Legacy copper/nickel mine tailings potentially harbor novel iron/sulfur cycling microorganisms within highly variable communities.

The oxidation of sulfide-bearing mine tailings catalyzed by acidophilic iron and sulfur-oxidizing bacteria releases toxic metals and other contaminants into soil and groundwater as acid mine drainage. Understanding the environmental variables that control the community structure and metabolic activity of microbes indigenous to tailings (especially the abiotic stressors of low pH and high dissolved metal content) is crucial to developing sustainable bioremediation strategies. We determined the microbial community composition along two continuous vertical gradients of Cu/Ni mine tailings at each of two tailings impoundments near Sudbury, Ontario. 16S rRNA amplicon data showed high variability in community diversity and composition between locations, as well as at different depths within each location. A temporal comparison for one tailings location showed low fluctuation in microbial communities across 2 years. Differences in community composition correlated most strongly with pore-water pH, Eh, alkalinity, salinity, and the concentration of several dissolved metals (including iron, but not copper or nickel). The relative abundances of individual genera differed in their degrees of correlation with geochemical factors. Several abundant lineages present at these locations have not previously been associated with mine tailings environments, including novel species predicted to be involved in iron and sulfur cycling.IMPORTANCEMine tailings represent a significant threat to North American freshwater, with legacy tailings areas generating acid mine drainage (AMD) that contaminates rivers, lakes, and aquifers. Microbial activity accelerates AMD formation through oxidative metabolic processes but may also ameliorate acidic tailings by promoting secondary mineral precipitation and immobilizing dissolved metals. Tailings exhibit high geochemical variation within and between mine sites and may harbor many novel extremophiles adapted to high concentrations of toxic metals. Characterizing the unique microbiomes associated with tailing environments is key to identifying consortia that may be used as the foundation for innovative mine-waste bioremediation strategies. We provide an in-depth analysis of microbial diversity at four copper/nickel mine tailings impoundments, describe how communities (and individual lineages) differ based on geochemical gradients, predict organisms involved in AMD transformations, and identify taxonomically novel groups present that have not previously been observed in mine tailings.

Improved precision in As speciation analysis with HERFD-XANES at the As K-edge: the case of As speciation in mine waste. Corrigendum.

The name of an author in the article by Saurette et al. (2022) [J. Synchrotron Rad. 29, 1198-1208] is corrected.

Improved precision in As speciation analysis with HERFD-XANES at the As K-edge: the case of As speciation in mine waste.

High-energy-resolution fluorescence-detected (HERFD) X-ray absorption near-edge spectroscopy (XANES) is a spectroscopic method that allows for increased spectral feature resolution, and greater selectivity to decrease complex matrix effects compared with conventional XANES. XANES is an ideal tool for speciation of elements in solid-phase environmental samples. Accurate speciation of As in mine waste materials is important for understanding the mobility and toxicity of As in near-surface environments. In this study, linear combination fitting (LCF) was performed on synthetic spectra generated from mixtures of eight measured reference compounds for both HERFD-XANES and transmission-detected XANES to evaluate the improvement in quantitative speciation with HERFD-XANES spectra. The reference compounds arsenolite (As2O3), orpiment (As2S3), getchellite (AsSbS3), arsenopyrite (FeAsS), kankite (FeAsO4·3.5H2O), scorodite (FeAsO4·2H2O), sodium arsenate (Na3AsO4), and realgar (As4S4) were selected for their importance in mine waste systems. Statistical methods of principal component analysis and target transformation were employed to determine whether HERFD improves identification of the components in a dataset of mixtures of reference compounds. LCF was performed on HERFD- and total fluorescence yield (TFY)-XANES spectra collected from mine waste samples. Arsenopyrite, arsenolite, orpiment, and sodium arsenate were more accurately identified in the synthetic HERFD-XANES spectra compared with the transmission-XANES spectra. In mine waste samples containing arsenopyrite and either scorodite or kankite, LCF with HERFD-XANES measurements resulted in fits with smaller R-factors than concurrently collected TFY measurements. The improved accuracy of HERFD-XANES analysis may provide enhanced delineation of As phases controlling biogeochemical reactions in mine wastes, contaminated soils, and remediation systems.

