Mineral/water interactions in tailings from a tungsten mine, Mount Pleasant, New Brunswick

The pore-water geochemistry and mineralogy of tailings derived from a granitic tungsten deposit were characterized by collecting pore-water samples at discrete depth intervals throughout the tailings for the analysis of major and minor element concentrations. Mineralogical samples from the oxidation zone were analyzed by X-ray diffraction, scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM/EDS), electron microprobe (EMP) combined with wavelength dispersive X-ray spectroscopy (WDS), and transmission electron microscopy (TEM). The oxidation of sulfide minerals in the near-surface tailings leads to a decrease in pore-water pH and elevated SO₄, As, and metal concentrations. The unusual mineralogy of this deposit, compared with that of commonly studied base-metal and gold deposits, results in several unique geochemical characteristics. The dissolution of fluorite releases F into the pore water; the F forms strong complexes with Al and enhances the dissolution of aluminosilicate minerals within the oxidation zone. As a result, high Al concentrations (up to 151.7 mg/L) are detected in the near-neutral pore water in the oxidation zone. The combined dissolution of aluminosilicates and carbonate minerals maintains the pH near 10 in the pore water at depth. Elevated concentrations of W (up to 7.1 mg/L) are detected in the pore water throughout the tailings, likely as a result of the dissolution of wolframite. Consistent with geochemical model calculations, results from SEM/EDS, EMP/WDS and TEM/EDS analyses indicate that secondary minerals, which occur as orange-brown coatings on grains of primary-minerals, are Fe oxyhydroxides. Examples of these secondary minerals display a fibrous habit at high resolution in the TEM. One of these minerals, which contains substantial amounts of Al, As, and Si as impurities, was identified by selected-area electron diffraction (SAED) analyses to be goethite. Another mineral contains relatively high amounts of Si, Pb, Bi, and As, and SAED analyses suggest that the mineral is two-line ferrihydrite.     

Arsenic attenuation in tailings at a former Cu–W–As mine,SW Finland

Nearly half a century after mine closure, release of As from the Ylöjärvi Cu–W–As mine tailings in groundwater and surface water run-off was observed. Investigations by scanning electron microscopy (SEM), electron microprobe analysis (EMPA), synchrotron-based micro-X-ray diffraction (μ-XRD), micro-X-ray absorption near edge structure (μ-XANES) and micro-extended X-ray absorption fine structure (μ-EXAFS) spectroscopy, and a sequential extraction procedure were performed to assess As attenuation mechanisms in the vadose zone of this tailings deposit. Results of SEM, EMPA, and sequential extractions indicated that the precipitation of As bearing Fe(III) (oxy)hydroxides (up to 18.4 wt.% As₂O₅) and Fe(III) arsenates were important secondary controls on As mobility. The μ-XRD, μ-XANES and μ-EXAFS analyses suggested that these phases correspond to poorly crystalline and disordered As-bearing precipitates, including arsenical ferrihydrite, scorodite, kaňkite, and hydrous ferric arsenate (HFA). The pH within 200 cm of the tailings surface averaged 5.7, conditions which favor the precipitation of ferrihydrite. Poorly crystalline Fe(III) arsenates are potentially unstable over time, and their transformation to ferrihydrite, which contributes to As uptake, has potential to increase the As adsorption capacity of the tailings. Arsenic mobility in tailings pore water at the Ylöjärvi mine will depend on continued arsenopyrite oxidation, dissolution or transformation of secondary Fe(III) arsenates, and the As adsorption capacity of Fe(III) (oxy)hydroxides within this tailings deposit.     

Element discharge from pyritic mine tailings at limited oxygen availability in column experiments

Sulfide mineral oxidation in mine tailings deposits poses a long term threat to surrounding ground water and surface waters. Soil or water cover remediation aims at reducing the rate of sulfide mineral oxidation by decreasing the O₂ ingress rate. In this study, the authors addressed the rate of sulfide oxidation and pH buffering in ∼33 months long, well-controlled laboratory studies of water saturated columns of sulfidic mine tailings from the Kristineberg site in Sweden at reduced O₂ availability. The element discharge rates slowly declined towards a quasi-steady state over hundreds of days. Non-reactive tracer tests showed an anomalously large dispersion, indicating strong flow heterogeneity, possibly including preferential flow and/or stagnant water zones. Congruent dissolution of pyrite and sphalerite by injected oxidants (dissolved O₂ and Fe(III)) adequately explained the discharge rate of Fe, S and Zn at quasi-steady state. Arsenic, Pb and Cu were partly retained in the tailings. Base cation discharge rates, and thus pH buffering, were apparently controlled by the rate of acidity production, with actual pH levels, available mineral surface area, and water residence times being of less importance.     

