minerals

Review
Mine Waste Rock: Insights for Sustainable
Hydrogeochemical Management
Bas Vriens 1, * , Benoît Plante 2 , Nicolas Seigneur 3 and Heather Jamieson 1
1 Department of Geological Sciences & Geological Engineering, Queen’s University, 36 Union St W,
Kingston, ON K7N1A1, Canada; [email protected]
2 Institut de Recherche en Mines et en Environnement, Université du Québec en Abitibi-Témiscamingue,
445 Boulevard de l’Université, Rouyn-Noranda, QC J9X 5E4, Canada; [email protected]
3 MINES ParisTech, PSL University, Centre de Géosciences, 35 rue St Honoré, 77300 Fontainebleau, France;
[email protected]
* Correspondence: [email protected]




Received: 7 July 2020; Accepted: 17 August 2020; Published: 19 August 2020


Abstract: Mismanagement of mine waste rock can mobilize acidity, metal (loid)s, and other
contaminants, and thereby negatively affect downstream environments. Hence, strategic long-term
planning is required to prevent and mitigate deleterious environmental impacts. Technical frameworks
to support waste-rock management have existed for decades and typically combine static and kinetic
testing, field-scale experiments, and sometimes reactive-transport models. Yet, the design and
implementation of robust long-term solutions remains challenging to date, due to site-specificity in
the generated waste rock and local weathering conditions, physicochemical heterogeneity in large-scale
systems, and the intricate coupling between chemical kinetics and mass- and heat-transfer processes.
This work reviews recent advances in our understanding of the hydrogeochemical behavior of mine
waste rock, including improved laboratory testing procedures, innovative analytical techniques,
multi-scale field investigations, and reactive-transport modeling. Remaining knowledge-gaps
pertaining to the processes involved in mine waste weathering and their parameterization are
identified. Practical and sustainable waste-rock management decisions can to a large extent be
informed by evidence-based simplification of complex waste-rock systems and through targeted
quantification of a limited number of physicochemical parameters. Future research on the key
(bio)geochemical processes and transport dynamics in waste-rock piles is essential to further optimize
management and minimize potential negative environmental impacts.

Keywords: mine waste; drainage; water quality; geochemistry; hydrogeology; modelling

1. Introduction

1.1. A global Environmental Perspective on Mine Wastes

Mineral resource extraction and ore processing operations around the world produce significant
amounts of waste, predominantly wastewater and non-profitable solid residues, i.e., waste rock and
tailings. While technical innovations in mining and processing techniques have increased the overall
efficiency of extraction, the great majority of raw material moved to access mineral ores is still discarded
as waste (e.g., up to 99% for precious metals). As a result, several gigatons of mine waste are produced
around the world each year [1,2], and this number is expected to grow as increasingly lower-grade
and larger-scale deposits are being mined to keep up with exponentially growing global demand for
mineral resources.
In the absence of economic incentive or technical ability to re-utilize and re-valorize mine
wastes [3–6], they are often stored on-site indefinitely. The impacts of these mine wastes, even when

Minerals 2020, 10, 728; doi:10.3390/min10090728 www.mdpi.com/journal/minerals

Minerals 2020, 10, 728 2 of 37

properly managed in engineered storage facilities, can be wide-ranging and include ecological,
hydrological, geotechnical, climatic, and environmental aspects pertaining to the quality of natural
habitat, i.e., the atmosphere, ground- and surface-water, and soils. High-profile mine waste catastrophes
are well-known by the public (e.g., tailings dam failures in Canada [7], Hungary or Brazil [8]),
but deterioration of environmental quality from mining waste more often occurs gradually [9,10] and
can even linger unnoticed for years or become apparent until decades after mine closure. An example
thereof is acid rock drainage (ARD); the weathering of sulfidic mine waste that leads to acidic drainage
with high metal concentrations [1,11] (the term acid mine drainage is increasingly substituted by acid
rock drainage to indicate that acidic drainage can originate from sources other than mines). Acid rock
drainage is an environmental problem of global scale and deterioration of water quality from acid rock
drainage which may persist for decades to millennia.
To minimize detrimental environmental impacts from mine wastes, mine sites are required to abide
by legislative environmental quality standards during the entire mining cycle, i.e., from exploration
and development to decades past closure [12,13]. To this end, effective long-term waste management
strategies need to be developed [14,15]. Wastewater quantity and quality predictions are a critical
component of these strategies, as some form of treatment is usually required before wastewater can be
released to receiving downstream environments, and most wastewater treatment requirements are
long-term. Drainage from on-site mine waste critically contributes to wastewater quantity and quality,
and the processes underlying mine waste weathering and drainage in practical, industry-relevant
settings thus need to be quantitatively understood.
Prediction of drainage quantity and quality from mine wastes requires knowledge on the local
geology and weathering climate, as well as the mine waste’s mineralogy, geochemistry, hydrogeology,
et cetera. While local weathering conditions and the geology at a mining site are typically well-known,
the properties of waste materials relevant to environmental management are usually unknown at early
mine development stages and can hardly be determined a priori from theoretical calculations or by
extrapolation of laboratory test results [13]. There can be a significant lag time between waste placement
and onset of ARD, the composition of waste varies from mine site to mine site and can be highly
heterogeneous even within sites, especially in complex geological settings. Therefore, the prediction of
mine wastewater quality and quantity poses a major challenge for scientists and practitioners at sites
around the world.

1.2. Waste Rock as Unique Class of Mine Waste

Mine waste rock and tailings are typically the two major waste types at mine sites, regardless
of the mineral commodity (e.g., coal or base/precious metals), deposit type or extraction method
(surface or open-pit mining versus in-situ or underground mining) [14]. Waste rock—distinct from
other overburden spoil—consists of excavated low-grade bedrock that has been transported away
to access profitable ore and is typically composed of relatively coarse, granular broken rock in the
size range of sands to boulders. In turn, tailings are a composite slurry of (process) water and finely
ground residuals that remain after ore comminution and beneficiation, which can contain secondary
precipitates and processing reagents such as blasting agents or extraction chemicals [16]. For many
types of ores, waste rock can behave in a geochemically contrasting way when compared to tailings,
due to the following critical differences between tailings and waste rock:

1. The finer-grained nature of tailings materials compared to coarser-grained waste rock may
yield elevated exposed mineral surface area (which can, depending on the mineralogy, increase
geochemical reaction rates), whereas the wider particle size range and textural properties of waste
rock give rise to quite unique (non-uniform) hydrodynamic behavior, and,
2. Storage practices for waste rock and tailings materials create distinct conditions that alter the
controls of certain geochemical processes and physical transport mechanisms. Namely, waste
rock is mostly placed in tall stockpiles that are porous, hydraulically unsaturated, and therefore
relatively exposed to atmospheric conditions (i.e., mostly oxic environments) [16]. In contrast,
Minerals 2020, 10, 728 3 of 37

tailings slurries are often pumped into tailings ponds, where particulates settle under limited
ambient exposure (i.e., fully saturated, inundated tailings that can exhibit sub-oxic, reducing
conditions [17], although tailings may also be stored as backfills or dry stacks).

At the same time, similar minerals, geochemical reactions, and physical transport processes can
occur in waste rock and tailings: the conceptual hydrogeochemical model is often comparable for
waste rock and tailings [2]. The dimensions of industrial-scale waste-rock piles and tailings facilities
are also comparable (i.e., hundreds of tons of material): once in place, both materials are prohibitively
expensive to move and therefore are practically stored indefinitely. In this review, we will discuss a
conceptual hydrogeochemical framework that largely applies to both types of mine waste, but, in our
discussion, place emphasis on waste rock.

1.3. Scope of This Review

In recent years, the understanding of processes controlling mine waste dynamics has critically
increased due to, e.g., breakthroughs in mineral characterization at nanoscales and in-situ geophysical
characterization to long-term field studies and applications of big data and mechanistic numerical
models. This work presents an overview of the key hydrogeochemical and physical processes
relevant to water quantity and quality from mine waste rock and ultimately sustainable wastewater
management. Novel insights into the geochemical and mineralogical characteristics of waste rock,
the in-situ assessment of mass- and heat transfer processes in large waste-rock piles and emerging
applications of advanced reactive-transport modeling are presented. Previous reviews on select aspects
of mine wastes are listed in Table 1. Certain processes discussed in this work also receive attention
in the context of hydrometallurgy and bioleaching/biomining, where often the opposite objective is
targeted, i.e., acceleration of mineral dissolution to mobilize and recover valuable metals (e.g., in heap
leaching [4,18–20]) rather than stabilizing wastes to prevent mobilization (e.g., through covers and
barriers [4,21–23]). This review is structured as follows: major geochemical mobilization reactions
(i.e., oxidation and dissolution) and relevant attenuation processes (i.e., sorption and secondary mineral
formation) are introduced in Section 2. Section 3 outlines relevant physical transport processes in
waste-rock piles and their parameterization in heterogeneous systems. In Section 4, we discuss the
couplings between physical and chemical processes and upscaling phenomena, as well as the role of
numerical modelling in resolving such couplings for practical long-term predictions.

Table 1. Reviews on various aspects of mine waste rock: weathering mechanisms, microbial interactions,
characterization of physicochemical (bulk) properties, management, and reclamation.

Title: Year Reference

Molecular (bio-)oxidation mechanisms
A review: Pyrite oxidation mechanisms and acid mine drainage prevention 1995 [24]
Leaching mechanisms of oxyanionic metalloid and metal species in alkaline solid
2008 [25]
wastes: a review
The mechanisms of pyrite oxidation and leaching: A fundamental perspective 2010 [26]
A review of the structure, and fundamental mechanisms and kinetics of the leaching
2013 [27]
of chalcopyrite
Principles of sulfide oxidation and acid rock drainage 2016 [28]
Minerals 2020, 10, 728 4 of 37

Table 1. Cont.

Title: Year Reference

Bioleaching: metal solubilization by microorganisms 1997 [29]
Geomicrobiology of sulfide mineral oxidation 1997 [30]
Heavy metal mining using microbes 2002 [31]
Microbial communities in acid mine drainage 2003 [32]
The microbiology of acidic mine waters 2003 [33]
The bioleaching of sulphide minerals with emphasis on copper sulphides—A review 2006 [34]
The microbiology of biomining: development and optimization of mineral-oxidizing
2007 [35]
microbial consortia
Heap bioleaching of chalcopyrite: a review 2008 [20]
Biomining-biotechnologies for extracting and recovering metals from ores and
2014 [36]
waste materials
Microbial ecology and evolution in the acid mine drainage model system 2016 [37]
Recent progress in biohydrometallurgy and microbial characterization 2018 [38]
Mine waste characterization and treatment techniques
The environmental impact of mine wastes—roles of microorganisms and their
1996 [39]
significance in treatment of mine wastes
Acid mine drainage remediation options: a review 2005 [22]
Acid mine drainage (AMD): causes, treatment, and case studies 2006 [40]
Passive treatment of acid mine drainage in bioreactors using sulfate-reducing bacteria:
2007 [41]
critical review and research needs
Geochemistry and mineralogy of solid mine waste: essential knowledge for predicting
2011 [15]
environmental impact
Remediation of acid mine drainage-impacted water 2015 [42]
Mineralogical characterization of mine wastes 2015 [43]
Characteristics and environmental aspects of slag: a review 2015 [44]
A critical review of acid rock drainage prediction methods and practices 2015 [45]
Acid rock drainage prediction: a critical review 2017 [46]
Acid mine drainage: prevention, treatment options, and resource recovery: A review 2017 [47]
Environmental indicators in metal mining 2017 [48]
Environmentally sustainable acid mine drainage remediation: research developments
2018 [49]
with a focus on waste/by-products
A review of recent strategies for acid mine drainage prevention and mine tailings
2019 [23]
recycling
Waste rock management
The geochemistry of acid mine drainage 2003 [2]
Sustainable mining practices 2005 [50]
Mine wastes: past, present, future 2011 [1]
Hydrogeochemical processes governing the origin, transport, and fate of major and
2011 [51]
trace elements from mine wastes and mineralized rock to surface waters
Management of sulfide-bearing waste, a challenge for the mining industry 2012 [52]
Acid mine drainage: challenges and opportunities 2014 [53]
Waste-rock hydrogeology and geochemistry 2015 [16]
Hydrogeochemistry and microbiology of mine drainage: an update 2015 [54]
Geochemical and mineralogical aspects of sulfide mine tailings 2015 [17]
Mine waste characterization, management, and remediation 2015 [14]
The mine of the future—even more sustainable 2017 [55]
Mining waste and its sustainable management: advances in worldwide research 2018 [56]
Guidance for the integrated use of hydrological, geochemical, and isotopic tools in
2020 [13]
mining operations

2. Geochemical Processes in Mine Waste Rock

The exposure of previously buried geological material to atmospheric conditions triggers oxidation
reactions and allows for water to infiltrate and percolate the waste rock (i.e., drainage) which can
transfer dissolved solutes into the environment. In this section, major geochemical processes that
affect drainage chemistry are discussed. On the broadest level, mine waste drainage pH is determined
by the balance between acid-producing and acid-neutralizing (buffering) reactions, whereas solute
Minerals 2020, 10, 728 5 of 37

concentrations are controlled by their waste-rock grade and solubility [16,51,54,57]. In addition,
attenuation processes such as adsorption and secondary mineral formation [2] may reduce the mobility
of solutes through (temporary) internal retention in the waste rock, as discussed below.

2.1. Acid-Producing Reactions

2.1.1. Metal-Sulfide Mine Waste

The majority of exploited chalcophile-metal ore deposits (e.g., Cu-, Zn-, Pb-bearing ores) are
sulfide-type. While many mined chalcophile-metal deposits have undergone significant oxidative
alteration of the ore zones prior to mining, sulfide minerals can remain abundant in the generated
waste. Of the sulfide minerals in waste rock, pyrite (FeS2 ) is typically the most abundant. Other major
phases include chalcopyrite (FeCuS2 ), covellite (CuS), sphalerite (ZnS), pyrrhotite (FeS), arsenopyrite
(FeAsS), and galena (PbS). Because of their economic and environmental importance, the crystal
structures, chemical compositions, physical properties, and phase relations of major sulfides have been
well-established and previously reviewed [58]. The oxidative dissolution of a generalized metal sulfide
(Mex Sy ) is illustrated in Figure 1a: this reaction consumes water and oxygen and produces protons,
metal and sulfate ions, and heat.
The reaction pathway for FeS2 oxidation has been studied extensively [26,59–61] and occurs via
an electrochemical mechanism wherein electron exchange takes place on specific surface sites of the
mineral [62]. Its overall congruent dissolution can be simplified by the equation:

7
FeS2 + O2 + H2 O → Fe2+ + 2H + + 2SO2−
4 (1)
2

Under oxic conditions, dissolved ferrous Fe2+ rapidly oxidizes into ferric Fe3+ which can act as an
additional oxidant:
1 1
Fe2+ + O2 + H + → Fe3+ + H2 O (2)
4 2
FeS2 + 14Fe3+ + 8H2 O → 15Fe2+ + 16H + + 2SO2−
4 (3)

Due to the capability of Fe3+ ions to break metal sulfide bonds more effectively than protons [59], the
Fe3+ reaction speeds up FeS2 oxidation by orders of magnitude and forms an important (auto)catalytic
feedback (Equation (3) versus Equation (1); Figure 1a). Because FeS2 is naturally abundant in many
chalcophile metal ores, Fe3+ also serves as an oxidant to other metal sulfides, e.g.,:

CuFeS2 + 16Fe3+ + 8H2 O → Cu2+ + 17Fe2+ + 16H + + 2SO2−

4 (4)

ZnS + 8Fe3+ + 4H2 O → Zn2+ + 8Fe2+ + 8H + + SO2−

4 (5)

PbS + 8Fe3+ + 4H2 O → Pb2+ + 8Fe2+ + 8H + + SO2−

4 (6)

The kinetics of abiotic sulfide oxidation by Fe3+ allow for much faster sulfide oxidation than by
oxygen alone, so that the above equations for sulfide oxidation with Fe3+ are more commonly used
than those with oxygen, e.g.,:

CuFeS2 + 4O2 → Cu2+ + Fe2+ + 2SO2−

4 (7)

ZnS + 2O2 → Zn2+ + SO2−

4 (8)

PbS + 2O2 → Pb2+ + SO2−

4 (9)
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Minerals 2020, 10, x FOR PEER REVIEW 8 of 38

Figure 1. Schematic grouping of key geochemical reactions (not balanced) that control mine waste-
Figure 1. Schematic grouping of key geochemical reactions (not balanced) that control mine waste-rock
rock drainage quality. The oxidative dissolution of sulfide minerals is the major acid-producing
drainage quality. The oxidative dissolution of sulfide minerals is the major acid-producing reaction
reaction (a), which has been extensively studied for pyrite and other major sulfides. Galvanic
(a), which has been extensively studied for pyrite and other major sulfides. Galvanic interactions
interactions (b) can promote the preferential dissolution of sulfide minerals (Section 2.5). Additional
(b) can promote the preferential dissolution of sulfide minerals (Section 2.5). Additional reactions
reactions (c) can introduce metals and other solutes into the waste rock drainage without directly
(c) can introduce metals and other solutes into the waste rock drainage without directly affecting
affecting drainage pH. The dissolution of carbonates, Fe/Al-(oxy)hydroxides, and silicates (simplified,
drainage pH. The dissolution of carbonates, Fe/Al-(oxy)hydroxides, and silicates (simplified, generalized
generalized stoichiometries; (d) consumes protons and thereby perform a net-buffering action.
stoichiometries; (d) consumes protons and thereby perform a net-buffering action.

2.3. The Geochemistry

Finally, ferrousofFe Neutral Drainage
3+ is very insoluble under oxic and near-neutral conditions and readily
precipitates as Fe 3+ -(oxy)hydroxide to release
While the environmental impacts of ARDadditional acidity:
have received extensive attention, neutral to alkaline
drainage can also compromise water quality: neutral rock drainage (NRD), also referred to as
Fe3+ + 3H2 O → Fe(OH )3 + 3 H + (10)
contaminated neutral drainage (CND; [129,130]) or metal leaching (ML; [131,132]), is the mobilization
of hardness (mostly Ca and Mg), major ions such as sulfate and chloride, metal(oid)s, and other
The overall reaction equation for pyrite oxidation (combining Equations (2), (3), and (10)) is
contaminants that are mobile under near-neutral, non-acidic conditions. Most metallic cations show
therefore often summarized as:
higher solubility in acidic conditions, such as Cu, Ni, Zn, Co, and Mn [133], but some can remain in
elevated concentrations at near-neutral15 values,
7 mostly because their oxyhydroxides precipitate at pH
FeS2 + O2 + H2 O → Fe(OH )3 + 2H2 SO4 (11)
4
between 6 and 10. Oxyanionic elements such 2 as As, Se, and Mo exhibit elevated mobility at near-
neutral pH, which has been demonstrated in a variety of hornfels, carbonate [126], and sedimentary
Despite the catalytic effect of Fe3+ on sulfide oxidation, the rates of the abiotic reactions described
[134] waste-rock types. Cations and oxyanions generally show inverse behavior in mine drainage in
above are relatively slow, especially at low pH [16,63]. Sulfide oxidation reactions are catalyzed by a
the sense that cations tend to adsorb or precipitate in near neutral and alkaline conditions, while
oxyanions tend to do more so under (slightly) acidic conditions (see Section 2.4.1). Despite a growing
Minerals 2020, 10, 728 7 of 37

variety of Fe- and S-oxidizing bacteria that metabolically tap into the energy released during Fe and S
oxidation [64]. Major chemolithotrophic bacteria involved in sulfide oxidation reactions include both
acidophilic and neutrophilic iron and sulfide oxidizing species, e.g., ferrooxidans and thiooxidans
species in the Thiobacillus, Leptospirillum, and Ferrobacillus genera [33,65,66]. The role of microbial
sulfide mineral oxidation in controlling mine waste weathering rates has been well-established and the
geomicrobiology of mine wastes previously reviewed [30,33,67,68] (Table 1).
Because oxidation of sulfidic minerals involves the transfer of many electrons from each sulfur
atom to an aqueous oxidant, various intermediate sulfur species can exist (i.e., polysulfides, thiosulfate,
and elemental sulfur) [59,69–71]. For major sulfides, (a)biotic oxidation pathways, intermediate reaction
products, and corresponding kinetics have been characterized in a variety of settings, i.e., under
ambient conditions versus at elevated temperatures to optimize leaching [27,72–79]. Various kinetic
models exist for pyrite oxidation [2], but the oxidation mechanisms and kinetics for less-abundant
sulfides remain comparatively underexplored (e.g., molybdenite (MoS2 ) [72,80]). The exact reaction
mechanisms and kinetics of sulfide oxidation vary with weathering conditions (e.g., as shown for
pyrite [75,81–83]). Yet, (hydro)metallurgical and geochemical studies often reveal similar overall rate
dependencies (e.g., on dissolved oxygen and Fe concentrations or mineral surface area) and may
deploy comparable kinetic models [84–86].
Metal sulfide minerals are rarely pure, especially in waste rock: e.g., Fe, Cu, or As, may be
readily substituted by a range of (trace) metals in solid-solutions: As, Co, and Ni can be present
in pyrite with up to several weight percent and sulfosalts typically contain a range of metalloids
including As, Sb, Bi, and Se. Mineralogical impurities have a demonstrated effect on abiotic weathering
kinetics [87], and even though microorganisms in mine waste appear quite tolerant to otherwise
harmful metals [88], impurities may also affect biotic oxidation rates through inhibitive effects or
shifts in community structure and functional diversity [89]. Finally, select other non-sulfur minerals
may also oxidize to produce acidity, e.g., selenide, arsenide, telluride, and antimonide minerals. Due
to their natural scarcity (typical abundances are <% of that of S), these metalloids tend to occur at
trace levels in sulfides rather than as distinct phases [90] and are usually not relevant to the overall
acid-producing capacity.