Nickel Isotope Fractionation As an Indicator of Ni Sulfide Precipitation Associated with Microbially Mediated Sulfate Reduction.

Microbially mediated sulfate reduction is a promising cost-effective and sustainable process utilized in permeable reactive barriers (PRB) and constructed wetlands to treat mine wastewater. Laboratory batch experiments were performed to evaluate nickel (Ni) isotope fractionation associated with precipitation of Ni-sulfides in the presence of the sulfate-reducing bacterium (SRB) Desulfovibrio desulfuricansT (DSM-642). Precipitates were collected anaerobically and characterized by synchrotron powder X-ray diffraction (PXRD), scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SEM-EDS), and transmission electron microscopy (TEM). Solid-phase analyses showed that the precipitates associated with bacteria attached to the serum bottle walls were characterized by enhanced size and crystallinity. Lighter Ni isotopes were preferentially concentrated in the solid phase, whereas the solution was enriched in heavier Ni isotopes compared to the input solution. This fractionation pattern was consistent with closed-system equilibrium isotope fractionation, yielding a fractionation factor of Δ60Nisolid-aq = -1.99‰. The Ni isotope fractionation measured in this study indicates multiple Ni reaction mechanisms occurring in the complex SRB-Ni system. The results from this study offer insights into Ni isotope fractionation during interaction with SRB and provide a foundation for the characterization and development of Ni stable isotopes as tracers in environmental applications.

Occurrence and distribution of emerging contaminants in mine-impacted lake water and potential use as co-tracers of anthropogenic activity in the subarctic region, Northwest Territories, Canada.

The emerging contaminant (EC) perchlorate (ClO4-), a blasting agent widely used in mining and refining operations, has been used as a practical indicator of mining activities. Widespread occurrence of ECs, such as pharmaceutical compounds, artificial sweeteners, and perfluoroalkyl substances, and their use as co-tracers of wastewater associated with anthropogenic activities in the urban and Arctic environments have been previously investigated. However, limited studies have reported the occurrence of these ECs and the feasibility of their use as co-tracers of anthropogenic activities in pristine waterbodies (e.g., continuous permafrost region) that receive effluent from mine sites. In this study, water samples were collected from the surface of 10 lakes within the Coppermine and Lockhart Watersheds in the continuous permafrost region in the Northwest Territories, Canada during the open water seasons of 2016, 2017, and 2018. Concentrations of 16 ECs were determined to delineate the spatial and temporal distribution of these compounds in waterbodies receiving effluent from mine sites. Slightly elevated concentrations of ClO4- (100-700 ng L-1), caffeine (0.2-5.9 ng L-1), acesulfame-K (0.5-1.5 ng L-1), perfluorooctanoic acid (PFOA; 5-34 ng L-1), perfluorooctane sulfonic acid (PFOS; 11-40 ng L-1), chloride (1.5-2.3 mg L-1), and sulfate (1.0-3.6 mg L-1) were observed across the two investigated watersheds, especially downstream of the mining sites. The concurrence of elevated concentrations of these target ECs combined with other dissolved constituents (chloride and sulfate) may indicate the influence of mining activity on the receiving waterbodies and the potential use of these compounds as co-indicators of anthropogenic activity. Results from this study provide novel information on the distribution of 16 ECs in pristine waterbodies that receive effluents from mining sites in the Canadian subarctic in advance of more expansive human development and increased warming and melting of mine sites, including mine wastes.

Microbiology of a multi-layer biosolid/desulfurized tailings cover on a mill tailings impoundment.

