Arsenic mobility in weathered gold mine tailings under a low-organic soil cover

Historical gold mining operations in Nova Scotia, Canada, resulted in numerous deposits of publicly accessible, arsenic (As)-rich mine waste that has weathered in situ for 75–150 years, resulting in a wide range of As-bearing secondary minerals. The geochemical heterogeneity of this mine waste creates a challenge for identifying a single remediation approach that will limit As mobility. A 30-cm-thick, low-organic content soil cover was evaluated in a laboratory leaching experiment where, to simulate natural conditions, the equivalent of 2 years of synthetic rainwater was leached through each column and two dry seasons were incorporated into the leaching protocol. Each column was a stratigraphic representation of the four major tailings types found at the historical Montague and Goldenville gold mine districts: hardpan tailings, oxic tailings, wetland tailings, and high Ca tailings. Hardpan tailings released acidic, As-rich waters (max 12 mg/L) under the soil cover but this acidity was buffered by surrounding oxic tailings. Leachate from the oxic tailings was circumneutral, with average As concentrations between 4.4 and 9.7 mg/L throughout the experiment. The presence of carbonates in the high Ca tailings resulted in near-neutral to weakly alkaline leachate pH values and average As concentrations between 2.1 and 6.1 mg/L. Oxidation of sulfides in the wetland tailings led to acidic leachate over time and a decrease in As concentrations to values that were generally less than 1 mg/L. This study shows that the use of a low-organic content soil cover does not create reducing conditions that would destabilize oxidized, As-bearing secondary phases in these tailings. However, oxygen penetration through the cover during dry seasons would continue to release As to tailings pore waters via sulfide oxidation reactions.     

Mercury mobility in unsaturated gold mine tailings,Murray Brook mine,New Brunswick,Canada

Elevated concentrations of Hg are present (averaging 36 μg/g), mainly as cinnabar, in the Murray Brook Au deposit, located in northern New Brunswick, Canada. After the mined ore was subjected to CN leaching, the tailings were deposited in an unsaturated pile, and 10 a after mine closure an estimated 4.7 × 10³ kg of CN and 1.1 × 10⁴ kg of Hg remain in the pile. Elevated Hg concentrations have been measured in the groundwater (up to 11,500 μg/L) and surface water (up to 32 μg/L) down-gradient of the tailings. To investigate the controls on Hg mobility and leaching persistence, laboratory experiments were conducted using unsaturated columns filled with tailings. Within the first 0.2 pore volumes (PV) eluted, the concentrations of Hg and CN increased to peak concentrations of 12,900 μg Hg/L and 16 mg CN/L, respectively. In the subsequent 0.9 PV, concentrations decreased to approximately 1300 μg Hg/L and 2.8 mg CN/L. Thermodynamic calculations demonstrate that >99.8% of the mobilized Hg in the tailings pore water is in the form of Hg–CN complexes, indicating that Hg mobility to the surrounding aquatic environment is directly dependent on the rate of CN leaching. One-dimensional transport simulations suggest that leached CN can be partitioned into conservative (24%) and non-conservative (76%) fractions. Extrapolation of simulation results to the field scale suggests that CN, and by extension Hg, will continue to elute from the tailings for at least an additional 130 a.     

Subsurface variations in arsenic mineralogy and geochemistry following long-term weathering of gold mine tailings

Variations in arsenic (As) mineralogy and geochemical controls on its mobility were evaluated in subsurface tailings at the historical Montague and Goldenville mine sites in Nova Scotia, Canada. Tailings at these sites contain some of the highest As concentrations in Nova Scotia and are located in close proximity to local communities. Pore water in the subsurface tailings is characterized by circumneutral to alkaline pH (6.2 to 8.7) and mildly reducing to oxidizing redox conditions (+130 mV to +347 mV). Bulk chemistry, scanning electron microscopy, and synchrotron micro-X-ray diffraction analyses showed As mineral hosts differ with depth. The deepest tailings (max. 2 m) are in direct contact with partially decomposed vegetation, which supports reducing conditions and the precipitation of authigenic As and Fe sulfides. Under reducing conditions, dissolved As concentrations are also controlled by desorption of As from dissolution of Fe and Mn oxides and the sorption or co-precipitation of As with carbonates. These geochemical controls differ from those influencing dissolved As concentrations under oxidizing conditions. In the near surface, As mobility is controlled by oxidative dissolution of primary arsenopyrite, precipitation of secondary Fe arsenates, Fe oxyhydroxides and Mn oxides, secondary Ca-Fe arsenates, and sorption onto Fe oxyhydroxides and gangue minerals. Some of these mineral species are stable under different conditions yet occur in close association, indicating the importance of microenvironments. The results of this study show that the weathering characteristics of these tailings vary with depth, leading to the formation of new As hosts that are distinct from those observed in the near surface. Identification of these As hosts provides an understanding of current controls on As mobility and has implications for future reprocessing and/or remediation efforts.     