2.1.2. Coal Mine Waste

In addition to metal-sulfides waste rock, coal mine wastes can also be a major source of ARD [91–97].
Sulfur can occur in coal in three main forms: (i) inorganic sulfides, including authigenic minerals
such as detrital pyrite, (ii) organically bound sulfur, including mercaptan, (di)sulfide and heterocyclic
compounds, and (iii) inorganic sulfates, particularly in weathered coals [98,99]. Because of the
relative abundance of inorganic sulfide compared to other forms of sulfur in coal waste rock, acidity
production is typically attributed to pyritic material, even though pyrite concentrations in coal vary
regionally [100–102]. While undesirable for the prevention of coal waste drainage acidification,
oxidative de-pyritization (or desulfurization) as a major coal ore beneficiation objective has been
extensively studied [103,104], including pathways [105] and kinetics [106–108].
An important difference between metal ore wastes versus coal wastes is that metal ore waste
typically contains negligible organic carbon, whereas coal wastes can have several wt% organic
carbon [93,98]. This organic material can, in the aqueous phase, subsequently ligate aqueous solutes
and mineral surfaces and thereby alter the mobility of metals in coal waste-rock drainage, depending on
the nature of the ligands and minerals (see Section 2.4.1). Organic matter may oxidize to induce oxygen
depletion and alter the Fe2+ /Fe3+ equilibrium (Equation (2)) as well as those of other redox-sensitive
elements (e.g., Mn, As, S) [109]. Subsequent shifts in the microbial community structure to favor Fe
and S reducers [110,111] may lead to net alkali generation (i.e., acid-neutralization) and in fact, certain
acid–rock drainage prevention or remediation strategies rely on the purposed addition of organic
matter to induce oxygen depletion [112–114].
Minerals 2020, 10, 728 8 of 37

2.2. Acid-Buffering Reactions

When present and abundant in waste rock, the dissolution of carbonate minerals (e.g., calcite,
dolomite, ankerite), Al- and Fe-(oxy)hydroxides (e.g., gibbsite, ferrihydrite, respectively) and silicate
minerals (e.g., feldspars, chlorites, smectites, micas, and amphiboles) consumes protons and introduces
alkalinity that offsets acidity produced by sulfide oxidation [2,16]. The following (simplified) equations
illustrate these reactions:
CaCO3 + H + → Ca2+ + HCO− 3 (12)

[Fe/Al]OOH + 3H + → [Fe/Al]3+ + 2H2 O (13)

CaSiO3 + 2H + + H2 O → Ca2+ + H4 SiO4 (14)

CaAl2 Si2 O8 + 8H + → Ca2+ + 2Al3+ + 2H4 SiO4 (15)

The acid-neutralizing dissolution reactions of carbonates, oxides and silicates accelerate at

decreasing pH, in accordance with their solubility, creating a so-called buffering sequence for acid–rock
drainage [16,115]: carbonates buffer acidity until they are typically depleted at pH < 6, Al- and
Fe-(oxy)hydroxides dissolve to buffer acidity at pH < 4–5 and pH < 3–4, respectively, and the
dissolution of aluminosilicates only significantly contributes to acid-buffering capacity at pH < 3.
Carbonate dissolution neutralizes protons through the carbonate equilibrium, but dissolution of
Fe-rich carbonate (e.g., siderite (FeCO3 )) also introduces dissolved ferrous Fe that upon oxidation
and hydrolysis (Equation (10)) releases surplus protons, reducing the net-neutralizing action [2,46].
Acid-buffering minerals dissolve simultaneously alongside progressing sulfide oxidation when they
are naturally co-located in the waste-rock matrix [115]. In addition, they may also be intentionally
mixed, blended, or added to sulfide-rich waste material as an active or passive acid–rock drainage
remediation strategy [116–118].
A wealth of information is available on the molecular mechanisms, kinetics, and pH-dependencies
of dissolution reactions of carbonate minerals [119–121], Fe-(oxy)hydroxides [122,123], and silicate
minerals commonly encountered in waste rock [124–126]. The kinetics of carbonate dissolution are
typically rapid compared to sulfide oxidation (i.e., far from equilibrium [127]), whereas the dissolution of
silicates is orders-of-magnitude slower [2]. This introduces important ramifications as to the timescales
required for effective acid-neutralization, for instsance when transport times are fast or experimental
durations short (e.g., static tests; Section 2.6.1). In addition to consuming protons, dissolution of
carbonate, oxide, or aluminosilicate minerals introduces additional solutes to a leachate, including
Ca, Mg, Mn, Al, and Fe, and possibly metal impurities if present at considerable levels [128,129].
Mobilization of such solutes and its effect on drainage quality must be considered if these neutralizing
materials are to be employed to prevent or remediate acid drainage [13]. Similar to sulfide oxidation,
mineralogical heterogeneities (Section 2.5) strongly affect the efficacy of acid-neutralizing reactions.
In contrast to sulfide-dominated acid-production, acid-neutralization can be governed by many
minerals: prediction of the extent and timing of neutralization therefore requires characterization of
the complete mineral assemblage.

2.3. The Geochemistry of Neutral Drainage

While the environmental impacts of ARD have received extensive attention, neutral to alkaline
drainage can also compromise water quality: neutral rock drainage (NRD), also referred to as
contaminated neutral drainage (CND; [129,130]) or metal leaching (ML; [131,132]), is the mobilization
of hardness (mostly Ca and Mg), major ions such as sulfate and chloride, metal(oid)s, and other
contaminants that are mobile under near-neutral, non-acidic conditions. Most metallic cations show
higher solubility in acidic conditions, such as Cu, Ni, Zn, Co, and Mn [133], but some can remain in
elevated concentrations at near-neutral values, mostly because their oxyhydroxides precipitate at pH
between 6 and 10. Oxyanionic elements such as As, Se, and Mo exhibit elevated mobility at near-neutral
pH, which has been demonstrated in a variety of hornfels, carbonate [126], and sedimentary [134]
Minerals 2020, 10, 728 9 of 37

waste-rock types. Cations and oxyanions generally show inverse behavior in mine drainage in the
sense that cations tend to adsorb or precipitate in near neutral and alkaline conditions, while oxyanions
tend to do more so under (slightly) acidic conditions (see Section 2.4.1). Despite a growing awareness
of its potential environmental impacts, there is currently no standardized definition of neutral mine
drainage [132]. Table 2 lists examples of reported NRD cases, illustrating how neutral drainage
composition can be widely different across sites (slightly acidic versus alkaline, and negligible versus
elevated concentrations of sulfate, metal(loid)s, and other (non-metallic) contaminants). NRD from
waste rock can arise in different situations:

(i) Sulfide oxidation in the presence of sufficient acid-buffering or weathering of non-acid generating
minerals (i.e., low-sulfide waste rock such as carbonates and silicates [135]), dissolution of
salts [136];
(ii) Insufficient treatment of ARD (e.g., abandoned mine sites using passive ARD treatment), where
the pH is successfully increased to near-neutral but certain contaminants remain present at
elevated concentrations;
(iii) Within reclaimed ARD-generating mine wastes, where the rate of acid generation is decreased to
levels that can be buffered by neutralizing minerals, but still allows for the leaching of metals.

Contaminant loads in neutral drainage can be controlled by their occurrence in sulfidic minerals
as well as carbonate or silicate phases, or through the dissolution of (secondary) salts and oxides
(Figure 1). For instance, elevated As levels in high-alkalinity drainage have been mostly attributed
to the oxidation of arsenopyrite or As-bearing pyrite that had been neutralized [137,138] but may
also originate from natively As-rich carbonate phases in the absence of Fe-oxides [128]. With the
increased interest in the development of rare earth element (REE) mines, there is an increasing interest
in REE geochemistry and ecotoxicity [139–141]. REE-bearing minerals can be found in many different
geological settings (although not necessarily at economic concentrations), and REEs can be found
as trace contaminants in other minerals. Therefore, they might represent an accessory contaminant
in mine drainage from non-REE operations. Indeed, they are found in many ARD cases [142,143]
but most REE deposits are within geological settings that are not prone to ARD generation, such as
pegmatites, carbonatites, and peralkaline igneous deposits, as well as within placers and clays ([144]
and references therein). Upon their release in near-neutral mine waters, REE concentrations are mostly
controlled by secondary precipitation and sorption phenomena (Section 2.4) [145–148]. However,
significant knowledge gaps remain as to the fate of REE released from mine wastes.

Table 2. Examples of neutral rock drainage (NRD) chemistries reported at different mine sites around
the world.

Beaver Greens
Hitura, Lac Tio, Giant Mine,
Antamina, Brook, Creek,
Finland Canada Canada
Peru [128] Canada United
[149,150] [130] [153]
[151] States [152]
pH 6.5–8.5 6.1–7.0 6.5–7.5 5.7–8.6 6.5–8.5 6.7
Ni (mg/L) N/R 0.2–14.3 0.1–8.8 N/R 0–1 0.029
Zn (mg/L) 0.1–80 25–660 N/R N/R 0–150 0.027
Mn (mg/L) 0.001–0.2 4.7–8.9 N/R N/R 0–35 0.446
Co (mg/L) N/R 0.05–7.2 N/R N/R N/R <0.007
As (mg/L) 0.001–1.0 N/R N/R 0–2.3 0–0.03 4060
Se (mg/L) 0.001–0.2 N/R N/R N/R 0–0.02 <0.03
Sb (mg/L) 0.001–0.2 N/R N/R 0–26 0–0.06 11.9
Mo (mg/L) 0.0–1.0 N/R N/R N/R 0–0.02 0.07
SO4 (g/L) 0.1–2 2.1–5.2 0.1–3.5 0.075–0.9 2–8 0.5
Ca (mg/L) 50–600 200–450 10–70 9–231 400–800 313
N/R: not reported.
Minerals 2020, 10, 728 10 of 37

2.4. Attenuation Processes

Attenuation processes can retain solutes in the waste-rock matrix and thereby influence drainage
quality [51,115,154]. Solute-specific attenuation through adsorption or secondary mineral formation
can lead to apparent discrepancies between the elemental composition of bulk waste rock and observed
drainage loads. A quantitative assessment of relevant attenuation mechanisms, informed by robust
mineralogical analyses and/or geochemical equilibrium modeling, can help predict such discrepancies
and optimize waste rock management.

2.4.1. Adsorption
Geochemical adsorption refers to the reversible attachment of aqueous solutes to mineral surfaces
(schematic in Figure 2a). While adsorption is highly surface- and solute-specific, the general relevance
of adsorption for mine waste drainage quality has been widely acknowledged [2]. Field and laboratory
waste-rock studies have demonstrated that sorption can be a dominant attenuation mechanism for
various mine
Minerals 2020, 10,waste-relevant solutes, from metal cations [155] to metal(oid) oxyanions [128]. 12 of 38
x FOR PEER REVIEW

Figure
Figure 2.
2. Schematic
Schematic of of
keykey
geochemical
geochemicalattenuation processes
attenuation in mine
processes wastewaste
in mine rock: adsorption (a) and
rock: adsorption
secondary
(a) mineralmineral
and secondary formation (b). Through
formation adsorption,
(b). Through (hydrated)
adsorption, ionic or
(hydrated) ligated
ionic solutes
or ligated and
solutes
complexes
and complexesadsorb to mineral
adsorb surface
to mineral groups
surface groups (-M-(x))
(-M-(x))through
throughcovalent
covalentbonding
bonding or electrostatic
or electrostatic
interaction.
interaction. Secondary
Secondaryminerals
mineralsform
formononmineral
mineralsurfaces or spontaneously
surfaces or spontaneously in solution
in solutionthrough (co-
through
)precipitation of cationic and anionic aqueous solutes. The occlusion of mineral surfaces
(co-)precipitation of cationic and anionic aqueous solutes. The occlusion of mineral surfaces by by secondary
mineral
secondaryprecipitation is referred is
mineral precipitation toreferred
as passivation or armoring
to as passivation or(c), discussed
armoring (c), in Section 2.5.
discussed in Section 2.5.

2.5. Mineral Reactivity

Adsorption can involve relatively strong covalent binding (inner-sphere) or weaker electrostatic
attraction between aqueous ions and oppositely charged mineral surfaces (outer-sphere). In both cases,
The generation of acidic and metal-bearing drainage from waste rock is the result of mineral-
adsorption is governed by the solute’s aqueous speciation as well as characteristics of the mineral
water interaction, and thus the nature of the fluid and the minerals themselves. The relative resistance
surface (e.g., pH-dependent surface charge). The aqueous speciation chemistry for major inorganic ions
to oxidation of common sulfide minerals in mine waste has been discussed: based mostly on field
in mine waste drainage has been previously reviewed (e.g., for Cu [156] and Zn [157]). Because most
observations, pyrrhotite is considered the most reactive, followed by galena, sphalerite, bornite,
solutes present in mine drainage have an aqueous speciation that is strongly dependent on the solution
pentlandite, arsenopyrite, marcasite, pyrite, and chalcopyrite [45,168,169]. The reactivity of
chemistry, and because the surface characteristics of minerals present at a site may equally vary with the
potentially neutralizing minerals also influences mine drainage quality, e.g., calcite is considered to
drainage type (i.e., acidic versus neutral versus alkaline), the many geochemical reactions underlying
be 180 times more reactive than the most reactive silicate (wollastonite). In addition to its mineral
adsorption typically require modeling to be resolved and quantified. Geochemical equilibrium models,
composition (or overall sulfide grade), overall waste-rock reactivity is determined by additional
informed by thermodynamic and kinetic parameters for these reactions, are frequently used to study
petrographic and mineralogical factors that include crystallinity and morphology [24,170,171],
and predict net-attenuating effects under practice-relevant conditions [132]. However, even with
surface defects and heterogeneities, and reduced liberation (i.e., reduced exposure to oxygen and
thermodynamic databases supplying equilibrium or stability constants for aqueous complexation
fluids) caused by inclusion in primary minerals (occlusion) or secondary mineral precipitation
and hydrolysis reactions, the complete aqueous speciation of mine drainage may be challenging to
(passivation or armoring; Figure 2c) [163,172–175].
predict, in particular for complex solutions that seasonally vary [115]. Evolving solution chemistries
Small-scale mineral features of waste rock are typically unknown in practice, since determining
them requires more advanced analytical techniques that can be costly to apply to sufficient samples
for a realistic assessment [45]. These factors, however, may explain why predictive laboratory testing
does not always match field results (Section 2.6.1) [129,176]. For instance, occluded (unliberated)
sulfides in silicates are less likely to oxidize, and both chemical and mineralogical acid–base
Minerals 2020, 10, 728 11 of 37

can induce desorption reactions, whereby previously adsorbed solutes may be re-introduced into the
drainage [2]. Even though Lewis acid–base interactions and aqueous complexation reactions for major
solutes are part of established geochemical equilibrium models, relevant aqueous ligands and potential
competitive solutes need to be experimentally determined to inform such models. This may be
especially challenging for e.g., coal waste-rock drainage [158,159] where a variety of organic acids can
occur. Furthermore, significant temperature variations can occur within waste-rock piles (Section 3.3)
and the ionic strengths of waste rock leachates can be unusually high, so that these aspects must be
considered in aqueous speciation modeling.
The modes of surface binding are documented for major waste-rock solutes and detailed adsorption
models exist for various mineral surfaces (e.g., multi-layer models, charge-distribution multi-site
complexation model [160]). Yet, the application of quantitative sorption models in drainage predictions
is scarce. This may be because the sorption properties of less-abundant solutes remain poorly studied
(e.g., Mo [161]) and stability constants deduced in laboratory studies may not be representative for
variable field conditions. Furthermore, the data required to inform sorption models, i.e., mineral
surface characteristics such as sorption-site density or solution chemistry, is typically unavailable
(or semi-quantitative at best) for large, heterogeneous waste-rock piles. Finally, the surface properties of
waste rock may evolve as weathering progresses, e.g., through precipitation of amorphous secondary
Fe-oxide coatings with elevated sorption capacity. As a result, adsorption modeling for waste rock
often relies on estimated parameters, adoption of synthetic idealized phases (e.g., hydrous ferric
oxide [128]), or extrapolation of generalized behavior (the Irving-Williams series) in stable drainage
types. Adsorption is often considered a precursor for secondary mineral formation (Section 2.4.2) but
the contribution of adsorption versus that of secondary minerals to overall attenuation remains to be
quantitatively resolved.

2.4.2. Secondary Mineral Formation

Secondary minerals in waste rock are considered those minerals that form after the waste material is
disposed (Figure 2b), i.e., distinct from primary minerals and oxidation products native to the excavated
(ore) material. Major secondary mineral phases in mine waste have been reviewed previously [2]
and include (oxy)hydroxides, (hydroxy)sulfates, (hydroxy)carbonates, and phosphates, or arsenates,
depending on the waste-rock primary mineralogy. Specific secondary phases encountered at many
mine sites include Fe-oxides (e.g., ferrihydrite, goethite, and lepidocrocite), the Fe-sulfates jarosite and
melanterite, as well as gypsum (CaSO4 ) [2,54,115].
Secondary mineral precipitates are typically composed of different polymorphs of variable
hydration: water-soluble salts may initially precipitate as hydrated or hydroxy-phases but recrystallize
into more stable forms as the precipitates age, accelerated by evaporation and drying of the waste
rock. The physical and hydrological conditions of waste-rock piles (size, particle size, hydraulic
retention time; discussed in Section 3) have a strong impact on the geochemical water-rock interaction
and therefore occurrence of secondary minerals. Secondary minerals often occur as distinct rims or
coatings on weathered host particles, but their occurrence is not necessarily related to the waste-rock
composition in their direct vicinity: mixing of different drainage types within heterogeneous waste-rock
piles [162] (Section 3.1) or generally rapid infiltration rates compared to slow precipitation rates may
facilitate secondary mineral precipitation seemingly unrelated to the local waste-rock composition [163].
While certain secondary phases readily precipitate (e.g., Fe-(hydroxy)oxides [2,16]), others may take
decades to precipitate and crystalize to detectable levels [115]. The bulk mineralogy and drainage
pH of waste-rock piles can indicate whether certain secondary mineral classes are likely to occur
(e.g., secondary phosphates and carbonates are unstable at drainage pH< 4 [164]; secondary phases
such as scorodite may be stable even under strongly acidic conditions [165]. Thus, secondary minerals
typically exhibit a widely different stability under oxic versus anoxic or acidic versus neutral drainage
conditions [2]. Their controls on long-term drainage quality may thus be difficult to quantify for
heterogeneous waste-rock piles with seasonally and spatially variable drainage signatures. For instance,
Minerals 2020, 10, 728 12 of 37

re-dissolution of secondary minerals under gradually acidifying drainage conditions or due to the
reductive dissolution of Fe-oxides, have both been invoked to explain spikes in loading rates on the
timescales of years [115].
Secondary minerals are often qualitatively inferred from chemical equilibrium modeling
(i.e., mineral saturation indices) rather than unequivocally identified analytically [115,165]. Yet, mineral
stability constants obtained in controlled laboratory experiments may not apply under field
conditions, and secondary mineral occurrence is dictated by their precipitation kinetics more than
by geochemical saturation (e.g., slower crystal growth rates occur under low degrees of saturation
whereas high precipitation rates may be sustained by spontaneous nucleation at high oversaturation).
The identification, let alone quantification, of secondary minerals in waste rock, e.g., with X-Ray
diffraction (XRD), remains challenging for dispersed and poorly crystalline phases. Yet, even secondary
phases with low overall bulk abundance can be substantial attenuating sinks: e.g., the scarce but
rapidly precipitating wulfenite (PbMoO4 ) has been shown to present an important control on Pb and
Mo drainage levels [161,166,167]. For successful drainage management, it is thus critical that the
secondary mineral assemblage is quantified and monitored over time.