The Strathcona Waste Water Treatment System (SWWTS; Sudbury, ON, Canada) has received mill tailings from Ni/Cu ore processing from 1970 to present. Demonstration-scale, multi-layer cover systems were installed on selected tailings deposition cells at the SWWTS. The cover systems are comprised of an upper layer of organic carbon-rich material, composed of a layer biosolids fertilizer along with composted municipal food and yard waste, then a layer of desulfurized, fine-grained tailings. Organic carbon components used in these covers promote microbial communities that consume O2, thus decreasing sulfide oxidation rates in the underlying tailings. The aim of this study was to investigate the microbiology of the cover systems and the underlying tailings, using a combination of culture-dependent (most probable number) and culture-independent (16S rRNA gene amplicon sequencing) techniques, and assess the impact of the organic component of the cover system four to six years after implementation. Most tailings samples were characterized by circumneutral bulk pH and low concentrations of dissolved metals. The presence of the organic cover resulted in elevated counts of sulfate-reducers (by two orders of magnitude, compared to control samples) immediately below the organic cover, as well as an increased abundance of heterotrophic species (∼108 cells g-1) at greater depth (∼4 m) in the tailings profile. Mineral-oxidizing microorganisms were also present in the tailings, with neutrophilic sulfur-oxidizers dominating the samples (mean ∼106 cells g-1). Relative abundances of sulfur- and/or iron-oxidizers determined by sequencing ranged from 0.5 to 18.3% of total reads (mean ∼5.6% in amended tailings) and indicated the presence of local microenvironments with ongoing sulfide oxidation. This work provides a detailed characterization of the microbiology of a tailings impoundment with an organic cover, highlighting the opportunities associated with monitoring microbial processes in such remediation systems.

Performance of a Geosynthetic-Clay-Liner Cover System at a Cu/Zn Mine Tailings Impoundment.

The abandoned Kam Kotia Mine (Canada) is undergoing remediation. A geosynthetic-clay-liner (GCL) cover system was installed in the Northern Impounded Tailings (NIT) area in 2008 to isolate acid-generating tailings from water and oxygen and to mitigate sulfide oxidation. The cover system includes a vegetated uppermost soil layer underlain by a granular protective layer (sand), a clay moisture-retaining layer, a GCL, a granular capillary-break material (cushion sand), and a crushed waste rock-capillary break layer installed above the tailings. The goal of this study was to characterize the microbiology of the covered tailings to assess the performance of the cover system for mitigating sulfide bio-oxidation. Tailings beneath the GCL were characterized by high sulfur and low carbon content. The bulk pH of the tailings pore water was circumneutral (∼5.5 to 7.3). Total genomic DNA was extracted from 36 samples recovered from the constituent layers of the cover system and the underlying tailings and was analyzed in triplicates using high-throughput amplicon sequencing of 16S rRNA genes. Iron-oxidizing, sulfur-oxidizing, sulfate-reducing, and aerobic heterotrophic microorganisms were enumerated by use of most probable number enumeration, which identified heterotrophs as the most numerous group of culturable microorganisms throughout the depth profile. Low relative abundances and viable counts of microorganisms that catalyze transformations of iron and sulfur in the covered tailings, compared to previous studies on unreclaimed tailings, indicate that sulfide oxidation rates have decreased due to the presence of the GCL. Characterization of the microbial community can provide a sensitive indicator for assessing the performance of remediation systems.IMPORTANCE Mining activities are accompanied by significant environmental and financial liabilities, including the release of acid mine drainage (AMD). AMD is caused by accelerated chemical and biological oxidation of sulfide minerals in mine wastes and is characterized by low pH and high concentrations of sulfate and metal(loid)s. Microorganisms assume important roles in the catalysis of redox reactions. Our research elucidates linkages among the biogeochemistry of mine wastes and remediation systems and microbial community and activity. This study assesses the performance and utility of geosynthetic-clay-liner cover systems for management of acid-generating mine wastes. Analyses of the microbial communities in tailings isolated beneath an engineered cover system provide a better understanding of the complex biogeochemical processes involved in the redox cycling of key elements, contribute to the remediation of mine wastes, and provide a valuable tool for assessment of the effectiveness of the remediation system.

A Method for Redox Mapping by Confocal Micro-X-ray Fluorescence Imaging: Using Chromium Species in a Biochar Particle as an Example.

