilicate minerals (e.g.,
Equations 7-9 in Table 1) is relatively slow,
but as these minerals are often present in
large quantities, the contribution to acid
attenuation may be significant, as has been
suggested in a number of field studies (e.g.,
Nesbitt and Jambor, 1998; Johnson et al.,
2000) and in a recent water saturated column
study with tailings (Jurjovec et al., 2002).
Decrease of proton production with time,
due to, for example, eventual depletion of
sulfide minerals in the unsaturated zone, will
lead to return of pH to higher levels (e.g.,
Banwart and Malmstrm, 2001).
Selected rate laws for aluminosilicate
minerals are given in Table 1. There is a
wealth of literature on the weathering rates
of aluminosilicate minerals under laboratory
conditions, including the dependence of
different mineral weathering rates on factors
such as pH and temperature (see e.g., review
in White and Brantley, 1995).

2.2 Prediction of AMD on field scale
A number of previous modelling studies of
AMD from tailings deposits presented in the
scientific literature focus on detailed
modelling of oxygen diffusion, coupled to
limited description of geochemical processes
(e.g., Jaynes et al., 1984; Elberling et al.,
1994; Scharer et al., 1994; Wunderly et al.,
1996; Werner and Berglund, 1999; Bain et
al., 2000; Romano et al., 2003). These
models provide valuable insight into the
coupling of, and feedback mechanisms
between, different physical processes and

9
oxidation of iron sulfide minerals. Other
geochemical reactions, such as pH-buffering
processes, have often been simplified or
neglected (e.g., MEND, 2000; Parker and
Robertson, 1999), thus limiting the
possibility to investigate geochemical
processes that contribute to the master
geochemical variable pH.
Detailed representations of kinetic
limitations on slow geochemical processes
are presented in Lichtner (1996) and Mayer
et al. (2003). Both studies use AMD
generation as one case study and, by fitting
to field observations, Mayer et al. (2003)
determined diffusion constants for a
shrinking core model of sulfide dissolution,
aluminosilicate mineral surface areas, and the
reaction order of the rate of pyrite oxidation
by Fe(III) with respect to ferric iron. The
thus calibrated model reproduced pH and
aqueous concentration profiles and
furthermore simulated attenuation of Cu
below the groundwater level due to covellite
formation. As calcite was depleted,
aluminosilicates were found to attenuate
acidity. Geometric surface areas were
calculated for aluminosilicates, based on an
average grain size of the tailings, and
compared with the surface areas obtained by
calibration; while some discrepancies were
observed, the authors concluded that
laboratory-derived rate expressions for
aluminosilicate minerals may be applicable in
tailings.
In the work of Lichtner (1996) and Mayer et
al. (2003), oxidation of aqueous Fe(II) was
represented by equilibrium rather than a
kinetic processes; Lichtner (1996) explained
this as an approximation to microbial
mediation leading to a rates that approach
equilibrium conditions. However, as
discussed in the previous section, the degree
of microbial activity in the field may be
limited by various environmental conditions,
such as low temperature, high pH, and
limited availability of nutrients.
In parallel developments, a large number of
laboratory studies have been performed on
aluminosilicate dissolution in order to
investigate processes such as acidification of
soils and watersheds and long-term global
climate change (see e.g., White and Brantley,
1995, and references therein). Comparison
of rates obtained from laboratory
experiments with field observations typically
yields rates in the laboratory that are up to 2
orders of magnitude greater than in the field
(e.g., Schnoor, 1990; White and Peterson,
1990; Strmberg and Banwart, 1994;
Malmstrm et al., 2000). For example,
application of rate laws obtained from the
literature for weathering of aluminosilicates
and sulfides at the Aitik waste rock site in
northern Sweden required a scaling down of
~2 orders of magnitude to reproduce
absolute field rates (Strmberg and Banwart,
1994). Orders of magnitude differences were
also observed in weathering rates in Aitik
waste rock on laboratory, large column, and
field scales; these differences were resolved
by explicit account of independently
quantified differences in temperature, pH-
dependence, mineral content, and water flow
conditions between different
experimental/observation scales
(Malmstrm et al., 2000).
Previous studies that have been briefly
outlined in this chapter have increased our
understanding of dominant geochemical
processes that may occur in mill tailings and
proposed different modelling tools for
quantitative reproduction of these processes.
A number of qualitative and quantitative
issues with regard to field scale prediction,
however, have also been opened and remain
open, thus requiring further investigation in
order to be resolved. The specific
investigation objectives of this thesis, which
have been summarised in Objectives 1-3 in
the Introduction, include some of these
open issues:
- the applicability of literature
monomineralic weathering rates laws
for reproduction of mineral
weathering rates in tailings;
- the importance of aluminosilicate
weathering and abiotic or microbially
mediated iron redox cycling for
tailings deposit groundwater
composition and pH, and

10
- whether sterilisation of tailings samples,
such as is required to investigate
abiotic vs biotic weathering processes,
affects mineral weathering rates.


11
1 km
Impoundment 4
Imp. 3
Imp. 2
Impoundment 1
Imp. 1B
Waste Rock Heap
Tailings
impoundment
surface
Water
surface
Vormbcken
Rvlidmyr-
bcken
Ditch
Sweden
Kristineberg:
Figure 2.. Location and overview of the Kristineberg site.
3 MILL TAILINGS CASE STUDY:
KRISTINEBERG IMPOUNDMENT 1
The case study used for model application is
a mill tailings deposit called "Impoundment
1" in Kristineberg, which is also the special
case study site of the Swedish multi-
disciplinary research program "Mitigation of
the environmental impact from mining
waste" (MiMi), funded by the Swedish
Foundation for Strategic Environmental
Research (MISTRA; see, e.g., MiMi, 2002).
Papers I-VI have been produced within the
framework of the MiMi research program.
The underground Kristineberg mine, owned
and still operated by Boliden Mineral AB, is
based on a massive sulfide Zn-Cu ore body
located in the Skellefte district 175 km
south-west of Lule, Sweden (Fig. 2). The
average annual air temperature at the site is
1 C with 5 months of average temperature
below 0
o
C. The tailings deposit referred to
as Impoundment 1 was in use from the
1940s to the 1950s for deposition of tailings
from the enrichment plant at Kristineberg,
which processed ore from other mines in
the area as well. The geology of the
Kristineberg mine is described in du Rietz
(1953); field data for pre-remediation
conditions in Impoundment 1 from
sampling campaigns in the 1980s and early
1990s (e.g., Qvarfort, 1983; Axelsson et al.,
1986, 1991; Ekstav and Qvarfort, 1989) have
been compiled and interpreted by
Malmstrm et al. (2001) and form the basis
of the case study used in the modelling
application in Chapters 4 and 5 of this
thesis. A summary of field data relevant for
the modelling study is also given in Paper I.
Impoundment 1 was remediated in 1997 by
combined dry cover application and raised
groundwater level. The remediation
programme for the site is summarised in
Lindvall et al. (1999) and Werner and
Salmon (2000). Post-remediation
characterisation of the deposit to date is
summarised in Holmstrm et al. (2001),
Werner et al. (2001), Corrge et al., (2001),
and Carlsson et al. (2002, 2003).
As part of the present work, the BET
surface area for tailings in Impoundment 1
(Papers I, III-V) and saturation indices for
both pre- (e.g., Paper I) and post-
(Holmstrm et al., 2001) remediation
conditions were determined. These
quantities provide missing key parameter
values and contribute to the conceptual
model of geochemical processes occurring in
Impoundment 1, which in turn is the basis
for the desktop modelling study described in
Chapters 4 and 5 (Papers I, II) and scaling of
laboratory rates to field conditions in
Chapter 7 (see also Paper V). Detailed
characterisation of the specific
Impoundment 1 tailings used in weathering
experiments was also performed; see
Chapter 6 and Papers III-V.
Impoundment 1 covers an area of
approximately 0.11 km
2
and is on average
5 m deep. The extent of the unsaturated

12
zone, that is, the average depth to the
groundwater, was 1 m prior to remediation.
The total water flow through the deposit,
consisting of effective infiltration and
recharge from moraine slopes surrounding
the deposit, was ~47 000 m
3
year
1
. Figure 3
summarises the main attributes of the water
balance over the deposit, along with the
position of the groundwater table and the
water sampling plane.
Neither concentrations of individual pore
gases, the influx of oxygen, the water
content of the unsaturated zone, nor the
oxygen diffusivity are reported for the pre-
remediation conditions.
The specific surface area of the tailings was
determined using five-point, nitrogen gas
adsorption data evaluated through the BET
equation, a method commonly used in
kinetic mineral weathering studies. The
specific surface area of eight samples from
seven locations within the deposit ranged
from 0.2 to 10.1 m
2
g
-1
, with an average
value of 2.96 m
2
g
-1
. The large variability in
specific surface area is consistent with the
reported highly variable particle size
distribution (see Paper I and Malmstrm et
al., 2001).
The tailings within the deposit are pyritic
and carbonate-depleted; the main minerals
are chlorite, talc, muscovite, plagioclase,
quartz, and pyrite. Sphalerite and
chalcopyrite are also present. More detailed
post-remediation characterisations of the
tailings confirmed this mineralogy and also
indicated the presence of feldspars and
minor amounts of pyrrhotite, galena, and
arsenopyrite (e.g., Holmstrm et al., 2001).
The tailings in the upper part of the deposit,
on average down to the groundwater table,
had been partly depleted in S, Fe, Zn, and
Cu, suggesting weathering of sulfides in the
water unsaturated zone. Volumetric
fractions of major minerals in the
unsaturated zone are given in Table 2.
The groundwater, which had been sampled
1.5 m below the groundwater table, had an
average pH of 4.9; redox potentials are not
available in the literature. The groundwater
contained high concentrations of dissolved
SO
4
2-
, Fe, Mg
2+
, Zn
2+
, Ca
2+
, and Al
3+
, as well
as lower concentrations of Na
+
, Cu
2+
, and
K
+
(see Table 3). In order to investigate
whether aqueous concentrations were
controlled by fast dissolution or
precipitation of secondary phases at
solubility equilibrium with solution,
1m
unsaturated zone
1.5m
depth of groundwater
to sampling points
drainage to ditches
etc
recharge from
adjacent slope
drainage to
fractures
infiltration
5m
depth of deposit
Groundwater
sampling plane

Figure 3. Schematic illustration of the hydrological situation in our case study,
Impoundment 1. The upper marked plane shows the average position of the water table
(see Appendix in Paper I). The lower marked plane indicates the plane, 1.5 m below the
groundwater surface, from which aqueous samples for the published groundwater quality
data (Table 4) used in this study had been collected.

13
saturation index calculations were performed
for the modelling study (see also Salmon,
2000, Salmon and Malmstrm, 2002) and on
porewater composition sampled soon after
remediation (Holmstrm et al., 2001) with
the PHREEQC code (Parkhurst, 1995) in
conjunction with the WATEQ4F database
(Ball and Nordstrom, 1991). The
calculations indicated that, of mineral phases
likely to be controlling aqueous
concentrations in AMD environments
(Nordstrom and Alpers, 1999), the
groundwater was close to saturation with
respect to gypsum (CaSO
4
2H
2
O
(s)
),
amorphous silica (SiO
2(am)
), and an
amorphous ferric hydroxide phase
(Fe(OH)
3(am)
). Saturation indices also
indicated that solution was close to solubility
equilibrium with gibbsite, as is often
observed in AMD environment (e.g.,
Johnson et al., 2000; Jurjovec et al., 2002).
However, the presence of the precipitate in
AMD environments has not been confirmed
(Jambor, 1994; Jurjovec, et al., 2002).
Solution was also undersaturated with
respect to amorphous aluminium hydroxide.