2.5. Mineral Reactivity

The generation of acidic and metal-bearing drainage from waste rock is the result of mineral-water
interaction, and thus the nature of the fluid and the minerals themselves. The relative resistance
to oxidation of common sulfide minerals in mine waste has been discussed: based mostly on field
observations, pyrrhotite is considered the most reactive, followed by galena, sphalerite, bornite,
pentlandite, arsenopyrite, marcasite, pyrite, and chalcopyrite [45,168,169]. The reactivity of potentially
neutralizing minerals also influences mine drainage quality, e.g., calcite is considered to be 180 times
more reactive than the most reactive silicate (wollastonite). In addition to its mineral composition
(or overall sulfide grade), overall waste-rock reactivity is determined by additional petrographic
and mineralogical factors that include crystallinity and morphology [24,170,171], surface defects
and heterogeneities, and reduced liberation (i.e., reduced exposure to oxygen and fluids) caused by
inclusion in primary minerals (occlusion) or secondary mineral precipitation (passivation or armoring;
Figure 2c) [163,172–175].
Small-scale mineral features of waste rock are typically unknown in practice, since determining
them requires more advanced analytical techniques that can be costly to apply to sufficient samples
for a realistic assessment [45]. These factors, however, may explain why predictive laboratory testing
does not always match field results (Section 2.6.1) [129,176]. For instance, occluded (unliberated)
sulfides in silicates are less likely to oxidize, and both chemical and mineralogical acid–base accounting
tests may thus overestimate potential acid generation, especially waste that has been exposed over
times such that the exposed sulfides have oxidized. Further, sulfide oxidation may be slowed by the
formation of secondary mineral rims of Fe-(oxyhydr)oxides, sulfates, or even secondary carbonates
such as smithsonite, whereas sulfides that do not contain iron, such as stibnite, may oxidize more
rapidly because they do not develop Fe-oxide rims [151]. Such passivation may thus occur selectively
on specific minerals but also throughout the waste-rock matrix [177], and extensive precipitation can
even reduce pore space and thereby alter the hydraulic properties of waste rock (Section 4). Deliberate
sulfide passivation has also been proposed as an active acid drainage prevention technique [178,179],
e.g., using metal-organic complex formation and passivation of sulfides [180,181]. Finally, the contact
of two sulfidic phases in waste rock can result in electron exchange (galvanic interaction) that
causes one phase to corrode more rapidly than the other (Figure 1b). For instance, the leaching
of chalcopyrite can be enhanced through association with pyrite [182]. Galvanic interactions can
substantially increase the leaching of one or both of the minerals that constitute the galvanic cell:
galvanically promoted dissolution has been reported in laboratory and field studies with mine waste
rock [163,183–185]. Even though mineral occlusion, passivation, and association are known to critically
determine waste-rock reactivity [115,186], and techniques such as electron microscopy and automated
Minerals 2020, 10, 728 13 of 37

mineralogy (e.g., MLA, QEMSCAN) now allow for such parameters to be quantified with increasing
ease, few waste-rock studies and drainage prediction models have given consideration to mineralogical
and petrographic aspects (e.g., through refinement of kinetic rates) [187–190], given the cost of a
representative assessment at full scale (Sections 2.6 and 3.4).
In general, the grain size of primary minerals is inversely correlated with reactivity, and thus
finely-crushed tailings are expected to be more reactive in terms of sulfide oxidation and carbonate
dissolution than coarse waste rock fragments. On the other hand, larger pore spaces and unsaturation
of waste rock may result in a higher ingress of oxygen and periodic wetting and drying of mineral
surfaces, which may increase reactivity (Section 3.2). The nature of the water interacting with the waste
rock also affects reactivity. Oxygen-rich, slightly acidic meteoric water interacting with recently blasted
waste rock will encounter freshly broken minerals surface, and possibly highly reactive mineral dust
from blasting. Porewater reaching the lower portions of a waste-rock pile may be oxygen depleted,
and Fe3+ may act as an oxidant under acid conditions in the absence of dissolved oxygen (Equation (3)).
Under anoxic conditions at the bottom of a pile, or if the waste rock is submerged, Fe-(oxyhydr)oxides
are susceptible to reductive dissolution, resulting in release of elements of concern that were attenuated
by adsorption or co-precipitation. Waste rock submerged in a marine environment is unlikely to
generate acidic drainage, given the strong buffering capacity of seawater, although the availability of
ligands may increase the solubility of some metals [191].

2.6. Characterization of Bulk Waste-Rock Reactivity

While the geochemical reactions in weathering waste rock are universal on a molecular level, there
is typically large variability in the weathering conditions and waste-rock composition and grain sizes
across mine sites. As a result, sulfide oxidation and bulk weathering rates reported from laboratory and
field experiments vary by orders-of-magnitude across sites (Table 3). Because it is virtually impossible
to resolve all molecular-scale mineralogical heterogeneity, waste-rock reactivity or weathering rates are
typically presented through representative bulk parameters such as drainage loads (i.e., net sulfate
leaching) or oxygen consumption or heat production rates [192–194]. Similarly, the estimation of the
acid-producing versus acid-neutralizing nature of waste-rock material is often based on bulk laboratory
tests (static testing or acid–base accounting (ABA)) rather than (or complementary to) microscale
mineralogical analyses.
Minerals 2020, 10, 728 14 of 37

Table 3. Selection of waste-rock weathering rates reported for mine sites around the world, including field studies, laboratory experiments, and numerical modeling.

Mine [Main Ore Rate in g S per kg Waste

Reported Rate [Varying Units] Waste-Rock Type Method of Estimation Reference
Product] Rock (Bulk) per Year *
Laboratory studies
5±1× 10−7[mol O2 m−3 s−1 ] up to 1.5% sulfides Aitik, Sweden [Cu] Oxygen consumption 0.3 [195,196]
up to 7 × 10−8 [mol O2 kg−1 s−1 ] up to 6 wt% py Doyon, Canada [Au] Oxygen consumption up to 40 [192]
6 to 60 [mg SO4 kg−1 wk−1 ] <0.5 wt% S Cluff Lake, Canada [U] Sulfate mass-loading 0.3 to 3 [183]
Duluth Complex, USA
1 × 10−12 to 4 × 10−11 [kg O2 kg−1 s−1 ] 0.6 – 1.4% S Drainage loading 1.8 to 52 [197]
[Cu, Ni]
Field experiments
3× 10−9 to 1 × 10−7[kg O2 m−3 s−1 ] Reactive (>3% S) Antamina, Peru [Cu, Zn] Oxygen consumption 0.1 to 3.4 [198]
6 × 10−11 to 4 × 10−10 [kg O2 m−3 s−1 ] Unreactive (<0.5% S) Antamina, Peru [Cu, Zn] Oxygen consumption 0.002 to 0.01 [198]
up to 3 × 10−3 (±87%) [kg S kg−1 yr−1 ] Reactive (1.6% S) Antamina, Peru [Cu, Zn] Sulfate mass-loading 3 [115]
up to 4 × 10−4 (±20%) [kg S kg−1 yr−1 ] Unreactive (0.5% S) Antamina, Peru [Cu, Zn] Sulfate mass-loading 0.4 [115]
1 × 10−7 [kg S m−3 s−1 ] Reactive (>10% S) Antamina, Peru [Cu, Zn] Heat production 1.8 [194]
2 × 10−7 [kg O2 m−3 s−1 ] Reactive (>10% S) Antamina, Peru [Cu, Zn] Oxygen consumption 6.7 [194]
0.05 to 0.3 [g S kg−1 yr−1 ] Mixed (0.5–1.6%S) Antamina, Peru [Cu, Zn] Heat production 0.05 to 0.3 [199]
1 × 10−8 to 1 × 10−10 [kg O2 m−3 s−1 ] 0.6 vol% Sulfides Aitik, Sweden [Cu] Oxygen consumption 0.002 to 0.2 [200,201]
1 × 10−9 to 1 × 10−10 [mol O2 kg−1 s−1 ] Up to 6 wt% py Doyon, Canada [Au] Heat and oxygen profiles 0.58 to 5.8 [192]
3 to 100 [mg SO4 kg−1 wk−1 ] <0.5 wt% S Cluff Lake, Canada [U] Sulfate mass-loading 0.05 to 1.7 [193]
7 to 70 [mg SO4 kg−1 wk−1 ] <0.5 wt% S Cluff Lake, Canada [U] Oxygen consumption 0.12 to 1.2 [193]
8 × 10−8 to 2 × 10−7 [kg Py m−2 s−1 ] Mixed (~3 wt% S) Rum Jungle, Australia [U] Thermal profiles 0.15 to 0.36 [202]
Numerical modelling
0.004–0.4 [kg O2 m−3 yr−1 ] Mixed (6–0.1% S) Doyon, Canada [Au] Simulated 0.004 to 0.4 [203]
0.02 [kg Py m−3 yr−1 ] Mixed (0.1% Py) Doyon, Canada [Au] Simulated 0.006 [204,205]
0.15 [kg Py m−3 yr−1 ] Mixed (0.05% Py) Nordhalde, Germany [U] Simulated 0.04 [204,205]
Calibrated to
5 ± 1 × 10−7 [mol O2 m−3 s−1 ] up to 1.5% sulfides Aitik, Sweden [Cu] 0.3 [195]
measurements
1× 10−7to 5 × 10−10
[kg O2 m−3 s−1 ] 0.1 to 1 wt% - Adopted 0.005 to 0.9 [206]
up to 292 [kg O2 m−3 day−1 ] 3.5% Questa, USA [Mo] Simulated up to 0.08 [207]
* Conversion performed using the stoichiometry of Equation (11) and bulk waste rock density and porosity values provided in the corresponding references.
Minerals 2020, 10, 728 15 of 37

2.6.1. Static and Kinetic Testing

Static tests aim to quantify the acid-generating and acid-neutralizing capabilities of bulk mine
waste materials [45]: paste-pH, acid-base accounting (ABA), and net acid generation (NAG) tests are
common waste-rock classification methods. The detailed procedures, advantages, and shortcomings
of static tests have been reviewed [45,46,132,208]. In brief, ABA is based on a determination of the
total sulfur, sulfide, and carbon content of a waste-rock sample. The acid-producing potential (AP)
is calculated by multiplying the sulfur or sulfide content by a stoichiometric factor [132], typically
differing with sulfide reactivity (Section 2.5) [209,210]. Acid-neutralization potential (NP) is typically
determined by titration with HCl (Sobek method [132,211,212]), although such NP determination
has been repeatedly revised [213–215] and equally deploys correction factors [45,216–218]. Both AP
and NP typically have units of kg CaCO3 per ton waste rock and ultimately aggregate unresolved
mineralogical heterogeneity into bulk waste-rock properties. From AP and NP, a net-neutralizing
potential (NNP = AP–NP; kg CaCO3 /ton waste rock) or neutralizing potential ratio (NPR = NP/AP;
unitless) can be calculated. Although different, site-specific cut-off values to assess acid-production
risks are used, it is often assumed that NNP < −20 kg CaCO3 /ton or NPR < 1 indicate potential net
acid-generating material, whereas material with NNP > 20 kg CaCO3 /ton or NPR > 3 is non-acid
generating [132]. Considerable uncertainty remains associated with these NNP or NPR classification
criteria and unexpected drainage acidification in high NPR materials, as well as non-acidic drainage
from high-sulfide materials [219], have been reported. Being practical and cost-efficient, ABA analyses
continue to be widely used and optimized, e.g., through (i) corrections for oxidation steps that dissolve
organic material, (ii) corrections for samples with abundant forms of S other than sulfide [220], and (iii)
improved determination of silicate NP [221,222].
Static testing is often complemented by kinetic testing to overcome the discrepancy between
conditions for (short-term) laboratory testing on crushed, sieved samples and the long-term behavior
of coarser waste rock observed in the field. Examples of kinetic tests include laboratory humidity cell
tests with artificial wetting- and drying cycles [129,132], column tests [68], as well as field cell tests of
a variety of sizes [128,177]. The benefits and limitations of humidity cell tests have been previously
reviewed [176,223]. Kinetic tests can be used to predict long-term weathering dynamics, investigate
specific geochemical processes, and test possible reclamation scenarios [175]. While long-term kinetic
testing (i.e., months to years) is comparably expensive, kinetic tests are generally performed after static
testwork has identified critical or uncertain samples. Field-based kinetic tests range from small (<1 m3 )
to large-scale (thousands of m3 ) experiments with waste-rock barrels, pads, or test piles, and although
field tests can account for site-specific climatic conditions, they usually cannot be established until
advanced stages of mine operation.
Several multi-scale field research programs with a combination of static and long-term kinetic
tests have been conducted/completed recently, e.g., at the Aitik [195,200,224], Diavik [225–228],
and Antamina [115,166,177,199,229,230] mines. These programs have investigated waste-rock
weathering dynamics and drainage quality evolution in small-scale laboratory tests, meso-scale
columns, and up to full-scale field experiments. A key advantage of such programs is the
opportunity to investigate geochemical reactions and transport processes under quasi-controlled
conditions across a range of scales, thereby providing a means to verify the reliability and accuracy
of static tests for model parameterization (Section 4.2) and practical industrial-scale predictions.
Additional multiscale investigations will be crucial to address remaining knowledge gaps, improve our
conceptual understanding of waste rock weathering processes, and inform practical drainage quality
prediction models.

2.6.2. Macroscale Geochemical Heterogeneity

Full-scale waste-rock piles, especially in complex geological settings [231], may exhibit a high
degree of geochemical heterogeneity, arising from the mixing of different waste-rock materials and
depositional practices (i.e., push- versus end-dumping [232]). On the one hand, such heterogeneities
Minerals 2020, 10, 728 16 of 37

can complicate the development of predictive water quality models when the location and nature
of more reactive waste materials is unknown. However, strategic placement of different materials
(e.g., co-location or blending of acid-producing and acid-neutralizing materials) can also be an
effective strategy to mitigate acid drainage risks [233]. Geochemical material heterogeneity can
cause unpredictable weathering dynamics [115,234–236] and representative sampling is critical to
characterize the spatial distribution of mineral reactivity that can significantly affect the overall drainage
signature of composite systems. Relevant geological, lithological, and alteration units must be sampled
relative to the amounts and particle size of each material [45,132]: inadequate sampling can contribute
to substantial variability or incorrect assessment of waste-rock reactivity. Sampling and analysis
of waste-rock properties or material heterogeneity must be fit-for-purpose to inform the deployed
prediction model: generalization and extrapolation from static tests may be insufficient when done in
lieu of appropriate kinetic testing, as illustrated by the wide range of weathering rates observed in the
field (Table 3).
Thus, bulk waste-rock parameters can be used to aggregate variability in mineralogical composition
of waste rock but static test results or bulk weathering indicators may not reflect in-situ sulfide oxidation
rates and acid-generation in spatially heterogeneous systems, e.g., when retention by secondary minerals
is insufficiently quantified. More accurate predictions of waste-rock drainage dynamics in full-scale
systems may be achieved when static tests, detailed mineralogical analyses and targeted kinetic tests
are effectively combined.

3. Physical Transport Processes

In addition to the geochemical weathering and attenuation processes discussed above, waste-rock
drainage quality and quantities are controlled by the transport of gas, water, and heat through porous
waste-rock piles: aqueous transport controls the ultimate export of solubilized solutes from the
waste-rock pile, and gas transport can affect weathering rates through controlling oxygen supply
required to sustain sulfide oxidation.

3.1. Aqueous Transport

Water flow within waste-rock piles is highly site-specific and varies with climate, (internal) pile
structure, and hydrogeological waste-rock properties. At the macroscale (Figure 3), drainage of a
waste-rock pile can be described by a water balance [16]:

P = E + R + G − R + ∆S (16)

in which P is precipitation, E is evapo(transpi)ration, R is runoff, G is groundwater exchange, R is

reaction, and ∆S is change in internal storage (i.e., infiltration or drainage). Modern waste-rock piles
are preferably placed onto relatively impermeable or lined surfaces to minimize interaction with
groundwater if present at the site. Further, the highest oxidation rates listed in Table 3 indicate that
water consumption by weathering reactions is maximally on the order of 0.01–0.1 kg H2 O m−3 year−1 ,
and thus only relevant to the water budget for tall piles stored at very dry conditions (<200 mm year−1 ).
Minerals 2020, 10, 728 17 of 37
Minerals 2020, 10, x FOR PEER REVIEW 18 of 38

Figure3.
Figure 3. Schematic
Schematic illustration
illustration of
of relevant
relevant aqueous
aqueous (blue)
(blue) and
and gaseous
gaseous (red)
(red) mass
mass transport
transport processes
processes
inwaste-rock
in waste-rockpiles,
piles,distinguishing
distinguishingbetween
betweenmacroscale
macroscale(a)
(a)and
andporescale
porescaleor
ormicroscale
microscale(b)
(b)processes.
processes.

Evaporation
3.2. Gas Transport has been investigated for engineered waste-rock covers [237,238] but less for bare
waste-rock piles [239]. Near-surface water and energy balances have been used to estimate evaporation
Oxygen consumption from sulfide oxidation and CO2 production from carbonate dissolution
rates for waste-rock piles by combining rainfall gauging, soil-water characteristic curves and suction
may induce poregas pressures and compositions that differ from atmospheric conditions,
measurements, in-situ moisture sensors, scintillometry, and eddy covariance measurements or surface
particularly in large waste-rock piles with reactive material [194,198,199,260]. In smaller-scale
heat mapping [240]. Evapo(transpi)ration rates inferred from local meteorological measurements
(laboratory) experiments with less-reactive waste rock, poregas variations are typically neglected yet
are poorly representative for the quite unique, coarse-textured nature of waste rock and empirical
rarely experimentally determined. Gradients in poregas composition and pressure trigger gas
relationships to estimate evaporation (e.g., Penman-Monteith) must be calibrated for such surface
transfer through diffusion and advection, respectively (Figure 3), which affect internal poregas
properties [241]. Water and energy balancing at various mine sites have indicated that evaporation may
distributions and the generally outward transport of CO2 versus inward replenishment of O2. The
be the dominant component (i.e., >70%) of the water balance of waste-rock piles [241,242]. A comparison
contribution of dissolved oxygen transport in percolating water is usually negligible (low solubility)
of twelve waste-rock piles [240] indicated that effective evaporation was lower for bare waste-rock
[16] and convection as a combined heat and gas transfer mechanism is discussed below.
piles compared to covered or vegetated piles. However, evaporation rates from waste-rock piles
Molecular diffusion typically dominates gas transport in low permeability waste-rock systems:
strongly differ from variability in local climatic conditions (wind speed, insolation [243]), slope aspects,
the controls of oxygen diffusion on sulfide oxidation rates have been estimated from mass-balance
as well as surface waste-rock properties (particle size, roughness, albedo). Further study is required
calculations (Fick’s laws) [192,194,261], and more advanced modeling of combined gas advection-
to resolve the controls on evaporative fluxes posed by thermal gradients [239,244] (e.g., quantifying
diffusion with spatially-discretized diffusion parameters [262]. In addition to diffusion, pressure
surface heating using infrared cameras) versus those of vapor pressure versus diffusive gradients [245]
gradients can result in advective gas transport in porous media [263]. Estimates of advective gas
(e.g., mapping of saturation and the evaporative ‘drying front’ [246]).
transport using e.g., pneumatic heads and Darcy’s law for gas, have shown that barometric
Surface runoff from waste-rock piles may be deliberately minimized to avoid erosion on the
fluctuations can be relevant for gas transport particularly through more permeable coarse rubble
pile batters, in which case it is typically insignificant for the water balance. Yet, certain reclamation
zones at the bases of waste-rock piles [194,243,264,265].
strategies rely on maximizing runoff from compacted (subsurface) cover layers to limit percolation
Both diffusive and advective gas transfer are strongly controlled by the properties of the waste
into underlying reactive material [236,247]. Material compaction (e.g., in traffic surfaces) can facilitate
rock, including its permeability, degree of porewater saturation, and spatial heterogeneity therein
surface runoff and ponding, especially under flashy precipitation patterns. Eventually, the non-runoff
[194,266]. Various empirical and semi-empirical formulae to estimate diffusivity and permeability
or evaporated fraction of precipitation will infiltrate the unsaturated waste-rock pile. Downward
from particle size distributions or porosity ranges exist [267–269] but these often invoke tortuosity or
propagation of precipitation forms a wetting front that becomes drainage constituting the base seepage.
constrictivity parameters that are poorly defined [266]. Typical effective permeability and gas-
Changes in internal water storage can be significant when drainage fronts successively migrate through
diffusivity ranges for waste rock have been reviewed [16] and vary orders of magnitude between and
unsaturated waste rock as a result of seasonal precipitation patterns or during so-called wetting-up
within sites [194]. As a result, gas transfer is usually only quantitatively constrained for waste-rock
phases in newly deposited piles [225,229,248].
piles, even though oxygen supply may be rate-limiting in full-scale prediction models. Site-specific
At the porescale (Figure 3), the drainage flow regime from a waste-rock pile is the result of
field determination of gas transport properties, especially in dual-porosity media, is particularly
infiltration through a typically large range of grain and pore sizes. Particle sizes in waste rock
challenging for full-sized waste-rock systems across large areal extents. Further research is therefore
can vary from greater than 1-m boulders to sub-millimeter clay-sized fractions (i.e., wide particle
required to assess the applicability and practicality of in-situ sensing or gas injection tracer tests for
size distributions and porosity ranges) [16]. Such variability must be accounted for conceptual
such parameterization, considering that a quantitative understanding of gas transport limitations can
be used to better assess weathering rates and optimize drainage quality predictions.
Minerals 2020, 10, 728 18 of 37

hydrological models aimed at capturing waste-rock flow dynamics and parameters such as hydraulic
conductivity can be highly non-uniform across poorly-sorted heterogeneous waste-rock piles [229,249].
Infiltration is often (conceptually) separated into a slower matric flow component, in which water
flows under capillary and gravity forces as described by Richards’ equation, and a faster macropore
(or non-capillary, preferential) flow component, which is more rapid and channelized [250]. Wetting
fronts move according to kinematic velocity under dominantly matrix flow conditions but can travel
hundreds of times faster than the average velocity as a result of preferential flow [251]. Preferential
flow phenomena have been extensively studied and reviewed [252,253], including in mine waste
rock [249,254–256].
Tracer tests with internal or externally applied conservative solutes can be used to identify
and quantify preferential flow phenomena. Calibration of hydraulic parameters from tracer tests is
often preferred over conventional field tests (e.g., infiltrometer, permeameter), which are challenging
for large-scale systems and boulder-sized particles. Approaches to describe non-uniform flow in
unsaturated porous media exist include advanced dual-domain (dual-porosity, dual-permeability)
models that have meanwhile been applied to waste rock [229,230]. While preferential flow will be
critical for the prediction of water quantity hydrographs and flushing dynamics, water quality may be
dominantly controlled by matrix flow that facilitates longer contact times with finer-grainer particles
with elevated reactive surface areas and thus solute mobilization [16]. Finally, freeze-and-thaw cycles
may completely alter the hydrological regime in waste-rock piles and can thereby critically affect
drainage dynamics [257,258]. The cryohydrogeology of waste-rock piles is strongly coupled to the
thermal regime through phase transitions (Section 3.3) and has been described by model approaches
that include the Clapeyron equation or Soil-Freezing Characteristic Curves [259]. Thus, waste-rock
flow dynamics are highly site-specific and further research is required to optimize and parameterize
hydrological models for full-scale waste-rock systems.