Redox mapping of solid-phase particles has been used for speciation mapping of near-surface materials or within grains through the use of thin-sections without depth information. Here, a procedure is presented for data collection and processing of depth-dependent redox mapping within solid particles using confocal micro-X-ray fluorescence imaging (CMXRFI). The procedure was applied to a biochar particle that was reacted with Cr(VI)-spiked water. The total Cr distribution was first obtained at an above-edge energy of the K-edge, and showed that Cr was primarily distributed near the surface of the particle. Redox mapping was conducted at 33 representative energies and linear combination fitting (LCF) was performed for the 33 data points from each pixel. The results indicate Cr(III) is the primary species with fractions ranging from 0.6 to 1 and that this fraction is greater in the interior pixels of the particle than at the surface; in contrast, the Cr(VI) fraction is greater at the surface than for interior pixels. The results likely indicate Cr(VI) was first adsorbed and diffused into the biochar, and then reduced to Cr(III). With more Cr(VI) adsorption and the exceedance of the reduction potential of the biochar, remaining Cr(VI) was accumulated on the surface. The redox mapping method was validated by micro-XANES (X-ray absorption near-edge structure) and XPS (X-ray photoelectron spectroscopy) results. This demonstration indicates the developed method combined with CMXRFI can be used to delineate the distribution of different oxidation states of an element within an intact particle or layer.

Geochemical and Isotope Study of Trichloroethene Degradation in a Zero-Valent Iron Permeable Reactive Barrier: A Twenty-Two-Year Performance Evaluation.

This study provides a twenty-two-year record of in situ degradation of chlorinated organic compounds by a granular iron permeable reactive barrier (PRB). Groundwater concentrations of trichloroethene (TCE) entering the PRB were as high as 10670 µg/L. Treatment efficiency ranged from 81 to >99%, and TCE concentrations from <1 µg/L to 165 µg/L were detected within and hydraulically down-gradient of the PRB. After 18 years, effluent TCE concentrations were above the maximum contaminant level (MCL) along segments of the PRB exhibiting upward trending influent TCE. Degradation products included cis-dichloroethene ( cis-DCE), vinyl chloride (VC), ethene, ethane, >C4 compounds, and possibly CO2(aq) and methane. Abiotic patterns of TCE degradation were indicated by compound-specific stable isotope data and the distribution of degradation products. δ13C values of methane within and down-gradient of the PRB varied widely from -94‰ to -16‰; these values cover most of the isotopic range encountered in natural methanogenic systems. Methanogenesis is a sink for inorganic carbon in zerovalent iron PRBs that competes with carbonate mineralization, and this process is important for understanding pore-space clogging and longevity of iron-based PRBs. The carbon isotope signatures of methane and inorganic carbon were consistent with open-system behavior and 22% molar conversion of CO2(aq) to methane.

Mercury Complexation with Dissolved Organic Matter Released from Thirty-Six Types of Biochar.

Previous studies show mercury (Hg) can be effectively removed from solution by biochar, but limited attention was paid on the complexation between Hg and components released from biochars, e.g. dissolved organic matter (DOM). Here, aqueous data from batch-style experiments were modeled using PHREEQC, incorporating thermodynamic constants between Hg and DOM, which was assumed to be composed of thiol, carboxylic, and phenolic functional groups. Modelling results suggest that > 99% Hg complexed with thiol groups in DOM. The modelled concentrations of Hg-DOM complexes from low-T (low-temperature, 300°C) biochars were greater than from high-T (600°C) biochars. The concentrations of Hg-DOM complexes were lower in wood-based than in agricultural residue- and manure-based biochars. Hg-DOM complexes may affect Hg speciation, bioavailability, transport, and methylation processes. This research describes a method to evaluate Hg-DOM interactions, and the results indicate extra caution regarding Hg-DOM complex formation is required in the selection of biochar for Hg remediation.

Real-Time XANES Measurement of Se Reduction by Zerovalent Iron in a Flow-through Cell, and Accompanying Se Isotope Measurements.