Table 3. Average concentrations (mol l
-1
) and
pH reported for Impoundment 1 (see Paper I
and Malmstrm et al., 2001).
Average field
values

Range of values
pH 4.87 4.05-6.15
SO4
2-
0.10 0.07-0.14
Fe(tot)

0.080 0.06-0.09
Mg
2+
0.011 0.007 - 0.017
Zn
2+
0.006 0.004 - 0.007
Ca
2+
0.005 0.002 - 0.012
Al
3+
0.002 9 x 10
-4
- 0.003
Cu
2+
6 x 10
-5
8 x 10
-6
- 2 x 10
-4

K
+
6 x 10
-5
3 x 10
-6
-2 x 10
-4

Na
+
4 x 10
-4
2 x 10
-4
- 5 x 10
-4

Table 2. Mineralogy of the unsaturated zone of Impoundment 1 as estimated for the
modelling study (see Paper I).
Average volumetric fractions () of minerals
Sulfides

Silicates
Pyrite Chlorite
Pyrrhotite
}
0.04

Talc
} 0.45
Chalcopyrite 0.002 Muscovite 0.15
Sphalerite 0.001 Plagioclase 0.10
Quartz 0.25


14

15
4 MODELLING OF PRE-REMEDIATION IMPOUNDMENT 1

Based on analysis of the available data from pre-remediation conditions in Impoundment 1, BET
surface determinations, and saturation index calculations for potential sources and sinks for the
aqueous components in Impoundment 1, a conceptual model was formed, as is describe in this
chapter. Solid phase data and the total water flow through the impoundment were used as model
input data; process rates and equilibria were quantified using rate laws and thermodynamic data
obtained from the literature. In Paper I (and this chapter), the resulting simulated aqueous
component concentrations and pH were compared with those reported for Impoundment 1, and
results were interpreted with respect to dominant geochemical processes.

4.1 Conceptual model
In the modelling study of Impoundment 1,
the unsaturated zone was considered to be
the major reactive zone in the tailings
deposits and the dominant source of
dissolved constituents in the groundwater.
For sulfide minerals, this was supported by
depletion above the groundwater level in
Impoundment 1. Given the low spatial and
temporal resolution of the available field
data, as a first approximation the
groundwater composition was modelled by
assessing the unsaturated zone only; this
zone was conceptualised as a single,
completely-mixed flow-through reactor
(box). The modelled leachate leaving the
unsaturated zone was compared with the
available data for groundwater quality from
1.5 m below the groundwater level (see Fig.
1).
The site-specific conceptual model for the
geochemical processes occurring in the
unsaturated zone of Impoundment 1 is
shown in Figure 4. Based on the reported
mineral abundance in Impoundment 1
(Table 2) and the composition of the
aqueous phase, the main primary sources of
groundwater solutes were considered to be
the slow oxidation of sulfide minerals
(pyrite, sphalerite, and chalcopyrite) by
dissolved molecular oxygen and ferric iron
and the slow weathering of aluminosilicates
chlorite, muscovite, and plagioclase
(reactions presented in Table 1). Although
ferric iron is the thermodynamically
favoured iron redox specie in the presence
of dissolved molecular oxygen, the high Fe
concentrations in the groundwater suggested
dominance of Fe(II), as Fe(III) is highly
insoluble at the impoundment groundwater
pH of 4.9. This implied a kinetic limitation
on the oxidation of Fe(II) to Fe(III).
Aqueous ferrous iron oxidation by dissolved
molecular oxygen was thus also
conceptualised as a relatively slow, kinetic
process (cf. Strmberg and Banwart, 1994).
Relatively fast, reversible geochemical
processes included aqueous speciation,
solubility equilibrium between the aqueous
solution and secondary mineral phases
(gypsum, ferrihydrite, and amorphous
silicate), and Henrys law equilibrium
between aqueous solution and oxygen and
carbon dioxide in the gaseous phase in the
unsaturated zone (see Table 3 in Paper I).
The yearly average of the total water
flowrate through the deposit was used and
all physico-chemical properties, such as the
water content, pore gas composition, and
mineral abundance, were assumed constant
over the modelled zone and in time. This
approach is consistent with the limited
spatial and temporal resolution of available
site data for Impoundment 1 (Malmstrm et
al., 2001) and for mine waste sites in general
(cf. Banwart and Malmstrm, 2001). The
geochemistry was furthermore assumed to
be at quasi-steady state (cf. Furrer et al.,
1989), as was later justified by the water
residence time in the saturated and
unsaturated zones (0.5-1 years; Malmstrm
et al., 2001) being much greater than the
mineral turnover time (see Chapter 4.3).


16
4.2 Process quantification
For each simulation, the partial pressure of
oxygen (Po
2
) was held constant, and the
resulting flux (Fo
2
) determined by mass
balances. Simulations were performed over a
range of oxygen partial pressures; results are
presented for i) surface reaction control
(Po
2
=0.2 atm) and ii) mixed or transport
controlled, Po
2
<0.2 atm (see Chapter 2.1).
Fast processes in the conceptual model were
quantified through mass action equations
(see Table 3 in Paper I); Fe(II) and Fe(III)
were specifically considered as separate
components, to allow investigation of slow
iron redox processes. The abiotic, kinetic
rate laws used were those given in Table 1,
that is, the basis for quantification of all
kinetic processes was independent of site
observations. Rate laws were not found in
the literature for oxidation of chalcopyrite
and sphalerite by dissolved molecular
oxygen; analogy was thus made with the rate
law for oxidation of pyrite and rate
constants were calculated from reported
(Scharer et al., 1994) abiotic rates of
oxidation of these minerals by dissolved
molecular oxygen.
Through consideration of the site specific
properties of the unsaturated zone, the rate
laws were converted to rate expressions, R
[mol dm
-2
s
-1
], normalised to the surface area
of the deposit; for heterogeneous reactions:
i i i
r A h R = (4)
where h and are the height and density of
the unsaturated zone. For homogeneous
reactions:
i i
r h R = (5)
where is the water content. Table 4 in
Paper 1 lists the final rate expressions,
together with associated rate constants that
have been adjusted for site temperature
using published activation energies.
Additional parameter values for
Impoundment 1 used in the rate expressions
are given in Table 2 in Paper I.
The specific mineral surface area, A
i
, to be
used in conjunction with surface area
normalised empirical rate laws in
quantification of weathering rates (see Table
4 in Paper I), was for the i
th
mineral
estimated by allocation of a fraction of the
total specific surface area of the tailings
(A
s,tot
)

in proportion to the volumetric
fraction,
i
, of the mineral:
sulfides
(alumino)-
silicates
aqueous
speciation
Impoundment groundwater
Impoundment surface
U
n
s
a
t
u
r
a
t
e
d
z
o
n
e
Saturated zone
O
2
(g)
Fe
2+
Fe
3+
Fe(OH)
s
(s)
CaSO
4
.
2H
2
O(s)
CO
2
(g)
SiO
2
(s)
Po
2
O
2
(aq)

Figure 4. Conceptual model for geochemical processes in the unsaturated zone of a mill
tailings deposit. Kinetically controlled processes (single headed arrows) include weathering of
aluminosilicate minerals (chlorite, muscovite, and plagioclase), oxidation of sulfide minerals
(pyrite, sphalerite, and chalcopyrite) by both dissolved molecular oxygen and Fe(III), and
oxidation of aqueous Fe(II). Fast, equilibrium controlled processes (double headed arrows)
include aqueous speciation, Henrys law equilibrium between the aqueous solution and pore
gases, and dissolution/precipitation of secondary minerals.

17
A
i
=
i
A
s,tot
(6).
This modelling approach is based on the
assumptions that weathering rate laws for
monomineralic samples can be applied to
mixtures of minerals, such as in tailings, that
minerals are evenly distributed over all the
particle size fractions, and that the specific
surface area is constant between the minerals
for a given particle size. Volumetric fractions
(
i
) for the case study are given in Table 2.
The mathematical model was implemented
through STEADYQL (Furrer et al., 1989),
which allows a numerical, geochemical
quasi-steady state box modelling approach
that previously has been successfully applied
to waste rock dumps and underground
mines (Strmberg and Banwart, 1994;
Brown and Lowson, 1997; Brown et al.,
2000). Processes such as depletion and
accumulation of minerals that are much
slower than the residence time of water can be
considered through successive steady state
simulations (see, e.g., Salmon, 2000, and
Chapter 5).

4.3 Model results
4.3.1 Comparison with field observations
Simulated concentrations in the
impoundment groundwater were assessed in
Papers I and II and are shown in Figure 5 vs
concentrations observed in the field; the
solid diagonal line indicates perfect
prediction. Uncalibrated results of the
model described in the previous section
(Po
2
=0.2 atm) are shown in Figure 5a, with
the exception that solubility equilibrium with
gypsum is not assumed. The model
successfully reproduced the pH in the
impoundment and the relative release rates,
with the exception of Zn
2+
and Ca
2+
.
Absolute rates were, however, one to two
orders of magnitude higher in the model
than in the field, despite accounting for field
relevant temperature, pH, mineral content,
and tailings surface area. This is consistent
with the commonly observed scale-
dependence of mineral weathering rates
from laboratory to the field scale (e.g., White
and Peterson, 1990; see also Malmstrm et
al., 2000, and references therein). Release of
Fe, SO
4
2-
, Zn
2+
, Cu
2+
, and pH were sensitive
to Po
2
. Decreased Po
2
implied decreased
concentrations of these components,
however, components from aluminosilicate
weathering still remained high, and pH
increased above the range of values reported
for the field.
In order to account for the scale dependence
of mineral weathering rates from laboratory
values reported in the literature to field
relevant rate values, a single calibration
factor, X
r
=10
-2
, was applied to all weathering
rate expressions (i.e., multiplying the right
hand side of Equation 4). In the
quantification of X
r
, the concentration of
Mg
2+
was used as a tracer for the field
weathering rates, as Mg
2+
originates from the
dominant (alumino)silicates, the weathering
rates of which do not depend (directly) upon
the dissolved molecular oxygen
concentration. A value of X
r
=10
-2
thus
resulted in a Mg
2+
concentration
corresponding to that reported for the field.
For all major components, the single
calibration factor X
r
=10
-2
sufficed to
account for the scale-dependence of mineral
weathering rates, and resulted in modelled
concentrations and pH that were close to
those reported for the field (Fig. 5b). The
possible physical reason for the difference
between absolute literature values of
weathering rates, used in the model, and the
field weathering rates were further
investigated in the laboratory study in Papers
III-VI (Chapters 6-7). With regards to the
field model, assumption of solubility
equilibrium between solution and gypsum
lead to improved reproduction of field Ca
2+

and SO
4
2-
concentrations (triangles in Fig.
5b), thereby supporting the inclusion of this
process in the conceptual model. Remaining
discrepancies between model results and
field observations are considered small,
given the uncertainty associated with, for
example, the limited availability of data from
only a small number of observation points.

