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Degraded water quality and environmental impacts caused by weathering of sulfide-bearing mine wastes are a legacy remaining at many historical mine sites. Release and mobilization of toxic metals (e.g., Zn and Cd) in mine drainage are often associated with weathering of primary sulfide minerals and precipitation and dissolution of secondary minerals. This study aims to couple field-scale measurements of physicochemical parameters with μm- and nm-scale mineralogical characterization to investigate sphalerite weathering and controls on Zn and Cd migration in an uncovered mine waste-rock pile. Elevated concentrations of Zn and Cd, potentially harmful to the receiving environment, were detected in waste-rock pore water and seepage. A suite of analytical techniques, including scanning electron microscopy – energy dispersive X-ray spectroscopy (SEM-EDS), scanning transmission electron microscopy (STEM) with EDS, electron microprobe analysis (EMPA), and synchrotron-based micro X-ray fluorescence (μ-XRF) mapping and micro X-ray absorption near edge structure (μ-XANES) spectroscopy were utilized in a high-resolution investigation of elemental- and secondary-mineral associations with sphalerite grains. EMPA and μ-XRF elemental maps and STEM investigations show depletion of Zn, Fe, S, and Cd, local enrichment of Cu, and distinct dissolution pits at the margins of sphalerite grains. Using μ-XANES, the speciation of solid phases containing Zn, Cu, Fe, and S indicates the dominance of primary sphalerite with microscopic inclusions of chalcopyrite, along with sparse occurrence of secondary Cu-bearing sulfides formed during weathering. These results suggest sphalerite oxidation leads to congruent dissolution without formation of distinct secondary-mineral coatings. Sphalerite weathering significantly contributes to elevated aqueous concentrations of Zn and Cd. Field-scale observations and mineralogical investigations indicate common occurrence of Fe-oxyhydroxides in the waste-rock pile. Seepage chemistry and surface complexation modeling results suggest that pH-dependent variations in reactions on the surfaces of the Fe-oxyhydroxides control aqueous concentrations of Zn and Cd, and the Zn/Cd ratio in the seepage. This work highlights the importance of understanding the mechanisms of sulfide-mineral oxidation and subsequent surface precipitation and adsorption, such that appropriate remediation action can be implemented to limit mobilization of metals to sensitive ecosystems.

Tracking the S oxidation pathway in sulfide-bearing mine waste-rock piles is complicated by variations in water content, O2 and Fe3+ concentrations, microbial diversity, mineralogy, the occurrence of a variety of S species associated with incomplete oxidation, and nonlinear coupling between physicochemical processes. Synchrotron-based S K-edge X-ray absorption near edge structure (XANES) spectroscopy facilitates the identification and quantification of S species (i.e., S2-, S22-, S8, S2O32-, and SO42-) in a naturally weathered mine waste-rock pile containing pyrite, sphalerite, galena, pyrrhotite, and chalcopyrite. Mineralogy-dependent polysulfide and thiosulfate pathways both affect the S oxidation within the waste-rock pile. Currently, the polysulfide pathway, with S8 as the intermediate S species, generates high concentrations of dissolved metals (from the rapid oxidation of monosulfides including sphalerite, galena, pyrrhotite, and chalcopyrite). As these monosulfides are depleted, the thiosulfate pathway of pyrite oxidation, including intermediate oxidation products (i.e., S8 and S2O32-), will become the dominant oxidation pathway, resulting in the potential for generation of additional acidic drainage. This information highlights the importance of identifying the sulfide-mineral oxidation reaction pathways when attempting to estimate acid generation potential, and when developing remediation strategies for the storage and management of sulfide-bearing waste rock.

Distinguishing municipal wastewater effluent (MWWE) from other industrial effluents or through an urbanized watershed can be challenging. In complex receiving environments, linking environmental responses to specific compounds or effluents is not always straight forward. In order to characterize the inherent complexity of tracing MWWE in aquatic systems influenced by multiple stressors, a proposed multi-tracer suite is intended to highlight areas of potential biological concern. Characterization and quantification of effluent exposure to aquatic biota in this manner is essential to shape policies intended to encourage wastewater infrastructure development (i.e. treatment plant upgrade) and broader environmental management. This paper describes the use of a comprehensive suite of tracers that includes isotopes in support of a core surveillance program, demonstrating its effectiveness both empirically and with respect to diagnostic value contributed to monitoring programs.

Emerging contaminants are widely detected and persistent in environmental waters. Advanced oxidation processes are among the most effective methods for removing emerging contaminants from water; however, high energy consumption greatly increases the operating costs and limits large-scale applications. In this study, a passive treatment system consisting of four columns packed with mixtures of silica sand, zero-valent iron (ZVI), biochar (BC), and a mixture of (ZVI + BC) were evaluated for simultaneous removal of eight pharmaceuticals, four artificial sweeteners, and two perfluoroalkyl substances (PFASs) from water. Overall, the passive treatment system was more effective for removing target pharmaceuticals (almost complete removal) than artificial sweeteners and PFASs (partial removal). Columns ZVI, BC, and (ZVI + BC) exhibited similarly effective removal (>97%) of target pharmaceuticals, including carbamazepine, caffeine, sulfamethoxazole, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, ibuprofen, gemfibrozil, and naproxen, from ~9 to 76% of input sucralose (~110 μg L−1) was removed in the three treatment columns. Reactive medium BC alone was more effective for removing target PFASs than ZVI and (ZVI + BC). Input perfluorooctanoic acid (PFOA) (~45 μg L−1) was partially removed in the columns containing BC but not ZVI alone. Between 10 and 80% of input perfluorooctane sulfonic acid (PFOS) (24 90 μg L−1) was removed in Column ZVI; greater removals (57 99%) were observed in Columns BC and (ZVI + BC).