An anoxic flow-through cell experiment was conducted to examine mechanisms controlling the real-time reduction of selenate (Se(VI)) by zerovalent iron (ZVI), which is commonly used in permeable reactive barriers to treat dissolved contaminants including Se(VI). Changes in selenium (Se) isotope composition were examined by increasing the influent Se concentration over time, thus changing the proportion of Se removed from solution. At the conclusion of the experiment, an anoxic Se-free solution was pumped through the cell to assess the stability of the reaction products. At all stages, X-ray absorption data were obtained from the solid phase and Se isotope data from the aqueous phase. Reduced Se in the form of adsorbed Se(IV), Fe2SeO4, Se(0), and iron selenides accumulated on the ZVI over time. A linear regression function was fit to the δ82/76Se values of the effluent, yielding an isotopic separation of 9.6‰. A Rayleigh curve was fit to the isotope data from the effluent samples collected during the rinse stage with an effective fractionation of 2.4‰. The results from this experiment can be used to elucidate the effect of multiple concurrent mechanisms on Se isotope behavior.

Fractionation of Selenium during Selenate Reduction by Granular Zerovalent Iron.

Batch experiments were conducted using granular zerovalent iron (G-ZVI) with either ultrapure water or CaCO3 saturated simulated groundwater to assess the extent of Se isotope fractionation in solution under the anaerobic conditions characteristic of many aquifers. G-ZVI is a common remediation material in permeable reactive barriers (PRB) to treat Se-contaminated groundwater, and stable isotopes are a potential tool for assessing removal mechanisms. The solution composition, speciation of Se, and Se isotope ratios were determined during both sets of experiments. Dissolved Se concentrations decreased from 10 to <2 mg L(-1) after 3 d in the CaCO3 system and below 0.4 mg L(-1) after 2 d in the ultrapure water system. XANES analysis of the solid phase showed spectra consistent with the formation of Se(IV), Fe2(SeO3)3, FeSe, FeSe2, and Se(0) on the G-ZVI. Selenium isotope ratio measurements in solution in the CaCO3 and ultrapure water experiments showed enrichment of δ(82/76)Se values from -0.94 ± 0.07‰ and -1.93 ± 0.20‰ to maximum values of 6.85 ± 0.52‰ and 5.68 ± 0.20‰ over 72 and 36 h, respectively. The effective fractionations associated with the reduction of Se(VI) were 4.3‰ within the CaCO3 saturated water and 3.0‰ in ultrapure water.

Dual Mechanism Conceptual Model for Cr Isotope Fractionation during Reduction by Zerovalent Iron under Saturated Flow Conditions.

Chromium isotope analysis is rapidly becoming a valuable complementary tool for tracking Cr(VI) treatment in groundwater. Evaluation of various treatment materials has demonstrated that the degree of isotope fractionation is a function of the reaction mechanism, where reduction of Cr(VI) to Cr(III) induces the largest fractionation. However, it has also been observed that uniform flow conditions can contribute complexity to isotope measurements. Here, laboratory batch and column experiments were conducted to assess Cr isotope fractionation during Cr(VI) reduction by zerovalent iron under both static and saturated flow conditions. Isotope measurements were accompanied by traditional aqueous geochemical measurements (pH, Eh, concentrations) and solid-phase analysis by scanning electron microscopy and X-ray absorption spectroscopy. Increasing δ(53)Cr values were associated with decreasing Cr(VI) concentrations, which indicates reduction; solid-phase analysis showed an accumulation of Cr(III) on the iron. Reactive transport modeling implemented a dual mechanism approach to simulate the fractionation observed in the experiments. The faster heterogeneous reaction pathway was associated with minimal fractionation (ε=-0.2‰), while the slower homogeneous pathway exhibited a greater degree of fractionation (ε=-0.9‰ for the batch experiment, and ε=-1.5‰ for the column experiment).

Perchlorate in Lake Water from an Operating Diamond Mine.

