Physics and Chemistry of the Earth 58–60 (2013) 13–21

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Physics and Chemistry of the Earth

journal homepage: www.elsevier.com/locate/pce

Impact of climate change on acid mine drainage generation and

contaminant transport in water ecosystems of semi-arid and arid
mining areas
Hossain Md. Anawar ⇑
School of Earth and Environment, The University of Western Australia, Crawley, WA 6009, Australia

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

Article history: Disposal of untreated and treated mining wastes and tailings exerts a significant threat and hazard for
Available online 18 April 2013 environmental contamination including groundwater, surface water, wetlands, land, food chain and ani-
mals. In order to facilitate remediation techniques, it is important to understand the oxidation of sulfidic
Keywords: minerals, and the hydrolysis of the oxidation products that result in production of acid mine drainage
Climate change (AMD), toxic metals, low pH, SO24 and Fe. This review has summarized the impacts of climate change
Mine waste on geochemical reactions, AMD generation, and water quality in semi-arid/arid mining environments.
Sulfide oxidation
Besides this, the study included the effects of hydrological, seasonal and climate change on composition
Contaminant transport
Groundwater
of AMD, contaminant transport in watersheds and restoration of mining sites. Different models have dif-
ferent types of limitations and benefits that control their adaptability and suitability of application in var-
ious mining environments. This review has made a comparative discussion of a few most potential and
widely used reactive transport models that can be applied to simulate the effect of climate change on sul-
fide oxidation and AMD production from mining waste, and contaminant transport in surface and
groundwater systems.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Geochemical weathering and oxidation of sulfide minerals in
mining waste and tailings creates a long-term threat to the sur-
rounding environment and, depending on their location and envi-
ronmental setting, present contrasting physical, hydrological and
chemical characteristics controlling the fate and transport of con-
taminants. Acid mine drainages (AMDs) generated from mining
wastes contain high acidity and typically high concentrations of
sulfate and toxic metals, create a potential threat to environmental
contamination, surface water, groundwater, soil quality and food
chain contamination, and may kill fish, flora and most organisms
in water and soils (Forstner and Wittmann, 1983; Malmstrom
et al., 2008; Chen and Jiang, 2012). The generation of AMD from
overburden spoil piles at open-pit lignite mines rendered the qual-
ity of groundwater to pH as low as 1, and impacted the mine pits
and surface water bodies (Gerke et al., 1998).
Considering that water is a valuable natural resource, conserva-
tion of water from the multiple threats of contamination is very
important for the economic growth, sustainable existence of nat-
⇑ Address: School of Earth and Environment, The University of Western Australia,
35 Stirling Highway, Crawley, WA 6009, Australia. Tel.: +61 8 6488 1714; fax: +61 8
6488 1050.
E-mail address: anawar4@hotmail.com
ure and well being of populations. Global climatic and environ-
mental changes will cause erratic rainfall, water scarcity,
increased incidence of flood and droughts, which will consequently
affect mining activities, agriculture, and livelihood in the semi-arid
and arid regions. The groundwater and surface water ecosystems
will be threatened due to both disposal of mining wastes and cli-
mate change. Therefore, the sustainable and long-lasting remedia-
tion and mitigation strategies are needed to confront the impacts
of climate change, and protect this valuable water resource in
the mining operated semi-arid and arid regions. Before adopting
the remediation strategies, it is essential to understand the tailings
dissolution, geochemical reactions, AMD production and contami-
nant transport in the groundwater and surface water ecosystems in
response to climate change.
Geochemical modeling is widely applicable and useful tech-
nique to investigate the geochemical reactions occurring in the
AMD, and contaminant transport in the groundwater and surface
water systems (Bertelli et al., 2009). The geochemical model incor-
porates chemical speciation, precipitation–dissolution reactions,
ion exchange, acid–base reactions, and redox reactions. Any geo-
chemical modeling exercise must be approached from an initial
conceptual model which is based on well constrained field obser-
vations, data collection and a number of geological and geochem-
ical assumptions. The validity of the model is strictly dependent
on the quality and quantity of the data, and on the consistency of

1474-7065/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.pce.2013.04.002
14 H.Md. Anawar / Physics and Chemistry of the Earth 58–60 (2013) 13–21
assumptions on which the model is based. In chemical models of
geological systems, one of the key areas of uncertainty is the chem-
ical composition of the fluids that interacted with the rocks. The
data from fluid inclusion analysis can now be employed to help
constrain the chemical system for input into geochemical models.
Accurate modeling of geochemical changes in dissolution of mine
tailings and waste evolving in AMD can be an important tool in
predicting post-mining environmental impacts and site manage-
ment (Bronswijk et al., 1993; Burke and Banwart, 2002; Brown
and Glynn, 2003; Kruse, 2007; Kruse and Younger, 2009).
Very few research studies are reported in the literatures that fo-
cused on the impacts of climate change on AMD in mining regions.
A recent review by Nordstorm (2009) described the natural pro-
cesses, that might change the concentrations of acidity and metals
in surface waters receiving AMD under the expected conditions of
climate change associated with global warming (e.g. rainfall
events) based on data from three mines sites in the United States.