Biochar has been used in many applications as a remediation material, but less attention has been paid to the potential release of various soluble components that may alter the effectiveness of the remediation process. Here, we report the release of nutrients, trace elements, anions and cations from 36 types of biochars. A batch-style experiment was performed by mixing biochar and water at a mass ratio of 1:75. Elevated concentrations of these components were observed in the majority of the solutions mixed with the biochars. No significant differences were observed between low-temperature (low-T, 300 °C) and high-temperature (high-T, 600 °C) biochars in terms of NO3−, Cl−, Na+, Ca2+, Fe, Cu, PO4-P, NH3-N, and K+ concentrations (P

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.

Acid mine drainage and the associated contaminants, including As and metals, are ongoing environmental issues. Passive remediation technologies have the potential to remove As from mine waste effluents. A series of laboratory column experiments was conducted to evaluate the effectiveness of varying mixtures of organic carbon (OC), zero-valent iron (ZVI), and limestone for the treatment of As, metals, SO42−, and acidity in groundwater from an abandoned gold mine. The onset of bacterially-mediated SO42− reduction was indicated by a decrease in Eh, a decline in aqueous SO42− concentrations coupled with enrichment of δ34S, and the presence of sulfate-reducing bacteria and H2S. Removal of As was observed within the first 3 cm of reactive material, to values below 10 µg L−1, representing > 99.9% removal. An increase in pH from 3.5 to circumneutral values and removal of metals including Al, Cu, and Zn was also observed. Synchrotron results suggest As was removed through precipitation of As-crystalline phases such as realgar and orpiment, or through adsorption as As(V) on ferrihydrite. The results indicate the potential for a mixture of OC and ZVI to remove As from acidic, mine-impacted water.

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.

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.

Land application of biosolids can improve soil fertility and enhance crop production. However, the occurrence and persistence of pharmaceutical compounds in the biosolids may result in leaching of these contaminants to surface water and groundwater, causing environmental contamination. This study evaluated the effectiveness of two organic amendments [biochar (BC) and woodchips (WC)] for reducing the concentration and leachability (mobility) of four pharmaceuticals in biosolids derived from wastewater treatment plants in southern Ontario, Canada. The effect of 360-d composting on fate and leachabilities of target pharmaceuticals in biosolid mixtures was also investigated. Composting decreased total and leachable concentrations of pharmaceuticals in unamended and BC- and WC-amended biosolids to various degrees, from 10% up to 99% depending on the compound. Blending BC or WC into the biosolids greatly increased the removal rates of the target pharmaceuticals, while simultaneously decreasing their half-lives (t0.5), compared to unamended biosolids. The t0.5 of contaminants in this study followed the order: carbamazepine (304-3053 d) > gemfibrozil (42.3-92.4 d) > naproxen (15.3-104 d) > ibuprofen (12.5-19.0 d). Amendment with BC and(or) WC significantly reduced the leachability of carbamazepine, ibuprofen, and gemfibrozil to variable extents, but significantly enhanced the leachability of naproxen, compared to unamended biosolids (P

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.

Acid mine/rock drainage (AMD/ARD) is generated by the microbially-accelerated oxidative dissolution of sulfide minerals in working and abandoned mine sites, and some natural environments. Iron-oxidizing microorganisms (IOM) regenerate the oxidant Fe3+, while sulfur-oxidizing microorganisms (SOM) contribute to AMD/ARD by generating H2SO4 via the oxidation of elemental S and reduced inorganic sulfur compounds. Bacterial and archaeal diversity in 34 samples of sulfide-bearing waste rock recovered from three boreholes at the Faro Mine Complex (Yukon Territory, Canada; Pb/Zn production from 1969 to 1998) was investigated using high-throughput amplicon sequencing of 16S rRNA genes. A majority of the borehole pore water samples had circum-neutral or mildly alkaline pH (6.3 − 8.7), while some had low pH (3.3 − 5.2). Mean relative abundance of prokaryotic SOM/IOM accounted for 3.4% of the total amplicons. The acidophilic genera Alicyclobacillus and Acidithiobacillus were the most abundant sulfur- and iron-metabolizing prokaryotes detected, followed by neutrophilic and moderately acidophilic (non-iron-oxidizing) SOM. Sulfate-reducing bacteria (SRB) were also detected, accounting for 0.6% of total reads. The presence of both acidophilic and neutrophilic prokaryotes catalyzing transformations of sulfur and iron in the same samples suggests development of microenvironments within the waste rock where dynamic biogeochemical transformations of these elements occur.

