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A mechanistic understanding of cesium (Cs) adsorption to soil mineral phases is essential for effective mitigation of Cs mobility in the subsurface environment. Todorokite, a common tunnel-structured manganese oxide in soil, exhibits sorption capacity for Cs comparable to the capacities of clay minerals. However, the adsorption sites and molecular species of Cs

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During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O2and the oxidation products of FeS [e.g.Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O2during XAS measurements. With strict O2exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO2and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

Changes in microbial community induced by acid shock were studied in the context of potential release of acids to the environment due to chemical accidents. The responses of microbial communities in three different soils to the exposure to sulfuric or hydrofluoric acid and to the subsequent neutralization treatment were investigated as functions of acid concentration and exposure time by using 16S-rRNA gene based pyrosequencing and DGGE (Denaturing Gradient Gel Electrophoresis). Measurements of soil pH and dissolved ion concentrations revealed that the added acids were neutralized to different degrees, depending on the mineral composition and soil texture. Hydrofluoric acid was more effectively neutralized by the soils, compared with sulfuric acid at the same normality. Gram-negative ß-Proteobacteria were shown to be the most acid-sensitive bacterial strains, while spore-forming Gram-positive Bacilli were the most acid-tolerant. The results of this study suggest that the Gram-positive to Gram-negative bacterial ratio may serve as an effective bio-indicator in assessing the impact of the acid shock on the microbial community. Neutralization treatments helped recover the ratio closer to their original values. The findings of this study show that microbial community changes as well as geochemical changes such as pH and dissolved ion concentrations need to be considered in estimating the impact of an acid spill, in selecting an optimal remediation strategy, and in deciding when to end remedial actions at the acid spill impacted site.

A partially Co2+-exchanged zeolite X was thermally treated to simulate the effect of decay heat on the leachability of extraframework Co2+. To have a mechanistic insight into thermal effect, X-ray diffraction, scanning electron microscopy, 27Al magic angle spinning nuclear magnetic resonance spectroscopy, and Co K-edge X-ray absorption spectroscopy were employed with leaching tests. Although thermal treatment at ≤ 600 °C did not lead to the collapse of zeolite framework, it removed H2O molecules from the coordination shell of extraframework Co2+, which in turn changed its coordination structure in a way to strengthen the interaction between Co2+ and the lattice oxygens. In leaching tests, the sample treated at higher temperature for a longer period showed less remobilized Co2+ by forming a Co(OH)2-like surface precipitate and a Co hydrotalcite-like phase. Notably, the formation of the latter phase indicated the abstraction of the framework Al, the extent of which increased with the treatment temperature and duration. Two mechanisms, the concurrent extraction of Al with Co2+ remobilization and the hydrolysis-promoted Al abstraction, were proposed to account for thermally promoted dealumination. This study suggests that the exposure of Co2+-exchanged zeolite X to decay heat lessen the risk of extraframework Co2+ to be reintroduced into groundwater.

Coastal areas where submarine groundwater discharge (SGD) occurs are active mixing zones with characteristic biogeochemical and ecological functions. In this study, we investigated the microbial community associated with the changes in groundwater discharge flux at a coastal beach site on Jeju Island, South Korea. We performed water chemistry analyses, 16S rRNA gene-based pyrosequencing, and microbial community statistical analyses on coastal water samples systematically collected as functions of tidal stage and distance from the groundwater discharge point. We also carried out groundwater level monitoring and numerical simulation of the coastal aquifer to reproduce tidally induced variations in the SGD rates of the study site. Pyrosequencing and statistical analyses revealed a periodic shift in the microbial communities in the coastal waters as functions of tidal stage and SGD rates. Interestingly, the community structures in the samples collected at flood and ebb tide were markedly different, despite the similarities in their water chemistry. Groundwater simulation and canonical correspondence analyses suggest that groundwater discharging at higher velocities at ebb tide can detach and transport subsurface bacteria from the aquifer to the coastal water body, resulting in an increase in facultative anaerobes in the ebb tide samples. In addition, release of the sand-attached bacteria as a result of particle resuspension and flushing of shallow subsurface bacteria in the intertidal zone could contribute to shaping the relative abundance of the coastal microbial community. We conclude that SGD rate is an important factor influencing the dynamics of the bacterial community structure at the coastal zone of the study site.