Influence of hardpan layers on arsenic mobility in historical gold mine tailings

Hardpans, or cemented layers, form by precipitation and cementation of secondary minerals in mine tailings and may act as both physical and chemical barriers. Precipitation of secondary minerals during weathering of tailings can sequester metal(loid)s, thereby limiting their release to the environment. At Montague Gold Mines in Nova Scotia, tailings are partially cemented by the Fe arsenate mineral scorodite (FeAsO₄·2H₂O). Previous studies have shown that the formation of scorodite can effectively limit aqueous As concentrations due to its relatively low solubility (<1 mg/L at pH 3–4) and high As content (43–52 wt.% As₂O₅, this study). Co-existing waters and solids were sampled at Montague Gold Mines to identify present-day field conditions influencing scorodite precipitation and dissolution, and to better understand the mineralogical and chemical relationship between hardpan and tailings. In addition to scorodite, hardpan cements were found to include amorphous Fe arsenate and Fe oxyhydroxide. Nearly all hardpan is associated with historical arsenopyrite-bearing concentrate which provides a source of acidity, As⁵⁺ and Fe³⁺ for secondary mineral precipitation. Pore waters sampled from the hardpan have pH values ranging from 2.43 to 7.06. Waters with the lowest pH values also have the highest As concentrations (up to 35.8 mg/L) and are associated with the most extensive hardpan and greatest amount of weathered sulfide. Samples from areas with discontinuous hardpan and less sulfide have near-neutral pH and lower As concentrations. Detailed petrographic observations indicate that the identity and stability of As-bearing secondary minerals depends on the continued availability of sulfide concentrate. The results of this study are being used to develop remediation strategies for highly weathered, hardpan-bearing tailings that consider the stability of both primary and secondary minerals under various cover scenarios.     

A transmission electron microscopy analysis of secondary minerals formed in tungsten-mine tailings with an emphasis on arsenopyrite oxidation

Grains of naturally oxidized arsenopyrite [FeAsS] collected from the oxidation zone in W-mine tailings were investigated, primarily using transmission electron microscopy. The grains are severely pitted and are surrounded by secondary minerals. The pitted nature of the grains is related to mechanisms governing the electrochemical oxidation of sulfide minerals, with prominent cusp-like features occurring at cathodic regions of the surface, and pits occurring at anodic regions. In general, the oxidation of arsenopyrite leads to the formation of an amorphous (or nanocrystalline) Fe–As–O-rich coating that contains small amounts of Si, Ca, Cu, Zn, Pb and Bi; nanoscale variation in the As, Pb, Bi and Zn contents of the coating was noted. Secondary Cu sulfides, thought to be chalcocite [Cu₂S] and (or) djurleite [Cu₃₁S₁₆], occur as a layer (generally <500 nm thick) along the arsenopyrite grain boundary, and also within the coating as aggregates, and as layers that parallel the grain boundary. Although the precipitation of secondary Cu minerals along the grain boundary is a nanoscale feature, the process of formation is thought to be analogous to the supergene enrichment that occurs in weathered sulfide deposits. As the oxidation of arsenopyrite proceeds, layers and clusters of secondary Cu sulfides become isolated in the Fe–As–O coating. Secondary wulfenite [PbMoO₄] and an unidentified crystalline Bi–Pb–As–O mineral occur in voids within the coating, suggesting that these minerals precipitated from the local pore-water. Small and variable amounts of W, Ca, Bi, As and Zn are associated with the wulfenite, and Zn, Fe and Ca are associated with the Bi–Pb–As–O mineral. Some of the wulfenite is in contact with inclusions of molybdenite [MoS₂], suggesting that the oxidation of molybdenite in the presence of aqueous Pb(II) led to the formation of wulfenite. Mineralogical analyses at the nanoscale have improved the understanding of geochemical sources and sinks at this location. The results of this study indicate that the mineralogical controls on aqueous elemental concentrations at this tailings site are complex and are not predicted by thermodynamic calculations.     