Various studies have focused on the performance and removal mechanism of aqueous Hg using biochars, but the specific Hg removal process has not been fully elucidated. Aqua regia digestion is considered a common Hg extraction method from solid samples, but uncertainties exist regarding Hg extraction from biochars. Aqueous Hg removal kinetic experiments followed by aqua regia digestion procedures and solid-phase analyses were conducted to investigate the Hg diffusion and transformation processes on oak biochar (BC) and evaluate the extraction efficiency of aqua regia as well as the stability of Hg adsorbed by biochars. Kinetic experiments indicated Hg adsorption capacity increased and adsorption rate decreased using oak biochar pretreated with calcium polysulfide (CP-BC) relative to unmodified BC. Confocal micro-X-ray fluorescence imaging illustrated Hg penetration into the interior of BC and accumulation on the CP-BC surface. Hg extended X-ray absorption fine structure spectra modeling indicated the Hg was first adsorbed as Hg(II)–O and transformed to Hg(II)–S forms on CP-BC, whereas only the Hg(II)–Cl forms of Hg were observed on BC. The results of aqua regia digestion suggest that Hg cannot be completely extracted from BC. These results provide information on the kinetic processes of Hg removal by biochars and incomplete extraction of Hg by aqua regia, which is critical for optimizing biochar modification methods and evaluating the long-term stability of adsorbed Hg in aqueous environments.

The effectiveness of activated carbon and four types of biochar, switchgrass (300 °C and 600 °C), poultry manure (600 °C), and oak (∼700 °C) with respect to mercury (Hg) and methylmercury (MeHg) control was assessed in microcosm experiments carried out for 524 d. Early in the study (

The Diavik Waste Rock Project consists of laboratory and field experiments developed for the investigation and scale-up of the geochemical evolution of sulfidic mine wastes. As part of this project, humidity cell experiments were conducted to assess the long-term geochemical evolution of a low-sulfide waste rock. Reactive transport modelling was used to assess the significant geochemical processes controlling oxidation of sulfide minerals and their dependence on temperature and sulfide mineral content. The geochemical evolution of effluent from waste rock with a sulfide content of 0.16 wt.% and 0.02 wt.% in humidity cells was simulated with the reactive transport model MIN3P, based on a conceptual model that included constant water flow, sulfide mineral content, sulfide oxidation controlled by the availability of oxidants, and subsequent neutralization reactions with carbonate and aluminosilicate minerals. Concentrations of Ni, Co, Cu, Zn, and SO4 in the humidity cell effluent were simulated using the shrinking core model, which represented the control of oxidant diffusion to the unreacted particle surface in the sulfide oxidation process. The influence of temperature was accounted for using the Arrhenius relation and appropriate activation energy values. Comparison of the experiment results, consisting of waste rock differentiated by sulfide mineral content and temperature, indicated surface area and temperature play important roles in rates of sulfide oxidation and release of sulfate and metals. After the model was calibrated to fit the effluent data from the higher sulfide content cells, subsequent simulations were conducted by adjusting only measured parameters, including sulfide mineral content and surface area.

Phosphorus (P) derived from the application of fertilizers to agricultural land can often reach surface water bodies through tile drainage systems. Phosphorus fate and transport are dependent on the geochemistry and biological activity of both the soil macropore linings/walls and soil matrix. Macropores can be especially important contaminant transport pathways to groundwater and tile drainage networks. In this study, we investigated P geochemistry and the soil microbiome of a macroporous clay loam soil under corn and soybean cropping practices typical for eastern Ontario, Canada. We used spectroscopic techniques including P K-edge X-ray absorption near-edge structure (XANES) spectroscopy, micro-X-ray fluorescence mapping, and micro-XANES for P speciation. We also used quantitative PCR to investigate the capacity of the soil microbiome to mobilize and transform organic (targeting the genes phoC, phoD, and phnX) and inorganic (targeting the gene pqqC) P pools. Phosphorus was retained in the soil predominantly as β-tricalcium phosphate and P sorbed to calcite. The microbial communities in both the macropore linings/walls and the matrix were functionally capable of transforming P from both organic and inorganic sources, with organic P cycling functions more abundant in surface soils and macropore domains and inorganic cycling P functions equally distributed throughout the soil. As a whole, the diverse biological capacity to cycle the different forms of P found in the soil represents a consistent source of crop-available P. The results of this study augment our understanding of the fate and transport and biogeochemistry of P in the matrix and the more highly transmissive macropores of agricultural soils.

Compound‐specific standardized sampling and storage methods are not available for artificial sweeteners found in groundwater. This study aimed to understand: (1) the appropriate length of storage time for samples containing acesulfame (ACE), sucralose (SUC), saccharin (SAC), and cyclamate (CYC) in simulated groundwater (SGW); (2) conditions of their stability; and (3) which sampling materials are appropriate for sample collection. The evaluated storage conditions included acidification, headspace, exposure to light, and refrigeration; the evaluated sampling materials included steel, stainless steel, aluminum, polyvinyl chloride, polyamide (nylon), polypropylene (PharMed BPT™) tubing, styrene‐ethylene‐butylene co‐polymer (MasterFlex™) tubing, and polytetrafluoroethylene (Teflon™) tubing. All compounds evaluated were stable in storage at 4 °C for 241 d (8 months). Concentrations of artificial sweeteners were consistently within 60% to 120% of original concentrations, except ACE and SAC that were substantially lower under acidified conditions at 25 °C after 241 d. Artificial sweetener concentrations remained nearly constant while in contact with all sampling materials except steel. SEM and TEM images showed oxidation of steel occurred; moreover, removal of all artificial sweetener compounds from aqueous solution had occurred after 289 d. These results suggest artificial sweetener analyses conducted within 14 d of sample collection produce optimal results; however, longer storage times may be acceptable under certain conditions. The results also suggest concentrations of artificial sweeteners in SGW are not affected by contact with typical well casing, sampling, and storage materials, with the exception of steel. The findings from this study will improve the use of artificial sweeteners as tracers in environmental studies.

