Characterization and environmental implications of selenate co-precipitation with barite.

This study investigated the sequestration of dissolved selenate (SeO42-) via co-precipitation in barite for a range of SeO42- concentrations (0-~8650 mg/L), as well as its release at near neutral pH conditions (pH = ~5.5-6.5). Solid precipitates were characterized via X-ray diffraction and subsequent Rietveld refinements, Raman spectroscopy, Brunauer-Emmett-Teller surface area analyses, scanning electron microscopy, electron probe microanalyses (EPMA), inductively coupled plasma optical emission spectroscopy (ICP-OES), and X-ray absorption spectroscopy (XAS). ICP-OES results suggested barite efficiently removed >99% of SeO42- from the test solutions during all co-precipitation experiments. EPMA results showed the SeO42- was sequestered from the aqueous phase via co-precipitation with barite. XAS analyses indicated the SeO42- tetrahedron is incorporated into the barite structure by substituting for sulfate (SO42-) and bonding to Ba2+ atoms through bidentate mononuclear and bidentate binuclear complexes. Dissolution data showed the release of SeO42- sequestered in barite to the aqueous phase is unlikely due to the low solubility and stability of the barite phase. As such, co-precipitation of SeO42- with barite could be effective for removing SeO42- from waters affected by mining and metallurgical operations.

Reservoirs of Selenium in Coal Waste Rock: Elk Valley, British Columbia, Canada.

Selenium (Se) reservoirs in coal waste rock from the Elk Valley, southeastern British Columbia, the location of Canada's major steelmaking coal mines, were characterized and quantified by analyzing samples collected from the parent rock, freshly blasted waste rock (less than 10 days old), and aged waste rock (deposited between 1982 and 2012). Se is present throughout the waste rock dumps at a mean digestible (SeD) concentration of 3.12 mg/kg. Microprobe analyses show that Se is associated with the primary minerals sphalerite, pyrite, barite, and chalcopyrite and secondary Fe oxyhydroxides. Selenium K-edge X-ray absorption near-edge spectroscopy analyses indicate that, on average, 21% of Se is present as selenide (Se(2-)) in pyrite and sphalerite, 19% of Se is present as selenite (Se(4+)) in barite, 21% of Se is present as exchangeable Fe oxyhydroxide and clay-adsorbed Se(4+), and 39% of Se is present as organoselenium associated with coaly matter. The dominant source minerals for aqueous-phase Se are pyrite and sphalerite. Secondary Fe oxyhydroxide sequesters, on average, 37% of Se released by pyrite oxidation. Measured long-term Se fluxes from a rock drain at the base of a waste dump suggest that at least 20% of Se(2-)-bearing sulfides were oxidized and released from that dump over the past 30 year period; however, the Se mass lost was not evident in SeD analyses.

Isotope hydrology of the intermontane Elk Valley, British Columbia: an assessment of water resources around coal mining operations.

This study aimed to synthesise and interpret stable isotopic data (δ2H and δ18O) from various sources to understand the isotope hydrology around coal mine operations in Elk Valley, B.C., Canada. The data, including precipitation, groundwaters, seeps, and mine rock drains, were used to construct a local meteoric water line (LMWL) for the Elk Valley, evaluate the spatiotemporal isotopic composition of its groundwater, and assess mine seepage and mine rock drain discharge. The study revealed a robust LMWL relation (δ2H = 7.4 ± 0.2 · δ18O - 4.3 ± 4.1). The groundwater and seep data indicated a winter season bias and a north-south latitudinal gradient, suggesting rapid near-surface groundwater flow without significant post-precipitation evaporation. Porewater isotope samples from unsaturated mine rock piles (MRPs) showed site-specific evaporation patterns, potentially due to convective air flows or exothermic sulphide oxidation. This research revealed the influence of groundwater and meltwater on rock drain discharge. Based on evaporative mass balance calculations, MRPs seasonally contributed ca. 5 %(December base flow) and 22 % (snowmelt) to drain discharge. The findings underscore the value of stable isotope data collections in the Elk Valley to help better define and quantify the hydrology-hydrogeology, including a better understanding of evaporative conditions in MRPs.