Submarine groundwater discharge (SGD) is a widely recognized process that carries considerable amounts of groundwater and dissolved chemicals to the coastal ocean. Despite its importance, a lack of suitable tools to assess SGD's spatial and temporal variability has hampered a complete understanding of the process. Here we report, for the first time, use of an unmanned aerial vehicle (UAV or “drone”) to assess SGD variations. An octocopter UAV platform equipped with a thermal infrared (TIR) system was flown along a coastline on Jeju Island, Korea. The UAV clearly captured thermal signatures of SGD plumes and their dynamic temporal fluctuations modulated by tidal variations. Based on a plume area-SGD flux relation we developed by combining aerial and field data, we estimated that the SGD flux of the study site ranged from 33,000 to 54,000 m3 d−1. The drone approach enabled acquisition of time series plume imagery with easy control of spatial resolution, flexible field operations, and remote sensing of SGD at low cost compared to conventional aerial surveys. Combining the UAV-TIR images with on-site sampling enables one to determine fluxes of nutrients and other dissolved species. UAV-TIR mapping can thus serve as a powerful tool for study of SGD and other coastal processes.

Submarine groundwater discharge (SGD) is a global phenomenon that carries large volumes of groundwater and dissolved chemical species such as nutrient, metals, and organic compounds to coastal zones. We report the influence of SGD on the coastal waters of Jeju Island, Korea, using high-resolution aerial thermal infrared (TIR) mapping techniques and field investigations. An aircraft-based system was implemented using a cost-effective TIR camera for aerial TIR mapping. Ground-based calibrations and system integration with GPS/IMU (global positioning system/inertial measurement unit) were performed for the aerial systems. The aerial surveys showed distinct low-temperature signatures of SGD along the coasts of Jeju Island, revealing large groundwater inputs from the coastal aquifers to the ocean. Multiple aerial surveys over a range of seasons and tidal stages revealed that SGD rates dynamically affect the sea surface temperature (SST) of the coastal zone. The in-situ measurements supported that SGD has a substantial influence on the coastal water chemistry as well as SST. Our observations highlight the extent to which aerial-based TIR mapping can serve as a powerful tool for studying SGD and other coastal processes. Copyright © 2016 John Wiley & Sons, Ltd.

We developed and applied a multidisciplinary approach to the impact of an accidentally spilled acid on the underlying geomedia and subsurface environment, based on the concept of geoecosystem. We used mineralogical, geochemical, microbiological, and ecotoxicological techniques to identify and assess the multiple aspects involved. First, we constructed a conceptual model for the acid interactions with the underlying subsurface environment by introducing the concept of a geoecosystem-a multicomponent system composed of inorganic, organic, and biological components to describe the subsurface environment. Second, we designed and manufactured a two dimensional cell to visualize acid transport through geomedia. Third, we hypothesized that the acids are neutralized through dissolution of minerals and protonation of functional groups on the surfaces of minerals and organic matter. We tested this hypothesis by conducting batch-type geomedia-acid reaction and surface titration experiments. Fourth, we observed changes in soil microbial communities before and after the acid exposure and neutralization treatment. Fifth, we performed flow-through experiments using columns packed with soil samples pre-contaminated with arsenic to investigate potential longer term, secondary effects of remnant acids on geoecosystems. Finally, we conducted ecotoxicological investigations using various geomedia and observed that suitability of the geoecosystem as a habitat deteriorated to different degrees depending on the respective systems' acid neutralizing power. We conclude that a holistic understanding of the interactions among the multiple components of geoecosystems and subsequent estimation of the influenced area requires a multidisciplinary approach such as those used in this study. Based on the findings of this study, we propose geoecosystems' vulnerability defined as the reciprocal of their acid-neutralizing capacity against the moving acid fronts and present this concept as central to a quantitative assessment of the impact of acid spills on geoecosystems. We also inventoried the essential components, factors, and parameters necessary in developing geoecosystems' acid vulnerability assessment system.