Research on the use of titanium dioxide (TiO2) for water treatment has expanded to include the degradation of pharmaceuticals and personal care products (PPCPs). PPCPs are typically introduced in aqueous solutions during TiO2 photocatalysis experiments using a water-miscible carrier solvent (e.g. methanol) to improve their solubility; however, carrier solvents may be detrimental to photocatalysis due to their scavenging effect. Although it is advisable to maintain the solvent at low concentrations, the influence of elevated concentrations of methanol or other solvents on photocatalysis has not been carefully explored. In this study, we examined the impacts of different methanol concentrations (0–0.2% v/v) on photocatalysis using P25 (commercial TiO2) and TiO2 nanomaterial synthesized via thermal and chemical oxidation (TCO). Scavenging of hydroxyl radicals by methanol was evident for both P25 and TCO but the effect was more prominent on TCO. Also, the photodegradation of some compounds using P25 were enhanced at low levels of methanol. Overall, this study highlights that trace amounts of methanol used as a carrier solvent can affect photocatalysis, especially in TiO2 nanomaterials with low reactivity. This should be considered carefully in future experiments so that the results are not biased by the introduction of carrier solvents.

Despite the large number of pharmaceutically active compounds found in natural environments little is known about their transport behavior in groundwater, which is complicated by their wide range of physical and chemical properties. The transport behavior of five widely used and often detected pharmaceutical compounds and one lifestyle drug has therefore been investigated, using a set of three column experiments. The investigated compounds were the anticonvulsant carbamazepine, the lifestyle drug caffeine, the antibiotic sulfamethoxazole, the lipid regulator gemfibrozil, and the nonsteroidal anti-inflammatories ibuprofen and naproxen. The columns were filled with three different types of sand. The substrates consisted of artificially prepared iron-coated sand, artificially prepared organic carbon sand (with 5% leaf compost), and natural aquifer sand from Long Point, Ontario (Canada). The experiments were conducted simultaneously under the same hydraulic conditions and with the same input solution of about 1μg·L-1 of each compound. The transport behavior of the organic compounds differed significantly between both the different columns and the different compounds. A strong correlation was observed between the retardation factors for carbamazepine, gemfibrozil, and ibuprofen and the organic carbon content of the substrate. While the retardation increased with increasing organic carbon content, no direct relationship was observed between the organic carbon content and the removal of these compounds. In contrast, the retardation factors for sulfamethoxazole and naproxen showed no correlation with the organic carbon content but these compounds were significantly removed in the presence of organic matter. The influence of the Fe3+ surfaces in the iron-coated sand was less significant than expected, with all compounds except for sulfamethoxazole having retardation factors

A flow-through cell experiment was conducted to evaluate Zn isotope fractionation during ZnS precipitation under microbially-mediated sulfate-reducing conditions. Synthetic groundwater containing 0.90 mM Zn was pumped through a cell containing creek sediment that was biostimulated to promote sulfate reducing conditions. Real-time, in situ X-ray absorption spectroscopy (XAS) was applied at the Zn K-edge to collect spectra via a Kapton® window in the front of the cell over the course of the experiment. Aqueous effluent samples were collected and analysed to determine concentrations of anions and cations, and Zn isotope ratios. The flow rate was increased step-wise during the experiment to modify the residence time and produce changes in the extent of sulfate reduction, which in turn controlled the extent of ZnS precipitation. Greater enrichment in the heavier isotope in the aqueous phase relative to the input solution was associated with more extensive Zn removal. A Rayleigh curve was fit to the isotope data, where e = −0.27 ± 0.06‰ (2σ). Evaluation of Zn isotope fractionation under controlled flow conditions is critical to improve the efficacy of this powerful analytical technique when applied to natural systems or remediation projects in the field.

Mercury (Hg) transport and methylmercury (MeHg) production in riverbank sediments are complex processes influenced by site-specific physical and biogeochemical conditions. The South River watershed in VA, USA, contains elevated concentrations of Hg in riverbank and floodplain sediments, which has the potential to methylate. The role of specific organic carbon sources in promoting methylation reactions in natural sediments under dynamic flow conditions is not well understood. Four saturated column experiments were conducted, including a control column, which received South River water as an influent solution, and three columns that received South River water amended with: acetate (5.8 mM); lactate (5.7 mM); and lactate (5.7 mM) with SO42− (10.1 mM). The amendments were selected to promote growth of different microorganisms to gain an understanding of the microbial processes, controlling rates of methylation. The column receiving lactate and SO42− had the highest MeHg concentrations in the effluent ...