Selenate bioreduction in a large in situ field trial.

Removing selenium (Se) from mine effluent is a common challenge. A long-term, in situ experiment was conducted to bioremediate large volumes (up to 7500 mc d-1) of Se(VI)-contaminated water (mean 87 µg L-1) by injecting the water into a saturated waste rock fill (SRF) at a coal mining operation in Elk Valley, British Columbia, Canada. To stimulate/maintain biofilm growth in the SRF, labile organic carbon (methanol) and nutrients were added to the water prior to its injection. A conservative tracer (Br-) was also added to track the migration of injected water across the SRF, identify wells with minimal dilution and used to quantify the extent of bioreduction. The evolution of the Se species through the SRF was monitored in time and space for 201 d. Selenium concentrations of <3.8 µg L-1 were attained in monitoring wells located 38 m from the injection wells after 114 to 141 d of operation. Concentrations of Se species in water samples from complementary long-term (351-498 d) column experiments using influent Se(VI) concentrations of 1.0 mg L-1 were consistent with the results of the in situ experiment. Solid samples collected at the completion of the column experiments confirmed the presence of indigenous Se-reducing bacteria and that the sequestered Se was present as insoluble Se(0), likely in Se-S ring compounds. Based on the success of this ongoing bioremediation experiment, this technology is being applied at other mine sites.

Quantifying denitrification in a field-scale bioremediation experiment.

Nitrate (NO3-) in mine waste rock derived from undetonated NH4NO3 can contaminate receiving waters. An in-situ bioremediation experiment was conducted at a coal mining operation in Elk Valley, British Columbia, Canada to remediate NO3- from large volumes of mine water. Over the test period (201 d), 5000 to 7500 m3 d-1 of NO3--rich (mean concentration 22 mg N L-1) mine water was injected into saturated waste rock along with methanol, nutrients, and a conservative tracer (Br-). Complete denitrification (<0.5 mg N L-1) was recorded in monitoring wells located 38 m from the injection wells after 114 to 141 d of operation. Plots of δ15N- and δ18O-NO3- versus NO3--N concentrations for monitoring wells yielded isotopic enrichment factors (ε) for δ15N- and δ18O-NO3- of -25.7 and -13.2 ‰ for high C/C0 NO3- concentrations (>10.5 mg N L-1) and -5.5 and -3.6 ‰ for lower C/C0 values. The fraction of NO3- denitrified (Dp) calculated using bi-linear ε values for δ15N- and δ18O reproduced the Dp determined independently using a conservative tracer indicating that stable isotope tracers of the NO3- reducing processes in bioremediation are invaluable to determine Dp. Based on the success of this ongoing bioremediation experiment, the technology is being applied at other sites.

Correcting for methane interferences on δ2H and δ18O measurements in pore water using H2Oliquid-H2Ovapor equilibration laser spectroscopy.

Cavity ring-down spectroscopy (CRDS) is a new and evolving technology that shows great promise for isotopic δ(18)O and δ(2)H analyses of pore water from equilibrated headspace H(2)O vapor from environmental and geologic cores. We show that naturally occurring levels of CH(4) can seriously interfere with CRDS spectra, leading to erroneous δ(18)O and δ(2)H results for water. We created a new CRDS correction algorithm to account for CH(4) concentrations typically observed in subsurface and anaerobic environments, such as ground waters or lake bottom sediments. We subsequently applied the correction method to a series of geologic cores that contain CH(4). The correction overcomes the spectral interference and provides accurate pore water δ(18)O and δ(2)H values with acceptable precision levels as well as accurate concentrations of CH(4).

Transformation of two-line ferrihydrite to goethite and hematite as a function of pH and temperature.