3.2. Gas Transport

Oxygen consumption from sulfide oxidation and CO2 production from carbonate dissolution may
induce poregas pressures and compositions that differ from atmospheric conditions, particularly in large
waste-rock piles with reactive material [194,198,199,260]. In smaller-scale (laboratory) experiments
with less-reactive waste rock, poregas variations are typically neglected yet rarely experimentally
determined. Gradients in poregas composition and pressure trigger gas transfer through diffusion
and advection, respectively (Figure 3), which affect internal poregas distributions and the generally
outward transport of CO2 versus inward replenishment of O2 . The contribution of dissolved oxygen
transport in percolating water is usually negligible (low solubility) [16] and convection as a combined
heat and gas transfer mechanism is discussed below.
Molecular diffusion typically dominates gas transport in low permeability waste-rock
systems: the controls of oxygen diffusion on sulfide oxidation rates have been estimated from
mass-balance calculations (Fick’s laws) [192,194,261], and more advanced modeling of combined gas
advection-diffusion with spatially-discretized diffusion parameters [262]. In addition to diffusion,
pressure gradients can result in advective gas transport in porous media [263]. Estimates of advective
gas transport using e.g., pneumatic heads and Darcy’s law for gas, have shown that barometric
fluctuations can be relevant for gas transport particularly through more permeable coarse rubble zones
at the bases of waste-rock piles [194,243,264,265].
Both diffusive and advective gas transfer are strongly controlled by the properties of the waste rock,
including its permeability, degree of porewater saturation, and spatial heterogeneity therein [194,266].
Various empirical and semi-empirical formulae to estimate diffusivity and permeability from particle
size distributions or porosity ranges exist [267–269] but these often invoke tortuosity or constrictivity
parameters that are poorly defined [266]. Typical effective permeability and gas-diffusivity ranges for
waste rock have been reviewed [16] and vary orders of magnitude between and within sites [194].
As a result, gas transfer is usually only quantitatively constrained for waste-rock piles, even though
Minerals 2020, 10, 728 19 of 37

oxygen supply may be rate-limiting in full-scale prediction models. Site-specific field determination of
gas transport properties, especially in dual-porosity media, is particularly challenging for full-sized
waste-rock systems across large areal extents. Further research is therefore required to assess the
applicability and practicality of in-situ sensing or gas injection tracer tests for such parameterization,
considering that a quantitative understanding of gas transport limitations can be used to better assess
weathering rates and optimize drainage quality predictions.

3.3. Heat Transport

Exothermic sulfide oxidation (e.g., 1000–1500 kJ·mol−1 for pyrite [270]) can cause internal
temperatures in waste-rock piles to rise to tens of degrees above average ambient temperatures,
e.g., up to 65 ◦ C at some sites [204]. Thermal profiles have been measured in a large number of
waste-rock piles [204,226,271,272], often by means of instrumented boreholes [194]. Heat transfer
from reactive ‘hotspots’ in waste-rock piles is dominated by convective heat transfer, the basis of the
so-called ‘chimney effect’ [206,273] (Figure 3). Convection is the combination of conduction (heat
diffusion) and advection (bulk fluid flow); radiative transfer and viscous dissipation are typically
assumed negligible in waste rock. Natural convection arises from buoyancy forces in waste-rock piles
generated by oxidation reactions that produce heat and alter the density of the poregas (e.g., through
water vapor [206]). Temperature gradients caused by internal heating trigger upward convection
against the downward diffusive transport of oxygen into a waste-rock pile. Mass transfer estimates
and modeling studies have shown that convective heat and gas transfer can sustain high waste-rock
weathering rates [204,274]. The onset and strength of convective transport is determined by the
temperature gradient (local atmospheric temperature versus the spatial distribution of reactive waste
rock [236,273]) and waste-rock permeability. As a result, parameterization of heat transfer properties is
not straightforward [16] and effective heat transfer properties vary widely as a function of porewater
saturation and porosity [204,236,266,272]. Further work is required to relate heat transfer mechanisms
to waste-rock properties and pile construction methods, and thereby help quantify the contribution of
convection to overall weathering rates and ultimately drainage quality.

3.4. Physical Heterogeneity

Physical heterogeneity within waste-rock piles induces variations in their hydrogeological
properties (water, air, and heat transport). In-situ investigation of temperature, poregas composition,
moisture distribution, infiltration, and solute transport can help assess these heterogeneities on practical
scales [275–277], e.g., by mapping flow channeling or diversion along structural features such as
intermittent traffic surfaces or tipping benches. Recent improvements in our ability to measure in-situ
properties at increasing resolution have helped characterize heterogeneity for improved drainage
quality predictions and numerical models (Section 4.2).
Soil moisture sensing techniques have been recently reviewed [278]. Point measurement techniques
provide precise measurements of hydrogeological properties but are challenging to extrapolate to larger
areas because of the waste-rock heterogeneities. Previous work on the hydrogeological properties
of waste-rock piles have used point measurements of water content, for instance using time-domain
reflectometry (TDR) sensors [16,279,280], frequency-domain (FDR) sensors [281], and soil water
potential sensors [282,283], or by oven-drying discrete waste-rock samples taken at several depths in
boreholes [162,163]. Remote sensing techniques offer larger scales of investigation, but often at the
expense of lower resolutions that might be inadequate to discriminate the internal fine structure of
waste-rock piles. Nevertheless, electrical resistivity techniques (ERT; [275,281]), ground penetrating
radar (GPR; [284–286]), electromagnetic induction (EMI; [284,287]), fibre optic distributed temperature
sensing (FO-DTS; [288]), or oxygen/hydrogen isotopic signatures [162] have all been applied successfully
to investigate hydrogeological dynamics in waste-rock piles. In addition, basal lysimeters are often
used to record internal mixing and drainage at the bottom of waste-rock piles [115,280,282]. In addition
to direct sensing and measurement techniques, physical and geochemical heterogeneity in waste-rock
 properties (Section 3.4), prediction of such a fluid composition constitutes a challenging task, due to
the coupled nature of the physicochemical processes described above [16,290]. Figure 4 schematically
illustrates the different physical transport processes and geochemical reactions controlling waste-
rock drainage quality and quantity and how they interact.
Minerals
A 2020, 10, 728 of these couplings has been previously investigated [16,205,266]. Many processes
selection 20 of 37

and associated feedbacks operate virtually simultaneously. For instance, sulfide oxidation produces
acidity
piles maythat
be induces carbonate and
reverse-engineered fromsilicate weatheringand
truck movement and secondary
placement mineral
records precipitation,
[289]. all of
Ideally, multiple
which affect pH and the subsequent progress of oxidation [172]. Sulfide oxidation
of the aforementioned methods are combined to gain a more comprehensive understanding of the may undergo
orders-of-magnitude
overall hydrogeologicalacceleration under acidifying
behavior of heterogeneous conditions,
waste-rock piles.due to a fractional-order rate
dependence on proton activity and due to increased oxidation by ferric ion. At the same time, sulfide
oxidation
3.5. Couplingis an exothermic
Between reaction:
Geochemical the reaction
Reactions rates Transport
and Physical of sulfide oxidation may increase by several
factors between every 10 °C increase in temperature, as per Arrhenius’ relation [194]. Temperature
The overall waste-rock drainage from a composite, heterogeneous waste-rock pile often reflects
also impacts geochemical reactions rates through minor changes in equilibrium and gas solubility
the mixed aggregate signal of individual reaction-infiltration pathways, each resulting from a sequence
constants, and fluid properties such as density and viscosity that can affect transport rates [266].
of interacting processes. The drainage composition arising at each individual pathway results from
While some couplings thus enforce controls on magnitudes of percentages or fractions at most, others
exposure to a usually wide range of physicochemical properties and the transport time of the infiltrating
impose orders-of-magnitude influences. The task at hand is to assess the strength of the coupling,
fluid. Even with a perfect description of the spatial heterogeneity in relevant properties (Section 3.4),
and many feedback mechanisms remain poorly quantified. One example is the cryo-hydrogeological
prediction of such a fluid composition constitutes a challenging task, due to the coupled nature of the
feedback between latent heat, gas, and fluid flow behavior and reaction rates: ice is approximately
physicochemical processes described above [16,290]. Figure 4 schematically illustrates the different
3.8 times more heat conductive than water at 0 °C and in cold climates, gas migration through
physical transport processes and geochemical reactions controlling waste-rock drainage quality and
partially frozen waste-rock piles can maintain oxidation reactions and control freeze–thaw dynamics
quantity and how they interact.
[257,258].

Figure 4.
Figure 4. Schematic
Schematic illustration
illustration of
of major
major couplings
couplings andand feedbacks
feedbacks between
between geochemical
geochemical reactions
reactions and
and
physical transport processes. Solid arrow lines indicate interactions or a control-hierarchy
physical transport processes. Solid arrow lines indicate interactions or a control-hierarchy between between
differentprocesses,
different processes,with
withthe
thewidth
widthofofthe
thearrow
arrow being
being (qualitatively)
(qualitatively) proportional
proportional to the
to the magnitude
magnitude or
or strength
strength of theoffeedback.
the feedback.
ExternalExternal
controlscontrols include
include that of sitethat of site meteorology
meteorology ontemperature,
on infiltration, infiltration,
temperature,
and gas pressureandandgasthat
pressure
of siteand that and
geology of site geology and
communition communition
method method
on waste-rock on waste-rock
particle sizes, as
particle sizes, as indicated
indicated by the asterisks. by the asterisks.

A selection
The of these
intricately couplings
coupled hasinbeen
processes previously
waste rock can investigated [16,205,266].
exert both positive Many processes
and negative feedbacks
and associated
towards poorerfeedbacks
drainage operate
quality virtually simultaneously.
(Figure 4). For instance,
As detailed above, sulfide oxidation
sulfide oxidation releasesproduces
heat and
acidity
acidity,that
bothinduces
of which carbonate and
accelerate silicate (Equation
oxidation weathering and
(1)) andsecondary mineral precipitation,
induce a convective all of
supply of oxygen
which affect
that can pH and
accelerate the subsequent
oxidation (‘chimneyprogress
effect’, of oxidation
Section [172].
3.3). For suchSulfide oxidation
positive feedback may undergo
loops, small
orders-of-magnitude acceleration under acidifying conditions, due to a fractional-order rate dependence
on proton activity and due to increased oxidation by ferric ion. At the same time, sulfide oxidation
is an exothermic reaction: the reaction rates of sulfide oxidation may increase by several factors
between every 10 ◦ C increase in temperature, as per Arrhenius’ relation [194]. Temperature also
impacts geochemical reactions rates through minor changes in equilibrium and gas solubility constants,
and fluid properties such as density and viscosity that can affect transport rates [266]. While some
couplings thus enforce controls on magnitudes of percentages or fractions at most, others impose
Minerals 2020, 10, 728 21 of 37

orders-of-magnitude influences. The task at hand is to assess the strength of the coupling, and many
feedback mechanisms remain poorly quantified. One example is the cryo-hydrogeological feedback
between latent heat, gas, and fluid flow behavior and reaction rates: ice is approximately 3.8 times
more heat conductive than water at 0 ◦ C and in cold climates, gas migration through partially frozen
waste-rock piles can maintain oxidation reactions and control freeze–thaw dynamics [257,258].
The intricately coupled processes in waste rock can exert both positive and negative feedbacks
towards poorer drainage quality (Figure 4). As detailed above, sulfide oxidation releases heat and
acidity, both of which accelerate oxidation (Equation (1)) and induce a convective supply of oxygen
that can accelerate oxidation (‘chimney effect’, Section 3.3). For such positive feedback loops, small
parameter variability can yield significant reinforcing perturbations in long-term predictions. In contrast,
drainage quality deterioration may also be lessened by negative feedbacks that decelerate the oxidation
process. For instance, waste-rock weathering rates can be lowered by mineral surface passivation
and pore clogging, a decreased microbial activity at elevated temperatures, or reduction of oxygen
replenishment by mass transport limitations [194]. Finally, while certain feedbacks operate directly or
on comparatively short time-scales (e.g., flow channeling and preferential flow), others can require
years to become relevant (e.g., progressive dissolution of reactive grain sizes [291,292] or secondary
mineral precipitation that affect reactive surface area [290,293] and porosity/permeability [266]).
Processes and their feedbacks can be accounted for in different layers of complexity. Firstly,
they are dependent on the molecular-scale to mineral-scale physical chemistry, i.e., passivation,
porosity, and grain size evolution. Secondly, large heterogeneous systems can display feedbacks that
are controlled by the large-scale structural make-up of the waste-rock pile (e.g., local oxygen content
and oxidation rates that vary with infiltrating precipitation fronts through compacted layers). The
scale of the studied system and according prediction model thus will determine which processes and
feedbacks need to be considered and parameterized.

4. Practical Waste-Rock Drainage Predictions

Prediction of drainage type, amount, and timing is required to reduce or prevent the potential
detrimental environmental impacts of waste-rock weathering [132]. Such prediction is typically
required already during mine planning/permitting stages, in which full-scale waste-rock storage
facilities do not yet exist. Drainage quality and quantity predictions for long-term planning need to
integrate a combination of geochemical and physical transport processes, while geochemistry and
mineralogy determine the occurrence, abundance, and reactivity of potential solutes and hydrogeology
determines their transport and mobility [51], and both are highly interconnected as discussed above.
The scope of investigation required to inform drainage predictions differs based on the cost-benefit
context or engineering problem at hand. For instance, static test results and mass-balance estimates
may suffice for shorter-term, smaller-scope problems (‘black box’ models), but long-term and full-size
water management strategies for entire mine sites require comprehensive data sets and/or coupled
reactive-transport models [13,294]. Experience is required to identify what data is needed for the
practical problem at hand and how prediction model outcomes can be interpreted or not (“all models
are wrong, some are useful” [295]). The development of mine waste-rock drainage models typically
includes baseline scenarios and multiple (conceptual) prediction models that are iteratively updated as
data becomes available during operation [296].

4.1. Scaling Phenomena

Direct extrapolation of waste-rock properties from small-scale and short-duration experiments
into long-term prediction models for full-size systems can lead to erroneous drainage quantity and
quality estimates because smaller-scale static tests of kinetic experiments do not reflect the complex
or variable weathering conditions in the field and extent of material heterogeneity encountered in
full-scale piles. In addition, many physicochemical processes have undetectable impacts below certain
spatiotemporal dimensions [297]: e.g., convection does not exist in humidity cell tests. So-called
Minerals 2020, 10, 728 22 of 37

scaling factors have been proposed to facilitate the use of laboratory parameters onto practice-relevant
waste-rock systems [130,298], but these are often semi-empirical correction factors based on limited
mechanistic evidence and remain poorly verified across different mine sites.
Upscaling phenomena arise when small-scale processes are extrapolated onto larger scales over
orders-of-magnitude, without accounting for changes in continuity or heterogeneity in the studied
system. Upscaling of drainage predictions must therefore address the difference between micro- versus
macroscale parameters for kinetic or transport processes [299]: the task at hand is to identify which
processes undergo relevant scale transitions that are not captured by model parameters (e.g., the onset
of thermal convection or transitioning out of a uniform Darcian flow domain).
As discussed in Section 3.4, quantification of spatial heterogeneity in waste-rock piles is pertinent
for successful drainage predictions. However, the degree of system heterogeneity may increase
with its spatial dimensions [235], and further study (e.g., using variogram models) is required to
assess for which parameters and to which extent increasing heterogeneity causes scaling phenomena.
An opportunity to investigate scale transitions in waste-rock piles may be provided by dimensionless
numbers: quantities relating the spatiotemporal scales of physicochemical processes. Examples include
the Damköhler number (transport versus reaction timescales) and Rayleigh number (buoyancy-driven
flow; convection), which has been used to assess waste-rock weathering dynamics in piles of
various dimensions [206]. Future work on upscaling phenomena is required to improve drainage
prediction models.

4.2. Reactive-Transport Models (RTMs)

Reactive transport modelling can be used to quantify the physicochemical processes and
interactions between reactive fluids and engineered or geological porous media and has been applied
for coupled geochemical and transport phenomena from the micrometer scale to the watershed
scale [290,300]. In contrast to the geochemical (aqueous-phase) equilibrium models described above
(Section 2.4.1), reactive-transport models (RTMs) are based on mass and energy conservation relations
and process-based equations that describe transport (hydraulic advection and dispersion, diffusion,
convection) as well as chemical reactions across solids, liquids, and gases [135,231,266,301]. As such,
RTMs can account for time-discretized mass and heat transport as well as surface complexation,
liquid-gas partitioning, mineral dissolution and precipitation reactions and various biogeochemical
reactions [290,292]. Reactive-transport models have been widely deployed for the investigation
of waste-rock weathering processes [135,203,296,302] and environmental impact assessment of
(abandoned) mines [303], using codes like MIN3P [304], PHREEQC [305], Hytec [306], Geochemist’s
Workbench [136], Toughreact [307], Crunchflow, or PFlotran [308].
Due to a typically modular approach, RTMs allow for the incremental inclusion of processes
and their interactions [290] and constitute powerful investigative tools. They offer the possibility
to quantitatively assess the relevance of certain processes through sensitivity analyses and can be
used to investigate the effects of potential engineering solutions to mitigate risks associated to poor
drainage quality, such as co-disposal techniques [235] and fluid control layers or covers [135,231,309].
While the versatility of RTMs may be their prime advantage, it also constitutes a limitation:
the choice and parametrization of the considered processes. An immediate drawback is that multiple
descriptions or solutions of a problem can yield the same drainage composition, which is referred to as
non-uniqueness [310]. Setting-up an RTM requires modelling choices, ranging from the selection of
relevant processes (heat generation, phase-changes, permeability evolution), solid phases, and their
reactive properties (kinetic reactions) to the physical description (flow behavior, physical heterogeneity).
While the challenge of such selections increases with the scale of the studied problem, the description
of individual subcomponents alone can be difficult (e.g., the initial waste-rock mineralogy can
consist of multiple (amorphous) phases present at levels below analytical detection limits for which
thermodynamic or kinetic data is unavailable). In addition, RTMs often rely on mathematical
equations for physical or chemical processes that simplify potential feedbacks or aggregate unresolved
Minerals 2020, 10, 728 23 of 37

heterogeneity (e.g., through adoption of bulk-averaged parameters) [297]. For instance, the dependence
of modelled waste-rock hydraulics on measurable parameters (e.g., matric suction) is often modeled
with Van Genuchten relations [250,311,312], which are dependent on particle size [313] and therefore
prone to change over time.
With increasing computational power and availability of big data, it has become possible
to represent large-scale pile dynamics with stochastic [234,235] or (fully-) coupled process-based
RTMs [227,301]. Emerging applications for mine waste-rock systems include dual-continuum
approaches [230]. In contrast, relatively few applications of reactive-transport models with
fully-coupled thermo-hydro-chemical descriptions (e.g., thermally-driven gas migration) have
been performed on large heterogeneous 3D waste-rock systems. A primary challenge in
reactive-transport drainage prediction models is not only to identify the processes that are relevant
in the studied waste-rock domain, but also to accurately parametrize them: more advanced
models for large heterogeneous piles are inherently more difficult to experimentally parametrize.
Mechanistic reactive-transport models can be parameterized practically through synoptic sampling
(e.g., tracer-tests [51]), and they have the potential to inform practical optimization of the design
and management or waste-rock piles, or the mitigation of poor drainage quality. While RTMs
have proven crucial to assess process-relevance and waste-rock weathering dynamics under various
conditions [231], their development and verification is also laborious. In order to justify and establish
their use for practical predictive purposes and management decision-making, it is critical that the
relative sensitivities of the model inputs and outputs are translated into actual design parameters.

