Matthew B.J. Lindsay

Mechanistic investigations of Se(VI) treatment in anoxic groundwater using granular iron and organic carbon: an EXAFS study.

The removal of aqueous Se(VI) from a simulated groundwater by granular iron (GI), organic carbon (OC), and a mixture of these reactive materials (GI-OC) was evaluated in laboratory batch experiments. The experiments were performed under anoxic conditions to simulate subsurface treatment. A total reaction time of 120 h (5 d) was chosen to investigate the rapid changes in speciation occurring over reaction times that are reasonable for permeable reactive barrier (PRB) systems. After 120 h, concentrations of Se decreased by >90% in the GI system, 15% in the OC system and 35% in the GI-OC mixture. Analysis of the materials after contact with Se using synchrotron-radiation based X-ray absorption spectroscopy (XAS) indicated the presence of Se(IV) and Se(0) on the margins of GI grains after 6h with evidence of SeO and SeSe bonding, whereas Se(VI) was not observed. After 72 h, Se(0) was the only form of Se present in the GI experiments. In the OC batches, the XAS analysis indicated binding consistent with sorption of aqueous Se(VI) onto the OC with only minor reduction to Se(IV) and Se(0) after 120 h. Selenium XAS spectra collected for the GI-OC mixture were consistent with spectra for Se(IV) and Se(0) on both the margins of GI grains and OC particles, suggesting that the presence of dissolved Fe may have mediated the reduction of sorbed Se(VI). The results suggest that the application of granular Fe is effective at inducing aqueous Se removal in anoxic conditions through reductive precipitation processes.

Chromium Isotope Fractionation During Reduction of Cr(VI) Under Saturated Flow Conditions

Chromium isotopes are potentially useful indicators of Cr(VI) reduction reactions in groundwater flow systems; however, the influence of transport on Cr isotope fractionation has not been fully examined. Laboratory batch and column experiments were conducted to evaluate isotopic fractionation of Cr during Cr(VI) reduction under both static and controlled flow conditions. Organic carbon was used to reduce Cr(VI) in simulated groundwater containing 20 mg L(-1) Cr(VI) in both batch and column experiments. Isotope measurements were performed on dissolved Cr on samples from the batch experiments, and on effluent and profile samples from the column experiment. Analysis of the residual solid-phase materials by scanning electron microscopy (SEM) and by X-ray absorption near edge structure (XANES) spectroscopy confirmed association of Cr(III) with organic carbon in the column solids. Decreases in dissolved Cr(VI) concentrations were coupled with increases in δ(53)Cr, indicating that Cr isotope enrichment occurred during reduction of Cr(VI). The δ(53)Cr data from the column experiment was fit by linear regression yielding a fractionation factor (α) of 0.9979, whereas the batch experiments exhibited Rayleigh-type isotope fractionation (α = 0.9965). The linear characteristic of the column δ(53)Cr data may reflect the contribution of transport on Cr isotope fractionation.

Microbiology and Geochemistry of Mine Tailings Amended with Organic Carbon for Passive Treatment of Pore Water

A field-scale experiment was conducted to evaluate organic carbon amendment of mine tailings as a technique for pore water and drainage treatment. Six test cells were constructed by amending sulfide- and carbonate- rich tailings with varied mixtures of peat, spent-brewing grain and municipal biosolids. Samples were collected for microbial, geochemical and mineralogical analysis approximately three years after commencing this experiment. Test cells amended with spent-brewing grain promoted sulfate reduction and effective removal of sulfate and metal(loid)s. The addition of municipal biosolids did not sustain enhanced sulfidogenesis after three years, and peat was an ineffective source of organic carbon. Terminal-restriction fragment length polymorphism revealed that test cells which supported sulfidogenesis exhibited the greatest microbial diversity. Indigenous bacteria identified using molecular and cultivation analyses were found to be related to Cellulomonas, Thiobacillus, Bacteroides, Paludibacter and Desulfovibrio, which was the only sulfate-reducing bacterial (SRB) isolated. The results demonstrate that mixtures of solid organic materials which supported complex anaerobic microbial communities, including sulfate- reducing bacteria, were most effective in promoting pore-water treatment.