Cis-1,2,-dichloroethylene (cis-DCE) is a toxic, persistent contaminant occurring mainly as a daughter product of incomplete degradation of perchloroethylene (PCE) and trichloroethylene (TCE). This paper reports on abiotic reductive dechlorination of cis-DCE by mackinawite (FeS1−x ), a ferrous monosulfide, under variable geochemical conditions. To assess in situ abiotic cis-DCE dechlorination by mackinawite in the field, mackinawite suspensions prepared in a field groundwater sample collected from a cis-DCE contaminated field site were used for dechlorination experiments. The effects of geochemical variables on the dechlorination rates were monitored. A set of dechlorination experiments were also carried out in the presence of aquifer sediment from the site over a range of pH conditions to better simulate the actual field situations. The results showed that the suspensions of freshly prepared mackinawite reductively transformed cis-DCE to acetylene, whereas the conventionally prepared powder form of mackinawite had practically no reactivity with cis-DCE under the same experimental conditions. Significant cis-DCE degradation by mackinawite has not been reported prior to this study, although mackinawite has been shown to reductively transform PCE and TCE. This study suggests feasibility of using mackinawite for in situ remediation of cis-DCE-contaminated sites with high S levels such as estuaries under naturally achieved or stimulated sulfate-reducing conditions.

Cu(II) coordination in the interlayer of an expandable clay mineral montmorillonite is studied using X-ray absorption spectroscopy (XAS) along with electron paramagnetic resonance (EPR) and X-ray diffraction (XRD). Ab initio calculations are performed using FEFF code to reproduce the X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) portion of the experimentally measured XAS spectra. Cu(II) coordination changes depending on the Cu(II) loading and hydration state of the interlayer. XRD shows that the Cu-saturated montmorillonite has d001-spacing values corresponding to the interlayer thickness of four and one water layer(s) for the hydrated and dehydrated interlayers, respectively. EPR shows that Cu(II) in the fully hydrated, unsaturated interlayer behaves similarly to free Cu(II) ion in a bulk aqueous solution, while Cu(II) forms a square planar complex in the dehydrated interlayer. Cu(II) in the fully hydrated, Cu-saturated montmorillonite has a characteristic singlet 1st derivative XANES spectrum. FEFF calculations show that this singlet feature originates from a quasi-regular octahedral coordination of water molecules around the interlayer Cu(II) atom. All other samples and model compounds including the dry Cu-saturated montmorillonite, wet and dry unsaturated montmorillonite, aqueous Cu(II), cupric nitrate salt (Cu(NO3)2·4.5H2O), and Cu(II) hydroxide precipitates have doublet 1st derivative XANES spectra. FEFF calculations suggest that the doublet features arise from an axially elongated octahedral coordination under the Jahn–Teller effect or square planar coordination. FEFF calculations of the EXAFS spectra as a function of the axial oxygen bond length demonstrate that a destructive interference between backscattering from equatorial oxygen (Oeq) and that from axial oxygen (Oax) atoms leads to an apparent coordination number (CN) less than six expected for the tetragonal coordination, with the farther, loosely bound axial oxygen atoms making a minor, yet negative contribution to the CN determined by the EXAFS analysis. This study shows that Cu(II) has interchangeable octahedral, tetragonal, and square planar coordinations in the interlayer of montmorillonite, depending on Cu(II) loading and degree of hydration. The quasi-regular octahedral coordination of the interlayer Cu(II) in montmorillonite is a new finding of this study.