18
The only major exception to the good
agreement between results of the calibrated
model and field observations was the Zn
2+

concentration, where the modelled
concentration was approximately three
orders of magnitude lower than the field
concentration (Fig. 5a and b). This suggested
that Zn
2+
release in the field was controlled
by processes other than oxidation of
sphalerite by oxygen or Fe(III), or that, for
example, dissolution of sphalerite is
accelerated by galvanic interactions with
other sulfide minerals (e.g., Kwong, 2001,
and references therein; see also Chapter
2.2.1 and Chapters 6 and 7).
4.3.2 Dominant processes and turnover times
The calibrated model was analysed for
dominant processes that contributed to the
proton balance, oxygen consumption, redox
cycling of iron, and composition of the
groundwater in the deposit. For full oxygen
availability, the major processes contributing
to the proton balance were pyrite oxidation
by dissolved molecular oxygen (proton
release) and chlorite dissolution (proton
-7
-6
-5
-4
-3
-2
-1
0
1
-6 -5 -4 -3 -2 -1 0
log average field concentration [M]
l
o
g

m
o
d
e
l

c
o
n
c
e
n
t
r
a
t
i
o
n

[
M
]

-
-

Fe(tot)
SO
4
2-
Ca
2+
Zn
2+
Al
3+
Na
+
K
+
Mg
2+
Cu
2+
/10
free H
+
a)

-7
-6
-5
-4
-3
-2
-1
0
1
-6 -5 -4 -3 -2 -1 0
log average field concentration [M]
l
o
g

m
o
d
e
l

c
o
n
c
e
n
t
r
a
t
i
o
n

[
M
]

Fe(tot)
SO
4
2-
Ca
2+
Zn
2+
Al
3+
Na
+
K
+
Mg
2+
Cu
2+
/10
free H
+
b)

Figure 5. Modelled concentrations of components (Paper I, Po2 = 0.2 atm) vs. reported (Ekstav
and Qvarfort, 1989) average concentrations in Impoundment 1 groundwater (see Table 3).
a) Initial model results; b) results after allowance for scale-dependent weathering rates through
application of Xr (Xr = 0.02). The source of SO4
2-
and Ca as indicated by diamonds is sulfide
oxidation and plagioclase weathering, respectively; triangles in b indicate effect of assuming
solubility equilibrium with gypsum, after application of Xr. The solid diagonal line indicates
perfect prediction, where modelled and observed concentrations coincide. Vertical bars
indicate the range of concentrations reported for the field.

19
consumption; Fig. 6a, filled bars). This
explains why the pH was not greatly affected
by application of X
r
(compare Figures 5a
and b); the rates of the reactions dominating
proton production and consumption were
scaled by the same factor. As well as being
the major source of protons, oxidation of
pyrite by dissolved molecular oxygen was
found to be the major source of Fe(II) and
SO
4
2-
and the major sink of dissolved
molecular oxygen (Fig. 6). Pyrite oxidation
by ferric iron was relatively low (Fig. 6), due
to low solubility of Fe
3+
at pH ~5. Ferrous
iron oxidation was also low; Fe(II) was
found to be the dominant redox form of
iron.
As well as being a major sink for protons
(Fig. 6), chlorite dissolution was also the
source of Mg
2+
, the main source of Al
3+
and
Si, and a minor source of Fe(II) and Fe(III).
Dissolution of muscovite and plagioclase
had only a minor effect on the proton
balance (not shown), but were sources of
K
+
, Na
+
, and Ca
2+
, as well as of Al
3+
and Si.
Evolution of groundwater impoundment
geochemistry will depend on factor such as
decrease in mineral content with time.
Nonetheless, first-hand estimates of
turnover times for primary minerals in the
unsaturated zone of the deposit can be made
by division of the amount of each mineral
(Table 2) by their respective, modelled
dissolution rate (see e.g., Strmberg and
Banwart, 1994; Banwart and Malmstrm,
2001) after application of X
r
. For full oxygen
availability (Po
2
= 0.2 atm), pyrite had the
shortest turnover time of in the order of 100
years. As pyrite is the major source of
protons, the characteristic turnover time of
pyrite also provides a first hand estimate of
the expected duration of AMD production
(e.g., Banwart and Malmstrm, 2001). The
characteristic turnover times for the other
primary minerals in the model, that is,
sphalerite, chalcopyrite, and aluminosilicates,
were in the order of 10
3
-10
4
years. As Zn
2+

-0.8 0.0 0.8
SO
4
2-
b)
-0.1 0.0 0.1
Fe(III)
2
d)
-1.0 0.0
O
2
(aq)
2
e)
-0.8 0.0 0.8
Fe(II)
2
c)
-0.8 0.0 0.8
H
+
a)
i) R
feo
ii) R
pyo
iii) R
pyf
iv) R
ch
v) Outflow
vi) Fe(OH)
3
(s)
vii) Gypsum
Fig. 6. Modelled fluxes of components from different processes normalised to the deposit surface area
[mol m
-2
s
-1
], of a) H
+
; b) SO4
2-
; c) Fe(II); d) Fe(III); and e) O2(aq) for a fixed Po2 of 0.2 atm (filled
bars) and 0.002 atm (open bars). Processes are i) ferrous iron oxidation, ii) pyrite oxidation by oxygen,
ii) pyrite oxidation by Fe(III), iv) chlorite dissolution. Processes vi)-vii) show the effect of solubility
equilibrium between aqueous solution and the given secondary phase.


20
release in the model underestimated Zn
2+

release in the impoundment by
approximately 3 orders of magnitude, the
turnover time of sphalerite is potentially
much lower.


21
5 MODEL SENSITIVITY AND REMEDIATION IMPLICATIONS
The sensitivity of model results to uncertainties such as may arise from natural variability in
physico-chemical characteristics of the deposit and individual minerals, uncertainty in the
experimentally determined kinetic parameters, and possible unquantified parallel reaction
pathways, is presented in the following Chapter 5.1 (see also Paper I, as well as Salmon, 2000, and
Salmon and Malmstrm, 2002). In Chapter 5.2, the model is used to approximate the evolution
of the impoundment groundwater geochemistry with time under unremediated and remediated
conditions (e.g., see Paper II); implications of this for Impoundment 1, and modelling of tailings
AMD in general, are highlighted.

5.1 Sensitivity analysis
5.1.1 Oxidation processes
Abiotic rate expressions were applied in the
model for pyrite oxidation by O
2(aq)
(R
pyo
) and
Fe(III) (R
pyf
), as well as Fe(II) oxidation (R
feo
;
see Reactions 1, 2, and 10 in Table 1; see
also Fig. 1). However, as discussed in
Chapter 2, these oxidation processes may be
accelerated by a variety of processes; in the
absence of rate laws explicitly defining the
rates of such parallel reactions, the sensitivity
of model results to such mediation was
tested by application of factors
2
O
,
Fe
, and
to R
pyo
, R
pyf,
, and R
feo
, respectively. The
values of
Fe
,
2
O
, and were varied over a
range of values that corresponds to the
effect of microbial mediation under
favourable laboratory conditions, as reported
in the literature (see Chapter 2.1.1). Testing
in this manner also reveals sensitivity to
uncertainty in rate expressions, for example
due to choice of rate law (Salmon and
Malmstrm, 2002), mineral surface area
(mineral content and tailings specific surface
area, cf. Equation 6), rate constant, and
activation energy (E
a
).
Model results indicated that the overall rate
of pyrite oxidation is the result of complex
interactions between the processes depicted
in Figure 1, pH, and O
2
availability, and also
depends upon the presence/absence of
Fe(OH)
3(s)
. For example, acceleration of
pyrite oxidation by Fe(III) (i.e., R
pyf,
with
Fe
>1) alone had almost no effect (not
shown). However, acceleration of Fe(II)
oxidation (>1; Fig. 7a-b, Po
2
=0.2 atm) lead
to an increase in R
pyf
(compare Fig. 8a and b)
and a decrease in the overall pH (Fig. 7b).
For in the order of 10
3
, R
pyf,
was the
dominant source of protons (Fig. 8b).
The rate of pyrite oxidation by Fe(III) was
also increased with an increase in R
pyo
. The
higher rate of proton production associated
with a value of
2
O
as small as 3.5 was not
compensated by an increase in the kinetically
limited chlorite dissolution rate, but by
increased Fe(OH)
3(s)
dissolution to maintain
solubility equilibrium with solution (Fig. 8c).
Dissolution of Fe(OH)
3(s)
also released Fe
3+
,
and by this means lead to increased
importance of R
pyf,
, which then contributed
up to ~ 40% and ~50% of the total proton
(Fig. 8c) and Fe(II) release, respectively. For
a given value of
2
O
> 1, removal of the
condition of solubility equilibrium between
Fe(OH)
3(s)
and solution led to lower pH (e.g.,
in Fig. 5b;
2
O

= 3.5), as then determined
by the balance between pyrite oxidation and
aluminosilicate dissolution only. Under these
conditions, the contribution by the ferric
iron pathway for pyrite oxidation was
insignificant, as there was no readily
available source of ferric iron.
All simulation results in Figure 7a-d are
plotted in Figures 7e and f as a function of
Fo
2
. Irrespective of the values of
2
O
,
Fe

and and dominance of R
pyo
or R
pyf,
, SO
4
2-

concentrations are determined by Fo
2
(Fig.
7e), as is consistent with conclusions of, e.g.,
Elberling and Nicholson (1996). However at
low Fo
2
, SO
4
2-
release is determined by
gypsum dissolution. The pH, on the other
hand, was sensitive to buffering processes,
for example, whether solution was at

22
solubility equilibrium with Fe(OH)
3(s)
, and to
values of
2
O
and , even at low Fo
2
(Fig.
7f).
Model results, and in particular, the proton
balance and pH, are thus sensitive to
relatively small changes in the rate of pyrite
oxidation, irrespective of whether the
changes are due to, for example, microbial
mediation or uncertainty in mineral surface
area. This implies that more detailed
quantification of microbial processes on the
field scale, and the surface area of the sulfide
minerals available for reaction, is important
for prediction of impoundment groundwater
composition and pH.
5.1.2 pH-buffering processes
Given the importance of pH for the
environmental impact of AMD, model
results were tested for sensitivity to
uncertainty in pH-buffering processes,
namely, chlorite dissolution and the
condition of solubility equilibrium between
aqueous solution and Fe(OH)
3(s)
. To start
with, simulation of pH-buffering by
aluminosilicate weathering alone, by removal
of the forced solubility equilibrium between
1 10 100 1000 10000
0.01
0.10
1.00
S
O
4
2
-

c
o
n
c
e
n
t
r
a
t
i
o
n

[
M
]
a)
1 10 100 1000 10000
1
2
3
4
5
6
7
8
p
H
b)

1 10 100 1000 10000
0.01
0.10
1.00
S
O
4
2
-

c
o
n
c
e
n
t
r
a
t
i
o
n

[
M
]
c)
1 10 100 1000 10000
1
2
3
4
5
6
7
8
p
H
d)

1E-7 1E-6 1E-5 1E-4
F
O
2
[moles m
-2
s
-1
]
0.01
0.10
1.00
S
O
4
2
-

c
o
n
c
e
n
t
r
a
t
i
o
n

[
M
]
e)
1E-7 1E-6 1E-5 1E-4
F
O
2
[moles m
-2
s
-1
]
1
2
3
4
5
6
7
8
p
H
f)

Figure 7. Modelled SO4
2-
concentrations and pH as function of (panel a-d) and Fo2
[mol m
-2
s
-1
] (panel e and f) with
Fe
= 1, where and
Fe
represent the magnitude of
acceleration of ferrous iron oxidation and the ferric iron pathway for pyrite oxidation,
respectively. Filled symbols indicate Po2 = 0.2 atm, open symbols indicate Po2 = 0.002 atm.
Symbol shapes indicate the value of
2
O
: o =1, =3.5, =10, =35. Black crosses indicate
simulations without solubility equilibrium between aqueous solution and Fe(OH)3(s) (
2
O
= 3.5,
Po2 = 0.2 atm).