Under oxic aqueous conditions, two-line ferrihydrite gradually transforms to more thermodynamically stable and more crystalline phases, such as goethite and hematite. This temperature- and pH-dependent transformation can play an important role in the sequestration of metals and metalloids adsorbed onto ferrihydrite. A comprehensive assessment of the crystallization of two-line ferrihydrite with respect to temperature (25, 50, 75, and 100 °C) and pH (2, 7, and 10) as a function of reaction time (minutes to months) was conducted via batch experiments. Pure and transformed phases were characterized by X-ray diffraction (XRD), X-ray absorption near-edge spectroscopy (XANES), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The rate of transformation of two-line ferrihydrite to hematite increased with increasing temperature at all pHs studied and followed first-order reaction kinetics. XRD and XANES showed simultaneous formation of goethite and hematite at 50 and 75 °C at pH 10, with hematite being the dominant product at all pHs and temperatures. With extended reaction time, hematite increased while goethite decreased, and goethite reaches a minimum after 7 days. Observations suggest two-line ferrihydrite transforms to hematite via a two-stage crystallization process, with goethite being intermediary. The findings of this study can be used to estimate rates of crystallization of pure two-line ferrihydrite over the broad range of temperatures and pH found in nature.

Effects of adsorbed arsenate on the rate of transformation of 2-line ferrihydrite at pH 10.

2-Line ferrihydrite, a form of iron in uranium mine tailings, is a dominant adsorbent for elements of concern (EOC), such as arsenic. As ferrihydrite is unstable under oxic conditions and can undergo dissolution and subsequent transformation to hematite and goethite over time, the impact of transformation on the long-term stability of EOC within tailings is of importance from an environmental standpoint. Here, studies were undertaken to assess the rate of 2-line ferrihydrite transformation at varying As/Fe ratios (0.500-0.010) to simulate tailings conditions at the Deilmann Tailings Management Facility of Cameco Corporation, Canada. Kinetics were evaluated under relevant physical (~1 °C) and chemical conditions (pH ~10). As the As/Fe ratio increased from 0.010 to 0.018, the rate of ferrihydrite transformation decreased by 2 orders of magnitude. No transformation of ferrihydrite was observed at higher As/Fe ratios (0.050, 0.100, and 0.500). Arsenic was found to retard ferrihydrite dissolution and transformation as well as goethite formation.

Transport and bacterial interactions of three bacterial strains in saturated column experiments.

The impact of bacteria-solid and bacteria-bacteria interactions on the transport of Klebsiella oxytoca, Burkholderia cepacia G4PR1, and Pseudomonas sp. #5 was investigated in saturated sand column experiments (L = 114 mm; ø = 33 mm) under constant water velocities (∼ 5 cm · h(-1)). Bacterial strains were injected into the columns as pulses either individually, simultaneously, or successively. A one-dimensional mathematical model for advective-dispersive transport and for irreversible and reversible bacterial kinetic sorption was used to analyze the bacterial breakthrough curves. Different sorption parameters were obtained for each strain in each of the three experimental setups. In the presence of other bacteria, sorption parameters for B. cepacia G4PR1 remained similar to results from individual experiments, indicating the presence of other bacteria generally had a lesser influence on its migration than for the other bacteria. K. oxytoca is more competitive for the sorption sites when simultaneously injected with the other bacteria. Ps. sp. #5 generally yielded the greatest detachment rates and the least affinity to attach to the sand, indicative of its mobility in groundwater systems. The results of this study clearly indicate both bacteria-solid and bacteria-bacteria interactions influence the migration of bacteria. A more complete understanding of such interactions is necessary to determine potential migration in groundwater systems.

Molybdenum speciation in uranium mine tailings using X-ray absorption spectroscopy.