We reviewed literature focusing on the amounts of domestic production, distribution, and consumption of strong acids and their spill cases. In particular, we investigated the chemistry and toxicity of four strong acids classified as “accident preparedness substances,” including hydrochloric, nitric, sulfuric, and hydrofluoric acid. We recommend sulfuric and hydrofluoric acid as the chemicals of priority control based on the amounts used and toxicity. An advanced prevention/ response system needs to be established along with an improved human and social infrastructure to prevent and efficiently respond to chemical accidents. Understanding the behavior and transport of spilled strong acids in the soil and groundwater environments requires a multi-disciplinary approach since they go through a variety of chemical and biogeochemical reactions with complex geomedia. However, no such research has been done in this area in Korea to the best of our knowledge. We expect the results of this study to contribute as basic data to future research.

Reactions with aqueous sulfide are important in determining uranium (U) geochemistry under sulfate reducing conditions. This paper reports on abiotic reduction of U(VI) by aqueous sulfide under a range of experimental conditions using batch reactors. Dissolved U concentration was measured as a function of time to study the effects of chemical variables including pH, U(VI), S(−II), total dissolved carbonate (CARB = H 2 CO 3 * + HCO 3 − + CO 3 2− ), and Ca 2+ concentration on the U(VI) reduction rate. Solid phase reaction products were characterized using X-ray diffraction, X-ray absorption spectroscopy, and transmission electron microscopy. The chemical variables had impacts on the solid phase U(VI) reaction products as well as the reduction rates by aqueous sulfide. The solid U reaction product at circumneutral pH was identified as uraninite (UO 2+ x (s) ). Under basic pH conditions, whether a precipitate occurred depended on Ca 2+ and CARB concentrations. U(VI) reduction was faster under higher S(−II) concentrations but was slowed by increased dissolved Ca 2+ or CARB concentration. In the absence of dissolved CARB and Ca 2+ , a rapid decrease in dissolved U concentration occurred at circumneutral pH, while virtually no decrease was observed at pH 10.7 within the experimental timeframe of two days. The U(VI) reduction rate was proportional to the total concentration of free uranyl plus its hydrolysis complexes even at minor to trace concentrations. Dissolved Ca 2+ and CARB slow abiotic U(VI) reduction by forming stable Ca–U(VI)–carbonato soluble complexes that are resistant to reaction with aqueous sulfide. U(VI) reduction was slow in a synthetic solution representative of groundwater at a uranium mill tailings site. This study illustrates that abiotic U reduction by aqueous sulfide can significantly vary under typical ranges of chemical conditions in groundwater and newly demonstrates the importance of dissolved Ca 2+ in the abiotic U(VI) reduction by aqueous sulfide. The results contribute to our understanding of the impact of sulfate reducing conditions on U speciation in groundwater systems undergoing bioreduction conversion of U(VI) to less mobile U(IV) solid phases.

The long-term success of in situ reductive immobilization of uranium (U) depends on the stability of U(IV) precipitates (e.g., uraninite) in the presence of natural oxidants, such as oxygen, Fe(III) hydroxides, and nitrite. Field and laboratory studies have implicated iron sulfide minerals as redox buffers or oxidant scavengers that may slow oxidation of reduced U(IV) solid phases. Yet, the inhibition mechanism(s) and reaction rates of uraninite (UO2) oxidative dissolution by oxic species such as oxygen in FeS-bearing systems remain largely unresolved. To address this knowledge gap, abiotic batch experiments were conducted with synthetic UO2 in the presence and absence of synthetic mackinawite (FeS) under simulated groundwater conditions of pH = 7, P O 2 = 0.02 atm, and P CO 2 = 0.05 atm. The kinetic profiles of dissolved uranium indicate that FeS inhibited UO2 dissolution for about 51 h by effectively scavenging oxygen and keeping dissolved oxygen (DO) low. During this time period, oxidation of structural Fe(II) and S(-II) of FeS were found to control the DO levels, leading to the formation of iron oxyhydroxides and elemental sulfur, respectively, as verified by X-ray diffraction (XRD), Mossbauer, and X-ray absorption spectroscopy (XAS). After FeS was depleted due to oxidation, DO levels increased and UO2 oxidative dissolution occurred at an initial rate of rm = 1.2 ± 0.4 × 10−8 mol g−1 s−1, higher than rm = 5.4 ± 0.3 × 10−9 mol g−1 s−1 in the control experiment where FeS was absent. XAS analysis confirmed that soluble U(VI)-carbonato complexes were adsorbed by iron oxyhydroxides (i.e., nanogoethite and lepidocrocite) formed from FeS oxidation, which provided a sink for U(VI) retention. This work reveals that both the oxygen scavenging by FeS and the adsorption of U(VI) to FeS oxidation products may be important in U reductive immobilization systems subject to redox cycling events.