Confocal micro-X-ray fluorescence imaging (C-μXRF-I), an emerging X-ray spectroscopy technique for collecting X-ray fluorescence (XRF) data within intact objects, is beginning to see widespread use in many fields of study. However, the XRF intensity is attenuated during data collection, and corrections are required prior to data interpretation. A beam path (pixel)-based correction method is presented that takes into account heterogeneity of a sample and C-μXRF-I setup geometry. The sample heterogeneity is addressed by assuming the mass distribution of an element is the same as the XRF intensity distribution of the element in each pixel. The beam path in each pixel is calculated using the C-μXRF-I step size and geometry. The Beer–Lambert law is then applied to correct the attenuated XRF. The XRF intensity used to calculate the mass distribution is updated iteratively using values from the previous step, until the difference in intensity between the previous and current step is less than a threshold value. This correction method was verified using two distinct standard reference materials (NIST SRM 1834 and 611), and was then applied to imaging of fresh and aged switchgrass biochars. The corrected intensity of SRM 1834 indicates most elements were distributed homogeneously, but the distribution of some trace elements was more heterogeneous (P < 0.05). The corrected intensities of SRM 611 indicate all the elements are homogeneously distributed. The difference between the raw and corrected intensities for the biochar samples was not as pronounced as for standard reference materials due to a lower density and fewer high Z elements.

Periodic flooding and drying conditions in floodplains affect the mobility and bioavailability of Hg in aquatic sediments and surrounding soils. Sulfurized materials have been recently proposed as Hg sorbents due to their high affinity to bind Hg, while sulfurizing organic matter may enhance methylmercury (MeHg) production, offsetting the beneficial aspects of these materials. This study evaluated hardwood biochar (OAK) and sulfurized-hardwood biochar (MOAK) as soil amendments for controlling Hg release in a contaminated floodplain soil under conditions representative of periodic flooding and drying in microcosm experiments in three stages: (1) wet biochar amended-systems with river water in an anoxic environment up to 200 d; (2) dry selected reaction vessels in an oxic environment for 90 d; (3) rewet such vessels with river water in an anoxic environment for 90 d. In Stage 1, greater Hg removal (17–98% for unfiltered total Hg (THg) and 47–99% for 0.45-μm THg) and lower MeHg concentrations (

Macropores can be important conduits for surface-derived nutrients to reach subsurface receptors. Accordingly, nutrient reactive transport processes in macroporous soils need to be well understood. In this study, steady-state two-dimensional reactive transport simulations with MIN3P-THCm (version 1.0.519.0) were used to elucidate how soil macropore connectivity to tile drains can influence N transformations following liquid swine manure (LSM) applications to soil. Four different soil scenarios were considered: homogeneous sand, homogeneous clay loam, and clay loam with discrete macropores connected to or disconnected from the bottom boundary used to represent tile drain outflow. In relation to the homogeneous soils, macropores, overall, facilitated chemical diffusion into the adjacent soil matrix along their length and broadly augmented O ingress into the soil profile. These processes combined to critically control the spatial distribution of NH oxidation reaction products. When used in transient simulation mode with field data observed at experimental tile-drained plots that received LSM application, the model showed that simulated nitrate mass losses to tile are considerably higher and most realistic under the connected macropore scenario compared with the homogeneous or disconnected macropore scenarios.

Mercury (Hg) was used during 1929–1950 as a catalyst to produce rayon acetate at the former DuPont plant in Waynesboro, Virginia, and released into the South River. Though the use of Hg ceased in the 1970s, the affected ecosystem is still a matter of concern. Here, high total mercury (THg) and total organomercury, stated as methylmercury (MeHg) are reported in historically contaminated floodplain soils and shallow groundwater from five locations sited 5.6 km downstream from the plant of one river edge site. In soils, THg ranged from 0.1 to 1201.5 mg/kg exceeding the health-based screening Hg levels for residential and industrial soils while MeHg varied between 0.1 and 54 µg/kg. Concentrations decreased sharply with depth indicating the stratification of legacy industrial Hg-rich soils underlain by the pre-industrial soils with minor Hg. Strong linear correlation between THg and MeHg was observed. Highest soil MeHg was associated with total carbon, poorly crystalline and amorphous Fe and/or Mn oxyhydroxides. Sequential extraction analyses indicated that Hg was present mostly in relatively recalcitrant forms, as determined with procedures that targeted β-HgS, HgS, HgSe, HgAu, thiol-bound Hg, Hg0, and some organo-complexed Hg, Hg2Cl2 phases. High Cu (≤ 404.3 mg/kg), Zn (≤ 151.3 mg/kg), Cr (≤ 123.9 mg/kg) were also identified. In shallow groundwater, THg ranged from 28 to 538 ng/L and MeHg varied between 1.2 and 137 ng/L. During the intermittent precipitation, the highest MeHg was linked to the highest Fe2+, Mn, SO42−, total alkalinity, and conductivity, which could be due to either the potential leaching and dissolution of soil minerals and/or the saturation of the vadose zone. A sharp increase in the soil moisture at the top 40–70 cm of the Hg-rich soils after rainfall and overbank flooding was followed by redox gradients from oxidizing (≈ + 600 mV) to reducing (≈ − 300 mV) and a reverse response in a transmissive gravel zone at the base of the bank (≈ − 400 to + 200 mV) with a defined lag with depth. These dynamic seasonal fluctuations at the South River might be crucial for solubilization of Hg, Fe, and Mn redox-sensitive minerals triggering the anoxic response for new MeHg production.