However, the impacts of climate change on AMD generation, geo-
chemical reactions in mining wastes, water quality of AMD af-
fected streams and transport mechanisms are poorly studied and
reviewed. Therefore, the main objective of this review is to explore
the implications of climate change on AMD generation from min-
ing waste and tailings, water inflows to surface and groundwater
system, water quality and contaminant transport in mining areas
of semi-arid and arid zones. In addition, this review also assessed
the sulfide oxidation in relation to changing hydrological condi-
tions, fundamental AMD formation and evolution processes, and
contaminant transport in surface and subsurface water ecosys-
tems. There are a number of mathematically based codes/models,
that are constantly developing, and widely used to describe the dif-
ferent aspects of groundwater and surface water geochemistry af-
fected by AMD. One objective of this review is to make a
comparative discussion of the most potential and widely used geo-
chemical models that can be useful in elucidation of metal specia-
tion, mineral saturation calculations, physical or geochemical and
coupled physical–geochemical simulators of processes, hydraulic
and geochemical changes in tailings and AMD systems.
2. Mechanism of sulfide mineral oxidation and acid mine
drainage
Oxidation of sulfidic minerals, particularly pyrite (FeS2), arseno-
pyrite and pyrrhotite and the hydrolysis of the oxidation products
(iron sulfates) in mining waste, mine dumps, and tailings impound-
ments generate acid drainage, SO24 and Fe, where O2 and water are
the oxidizing agents (Balistrieri et al., 1999; Dold and Fontbote,
2001; Abbassi et al., 2009). The second pathway for sulfide oxida-
tion is by reaction with Fe(III). Both pathways are fast. They yield
a low pH and Fe(II), which may become oxidized by O2(aq) to Fe(III).
Fig. 1. Conceptual model to present the pyrite oxidation from mining waste, and dynamics of contaminants in shallow and deeper groundwater.
The detailed processes involved in pyrite oxidation from mining
waste, generation of acidity, sulfate, metals and metalloids is shown
by the conceptual model in Fig. 1. The model also exhibits the con-
taminant transport and mechanisms of redox reactions controlling
the contaminants in shallow and deeper groundwater systems. This
oxidation is known to be very slow and unstable at low pH (Singer
and Stumm, 1970) except in the presence of microorganisms, which
can increase the rate of Fe(III) production by up to six orders of
magnitude and more stable at a pH of approximately 8. Acid gener-
ation is also demonstrated by chalcopyrite and sphalerite with an
indefinite composition ((Zn, Fe)S) (Schroeter et al., 2001). Minerals
such as chalcocite and galena, which sometimes occur in different
types of mines, oxidize, but do not produce acidity (Matthews
et al., 2008). Arsenic sulfide (AsS (am), As2S3 (am), orpiment, and
realgar) oxidation rates increase with increasing pH values (Lengke
and Tempel, 2005).
The rate of pyrite oxidation in the mining waste and tailings is
mainly controlled by the availability of oxygen and water at the
mineral grain surface (Gerke et al., 1998). Most of the previous
models considered the one-dimensional vertical oxygen diffusion
within the spoil using Fick’s first law (e.g. Bronswijk et al., 1993),
and first-order kinetics (Elberling et al., 1994). Wunderly et al.
(1996) further developed the model by coupling a one-dimensional
oxygen diffusion to a two-dimensional transport model where the
physical transport of oxygen to the reaction site is the most impor-
tant rate-limiting step for the oxidation of pyrite. However, they ig-
nored geochemical reaction kinetics (Williamson and Rimstidt,
1994) and the role of bacteria. The kinetics of pyrite oxidation com-
bined with the spatial variability of solute transport and geochem-
ical properties may have a significant effect on the duration of the
acidification process, the spatio-temporal movement of the oxida-
tion front, and the long-term evolution of contaminant leaching
through the relatively large vadose zone of overburden spoil piles.
Gerke et al. (1998) justified the decoupling of kinetic oxygen diffu-
sion from aqueous phase reactive transport in their model because:
first, oxygen diffusion was restricted to the air phase; and second,
the oxidation products appeared in the aqueous transport equation
as source terms only.
3. Geochemical reactions and dynamics of AMD in the
environment
Many factors affect the chemistry of mine drainage that de-
pends on a variety of geological and geochemical controls includ-
ing the type and abundance of metal-bearing sulfides in ore and
wall rock, kinetic rates of ore and wall rock dissolution, permeabil-
ity of the ore deposit or mine tailings, and the ability of the host
rock to buffer acidity (Plumlee et al., 1993). In and around the min-
ing sites, metal content attenuates to background concentrations
 H.Md. Anawar / Physics and Chemistry of the Earth 58–60 (2013) 13–21
through acid neutralization if host rock has buffering minerals
(Chapman et al., 1983). A quantitative model suggests that the bal-
ance between proton producing from pyrite oxidation and proton
consuming processes resulting in pH control is important in the
modeling of tailings leachate composition (Salmon and
Malmstrom, 2004). As pH increases, aqueous metal species tend
to precipitate as hydroxide, oxyhydroxide, or hydroxysulfate
phases (Kimball et al., 2010) and also adsorb onto surfaces of these
newly formed mineral precipitates (Nordstrom, 1982; Chapman
et al., 1983). As well, simple dilution can attenuate metal concen-
tration, independent of chemical reaction.