Uranium (U) mill tailings in northern Saskatchewan, Canada, contain elevated concentrations of molybdenum (Mo). The potential for long-term (>10,000 years) mobilization of Mo from the tailings management facilities to regional groundwater systems is an environmental concern. To assist in characterizing long-term stability, X-ray absorption spectroscopy was used to define the chemical (redox and molecular) speciation of Mo in tailings samples from the Deilmann Tailings Management Facility (DTMF) at the Key Lake operations of Cameco Corporation. Comparison of Mo K near-edge X-ray absorption spectra of tailings samples and reference compounds of known oxidation states indicates Mo exists mainly as molybdate (+6 oxidation state). Principal component analysis of tailings samples spectra followed by linear combination fitting using spectra of reference compounds indicates that various proportions of NiMoO(4) and CaMoO(4) complexes, as well as molybdate adsorbed onto ferrihydrite, are the Mo species present in the U mine tailings. Tailings samples with low Fe/Mo (<708) and high Ni/Mo (>113) molar ratios are dominated by NiMoO(4), whereas those with high Fe/Mo (>708) and low Ni/Mo (<113) molar ratios are dominated by molybdate adsorbed onto ferrihydrite. This suggests that the speciation of Mo in the tailings is dependent in part on the chemistry of the original ore.

The geochemistry and hydrology of coal waste rock dumps: A systematic global review.

Coal has been a major global resource for at least the past 250 years. The major waste product of coal mining is waste rock, which is stored in dumps of various sizes. Although the adverse effects of coal waste rock dumps on ecosystems and human health are widely recognised, there is little information on their internal hydrological and geochemical processes in the peer-reviewed literature. Coal and conventional waste rock dumps share many similarities, but coal waste rock dumps differ in structure, organic matter content, and size, which can affect the timing and rate of aqueous chemical release. In this global systematic review, we identify limited links to climate setting and dump construction, and inconsistent reporting of sampling and monitoring approaches, as limitations to the generalisation of findings. Furthermore, sources of aqueous constituents of interest (COIs) are not routinely or adequately identified, which can lead to incorrect assumptions regarding COI availability and geochemical mobility. Water flow regimes within dumps are dominated by matrix and/or preferential flow, depending on dump texture; these flow mechanisms exert a primary control on patterns of aqueous COI release. The inability to successfully transfer COI release rates from laboratory or field scale trials to operational scale dumps is primarily due to limitations of testing methods and fundamental characteristics of scale. Prediction of future release rates is hampered by a lack of long-term studies that fully characterise geochemistry (e.g., source and COI production rates) as well as dump hydrology (e.g., water balance, water migration). Five critical elements to include in best practice investigations are climate setting, dump physical characteristics, geochemical processes, water regime, and environmental load over time, as aqueous release of COIs from coal waste rock dumps occurs over decades to centuries. Key considerations are identified for each of these elements to guide best practice.

Simulating nitrate release from an unsaturated coal waste rock dump.

Knowledge of the controls affecting the release of contaminants from waste rock dumps is critical for developing strategies to mitigate downstream impacts on water quality. In this study, a three-dimensional model of a large coal waste rock dump constructed in the Elk Valley, British Columbia, Canada was developed to capture the impact of construction history (1981-2012) and solute transport on nitrate (NO3-) release over a 100-year timeframe. The model consisted of 21, one-dimensional finite element models that represented the temporal evolution of the dump. Nitrate, derived from undetonated blast products, was assumed to be present at the time of waste rock placement and was simulated as a conservative species. The simulated pattern of NO3- release to the surface water receptor occurred approximately 8 years before its measured arrival. This time lag is attributed to displacement of the water within a basal alluvial aquifer by dump effluent. The simulated patterns of historic releases corrected for the 8-year time lag, compare favourably with monitoring data and suggest the dominant hydrogeological and geochemical mechanisms are captured in the model. The model indicated the flushing of NO3- from the dump should be complete by about 2042 with a peak effluent concentration of NO3- in 2008. The addition of reclamation covers to the model resulted in an immediate decrease in the annual NO3- loading rate but extended the time frame for NO3- release from the dump relative to the no cover case. The model also showed that the timing of cover placement had little impact on NO3- release relative to the no cover case due to long duration of waste rock placement (~30 years) over a relatively large footprint.

Assessing the fate of explosives derived nitrate in mine waste rock dumps using the stable isotopes of oxygen and nitrogen.