5. Concluding Remarks
In this review, we discussed critical hydrogeochemical processes affecting the weathering of
mine waste rock and its potential environmental impacts. Geochemical and mineralogical reactions,
in addition to water, air, and heat transport, are all of key importance in determining waste-rock
weathering rates and thus drainage quality as well as quantity. The research reviewed here has been
instrumental in providing an understanding of the controls on these individual physicochemical
processes, as well as their coupling. Studying the mobility of mine waste pollutants and the underlying
mechanisms from the micro- to the macroscale remains important, as expanding mining operations
around the world pose increasing potential environmental risks: forward-thinking in the design of
long-term dumps that could pose potential leachate quality problems is critical. An improved and
quantitative understanding of the factors controlling mine waste-rock drainage dynamics, paired with
a growing ability to map in-situ heterogeneity in full-scale systems and the power to harness large-scale,
high-resolution data in practical models, will allow engineers and practitioners to develop more robust
prediction models and sustainable management decisions. Continuing research can facilitate optimized
waste management and thereby prevent waste-rock related environmental deterioration in the future.

Author Contributions: Conceptualization, B.V.; Investigation, B.V., N.S., B.P., H.J.; Writing-Review & Editing,
B.V., N.S., B.P., H.J. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Hudson-Edwards, K.A.; Jamieson, H.E.; Lottermoser, B.G. Mine Wastes: Past, Present, Future. Elements 2011,
7, 375–380. [CrossRef]
2. Blowes, D.W.; Ptacek, C.J.; Jambor, J.L.; Weisener, C.G. The geochemistry of acid mine drainage. Environ.
Geochem. 2003, 9, 149–204. [CrossRef]
3. Dino, G.A.; Cavallo, A.; Rossetti, P.; Garamvölgyi, E.; Sándor, R.; Coulon, F. Towards Sustainable Mining:
Exploiting Raw Materials from Extractive Waste Facilities. Sustainability 2020, 12, 2383. [CrossRef]
4. Lottermoser, B.G. Recycling, Reuse and Rehabilitation of Mine Wastes. Elements 2011, 7, 405–410. [CrossRef]
Minerals 2020, 10, 728 24 of 37

5. Lèbre, É.; Corder, G.D.; Golev, A. Sustainable practices in the management of mining waste: A focus on the
mineral resource. Miner. Eng. 2017, 107, 34–42. [CrossRef]
6. Bian, Z.; Miao, X.; Lei, S.; Chen, S.; Wang, W.; Struthers, S. The challenges of reusing mining and
mineral-processing wastes. Science 2012, 337, 702–703. [CrossRef]
7. Byrne, P.; Hudson-Edwards, K.A.; Bird, G.; Macklin, M.G.; Brewer, P.A.; Williams, R.D.; Jamieson, H.E. Water
quality impacts and river system recovery following the 2014 Mount Polley mine tailings dam spill, British
Columbia, Canada. Appl. Geochem. 2018, 91, 64–74. [CrossRef]
8. Santamarina, J.C.; Torres-Cruz, L.A.; Bachus, R.C. Why coal ash and tailings dam disasters occur. Science
2019, 364, 526–528. [CrossRef]
9. Fischer, S.; Rosqvist, G.; Chalov, S.; Jarsjö, J. Disproportionate water quality impacts from the century-old
nautanen copper mines, Northern Sweden. Sustainability 2020, 12, 1394. [CrossRef]
10. Demchak, J.; Skousen, J.; McDonald, L.M. Longevity of acid discharges from underground mines located
above the regional water table. J. Environ. Qual. 2004, 33, 656–668. [CrossRef]
11. Lottermoser, B.G. Mine Wastes: Characterization, Treatment and Environmental Impacts, 3rd ed.; Springer:
Berlin/Heidelberg, Germany, 2010; ISBN 3-642-12419-4. [CrossRef]
12. Mudd, G.M. The Environmental sustainability of mining in Australia: Key mega-trends and looming
constraints. Resour. Policy 2010, 35, 98–115. [CrossRef]
13. Wolkersdorfer, C.; Nordstrom, D.K.; Beckie, R.D.; Cicerone, D.S.; Elliot, T.; Edraki, M.; Valente, T.;
França, S.C.A.; Kumar, P.; Oyarzún, R.; et al. Guidance for the Integrated Use of Hydrological, Geochemical,
and Isotopic Tools in Mining Operations. Mine Water Environ. 2020, 39, 204–228. [CrossRef]
14. Hudson-Edwards, A.K.; Dold, B. Mine waste characterization, management and remediation. Minerals 2015,
5, 82–85. [CrossRef]
15. Jamieson, H.E. Geochemistry and mineralogy of solid mine waste: Essential knowledge for predicting
environmental impact. Elements 2011, 7, 381–386. [CrossRef]
16. Amos, R.T.; Blowes, D.W.; Bailey, B.L.; Sego, D.C.; Smith, L.; Ritchie, A.I.M. Waste-rock hydrogeology and
geochemistry. Appl. Geochem. 2015, 57, 140–156. [CrossRef]
17. Lindsay, M.B.J.; Moncur, M.C.; Bain, J.G.; Jambor, J.L.; Ptacek, C.J.; Blowes, D.W. Geochemical and
mineralogical aspects of sulfide mine tailings. Appl. Geochem. 2015, 57, 157–177. [CrossRef]
18. Ghorbani, Y.; Franzidis, J.-P.; Petersen, J. Heap leaching technology—current state, innovations, and future
directions: A review. Miner. Process. Extr. Metall. Rev. 2016, 37, 73–119. [CrossRef]
19. Marsden, J.O.; Botz, M.M. Heap leach modeling—A review of approaches to metal production forecasting.
Miner. Metall. Process. 2017, 34, 53–64. [CrossRef]
20. Pradhan, N.; Nathsarma, K.C.; Srinivasa Rao, K.; Sukla, L.B.; Mishra, B.K. Heap bioleaching of chalcopyrite:
A review. Miner. Eng. 2008, 21, 355–365. [CrossRef]
21. Dold, B. Sustainability in metal mining: From exploration, over processing to mine waste management.
Rev. Environ. Sci. Bio/Technol. 2008, 7, 275. [CrossRef]
22. Johnson, D.B.; Hallberg, K.B. Acid mine drainage remediation options: A review. Sci. Total Environ. 2005,
338, 3–14. [CrossRef] [PubMed]
23. Park, I.; Tabelin, C.B.; Jeon, S.; Li, X.; Seno, K.; Ito, M.; Hiroyoshi, N. A review of recent strategies for acid
mine drainage prevention and mine tailings recycling. Chemosphere 2019, 219, 588–606. [CrossRef]
24. Evangelou, V.P.; Zhang, Y.L. A review: Pyrite oxidation mechanisms and acid mine drainage prevention.
Crit. Rev. Environ. Sci. Technol. 1995, 25, 141–199. [CrossRef]
25. Cornelis, G.; Johnson, C.A.; Van Gerven, T.; Vandecasteele, C. Leaching mechanisms of oxyanionic metalloid
and metal species in alkaline solid wastes: A review. Appl. Geochem. 2008, 23, 955–976. [CrossRef]
26. Chandra, A.P.; Gerson, A.R. The mechanisms of pyrite oxidation and leaching: A fundamental perspective.
Surf. Sci. Rep. 2010, 65, 293–315. [CrossRef]
27. Li, Y.; Kawashima, N.; Li, J.; Chandra, A.P.; Gerson, A.R. A review of the structure, and fundamental
mechanisms and kinetics of the leaching of chalcopyrite. Adv. Colloid Interface Sci. 2013, 197–198, 1–32.
[CrossRef]
28. Parbhakar-Fox, A.; Lottermoser, B. Principles of Sulfide Oxidation and Acid Rock Drainage. In Environmental
Indicators in Metal Mining; Springer: Berlin/Heidelberg, Germany, 2016; pp. 15–34. ISBN 978-3-319-42729-4.
29. Bosecker, K. Bioleaching: Metal solubilization by microorganisms. FEMS Microbiol. Rev. 1997, 20, 591–604.
[CrossRef]
Minerals 2020, 10, 728 25 of 37

30. Nordstrom, D.K.; Southam, G. Geomicrobiology of sulfide mineral oxidation. In Reviews in Mineralogy;
Banfield, J.F., Nealson, K.H., Eds.; Mineralogical Society of America: Chantilly, VA, USA, 1997; Volume 35,
pp. 361–390.
31. Rawlings, D.E. Heavy metal mining using microbes. Annu. Rev. Microbiol. 2002, 56, 65–91. [CrossRef]
32. Baker, B.J.; Banfield, J.F. Microbial communities in acid mine drainage. FEMS Microbiol. Ecol. 2003, 44,
139–152. [CrossRef]
33. Johnson, D.B.; Hallberg, K.B. The microbiology of acidic mine waters. Res. Microbiol. 2003, 154, 466–473.
[CrossRef]
34. Watling, H.R. The bioleaching of sulphide minerals with emphasis on copper sulphides—A review.
Hydrometallurgy 2006, 84, 81–108. [CrossRef]
35. Rawlings, D.E.; Johnson, D.B. The microbiology of biomining: Development and optimization of
mineral-oxidizing microbial consortia. Microbiology 2007, 153, 315–324. [CrossRef] [PubMed]
36. Johnson, D.B. Biomining-biotechnologies for extracting and recovering metals from ores and waste materials.
Curr. Opin. Biotechnol. 2014, 30, 24–31. [CrossRef] [PubMed]
37. Huang, L.-N.; Kuang, J.-L.; Shu, W.-S. Microbial ecology and evolution in the acid mine drainage model
system. Trends Microbiol. 2016, 24, 581–593. [CrossRef]
38. Kaksonen, A.H.; Boxall, N.J.; Gumulya, Y.; Khaleque, H.N.; Morris, C.; Bohu, T.; Cheng, K.Y.; Usher, K.M.;
Lakaniemi, A.M. Recent progress in biohydrometallurgy and microbial characterisation. Hydrometallurgy
2018, 180, 7–25. [CrossRef]
39. Ledin, M.; Pedersen, K. The environmental impact of mine wastes—roles of microorganisms and their
significance in treatment of mine wastes. Earth-Sci. Rev. 1996, 41, 67–108. [CrossRef]
40. Akcil, A.; Koldas, S. Acid Mine Drainage (AMD): Causes, treatment and case studies. J. Clean. Prod. 2006, 14,
1139–1145. [CrossRef]
41. Neculita, C.M.; Zagury, G.J.; Bussière, B. Passive treatment of acid mine drainage in bioreactors using
sulfate-reducing bacteria: Critical review and research needs. J. Environ. Qual. 2007, 36, 1–16. [CrossRef]
42. RoyChowdhury, A.; Sarkar, D.; Datta, R. Remediation of acid mine drainage-impacted water. Curr. Pollut. Rep.
2015, 1, 131–141. [CrossRef]
43. Jamieson, H.E.; Walker, S.R.; Parsons, M.B. Mineralogical characterization of mine waste. Appl. Geochem.
2015, 57, 85–105. [CrossRef]
44. Piatak, N.M.; Parsons, M.B.; Seal, R.R. Characteristics and environmental aspects of slag: A review.
Appl. Geochem. 2015, 57, 236–266. [CrossRef]
45. Parbhakar-Fox, A.; Lottermoser, B.G. A critical review of acid rock drainage prediction methods and practices.
Miner. Eng. 2015, 82, 107–124. [CrossRef]
46. Dold, B. Acid rock drainage prediction: A critical review. J. Geochem. Explor. 2017, 172, 120–132. [CrossRef]
47. Kefeni, K.K.; Msagati, T.A.M.; Mamba, B.B. Acid mine drainage: Prevention, treatment options, and resource
recovery: A review. J. Clean. Prod. 2017, 151, 475–493. [CrossRef]
48. Lottermoser, B.G. Environmental Indicators in Metal. Mining; Springer: Berlin/Heidelberg, Germany, 2017;
ISBN 978-3-319-42729-4. [CrossRef]
49. Moodley, I.; Sheridan, C.M.; Kappelmeyer, U.; Akcil, A. Environmentally sustainable acid mine drainage
remediation: Research developments with a focus on waste/by-products. Miner. Eng. 2018, 126, 207–220.
[CrossRef]
50. Rajaram, V.; Dutta, S.; Parameswaran, K. Sustainable Mining Practices: A Global Perspective; A.A. Balkema:
Leiden, The Netherlands, 2005; ISBN 9058096890.
51. Nordstrom, D.K. Hydrogeochemical processes governing the origin, transport and fate of major and trace
elements from mine wastes and mineralized rock to surface waters. Appl. Geochem. 2011, 26, 1777–1791.
[CrossRef]
52. Öhlander, B.; Chatwin, T.; Alakangas, L. Management of sulfide-bearing waste, a challenge for the mining
industry. Minerals 2012, 2, 1–10. [CrossRef]
53. Simate, G.S.; Ndlovu, S. Acid mine drainage: Challenges and opportunities. J. Environ. Chem. Eng. 2014, 2.
[CrossRef]
54. Nordstrom, D.K.; Blowes, D.W.; Ptacek, C.J. Hydrogeochemistry and microbiology of mine drainage:
An update. Appl. Geochem. 2015, 57, 3–16. [CrossRef]
55. Batterham, R.J. The mine of the future—Even more sustainable. Miner. Eng. 2017, 107, 2–7. [CrossRef]
Minerals 2020, 10, 728 26 of 37

56. Aznar-Sánchez, J.A.; García-Gómez, J.J.; Velasco-Muñoz, J.F.; Carretero-Gómez, A. Mining waste and its
sustainable management: Advances in worldwide research. Minerals 2018, 8, 284. [CrossRef]
57. Li, J.; Kawashima, N.; Fan, R.; Schumann, R.C.; Gerson, A.R.; Smart, R.S.C. Method for distinctive estimation
of stored acidity forms in acid mine wastes. Environ. Sci. Technol. 2014, 48, 11445–11452. [CrossRef]
[PubMed]
58. Vaughan, D.J. Minerals Sulphides. In Reference Module in Earth Systems and Environmental Sciences; Elsevier:
Amsterdam, The Netherlands, 2013; ISBN 978-0-12-409548-9.
59. Elberling, B.; Schippers, A.; Sand, W. Bacterial and chemical oxidation of pyritic mine tailings at low
temperatures. J. Contam. Hydrol. 2000, 41, 225–238. [CrossRef]
60. Singer, P.C.; Stumm, W. Acidic mine drainage: The rate-determining step. Science 1970, 167, 1121–1123.
[CrossRef] [PubMed]
61. Dos Santos, E.C.; de Mendonça Silva, J.C.; Duarte, H.A. Pyrite oxidation mechanism by oxygen in aqueous
medium. J. Phys. Chem. C 2016, 120, 2760–2768. [CrossRef]
62. Tabelin, C.B.; Suchol, V.; Mayumi, I.; Naoki, H.; Toshifumi, I. Pyrite oxidation in the presence of hematite and
alumina: II. Effects on the cathodic and anodic half-cell reactions. Sci. Total Environ. 2017, 581–582, 126–135.
[CrossRef]
63. Schippers, A.; Breuker, A.; Blazejak, A.; Bosecker, K.; Kock, D.; Wright, T.L. The biogeochemistry and
microbiology of sulfidic mine waste and bioleaching dumps and heaps, and novel Fe(II)-oxidizing bacteria.
Hydrometallurgy 2010, 104, 342–350. [CrossRef]
64. Luther, G.W.; Findlay, A.; MacDonald, D.; Owings, S.; Hanson, T.; Beinart, R.; Girguis, P. Thermodynamics
and kinetics of sulfide oxidation by oxygen: A look at inorganically controlled reactions and biologically
mediated processes in the environment. Front. Microbiol. 2011, 2, 62. [CrossRef]
65. Schrenk, M.O.; Edwards, K.J.; Goodman, R.M.; Hamers, R.J.; Banfield, J.F. Distribution of thiobacillus
ferrooxidans and Leptospirillum ferrooxidans: Implications for generation of acid mine drainage. Science
1998, 279, 1519–1522. [CrossRef]
66. Korehi, H.; Blöthe, M.; Schippers, A. Microbial diversity at the moderate acidic stage in three different sulfidic
mine tailings dumps generating acid mine drainage. Res. Microbiol. 2014, 165, 713–718. [CrossRef]
67. Hallberg, K.B. New perspectives in acid mine drainage microbiology. Hydrometall. 2010, 104, 448–453.
[CrossRef]
68. Blackmore, S.; Vriens, B.; Sorensen, M.; Power, I.M.; Smith, L.; Hallam, S.J.; Mayer, U.K.; Beckie, R.D. Microbial
and geochemical controls on waste rock weathering and drainage quality. Sci. Total Environ. 2018, 640–641,
1004–1014. [CrossRef] [PubMed]
69. Rimstidt, J.D.; Vaughan, D.J. Pyrite oxidation: A state-of-the-art assessment of the reaction mechanism.
Geochim. Cosmochim. Acta 2003, 67, 873–880. [CrossRef]
70. Schippers, A.; Sand, W. Bacterial leaching of metal sulfides proceeds by two indirect mechanisms via
thiosulfate or via polysulfides and sulfur. Appl. Environ. Microbiol. 1999, 65, 319–321. [CrossRef] [PubMed]
71. Borilova, S.; Mandl, M.; Zeman, J.; Kucera, J.; Pakostova, E.; Janiczek, O.; Tuovinen, O.H. Can sulfate be the
first dominant aqueous sulfur species formed in the oxidation of pyrite by acidithiobacillus ferrooxidans?
Front. Microbiol. 2018, 9, 3134. [CrossRef]
72. Johnson, A.C.; Romaniello, S.J.; Reinhard, C.T.; Gregory, D.D.; Garcia-Robledo, E.; Revsbech, N.P.;
Canfield, D.E.; Lyons, T.W.; Anbar, A.D. Experimental determination of pyrite and molybdenite oxidation
kinetics at nanomolar oxygen concentrations. Geochim. Cosmochim. Acta 2019, 249, 160–172. [CrossRef]
73. Kameia, G.; Ohmotob, H. The kinetics of reactions between pyrite and O2-bearing water revealed from in situ
monitoring of DO, Eh and pH in a closed system. Geochim. Cosmochim. Acta 2000, 64, 2585–2601. [CrossRef]
74. Janzen, M.P.; Nicholson, R.V.; Scharer, J.M. Pyrrhotite reaction kinetics: Reaction rates for oxidation by oxygen,
ferric iron, and for nonoxidative dissolution. Geochim. Cosmochim. Acta 2000, 64, 1511–1522. [CrossRef]
75. Nicholson, R.V.; Gillham, R.W.; Reardon, E.J. Pyrite oxidation in carbonate-buffered solution: 1. Experimental
kinetics. Geochim. Cosmochim. Acta 1988, 52, 1077–1085. [CrossRef]
76. Williamson, M.A.; Rimstidt, J.D. The kinetics and electrochemical rate-determining step of aqueous pyrite
oxidation. Geochim. Cosmochim. Acta 1994, 58, 5443–5454. [CrossRef]
77. Rimstidt, J.D.; Chermak, J.A.; Gagen, P.M. Rates of Reaction of Galena, Sphalerite, Chalcopyrite,
and Arsenopyrite with Fe(III) in Acidic Solutions. In Environmental Geochemistry of Sulfide Oxid; American
Chemical Society: Washington, DC, USA, 1993; Volume 550, pp. 1–2. ISBN 9780841227729.
Minerals 2020, 10, 728 27 of 37