Field experiments previously conducted to assess organic carbon (OC) amendments for in situ biological treatment of tailings porewater at the Greens Creek Mine (Alaska, USA) showed sulfate reduction, metal-sulfide precipitation, and decreased fluxes of sulfate and dissolved metals. Here, we develop two reactive transport models using the reactive transport code MIN3P to simulate hydrogeochemical processes and δ 34S–SO4 isotope fractionation over four years in test cells containing unamended (control) and amended (5 vol % OC) tailings. These models successfully simulate observed data including pH, SO4, δ 34S–SO4, Ca, Fe, K, Mg, Mn, Si, and Zn. The models also indicate that dissolution of carbonate and, to a lesser extent, aluminosilicate minerals neutralize acidic porewater generated from sulfide mineral oxidation and sulfate reduction reactions. Application of a constant kinetic fractionation factor of 0.9820 to simulate measured δ 34S–SO4 trends confirms that sulfate removal principally results from microbially-mediated sulfate reduction in conjunction with OC oxidation and subsequent metal-sulfide precipitation. Gypsum precipitation/dissolution and thiosulfate disproportionation have negligible effects on modelled porewater δ 34S–SO4 signatures. Our simulations are consistent with the previous findings that metal-sulfide precipitation controls Fe and Zn attenuation in amended tailings and that coprecipitation reactions contribute to metal removal. Overall, these simulations demonstrate that coupled reactive transport modelling incorporating stable isotope fractionation can improve the understanding of hydrogeochemical and biogeochemical controls within in situ treatment systems, further illustrating the benefits and limitations of this technique for improving water quality of mine drainage.

This study evaluates spatiotemporal variability in the behavior of septic system derived nutrients in a sandy nearshore aquifer and their discharge to a large lake. A groundwater nutrient-rich plume was monitored over a two-year period with the septic system origin of the plume confirmed using artificial sweeteners. High temporal variability in NO3-N attenuation in the nearshore aquifer prior to discharge to the lake (42–96%) reveals the complex behavior of NO3-N and potential importance of changing hydrological and geochemical conditions in controlling NO3-N discharge to the lake. While PO4-P was retarded in the nearshore aquifer, the PO4-P plume extended over 90 m downgradient of the septic system. It was estimated that the PO4-P plume may reach the lake within 10 years and represents a legacy issue whereby PO4-P loads to the lake may increase over time. To provide broader assessment of the contribution of septic systems to P and N loads to a large lake, a regional scale geospatial model was developed that considers the locations of individual septic systems along the Canadian Lake Erie shoreline. The estimated P and N loads indicate that septic systems along the shoreline are only a minor contributor to the annual P and N loads to Lake Erie. However, it is possible that nutrients from septic systems may contribute to localized algal blooms in shoreline areas with high septic system density. In addition, disproportionate P and N loads in discharging groundwater may change the N:P ratio in nearshore waters and promote growth of harmful cyanobacteria. The study provides new insights into factors controlling the function of the reaction zone near the groundwater-lake interface including its impact on groundwater-derived nutrient inputs to large lakes. Further, the study findings are needed to inform septic system and nutrient management programs aimed at reducing lake eutrophication.

Frequent drying and rewetting due to flooding/precipitation and drainage events in floodplains induces changes in biogeochemical conditions that may influence the effectiveness of in situ Hg stabilization using biochars as soil amendments. This study evaluated two selected biochars anaerobic digestate (DIG) and sulfurized hardwood (MOAK)) as potential amendment materials in moderately reduced floodplain soil under repeated drying and rewetting events using a modified humidity cell protocol. Enhanced release of filter-passing (0.45-μm) total Hg (THg) and MeHg was observed at early times. Elevated concentrations of 0.45-μm THg were associated with DOC and Mn in sediment control and biochar-amended systems. Elevated concentrations of MeHg were associated with Mn in the MOAK-amended system. Thereafter, decreases in 0.45-μm (up to 57%) and unfiltered THg (up to 93%) were observed. As wetting and drying events continued, decreases in pH and alkalinity as well as increases in SO42− (up to 796 mg L−1) and Ca (up to 215 mg L−1) were observed in the MOAK-amended systems with the microbial community shifted towards sulfur-oxidizing bacteria, indicating microbially-driven oxidation of MOAK. Although results of S K-edge X-ray absorption near edge structure (XANES) analysis suggest polysulfur is the predominant S phase in both MOAK- and DIG-amended systems, microbially-driven oxidation of DIG was not observed. Polysulfur in MOAK from the sulfurization process is more bioavailable to sulfur oxidizing communities than in DIG under the repeated drying and wetting conditions. Results of this study suggest biogeochemical conditions as well as biochar properties should be considered when planning full-scale field applications.