The capability sequence of minerals for buffering the AMD is
carbonate > aluminosilicate > (hydr)oxide minerals at full O2 avail-
ability. Using the conceptual model, Salmon and Malmstrom
(2004) reported that aluminosilicate weathering plays an impor-
tant role in prolonging the lifetime of fast reacting buffer capacity
in the deposit, and therefore, influences the time during which pH
is buffered at relatively high levels. The evolution of tailings
impoundments is also controlled by the precipitation of secondary
phases into the pores of waste materials and/or over their surface.
Thus, the SO4, Fe(III) and K generated from dissolution are con-
sumed by gypsum (CaSO4
2H2O), K-jarosite (KFe(SO4)2(OH)6) and
goethite (FeO(OH)). Major cations such as Ca2+, Mg2+, Cu2+, Na+
and K+ could be exchanged onto the clay fraction of mining waste,
thus modifying the major cation relationships (Bea et al., 2010).
4. Influence of climate change on water quality
Climatic change has high impacts on the freshwater ecosystems
composition and functioning (Cole et al., 2000; Brooks et al., 2011).
Due to climate change, rainfall pattern and frequency are changing
in many parts of the world. Climate change and drought conditions
resulting in elevated temperature, high evaporation, reduced pre-
cipitation and decreased freshwater inflows to reservoirs, espe-
cially in summer and autumn months (Peterson et al., 1984;
Brooks et al., 2005, 2011; Barnett et al., 2008; Marce et al., 2010)
are deteriorating the quality of surface water and groundwater in
semi-arid and arid zones; these are associated with reduced in-
stream flows, diel pH variability, and resulting site-specific uncer-
tainty associated with aquatic risk assessments of ionisable
contaminants in acid mine drainage. The stream inflows to reser-
voirs may receive, and/or be dominated by flow effluents from min-
ing waste and dumps in semi-arid and arid regions (Brooks et al.,
2011). The influences of climate change on site-specific hydrology
and altered water inflows can significantly influence physical,
chemical, and biological processes in acid mine drainage, which
may in turn complicate reservoir water quality (Brooks et al., 2011).
The increase of temperature due to climate change is widely
recognized to modify the chemistry of a number of chemical pollu-
tants resulting in significant alterations in their toxicities, e.g. for
Fig. 2. Conceptual model to show the pyrite oxidation from mining waste and influence of climate change and hydrology on contaminant transport in groundwater.
15
fish; a higher temperature increases the rate of uptake of pollu-
tants via changes in ventilation rate in response to an increased
metabolic rate and decrease in oxygen solubility (Kennedy and
Walsh, 1997; Schiedek et al., 2007; Vale et al., 2011). Whilst the
contaminant pathways, e.g. volatilization, adsorption, hydrolysis,
biodegradation, photodegradation, photo-enhanced toxicity, up-
take and metabolism are altered by climate change, the rates of
some of these processes increase with increasing temperature
(Schiedek et al., 2007). Temperature has a direct effect on degrada-
tion of litter and therefore, in the metal release, and decomposing
plant tissues may be either a source of metals, or sink through
adsorption on litter (Pereira et al., 2007; Vale et al., 2011).
5. Impact of climate change on geochemical reactions of AMD
affected streams
The transport of acidity and toxic elements from AMD to the riv-
er basins, and groundwater depends primarily on receiving envi-
ronments: in the transition zone between acidic and near-neutral
pH water, rapid precipitation of Fe, Al and Mn oxyhydroxides re-
moves trace metals and metalloids by sorption and/or coprecipita-
tion (Casiot et al., 2009). Different biogeochemical and hydrological
processes, that can be affected by climate change, controlled the
variations in metal and As concentrations in a small Mediterranean
river contaminated by AMD water from a mining creek (Casiot et al.,
2009). The temperature increase, an important parameter of cli-
mate change, in summer favors the development of anoxic or sub-
oxic conditions in sediments, boosts bacterial activity and favors
the reduction of oxide phases and the mobilization of associated
metals and metalloids (Masson et al., 2007). An increase in temper-
ature and/or pH also favors metalloid desorption in AMD-affected
alkaline water (Nimick et al., 2003; Gammons et al., 2007). Yunmei
et al. (2007) determined that the rate of arsenopyrite oxidation in-
creases exponentially with increasing Fe(III) concentration, espe-
cially at Fe2(SO4)3 concentrations greater than 10 4 mol/kg, and
with increasing temperature. The reaction order was found to be
constant with a value of 0.41 at temperatures from 15 to 35 °C,
but for experiments conducted at 45 °C, this was significantly high-
er (0.64), possibly indicating a different reaction mechanism at
higher temperatures (Corkhill and Vaughan, 2009). Therefore, cli-
mate change, that is predicted to further increase the global tem-
perature, will thus certainly increase the reaction rate and
kinetics of oxidation of sulfide mineral in mining waste. A concep-
tual model is presented to depict the impacts of climate change on
pyrite oxidation, and generation of acidity, sulfate, and contaminat-
ing elements (Fig. 2). The influence of climate change and hydrology
on the contaminant transport and mechanisms of redox reactions
controlling the contaminants in groundwater systems has also been
shown in the model. The photoreduction of colloidal Fe oxides has
16 H.Md. Anawar / Physics and Chemistry of the Earth 58–60 (2013) 13–21
been reported to cause diel changes in element concentrations in
streams affected by AMD (Gammons et al., 2005a,b).