The physical, chemical and mineralogical properties of three cemented layers within sulfide-bearing mine tailings

The oxidation and subsequent dissolution of sulfide minerals within mine tailings impoundments releases H⁺, Fe(II), SO₄ and trace elements to the tailings pore water. Subsequent pH-buffering and hydrolysis reactions result in the precipitation of secondary phases such as gypsum, goethite and jarosite. In areas of intense precipitation, cemented layers or “hardpans” often form within the shallow tailings. Three cemented layers within pyrrhotite-bearing mine tailings at the Fault Lake, Nickel Rim and East Mine impoundments located near Sudbury, Canada, were examined. The location of the three cemented layers within the tailings stratigraphy varies as does their location relative to the water table. The morphology, mineralogy and chemical composition of the cemented layers also vary between sites. The bulk density within the three cemented layers all showed an increase relative to the surrounding uncemented tailings ranging from 9% to 29%. The porosity of each cemented layer decreased relative to the surrounding uncemented tailings ranging from an 8% to 18% decrease. The cemented layers also showed relative enrichment of total sulfur, carbon and trace elements relative to the surrounding uncemented tailings. Arsenic concentrations showed an enrichment in the cemented layers of up to 132%, Cd up to 99%, Co up to 84%, Cu up to 144%, Ni up to 693% and Zn up to 145% relative to the surrounding uncemented tailings. All the cemented layers studied show an evolution of the secondary phases with time from a gypsum–jarosite-based cement to a goethite-rich cement. The formation of these layers could potentially have a significant effect on the environmental impacts of sulfide-bearing mine waste.     

尾矿中硫化物风化氧化模拟实验研究

为防治矿山尾矿造成环境污染，对方铅矿，闪锌矿，磁黄铁矿、黄铜矿，黄铁矿进行了风化氧化实验研究，结果显示，硫化物的氧化速率顺序为：方铅矿＞闪锌矿＞磁黄铁矿＞黄铜矿＞黄铁矿，侵蚀液pH值越低，硫化物氧化速率越大，有机物存在对硫化物氧化起缓冲和抑制作用。     

Acid neutralization mechanisms and metal release in mine tailings: a laboratory column experiment

Mining and milling of base metal ore deposits can result in the release of metals to the environment. When sulfide minerals contained in mine tailings are exposed to oxygen and water, they oxidize and dissolve. Two principal antagonistic geochemical processes affect the migration of dissolved metals in tailings impoundments: sulfide oxidation and acid neutralization. This study focuses on acid neutralization reactions occurring in the saturated zone of tailings impoundments. To simulate conditions prevailing in many tailings impoundments, 0.1 mol/L sulfuric acid was passed continuously through columns containing fresh, unoxidized tailings, collected at Kidd Creek metallurgical site. The results of this column experiment represent a detailed temporal observation of pH, Eh, and metal concentrations. The results are consistent with previous field observations, which suggest that a series of mineral dissolution-precipitation reactions control pH and metal mobility. Typically, the series consists of carbonate minerals, Al and Fe(III) hydroxides, and aluminosilicates. In the case of Kidd Creek tailings, the dissolution series consists of ankerite-dolomite, siderite, gibbsite, and aluminosilicates. In the column experiment, three distinct pH plateaus were observed: 5.7, 4.0, and 1.3. The releases of trace elements such as Cd, Co, Cr, Cu, Li, Ni, Pb, V, and Zn were observed to be related to the pH buffering zones. High concentrations of Zn, Ni, and Co were observed at the first pH plateau (pH 5.7), whereas Cd, Cr, Pb, As, V, and Al were released as the pH of the pore water decreased to 4.0 or less.     