This study evaluated three biochars derived from bioenergy by-products — manure-based anaerobic digestate (DIG), distillers’ grains (DIS), and a mixture thereof (75G25S) — as amendments to stabilize Hg in contaminated floodplain soil under long-term saturated (up to 200 d) and cyclic drying and rewetting conditions. Greater total Hg (THg) removal (72 to nearly 100%) and limited MeHg production (

Thirty-six biochars produced from distinct feedstocks at different temperatures were evaluated for their potential to remove mercury (Hg) from aqueous solution at environmentally relevant concentrations. Concentrations of total Hg (THg) decreased by >90% in batch systems containing biochars produced at 600 and 700 °C and by 40-90% for biochars produced at 300 °C. Elevated concentrations of SO4(2-) (up to 1000 mg L(-1)) were observed in solutions mixed with manure-based biochars. Sulfur X-ray absorption near edge structure (XANES) analyses indicate the presence of both reduced and oxidized S species in both unwashed and washed biochars. Sulfur XANES spectra obtained from biochars with adsorbed Hg were similar to those of washed biochars. Micro-X-ray fluorescence mapping results indicate that Hg was heterogeneously distributed across biochar particles. Extended X-ray absorption fine structure modeling indicates Hg was bound to S in biochars with high S content and to O and Cl in biochars with low S content. The predominant mechanisms of Hg removal are likely the formation of chemical bonds between Hg and various functional groups on the biochar. This investigation provides information on the effectiveness and mechanisms of Hg removal that is critical for evaluating biochar applications for stabilization of Hg in surface water, groundwater, soils, and sediments.

Sustained oxidation of sulfide minerals in waste rock generates acid mine drainage for time frames of hundreds to thousands of years. Management to minimize long-term degradation of water supplies and ecosystem health requires a thorough understanding of geochemical processes occurring within the waste rock. A comprehensive field investigation was conducted on sulfide and carbonate-rich waste-rock dumps at the Faro Mine Complex, south-central Yukon Territory, Canada. This investigation included installation of three highly instrumented boreholes, in situ measurements of physical and geochemical parameters (e.g., water content, temperature, air permeability, and pore-gas O2 and CO2 concentration), and collection of pore-water, pore-gas, and solid-phase samples. Field and laboratory measurements indicate the waste rock is lithologically and mineralogically segregated, with sulfide-rich (>20 wt% S) waste rock dominating in the lower benches (20–50 mbgs) and carbonate-bearing waste rock dominating in the upper benches and other parts of the dumps. The observed segregation strongly influences spatial variability of geochemical parameters. Three distinct geochemical zones are observed within the waste-rock dumps, including a rapid O2-supply zone, with near-atmospheric concentrations of O2 (0–30 mbgs); a strong O2-depletion zone (30–50 mbgs), characterized by abundant sulfide minerals and significant O2 depletion to

Advanced oxidation and reduction processes have been intensively investigated as potential methods to promote the decomposition of perfluoroalkyl substances (PFASs). However, extreme operational conditions such as highly acidic pH, high temperature, and high pressure are required to promote degradation reactions, which makes these technologies costly and less feasible for full-scale applications. The objective of this study was to evaluate the effectiveness of zero-valent iron (ZVI) alone and a mixture of ZVI and biochar (ZVI + BC) for removal of seven target PFASs from water under ambient environmental conditions. Target PFASs included three perfluoroalkyl carboxylic acids (PFCAs) [perfluorooctanoic acid (PFOA, C8-PFCA), perfluoroheptanoic acid (C7-PFCA), and perfluorohexanoic acid (C6-PFCA)] and four perfluoroalkyl sulfonic acids (PFSAs) [perfluorooctane sulfonic acid (PFOS, C8-PFSA), perfluoroheptane sulfonic acid (C7-PFSA), perfluorohexane sulfonic acid (C6-PFSA), and perfluorobutane sulfonic acid (C4-PFSA)]. Batch test results show that PFSAs (up to 94% removal) were more effectively removed than PFCAs (up to 60% removal) when utilizing either ZVI or (ZVI + BC). About 20–60% of input PFOA (~18,550 μg L−1) and 90–94% of input PFOS (~18,580 μg L−1) were removed by ZVI alone or the mixture of (ZVI + BC). The removal efficiencies of PFCAs and PFSAs by reactive media increased with increasing chain length, from 0 to 17% for short-chain PFCAs (C6–C7) and 20 to 70% for short-chain PFSAs (C4–C7). About 5–10% of input PFOA and PFOS was partially defluorinated by ZVI alone as indicated by F− release; however, the defluorination efficiency may be underestimated due to the sorption of F− by the reactive media. Overall, the reactive mixture (ZVI + BC) may be an effective and environmentally sustainable material for removing PFASs from water under ambient environmental conditions.

A previous long-term microcosm experiment showed mercury (Hg) in the aqueous phase of contaminated sediment was effectively stabilized through the addition of biochar. The present study focuses on the application of synchrotron-related methods to evaluate the distribution and speciation of Hg in the biochar particles reacted for 235, 387, and 1030 days. The study provided more information on Hg stabilization mechanisms in addition to the information obtained by the previous studies. Confocal micro-X-ray fluorescence imaging (CMXRFI) and micro-X-ray fluorescence (micro-XRF) maps show that mercury co-exists with S, Cu, Fe, Mn, and Zn on the surface and inside the particles of biochar. Extended X-ray absorption fine structure (EXAFS) modeling shows that Hg is in an oxide form on the surface of an iron (hydro)oxide particle from fresh sediment and in Hg-sulfide forms in biochar samples. S X-ray absorption near-edge structure (XANES) analyses show that sulfide is present within the biochar particles. After amendment with biochars, a fraction of the Hg originally present in unstable forms (dissolvable, HgO, colloidal, nano, etc.) in the sediment was likely stabilized as less soluble Hg-sulfide phases on the surface or within the biochar particle. These results suggest Hg accumulation by the biochar particles renders it less potential for transport and bioavailability.