Local climate, climate change, hydrology, structural geology,
composition of ore deposits, and host rocks govern the contamina-
tion levels in AMD in the mining region (Dold and Fontbote, 2001).
The hydrodynamic and chemical processes reduces the contami-
nant concentrations in water and sediment downstream of river
systems (Hudson-Edwards et al., 1996). The rainwater dilution
controls the natural attenuation at high flow of streams, while at
low flow, natural attenuation processes are dominated by solid
phase precipitation, efflorescent salt formation due to evaporation,
and dilution by uncontaminated surface and/or groundwater in-
flow (Cidu et al., 2011). Chen and Jiang (2012) found the clear influ-
ence of waterfall aeration and seasonal temperature variation on
the iron and As attenuation rates by precipitate of secondary min-
erals in an AMD system. The adsorption onto or co-precipitation
with mineral precipitates through diverse mechanisms is one of
the most effective ways to remove toxic metals and As from
AMD, e.g. adsorption onto or co-precipitation of arsenate with
schwertmannite at low pH (Regenspurg and Peiffer, 2005; Asta
et al., 2010). Oxidation and precipitation rates of Fe and other met-
als and metalloids measured in the field can be highly variable and
change with the season and the study areas, because solution
chemistry, temperatures, and types and concentrations of mi-
crobes are variably controlled by local climate and climate change
(Sánchez España et al., 2007; Chen and Jiang, 2012).
6. Effect of hydrology and climate change on contaminant
transport in AMD
Crouch et al. (2013) showed that changes in hydrologic regime
may cause changes in biogeochemical processes in aquatic ecosys-
tems associated with AMD. Given the strong hydrological and wa-
tershed-scale controls on water quality, changes to the climate
have the potential to influence water quality (Fig. 2). Acid mine
drainage originating from the mining waste is transported to
streams in both surface and subsurface inflows, that cause both lon-
gitudinal changes and diffuse subsurface spread of AMD influencing
significantly metal concentration in a stream ecosystem for the long
term (Belanger, 2002). The physical, temporal, and chemical frame-
work for mobilization of major ions in AMD systems are mainly
controlled by watershed hydrology (Nordstrom, 2009). The sea-
sonal/annual characteristics of water flows, shallow subsurface
flow and shifts in the groundwater table or recharge flow paths con-
trol the stream chemistry and changes in pH (Nordstrom, 2009)
emphasizing that watershed-scale assessments are important for
determining sources of AMD loads to a stream (Fig. 2).
Hydrology is the most important factor determining wetland
biogeochemical processes because the saturated conditions estab-
lish anaerobic conditions in the soil, where decomposed/reduced
organic matter accumulates on the substrate and forms complexes
with heavy metals from AMD (Sheoran and Sheoran, 2006). Stream
flow through wetlands can affect stream chemistry, because wet-
lands can absorb and bind heavy metals in sediments as inorganic
solids or precipitated metal oxides in aerobic zones and metal sul-
fides in sulfide-rich anaerobic zones (August et al., 2002). The in-
creases in mean annual and summer temperatures and a two- to
three-week advancement in spring snowmelt have increased
four-to sixfold zinc concentrations in summer low-flow streams
for the upper Snake River in Colorado, USA (Crouch et al., 2013).
The simultaneous increase of Fe, metals and sulfate concentrations
in AMD impacted streams in the Rocky Mountain region suggested
the accelerated weathering of disseminated pyrite within the wa-
tershed (Todd et al., 2012) that is presumed due to the climate
change, because the land disturbances in the watershed during
the study period were absent. The increasing summer tempera-
tures (at a rate of 0.2–1.2 °C/decade since the 1980s) and changes
in snowmelt timing are associated with the increases in metal con-
centrations in different naturally acidic mountain streams (Todd
et al., 2012).
7. Climate and seasonal effect on composition of AMD
Climate change may cause the variations in the duration and
climate of different seasons, that will subsequently have impacts
on the quality of AMD contaminated water streams (Fig. 2).
7.1. Case of the Odiel river Basin
The climate and seasonal variations, contamination levels and
location of the basin provide different patterns of hydrochemical
and mineralogical AMD-processes in the Odiel river Basin of Spain
(Sarmiento et al., 2009). As for example, in autumn coinciding with
the first rains, SO24 and metal concentration increases in the
uncontaminated streams, while pH and HCO3 concentrations de-
crease due to the natural weathering of sulfide materials outcrop-
ping in the zone. Although SO24 , metal and metalloid contents
decreased due to dilution processes by rainfall in the contaminated
streams, the temporal evolution was significantly different
depending on the stream pollution level. The contamination level
increased as rainfall decreased. Metal/Fe ratio increases from wet
to dry season in the slightly affected samples, while it decreases
in the strongly affected samples. The similar evolution was found
for most elements along the Odiel river. In general, the concentra-
tions increased during the dry season and decreased in the wet
period. However, the opposite results were found for Fe concentra-
tion in the first months of the dry season in the lowest part of the
Odiel river (Sarmiento et al., 2009). The strongly affected samples
were generally saturated in K-jarosite, while the slightly affected
samples were saturated in ferrihydrite. The schwertmannite and
ferrihydrite showed the higher saturation indexes in the wet sea-
son in the lowest part of the river, while in the dry season the val-
ues were higher in the upper part.