Ammonium nitrate (NH4NO3) mixed with fuel oil is a common blasting agent used to fragment rock into workable size fractions at mines throughout the world. The decomposition and oxidation of undetonated explosives can result in high NO3- concentrations in waters emanating from waste rock dumps. We used the stable isotopic composition of NO3- (δ15N- and δ18O-NO3-) to define and quantify the controls on NO3- composition in waste rock dumps by studying water-unsaturated and saturated conditions at nine coal waste rock dumps located in the Elk Valley, British Columbia, Canada. Estimates of the extent of nitrification of NH4NO3 in oxic zones in the dumps, initial NO3- concentrations prior to denitrification, and the extent of NO3- removal by denitrification in sub-oxic to anoxic zones are provided. δ15N data from unsaturated waste rock dumps confirm NO3- is derived from blasting. δ15N- and δ18O-NO3- data show extensive denitrification can occur in saturated waste rock and in localized zones of elevated water saturation and low oxygen concentrations in unsaturated waste rock. At the mine dump scale, the extent of denitrification in the unsaturated waste rock was inferred from water samples collected from underlying rock drains.

Quantifying uranium complexation by groundwater dissolved organic carbon using asymmetrical flow field-flow fractionation.

The long-term mobility of actinides in groundwaters is important for siting nuclear waste facilities and managing waste-rock piles at uranium mines. Dissolved organic carbon (DOC) may influence the mobility of uranium, but few field-based studies have been undertaken to examine this in typical groundwaters. In addition, few techniques are available to isolate DOC and directly quantify the metals complexed to it. Determination of U-organic matter association constants from analysis of field-collected samples compliments laboratory measurements, and these constants are needed for accurate transport calculations. The partitioning of U to DOC in a clay-rich aquitard was investigated in 10 groundwater samples collected between 2 and 30 m depths at one test site. A positive correlation was observed between the DOC (4-132 mg/L) and U concentrations (20-603 microg/L). The association of U and DOC was examined directly using on-line coupling of Asymmetrical Flow Field-Flow Fractionation (AsFlFFF) with UV absorbance (UVA) and inductively coupled plasma-mass spectrometer (ICP-MS) detectors. This method has the advantages of utilizing very small sample volumes (20-50 microL) as well as giving molecular weight information on U-organic matter complexes. AsFlFFF-UVA results showed that 47-98% of the DOC (4-136 mg C/L) was recovered in the AsFlFFF analysis, of which 25-64% occurred in the resolvable peak. This peak corresponded to a weight-average molecular weight of about 900-1400 Daltons (Da). In all cases, AsFlFFF-ICP-MS suggested that

Clay aquitards as archives of holocene paleoclimate: delta18O and thermal profiling.

Paleoclimatic conditions in the Holocene were reconstructed from a detailed vertical profile of pore water delta(18)O and a series of downhole thermal profiles at a thick, hydrogeologically simple, aquitard research site in the Northern Great Plains of Saskatchewan. Reconstructions were obtained using the theory of one-dimensional diffusive transport and an empirical Bayesian inversion technique. Inversion of the delta(18)O profile shows that input signal consists of a sudden increase of +6 per thousand (corresponding to a temperature increase of about 18 degrees C) at about 12,000 years before present (BP), after which no measurable change in delta(18)O is apparent to present day. This research shows, at this location, that there is no evidence of large amplitude temperature shifts in the Holocene and supports the commonly used assumption in ground water studies of constant atmospheric delta(18)O values throughout the Holocene. Inversion of the temperature profiles suggests the ground surface temperature increased primarily in the last half of the 20th century, with a peak temperature (about 3 degrees C) circa 1990. For both profiles, the ability to resolve historical variability decays rapidly with time. For the temperature profiles, the decay in resolution precluded the development of reliable estimates of climatic conditions prior to about 1950 and, in the case of the delta(18)O profile, it prevented the precise definition of climate changes (e.g., Hypsithermal and Little Ice Age) in the Holocene.

Complexation of aqueous elements by DOC in a clay aquitard.