23
Fe(OH)
3(s)
and the aqueous phase, had little
effect on pH and component
concentrations, as Fe(OH)
3(s)
dissolution was
not a major process (cf. Fig. 6a).
The sensitivity of the groundwater
composition and pH to uncertainty in the
chlorite rate constant and/or chlorite
content was tested by increasing or
decreasing the rate expression for chlorite
weathering, R
ch
, by a factor
ch
, the
magnitude of which was varied by up to an
order of magnitude. The impact of this on
the proton balance and pH is shown in
Figure 9. Increase in R
ch
by as little as a
factor of two led to an increase in pH to
around neutral (Fig. 9f). Further increase in
R
ch
lead, as expected as a result of the
associated increase in proton consumption,
to further increase in pH (Fig. 9e and f), and
correspondingly higher concentrations of
Mg
2+
and Al
3+
.
A decrease in R
ch
by a factor of two led to a
drop in pH by about half a unit (Fig. 9f).
With further decrease in R
ch
,

the influence of
the chlorite weathering rate on the proton
balance became insignificant
(Fig. 9a). As for increased
2
O
in Chapter
5.1.1, the expected decrease in pH was
mitigated to an extent by increased
dissolution of Fe(OH)
3(s)
. This maintained
the pH at ~4.3, but also implied faster
depletion of Fe(OH)
3(s)
(compare Fig. 9a-c).
Removal of both aluminosilicate weathering
and Fe(OH)
3(s)
dissolution from the model,
that is, simulation of the conditions after the
depletion of Fe(OH)
3(s)
without
consideration of aluminosilicate weathering,
resulted in a pH below 2.
These simulations indicated that, while Fe
and SO
4
2-
concentrations and pH in
Impoundment 1 could be reproduced
without aluminosilicate dissolution as long
as fast-dissolving minerals were present in
the model, accurate representation of a) the
proton balance, and thus the rate of
dissolution of Fe(OH)
3(s)
and duration of
pH-buffering by this phase, and b) the pH
after depletion of Fe(OH)
3(s)
, required
consideration of aluminosilicate dissolution.
Furthermore, neglect of aluminosilicate
weathering reactions excluded the possibility
to quantify the primary sources of
components, such as Al
3+
, Mg
2+
, Na
+
, K
+
,
and Ca
2+
, which are released by these
processes, and which may participate in
other geochemical reactions subsequent to
release.

2
O

1 1 3.5 3.5
1 1000 1 1000
pH 4.9 4.1 4.1 3.7
R
feo

R
pyo

R
pyf,

R
ch

Fe(OH)
3(s)

-20 0 20
a)
-20 0 20
b)
-20 0 20
c)

-50 -25 0 25 50
d)
Figure 8. Effect of acceleration of pyrite oxidation by O2(aq) (Rpyo) and Fe(II) oxidation (Rfeo),
through application of given values of
2
O
and , respectively (Po2=0.2 atm), on rates of proton
release and consumption [mol m
-2
s
-1
] by various processes and pH. Process notation as in
Figure 6.

24
5.2 Implications for Impoundment 1
The box model presented in Chapter 4 was
used to provide a first hand approximation
of the temporal evolution of the
impoundment geochemistry, in terms of
processes that have occurred since
deposition and potential future evolution of
a tailings impoundment under continued
unremediated conditions (Chapter 5.2.1 and
Salmon, 2000), as well as potential effects of
changed conditions such as may be caused
by remediation (Chapter 5.2.2 and Paper II).
5.2.1 Geochemical evolution of Impoundment 1
Indications from saturation index
calculations on field data (Chapter 3) were
that Fe(OH)
3(s)
and gypsum exerted
solubility control on aqueous solution; the
modelling study presented in Chapter 4
indicated that these phases were dissolving
to maintain solubility equilibrium with
aqueous solution, raising questions with
regards to where these phases could have
originated from.
The temporal evolution of the
impoundment geochemistry was therefore
approximated by considering consecutive
steady-state periods, or stages. Initial
conditions of mineral content were
16 vol-% pyrite, which was the pyrite
content of the saturated zone of
Impoundment 1, 10 vol-% calcite, as was
reported for the Kristineberg mine
(Qvarfort, 1983), and other minerals in the
same proportions as given in Table 2.
Conditions were kept constant for each
steady-state period; if solution was
oversaturated with respect to a phase likely
to be at solubility equilibrium with aqueous
solution in AMD environments (Nordstrom
and Alpers, 1999), or if such a phase had
precipitated at an earlier stage, solubility
equilibrium between this phase and aqueous
solution was assumed. The duration of each
stage was determined by the turnover time
of the mineral that mass balances indicated
would be the first to be consumed. After
each stage, remaining or accumulated
amounts of minerals were calculated and
used as input conditions for the next steady-
state period (for mathematical formulation,
see Salmon, 2000).
It is not implied that accurate predictions of
the temporal evolution of the impoundment
geochemistry can be made with these simple
calculations; however, this approach
provides a qualitative insight into the time

Rfeo
Rpyo
Rpyf,
Rch
Outflow
Fe(OH)3(s)

-10 0 10
a)

-10 0 10
b)

-10 0 10
c)

-10 0 10
d)

-
5
0
-
4
0
-
3
0
-
2
0
-
1
0
01
0
2
0
3
0
e)

4
5
6
7
8
0 . 1 0 . 5 1 2 1 0

c h
p H
f )
Figure 9. Effect of application of ch on the balance of proton release and consumption [mol m
-
2
s
-1
] for a) ch= 0.1, b) ch= 0.5, c) ch= 1, d) ch= 2, e) ch= 10, and on f) pH.

25
evolution of the processes controlling the
pH and the concentrations of major
components.
Simulations resulted in a sequence of
precipitation and dissolution reactions and
associated consecutive drops in pH (Fig. 10)
similar to that which has previously been
described in the literature (e.g., Blowes and
Ptacek, 1994). Buffering of the pH was due
to the fast dissolution of, in order of
succession, calcite, siderite (FeCO
3(s)
) and
aluminium and ferric iron hydroxides. After
depletion of ferric iron hydroxide, the pyrite
content was 11 vol-%; the pH was
controlled only by the relative rates of pyrite
oxidation and aluminosilicate dissolution,
resulting in a pH below three. The lifetime
of the pyrite in this simulation, and hence
the duration of the acidic pH, was in the
order of 1000 years. After depletion of
pyrite, the modelled pH returned to above
neutral (not shown).
As indicated in Chapter 5.1.2, the rate of
dissolution of fast-reacting minerals, such as
carbonates and hydroxides, required to
maintain solubility equilibrium with solution
would be greater in the absence of proton
attenuation by aluminosilicates. Modelling
without consideration of aluminosilicates
would in a scenario such as that depicted in
Figure 10 lead to underestimation of the
time to reach acid pH, and furthermore, the
simulated final low pH, as determined only
by pyrite oxidation and iron redox processes,
would be lower. Implications for the
geochemical modelling of the groundwater
composition of Impoundment 1 include that
it may be plausible that a sufficient amount
of Fe(OH)
3(am)
and gypsum accumulated in
Impoundment 1 to be the dissolving at the
point in time represented by the case study,
~30 years after deposition.
5.2.2 Effect of remediation
Following a post-remediation investigation
of the performance of a composite soil
cover applied on parts of Impoundment 1,
Werner et al. (2001) reported an oxygen flux
of ~ 1 x 10
-8
mol m
2
s
-1
and a water
infiltration rate of <1 x 10
-9
m s
-1
. These
values correspond, compared to the pre-
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 10 20 30 40 50
Time (years)
C
o
n
c
e
n
t
r
a
t
i
o
n

(
m
o
l

l

-
1
)
0
1
2
3
4
5
6
7
8
p
H
SO
Fe(II)
Al
pH
Stage i)
calcite
siderite
Al(OH)
3
Fe(OH)
3
gypsum
ii) siderite
Al(OH)
3
Fe(OH)
3
gypsum
iii) Al(OH)
3
Fe(OH)
3
gypsum
v) gypsum
iv) Fe(OH)
3
gypsum
4
2-
3+

Figure 10. Evolution of modelled pH and concentrations of SO4
2-
, Fe(II), and Al(III) with time.
Mineral phases noted are those at solubility equilibrium with aqueous solution during the
various different stages. Stage v) is estimated to continue for another ~120 years, after which
gypsum will be totally depleted. Pyrite oxidation is estimated to continue for an additional
10
3
years. Parameter values:
2
O
=
Fe
=3.5; =1: flowrate, q=7.7x10
-8
dm s
-1
; Po2= 0.1 atm.

26
remediation situation assessed in the case
study, to a 1-2 order of magnitude decrease
in both the oxygen and water fluxes.
As shown in Figure 7e and f, such a
dramatic decrease in the oxygen influx
would be sufficient to slow down pyrite
oxidation to a level where the resulting pH is
above 7. Inclusion of the kinetic
representation of Fe redox processes
allowed testing of the hypothesis that, with
decreasing oxygen availability, the oxidation
of pyrite by ferric iron would dominate over
the oxygen path; however, this hypothesis
was not supported by the model results,
even in simulations with the maximum
degree of acceleration that is reportedly
possible due to microbial mediation
(
2
O
=
Fe
= 35, = 10
4
- 10
6
). Simulations
with low Fo
2
and in the absence of
aluminosilicate dissolution resulted in lower
predicted pH, of ~5, as controlled by
solubility equilibrium with Fe(OH)
3(s)
.
Decrease in the water flux alone, with the
fixed partial pressure of oxygen of 0.2 atm,
had little effect on the pH, but did, however,
result in higher concentrations of dissolved
components (Paper II). As the
impoundment has only relatively recently
been remediated, the long-term efficiency of
the applied techniques has not been
assessed. However, comparison of release
rates in saturated column experiments with
Impoundment 1 tailings (Paper VI) with
pre-remediation release rates (see Chapter 7)
indicated that sulfide oxidation rates do
decrease under saturated conditions.
Holmstrm et al. (2001) and Corrge et al.
(2001) also report positive trends in the
impoundment water quality a few years after
remediation.

27
6 QUANTIFICATION OF ELEMENT RELEASE RATES FROM BATCH
EXPERIMENTS

The modelling study of Impoundment 1 indicated that mineral weathering rates from literature,
based on experiments on freshly prepared, monomineralic samples, overestimated rates observed
in the field by 1-2 orders of magnitude, despite consideration of dependence of rates on pH,
temperature, mineral content, and (BET) surface area of tailings, and differences in these
physico-chemical conditions between the laboratory and the field. This chapter presents results
of weathering experiments that were then performed on different tailings samples and sulfide
minerals in order to test whether literature rates and rate dependencies were applicable for
weathering of minerals in tailings (Papers III-V). In addition, the effect of application of various
sterilisation techniques, as is necessary to obtain abiotic weathering rates in tailings samples, on
the weathering characteristics of tailings were tested (Paper IV). The experimental method is only
briefly described below; Papers III-V are referred to for details.