7.2. Case study of arctic area in Svalbard
Søndergaard et al. (2007) evaluated the seasonal trends in the
release of AMD from high arctic sulfide-containing coal mine waste
rock in Svalbard (78°N). High correlations between element con-
centrations suggested that the processes of sulfide oxidation, ion
exchange and silicate weathering occurring within the waste pile
released high concentrations of alkali- and alkaline earth metals,
Fe, Al, Mn, Zn and Ni in the runoff. In the winter and dry periods
during the summer the high concentrations of contaminants accu-
mulated in sulfide-containing high arctic waste rock piles. The
highest concentrations of metals, lowest pH values and a very high
daily release of acid and SO24 were found during the first week of
thaw that is presumed due to an accumulation of weathering prod-
ucts, generated within the waste pile during winter, and released
as a pollution-flush during early spring. The similar phenomena oc-
curred later in the summer, where rain events following relatively
long dry periods caused high daily metal fluxes (Søndergaard et al.,
2007).
7.3. Case study of Rum Jungle and Mt. Todd mine in Australia
The elemental composition and bacteria communities of AMD
at two mine sites, Rum Jungle and Mt. Todd, in the Northern Terri-
tory of Australia were influenced by climate, season, mine site
practices and geological characteristics of the ore body (Streten-
 H.Md. Anawar / Physics and Chemistry of the Earth 58–60 (2013) 13–21
Joyce et al., 2013). In the dry season the concentration of dissolved
metals increased in the AMD at Rum Jungle due to evaporation
during the extended dry period, but at Mt. Todd the elemental
composition of AMD changed with year, rather than season. The
bacteria community in AMD at Rum Jungle changed between the
wet and dry season while in Mt. Todd AMD the bacteria
community from year 1 was significantly different from year 2.
The iron oxidizing bacteria Leptospirillum and Acidithiobacillus,
that are commonly found in AMD in temperate regions, were not
prevalent at these two tropical mine sites (Streten-Joyce et al.,
2013).
The composition of AMD is not only influenced by geological
characteristics including the neutralising capacity in the host ore,
rock type hosting the deposit, nature of the ore, trace element con-
centration in the deposit and host rock, and pyrite and iron sulfide
content, but also by the climatic regime (Nordstrom and Alpers,
1999; Plumlee et al., 1999). Mine sites located in the wet–dry tro-
pics of Northern Australia experience an extended dry period be-
tween May and October that produced AMD with a lower pH and
higher metal concentrations compared to the wet season AMD
(Nordstrom and Alpers, 1999; Streten-Joyce et al., 2013). The oxida-
tion of pyrite and sulfide minerals produce acidity, sulfate salts and
toxic metals in the dry period, and when the first rains come, the
salts are drained away with an increase in metal concentrations
in the AMD (Plumlee et al., 1999). The drop in pH and increase in
metal concentrations of AMD is caused by the first rain flush of
AMD that accumulates in the AMD during the dry period (Nord-
strom, 2009). After this rain flush, metal concentrations revert to
the initial concentration as it was before the rain event, but if the
rainfall continues long time, then the metal levels decrease and
the pH increases (Plumlee et al., 1999; Nordstrom, 2009).
8. Impacts of climate change on AMD generation in semi-arid/
arid zone
There are a plenty of research works already published in the
literature regarding AMD production and environmental contami-
nation within various climatic and geographical settings, but
mostly in humid environments where water and oxygen are
non-limiting. By contrast, water scarcity is frequently found in
semiarid/arid environments, although oxygen is non-limiting. In
semiarid/arid regions, most of the mining activities occur in the re-
mote areas situated far away from the urban areas where there is
very poor water supply systems. There are dry and drought-prone
climate, several times higher evaporation than the average annual
precipitation creating water deficit and drought, and occasionally,
serious flooding in some areas. Due to global climatic and environ-
mental changes, the frequency and intensity of extreme climate
events are increasing (e.g., very hot temperature, low rainfall, erra-
tic rainfall, drought, high evaporative demand, high runoff poten-
tial, extreme cooler weather, flood, storm, etc.) resulting in more
rainfall somewhere and reduced rainfall elsewhere.
In the mining areas, potential sources of toxic elements are the
sulfidic minerals that are oxidized in contact with oxygen and
water. In strongly-evaporative environments of semi-arid/arid re-
gions, the increase in rainfall intensity, water content and flow re-
gime has strong influence on pyrite/sulfidic minerals oxidation
resulting in release of acidity, sulfate, toxic elements and other ions
in aquatic ecosystems, whereas the reduced rainfall will lessen the
oxidation of sulfide minerals and AMD generation. Slow weather-
ing of pyritic minerals and lower AMD and contaminant release oc-
curs beneath vegetated soil/tailings covers due to the formation of
protective coatings on pyrite-grain surfaces. However, water scar-
city and hotter temperature resulting in decreased soil moisture
content will make it more difficult to re-establish vegetative cover
on mine tailings i.e. phytostabilization, and will put stress on envi-
17
ronmental mitigation measures in some regions due to climate
change. However, the benefit of climate change creating more rain-
fall can increase the re-vegetative cover on mine tailings in some
semi-arid/arid regions.