The effects of hardpan layers on the water chemistry from the leaching of pyrrhotite-rich tailings material

Column leaching experiments were used to determine the effects of an iron-rich hardpan layer, on the rate of tailings oxidation and the composition of leachate waters, from the Renison Bell tailings dams in western Tasmania, Australia. One-meter-long PVC columns, filled with tailings, cover material (Cassiterite Flotation Tailings) and hardpan samples from the tailings dams, were leached over a period of 14 weeks. Under dry cover conditions, when hardpan was present, the solute loads peaked at 21–49 days (Fe at 2,294 ppm and SO ₄ ^2- at 4,700 ppm), and stabilised at much lower concentrations after 9 weeks. In contrast, the solute loads steadily increased over time in the column where hardpan was absent (SO ₄ ^2- from 1,800 to 3,100 ppm, and Fe from 407 to 1,692 ppm). Under saturated cover conditions, the solute concentrations in the leachate also increased with time (SO ₄ ^2-from 1,900 to 17,000 ppm, and Fe from 480 to 8,500 ppm). The presence of a hardpan layer between the reactive tailings and cover material has been found to improve leachate water chemistry and lessen the rate of sulphide oxidation.     

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.     

Geochemistry of arsenic in uranium mine mill tailings,Saskatchewan, Canada

The Rabbit Lake U mine in-pit tailings management facility (TMF) (425 m long×300 m wide×91 m deep) is located in northern Saskatchewan, Canada. The objectives of this study were to quantify the distribution of As phases in the tailings and evaluate the present-day geochemical controls on dissolved As. These objectives were met by analyzing pore fluid samples collected from the tailings body for dissolved constituents, measuring Eh, pH, and temperature of tailings core and pore fluid samples, conducting sequential extractions on solid samples, conducting geochemical modeling of pore fluid chemistry using available thermodynamic data, and by reviewing historical chemical mill process records. Dissolved As concentrations in 5 monitoring wells installed within the tailings body ranged from 9.6 to 71 mg/l. Pore fluid in the wells had a pH between 9.3 and 10.3 and Eh between +58 and +213 mV. Sequential extraction analyses of tailings samples showed that the composition of the solid phase As changed at a depth of 34 m. The As above 34 m was primarily associated with amorphous Fe and metal hydroxides while the As below 34 m was associated with Ca, likely as amorphous poorly ordered calcium arsenate precipitates. The change in the dominant As solid phases at this depth was attributed to the differences in the molar ratio of Fe to As in the mill tailings. Below 34 m it was <2 whereas above 34 m it was >4. The high Ca/As ratio during tailings neutralization would likely precipitate Ca₄(OH)₂(AsO₄)₂:4H₂O type Ca arsenate minerals. Geochemical modeling suggested that if the pore fluids were brought to equilibrium with this Ca-arsenate, the long-term dissolved As concentrations would range between 13 and 126 mg/l.     

Mobility of arsenic and environmentally significant elements in mine tailings following liming