78. Walker, F.P.; Schreiber, M.E.; Rimstidt, J.D. Kinetics of arsenopyrite oxidative dissolution by oxygen. Geochim.
Cosmochim. Acta 2006, 70, 1668–1676. [CrossRef]
79. Heidel, C.; Tichomirowa, M.; Breitkopf, C. Sphalerite oxidation pathways detected by oxygen and sulfur
isotope studies. Appl. Geochem. 2011, 26, 2247–2259. [CrossRef]
80. Olson, G.J.; Clark, T.R. Bioleaching of molybdenite. Hydrometallurgy 2008, 93, 10–15. [CrossRef]
81. Jerz, J.K.; Rimstidt, J.D. Pyrite oxidation in moist air Associate editor: M. A. McKibben. Geochim. Cosmochim.
Acta 2004, 68, 701–714. [CrossRef]
82. Moses, C.O.; Herman, J.S. Pyrite oxidation at circumneutral pH. Geochim. Cosmochim. Acta 1991, 55, 471–482.
[CrossRef]
83. Sun, H.; Chen, M.; Zou, L.; Shu, R.; Ruan, R. Study of the kinetics of pyrite oxidation under controlled redox
potential. Hydrometallurgy 2015, 155, 13–19. [CrossRef]
84. Long, H.; Dixon, D.G. Pressure oxidation of pyrite in sulfuric acid media: A kinetic study. Hydrometallurgy
2004, 73, 335–349. [CrossRef]
85. Boon, M.; Heijnen, J.J. Chemical oxidation kinetics of pyrite in bioleaching processes. Hydrometallurgy 1998,
48, 27–41. [CrossRef]
86. McKibben, M.A.; Barnes, H.L. Oxidation of pyrite in low temperature acidic solutions: Rate laws and surface
textures. Geochim. Cosmochim. Acta 1986, 50, 1509–1520. [CrossRef]
87. Lehner, S.; Savage, K. The effect of As, Co, and Ni impurities on pyrite oxidation kinetics: Batch and
flow-through reactor experiments with synthetic pyrite. Geochim. Cosmochim. Acta 2008, 72, 1788–1800.
[CrossRef]
88. Navarro, C.A.; von Bernath, D.; Jerez, C.A. Heavy Metal Resistance Strategies of Acidophilic Bacteria and
Their Acquisition: Importance for Biomining and Bioremediation. Biol. Res. 2013, 46, 363–371. [CrossRef]
89. Chen, J.; He, F.; Zhang, X.; Sun, X.; Zheng, J.; Zheng, J. Heavy metal pollution decreases microbial abundance,
diversity and activity within particle-size fractions of a paddy soil. FEMS Microbiol. Ecol. 2014, 87, 164–181.
[CrossRef] [PubMed]
90. Hendry, M.J.; Biswas, A.; Essilfie-Dughan, J.; Chen, N.; Day, S.J.; Barbour, S.L. Reservoirs of Selenium in Coal
Waste Rock: Elk Valley, British Columbia, Canada. Environ. Sci. Technol. 2015, 49, 8228–8236. [CrossRef]
[PubMed]
91. Chon, H.-T.; Hwang, J.-H. Geochemical Characteristics of the Acid Mine Drainage in the Water System in the
Vicinity of the Dogye Coal Mine in Korea. Environ. Geochem. Health 2000, 22, 155–172. [CrossRef]
92. Black, A.; Craw, D. Arsenic, copper and zinc occurrence at the Wangaloa coal mine, southeast Otago,
New Zealand. Int. J. Coal Geol. 2001, 45, 181–193. [CrossRef]
93. Qureshi, A.; Maurice, C.; Öhlander, B. Potential of coal mine waste rock for generating acid mine drainage.
J. Geochem. Explor. 2016, 160, 44–54. [CrossRef]
94. Equeenuddin, S.M.; Tripathy, S.; Sahoo, P.K.; Panigrahi, M.K. Hydrogeochemical characteristics of acid mine
drainage and water pollution at Makum Coalfield, India. J. Geochem. Explor. 2010, 105, 75–82. [CrossRef]
95. Sahoo, P.K.; Tripathy, S.; Equeenuddin, S.M.; Panigrahi, M.K. Geochemical characteristics of coal mine
discharge vis-à-vis behavior of rare earth elements at Jaintia Hills coalfield, northeastern India. J. Geochem.
Explor. 2012, 112, 235–243. [CrossRef]
96. Szczepanska, J.; Twardowska, I. Distribution and environmental impact of coal-mining wastes in Upper
Silesia, Poland. Environ. Geol. 1999, 38, 249–258. [CrossRef]
97. Banks, S.B.; Banks, D. Abandoned mines drainage: Impact assessment and mitigation of discharges from
coal mines in the UK. Eng. Geol. 2001, 60, 31–37. [CrossRef]
98. Hughes, J.; Craw, D.; Peake, B.; Lindsay, P.; Weber, P. Environmental characterisation of coal mine waste rock
in the field: An example from New Zealand. Environ. Geol. 2007, 52, 1501–1509. [CrossRef]
99. Calkins, W.H. The chemical forms of sulfur in coal: A review. Fuel 1994, 73, 475–484. [CrossRef]
100. Kazadi Mbamba, C.; Harrison, S.T.L.; Franzidis, J.-P.; Broadhurst, J.L. Mitigating acid rock drainage risks
while recovering low-sulfur coal from ultrafine colliery wastes using froth flotation. Miner. Eng. 2012, 29,
13–21. [CrossRef]
101. Banerjee, D. Acid drainage potential from coal mine wastes: Environmental assessment through static and
kinetic tests. Int. J. Environ. Sci. Technol. 2014, 11, 1365–1378. [CrossRef]
Minerals 2020, 10, 728 28 of 37

102. Dutta, M.; Saikia, J.; Taffarel, S.R.; Waanders, F.B.; de Medeiros, D.; Cutruneo, C.M.N.L.; Silva, L.F.O.;
Saikia, B.K. Environmental assessment and nano-mineralogical characterization of coal, overburden and
sediment from Indian coal mining acid drainage. Geosci. Front. 2017, 8, 1285–1297. [CrossRef]
103. Ghosh, W.; Dam, B. Biochemistry and molecular biology of lithotrophic sulfur oxidation by taxonomically
and ecologically diverse bacteria and archaea. FEMS Microbiol. Rev. 2009, 33, 999–1043. [CrossRef]
104. Acharya, C.; Sukla, L.B.; Misra, V.N. Biodepyritisation of coal. J. Chem. Technol. Biotechnol. 2004, 79, 1–12.
[CrossRef]
105. Schippers, A.; Rohwerder, T.; Sand, W. Intermediary sulfur compounds in pyrite oxidation: Implications for
bioleaching and biodepyritization of coal. Appl. Microbiol. Biotechnol. 1999, 52, 104–110. [CrossRef]
106. Davalos, A.; Pecina, E.T.; Soria, M.; Carrillo, F.R. Kinetics of Coal Desulfurization in An Oxidative Acid
Media. Int. J. Coal Prep. Util. 2009, 29, 152–172. [CrossRef]
107. Juszczak, A.; Domka, F.; Kozłowski, M.; Wachowska, H. Microbial desulfurization of coal with Thiobacillus
ferrooxidans bacteria. Fuel 1995, 74, 725–728. [CrossRef]
108. Hoffmann, M.R.; Faust, B.C.; Panda, F.A.; Koo, H.H.; Tsuchiya, H.M. Kinetics of the Removal of Iron Pyrite
from Coal by Microbial Catalysis. Appl. Environ. Microbiol. 1981, 42, 259–271. [CrossRef] [PubMed]
109. Liang, L.; McNabb, J.A.; Paulk, J.M.; Gu, B.; McCarthy, J.F. Kinetics of iron(II) oxygenation at low partial
pressure of oxygen in the presence of natural organic matter. Environ. Sci. Technol. 1993, 27, 1864–1870.
[CrossRef]
110. Kalin, M.; Cairns, J.; McCready, R. Ecological engineering methods for acid mine drainage treatment of coal
wastes. Resour. Conserv. Recycl. 1991, 5, 265–275. [CrossRef]
111. Kaksonen, A.H.; Puhakka, J.A. Sulfate reduction based bioprocesses for the treatment of acid mine drainage
and the recovery of metals. Eng. Life Sci. 2007, 7, 541–564. [CrossRef]
112. Lefticariu, L.; Walters, E.R.; Pugh, C.W.; Bender, K.S. Sulfate reducing bioreactor dependence on organic
substrates for remediation of coal-generated acid mine drainage: Field experiments. Appl. Geochem. 2015, 63,
70–82. [CrossRef]
113. Küsel, K. Microbial cycling of iron and sulfur in acidic coal mining lake sediments. Water Air Soil Pollut.
Focus 2003, 3, 67–90. [CrossRef]
114. Ayora, C.; Caraballo, M.A.; Macias, F.; Rötting, T.S.; Carrera, J.; Nieto, J.-M. Acid mine drainage in the Iberian
Pyrite Belt: 2. Lessons learned from recent passive remediation experiences. Environ. Sci. Pollut. Res. 2013,
20, 7837–7853. [CrossRef]
115. Vriens, B.; Peterson, H.E.; Laurenzi, L.; Smith, L.; Aranda, C.; Mayer, K.U.; Beckie, R.D. Long-term monitoring
of waste-rock weathering at Antamina, Peru. Chemosphere 2019, 215, 858–869. [CrossRef]
116. Maree, J.P.; de Beer, M.; Strydom, W.F.; Christie, A.D.M.; Waanders, F.B. Neutralizing Coal Mine Effluent with
Limestone to Decrease Metals and Sulphate Concentrations. Mine Water Environ. 2004, 23, 81–86. [CrossRef]
117. Alakangas, L.; Andersson, E.; Mueller, S. Neutralization/prevention of acid rock drainage using mixtures of
alkaline by-products and sulfidic mine wastes. Environ. Sci. Pollut. Res. 2013, 20, 7907–7916. [CrossRef]
118. Davies, H.; Weber, P.; Lindsay, P.; Craw, D.; Peake, B.; Pope, J. Geochemical changes during neutralisation
of acid mine drainage in a dynamic mountain stream, New Zealand. Appl. Geochem. 2011, 26, 2121–2133.
[CrossRef]
119. Chou, L.; Garrels, R.M.; Wollast, R. Comparative study of the kinetics and mechanisms of dissolution of
carbonate minerals. Chem. Geol. 1989, 78, 269–282. [CrossRef]
120. Morse, J.W.; Arvidson, R.S. The dissolution kinetics of major sedimentary carbonate minerals. Earth-Sci. Rev.
2002, 58, 51–84. [CrossRef]
121. Kaufmann, G.; Dreybrodt, W. Calcite dissolution kinetics in the system CaCO3 –H2 O–CO2 at high
undersaturation. Geochim. Cosmochim. Acta 2007, 71, 1398–1410. [CrossRef]
122. Stumm, W.; Wollast, R. Coordination chemistry of weathering: Kinetics of the surface-controlled dissolution
of oxide minerals. Rev. Geophys. 1990, 28, 53–69. [CrossRef]
123. Schwertmann, U. Solubility and dissolution of iron oxides. Plant. Soil 1991, 130, 1–25. [CrossRef]
124. White, A.F.; Brantley, S.L. Chemical weathering rates of silicate minerals; an overview. Rev. Mineral. Geochem.
1995, 31, 1–22.
125. Gruber, C.; Kutuzov, I.; Ganor, J. The combined effect of temperature and pH on albite dissolution rate under
far-from-equilibrium conditions. Geochim. Cosmochim. Acta 2016, 186, 154–167. [CrossRef]
Minerals 2020, 10, 728 29 of 37

126. Rimstidt, J.D.; Dove, P.M. Mineral/solution reaction rates in a mixed flow reactor: Wollastonite hydrolysis.
Geochim. Cosmochim. Acta 1986, 50, 2509–2516. [CrossRef]
127. Kirste, D.; Pearce, J.; Golding, S. Parameterizing Geochemical Models: Do Kinetics of Calcite Matter? Procedia
Earth Planet. Sci. 2017, 17, 606–609. [CrossRef]
128. Vriens, B.; Skierszkan, E.K.; St-Arnault, M.; Salzsauler, K.A.; Aranda, C.; Mayer, K.U.; Beckie, R.D. Mobilization
of metal(loid) oxyanions through circumneutral waste-rock drainage. ACS Omega 2019, 4, 10205–10215.
[CrossRef]
129. Plante, B.; Benzaazoua, M.; Bussière, B. Predicting Geochemical Behaviour of Waste Rock with Low Acid
Generating Potential Using Laboratory Kinetic Tests. Mine Water Environ. 2011, 30, 2–21. [CrossRef]
130. Plante, B.; Bussière, B.; Benzaazoua, M. Lab to field scale effects on contaminated neutral drainage prediction
from the Tio mine waste rocks. J. Geochem. Explor. 2014, 137, 37–47. [CrossRef]
131. Nicholson, R.V.; Rinker, M.J. Metal leaching from sulphide mine waste under neutral pH conditions.
In Proceedings of the 5th International Conference on Acid Rock Drainage (ICARD), Denver, CO, USA,
21–24 May 2000; pp. 951–958.
132. Price, W.A. Prediction Manual for Drainage Chemistry from Sulphidic Geologic Materials. MEND
Report 1.20.1. Available online: https://www.fs.usda.gov/Internet/FSE_DOCUMENTS/stelprdb5336546.pdf
(accessed on 1 July 2020).
133. Tabelin, C.B.; Silwamba, M.; Paglinawan, F.C.; Mondejar, A.J.S.; Duc, H.G.; Resabal, V.J.; Opiso, E.M.;
Igarashi, T.; Tomiyama, S.; Ito, M.; et al. Solid-phase partitioning and release-retention mechanisms of
copper, lead, zinc and arsenic in soils impacted by artisanal and small-scale gold mining (ASGM) activities.
Chemosphere 2020, 260, 127574. [CrossRef]
134. Tamoto, S.; Tabelin, C.B.; Igarashi, T.; Ito, M.; Hirojohsi, N. Short and long term release mechanisms of arsenic,
selenium and boron from a tunnel-excavated sedimentary rock under in situ conditions. J. Cont. Hydr. 2015,
175–176, 60–71. [CrossRef]
135. Demers, I.; Molson, J.; Bussière, B.; Laflamme, D. Numerical modeling of contaminated neutral drainage
from a waste-rock field test cell. Appl. Geochem. 2013, 33, 346–356. [CrossRef]
136. Tabelin, C.B.; Sasaki, R.; Igarashi, T.; Park, I.; Tamoto, S.; Arima, T.; Ito, M.; Hiroyoshi, N. Simultaneous
leaching of arsenite, arsenate, selenite and selenate, and their migration in tunnel-excavated sedimentary
rocks: II. Kinetic and reactive transport modeling. Chemosphere 2017, 188, 444–454. [CrossRef]
137. Nordstrom, D.K.; Archer, D.G. Arsenic Thermodynamic Data and Environmental Geochemistry—Arsenic in Ground
Water: Geochemistry and Occurrence; Welch, A.H., Stollenwerk, K.G., Eds.; Springer: Boston, MA, USA, 2003;
pp. 1–25. ISBN 978-0-306-47956-4.
138. Kocourková, E.; Sracek, O.; Houzar, S.; Cempírek, J.; Losos, Z.; Filip, J.; Hršelová, P. Geochemical and
mineralogical control on the mobility of arsenic in a waste rock pile at Dlouhá Ves, Czech Republic. J. Geochem.
Explor. 2011, 110, 61–73. [CrossRef]
139. Wei, X.; Zhang, S.; Shimko, J.; Dengler, R.W., II. Mine drainage: Treatment technologies and rare earth
elements. Water Environ. Res. 2019, 91, 1061–1068. [CrossRef]
140. González, V.; Vignati, D.; Leyval, C.; Giamberini, L. Environmental fate and ecotoxicity of lanthanides: Are
they a uniform group beyond chemistry? Environ. Int. 2014, 71, 148–157. [CrossRef] [PubMed]
141. Romero-Freire, A.; Turlin, F.; André-Mayer, A.-S.; Pelletier, M.; Cayer, A.; Giamberini, L. Giamberini
Biogeochemical Cycle of Lanthanides in a Light Rare Earth Element-Enriched Geological Area
(Quebec, Canada). Minerals 2019, 9, 573. [CrossRef]
142. Ayora, C.; Macías, F.; Torres, E.; Lozano, A.; Carrero, S.; Nieto, J.-M.; Pérez-López, R.; Fernández-Martínez, A.;
Castillo-Michel, H. Recovery of rare earth elements and yttrium from passive-remediation systems of acid
mine drainage. Environ. Sci. Technol. 2016, 50, 8255–8262. [CrossRef]
143. Royer-Lavallée, A.; Neculita, C.M.; Coudert, L. Removal and potential recovery of rare earth elements from
mine water. J. Ind. Eng. Chem. 2020, 89, 47–57. [CrossRef]
144. Edahbi, M.; Plante, B.; Benzaazoua, M. Environmental challenges and identification of the knowledge gaps
associated with REE mine wastes management. J. Clean. Prod. 2019, 212, 1232–1241. [CrossRef]
145. Jamieson, H.; Laidlow, A.; Parsons, M. Characterization of U and REE Mobility Downstream of U Tailings
near Bancroft, Ontario. In Proceedings of the International Conference on Acid Rock Drainage (ICARD),
Santiago, Chile, 21–24 April 2015.
Minerals 2020, 10, 728 30 of 37

146. Edahbi, M.; Plante, B.; Benzaazoua, M.; Pelletier, M. Geochemistry of rare earth elements within waste rocks
from the Montviel carbonatite deposit, Québec, Canada. Environ. Sci. Pollut. Res. 2018, 25, 10997–11010.
[CrossRef]
147. Edahbi, M.; Plante, B.; Benzaazoua, M.; Kormos, L.; Pelletier, M. Rare earth elements (La, Ce, Pr, Nd, and Sm)
from a carbonatite deposit: Mineralogical characterization and geochemical behavior. Minerals 2018, 8, 55.
[CrossRef]
148. Edahbi, M.; Plante, B.; Benzaazoua, M.; Ward, M.; Pelletier, M. Mobility of rare earth elements in mine
drainage: Influence of iron oxides, carbonates, and phosphates. Chemosphere 2018, 199, 647–654. [CrossRef]
149. Kauppila, P.; Räisänen, M. Mineralogical and geochemical alteration of Hitura sulphide mine tailings with
emphasis on nickel mobility and retention. J. Geochem. Explor. 2008, 97, 1–20. [CrossRef]
150. Kauppila, P.; Räisänen, M.; Johnson, R. Geochemical Characterisation of Seepage and Drainage Water Quality
from Two Sulphide Mine Tailings Impoundments: Acid Mine Drainage versus Neutral Mine Drainage. Mine
Water Environ. 2008, 28, 30–49. [CrossRef]
151. Radkova, A.; Jamieson, H.; Campbell, K. Antimony mobility during the early stages of stibnite weathering
in tailings at the Beaver Brook Sb deposit, Newfoundland. Appl. Geochem. 2020, 115, 104528. [CrossRef]
152. Lindsay, M.B.J.; Condon, P.D.; Jambor, J.L.; Lear, K.G.; Blowes, D.W.; Ptacek, C.J. Mineralogical, geochemical,
and microbial investigation of a sulfide-rich tailings deposit characterized by neutral drainage. Appl. Geochem.
2009, 24, 2212–2221. [CrossRef]
153. Jamieson, H.E.; Bromstad, M.; Nordstrom, D.K. Extremely arsenic-rich, pH-neutral waters from the Giant
mine, Canada. In Proceedings of the First International Conference on Mine Water Solutions in Extreme
Environments, Lima, Peru, 15–17 April 2013; pp. 82–94.
154. Kwong, Y.T.J.; Percival, J.B.; Soprovich, E.A. Arsenic Mobilization and Attenuation in Near-Neutral
Drainage—Implications for Tailings and Waste Rock Management for Saskatchewan Uranium Mines; Canadian
Institute of Mining, Metallurgy and Petroleum: Montreal, QC, Canada, 2000; ISBN 1-894475-05-4.
155. Plante, B.; Benzaazoua, M.; Bussière, B.; Biesinger, M.C.; Pratt, A.R. Study of Ni sorption onto Tio mine waste
rock surfaces. Appl. Geochem. 2010, 25, 1830–1844. [CrossRef]
156. Powell, K.J.; Brown, P.L.; Byrne, R.H.; Gajda, T.; Hefter, G.; Sjöberg, S.; Wanner, H. Chemical speciation of
environmentally significant metals with inorganic ligands Part 2: The Cu2+ + OH- , Cl- , CO3 2- , SO4 2- , and
PO4 3- systems (IUPAC Technical Report). Pure Appl. Chem. 2007, 79, 895–950. [CrossRef]
157. Powell, K.J.; Brown, P.L.; Byrne, R.H.; Gajda, T.; Hefter, G.; Leuz, A.-K.; Sjöberg, S.; Wanner, H. Chemical
speciation of environmentally significant metals with inorganic ligands. Part 5: The Zn2+ + OH- , Cl- , CO3 2- ,
SO4 2- , and PO4 3- systems (IUPAC Technical Report). Pure Appl. Chem. 2013, 85, 2249–2311. [CrossRef]
158. Grafe, M.; Eick, M.J.; Grossl, P.R.; Saunders, A.M. Adsorption of Arsenate and Arsenite on Ferrihydrite in the
Presence and Absence of Dissolved Organic Carbon. J. Environ. Qual. 2002, 31, 1115–1123. [CrossRef]
159. Zhou, Y.-F.; Haynes, R.J. Sorption of Heavy Metals by Inorganic and Organic Components of Solid Wastes:
Significance to Use of Wastes as Low-Cost Adsorbents and Immobilizing Agents. Crit. Rev. Environ.
Sci. Technol. 2010, 40, 909–977. [CrossRef]
160. Stumm, W.; Morgan, J.J. Aquatic Chemistry—Chemical Equilibria and Rates in Natural Waters, 3rd ed.;
Wiley-Interscience: Hoboken, NJ, USA, 1995; ISBN 978-0471511854.
161. Skierszkan, E.K.; Stockwell, J.S.; Dockrey, J.W.; Weis, D.; Beckie, R.D.; Mayer, K.U. Molybdenum (Mo) stable
isotopic variations as indicators of Mo attenuation in mine waste-rock drainage. Appl. Geochem. 2017, 87,
71–83. [CrossRef]
162. Bao, Z.; Blowes, D.W.; Ptacek, C.J.; Bain, J.; Holland, S.P.; Wilson, D.; Wilson, W.; MacKenzie, P. Faro waste
rock project: Characterizing variably saturated flow behavior through full-scale waste-rock dumps in the
continental subarctic region of northern Canada using field measurements and stable isotopes of water.
Water Resour. Res. 2020, 56. [CrossRef]
163. St-Arnault, M.; Vriens, B.; Klein, B.; Blaskovich, R.; Aranda, C.; Mayer, K.U.; Beckie, R.D. Geochemical and
mineralogical assessment of localized reactive zones through a full scale heterogeneous waste rock pile.
Miner. Eng. 2020, 145, 106089. [CrossRef]
164. Al, T.A.; Martin, C.J.; Blowes, D.W. Carbonate-mineral/water interactions in sulfide-rich mine tailings.
Geochim. Cosmochim. Acta 2000, 64, 3933–3948. [CrossRef]
Minerals 2020, 10, 728 31 of 37