Examining mechanisms of groundwater Hg(II) treatment by reactive materials: an EXAFS study.

Laboratory batch experiments were conducted to examine mechanisms of Hg(II) removal by reactive materials proposed for groundwater treatment. These materials included granular iron filings (GIF), 1:1 (w/w) mixtures of metallurgical granular Fe powder + elemental S (MGI+S) and elemental Cu + elemental S (Cu+S), granular activated carbon (GAC), attapulgite clay (ATP), ATP treated with 2-amino-5-thiol-1,3,4-thiadiazole (ATP-a), and ATP treated with 2,5-dimercapto-1,3,4-thiadiazole (ATP-d). Following treatment of simulated groundwater containing 4 mg L(-1) Hg for 8 or 16 days, the solution pH values ranged from 6.8 to 8.8 and Eh values ranged from +400 to -400 mV. Large decreases in aqueous Hg concentrations were observed for ATP-d (>99%), GIF (95%), MGI+S (94%), and Cu+S (90%). Treatment of Hg was less effective using ATP (29%), ATP-a (69%), and GAC (78%). Extended X-ray absorption fine structure (EXAFS) spectra of Hg on GIF, MGI+S, and GAC indicated the presence of an Hg-O bond at 2.04-2.07 Å, suggesting that Hg was bound to GIF corrosion products or to oxygen complexes associated with water sorbed to activated carbon. In contrast, bond lengths ranging from 2.35 to 2.48 Å were observed for Hg in Cu+S, ATP-a, and ATP-d treatments, suggesting the formation of Hg-S bonds.

Initial geochemical characteristics of fluid fine tailings in an oil sands end pit lake

Geochemical characteristics of fluid fine tailings (FFT) were examined in Base Mine Lake (BML), which is the first full-scale demonstration oil sands end pit lake (EPL) in northern Alberta, Canada. Approximately 186Mm(3) of FFT was deposited between 1994 and 2012, before BML was established on December 31, 2012. Bulk FFT samples (n=588) were collected in July and August 2013 at various depths at 15 sampling sites. Temperature, solid content, electrical conductivity (EC), pH, Eh and alkalinity were measured for all samples. Detailed geochemical analyses were performed on a subset of samples (n=284). Pore-water pH decreased with depth by approximately 0.5 within the upper 10m of the FFT. Major pore-water constituents included Na (880±96mgL(-1)) and Cl (560±95mgL(-1)); Ca (19±4.1mgL(-1)), Mg (11±2.0mgL(-1)), K (16±2.3mgL(-1)) and NH3 (9.9±4.7mgL(-1)) were consistently observed. Iron and Mn concentrations were low within FFT pore water, whereas SO4 concentrations decreased sharply across the FFT-water interface. Geochemical modeling indicated that FeS(s) precipitation was favoured under SO4-reducing conditions. Pore water was also under-saturated with respect to gypsum [CaSO4·2H2O], and near saturation with respect to calcite [CaCO3], dolomite [CaMg(CO3)2] and siderite [FeCO3]. X-ray diffraction (XRD) suggested that carbonate-mineral dissolution largely depleted calcite and dolomite. X-ray absorption near edge structure (XANES) spectroscopy revealed the presence of FeS(s), pyrite [FeS2], and siderite. Carbonate-mineral dissolution and secondary mineral precipitation have likely contributed to FFT dewatering and settlement. However, the long-term importance of these processes within EPLs remains unknown. These results provide a reference for assessing the long-term geochemical evolution of oil sands EPLs, and offer insight into the chemistry of pore water released from FFT to the overlying water cover.