Remediation of a legacy tin-tailings site in northeast Tasmania, Australia was carried out by statutory authorities. This study evaluated the fate of As and other deleterious trace metals Cd, Cu, Fe and Zn (among others) following the application of lime and fertiliser. Arsenic concentrations in the tailings ranged from 86 mg/kg to 0.26 wt%. Surface application of lime resulted in a 100-fold reduction in dissolved As concentrations in on-site surface waters; from an average of 196 µg/L prior to lime addition, to between 2.0 and 7.4 µg/L post-amendment. The concentration of other deleterious elements, however, varied between dry and wet cycles. The concentrations of Cd, Cu and Zn in surface waters were high and similar to pre-remediation levels during dry conditions (0.4, 13.5 and 6.1 mg/L, respectively), and only below freshwater ecosystem protection values during wet conditions. Bioaccumulation of Cd was observed in the naturally occurring coloniser, Juncus pallidus, with 4–5 times more Cd in the above-ground biomass relative to the tailings. Ferric arsenate (scorodite) was the dominant source of As identified in the tailings mineralogy. Hydrous ferric oxides and Fe-bearing cassiterite were also identified as hosting As. The pH increase in the surface lime-amended tailings was inferred to result in precipitation of observed hydrous ferric oxides, hematite and goethite, providing high-surface area for adsorption of arsenate onto positively charged surfaces. Jarosite was observed in both the surface lime-amended and subsurface non-amended tailings and suggests a continued supply of acidity to the pore waters despite the application of lime. Leaching experiments showed that As was more mobile in the lime-dosed tailings than in subsurface non-amended tailings, likely owing to desorption in alkaline pH conditions. By contrast, the mobility of Cd, Cu and Zn in the surface lime-amended tailings was reduced by at least two orders of magnitude compared with subsurface non-amended tailings. Evaluation of the applied rehabilitation strategy highlights the limits of a single chemical remediation approach to a polymetallic (including metalloids) waste with complex mineralogy and large seasonal fluctuations. Rehabilitation of metalliferous mine sites requires a complete understanding of all environmentally significant elements and their pathways into local receptors.     

Organic matter degradation in paper sludge amendments over gold mine tailings

The long-term stability of paper sludge amendments as covers for reclaimed mine waste storage facilities must be assessed by the mining industry. This study examines a 6 yr old sequence of paper sludge amendments applied over wastes from historic Au mines located in Northern Ontario, Canada. As paper sludge is mostly comprised of C-rich organic compounds, elemental quantification, ¹³C cross polarization/magic angle spinning nuclear magnetic resonance (¹³C CP/MAS NMR) spectroscopy, and Fourier transform infrared (FTIR) spectroscopy were used to examine the minimal changes in the C content and speciation observed of the amendments over time. These results suggest that paper sludge covers are suitable for use in medium to long-term mining reclamation strategies.     

Manganese-reducing Pseudomonas fluorescens-group bacteria control arsenic mobility in gold mining-contaminated groundwater

Previous studies show the importance of iron- and arsenate-reducing bacteria in mobilizing arsenic in groundwater. Here the authors present experimental evidence of arsenic mobilization in connection with bacterially mediated manganese reduction in groundwater affected by mining activities. Manganese-reducing Pseudomonas species were enriched, isolated and identified by 16S rRNA gene phylogeny from groundwater containing high co-dissolved arsenic (as As^III) and manganese. Enrichment cultures dissolved synthetic birnessite and hausmannite efficiently, but Mn reduction by isolates was reduced at the upper range of environmental levels of dissolved As^III. Results suggest either a self-limiting release of arsenic coupled to bacterial manganese reduction, in the absence of other electron donors like sulfide, or increased arsenic resistance conferred to Mn-reducing bacteria in consortia.     

Chemical availability of arsenic and heavy metals in sediments from abandoned cinnabar mine tailings

The understanding of the solid-phase speciation of arsenic in soils and sediments is important in the evaluations of its potential mobility and availability in the environment. The spoil heaps of abandoned mercury mines contain waste materials with high arsenic and heavy metals concentrations. The weathering of these tailings can cause their mobilization to the surroundings. In this work, the mobility and availability of arsenic and some heavy metals were evaluated in sediments from two heavily polluted mercury mining districts in Asturias (NW Spain). For this purpose, a slightly modified version of the Bureau Community of Reference sequential extraction scheme was applied to sediments. The total contents in the operationally defined fractions were analysed by inductively coupled plasma-atomic emission spectrometry. Extremely high total arsenic concentrations were found in all sediments ranging from 4,000 to 24,800 mg kg^?1. High easily mobilizable arsenic contents were found in the first mining area, related to the solubilization of Ca-bearing phases, supported by extracts analyses, X-ray diffraction results and the positive correlation found among the As and Ca fractionations. Ni and Zn were the most mobile among heavy metals, being Cr the least mobile, suggesting an anthropogenic origin due to the metallurgical processes, transport or dispersion generated from neighbour spoil heaps. In the second mining area, the bulk of As was concentrated in the residual phase, as well as Cr, Cu, Fe, Pb, Ti, indicating a mineralogical origin and the low availability of these elements. The strong correlations established between As and Fe and Ti distributions support the hypothesis that As is mainly associated to structural mineral phases in these sediments.     