165. Tabelin, C.B.; Corpuz, R.D.; Igarashi, T.; Villacorte-Tabelin, M.; Diaz Alorro, R.; Yoo, K.; Raval, S.; Ito, M.;
Hiroyoshi, N. Acid mine drainage formation and arsenic mobility under strongly acidic conditions:
Importance of soluble phases, iron oxyhydroxides/oxides and nature of oxidation layer on pyrite.
J. Hazard. Mat. 2020, 399, 122844. [CrossRef]
166. Hirsche, D.T.; Blaskovich, R.; Mayer, K.U.; Beckie, R.D. A study of Zn and Mo attenuation by waste-rock
mixing in neutral mine drainage using mixed-material field barrels and humidity cells. Appl. Geochem. 2017,
84, 114–125. [CrossRef]
167. Conlan, M.J.W.; Mayer, K.U.; Blaskovich, R.; Beckie, R.D. Solubility controls for molybdenum in neutral rock
drainage. Geochem. Explor. Environ. Anal. 2012, 12, 21–32. [CrossRef]
168. Moncur, M.C.; Jambor, J.L.; Ptacek, C.J.; Blowes, D.W. Mine drainage from the weathering of sulfide minerals
and magnetite. Appl. Geochem. 2009, 24, 2362–2373. [CrossRef]
169. Plumlee, G.S. The environmental geology of mineral deposis. In The Environmental Geochemistry of Mineral
Deposits. Part A: Processes, Techniques and Health Issues; Plumlee, G.S., Longsdon, M.S., Eds.; Society of
Economic Geologists: Littleton, CO, USA, 1999; pp. 71–116.
170. Weisener, C.G.; Weber, P.A. Preferential oxidation of pyrite as a function of morphology and relict texture.
N. Z. J. Geol. Geophys. 2010, 53, 167–176. [CrossRef]
171. Dold, B. Dissolution kinetics of schwertmannite and ferrihydrite in oxidized mine samples and their detection
by differential X-ray diffraction (DXRD). Appl. Geochem. 2003, 18, 1531–1540. [CrossRef]
172. Huminicki, D.M.C.; Rimstidt, J.D. Iron oxyhydroxide coating of pyrite for acid mine drainage control.
Appl. Geochem. 2009, 24, 1626–1634. [CrossRef]
173. V. Nicholson, R.; Gillham, R.W.; Reardon, E.J. Pyrite oxidation in carbonate-buffered solution: 2. Rate control
by oxide coatings. Geochim. Cosmochim. Acta 1990, 54, 395–402. [CrossRef]
174. Stott, M.B.; Watling, H.R.; Franzmann, P.D.; Sutton, D. The role of iron-hydroxy precipitates in the passivation
of chalcopyrite during bioleaching. Miner. Eng. 2000, 13, 1117–1127. [CrossRef]
175. Roy, V.; Demers, I.; Plante, B.; Thériault, M. Kinetic Testing for Oxidation Acceleration and Passivation of
Sulfides in Waste Rock Piles to Reduce Contaminated Neutral Drainage Generation Potential. Mine Water
Environ. 2020, 39, 242–255. [CrossRef]
176. Maest, A.S.; Nordstrom, D.K. A geochemical examination of humidity cell tests. Appl. Geochem. 2017, 81,
109–131. [CrossRef]
177. St-Arnault, M.; Vriens, B.; Klein, B.; Mayer, K.U.; Beckie, R.D. Mineralogical controls on drainage quality
during the weathering of waste rock. Appl. Geochem. 2019, 108, 104376. [CrossRef]
178. Fan, R.; Short, M.D.; Zeng, S.-J.; Qian, G.; Li, J.; Schumann, R.C.; Kawashima, N.; Smart, R.S.C.; Gerson, A.R.
The Formation of Silicate-Stabilized Passivating Layers on Pyrite for Reduced Acid Rock Drainage. Environ.
Sci. Technol. 2017, 51, 11317–11325. [CrossRef] [PubMed]
179. Zhou, Y.; Fan, R.; Short, M.D.; Li, J.; Schumann, R.C.; Xu, H.; Smart, R.S.C.; Gerson, A.R.; Qian, G. Formation
of aluminum hydroxide-doped surface passivating layers on pyrite for acid rock drainage control. Environ.
Sci. Technol. 2018, 52, 11786–11795. [CrossRef] [PubMed]
180. Li, X.; Hiroyoshi, N.; Tabelin, C.B.; Naruwa, K.; Harada, C.; Ito, M. Suppressive effects of ferric-catecholate
complexes on pyrite oxidation. Chemosphere 2019, 214, 70–78. [CrossRef] [PubMed]
181. Park, I.; Tabelin, C.B.; Seno, K.; Jeon, S.; Ito, M.; Hiroyoshi, N. Simultaneous suppression of acid mine drainage
formation and arsenic release by Carrier-microencapsulation using aluminum-catecholate complexes.
Chemosphere 2018, 205, 414–425. [CrossRef] [PubMed]
182. Berry, V.K.; Murr, L.E.; Hiskey, J.B. Galvanic interaction between chalcopyrite and pyrite during bacterial
leaching of low-grade waste. Hydrometall. 1978, 3, 309–326. [CrossRef]
183. Kwong, Y.T.J.; Swerhone, G.W.; Lawrence, J.R. Galvanic sulphide oxidation as a metal-leaching mechanism
and its environmental implications. Geochem. Explor. Environ. Anal. 2003, 3, 337–343. [CrossRef]
184. Qian, G.; Fan, R.; Short, M.D.; Schumann, R.C.; Li, J.; St.C. Smart, R.; Gerson, A.R. The effects of galvanic
interactions with pyrite on the generation of acid and metalliferous drainage. Environ. Sci. Technol. 2018, 52,
5349–5357. [CrossRef]
185. Chopard, A.; Plante, B.; Benzaazoua, M.; Bouzahzah, H.; Marion, P. Geochemical investigation of the galvanic
effects during oxidation of pyrite and base-metals sulfides. Chemosphere 2017, 166, 281–291. [CrossRef]
186. Hudson-Edwards, K.A.; Schell, C.; Macklin, M.G. Mineralogy and geochemistry of alluvium contaminated
by metal mining in the Rio Tinto area, southwest Spain. Appl. Geochem. 1999, 14, 1015–1030. [CrossRef]
Minerals 2020, 10, 728 32 of 37

187. Parbhakar-Fox, A.; Lottermoser, B.; Bradshaw, D. Evaluating waste rock mineralogy and microtexture during
kinetic testing for improved acid rock drainage prediction. Miner. Eng. 2013, 52, 111–124. [CrossRef]
188. Parbhakar-Fox, A.K.; Edraki, M.; Walters, S.; Bradshaw, D. Development of a textural index for the prediction
of acid rock drainage. Miner. Eng. 2011, 24, 1277–1287. [CrossRef]
189. Brough, C.P.; Warrender, R.; Bowell, R.J.; Barnes, A.; Parbhakar-Fox, A. The process mineralogy of mine
wastes. Miner. Eng. 2013, 52, 125–135. [CrossRef]
190. Wang, H.; Dowd, P.A.; Xu, C. A reaction rate model for pyrite oxidation considering the influence of water
content and temperature. Miner. Eng. 2019, 134, 345–355. [CrossRef]
191. Dold, B. Evolution of Acid Mine Drainage Formation in Sulphidic Mine Tailings. Minerals 2014, 4, 621–641.
[CrossRef]
192. Sracek, O.; Gélinas, P.; Lefebvre, R.; Nicholson, R. V Comparison of methods for the estimation of pyrite
oxidation rate in a waste rock pile at Mine Doyon site, Quebec, Canada. J. Geochem. Explor. 2006, 91, 99–109.
[CrossRef]
193. Hollings, P.; Hendry, M.J.; Nicholson, R.V.; Kirkland, R.A. Quantification of oxygen consumption and sulphate
release rates for waste rock piles using kinetic cells: Cluff lake uranium mine, northern Saskatchewan,
Canada. Appl. Geochem. 2001, 16, 1215–1230. [CrossRef]
194. Vriens, B.; St.Arnault, M.; Laurenzi, L.; Smith, L.; Mayer, K.U.; Beckie, R.D. Localized Sulfide oxidation
limited by oxygen availability in a full-scale waste-rock pile. Vadose Zone J. 2018, 17, 1–68. [CrossRef]
195. Eriksson, N.; Destouni, G. Combined effects of dissolution kinetics, secondary mineral precipitation, and
preferential flow on copper leaching from mining waste rock. Water Resour. Res. 1997, 33, 471–483. [CrossRef]
196. Strömberg, B.; Banwart, S. Weathering kinetics of waste rock from the Aitik copper mine, Sweden: Scale
dependent rate factors and pH controls in large column experiments. J. Contam. Hydrol. 1999, 39, 59–89.
[CrossRef]
197. Lapakko, K. Comparison of Duluth Complex rock dissolution in the laboratory and field. In Proceedings
of the Proceedings American Society of Mining and Reclamation, Pittsburgh, PA, USA, 24–29 April 1994;
pp. 419–428.
198. Lorca, M.E.; Mayer, K.U.; Pedretti, D.; Smith, L.; Beckie, R.D. Spatial and temporal fluctuations of pore-gas
composition in sulfidic mine waste rock. Vadose Zone J. 2016, 15. [CrossRef]
199. Vriens, B.; Smith, L.; Mayer, K.U.; Beckie, R.D. Poregas distributions in waste-rock piles affected by climate
seasonality and physicochemical heterogeneity. Appl. Geochem. 2019, 100, 305–315. [CrossRef]
200. Linklater, C.M.; Sinclair, D.J.; Brown, P.L. Coupled chemistry and transport modelling of sulphidic waste
rock dumps at the Aitik mine site, Sweden. Appl. Geochem. 2005, 20, 275–293. [CrossRef]
201. Strömberg, B.; Banwart, S. Kinetic modelling of geochemical processes at the Aitik mining waste rock site in
northern Sweden. Appl. Geochem. 1994, 9, 583–595. [CrossRef]
202. Harries, J.R.; Ritchie, A.I.M. The use of temperature profiles to estimate the pyritic oxidation rate in a waste
rock dump from an opencut mine. Water. Air. Soil Pollut. 1981, 15, 405–423. [CrossRef]
203. Molson, J.W.; Fala, O.; Aubertin, M.; Bussière, B. Numerical simulations of pyrite oxidation and acid mine
drainage in unsaturated waste rock piles. J. Contam. Hydrol. 2005, 78, 343–371. [CrossRef]
204. Lefebvre, R.; Hockley, D.; Smolensky, J.; Geélinas, P. Multiphase transfer processes in waste rock piles
producing acid mine drainage. 1: Conceptual model and system characterization. J. Contam. Hydrol. 2001,
52, 137–164. [CrossRef]
205. Lefebvre, R.; Hockley, D.; Smolensky, J.; Lamontagne, A. Multiphase transfer processes in waste rock piles
producing acid mine drainage: 2. Applications of numerical simulation. J. Contam. Hydrol. 2001, 52, 165–186.
[CrossRef]
206. Kuo, E.Y.; Ritchie, A.I.M. The impact of convection on the overall oxidation rate in sulfidic waste rock dumps.
In Proceedings Mining and the Environment II; Goldsack, D., Belzile, N., Yerwood, P., Hall, G., Eds.; Laurentian
University: Sudbury, ON, Canada, 1999; pp. 211–220.
207. Lefebvre, R.; Lamontagne, A.; Wels, C. Numerical simulations of acid drainage in the Sugar Shack South
rock pile, Questa Mine, New Mexico, USA. In Proceedings of the Proceedings 2nd Joint IAH-CNC and
CGS Groundwater Specialty Conference, 54th Canadian Geotechnical Conference, Calgary, AB, Canada,
16–19 September 2001.
208. Karlsson, T.; Räisänen, M.L.; Lehtonen, M.; Alakangas, L. Comparison of static and mineralogical ARD
prediction methods in the Nordic environment. Environ. Monit. Assess. 2018, 190, 719. [CrossRef]
Minerals 2020, 10, 728 33 of 37

209. Chopard, A.; Benzaazoua, M.; Bouzahzah, H.; Plante, B.; Marion, P. A contribution to improve the calculation
of the acid generating potential of mining wastes. Chemosphere 2017, 175, 97–107. [CrossRef] [PubMed]
210. Schumann, R.; Stewart, W.; Miller, S.; Kawashima, N.; Li, J.; Smart, R. Acid–base accounting assessment of
mine wastes using the chromium reducible sulfur method. Sci. Total Environ. 2012, 424, 289–296. [CrossRef]
[PubMed]
211. Weber, P.A.; Thomas, J.E.; Skinner, W.M.; Smart, R.S.C. A methodology to determine the acid-neutralization
capacity of rock samples. Can. Mineral. 2005, 43, 1183–1192. [CrossRef]
212. Paktunc, A.D. Mineralogical constraints on the determination of neutralization potential and prediction of
acid mine drainage. Environ. Geol. 1999, 39, 103–112. [CrossRef]
213. Skousen, J.; Renton, J.; Brown, H.; Evans, P.; Leavitt, B.; Brady, K.; Cohen, L.; Ziemkiewicz, P. Neutralization
potential of overburden samples containing siderite. J. Environ. Qual. 1997, 26, 673–681. [CrossRef]
214. Weber, P.A.; Thomas, J.E.; Skinner, W.M.; Smart, R.S.C. Improved acid neutralisation capacity assessment of
iron carbonates by titration and theoretical calculation. Appl. Geochem. 2004, 19, 687–694. [CrossRef]
215. Skousen, J.; Simmons, J.; McDonald, L.M.; Ziemkiewicz, P. Acid–base accounting to predict post-mining
drainage quality on surface mines. J. Environ. Qual. 2002, 31, 2034–2044. [CrossRef] [PubMed]
216. Morin, K.A.; Hutt, N.M. On the Nonsense of Arguing the Superiority of an Analytical Method for
Neutralization Potential. Minesite Drainage Assessment Group, case study# 32. Available online:
www.mdag.com/case_studies/cs32.html (accessed on 1 July 2020).
217. Bouzahzah, H.; Benzaazoua, M.; Plante, B.; Bussiere, B. A quantitative approach for the estimation of the
“fizz rating” parameter in the acid-base accounting tests: A new adaptations of the Sobek test. J. Geochem.
Explor. 2015, 153, 53–65. [CrossRef]
218. Bouzahzah, H.; Benzaazoua, M.; Bussiere, B.; Plante, B. Prediction of acid mine drainage: Importance of
mineralogy and the test protocols for static and kinetic tests. Mine Water Environ. 2014, 33, 54–65. [CrossRef]
219. Gerson, A.R.; Rolley, P.J.; Davis, C.; Feig, S.T.; Doyle, S.; Smart, R.S.C. Unexpected non-acid drainage from
sulfidic rock waste. Sci. Rep. 2019, 9, 4357. [CrossRef]
220. Pope, J.; Weber, P.; Mackenzie, A.; Newman, N.; Rait, R. Correlation of acid base accounting characteristics
with the Geology of commonly mined coal measures, West Coast and Southland, New Zealand. N. Z. J. Geol.
Geophys. 2010, 53, 153–166. [CrossRef]
221. Miller, S.D.; Stewart, W.S.; Rusdinar, Y.; Schumann, R.E.; Ciccarelli, J.M.; Li, J.; Smart, R.S.C. Methods for
estimation of long-term non-carbonate neutralisation of acid rock drainage. Sci. Total Environ. 2010, 408,
2129–2135. [CrossRef] [PubMed]
222. Jambor, J.L.; Dutrizac, J.E.; Raudsepp, M. Measured and computed neutralization potentials from static tests
of diverse rock types. Environ. Geol. 2007, 52, 1173–1185. [CrossRef]
223. Sapsford, D.J.; Bowell, R.J.; Dey, M.; Williams, K.P. Humidity cell tests for the prediction of acid rock drainage.
Miner. Eng. 2009, 22, 25–36. [CrossRef]
224. Strömberg, B.; Banwart, S.A. Experimental study of acidity-consuming processes in mining waste rock: Some
influences of mineralogy and particle size. Appl. Geochem. 1999, 14, 1–16. [CrossRef]
225. Smith, L.J.D.; Bailey, B.L.; Blowes, D.W.; Jambor, J.L.; Smith, L.; Sego, D.C. The Diavik waste rock project:
Initial geochemical response from a low sulfide waste rock pile. Appl. Geochem. 2013, 36, 210–221. [CrossRef]
226. Pham, N.H.; Sego, D.C.; Arenson, L.U.; Blowes, D.W.; Amos, R.T.; Smith, L. The Diavik Waste Rock Project:
Measurement of the thermal regime of a waste-rock test pile in a permafrost environment. Appl. Geochem.
2013, 36, 234–245. [CrossRef]
227. Wilson, D.; Amos, R.; W. Blowes, D.; B. Langman, J.; Smith, L.; C. Sego, D. Diavik Waste Rock Project:
Scale-up of a reactive transport model for temperature and sulfide-content dependent geochemical evolution
of waste rock. Appl. Geochem. 2018, 96, 177–190. [CrossRef]
228. Langman, B.J.; Moore, L.M.; Ptacek, J.C.; Smith, L.; Sego, D.; Blowes, W.D. Diavik Waste Rock Project:
Evolution of mineral weathering, element release, and acid generation and neutralization during a five-year
humidity cell experiment. Minerals 2014, 4, 257–278. [CrossRef]
229. Blackmore, S.; Smith, L.; Ulrich Mayer, K.; Beckie, R.D. Comparison of unsaturated flow and solute transport
through waste rock at two experimental scales using temporal moments and numerical modeling. J. Contam.
Hydrol. 2014, 171, 49–65. [CrossRef]
Minerals 2020, 10, 728 34 of 37