Vanadium Geochemistry of Oil Sands Fluid Petroleum Coke

Vanadium has previously been linked to elevated toxicity of leachates derived from oil sands petroleum coke. However, geochemical controls on V mobility within coke deposits remain poorly constrained. Detailed examinations of porewater and solid-phase V geochemistry were therefore performed on oil sands fluid petroleum coke deposits in Alberta, Canada. Sample collection focused on both active and reclaimed deposits, which contained more than 3 × 107 m3 of fluid petroleum coke. Dissolved V concentrations were highest (up to 3.0 mg L-1) immediately below the water table but decreased rapidly with increasing depth. This trend corresponded to a transition from mildly acidic (pH 6-7) and oxic conditions to mildly alkaline (pH 7-8.5) and anoxic conditions. Scanning electron microscopy (SEM), electron microprobe analysis (EMPA), and micro-X-ray fluorescence (μXRF) mapping revealed coke particles exhibited an internal structure characterized by successive concentric layers. The outer margins of these layers were characterized by elevated V, Fe, Si, and Al concentrations, indicating the presence of inorganic phases. Micro-X-ray absorption near-edge structure (μXANES) spectroscopy revealed that V speciation was dominated by V(IV) porphyrins except at outer margins of layers, where octahedrally coordinated V(III) was a major component. Minor to trace V(V) was also detected within fluid petroleum coke particles.

Chemical mass transport between fluid fine tailings and the overlying water cover of an oil sands end pit lake

Fluid fine tailings (FFT) are a principal by-product of the bitumen extraction process at oil sands mines. Base Mine Lake (BML) – the first full-scale demonstration oil sands end pit lake (EPL) – contains approximately 1.9 x108 m3 of FFT stored under a water cover within a decommissioned mine pit. Chemical mass transfer from the FFT to the water cover can occur via two key processes: (1) advection-dispersion driven by tailings settlement; and (2) FFT disturbance due to fluid movement in the water cover. Dissolved chloride (Cl) was used to evaluate the water cover mass balance and to track mass transport within the underlying FFT based on field sampling and numerical modeling. Results indicated that FFT was the dominant Cl source to the water cover and that the FFT is exhibiting a transient advection-dispersion mass transport regime with intermittent disturbance near the FFT-water interface. The advective pore water flux was estimated by the mass balance to be 0.002 m3 m−2 d−1, which represents 0.73 m of FFT settlement per year. However, the FFT pore water Cl concentrations and corresponding mass transport simulations indicated that advection rates and disturbance depths vary between sample locations. The disturbance depth was estimated to vary with location between 0.75 and 0.95 m. This investigation provides valuable insight for assessing the geochemical evolution of the water cover and performance of EPLs as an oil sands reclamation strategy.

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 SO42–. Environmentally relevant Se(VI) (1 mg L–1), NO3– ([NO3—N] = 15 mg L–1), and SO42– (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 SO42– 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 SO42–; 90% of Se(VI) removal was measured after 50–191 h for SO42– and after 150–194 h for SO42– 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.

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)-β-D-glucanase, endo-(1,4)-β-D-glucanase, and β-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.

The Persistence of Brines in Sedimentary Basins

Brines are commonly found at depth in sedimentary basins. Many of these brines are known to be connate waters that have persisted since the early Paleozoic Era. Yet questions remain about their distribution and mechanisms for retention at depth in the Earth’s crust. Here we demonstrate that there is insufficient topography to drive these dense fluids from the bottom of deep sedimentary basins. Our assessment based on driving force ratio indicates that sedimentary basins with driving force ratio> 1 contain connate waters and frequently host large evaporite deposits. These stagnant conditions appear to be relatively stable over geological time and insensitive to factors such as glaciations, erosion, compaction, and hydrocarbon generation. Plain Language Summary Brines that are millions of years old are present at the bottom of many sedimentary basins. Regional groundwater flow should have flushed these brines out of these systems if not for the presence of some trapping mechanism. Here we demonstrate that there is insufficient topography to drive dense brines out of the bottom of many deep sedimentary basins. We provide geochemical evidence that brines within these basins originated as ancient seawater that was trapped during deposition of the sediments in these basins. Our findings may have applications in determining where stagnant groundwaters are present in sedimentary basins.