The extent of partitioning of several elements (Cu, Mn, Mo, Ni, Sr, U, and Zn) on dissolved organic carbon (DOC) was investigated in pore water samples collected from a clay-rich aquitard. High DOC concentrations in the aquitard, ranging from 21 to 143 mg C/L, and natural aqueous metal concentrations higher than in most ground water environments facilitated complexation studies at this site. Analyses were conducted using on-line coupling of asymmetrical flow field-flow fractionation with ultraviolet, total organic carbon, and inductively coupled plasma-mass spectrometry detectors. Of the elements investigated, only U and Zn were complexed with all DOC samples, ranging from 2.2 to 60 microg U/g DOC (0.4% to 3% of the total U in the pore water) and 0.04 to 0.5 microg Zn/g DOC (0.1% to 0.9% of the total Zn in the pore water), respectively. Laboratory experiments conducted over a range in pH (1.3 to 9.7) and geochemical modeling supported the measured complexation of U and Zn on the DOC. The in situ association constant, K(d), for U decreased with depth from 76 mL/g C for pore water samples at 2.2 m below ground (BG) to 24 mL/g C at 9.7 m BG. The decrease was attributed to a decrease in aromaticity of the DOC with depth. Zn K(d)constants ranged from 2 to 12 mL/g C and exhibited no trend with depth. Results of the current study suggest minor masses of U and Zn (less than or equal to 4% of total) complex with this DOC under in situ pH conditions. Our data suggest that competitive complexation by other ligands may limit the importance of DOC-facilitated transport of the elements studied in water of similar chemical composition.

Geochemistry of arsenic in low sulfide-high carbonate coal waste rock, Elk Valley, British Columbia, Canada.

This study investigated the geochemistry of arsenic (As) in low sulfide-high carbonate coal waste rock of the Elk Valley, British Columbia, Canada. Its abundance and mineralogical associations in waste rock of different placement periods were determined in addition to its mobilization into porewater and rock-drain effluent. The mean (5.34mg/kg; 95% confidence interval: 4.95-5.73mg/kg) As concentration in the waste rock was typical of sedimentary rock. Electron microprobe and As K-edge X-ray absorption near-edge spectroscopic analyses showed the As is predominantly associated with primary pyrites in both source and freshly blasted waste rock. However, in aged waste rock the As is associated with both primary pyrites and secondary Fe oxyhydroxides. Oxidation of pyrite in waste rock dumps was reflected by the presence of high concentrations of SO42- in porewater and oxidation rims of Fe oxyhydroxides around pyrite grains. Acid released from pyrite oxidation to Fe oxyhydroxides is neutralized by carbonate mineral dissolution that buffers the pH in the waste rock to circumneutral values. Adsorption of As onto secondary Fe oxyhydroxides provides an internal geochemical control on As release during pyrite oxidation and porewater flushing from the dump, resulting in the low As concentrations observed in porewater (median: 9.91µg/L) and rock-drain effluent (median: 0.31µg/L). Secondary Fe oxyhydroxides act as a long-term sink for As under present day hydrologic settings in waste rock dumps in the Elk Valley.

Nitrate release from waste rock dumps in the Elk Valley, British Columbia, Canada.

The origin, distribution and leaching of nitrate (NO3-) from coal waste rock dumps in the Elk Valley, British Columbia, Canada were defined using chemical and NO3- isotope analyses (δ15N- and δ18O-NO3-) of solids samples of pre- and post-blast waste rock and from thick (up to 180m) unsaturated waste rock dump profiles constructed between 1982 and 2012 as well as water samples collected from a rock drain located at the base of one dump and effluent from humidity cell (HC) and leach pad (LP) tests on waste rock. δ15N- and δ18O-NO3- values and NO3- concentrations of waste rock and rock drain waters confirmed the source of NO3- in the waste rock to be explosives and that limited to no denitrification occurs in the dump. The average mass of N released during blasting was estimated to be about 3-6% of the N in the explosives. NO3- concentrations in the fresh-blast waste rock and recently placed waste rock used for the HC and LP experiments were highly variable, ranging from below detection to 241mg/kg. The mean and median concentrations of these samples ranged from 10-30mg/kg. In this range of concentrations, the initial aqueous concentration of fresh-blasted waste rock could range from approximately 200-600mg NO3--N/L. Flushing of NO3- from the HCs, LPs and a deep field profile was simulated using a scale dependent leaching efficiency (f) where f ranged from 5-15% for HCs, to 35-80% for the LPs, to 80-90% for the field profile. Our findings show aqueous phase NO3- from blasting residuals is present at highly variable initial concentrations in waste rock and the majority of this NO3- (>75%) should be flushed by recharging water during displacement of the first stored water volume.