230. Blackmore, S.; Pedretti, D.; Mayer, K.U.; Smith, L.; Beckie, R.D. Evaluation of single- and dual-porosity
models for reproducing the release of external and internal tracers from heterogeneous waste-rock piles.
J. Contam. Hydrol. 2018, 214, 65–74. [CrossRef] [PubMed]
231. Lahmira, B.; Lefebvre, R.; Aubertin, M.; Bussière, B. Effect of heterogeneity and anisotropy related to the
construction method on transfer processes in waste rock piles. J. Contam. Hydrol. 2016, 184, 35–49. [CrossRef]
[PubMed]
232. Pearce, S.; Birkham, T.; O’Kane, M.; Dobchuk, D. Linking Waste Rock Dump Construction and Design with AMD
Risk: A Quantitative Approach; British Columbia Mine Reclamation Symposium, The University of British
Columbia: Vancouver, BC, Canada, 2016. [CrossRef]
233. Parbhakar-Fox, A.; Fox, N.; Jackson, L.; Cornelius, R. Forecasting geoenvironmental risks: Integrated
applications of mineralogical and chemical data. Minerals 2018, 8, 541. [CrossRef]
234. Pedretti, D.; Mayer, K.U.; Beckie, R.D. Stochastic multicomponent reactive transport analysis of low quality
drainage release from waste rock piles: Controls of the spatial distribution of acid generating and neutralizing
minerals. J. Contam. Hydrol. 2017, 201, 30–38. [CrossRef] [PubMed]
235. Pedretti, D.; Mayer, K.U.; Beckie, R.D. Controls of uncertainty in acid rock drainage predictions from waste
rock piles examined through Monte-Carlo multicomponent reactive transport. Stoch. Environ. Res. Risk
Assess. 2020, 34, 219–233. [CrossRef]
236. Lahmira, B.; Lefebvre, R.; Aubertin, M.; Bussière, B. Effect of material variability and compacted layers
on transfer processes in heterogeneous waste rock piles. J. Contam. Hydrol. 2017, 204, 66–78. [CrossRef]
[PubMed]
237. Swanson, D.A.; Barbour, S.L.; Wilson, G.W.; O’Kane, M. Soil-atmosphere modelling of an engineered soil
cover for acid generating mine waste in a humid, alpine climate. Can. Geotech. J. 2003, 40, 276–292. [CrossRef]
238. Nicholls, E.M.; Drewitt, G.B.; Fraser, S.; Carey, S.K. The influence of vegetation cover on evapotranspiration
atop waste rock piles, Elk Valley, British Columbia. Hydrol. Process. 2019, 33, 2594–2606. [CrossRef]
239. Carey, S.K.; Barbour, S.L.; Hendry, M.J. Evaporation from a waste-rock surface, Key Lake, Saskatchewan.
Can. Geotech. J. 2005, 42, 1189–1199. [CrossRef]
240. Birkham, T.; O’Kane, M.; Goodbrand, A.; Barbour, S.L.; Carey, S.K.; Straker, J.; Baker, T.; Klein, R. Near-surface
water balances of waste rock dumps. In Proceedings of the British Columbia Mine Reclamation Symposium,
Prince George, BC, Canada, 22–25 September 2014.
241. Peterson, H.E. Unsaturated Hydrology, Evaporation, and Geochemistry of Neutral and Acid Rock Drainage
in Highly Heterogeneous Mine Waste Rock at the Antamina Mine, Peru. Ph.D. Thesis, The University of
British Columbia, Vancouver, BC, Canada, 2014.
242. Rohde, T.K.; Defferrard, P.L.; Lord, M. Store and release cover water balance for the south waste rock
dump at Century mine. In Proceedings of the 11th International Conference on Mine Closure 2016, Perth,
Australia, 15–17 March 2016; Fourie, A.B., Fourie, A.B., Tibbett, M., Tibbett, M., Eds.; Australian Centre for
Geomechanics PP—Perth: Perth, Australia, 2016; pp. 47–59.
243. Chi, X.; Amos, R.T.; Stastna, M.; Blowes, D.W.; Sego, D.C.; Smith, L. The Diavik Waste Rock Project:
Implications of wind-induced gas transport. Appl. Geochem. 2013, 36, 246–255. [CrossRef]
244. Sjoberg, D.B.; Lee, B.S.; Jian, Z. Prediction of water vapor movement through waste rock. J. Geotech.
Geoenvironmental Eng. 2004, 130, 293–302. [CrossRef]
245. Haghighi, E.; Or, D. Evaporation from porous surfaces into turbulent airflows: Coupling eddy characteristics
with pore scale vapor diffusion. Water Resour. Res. 2013, 49, 8432–8442. [CrossRef]
246. Wilson, G.W.; Fredlund, D.G.; Barbour, S.L. The effect of soil suction on evaporative fluxes from soil surfaces.
Can. Geotech. J. 1997, 34, 145–155. [CrossRef]
247. Ramasamy, M.; Power, C. Evolution of acid mine drainage from a coal waste rock pile reclaimed with a
simple soil cover. Hydrology 2019, 6, 83. [CrossRef]
248. Neuner, M.; Smith, L.; Blowes, D.W.; Sego, D.C.; Smith, L.J.D.; Fretz, N.; Gupton, M. The Diavik waste rock
project: Water flow through mine waste rock in a permafrost terrain. Appl. Geochem. 2013, 36, 222–233.
[CrossRef]
249. Trinchero, P.; Beckie, R.; Sanchez-Vila, X.; Nichol, C. Assessing preferential flow through an unsaturated
waste rock pile using spectral analysis. Water Resour. Res. 2011, 47, W07532. [CrossRef]
Minerals 2020, 10, 728 35 of 37

250. Šimůnek, J.; Jarvis, N.J.; van Genuchten, M.T.; Gärdenäs, A. Review and comparison of models for describing
non-equilibrium and preferential flow and transport in the vadose zone. J. Hydrol. 2003, 272, 14–35.
[CrossRef]
251. Nimmo, J.R. Simple predictions of maximum transport rate in unsaturated soil and rock. Water Resour. Res.
2007, 43. [CrossRef]
252. Gerke, H.H. Preferential flow descriptions for structured soils. J. Plant. Nutr. Soil Sci. 2006, 169, 382–400.
[CrossRef]
253. Jarvis, N.J. A review of non-equilibrium water flow and solute transport in soil macropores: Principles,
controlling factors and consequences for water quality. Eur. J. Soil Sci. 2007, 58, 523–546. [CrossRef]
254. Shahhosseini, M.; Doulati Ardejani, F.; Amini, M.; Ebrahimi, L. The spatial assessment of acid mine drainage
potential within a low-grade ore dump: The role of preferential flow paths. Environ. Earth Sci. 2019, 79, 28.
[CrossRef]
255. Nichol, C.; Smith, L.; Beckie, R. Field-scale experiments of unsaturated flow and solute transport in a
heterogeneous porous medium. Water Resour. Res. 2005, 41, 1–11. [CrossRef]
256. Eriksson, N.; Gupta, A.; Destouni, G. Comparative analysis of laboratory and field tracer tests for investigating
preferential flow and transport in mining waste rock. J. Hydrol. 1997, 194, 143–163. [CrossRef]
257. Sinclair, S.A.; Pham, N.; Amos, R.T.; Sego, D.C.; Smith, L.; Blowes, D.W. Influence of freeze–thaw dynamics
on internal geochemical evolution of low sulfide waste rock. Appl. Geochem. 2015, 61, 160–174. [CrossRef]
258. Langman, J.B.; Blowes, D.W.; Amos, R.T.; Atherton, C.; Wilson, D.; Smith, L.; Sego, D.C.; Sinclair, S.A.
Influence of a tundra freeze-thaw cycle on sulfide oxidation and metal leaching in a low sulfur, granitic
waste rock. Appl. Geochem. 2017, 76, 9–21. [CrossRef]
259. Kurylyk, B.L.; Watanabe, K. The mathematical representation of freezing and thawing processes in
variably-saturated, non-deformable soils. Adv. Water Resour. 2013, 60, 160–177. [CrossRef]
260. Birkham, T.K.; Hendry, M.J.; Wassenaar, L.I.; Mendoza, C.A.; Lee, E.S. Characterizing Geochemical Reactions
in Unsaturated Mine Waste-Rock Piles Using Gaseous O2 , CO2 , 12 CO2 , and 13 CO2 . Environ. Sci. Technol.
2003, 37, 496–501. [CrossRef]
261. Elberling, B.; Nicholson, R.V.; Scharer, J.M. A combined kinetic and diffusion model for pyrite oxidation in
tailings: A change in controls with time. J. Hydrol. 1994, 157, 47–60. [CrossRef]
262. Pantelis, G.; Ritchie, A.I.M. Rate-limiting factors in dump leaching of pyritic ores. Appl. Math. Model. 1992,
16, 553–560. [CrossRef]
263. Massmann, J.; Farrier, D. Effects of atmospheric pressures on gas transport in the vadose zone.
Water Resour. Res. 1992, 28, 777–791. [CrossRef]
264. Amos, R.T.; Blowes, D.W.; Smith, L.; Sego, D.C. Measurement of Wind-Induced Pressure Gradients in a
Waste Rock Pile. Vadose Zone J. 2009, 8, 953–962. [CrossRef]
265. Lahmira, B.; Lefebvre, R.; Hockley, D.; Phillip, M. Atmospheric Controls on Gas Flow Directions in a Waste
Rock Dump. Vadose Zone J. 2014, 13. [CrossRef]
266. Pantelis, G.; Ritchie, A.I.M.; Stepanyants, Y.A. A conceptual model for the description of oxidation and
transport processes in sulphidic waste rock dumps. Appl. Math. Model. 2002, 26, 751–770. [CrossRef]
267. Collin, M.; Rasmuson, A. A comparison of gas diffusivity models for unsaturated porous media. Soil Sci. Soc.
Am. J. 1988, 52, 1559–1565. [CrossRef]
268. Millington, R.J.; Quirk, J.P. Permeability of porous solids. Trans. Faraday Soc. 1961, 57, 1200–1207. [CrossRef]
269. Wang, T.; Huang, Y.; Chen, X.; Chen, X. Using grain-size distribution methods for estimation of air
permeability. Groundwater 2016, 54, 131–142. [CrossRef]
270. Rohwerder, T.; Schippers, A.; Sand, W. Determination of reaction energy values for biological pyrite oxidation
by calorimetry. Thermochim. Acta 1998, 309, 79–85. [CrossRef]
271. Sracek, O.; Choquette, M.; Gélinas, P.; Lefebvre, R.; Nicholson, R. V Geochemical characterization of acid
mine drainage from a waste rock pile, Mine Doyon, Québec, Canada. J. Contam. Hydrol. 2004, 69, 45–71.
[CrossRef]
272. Tan, Y.; Ritchie, A.I.M. In situ determination of thermal conductivity of waste rock dump material. Water. Air.
Soil Pollut. 1997, 98, 345–359. [CrossRef]
273. Ning, L.; Zhang, Y. Onset of thermally induced gas convection in mine wastes. Int. J. Heat Mass Transf. 1997,
40, 2621–2636. [CrossRef]
Minerals 2020, 10, 728 36 of 37

274. Gou, W.; Parizek, R.R.; Rose, A.W. The role of thermal convection in resupplying O2 to strip coal-mine spoil.
Soil Sci. 1994, 158, 47–55. [CrossRef]
275. Anterrieu, O.; Chouteau, M.; Aubertin, M. Geophysical characterization of the large-scale internal structure
of a waste rock pile from a hard rock mine. Bull. Eng. Geol. Environ. 2010, 69, 533–548. [CrossRef]
276. Dobriyal, P.; Qureshi, A.; Badola, R.; Hussain, S.A. A review of the methods available for estimating soil
moisture and its implications for water resource management. J. Hydrol. 2012, 458, 110–117. [CrossRef]
277. Appels, W.M.; Ireson, A.M.; Barbour, S.L. Impact of bimodal textural heterogeneity and connectivity on flow
and transport through unsaturated mine waste rock. Adv. Water Resour. 2018, 112, 254–265. [CrossRef]
278. Babaeian, E.; Sadeghi, M.; Jones, S.B.; Montzka, C.; Vereecken, H.; Tuller, M. Ground, proximal, and satellite
remote sensing of soil moisture. Rev. Geophys. 2019, 57, 530–616. [CrossRef]
279. Nichol, C.; Smith, L.; Beckie, R. Time domain reflectrometry measurements of water content in coarse waste
rock. Can. Geotech. J. 2003, 40, 137–148. [CrossRef]
280. Smith, L.J.D.; Moncur, M.C.; Neuner, M.; Gupton, M.; Blowes, D.W.; Smith, L.; Sego, D.C. The Diavik
waste rock project: Design, construction, and instrumentation of field-scale experimental waste-rock piles.
Appl. Geochem. 2013, 36, 187–199. [CrossRef]
281. Dimech, A.; Chouteau, M.; Aubertin, M.; Bussière, B.; Martin, V.; Plante, B. Three-dimensional time-lapse
geoelectrical monitoring of water infiltration in an experimental mine waste rock pile. Vadose Zone J. 2019, 18.
[CrossRef]
282. Dubuc, J.; Pabst, T.; Aubertin, M. An assessment of the hydrogeological response of the flow control layer
installed on the experimental waste rock pile at the lac Tio mine. In Proceedings of the GeoOttawa 2017—70th
Canadian Geotechnical Conference, Ottawa, ON, Canada, 1–4 October 2017.
283. Keller, J.; Busker, L.; Milczarek, M.; Rice, R.; Williamson, M. Monitoring of the geochemical evolution of
waste rock facilities at Newmont’s Phoenix Mine. In Proceedings of the VI International Seminar on Mine
Closure, Lake Louise, AB, Canada, 18–21 September 2011.
284. Poisson, J.; Chouteau, M.; Aubertin, M.; Campos, D. Geophysical experiments to image the shallow internal
structure and the moisture distribution of a mine waste rock pile. J. Appl. Geophys. 2009, 67, 179–192.
[CrossRef]
285. Van Dam, R.; Gutierrez, L.; Mclemore, V.; Wilson, G.; Hendrickx, J.; Walker, B. Near Surface Geophysics for
the Structural Analysis of a Mine Rock Pile, Northern New Mexico. J. Am. Soc. Min. Reclam. 2005, 2005,
1178–1201. [CrossRef]
286. Liu, X.; Chen, J.; Cui, X.; Liu, Q.; Cao, X.; Chen, X. Measurement of soil water content using ground-penetrating
radar: A review of current methods. Int. J. Digit. Earth 2019, 12, 95–118. [CrossRef]
287. Power, C.; Tsourlos, P.; Ramasamy, M.; Nivorlis, A.; Mkandawire, M. Combined DC resistivity and induced
polarization (DC-IP) for mapping the internal composition of a mine waste rock pile in Nova Scotia, Canada.
J. Appl. Geophys. 2018, 150, 40–51. [CrossRef]
288. Wu, R.; Martin, V.; McKenzie, J.; Broda, S.; Bussière, B.; Aubertin, M.; Kurylyk, B.L. Laboratory-scale
assessment of a capillary barrier using fibre optic distributed temperature sensing (FO-DTS). Can. Geotech. J.
2020, 57, 115–126. [CrossRef]
289. Li, Y.; Topal, E.; Ramazan, S. Optimising the long-term mine waste management and truck schedule in a
large-scale open pit mine. Min. Technol. 2016, 125, 35–46. [CrossRef]
290. Seigneur, N.; Ulrich Mayer, K.; Steefel, C.I. Reactive transport in evolving porous media. In Reviews in
Mineralogy and Geochemistry; Mineralogical Society: Twickenham, UK, 2019; pp. 197–238.
291. Beckingham, L.E.; Mitnick, E.H.; Steefel, C.I.; Zhang, S.; Voltolini, M.; Swift, A.M.; Yang, L.; Cole, D.R.;
Sheets, J.M.; Ajo-Franklin, J.B.; et al. Evaluation of mineral reactive surface area estimates for prediction of
reactivity of a multi-mineral sediment. Geochim. Cosmochim. Acta 2016, 188, 310–329. [CrossRef]
292. Steefel, C.I.; Lichtner, P.C. Multicomponent reactive transport in discrete fractures: I. Controls on reaction
front geometry. J. Hydrol. 1998, 209, 186–199. [CrossRef]
293. Wunderly, D.M.; Blowes, D.W.; Frind, O.E.; Ptacek, C. Sulfide mineral oxidation and subsequent reactive
transport of oxidation products in mine tailings impoundments: A numerical model. Water Resour. Res.
1996, 32, 3173–3187. [CrossRef]
294. Maest, A.S.; Kuipers, J.R.; Travers, C.L.; Atkins, D.A. Predicting Water Quality at Hardrock Mines; 90 pages,
Kuipers & Associates and Buka Environmental. Available online: http://pebblescience.org/Pebble-Mine/acid-
drainage-pdfs/PredictionsReportFinal.pdf (accessed on 1 July 2020).
Minerals 2020, 10, 728 37 of 37

295. Box, G.E.P. Science and statistics. J. Am. Stat. Assoc. 1976, 71, 791–799. [CrossRef]
296. Muniruzzaman, M.; Kauppila, P.M.; Karlsson, T. Water Quality Prediction of Mining Waste Facilities Based on
Predictive Models; GTK Open File Research Report 16/2018; GTK: Espoo, Finland, 2018; Available online:
http://tupa.gtk.fi/raportti/arkisto/16_2018.pdf (accessed on 1 August 2020).
297. Beckie, R. Analysis of Scale Effects in Large-Scale Solute-Transport Models. In Scale Dependence and Scale
Invariance in Hydrology; Sposito, G., Ed.; Cambridge University Press: Cambridge, UK, 1998; pp. 314–334.
ISBN 9780521571258.
298. Malmström, M.E.; Destouni, G.; Banwart, S.A.; Strömberg, B.H.E. Resolving the scale-dependence of mineral
weathering rates. Environ. Sci. Technol. 2000, 34, 1375–1378. [CrossRef]
299. Morin, K.A.; Hutt, N.M. Environmental Geochemistry of Minesite Drainage: Practical Theory and Case Studies,
Digital Edition; MDAG Publishing: Surrey, BC, Canada, 2001.
300. Molins, S.; Knabner, P. Multiscale approaches in reactive transport modeling. Rev. Mineral. Geochem. 2019,
85, 27–48. [CrossRef]
301. Molson, J.; Aubertin, M.; Bussière, B. Reactive transport modelling of acid mine drainage within discretely
fractured porous media: Plume evolution from a surface source zone. Environ. Model. Softw. 2012, 38,
259–270. [CrossRef]
302. Pabst, T.; Molson, J.; Aubertin, M.; Bussière, B. Reactive transport modelling of the hydro-geochemical
behaviour of partially oxidized acid-generating mine tailings with a monolayer cover. Appl. Geochem. 2017,
78, 219–233. [CrossRef]
303. Tomiyama, S.; Igarashi, T.; Tabelin, C.B.; Tangviroon, P.; Hiroyuki, I. Modeling of the groundwater flow
system in excavated areas of an abandoned mine. J. Cont. Hydr. 2020, 230, 103617. [CrossRef]
304. Mayer, K.U.; Frind, E.O.; Blowes, D.W. Multicomponent reactive transport modeling in variably saturated
porous media using a generalized formulation for kinetically controlled reactions. Water Resour. Res. 2002,
38, 13–21. [CrossRef]
305. Parkhurst, D.L.; Appelo, C.A.J. User’s guide to PHREEQC (Version 2): A computer program for speciation,
batch-reaction, one-dimensional transport, and inverse geochemical calculations. USGS Water Resources
Investigations Report 99-4259. Available online: https://pubs.er.usgs.gov/publication/wri994259 (accessed on
1 July 2020).
306. van der Lee, J.; De Windt, L.; Lagneau, V.; Goblet, P. Module-oriented modeling of reactive transport with
HYTEC. Comput. Geosci. 2003, 29, 265–275. [CrossRef]
307. Xu, T.; Sonnenthal, E.; Spycher, N.; Pruess, K. TOUGHREACT User’s Guide: A Simulation Program for
Non-Isothermal Multiphase Reactive Geochemical Transport in Variable Saturated Geologic Media; University of
California: Berkeley, CA, USA, 2004. [CrossRef]
308. Steefel, C.I.; Appelo, C.A.J.; Arora, B.; Jacques, D.; Kalbacher, T.; Kolditz, O.; Lagneau, V.; Lichtner, P.C.;
Mayer, K.U.; Meeussen, J.C.L.; et al. Reactive transport codes for subsurface environmental simulation.
Comput. Geosci. 2015, 19, 445–478. [CrossRef]
309. Raymond, K.; Seigneur, N.; Su, D.; Plante, B.; Poaty, B.; Bussiere, B.; Mayer, K. Numerical modeling of a
laboratory-scale waste rock pile featuring an engineered cover system. Minerals 2020, 10, 652. [CrossRef]
310. Li, L.; Maher, K.; Navarre-Sitchler, A.; Druhan, J.; Meile, C.; Lawrence, C.; Moore, J.; Perdrial, J.; Sullivan, P.;
Thompson, A.; et al. Expanding the role of reactive transport models in critical zone processes. Earth-Sci.
Rev. 2017, 165, 280–301. [CrossRef]
311. Wösten, J.H.M.; van Genuchten, M.T. Using texture and other soil properties to predict the unsaturated soil
hydraulic functions. Soil Sci. Soc. Am. J. 1988, 52, 1762–1770. [CrossRef]
312. Arya, L.M.; Leij, F.J.; Shouse, P.J.; van Genuchten, M.T. Relationship between the Hydraulic Conductivity
Function and the Particle-Size Distribution. Soil Sci. Soc. Am. J. 1999, 63, 1063–1070. [CrossRef]
313. Mishra, S.; Parker, J.C.; Singhal, N. Estimation of soil hydraulic properties and their uncertainty from particle
size distribution data. J. Hydrol. 1989, 108, 1–18. [CrossRef]

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