Hardwood biochar (pyrolyzed at 700 °C), a potential candidate for Hg removal, has been proposed for use as reactive capping mats along groundwater discharge zones or riverbanks to control release of Hg from contaminated riverbank sediments. Frequent flooding and drainage in fluvial settings can influence the effectiveness of remediation systems in contaminated riverbank sediments and floodplain soils. This study evaluated the effectiveness of Hg removal using hardwood biochar under hydrogeochemical conditions representative of those present within a reactive capping mat installed in a fluvial setting. Two sets of treatment columns, containing 50% v.v biochar and quartz sand, were subjected to 100 weekly wetting/drying cycles that included dry air, water-saturated air, and drainage using leachate derived from two source columns as input solutions: 1. Passing simulated acid rain water through floodplain soil, 2. Passing river water through riverbank sediment. In both treatment columns, >80% of the Hg was retained on the biochar without promoting Hg methylation and the release of other unintended dissolved constituents (including N, P, DOC). Results from solidphase extraction analyses suggest that Hg accumulated near the air/biochar-sand interface (0–2 cm) in the treatment columns at low loadings but was present at greater depths at higher loadings. Results of micro X-ray fluorescence (μ-XRF) mapping and micro X-ray absorption near edge structure (μ-XANES) for the biochar collected at depths 0–2 cm in treatment columns suggest retention of Hg-bearing particles derived from riverbank sediment and floodplain soil within the pore structure of the biochar. Sulfur K-edge XANES analysis of the unused biochar and the biochar after treatment suggest formation of Hg complexes on the biochar surface. These results indicate that hardwood biochar is potentially an effective media for application in reactive mats for controlling Hg discharging from contaminated riverbank sediments.

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 ...

Arsenic (As) concentrations as high as 179 μg/L have been observed in shallow groundwater in the Alberta’s Southern Oil Sand Regions. The geology of this area of Alberta includes a thick cover (up to 200 m) of unconsolidated glacial deposits, with a number of regional interglacial sand and gravel aquifers, underlain by marine shale. Arsenic concentrations observed in 216 unconsolidated sediment samples ranged from 1 and 17 ppm. A survey of over 800 water wells sampled for As in the area found that 50% of the wells contained As concentrations exceeding drinking water guidelines of 10 μg/L. Higher As concentrations in groundwater were associated with reducing conditions. Measurements of As speciation from 175 groundwater samples indicate that As(III) was the dominant species in 74% of the wells. Speciation model calculations showed that the majority of groundwater samples were undersaturated with respect to ferrihydrite, suggesting that reductive dissolution of Fe-oxyhydroxides may be the source of some As in groundwater. Detailed mineralogical characterization of sediment samples collected from two formations revealed the presence of fresh framboidal pyrite in the deeper unoxidized sediments. Electron microprobe analysis employing wavelength dispersive spectrometry indicated that the framboidal pyrite had variable As content with an average As concentration of 530 ppm, reaching up to 1840 ppm. In contrast, the oxidized sediments did not contain framboidal pyrite, but exhibited spheroidal Fe-oxyhydroxide grains with elevated As concentrations. The habit and composition suggest that these Fe-oxyhydroxide grains in the oxidized sediment were an alteration product of former framboidal pyrite grains. X-ray absorption near edge spectroscopy (XANES) indicated that the oxidized sediments are dominated by As(V) species having spectral features similar to those of goethite or ferrihydrite with adsorbed As, suggesting that Fe-oxyhydroxides are the dominant As carriers. XANES spectra collected on unoxidized sediment samples, in contrast, indicated the presence of a reduced As species (As(−I)) characteristic of arsenopyrite and arsenian pyrite. The results of the mineralogical analyses indicate that the oxidation of framboidal pyrite during weathering may be the source of As released to shallow aquifers in this region.

The former Sherritt–Gordon sulfide deposit in Sherridon, Manitoba, Canada, was mined for zinc, copper, silver, and gold between 1930 and 1951. Since mine closure, two high-sulfide tailings impoundments underwent extensive oxidation, resulting in the release of very high concentrations of dissolved sulfate and metals to the tailings porewater. During precipitation events and Spring freshet, surface seeps develop along the flanks of the impoundments, discharging groundwater with a pH as low as 0.39 and dissolved concentrations of sulfate and iron up to 203 g L−1 and 68 g L−1, respectively, along with other metals at elevated concentrations. Several efflorescent minerals were observed within groundwater-seepage areas. Using a combination of powder X-ray diffraction and energy-dispersive spectroscopy, secondary efflorescent sulfate minerals at seepage zones were identified, including melanterite, rozenite, halotrichite, chalcanthite, alpersite, copiapite, hexahydrite, jurbanite, pickeringite, jarosite, and gypsum. According to geochemical modeling of seepage waters using a modified WATEQ4F database for ferrous and ferric sulfate minerals, the occurrence of most of the observed sulfate salts was favored. In the geochemical modeling, we used data available for seepage waters that were representative of discharging water after mineral precipitation had already occurred. Discrepancies between some of the observed and modeled results likely reflect the use of water compositions representative of the later stages in the reaction sequence rather than the composition during actual formation of the minerals. The formation of these secondary efflorescent minerals resulted in a temporary removal of sulfate and metals from solution. These minerals rapidly dissolved during laboratory dissolution tests; this would result in increased loading to receiving surface waters during precipitation events and Spring freshet.

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.