Acero et al. (2009) reported that in the humid areas with rela-
tively high precipitation, pore-water evolution is controlled by
infiltration; and geochemical changes in the vadose zone can be
comparatively slow. By contrast, in semiarid areas, sparse, sporadic
and intense rainfall events occurring in short bursts, transient
water flow and episodic influx of reactants favors evaporative con-
ditions, O2 access into the tailings, faster sulfide dissolution rates
and enhanced solute transport and precipitation of secondary
phases (Hawkins, 1998). Therefore, the impacts of climate change
will accelerate the geochemical reactions causing high sulfide oxi-
dation and AMD production, and subsequently deteriorate the
groundwater and surface water quality of semi-arid areas.
9. Impact of climate change on restoration of mining site
Various remediation and restoration of mining wastes including
geotechnical stabilization, revegetation of waste piles, construction
of rain water drainage systems and sealing of mine adits, as well as
passive treatments such as anoxic limestone drainage and anaero-
bic compost wetlands are generally applied (Espana et al., 2005).
However, chemical and climatic constraints (high acidity and me-
tal contents and seasonal variability of water discharge) can make
these restoration activities difficult.
Ouangrawa et al. (2010) evaluated the elevated water table
technique, a promising and economic alternative, for the manage-
ment and closure of tailings impoundments and for the long-term
control of AMD. Their results indicated that an elevated water table
can be an effective means for controlling the production of AMD
when the design conditions are properly selected and applied. In
this technique the position of the water table is controlled to main-
tain, by capillarity, a sufficiently high degree of water saturation in
the reactive tailings: the effective diffusion coefficient of oxygen is
very low in saturated or nearly saturated porous media that reduce
the oxidation rate of sulfide minerals (Mbonimpa et al., 2003). Cli-
mate change and climate variability, that have large impacts on the
water saturation and moisture content in mine tailings and hydrol-
ogy, will affect the remediation activities in some places and ben-
efit it elsewhere by reducing the AMD production.
Depending on the nature and location of a mine, in most cases,
mine infrastructure (e.g. tailing ponds, embankments, spoil heaps,
etc.) and AMD may be affected by climate change (e.g. permafrost
thaw, rising average temperatures, stronger winds, changing water
levels and ice composition, greater intensity and frequency of pre-
cipitation, flooding from increased rainfall and natural disasters)
(Pearce et al., 2011). This will cause discharge of contaminated
AMD into surrounding watershed, accompanying remediation
costs, increases in environmental liability, and impacts on commu-
nity health and safety (ACIL Tasman, 2007). Some of the mine sites,
that are left abandoned and are not designed considering the fu-
ture risk of climate change, will pose significant risks to the envi-
ronment and surrounding communities, especially in light of
changing climatic conditions. As for example, the Clinton Creek
asbestos mine in Yukon, northern region, Canada that operated
from October 1967 until August of 1978 and created approxi-
mately 60 million tonnes of waste rock was abandoned without
considering the possibility of climate change: it was thought that
permafrost would remain frozen forever. The failure of tailings
dumps blocked the flow of Wolverine Creek that eroded both the
tailings piles and waste rock dumps destroying the fish habitat of
the upper Clinton Creek and Wolverine Creek (Pearce et al., 2011).
18 H.Md. Anawar / Physics and Chemistry of the Earth 58–60 (2013) 13–21
10. Reactive transport models
Many reactive transport models have been developed to simu-
late the evolution of AMD within an unsaturated and saturated
zone for both homogeneous and heterogeneous material, chemical
evolution and biogeochemistry of groundwaters, mineral–fluid
reactions, chemical equilibrium, geochemical processes (reversible
sorption, dissolution and precipitation of acid generating salts and
mineral precipitation), reaction kinetics, speciation, saturation
indices of minerals, and contaminant transport processes in multi-
ple flow systems occurring in a mining area (Kruse, 2007; Kruse
and Younger, 2009). Most of these models have been developed
without considering the impact of climate change on the above
reaction processes. However, the effects of climate change are get-
ting more and more known and recognized nowadays. Therefore,
although it is unclear to what degree existing reactive transport
models are useful in solving potential physical–geochemical and
even biogeochemical problems developing within a mine site in re-
sponse to climate change and climate variability, the present study
will comparatively review the potentials of a few selected model-
ing codes to interpret the impacts of climate change on water qual-
ity, AMD generation and contaminant transport.