6.1 Materials and methods

Tailings were obtained from Impoundment
1 in August 1999 from near the original
tailings dam wall, far from the original
tailings slurry discharge point (fine tailings
sample) and in August 2000 from near the
original discharge point (coarse tailings
sample); this distribution of fine and coarse
particles is typical for tailings impoundments
(e.g., Robertson, 1994). A sulfide
concentrate was obtained from the coarse
tailings by decanting of fine particles,
gravimetric separation of the heavy fraction,
and sieving to 0.035-0.5 mm size. Pyrite
crystals were purchased (geographic origin
unknown), crushed in a ceramic mortar and
pestle and sieved to obtain a 0.125-0.25 mm
fraction. Both sulfide concentrate and pyrite
crystals were treated briefly with ultrasound
in order to remove fine particles, which may
otherwise result in unrepresentative high
initial release rates (e.g., Nicholson, 1994).
The mineralogy of the 2 tailings samples, the
sulfide ore concentrate, and the pure pyrite
was determined by X-ray diffraction (XRD),
and samples were analysed for total chemical
composition. Tailings samples were further
characterised by infrared spectroscopy (IR)
and optical microscopy (including point
counting of opaque minerals in thin
sections). The particle size distribution of
the tailings was determined with a laser
granulometer, and the specific surface area
of all samples was determined by evaluation
of 5- and/or 1-pt N
2
adsorption data. The
results of the mineralogical determinations
were consistent with other determinations
for the major minerals in Impoundment 1 as
reported in Malmstrm et al. (2001),
Holmstrm et al. (2001), and Carlsson et al.,
2002); based on the mineralogy and total
chemical composition, the mineral content
of the tailings samples was estimated (Table
4; see Paper V).
Table 4. Estimated mineral content and
BET surface area
Fine
tailings
Coarse
tailings
Pyrite 18 18
Chalcopyrite 1 0.2
Sphalerite 0.6 1
Quartz 28 40
Chlorite
a
26 25
Muscovite
b
14 7
Plagioclase
c
12 6
Surface area
[m
2
g
-1
]
10.0 1.2
a
Chlorite and talc represented as chlinochlore,
(Mg5Al)Si3AlO10(OH)8
b
KAl2(AlSi3)O10(OH)2
c
Na0.55Ca0.45Al1.45Si2.55O8


28
The higher pyrite content in the tailings
samples (~18 vol-%; Table 4), which were
collected from the saturated zone, than was
estimated for the unsaturated zone (~4
vol%; Table 2) is consistent with other
reported solid phase characterisation of the
saturated zone (e.g., Malmstrm et al., 2001;
Holmstrm et al., 2001). The difference in
mineral contents between the water
saturated and unsaturated zone is likely due
to partial depletion of sulfides in the upper
part of the impoundment (see Chapter 3
and 4.1).
The XRD analyses confirmed that the pyrite
sample was pure within the detection limits
of the XRD (~5 %). The sulfide concentrate
was found to consist predominantly of
pyrite with some traces of feldspar,
pyrrhotite, and possibly sphalerite.

6.2 Effect of pH, temperature, and
surface area
6.2.1 Weathering experiments
Weathering experiments were performed on
fine and coarse tailings, sulfide concentrate,
and pure pyrite over 89-480 days, at
different conditions of pH, temperature, and
acid medium; selected conditions are given
in Table 5. Approximately two to six grams
of samples were placed in 200 or 400 mL
solution. Reactors were continually agitated
and air-sparged. The pH and (in all but B4)
redox potential were measured either in
filtered samples or in reactors. Direct
measurement of redox potential in fine
tailings reactors with H
2
SO
4
(C1, C7, C8),
and on last 2 sampling occasions in the pure
pyrite reactor (C12) lead to influx of the
redox electrode electrolyte (KNO
3
) to the
reactor solution. Redox measurement over
an extended period of time on Day 74 in C7
and Day 94 in C1 directly preceded an
increase in the SO
4
2-
release rate in these
reactors, as is discussed in the results section
below (see also Paper V). For the C-series
experiments, the solid phase was collected
after closure of the experiments for
mineralogical analysis using XRD and IR.
Samples were analysed for concentrations of
SO
4
2-
and major cations (see Papers III-V
for analysis techniques). Calculation of
saturation indices indicated that, for the
majority of components during the period of
time over which release rates are derived,
aqueous concentrations were generally not
controlled by solubility equilibrium with
typical phases for AMD, with the major
exception of iron.

Table 5: Experimental conditions
a
C-series G-series
d
E-series
Reactor
B4
b

C1 C7 C8
c
C12 G1 G2 E1 E2 E3
Material Fine
tailings
Fine
tailings
Fine
tailings
Fine
tailings
Pyrite Coarse
tailings
Coarse
tailings
Sulfide
conc.
Sulfide
conc.
Sulfide
conc.
pH

~3 ~3 ~2 ~3 ~3 ~2 ~2 ~2 ~3 ~5
Acid medium HNO3 H2SO4 H2SO4 H2SO4 H2SO4 H2SO4 HNO3 HNO3 HNO3 NaHCO3
Start Dec99 Nov00 Nov00 Dec00 Dec00 Nov01 Nov01 Jun02 Jun02 Jun02
Duration
[day]
89 480 480 343 455 100 100 35 35 35
a
See also Table 4, Paper V
b
Preliminary results reported in Salmon and Malmstrm (2001; Paper III)
c
5C; other experiments at ~231 C.
d
Preliminary results reported in Salmon and Malmstrm (2003; Paper IV)


29
6.2.2 Results
Sulfate release in fine tailings under
different conditions of pH, acid medium,
and temperature are shown in Figure 11a.
For fine tailings at 25 C, two release rate
regimes were observed. In the experiment
with pH ~3 in HNO
3
, performed soon after
collection of tailings, a typical pattern for
bacterial leaching (e.g., Rossi, 1990) was
observed, with a fast release rate, or
accelerated release, after a lag phase of ~8
days (Fig. 11a). By contrast, in later
experiments with the same tailings and pH,
but in H
2
SO
4
medium, the SO
4
2-
release rate
remained approximately constant until ~Day
96, after which a similarly accelerated release
was observed. A similar pattern was also
observed in the pH 2 H
2
SO
4
reactor (Fig.
11a). After the period of high release rate in
all reactors, approximately 70-90% of the S
initially present in the solid phase in each
reactor had been released to solution,
suggesting that the main S-source, pyrite,
was completely or effectively depleted at this
point or soon after. The greater delay before
the accelerated rate in the H
2
SO
4
reactors
may be due to an extended lag phase after
approximately a year of storage, and/or
addition of K
+
and NO
3
-
, possibly acting as
nutrients for the micro-organisms, on the
preceding sampling occasion (see above).
The similar release rates at pH ~2 and pH
~3 in both the accelerated and non-
accelerated period suggests low to negligible
pH-dependence of the dominant S-releasing
process.
In the reactor with coarse tailings in HNO
3

(not shown; see Paper V), the final SO
4
2-

release rate was by contrast somewhat lower
than the initial rate; the mass-normalised
release rate [mol g
-1
day
-1
] was also lower
0.E+00
2.E-03
4.E-03
0 100 200 300 400
time [day]
A
c
c
.

S
O
4
2
-

r
e
l
e
a
s
e

[
m
o
l
/
g
]
25 C, pH ~3, HNO3
25 C, pH ~3, H2SO4
25 C, pH ~2, H2SO4
5 C, pH ~3, H2SO4
a) fine tailings

0.E+00
1.E-04
2.E-04
0 100 200 300 400 500
time [day]
A
c
c

M
g

r
e
l
e
a
s
e

[
m
o
l
/
g
]
coarse tailings, pH ~2
fine tailings, pH ~2
fine tailings, pH ~3
b) 25 C, H
2
SO
4
medium
0.E+00
4.E-05
8.E-05
0 100 200 300 400 500
time [day]
A
c
c

Z
n

r
e
l
e
a
s
e
[
m
o
l
/
g
]
25 C, coarse tailings, pH ~2
25 C, fine tailings, pH ~3
5 C, fine tailings, pH ~3
c) H
2
SO
4
medium

Figure 11. a) Accumulated release of SO4
2-
in fine tailings experiments, and b) Mg
2+
and c) Zn
2+
in
fine and coarse tailings experiments.

30
than the non-accelerated rate in the fine
tailings. The coarse tailings did not exhibit a
period of accelerated SO
4
2-
release in either
HNO
3
or H
2
SO
4
medium. A possible
explanation for the accelerated release
period in the fine tailings but not in the
coarse is that in the absence of other
nitrogen sources, the low levels of nitrate in
the fine tailings reactors were utilised as a N
source (Erlich, 1996, and references therein).
At higher concentrations, however, nitrate
has been reported to inhibit microbial
activity (e.g., Harahuc et al., 2000); it is also
reported to have greater toxicity at lower pH
(Alexander et al., 1987), and may therefore
have had an inhibiting effect on microbial
activity in the coarse tailings reactor with
HNO
3
. Over the course of the coarse
tailings experiment (~100 days), less than
10% of the S in the coarse tailings was
released to solution.
In the reactor with fine tailings (H
2
SO
4
) at
5C (Fig. 11a), the SO
4
2-
release rate was
lower than that at 25C, and constant over
the ~340 days of the experiment. Sulfate
release rates in the sulfide concentrate
reactors (not shown, see Paper V) were
constant with time, over the ~40 days of
experiments. Release in the pure pyrite
reactors was constant for the first ~150
days, and also for the latter 300 days of the
experiments, but at a lower rate.
The increase in SO
4
2-
release in all fine
tailings reactors was accompanied by a drop
in pH, by up to 1 pH unit in rectors at pH 3,
and an increase in redox potentials (not
shown). In reactors where pH decreased by
up to one pH unit over the experiments, an
increase in the release rate of base cations
was observed (e.g., Fig. 11b; see also Fig.3
in Paper V). However, in reactors at pH ~2,
where the pH remained relatively constant,
base cation release generally decreased with
time (Fig. 11b), a phenomenon commonly
observed in aluminosilicate weathering
experiments (e.g., Malmstrm and Banwart,
1997; Brandt et al., 2003; Gustafsson and
Puigomenech, 2003), and suggested to be
due to processes such as preferential
leaching of metal ions, weathering and
depletion of fine particles and/or more
reactive sites on freshly exposed mineral
surfaces (e.g., White and Brantley, 1995).
Indications were that initial Ca
2+
release in
coarse tailings was affected by gypsum
dissolution (see Paper V); if this process
occurred in the fine tailings, it did not
appear to affect Ca
2+
release rates.
For fine and coarse tailings and the sulfide
concentrate, Zn
2+
and Cu
2+
release was
initially fast, then decreased to level off
before 100% was released to solution (e.g.,
Zn
2+
in Fig. 11c), irrespective of SO
4
2-

release pattern, acid medium (HNO
3
/
H
2
SO
4
), or temperature (5/25C). In the
reactors with fine tailings at 25C, the
remaining Zn
2+
was released to solution at
the same time as the accelerated SO
4
2-

release rate; the accumulated Cu
2+
release
was not affected. Both Zn
2+
and Cu
2+
release
rates displayed low dependence on pH but
high dependence on temperature. A
decrease in leaching rates with time is
commonly observed in leaching experiments
of chalcopyrite and sphalerite, and is
suggested to be due to, for example,
decrease in surface area due to reduction of
particle size, or formation of a leached layer
on the mineral surface such that dissolution
becomes transport-limited. A shrinking
radius model relatively successfully explained
the Zn
2+
and Cu
2+
release (Papers III and V).
In summary, release rates of base cations
and Al
3+
and Si were affected by pH, which
was not the case for release of SO
4
2-
, Zn
2+
,
or Cu
2+
. Some fine tailings reactors exhibited
periods of accelerated sulfate release, which
was tentatively assigned to microbial
mediation. In experiments with relatively
constant pH, initial release rates of, for
example, Mg
2+
were higher than final release
rates. Release rates [mol/g/day] were
generally lower in coarse tailings than in fine
tailings, and at low temperature than at high
temperature.