Characterization of Kolar gold field mine tailings for cyanide and acid drainage

The gold mining process at Kolar gold field (KGF) mines has generated about 32 million tons of tailings. Gold was extracted from the mined ores using cyanidation technique that involved dissolution of gold in the ore by water soluble alkali metal cyanides (example, sodium cyanide or potassium cyanide). Of the several dumps that received the mine tailings only the Kennedy’s Line dump was active prior to closure of the KGF mines in the year 2000. The Kennedy’s Line dump received sulfide bearing tailings in slurry form that comprised of spent ore and process water bearing soluble alkali metal cyanide. Depending on the pH of the tailing slurry, the free cyanides may exist as aqueous hydrogen cyanide that can escape to the atmosphere as hydrogen cyanide gas or occur as soluble cyanide (CN⁻) ions that can be leached by infiltrating water to the sub-surface environment. Additionally, the presence of pyrite minerals in the Kennedy’s Line dump makes them susceptible to acid drainage. This study examines the potential of gold tailings of Kennedy’s Line dump to release cyanide ions (CN⁻) and acid drainage to the sub-surface environment by performing physico-chemical and leaching tests with tailing samples collected from various depths of the dump, sub-surface soil samples beneath the dump and groundwater samples from vicinity of Kennedy’s Line dump. The chemical mechanisms responsible for the ambient cyanide and pH levels of the tailing dump, sub-surface soil samples and groundwater are also inferred from the laboratory results.     

Formation and composition of cemented layers in low-sulphide mine tailings, Laver, northern Sweden

Cemented layers (hardpans) are common in carbonate or sulphide-rich mine tailings and where pyrrhotite is the predominating Fe-sulphide. Laver, northern Sweden, is an abandoned Cu-mine where the tailings have low pyrrhotite content, almost no pyrite and no carbonates. Two cemented layers at different locations in the Laver tailings impoundment were investigated, with the aim to determine their effects on metal mobility. The cementing agents were mainly jarosite and Fe-oxyhydroxides in the layer formed where the tailings have a barren surface, whereas only Fe-oxyhydroxides were identified below grass-covered tailings surface. Arsenic was enriched in both layers which also exhibit high concentrations of Mo, V, Hg and Pb compared to unoxidised tailings. Sequential extraction indicates that these metals and As were mainly retained with crystalline Fe-oxides, and therefore potentially will be remobilised if the oxic conditions become more reducing, for instance as a result of remediation of the tailings impoundment.An erratum to this article can be found at     

Mineralogical and geochemical alteration of Hitura sulphide mine tailings with emphasis on nickel mobility and retention

Weathering of Hitura (W Finland) nickel sulphide mine tailings and release of heavy metals into pore water was studied with mineralogical (optical and electron microscopy, X-ray diffraction) and geochemical methods (selective extractions). Tailings were composed largely of serpentine, micas and amphiboles with only minor carbonates and sulphides. Sulphides, especially pyrrhotite, have oxidized intensively in the shallow tailings in 10–15 years, but a majority of the tailings have remained unchanged. Oxidation has resulted in depletion of carbonates, slightly decreased pH, and heavy metal (Ni, Zn) release in pore water as well as in the precipitation of secondary Fe precipitates. Nevertheless, in the middle of the tailings area, where the oxidation front moves primarily downward, released heavy metals have been adsorbed and immobilized with these precipitates deeper in the oxidation zone. In contrast to what was seen in pore water pH, but in accordance with static tests of the previous studies, the neutralisation potential ratio (NPR) calculated based on the mineralogical composition and the total sulphur content suggested that tailings are ‘not potentially acid mine drainage (AMD) generating’. However, the calculated buffering capacity of the tailings resulted largely from the abundant serpentine because of the low carbonate content. Despite its slow weathering rate, serpentine may buffer the acidity to some extent through ion exchange processes in fine ground tailings. Nevertheless, in practice, acid production capacity of the tailings depends primarily on the balance between Ca–Mg carbonates and iron sulphides. NPR calculation based on carbonate and sulphur contents suggested, that the Hitura tailings are ‘likely AMD generating’. The study shows that sulphide oxidation can be significant in mobilisation of heavy metals even in apparently non-acid producing, low sulphide tailings. Therefore, prevention of oxygen diffusion into tailings is also essential in this type of sulphide tailings.     