The fate and transport of inorganic nitrogen (N) is a critically important issue for human and aquatic ecosystem health because discharging N-contaminated groundwater can foul drinking water and cause algal blooms. Factors controlling N-processing were examined in sediments at three sites with contrasting hydrologic regimes at a lake on Cape Cod, MA. These factors included water chemistry, seepage rates and direction of groundwater flow, and the abundance and potential rates of activity of N-cycling microbial communities. Genes coding for denitrification, anaerobic ammonium oxidation (anammox), and nitrification were identified at all sites regardless of flow direction or groundwater dissolved oxygen concentrations. Flow direction was, however, a controlling factor in the potential for N-attenuation via denitrification in the sediments. Potential rates of denitrification varied from 6 to 4500 pmol N/g/h from the inflow to the outflow side of the lake, owing to fundamental differences in the supply of labile organic matter. The results of laboratory incubations suggested that when anoxia and limiting labile organic matter prevailed, the potential existed for concomitant anammox and denitrification. Where oxic lake water was downwelling, potential rates of nitrification at shallow depths were substantial (1640 pmol N/g/h). Rates of anammox, denitrification, and nitrification may be linked to rates of organic N-mineralization, serving to increase N-mobility and transport downgradient.

A novel bioreactor system, consisting of two biologically active carbon (BAC) reactors in series, was developed for the simultaneous removal of nitrate and arsenic from a synthetic groundwater supplemented with acetic acid. A mixed biofilm microbial community that developed on the BAC was capable of utilizing dissolved oxygen, nitrate, arsenate, and sulfate as the electron acceptors. Nitrate was removed from a concentration of approximately 50 mg/L in the influent to below the detection limit of 0.2 mg/L. Biologically generated sulfides resulted in the precipitation of the iron sulfides mackinawite and greigite, which concomitantly removed arsenic from an influent concentration of approximately 200 ug/L to below 20 ug/L through arsenic sulfide precipitation and surface precipitation on iron sulfides. This study showed for the first time that arsenic and nitrate can be simultaneously removed from drinking water sources utilizing a bioreactor system.

Iron sulfide minerals commonly found in natural anoxic Fe-S systems have been shown to reductively transform chlorinated hydrocarbons including trichloroethylene (TCE). In the present study, we tested the feasibility of applying an Fe(II) solution to a TCE-contaminated aquifer groundwater under simulated sulfide reducing conditions to enhance reductive transformation of TCE to nontoxic compounds. To achieve this goal, iron sulfide particles were precipitated under a range of pH and Fe:S molar ratios in aquifer groundwater samples from the Dugway Proving Grounds, Utah. Batch tests for abiotic reductive dechlorination of TCE were performed using the precipitates to establish the conditions for most favorable solids for dechlorination. Under all experimental conditions, the solids formed consisted mainly of mackinawite, a tetragonal reduced iron monosulfide FeS1-x . However, the precipitation conditions strongly affected the reactivity of the mackinawite particles formed. The results indicated that addition ...