31
6.3 Effect of sterilisation
6.3.1 Experimental method
Weathering experiments and BET surface
area determinations were performed on
coarse tailings sub-samples that had been
subjected to various traditional and novel
methods of sterilisation (see Table 6, Paper
IV and Herbert et al., 2003). Sterilisation was
found to have little effect on the bulk
mineralogy or total chemical composition;
however, oxidised sulfur surface species and
non-hydrocarbon surface C, as well as
ascorbate-extractable metals, increased as a
result of some treatments (see Herbert et al.,
2003).
Procedures for weathering experiments were
similar to in the other experiments (Chapter
6.2.1) with the exception that measures were
taken (see Paper IV) to prevent microbial
contamination of reactors. Extra samples
were also collected from all reactors for
staining with 46-diamidino-2-phenylidole
(DAPI). This process leads to fluorescence
of DNA and organic material under UV
light, and is generally used for total count of
viable bacteria in aqueous solution.
6.3.2 Results
In the sterilisation experiments, the BET
surface area of the sterilised samples was
found to be on average slightly lower than in
the untreated samples, possibly due to, e.g.,
loss of fine particles during the sterilisation
treatments. However, the mineralogical and
chemical analysis of the tailings, as
mentioned above, indicated that the bulk
composition did not vary more between
treated and untreated samples than between
untreated controls. Release rates in the
sterilisation experiments generally followed
the same pattern as in the untreated controls
(coarse tailings reactors G1 and G2, see
Chapter 6.2), with the exception of reactors
where inspection by fluorescent microscopy
revealed the presence of large amounts of
organic filaments, probably fungal.
Filaments were only observed in reactors
where sterilisation of tailings had not been
performed or was reportedly unsuccessful
(see Table 6).
Final and initial element release rates,
obtained from linear regression on element
release data in the reactors containing
sterilised (G3-9) and untreated controls and
normalised to the BET-surface area of each
sample, are given in Figure 12. In both
treated and untreated samples, initial rates
Table 6. Applied sterilisation technique and degree of microbial activity.
Phase Reactor
a
Tailings treatment
Degree of
microbial activity
c

G1 Phase I control - untreated
b
high
G2 Phase I control - untreated high
G3 autoclave none
G4 repeated heating to 70C none
I
G5 ethanol none
G6 antibiotics mixture medium
G7
-irradiation 10 kGy
none
G8
-irradiation 25 kGy
none
G9 rinsed with distilled water
e
high
II
G10 Phase II control- untreated high
a
Reactor name in weathering experiments.
b
Solution was 0.05 M H2SO4, as opposed to 0.1 M HNO3 as used in the other reactors.
c
Detected after 30 days (Herbert et al., 2003).


32
exceeded final rates by up to a factor of 35.
Higher initial release rates may be due to, for
example, dissolution and depletion of fine
particles with high specific surface area or of
secondary minerals present in the tailings.
Final release rates of all elements were
similar in most of the reactors (Fig. 12),
irrespective of the presence/absence of
filaments and which/whether a sterilisation
technique had been applied (cf. Table 6),
with the exception of reactors where large
amounts of filaments were observed, that is,
G6, G9 and final Cu
2+
release rate in G10
(see Paper IV). The similarity of final release
rates from the majority of reactors suggested
that the sterilisation methods, other than
treatment with antibiotics, do not
mechanically or chemically affect the long-
term weathering of the tailings, given the
experimental conditions. Normalisation to
sample weight instead of the BET-surface
area of each sample does not affect this
conclusion (compare Fig.12 with Fig. 2 in
Paper IV). An implication of the decline in
release rates with time is that long-term
experiments (> 30 days) are to be
recommended for establishment of
weathering rates in untreated and sterilised
mill tailings samples.
The results also indicated similar release
rates of elements between sterilised and
untreated samples at the end of the
experiments. While other explanations were
possible (see Paper IV), these results indicate
that biological mediation of sulphide
oxidation is not favoured at the experimental
conditions, possibly due to, e.g., nutrient
limitation or inhibition due to high nitrate
concentration at low pH (e.g., Alexander et
al., 1987), and that abiotic processes
dominate the release of elements.

0.0E+00
6.0E-06
1.2E-05
G
1
G
2
G
3
G
4
G
5
G
6
G
7
G
8
G
9
G
1
0
r
a
t
e

S

r
e
l
.

[
m
o
l

m
-
2

d
a
y
-
1
]
-
-
-

initial rate
final rate
a)
0.E+00
5.E-08
1.E-07
G
1
G
2
G
3
G
4
G
5
G
6
G
7
G
8
G
9
G
1
0
r
a
t
e

C
u

r
e
l
.

[
m
o
l

m
-
2

d
a
y
-
1
]
b)

0.0E+00
4.5E-07
9.0E-07
G
1
G
2
G
3
G
4
G
5
G
6
G
7
G
8
G
9
G
1
0
r
a
t
e

M
g

r
e
l
.

[
m
o
l

m
-
2

d
a
y
-
1
]
c)
0.0E+00
1.0E-06
2.0E-06
G
1
G
2
G
3
G
4
G
5
G
6
G
7
G
8
G
9
G
1
0
r
a
t
e

Z
n

r
e
l
.

[
m
o
l

m
-
2

d
a
y
-
1
]
d)

Figure 12. Initial and final element release rates normalised to tailings surface area
[mol m
-2
day
-1
] for a) SO
4
2-
, b) Cu
2+
, c) Mg
2+
, and d) Zn
2+
.


33
7 MODELLING WEATHERING
RATES ON BATCH, COLUMN,
AND FIELD SCALE
7.1 Model interpretation of element
release rates
Conceptual understanding of element release
rates, as is important for interpretation of
impoundment groundwater composition
and prediction of its evolution with time,
relies on identification of source processes.
In Papers III and V, element release from
tailings samples were thus attributed to, and
interpreted in terms of, specific mineral
weathering reactions. Element release rates
(R
j
) from batch experiments were used as
tracers for mineral weathering reactions
(Reactions 1, 3, 5, and 7-9 in Table 1).
Copper and Zn
2+
were used as tracers for
the chalcopyrite and sphalerite weathering,
respectively, and Mg
2+
, K
+
and Ca
2+
(or Na
+
)
as tracers for chlorite, muscovite and
plagioclase weathering, respectively. The
pyrite weathering rates was obtained from
release of SO
4
2-
after correction for
contribution of ZnS and CuFeS
2
weathering.
(see Papers III and V). From the obtained
rates [mol g
-1
s
-1
] and the mineral surface
area as estimated by Equation 6, the surface-
area normalised weathering rate of the i
th

mineral, r
i
[mol m
-2
s
-1
] was obtained from:
j i i
j
i
A
R
r
,
= [mol m
-2
s
-1
] (7).
where
i,j
is the stoichiometric coefficient of
tracer j in the weathering reaction of mineral
i. This approach, combined with check of
solubility equilibrium control of tracer
concentrations, correction for multiple
source minerals where possible, and
estimation of surface area through Equation
6, is also applied in consideration of rates
from column experiments (see Chapter 7.3)
and the field study (Chapter 3 and 7.3).
For comparison of results from experiments
at different temperatures, rates were
converted to 23 C using the Arrhenius
equation and the activation energies, E
a
,
given in Table 4 in Paper I, with the
exception of chlorite, where E
a
=60 kJ/mol
was used, in keeping with recent chlorite
weathering studies (Brandt et al., 2003, and
references therein).

7.2 Mineral weathering rates in tailings
compared to monomineralic
samples
7.2.1 Pyrite
Figure 13 shows the obtained pyrite
weathering rates vs the average pH for the
time interval over which the rate was
determined. Despite a decrease in rate with
time, both initial and final rates of pyrite
weathering in the pure pyrite reactor (crosses
in Fig. 13b) were within the range of
reported abiotic pyrite weathering rates in
the literature. This indicates that the applied
experimental method can achieve
comparative rates to those reported in the
literature.
Determination of the pyrite weathering rate
using Equation 7 lead to rates from the
coarse tailings, the non-accelerated release
period of the fine tailings, and the sulfide
concentrate that agreed internally within a
factor ~4 (Fig. 13a). In addition, the rate in
the fine tailings reactor at low temperature
(squares in Fig. 13a), when scaled up to
room temperature, was in the same range.
However, these non-accelerated rates (Fig.
13a) were up to an order of magnitude lower
than the lowest abiotic rates reported in the
literature. Possible explanations may include
that the pyrite weathering rates in the
literature are generally performed on freshly
exposed mineral surfaces, whereas the
reactivity of the pyrite in the tailings had
decreased after 40 years of exposure in the
tailings impoundment, resulting in slower
dissolution rates in the laboratory
experiments. Lower weathering rates in aged
samples has been reported in a number of
weathering studies (e.g., Anbeek, 1993, for
feldspar), and is further supported by the
decrease in the pure pyrite weathering rate
with time in this study.

34
The fact that pyrite weathering rates in the
sulfide concentrate, which was a relatively
well-defined size fraction, also were low
compared to the reported abiotic literature
rates, suggests that the relatively lower rates
in the batch tailings experiments are not due
to overestimation of the pyrite surface area
by Equation 6, which for example may be
the case if pyrite was predominantly present
in coarse size fractions. A further possibility
is that the surface area normalised release
rate is not constant over the different
particle size fractions, as is assumed in
application of literature rate laws,
determined on one particle size, to a particle
size distribution such as in tailings.
Figure 13 highlights that the pyrite
weathering in the tailings and its sulfide
concentrate exhibited low to negligible pH-
dependence for 2 < pH < 4.5, as has
previously been reported in the literature for
monomineralic weathering studies of pyrite
(e.g., Nicholson, 1994; Williamson and
Rimstidt, 1994).
The accelerated rates observed in fine
tailings reactors (Fig. 13b) at 25 C may be
due to microbial mediation. However, rates
are lower than reported microbially mediated
rates (e.g., Olson, 1991; surface area
normalisation reported in Nordstrom and
Alpers, 1999); it is possible that the rates are
limited by the same factor as limiting abiotic
rates, by low concentrations of nutrients, or
by another, unknown factor. The low rates
relative to reported biotic rates are
consistent with the findings described in
Chapter 6.3 and Paper IV, where similar
element release rates were observed in
sterilised and untreated tailings samples,
leading to the conclusion that microbial
mediation was not favoured under the
experimental conditions.
7.2.2 Sphalerite and chalcopyrite
As for pyrite, utilisation of Equation 7 gave
weathering rates from all samples that were
the same to within a factor of approximately
10 for sphalerite (Fig. 14a). Figure 14 also
highlights the low pH-dependence of the
weathering rates of these minerals and that
conversion of sphalerite release from 5 C
using reported activation energies gave
similar rates to those at 25 C (squares in
Fig. 14). For chalcopyrite, rates agree within
a factor 14, and rates for coarse tailings and
fine reactors in H
2
SO
4
at 25 C agree within
a factor 8 (Fig. 14b). The lower rate for
chalcopyrite at 5 C may indicate that the
1.E-11
1.E-10
1.E-09
1.E-08
1.E-07
1.5 2.5 3.5 4.5
pH
[
m
o
l

m
-
2

s
-
1
]
a)
1.E-11
1.E-10
1.E-09
1.E-08
1.E-07
1.5 2.5 3.5 4.5
pH
[
m
o
l

m
-
2

s
-
1
]
b)

Fig 13: Pyrite oxidation rate [mol m
-2
s
-1
] vs pH, 23 C, Po2=0.2 atm. a) Non-accelerated pyrite
oxidation rates; and b) Accelerated pyrite oxidation rate. Data points from this study: pyrite sample
(), sulfide concentrate (), coarse tailings (HNO3-; H2SO4-), fine tailings (HNO3, pH ~3-o;
H2SO4, at pH~3 -, pH~2-, and pH ~3, scaled up from 5 C-). Small/large symbols indicated
initial/final rates. Lines and bars indicate literature values. Abiotic rates in a: horizontal line,
Nicholson (1994: 25 C); diagonal line, Williamson and Rimstidt (1994; 25 C); (
_
), Nicholson and
Scharer, (1994; 22C). Whole and dotted bars in b: Scharer et al. (1994; 30C) and Olson (1991;
28 C), respectively, indicating range of abiotic (lower) and biotic (upper) rates.