Mining-related perchlorate [ClO4(-)] in the receiving environment was investigated at the operating open-pit and underground Diavik diamond mine, Northwest Territories, Canada. Samples were collected over four years and ClO4(-) was measured in various mine waters, the 560 km(2) ultraoligotrophic receiving lake, background lake water and snow distal from the mine. Groundwaters from the underground mine had variable ClO4(-) concentrations, up to 157 µg L(-1), and were typically an order of magnitude higher than concentrations in combined mine waters prior to treatment and discharge to the lake. Snow core samples had a mean ClO4(-) concentration of 0.021 µg L(-1) (n=16). Snow and lake water Cl(-)/ClO4(-) ratios suggest evapoconcentration was not an important process affecting lake ClO4(-) concentrations. The multiyear mean ClO4(-) concentrations in the lake were 0.30 µg L(-1) (n = 114) in open water and 0.24 µg L(-1) (n = 107) under ice, much below the Canadian drinking water guideline of 6 µg L(-1). Receiving lake concentrations of ClO4(-) generally decreased year over year and ClO4(-) was not likely [biogeo]chemically attenuated within the receiving lake. The discharge of treated mine water was shown to contribute mining-related ClO4(-) to the lake and the low concentrations after 12 years of mining were attributed to the large volume of the receiving lake.

Aqueous leaching of organic acids and dissolved organic carbon from various biochars prepared at different temperatures.

Biochar has been used as a soil amendment, as a water treatment material, and for carbon (C) sequestration. Thirty-six biochars, produced from wood, agricultural residue, and manure feedstocks at different temperatures, were evaluated for the aqueous leaching of different forms of soluble C. The release of inorganic C (alkalinity), organic acids (OAs), and total dissolved organic C (DOC) was highly variable and dependent on the feedstock and pyrolysis temperature. The pH and alkalinity increased for the majority of samples. Higher pH values were associated with high-temperature (high-T) (600 and 700°C) biochars. Statistically significant differences in alkalinity were not observed between low-temperature (low-T) (300°C) and high-T biochars, whereas alkalinity released from wood-based biochar was significantly lower than from others. Concentrations of OAs and DOC released from low-T biochars were greater than from high-T biochars. The C in the OAs represented 1 to 60% of the total DOC released, indicating the presence of other DOC forms. The C released as DOC represented up to 3% (majority <0.1%) of the total C in the biochar. Scanning electron microscopy with energy dispersive X-ray spectroscopy showed the high-T biochars had a greater proportion of micropores. Fourier transform infrared spectroscopy showed that hydroxyl, aliphatic, and quinone were the predominant functional groups of all biochars and that the abundance of other functional groups was dependent on the feedstock. The release of DOC, especially bioavailable forms such as OAs, may promote growth of organisms and heavy metal complexation and diminish the potential effectiveness of various biochars for C sequestration.

Treatment of dissolved perchlorate, nitrate, and sulfate using zero-valent iron and organic carbon.

Waters containing ClO and dissolved NO, derived from detonated explosives and solid propellants, often also contain elevated concentrations of other dissolved constituents, including SO. Four column experiments, containing mixtures of silica sand, zero-valent Fe (ZVI) and organic C (OC) were conducted to evaluate the potential for simultaneous removal of NO, SO and ClO. Initially, the flow rate was maintained at 0.5 pore volumes (PV) d and then decreased to 0.1 PV d after 100 PV of flow. Nitrate concentrations decreased from 10.8 mg L (NO-N) to trace levels through NO reduction to NH using ZVI alone and through denitrification using OC. Observations from the mixture of ZVI and OC suggest a combination of NO reduction and denitrification. Up to 71% of input SO (24.5 ± 3.5 mg L) was removed in the column containing OC, and >99.7% of the input ClO (857 ± 63 µg L) was removed by the OC- and (ZVI + OC)-containing columns as the flow rate was maintained at 0.1 PV d. Nitrate and ClO removal followed first-order and zero-order rates, respectively. Nitrate >2 mg L (NO-N) inhibited ClO removal in the OC-containing column but not in the (ZVI + OC)-containing column. Sulfate did not inhibit ClO degradation within any of the columns.

Reactive transport modelling of tailings hydrogeochemistry under a composite cover.