Dissolved Selenium(VI) Removal by Zero-Valent Iron under Oxic Conditions: Influence of Sulfate and Nitrate.

Dissolved Se(VI) removal by three commercially available zero-valent irons (ZVIs) was examined in oxic batch experiments under circumneutral pH conditions in the presence and absence of NO3 - and SO4 2-. Environmentally relevant Se(VI) (1 mg L-1), NO3 - ([NO3-N] = 15 mg L-1), and SO4 2- (1800 mg L-1) were employed to simulate mining-impacted waters. Ninety percent of Se(VI) removal was achieved within 4-8 h in the absence of SO4 2- and NO3 -. A similar Se(VI) removal rate was observed after 10-32 h in the presence of NO3 -. Dissolved Se(VI) removal rates exhibited the highest decrease in the presence of SO4 2-; 90% of Se(VI) removal was measured after 50-191 h for SO4 2- and after 150-194 h for SO4 2- plus NO3 - depending on the ZVI tested. Despite differences in removal rates among batches and ZVI materials, Se(VI) removal consistently followed first-order reaction kinetics. Scanning electron microscopy, Raman spectroscopy, and X-ray diffraction analyses of reacted solids showed that Fe(0) present in ZVI undergoes oxidation to magnetite [Fe3O4], wüstite [FeO], lepidocrocite [γ-FeOOH], and goethite [α-FeOOH] over time. X-ray absorption near-edge structure spectroscopy indicated that Se(VI) was reduced to Se(IV) and Se(0) during removal. These results demonstrate that ZVI can be effectively used to control Se(VI) concentrations in mining-impacted waters.

Geochemical and mineralogical characterization of sulfur and iron in coal waste rock, Elk Valley, British Columbia, Canada.

Exposure of coal waste rock to atmospheric oxygen can result in the oxidation of sulfide minerals and the release of sulfate (SO42-) and associated trace elements (e.g., Se, As, Cd, and Zn) to groundwaters and surface waters. Similarly, reduced iron minerals such as siderite, ankerite, and the sulfide, pyrite, present in the waste rock can also undergo oxidation, resulting in the formation of iron oxyhydroxides that can adsorb trace elements released from the oxidation of the sulfide minerals. Characterization and quantification of the distribution of sulfide and iron minerals, their oxidation products, as well as leaching rates are critical to assessing present-day and future impacts of SO42- and associated trace elements on receiving waters. Synchrotron-based X-ray absorption near edge spectroscopic analysis of coal waste rock samples from the Elk Valley, British Columbia showed Fe present as pyrite (mean 6.0%), siderite (mean 44.3%), goethite (mean 35.4%), and lepidocrocite (mean 14.3%) with S present as sulfide (mean 26.9%), organic S (mean 58.7%), and SO42- (mean 14.4%). Squeezed porewater samples from dump solids yielded mean concentrations of 0.28mg/L Fe and 1246mg/L SO42-. Geochemical modeling showed the porewaters in the dumps to be supersaturated with respect to Fe oxyhydroxides and undersaturated with respect to gypsum, consistent with solids analyses. Coupling Fe and S mineralogical data with long-term water quality and quantity measurements from the base of one dump suggest about 10% of the sulfides (which represent 2% of total S) in the dump were oxidized over the past 30years. The S from these oxidized sulfides was released to the receiving surface water as SO42- and the majority of the Fe precipitated as secondary Fe oxyhydroxides (only 3.0×10-5% of the Fe was released to the receiving waters over the past 30years). Although the data suggest that the leaching of SO42- from the waste rock dump could continue for about 300years, assuming no change in the rate of oxidation of sulfides, SO42- is currently not a concern in receiving surface waters as the concentration levels are below regulatory limits.