35
employed literature value of E
a
is not
representative of chalcopyrite oxidation in
tailings, or that another process, with a
higher E
a
, controls Cu
2+
release. Release was
also higher in the reactor with fine tailings in
HNO
3
(circle in Fig. 14b); of note may be
that this greater release rate occurred at the
same time as the accelerated SO
4
2-
release in
this reactor.
In contrast to the pyrite rates, the
chalcopyrite and sphalerite weathering rates
determined in the batch experiments were
orders of magnitude higher than reported
abiotic rates in the literature, although lower
than reported biotic (Fig. 14) The observed
rates were close to reported abiotic rates for
mineral dissolution in a mixture with pyrite.
As mentioned in Section 2, it was observed
that opaque minerals in the tailings (i.e.,
predominantly sulfides) are often
intergrown; accelerated dissolution of
sphalerite, and other minerals with lower
rest potentials than pyrite in the
electrochemical series, has been reported in
the presence of pyrite (e.g., Kwong, 1993,
2001), and may be the cause of the relatively
higher rates. Further possibilities may
include oxidation of these minerals by
aqueous Fe(III), or predominance of these
minerals in the fine tailings fraction, which
would lead to underestimation of surface
area by Equation 6 and therefore
overestimation of the rate in Equation 7.
7.2.3 Aluminosilicate minerals
Normalisation of aluminosilicate weathering
rates to the BET surface area using Equation
6 and 7 lead to generally higher initial rates
for coarse tailings for chlorite (Fig. 15a) and
plagioclase (Fig. 15c), whereas rates of
muscovite dissolution were similar in coarse
and fine tailings (Fig. 15e,f). For the
plagioclase rate, which is derived from the
Ca
2+
release rate, this would appear to be
due to gypsum dissolution in the initial
stages of the coarse experiments, and is
resolved only by considering later rates of
Ca
2+
release or plagioclase weathering based
on Na release (Figure 15c,d). Higher chlorite
weathering was also found in the fine tailings
reactor at pH ~2; this suggests that the
higher release is a function of preferential
leaching at low pH (e.g., Schnoor, 1990;
Malmstrm and Banwart, 1997; Gustafsson
and Puigdomenech, 2003), and that Mg
2+

release at low pH does not necessarily reflect
chlorite weathering.
While final weathering rates were generally
1-2 orders of magnitude lower than those
reported in the literature, the pH-
dependence of mineral weathering in general
displays the same trends as reported in the

1.E-13
1.E-12
1.E-11
1.E-10
1.E-09
1.E-08
1.E-07
1.5 2.5 3.5 4.5
pH

[
m
o
l

m
-
2

s
-
1
]
a)
1.E-13
1.E-12
1.E-11
1.E-10
1.E-09
1.E-08
1.E-07
1.5 2 2.5 3 3.5 4
pH
[
m
o
l

m
-
2

s
-
1
]
b)

Fig 14: Weathering rates [mol m
-2
s
-1
] vs pH at 23 C. a) sphalerite; and b) chalcopyrite. Markers
denote fine tailings (HNO3, pH ~3-o; H2SO4, at pH~3 -, pH~2-, and pH ~3, scaled up from
5 C-), coarse tailings (HNO3-; H2SO4-), and sulfide concentrate (). Bars indicate the range
of rates reported in the literature (Scharer et al., 1994; 30C); dotted bar - sphalerite/chalcopyrite
alone, dashed bar - sphalerite/chalcopyrite in the presence of pyrite, indicating range of abiotic
(lower) and biotic (upper) rates.

36
literature (e.g., Fig.15b).

1.E-14
1.E-13
1.E-12
1.E-11
1.E-10
1.5 2 2.5 3 3.5 4
pH
r
a
t
e

[
m
o
l

m
-
2

s
-
1
]
a) initial chlorite
1.E-14
1.E-13
1.E-12
1.E-11
1.E-10
1.5 2 2.5 3 3.5 4
b) final chlorite
1.E-13
1.E-12
1.E-11
1.E-10
1.E-09
1.5 2 2.5 3 3.5 4
pH
r
a
t
e

[
m
o
l

m
-
2

s
-
1
]
c) initial plagioclase
1.E-13
1.E-12
1.E-11
1.E-10
1.E-09
1.5 2 2.5 3 3.5 4
pH
r
a
t
e

[
m
o
l

m
-
2

s
-
1
]
d) final plagioclase
1.E-14
1.E-13
1.E-12
1.E-11
1.5 2 2.5 3 3.5 4
pH
r
a
t
e

[
m
o
l

m
-
2

s
-
1
]
e) initial muscovite
1.E-14
1.E-13
1.E-12
1.E-11
1.5 2 2.5 3 3.5 4
pH
r
a
t
e

[
m
o
l

m
-
2

s
-
1
]
f) final muscovite

Fig 15: Initial (left panel) and final (right panel) weathering rates [mol m
-2
s
-1
] (23 C) vs pH.
a, b) chlorite; c, d) plagioclase; and e, f) muscovite; Markers denote fine tailings (HNO3, pH ~3-
o; H2SO4, at pH~3 -, pH~2-, and pH ~3, scaled up from 5 C-) and coarse tailings (HNO3 -;
H2SO4 -). Additional symbols in panel c and d indicate weathering rates derived from Na release
for coarse tailings (HNO3-; H2SO4 -) and fine tailings (H2SO4, pH~2 -). Dashed lines
indicate rates from literature rate laws (chlorite Malmstrm et al., 1995; plagioclase, Oxburgh et
al., 1994; muscovite Knauss and Wolery, 1989). Solid line in b: regression on fine tailings points.
Error bars indicate uncertainty due to unknown tracer stoichiometry (see Table 1 in Paper V).

37
7.3 Comparison: Batch, column and
field rates
In order to further assess the 1-2 orders of
magnitude discrepancy between field and
laboratory weathering rates observed in
Papers I and III, experimental mineral
weathering rates obtained on different scales
were compared directly, before and after
correction for field conditions (Papers III
and V). Element release rates determined on
a mesoscale in water saturated columns
(Table 2 in Paper VI), using similar coarse
and fine tailings as used in the batch
experiments, were preliminarily interpreted
in terms of weathering rates and utilised in
the comparison between different scales. As
the tailings surface area-normalised element
release rates obtained for the two columns
agreed within a factor 3, results from the
coarse tailings column are used here. The
effluent pH from the column over 11
month-experiment was similar to that in the
field, ~5.
Element release rates from the field and
column experiment were assessed as
concentration x flowrate and were
normalised to the mass of material present
(see Papers V and VI). For Impoundment 1,
the mass of tailings in the unsaturated zone
was used, assuming, as in the modelling
study, that the unsaturated zone is the major
source of solutes in the impoundment
groundwater (see also Banwart and
Malmstrm, 2001).
Comparison of data in Figure 16, where
laboratory rates for batch experiments on
fine tailings at 25 and 5 C and coarse
tailings, as well as rates in columns, are
normalised to field rates, indicates that for
most components, rates determined in batch
experiments overestimate field rates by 1-5
orders of magnitude, which is consistent
with the commonly observed scale
dependence of mineral weathering rates. In
contrast, rates from columns underestimated
the majority of components.
7.4 Prediction of field weathering rates
from laboratory experiments
In order to predict field element release
rates, kinetic data from the laboratory
experiments were scaled with factors
accounting for the effect of differences in
temperature, mineral surface area (as
estimated by Equation 6), and, where
appropriate, pH and Po
2
, between the scales
on the weathering rates, in an approach
similar to that proposed by Malmstrm et al.
(2000):

2
, ,
Po
i
pH
i
T
i
B
i
F
i j i
F B
i
F
i j i
F B
j
r A r A R = =

(8)
-3
-2
-1
0
1
2
3
4
5
6
S Fe-
pyr
Cu Zn Mg Na K Ca Al-
mod
l
o
g

(
R
/
R
F
)

Figure 16. Comparison of element release rates [mol g
-1
day
-1
] in batch reactors (fine
tailings, 25 C, HNO3, pH~3, ; fine tailings, 5 C, H2SO4, pH~3, ; coarse tailings,
25 C, HNO3, pH~2 ) and coarse tailings column (), normalised to field rates.

38
where
T
i
is the correction factor for
temperature based on the Arrhenius
equation,
pH
i
and
2
Po
i
are correction for
pH and Po
2
based on the dependencies
given in rate laws in Table 1 (see Paper V for
details), and superscripts B, F, and B-F
denote batch, field, and batch scaled to field.
The quantification of s caling factors for
Po
2
, pH, and temperature are thus
independent of the laboratory experiments
presented in this thesis. An analogous
approach was applied for adjustment of the
column rates, with the exception for the
correction for field Po
2
. Given the
sensitivity of the release rate of S, Fe, Cu
2+

and Zn
2+
to the partial pressure of oxygen
(e.g., Table 1) and that this quantity was not
measured in the columns, release rates of
these elements were not corrected for field
Po
2
(i.e.
2
Po
i
=1 for all minerals). The
predicted field rates from the column studies
thus applies to water saturated conditions in
the field, such as was aimed for with the
applied remediation measures at the site,
rather than prevailing partly water-
unsaturated conditions at the time of field
sampling. Aluminium release was predicted
from aluminosilicate mineral weathering
rates and stoichiometry (i.e., the aluminium
model applied in Papers III and V, see, e.g.,
Equation 8 and Figure 8 in Paper V); as the
modelling study indicated a low degree of
iron oxidation or immobilisation in
Impoundment 1, Fe release was predicted
from SO
4
2-
release and pyrite stoichiometry.
Adjustment for field conditions (Fig. 17a-c)
brought batch experiment-derived rates for
all elements, except Ca
2+
, closer to those
observed in the field, particularly for those
derived at low temperature (Fig. 17b) and
from the coarse tailings (Fig. 17c), which
agreed with field rates to within a factor 10,
except for Cu
2+
, K
+
and Ca
2+
. Sulfate release
(and thus, Fe release) is overestimated by the
accelerated SO
4
2-
release rate observed in the
25 C fine batch reactor in HNO
3
medium
(Fig. 17a; cf. Fig. 11a). This result is
consistent with conclusions of the earlier
modelling study (Chapters 4-5) that
-3
-2
-1
0
1
2
3
4
5
6
S Fe-
pyr
Cu Zn Mg Na K Ca Al
l
o
g

(
R
/
R
F
)
a) fine tailings, 25 C
-3
-2
-1
0
1
2
3
4
5
6
S Fe-
pyr
Cu Zn Mg Na K Ca Al
l
o
g

(
R
/
R
F
)
c) coarse tailings
-3
-2
-1
0
1
2
3
4
5
6
S Fe-
pyr
mod
l
o
g

(
R
/
R
F
)
b) fine tailings, 5 C
-3
-2
-1
0
1
2
3
4
5
6
S Fe-
pyr
mod

l
o
g

(
R
/
R
F
)
d) column
Figure 17. Prediction of field-scale element release rates ([mol g
-1
day
-1
], normalised to field rates),
based on batch experiments in this study (Papers III-V), a) fine tailings at 25 C in HNO3, b) fine
tailings, at 5 C, c) coarse tailings at 25 C. d) Release rates from a column study on similar coarse
tailings materials (Paper VI).