Speciation and colloid transport of arsenic from mine tailings

In addition to affecting biogeochemical transformations, the speciation of As also influences its transport from tailings at inoperative mines. The speciation of As in tailings from the Sulfur Bank Mercury Mine site in Clear Lake, California (USA) (a hot-spring Hg deposit) and particles mobilized from these tailings have been examined during laboratory-column experiments. Solutions containing two common, plant-derived organic acids (oxalic and citric acid) were pumped at 13 pore volumes d⁻¹ through 25 by 500 mm columns of calcined Hg ore, analogous to the pedogenesis of tailings. Chemical analysis of column effluent indicated that all of the As mobilized was particulate (1.5 mg, or 6% of the total As in the column through 255 pore volumes of leaching). Arsenic speciation was evaluated using X-ray absorption spectroscopy (XAS), indicating the dominance of arsenate [As(V)] sorbed to poorly crystalline Fe(III)-(hydr)oxides and coprecipitated with jarosite [KFe₃(SO₄, AsO₄)₂(OH)₆] with no detectable primary or secondary minerals in the tailings and mobilized particles. Sequential chemical extractions (SCE) of <45 μm mine tailings fractions also suggest that As occurs adsorbed to Fe (hydr)oxides (35%) and coprecipitated within poorly crystalline phases (45%). In addition, SCEs suggest that As is associated with 1 N acid-soluble phases such as carbonate minerals (20%) and within crystalline Fe-(hydr)oxides (10%). The finding that As is transported from these mine tailings dominantly as As(V) adsorbed to Fe (hydr)oxides or coprecipitated within hydroxysulfates such as jarosite suggests that As release from soils and sediments contaminated with tailings will be controlled by either organic acid-promoted dissolution or reductive dissolution of host phases.     

Mobilization and attenuation of heavy metals within a nickel mine tailings impoundment near Sudbury, Ontario, Canada

 The oxidation and the subsequent dissolution of sulfide minerals within the Copper Cliff tailings area have led to the release of heavy metals such as Fe, Ni, and Co to the tailings pore water. Dissolved concentrations in excess of 10 g/l Fe and 2.2 g/l Ni have been detected within the shallow pore water of the tailings, with increasing depth these concentrations decrease to or near analytical detection limits. Geochemical modelling of the pore-water chemistry suggests that pH-buffering reactions are occurring within the shallow oxidized zones, and that secondary phases are precipitating at or near the underlying hardpan and transition zones. Mineralogical study of the tailings confirmed the presence of goethite, jarosite, gypsum, native sulfur, and a vermiculite-type clay mineral. Goethite, jarosite, and native sulfur form alteration rims and pseudo-morphs of the sulfide minerals. Interstitial cements, composed of goethite, jarosite, and gypsum, locally bind the tailings particles, forming hardpan layers. Microprobe analyses of the goethite indicate that it contains up to 0.6 weight % Ni, suggesting that the goethite is a repository for Ni. Other sinks detected for heavy metals include jarosite and a vemiculite-type clay mineral which locally contains up to 1.6 weight % Ni. To estimate the mass and distribution of heavy metals associated with the secondary phases within the shallow tailings, a series of chemical extractions was completed. The experimental design permitted four fractions of the tailings to be evaluated independently. These four fractions consisted of a water-soluble, an acid-leachable, and a reducible fraction, as well as the whole-rock total. Twenty-five percent of the total mass of heavy metals was removed in the acid-leaching experiments, and 100% of the same components were removed in the reduction experiments. The data suggest that precipitation/coprecipitation reactions are providing an effective sink for most of the heavy metals released by sulfide mineral oxidation. In light of these results, potential decommissioning strategies should be evaluated with the recognition that changing the geochemical conditions may alter the stability of the secondary phases within the shallow tailings. Received: 9 April 1997 · Accepted: 21 July 1997     

Influences of Microbial Oxidation/Reduction on Mineral Transformation in Sulfide Tailings and Environmental Consequence in Shizishan Cu-Au Mine,Tongling, Eastern China

Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoundments and thus are exposed to microbial oxidation. Microbial activities greatly enhance sulfide oxidation and result in the release of heavy metals and the precipitation of iron (oxy) hydroxides and sulfates. These secondary minerals in turn influence the mobility of dissolved metals and play important roles in the natural attenuation of heavy metals. Elucidating the microbe–mineral interactions in tailings will improve our understanding of the environmental consequence of mining activities.     