The effect of mineralogy on the mobility of heavy metals in mine tailings: a case study in the Samsanjeil mine,Korea

This study examined the chemical speciation and mobility of As and heavy metals in a tailings impoundment in Samsanjeil mine located in Gosung, Korea, as well as the factors affecting them. XRD, SEM, and 5-step sequential extraction were used to examine the samples at two sampling sites (NN and SN sites). The pH of the tailings decreased with increasing depth at the NN site (from 7.2 to 2.8), whereas no significant differences were observed at the SN site (8.1–8.8). The samples at the SN site showed a larger amount of calcite than those at the NN site, indicating that calcite plays an important role buffering the pH in the study sites. Jarosite was found only at the lower part of the NN site, where calcite was not found. The mineralogical observation of jarosite and calcite was also confirmed by SEM. The concentrations of As and heavy metals in the tailings were as follows: Cu > As > Zn > > Pb > Co > Cr > Ni > Cd. The total concentrations of Ni, Zn, Co, and Cd were higher at the SN site than those at the NN site. On the other hand, the concentrations of As and Cr existing as oxyanions were higher at the NN site, which can be explained by the mobility changes of those elements affected by pH variations. At the NN site, the fractions of heavy metals bound to the Fe/Mn oxides, except for As and Cr, decreased, and Cu, Zn, and Co showed an increasing fraction of exchangeable metals with increasing depth. This suggests that the pH and resulting surface charge of minerals, such as goethite and jarosite, are the dominant factors controlling the chemical speciation of metals. These results highlight the importance of mineralogy in controlling the mobility and possible bioavailability of heavy metals in tailings.     

Mobilization of arsenic from mine tailings through reductive dissolution of goethite influenced by organic cover

Mine tailings at the former Delnite gold mine in northern Ontario were characterized to assess the impact of a biosolids cover on the stability of As species and evaluate options for long-term management of the tailings. Arsenic concentrations in the tailings range from 0.15 to 0.36 wt% distributed among goethite, pyrite and arsenopyrite. Pyrite and arsenopyrite occur as small and liberated particles that are enveloped by goethite in the uncovered tailings and the deeper portions of the biosolids-covered tailings. Sulfide particles in the shallower portions of the biosolids-covered tailings are free of goethite rims. Arsenic occurs predominantly as As⁵⁺ with minor amount of As¹⁻ in the uncovered tailings. Coinciding with the disappearence of goethite rims on sulfide particles, the biosolids-covered tailings have As³⁺ species gradually increasing in proportion towards the cover. Leaching tests indicated that the As concentrations in the leachate gradually increase from less than 0.085 to 13 mg/L and Fe from 28 to 179 mg/L towards the biosolids cover. These are in sheer contrast to the leachate concentrations of less than 0.085 mg/L As and 24–64 mg/L Fe obtained from the uncovered tailings confirming the role of biosolids-influenced reduction and mobilization of As in the form of As³⁺ species. The evidence suggests that reductive dissolution of goethite influenced by the biosolids-cover caused the mobilization of As as As³⁺ species.     

Mineralogical controls on environmental mobility of arsenic from historic mine processing residues,New Zealand

Processing of arsenopyrite ore took place at Blackwater Au mine, New Zealand, between 1908 and 1951 and no rehabilitation was undertaken after mine closure. High As concentrations in solid processing residues (up to 40 wt% As) are due to secondary As minerals. Site pH regimes vary from 4.1 to circum-neutral. Originally, all processed As was present as arsenolite (arsenic trioxide polymorph, As^III), a by-product of arsenopyrite roasting. Near the roaster, scorodite precipitated as a result of the high dissolved As concentration during arsenolite dissolution. The formation of scorodite has two major consequences. Firstly, the scorodite precipitate cements the ground in the vicinity of the roaster area, thereby creating an impermeable surface crust (up to 30 wt% As) and encapsulating weathered arsenolite grains within the cement. Secondly, formation of scorodite temporarily immobilizes some of the dissolved As that is generated during nearby arsenolite dissolution. Where all the available arsenolite has dissolved, scorodite becomes soluble, and the dissolved As concentrations are controlled by scorodite solubility, which is at least two orders of magnitudes lower than arsenolite solubility. Downstream Eh conditions fall below the As^V/As^III boundary, so that scorodite does not precipitate and dissolved As concentrations are controlled by arsenolite solubility. Dissolved As reaches up to 52 mg/L in places, and exceeds the current WHO drinking water guideline of 0.01 mg/L by 5200 times. This study shows that dissolved As concentrations in discharge waters at historic mine sites are dependent on the processing technology and associated mineralogy.     

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.