10.1. Conceptual model
The conceptual model is created to avoid significant simplifying
assumptions that decrease the accuracy and defensibility of model
solutions. Due to complexity, most of the models did not include
the various parameters of climate change, that will have obvious
impacts on the geochemical reactions and quality of AMD im-
pacted water bodies. Conceptual model will be the best to incorpo-
rate these criteria and evaluate the geochemical evolution of AMD
from mining waste in response to various climate change scenar-
ios. Gerke et al. (1998) simulated the evolution of AMD resulting
from sulfide oxidation within an unsaturated overburden spoil pile
near an open-pit mine site for both homogeneous and heteroge-
neous material distributions by using conceptual model develop-
ment (generic two-dimensional flow system). Kruse and Younger
(2009) developed purpose built model or conceptual model like
POSSUM (Pollutant Sources and Sinks in Underground Mines)
and PLAYING POSSUM (Pollutant Loadings Above Average Pyrite
Influenced Geochemistry POSSUM) to reflect the rocks, fractures,
workings, hydraulics and air flow, mineralogy, transport processes
and geochemical processes of abandoned underground mines
(Kruse, 2007).
10.2. PHREEQC modeling
PHREEQC is a geochemical equilibrium model and computer
program written in the C programming language that is designed
to perform a wide variety of aqueous geochemical calculations,
simple 1D reactive-transport modeling calculations involving
water–rock interaction processes and simulating the advection of
solutions through a solid column, with or without dispersion
and/or diffusion effects (Parkhurst and Appelo, 1999). Forward
modeling determines the states of saturation with various solid
phases, and the inverse geochemical modeling identifies the spe-
cific dissolution and precipitation reactions in mining sites (Eary
et al., 2003). PHREEQC can be used to calculate saturation indices,
element speciation, and ion activities in the water sample of sul-
fide-rich mine tailings (Bhattacharya et al., 2006; Smuda et al.,
2008), and simulate the interaction processes involving the pri-
mary mineralization and the weakly acidic and oxidizing rainwater
exiting from the mine site, and formation or dissolution of second-
ary minerals (Eary et al., 2003; Arcos et al., 2008; Song and Yanful,
2011). Gomez et al. (2006) modeled the mobilization of uranium
(U) in groundwater that involved the percolation of oxidized
waters through the fractured granite, leading to the oxidation of
pyrite and arsenopyrite, precipitation of iron oxyhydroxides, other
geochemical reactions, dissolution of the primary U ore pitch-
blende and, subsequently, the release of U(VI) species to the
groundwater.
10.2.1. Probabilistic LaSAR-PHREEQC model
A variety of hydrological conditions and (bio)geochemical pro-
cesses are acting to immobilize or transform the transported sol-
utes, while AMD is transported from the origin to the
downstream and, on the way, partitioned into groundwater-
surface water systems. Malmstrom et al. (2008) estimated the
spreading of AMD in groundwater around the mining sites using
the probabilistic LaSAR (Lagrangian Stochastic Advective Reactive)
– PHREEQC model. In general, field data may prove insufficient for
deterministic process descriptions due to subsurface heterogene-
ity, even at well-characterized sites. However, this model can
consider the multicomponent reactions and transport in
heterogeneous (flow and geochemistry) groundwater surrounding
a mine waste site, with specific focus on the spreading of metals.
The model showed that even a low degree of flow heterogeneity
may create distinctive temporal concentration changes due to
the chemical reactions masking the attenuation processes. The
model can be applied to estimate the impacts of climate change,
especially hydrological processes on AMD production and quality
of groundwater and surface water systems impacted by AMD.
10.2.2. Mass-balance inverse geochemical models
Mass-balance inverse geochemical models, that use the code
PHREEQC1 (Parkhurst and Appelo, 1999) as a simulation platform,
can be used to estimate the impact of climate change on AMD con-
taminated water bodies. The timing and duration of rainfall in the
semi-arid and arid areas are altered by climate change affecting the
quantity and the quality of water resources. Mass-balance inverse
geochemical models can be applied to different water catchments
for different seasons, e.g. wet and dry to process the information
extracted from the sparse physical measurement available in the
remote arid and semi-arid zones (Driscoll et al., 2011). The hydro-
chemistry of initial and final catchments and a catchment-specific
suite of mineral weathering reactions will be used as the inputs for
the models.
10.3. MIN3P modeling approach
MIN3P is a multicomponent reactive transport model and a
powerful tool for investigating the processes like mineral dissolu-
tion–precipitation reactions, aqueous complexation, and oxida-
tion–reduction reactions (Mayer, 1999). This 3D finite volume
code has been previously tested and applied to several different
types of mine waste systems including laboratory and large-scale
mine impact studies and laboratory column experiments (e.g.
Mayer et al., 2002; Jurjovec et al., 2004; Amos et al., 2004; Ouangr-
awa et al., 2009). Using this model Bain et al. (2001) evaluated the
geochemical evolution of U mine water upon flooding, and as-
sessed the resulting potential for groundwater contamination by
metals, low-pH, and high dissolved solid by simulating the coupled
processes of transport and chemical reactions. Climate change may
cause storm, flood and cyclone in different mining sites, and the
MIN3P model can be applied to predict the impact of these disas-
ters on the geochemical reactions and water quality of AMD im-
pacted water flows and catchments in/around mining sites.
 H.Md. Anawar / Physics and Chemistry of the Earth 58–60 (2013) 13–21
10.4. RETRASO
RETRASO is a latest model formulated in a multiphase perspec-
tive: solid phase (mineral), liquid phase (water and dissolved air),
gas phase (mixture of dry air and water vapor), and several other
thermal and hydraulic aspects of the porous media. These are con-
sidered in an integrated way and a mass balance equation for each
component (Saaltink et al., 2004). Acero et al. (2009) reported the
multiphase flow and reactive transport model in vadose mine tail-
ings, that can solve the problems of previous models assuming
time-invariant boundary conditions, and vadose mine tailings as
a single reactor (Molson et al., 2005; Molins and Mayer, 2007).