Effect of acid mine drainage on a karst basin: a case study on the high-As coal mining area in Guizhou province,China

Acid mine drainage (AMD) is a common pollution in mining areas due to the oxidation of pyrite and associated sulfide minerals at mines, tailings and mine dumps. Elevated metals (Fe, Mn, Al) and metalloids (As, Hg) in AMD would deteriorate the local aquatic environment and influence the water supply. A carbonate basin with deposits of high-arsenic coal in Xingren County, southwestern China, was chosen to study the behavior of As and other chemical constituents along a river receiving AMD. Heavy metals (Fe, Mn) and major ions such as (Ca²⁺, Mg²⁺, Cl⁻, SO₄ ²⁻) in surface water, and As in sediment and surface water were analyzed. It was found that high concentrations of SO₄ ²⁻ (1,324–7,560 mg/L) and Fe (369–1,472 mg/L) in surface water were mainly controlled by the interactions between water and rocks such as the oxidation of pyrite in the local coal seams, precipitation and adsorption of iron minerals. Although ubiquitous carbonate minerals in the bedrock and the riverbeds, low pH (<3) water was maintained until 2 km downstream from the AMD source due to the Fe(hydro)oxide minerals coating on the surface of carbonate minerals to restrain the neutralization of acidic water. Moreover, the formation of Fe(hydro)oxide precipitations absorbed As was dominated the attenuation of As from water to sediment. Whereas, the dilution also played an important role in decrease of As in river water.     

Mineralogical,geochemical, and microbial investigation of a sulfide-rich tailings deposit characterized by neutral drainage

Mineralogical, geochemical and microbial characterization of tailings solids from the Greens Creek Mine, Juneau, Alaska, was performed to evaluate mechanisms controlling aqueous geochemistry of near-neutral pH pore water and drainage. Core samples of the tailings were collected from five boreholes ranging from 7 to 26 m in depth. The majority of the 51 samples (77%) were collected from the vadose zone, which can extend >18 m below the tailings surface. Mineralogical investigation indicates that the occurrence of sulfide minerals follows the general order: pyrite [FeS₂] >> sphalerite [(Zn,Fe)S] > galena [PbS], tetrahedrite [(Fe,Zn,Cu,Ag)₁₂Sb₄S₁₃] > arsenopyrite [FeAsS] and chalcopyrite [CuFeS₂]. Pyrite constitutes <20 to >35 wt.% of the tailings mineral assemblage, whereas dolomite [CaMg(CO₃)₂] and calcite [CaCO₃] are present at ?30 and 3 wt.%, respectively. The solid-phase geochemistry generally reflects the mineral assemblage. The presence of additional trace elements, including Cd, Cr, Co, Mo, Ni, Se and Tl, is attributed to substitution into sulfide phases. Results of acid–base accounting (ABA) underestimated both acid-generating potential (AP) and neutralization potential (NP). Recalculation of AP and NP based on solid-phase geochemistry and quantitative mineralogy yielded more representative results. Neutrophilic S-oxidizing bacteria (nSOB) and SO₄-reducing bacteria (SRB) are present with populations up to 10⁷ and 10⁵ cells g⁻¹, respectively. Acidophilic S-oxidizing bacteria (aSOB) and iron-reducing bacteria (IRB) were generally less abundant. Primary influences on aqueous geochemistry are sulfide oxidation and carbonate dissolution at the tailings surface, gypsum precipitation–dissolution reactions, as well as Fe reduction below the zone of sulfide oxidation. Pore-water pH values generally ranged from 6.5 to 7.5 near the tailings surface, and from approximately 7–8 below the oxidation zone. Elevated concentrations of dissolved SO₄, S₂O₃, Fe, Zn, As, Sb and Tl persisted under these conditions.     

Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II)_(aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III)_(s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.     