Quantitative forecasts of acid mine drainage (AMD) production are important for remediation planning. Reactive transport simulations corresponding to a detailed sampling location at a covered legacy tailings impoundment in northern Ontario, Canada, were conducted to quantitatively assess the predominant hydrogeochemical reactions. The simulations span the period from the end of tailings deposition (circa 1970) to early 2020, 12 years after remediation by a five-layer composite cover. The conceptual model of uncovered tailings weathering and subsequent geochemistry of the covered tailings system was implemented in 1D using the multi-component reactive transport code MIN3P. Transient monthly infiltration, post-cover boundary condition changes, and a dynamic temperature regime were incorporated. The shrinking core model, including parallel O2(aq) and Fe3+ oxidation reactions for the waste rock in the cover and the underlying tailings, was implemented to simulate the oxidation of As-bearing pyrite, chalcopyrite, and sphalerite. Primary carbonate and aluminosilicate host minerals promoted acid-neutralization reactions. Precipitation of secondary phases and sorption/desorption of Cu, Zn, and arsenite were incorporated into the model. The overall agreement between key simulated and field-measured post-cover aqueous geochemical parameters suggests that the conceptual model captured the primary hydrogeochemical processes in the covered tailings. A lack of reliable data on initial tailings mineralogy and pre-cover hydrogeochemistry increased simulation uncertainty. Simulated reaction rates indicate that where intact, the cover decreased sulfide oxidation rates by both O2(aq) and Fe3+ and improved pore-water quality over time. Simulation results indicate that elevated concentrations of Zn and As are likely to persist in the tailings regardless of cover performance, whereas concentrations of Cu and Al are the parameters most sensitive to cover effectiveness.

Microbiological and geochemical characterization of As-bearing tailings and underlying sediments.

Over the past 100 years, extensive oxidation of As-bearing sulfide-rich tailings from the abandoned Long Lake Gold Mine (Canada) has resulted in the formation of acid mine drainage (pH 2.0-3.9) containing high concentrations of dissolved As (∼400 mg L-1), SO42-, Fe and other metals. Dissolved As is predominantly present as As(III), with increased As(V) near the tailings surface. Pore-gas O2 is depleted to < 1 vol% in the upper 30-80 cm of the tailings profile. The primary sulfides, pyrite and arsenopyrite, are highly oxidized in the upper portions of the tailings. Elevated proportions of sulfide-oxidizing prokaryotes are present in this zone (mean 32.3% of total reads). The tailings are underlain by sediments rich in organic C. Enrichment in δ34S-SO4 in pore-water samples in the organic C-rich zone is consistent with dissimilatory sulfate reduction. Synchrotron-based spectroscopy indicates an abundance of ferric arsenate phases near the impoundment surface and the presence of secondary arsenic sulfides in the organic-C beneath the tailings. The persistence of elevated As concentrations beneath the tailings indicates precipitation of secondary As sulfides is not sufficient to completely remove dissolved As. The oxidation of sulfides and release of As is expected to continue for decades. The findings will inform future remediation efforts and provide a foundation for the long-term monitoring of the effectiveness of the remediation program.

Assessing cellulolysis in passive treatment systems for mine drainage: a modified enzyme assay.

A modified cellulase enzyme assay was developed to monitor organic matter degradation in passive treatment systems for mine drainage. This fluorogenic substrate method facilitates assessment of exo-(1,4)-ß-D-glucanase, endo-(1,4)-ß-D-glucanase, and ß-glucosidase, which compose an important cellulase enzyme system. The modified method was developed and refined using samples of organic carbon-amended mine tailings from field experiments where sulfate reduction was induced as a strategy for managing water quality. Sample masses (3 g) and the number of replicates ( ≥ 3) were optimized. Matrix interferences within these metal-rich samples were found to be insignificant. Application of this modified cellulase assay method provided insight into the availability and degradation of organic carbon within the amended tailings. Results of this study indicate that cellulase enzyme assays can be applied to passive treatment systems for mine drainage, which commonly contain elevated concentrations of metals.

Extracting resources from abandoned mines.

Recovering minerals and metals from aband on ed mines could aid decarbonization.