The model can be applied to estimate the effect of climate change
on AMD generation and water quality in arid and semi-arid areas,
because it can characterize the geochemical evolution of AMD from
mine wastes under similar drying and evaporative conditions as
found in arid or semiarid climatic zones, that are controlled not
only by geochemical processes, but also by thermohydraulic pro-
cesses. The RETRASO-CODEBRIGHT (RCB) code (Saaltink et al.,
2004), which links the approach of Olivella et al. (1996) for the
thermohydraulic model with that of Saaltink et al. (1998) for the
geochemical model, can solve the above processes.
10.5. The Geochemist’s WorkbenchÒ
Climate change is creating the significant variations in rainfall,
duration of dry and wet seasons, hydrological processes, and tem-
perature. The Geochemist’s WorkbenchÒ is a set of software tools
used to determine the resulting water chemistry when different
water types are mixed together, controlled and diluted by rainfall
and hydrological processes, to identify the chemicals needed to
remediate impacted water, and seasonal variation induced by cli-
mate change in mine discharges (Bastrakov et al., 2004; Cleverley
and Bastrakov, 2005; Bertelli et al., 2009). Using one or more of
the five geochemical analysis modules and two reaction-path
modeling modules, the scientist can balance theoretical chemical
reactions, and examine their stability in natural or mining environ-
ments (Bethke, 1996, 2002).
10.6. Global modeling based on a Network of Chemical Reactors
approach
The impact of mines on groundwater is most often treated either
hydrodynamically or chemically. Distributed hydrodynamic mod-
els require a precise knowledge of a system’s structure and hydro-
geological parameters (Hauns et al., 2001). The following global
models have been proposed to overcome this problem: semi-
spatially distributed Groundwater Rebound in Abandoned
Mineworkings (GRAMs) model (Burke and Banwart, 2000) and in-
verse models using time series and signal-processing methods
(Vaute et al., 2004). Collon et al. (2006) and Hamm et al. (2008) used
the global modeling based on a Network of Chemical Reactors
(NCRs) approach to simulate the long-term evolution of the chem-
ical composition of the overflowing water quality in the reservoirs,
and the impacts of mine waste on groundwater quality. Hamm et al.
(2008) further examined the second approach based on a physically
distributed pipe network model (PNM) built with EPANET2 soft-
ware to support water-resource management. This approach con-
siders the mine as a network of pipes defined by their geometric
and chemical parameters. Both modeling methods require hydro-
logical and chemical parameters (recharge flow rate, outflows, vol-
ume of mine voids, mass of solids, and kinetic constants of the
dissolution–precipitation reactions). Therefore, these models can
be applied to incorporate the climate parameters and predict the
water quality of surface and groundwater impacted by AMD.
19
11. Conclusions
The oxidation of iron sulfides (pyrite, arsenopyrite and marca-
site) and metal sulfide minerals in mining aqueous environments
involves hydration, oxidation, and hydrolysis reactions resulting
in the transformation of sulfides into sulfates, acid generation,
and the solubilization of toxic elements. The significant amounts
of calcite, dolomite, and limestone, dissolution of native and rock
dust gypsum, and weathering of aluminosilicate minerals may
increase the pH and result in the precipitation of oxides and
hydroxysulfates that scavenge metals from solution.
Climate change will have direct impacts on water resources,
mine waste morphology, and hydrogeologic/geochemical condi-
tions affecting the flow of water, geochemical reactions and con-
taminant transport at mine sites. Heavy rainfall and flooding
events caused by climate change may disrupt the hydraulic struc-
tures (dams, ditches, spillways and holding ponds) at mine sites,
and will result in more contaminant runoff or shutdowns of mining
operations. It will also affect the mine tailings covers (simple soil
covers, store and release, permafrost, etc.) and dams, that are re-
quired for long-term storage of tailings and other contaminants
after mine closure. Changes in rainfall patterns, evapotranspira-
tion, and hotter temperature will affect vegetation covers and phy-
toremediation of mining waste. Mining sites with inadequate
design, management, or regulatory oversight will be more vulner-
able to impacts of climate change. Therefore, in addition to adopt-
ing the migitation options, adaptive measures will be more
effective and economic to confront the impacts of climate change
in the mining sites.
Conceptual model will be the best to incorporate the criteria of
climate change and evaluate the geochemical evolution of AMD
from mining waste in response to various climate change scenar-
ios. Furthermore, the following reactive transport models can be
used to predict the impacts of climate change (erratic, reduced or
heavy rainfall, high temperature and flood) and hydrological pro-
cesses on AMD production and quality of groundwater and surface
water systems impacted by AMD: PHREEQC geochemical equilib-
rium model; Probabilistic LaSAR-PHREEQC; Mass-balance inverse
geochemical models; MIN3P modeling approach; RETRASO or
RETRASO-CODEBRIGHT; Geochemist’s WorkbenchÒ; Global mod-
eling based on a Network of Chemical Reactors approach.
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