Release,transport and attenuation of metals from an old tailings impoundment

The oxidation of sulfide minerals from mine wastes results in the release of oxidation products to groundwater and surface water. The abandoned high-sulfide Camp tailings impoundment at Sherridon, Manitoba, wherein the tailings have undergone oxidation for more than 70 a, was investigated by hydrogeological, geochemical, and mineralogical techniques. Mineralogical analysis indicates that the unoxidized tailings contain nearly equal proportions of pyrite and pyrrhotite, which make up to 60 wt% of the total tailings, and which are accompanied by minor amounts of chalcopyrite and sphalerite, and minute amounts of galena and arsenopyrite. Extensive oxidation in the upper 50 cm of the tailings has resulted in extremely high concentrations of dissolved SO₄ and metals and As in the tailings pore water (pH < 1, 129,000 mg L⁻¹ Fe, 280,000 mg L⁻¹ SO₄, 55,000 mg L⁻¹ Zn, 7200 mg L⁻¹ Al, 1600 mg L⁻¹ Cu, 260 mg L⁻¹ Mn, 110 mg L⁻¹ Co, 97 mg L⁻¹ Cd, 40 mg L⁻¹ As, 15 mg L⁻¹ Ni, 8 mg L⁻¹ Pb, and 3 mg L⁻¹ Cr). The acid released from sulfide oxidation has been extensive enough to deplete carbonate minerals to 6 m depth and to partly deplete Al-silicate minerals to a 1 m depth. Below 1 m, sulfide oxidation has resulted in the formation of a continuous hardpan layer that is >1 m thick. Geochemical modeling and mineralogical analysis indicate that the hardpan layer consists of secondary melanterite, rozenite, gypsum, jarosite, and goethite. The minerals indicated mainly control the dissolved concentrations of SO₄, Fe, Ca and K. The highest concentrations of dissolved metals are observed directly above and within the massive hardpan layer. Near the water table at a depth of 4 m, most metals and SO₄ sharply decline in concentration. Although dissolved concentrations of metals and SO₄ decrease below the water table, these concentrations remain elevated throughout the tailings, with up to 60,600 mg L⁻¹ Fe and 91,600 mg L⁻¹ SO₄ observed in the deeper groundwater. During precipitation events, surface seeps develop along the flanks of the impoundment and discharge pore water with a geochemical composition that is similar to the composition of water directly above the hardpan. These results suggest that shallow lateral flow of water from a transient perched water table is resulting in higher contaminant loadings than would be predicted if it were assumed that discharge is derived solely from the deeper primary water table. The abundance of residual sulfide minerals, the depletion of aluminosilicate minerals in the upper meter of the tailings and the presence of a significant mass of residual sulfide minerals in this zone after 70 a of oxidation suggest that sulfide oxidation will continue to release acid, metals, and SO₄ to the environment for decades to centuries.     

Heterogeneous Fe(II) oxidation and zeta potential

The determination of electrophoretic mobility and zeta potential was used as a diagnostic tool, alongside kinetic experiments, to delineate between three plausible mechanisms for the heterogeneous oxidation of Fe(II) by dissolved oxygen. One of these mechanisms is dependant on the positive surface charge that exists on Fe(III) (oxy)hydroxide surfaces at pH values below the Iso-Electric Point (IEP). However, this mechanism can be disputed as catalysis is observed on Fe(III) (oxy)hydroxide surfaces above the IEP despite a negative zeta potential. As well as an IEP shift an overall reduction of the magnitude of the zeta potential is observed in samples of field Fe(III) (oxy)hydroxide collected from the Taff Merthyr mine water treatment site in South Wales, UK. Low zeta potentials determined in mine water treatment systems will have beneficial effects for particle coagulation and settling in passive mine water treatment systems.     

Hydrogeochemistry and microbiology of mine drainage: An update

The extraction of mineral resources requires access through underground workings, or open pit operations, or through drillholes for solution mining. Additionally, mineral processing can generate large quantities of waste, including mill tailings, waste rock and refinery wastes, heap leach pads, and slag. Thus, through mining and mineral processing activities, large surface areas of sulfide minerals can be exposed to oxygen, water, and microbes, resulting in accelerated oxidation of sulfide and other minerals and the potential for the generation of low-quality drainage. The oxidation of sulfide minerals in mine wastes is accelerated by microbial catalysis of the oxidation of aqueous ferrous iron and sulfide. These reactions, particularly when combined with evaporation, can lead to extremely acidic drainage and very high concentrations of dissolved constituents. Although acid mine drainage is the most prevalent and damaging environmental concern associated with mining activities, generation of saline, basic and neutral drainage containing elevated concentrations of dissolved metals, non-metals, and metalloids has recently been recognized as a potential environmental concern. Acid neutralization reactions through the dissolution of carbonate, hydroxide, and silicate minerals and formation of secondary aluminum and ferric hydroxide phases can moderate the effects of acid generation and enhance the formation of secondary hydrated iron and aluminum minerals which may lessen the concentration of dissolved metals. Numerical models provide powerful tools for assessing impacts of these reactions on water quality.     