39
microbial processes do not contribute
greatly to the geochemical processes
occurring in Impoundment 1. Consideration
of microbial conditions when deriving
laboratory sulfide oxidation rates to
extrapolate to other scales is thus of
importance, particularly as model results
were sensitive to small changes in the pyrite
weathering rate (Chapter 5.5.1).
Calcium release is underestimated by the
adjusted plagioclase rates in all reactors; this
is consistent with control of calcium release
in the field by dissolution of gypsum rather
than plagioclase weathering, as was also
concluded from the modelling study (cf.
Figure 5). The prediction based on batch
experiments for Cu
2+
, Zn
2+
, K
+
and Al
3+
,
and, from coarse tailings, Mg
2+
,
overestimated the field release rates,
indicating a remaining unresolved difference
between the laboratory results and field
rates. Possible reasons for remaining
discrepancies include that additional
processes affect the component discharge
rate at the somewhat higher pH in the field.
This suggests a need for experiments at pH
values that are similar to those that will
occur in the field, long term experiments so
that mineral weathering reaches steady state,
and further investigation and quantification
of potential immobilising processes in the
field.
Lower rates of SO
4
2-
, Fe, Cu
2+
and Zn
2+
as
predicted from columns-derived rates are
due to the low oxygen availability in these
experiments; low aluminosilicate dissolution
may be due to the decreased proton release
(e.g., Banwart et al., 2002), or greater
preferential flow in the column than in the
field. This implies that rates of contaminant
release will be lower at water saturated
conditions, which is consistent with
modelling studies and reported preliminary
post-remediation studies of Impoundment 1
(Chapter 5.2.2). However, it also indicates
that prediction of unremediated conditions
(ie with the presence of an unsaturated zone)
from saturated columns will be difficult
without consideration of the dependence of
aluminosilicate weathering rates on acid
production rather than just pH.
Field rates were also predicted from mineral
weathering rate laws from the literature
(Paper V, Figure 9d). However, in general,
prediction using kinetic data of the site
specific tailings resulted in better prediction
of element release rates in the field. This
indicates that factors that contribute to
discrepancies between laboratory weathering
rates of minerals in the tailings and in
monomineralic museum specimens (see
Chapter 7.2) also are important in the field.


40

41
8 CONCLUSIONS AND
IMPLICATIONS
A methodology is presented for studying
and quantifying geochemical processes that
contribute to AMD generation in base metal
sulfide ore mill tailings. The methodology
builds on first principles regarding
geochemical processes, using site-specific
quantification of factors that are commonly
observed to exert a large influence on
mineral weathering rates, such as
temperature, pH, and mineral surface area.
Similar modelling approaches have been
applied to waste rock and other geochemical
systems in the past, however the bulk of
literature on prediction of AMD from mill
tailings currently focuses on static and
kinetic laboratory testing. Such testing is
reported to be associated with a high degree
of uncertainty, and furthermore largely
neglects coupling between geochemical
processes and oxygen availability. The
transparent modelling methodology and
results presented in this thesis will hopefully
contribute to increased general
understanding of dominant processes
affecting AMD generation, increased
capacity to quantify these processes, and
wider application of such quantification,
with improved mitigation of the
environmental impact of mining as the
ultimate result.
Application of the modelling methodology
to the case study site, Impoundment 1 of the
Kristineberg mine site in northern Sweden,
involved consideration of site-specific
tailings mineralogy, quantification of slow
weathering processes using rate laws
obtained from the literature, and coupling to
fast equilibrium processes, such as aqueous
speciation and precipitation/dissolution of
secondary phases. This approach
successfully reproduced the pH at the site;
the major processes contributing to the
balance of proton production and
consumption were found to be pyrite
oxidation and aluminosilicate and Fe(OH)
3(s)

dissolution. Relative release rates of most
major ions were also the same as in the
impoundment. Uncalibrated, absolute
weathering rates and thereby also resulting
model concentrations were however 1-2
orders of magnitude higher than observed in
the field. For all major components, a single
calibration factor, X
r
=10
-2
, applied similarly
to all weathering rate expressions, sufficed to
account for this (commonly observed)
apparent scale dependence of mineral
weathering rates, from laboratory values
reported in the literature (uncalibrated
model) to field relevant rate values
(calibrated model).
Subsequent laboratory studies of mineral
weathering rates in site-specific tailings
material taken from the field indicated that
weathering rates for pyrite and
aluminosilicates, normalised to mineral
surface area, were in fact 1-2 orders of
magnitude lower in the ~50-year-old tailings
than the rates reported in the literature,
which are usually determined on freshly
exposed mineral surfaces. Observations of
similarly low, surface area-normalised
weathering rates in a sulfide concentrate
(where extraction of this fraction from the
tailings removed a number of assumptions
otherwise required for determination of
mineral surface area in tailings) indicated
that the applied method of sulfide surface
area estimation in the experimental tailings
material was a reasonable approximation,
and that the observed difference in
weathering rates was likely due to
differences in mineral properties between
freshly exposed minerals and old tailings
material. Exact reasons for the observed
decrease with time of weathering rates
normalised to mineral surface area is a topic
of ongoing scientific discussion (e.g., White
and Brantley, 1995; Hodson and Langan,
1999), and remains yet to be explicitly
quantified in predictive geochemical models.
The results of the present laboratory study,
however, indicated that model results of
dominant processes in tailings
impoundments were valid after the scaling
down of all weathering rates in the model by
the single factor ~10
2
. Furthermore, the
laboratory study indicted that pyrite and
aluminosilicate minerals exhibited the same

42
dependence on pH and temperature, and for
some minerals, also on surface area, as
reported in the literature. This observation
further supported the hypothesis that
literature weathering rate laws, obtained
from monomineralic samples, are applicable
for tailings, once allowance is made for the
scale dependence in absolute rate values.
The modelling study demonstrated the
importance of kinetic representation of
aluminosilicate dissolution and iron redox
reactions for prediction of pH, which results
from the balance of proton production and
attenuation, and major ion composition of
the impoundment groundwater. At the case
study site, kinetic aluminosilicate dissolution
was found to provide the bulk of proton
attenuation and, as a result, considerably
affect the rate of depletion of fast-reacting
pH-buffering minerals, such as calcite, which
are able to keep pH at a circum neutral level.
Inclusion of the kinetics of aluminosilicate
dissolution and of the feedbacks between
slow and fast processes is thus potentially
crucial for prediction of the proton balance
and the long-term evolution of pH in
general.
Simulations further indicated that the iron
redox cycling, which may be accelerated by
acidophilic bacteria, was low at the case
study site, where conditions of low
temperature and near-neutral pH prevail.
However, the sensitivity of the modelled
groundwater composition and pH to sulfide
and iron redox reactions indicated that
quantification of microbial mediation of
these reactions at other sites may be
necessary for predicting the overall oxidation
rate. Limited oxygen availability has in
previous modelling studies been assumed to
be the overall limiting factor on AMD
quality; however, even for a given, low
oxygen flux, the modelled pH was sensitive
to the balance between pyrite oxidation
pathways. Consideration of the possibility of
microbial mediation and other factors that
lead to uncertainty in the iron redox cycling
therefore require closer investigation.
Comparison of rates in the field and in the
laboratory studies, however, also indicated
that further investigation is also needed of
other factors, such as nutrient availability,
which may limit microbial mediation in the
field. To this end, the present laboratory
experiments indicate that commonly applied
sterilisation methods do not affect long-term
(>30 days) abiotic element release rates in
tailings.
In contrast to findings for pyrite and
aluminosilicate weathering rates, heavy metal
(Zn
2+
, Cu
2+
) release rates derived here from
batch laboratory experiments exceeded
reported literature rates for oxidation of
sphalerite and chalcopyrite by 1-3 orders of
magnitude. For Zn
2+
, uncalibrated
extrapolation of this batch rate from
laboratory to field conditions lead to
reproduction of the field rate within a factor
10; for Cu
2+
release, however, the
corresponding field rate was overestimated
by 2-4 orders of magnitude. Possible
differences in the mechanisms of release and
immobilisation of Zn
2+
and Cu
2+
(and also
Al
3+
and K
+
) between the laboratory and the
field require further investigation.
This study suggests that within certain limits,
which appear narrower than recognised in
current prediction practices in industry, it is
possible to predict the weathering behaviour
of major minerals, and hence proton release
and attenuation, in base metal tailings under
relevant field environmental conditions.
Remaining issues to resolve for further
improved confidence in predictive modelling
of leachate composition from tailings
impoundment include changes in mineral
weathering rates with time and the
mechanisms controlling heavy metal release
and retention. The herein proposed
methodology of integrating model
quantification, geochemical characterisation
and observations on different scales may
considerably aid in such issue resolution.
Furthermore, more sophisticated
mathematical-numerical models than used in
this thesis provide means to couple more
detailed representations of transport and
mass transfer processes with the
geochemical processes and principles
focussed upon here. Important

43
complementary studies to those presented in
this thesis include prediction of AMD
potential already during the mining
exploration stage (e.g., Kwong, 1993, 2003),
and assessment of the effect of subsurface
heterogeneity on soil cover remediation of
mine wastes (e.g., Werner, 2000) and on
downstream contaminant transport (e.g.,
Berglund et al., 2003), which all indicate that
the improved source term quantification
attempted here will contribute to improved
prediction reliability of the environmental
impacts of AMD. Such improved reliability
will in turn assist in optimisation of
remediation expenditure on both site
(OKane and Wels, 2003) and water
catchment (Baresel et al., 2003) scales, and
thereby facilitate efficient attainment of
environmental water quality goals.

44


45
9 ACKNOWLEDGEMENTS

Financial support from MISTRA, the Swedish Foundation for Strategic Environmental Research,
through the MiMi programme ("Mitigation of the environmental impact from mining waste"),
and from the EU project ERMITE ("Environmental regulation of mine waters in the EU"),
funded within the European Commission Fifth Framework Programme under Contract No
EVK1-CT-2000-0078, is gratefully acknowledged. Participation in the MiMi and ERMITE
programmes has furthermore allowed interdisciplinary problem formulation and collaboration,
and formation of friendships, with other PhD students and various experts in their (diverse)
fields, for which I am also very grateful.

I wish to sincerely thank Georgia Destouni, my official supervisor, for giving me the chance to
work with the environmental impact of mining. As a student of Gias Ive also had the good
fortune to witness at first hand application of critical thought to, among other things, research, as
well as masterful written communication of research, lessons that I value greatly. I will also
forever be indebted to my assisting supervisor Maria Malmstrm, who has been a pillar of
technical and moral support throughout this postgraduate study period. Marias scientific
curiosity, rigour, and skill have lit up the path of my wanderings through geochemistry, and
without Marias help, the work in this thesis probably never would have happened. Furthermore,
I probably still wouldnt be able to hold a conversation in Swedish. TACK, Maria!

Ive been very lucky to be surrounded by a great bunch of usual suspects at the Department of
Land and Water Resources Engineering. Despite my poor attendance at fika over the last
couple of years, your smiling faces in the corridors have always inspired. Special thanks must also
go to Monica Lwn and Ann Fylkner for help in the LWR laboratory, and to Aira Saarelainen
for help with all administrative matters, no matter how short the notice.

To my friends and family far away thanks for being here in spirit (if thats what SMSs and
emails are called) and quite often in person too. To Patriks family in Karlstad and our friends in
Stockholm, and especially Cate and fam, Jad, and Mike: thanks for considering me as one of the
family, keeping me sane, and making Stockholm so much more than just a pretty place to do a
PhD.

To Mum, Dad, and Rob: thanks for not mentioning too often how far away I am, and for always
being there.

To Patrik: Thankyou for all your patience and support, all these years. I dont know how other
people get through PhDs without you.


46


47

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