Iron-hydroxide, iron-sulfate and hydrous-silica coatings in acid-mine tailings facilities: A comparative study of their trace-element composition

Surface alteration-layers often coat minerals in acid-mine drainage systems and the characterization of their chemical composition is required to understand the uptake or release of potentially toxic elements. Samples with micrometer-thick rock coatings were collected from bedrock in contact with three acidic tailings ponds and a small lake, all located within the Copper Cliff mine tailings disposal area in Sudbury, Ontario, Canada. Distribution and concentration of trace-metals in the rock coatings were characterized with Laser-Ablation Inductively-Coupled Plasma Mass Spectroscopy and Micro X-ray Fluorescence Spectroscopy. The rock coatings are composed of goethite, ferrihydrite, schwertmannite, jarosite and amorphous silica. The latter phase is a product of the non-stoichiometric weathering of the underlying siliceous rock. Layers within the coatings are distinguished on the basis of their atomic Fe:Si ratios: FeO_x coatings have Fe:Si > 4:1, Si-FeO_x coatings have Fe:Si = 4:1 to 1:1 and SiO_x coatings have Si > Fe. Iron-rich coatings (FeO_x) in contact with acidic tailings ponds (pH < 3.5) have lower trace-metal concentrations than their Si-rich counterparts, whereas FeO_x in contact with lake water at near neutral pH have similar trace-metal concentrations than Si-FeO_x and SiO_x, most likely the result of higher adsorption rates of metals at near neutral pH conditions. High trace-metal concentrations in Si-FeO_x and SiO_x are explained by the presence of jarosite-group minerals, which formed within Si-rich alteration layers through mixing of leached alkaline cations and trace elements from the underlying rock and Fe³⁺-sulfate solutions from the pond. Calculated enrichment factors for trace metals and metalloids in the coatings (relative to the pond) indicate that the mobility for Pb, As, Cr and Cu in the upper part of tailings ponds is commonly lower than the mobility for Zn, Mn, Co and Ni. The environmental significance of these findings is discussed in terms of the attenuation of trace metals in the coatings and the widespread occurrences of silica gels and jarosite-group minerals.     

Evaluation of phosphate fertilizers for ameliorating acid mine waste

The aim of the study was to determine whether the application of bulk industrial chemicals (potassium permanganate and water-soluble phosphate fertilizer) to partly oxidized, polyminerallic mine wastes can inhibit sulfide oxidation, and metal and metalloid mobility. The acid producing waste rocks were metal (Pb, Zn, Cu) and metalloid (As, Sb) rich and consisted of major quartz, dickite, illite, and sulfide minerals (e.g., galena, chalcopyrite, tetrahedrite, sphalerite, pyrite, arsenopyrite), as well as minor to trace amounts of pre- and post-mining oxidation products (e.g., hydrated Fe, Cu, Pb, and alkali mineral salts). SEM-EDS observations of treated waste material showed that metal, metal–alkali, and alkali phosphate coatings developed on all sulfides. The abundance of phosphate phases was dependant on the fertilizer type and the availability of metal and alkali cations in solution. In turn, the release of cations was dependent on the amount of sulfide oxidation induced by KMnO₄ during the experiment and the dissolution of soluble sulfates. Mn, Ca, Fe, and Pb phosphates remained stable during H₂O₂ leaching, preventing acid generation and metal release. In contrast, the lack of complete phosphate coating on arsenopyrite allowed oxidation and leaching of As to proceed. The mobilized As did not form phosphate phases and consequently, As displayed the greatest release from the coated waste. Thus, the application of KMnO₄ and the water-soluble phosphate fertilizer Trifos (Ca(H₂PO₄)₂) to partly oxidized, polyminerallic mine wastes suppresses sulfide oxidation and is most effective in inhibiting Cu, Pb, and Zn (Sb) release. However, the technique appears ineffective in suppressing oxidation of arsenopyrite and preventing As leaching.