Cu(II) sorbed on kaolinite (KGa-1b) was studied using electron paramagnetic resonance (EPR) spectroscopy over various pH, ionic strength, and Cu(II) concentration conditions. Two different absorption lines, namely, an isotropic ( g iso = 2.193) and an anisotropic signal ( g || = 2.365 and g ⊥ = 2.088) were observed at room temperature. The signals were assigned to an outer-sphere and an inner-sphere Cu(II) surface complex, respectively. The intensity of the two signals varied with the sorption conditions or post-sorptional treatments such as rinsing and dehydration/rehydration. The intensity of the isotropic signal was not directly proportional to the amount of sorbed Cu(II). Rinsing of the Cu-loaded surface had a different impact on the signal intensity depending on the sorption pH. The isotropic signal together with the anisotropic signal was simultaneously observed on the kaolinite surface air-dried at room temperature for as long as 13 months. On the other hand, only the anisotropic signal was observed on the surface dried at 105 °C overnight. The re-wetting of the once dried kaolinite with deionized water immediately restored the isotropic signal. These results show that an outer-sphere surface complex is the dominant form of the sorbed copper ions and that the drying and aging of the surface convert the outer-sphere complex into the inner-sphere complex or surface precipitate, at least a part of which was reversibly converted back into the outer-sphere complex by the rehydration of the surface. This work suggests that dehydration during aging as well as solution variables such as pH, concentrations of Cu(II) and competing cations can have an impact on the amount and long-term fate of the outer-sphere Cu(II) complex formed on the kaolinite surface.

The nature of the interaction among Cu(II), adsorbed water, and quartz surface was studied using electron paramagnetic resonance (EPR) spectroscopy. The EPR lineshape gave information concerning the motional status of sorbed Cu(II) that revealed its binding strength at the surface. Two distinct absorption lines of sorbed Cu(II), namely, the liquid-type and the solid-type signal, were simultaneously observed at the fully hydrated surface at room temperature. The absorption lines and the variation of their intensity with experimental and measurement conditions such as degree of hydration, pH, ionic strength, and surface coverage indicated that there exist three kinds of Cu(II) entities, the inner-sphere surface complex, the outer-sphere surface complex, and the surface precipitate on the quartz surface, and that their concentrations change with experimental conditions. The reversible conversion of the liquid-type signal to the solid-type one during the drying-wetting or freezing-melting of the surface suggested the development of multiple layers of adsorbed water molecules on the quartz surface. It is assumed that the innermost layer of the water layers contains the inner-sphere Cu(II) surface complexes, while the outer layers contain the outer-sphere complexes whose binding strength decreases outward with increasing distance from the surface. The result of this work suggests that the sorption mechanism of a metal cation on a given mineral surface; hence its mobility in the environment may change significantly with the solution pH, the ionic strength, and the surface coverage.

The capacity of Desulfovibrio vulgaris to reduce U(VI) was studied previously with nongrowth conditions involving a high biomass concentration; thus, bacterial growth through respiration of U(VI) was not proven. In this study, we conducted a series of batch tests on U(VI) reduction by D. vulgaris at a low initial biomass (10 to 20 mg/L of protein) that could reveal biomass growth. D. vulgaris grew with U(VI) respiration alone, as well as with simultaneous sulfate reduction. Patterns of growth kinetics and solids production were affected by sulfate and Fe(2+). Biogenic sulfide nonenzymatically reduced 76% of the U(VI) and greatly enhanced the overall reduction rate in the absence of Fe(2+) but was rapidly scavenged by Fe(2+) to form FeS in the presence of Fe(2+). Biogenic U solids were uraninite (UO2) nanocrystallites associated with 20 mg/g biomass as protein. The crystallite thickness of UO2 was 4 to 5 nm without Fe(2+) but was1.4 nm in the presence of Fe(2+), indicating poor crystallization inhibited by adsorbed Fe(2+) and other amorphous Fe solids, such as FeS or FeCO3. This work fills critical gaps in understanding the metabolic utilization of U by microorganisms and formation of UO2 solids in bioremediation sites.

Abiotic degradation of cis-dichloroethylene (cis-DCE) and vinyl chloride (VC) was investigated using Fe hydroxides obtained by hydrolyzing Fe(II) salts over a pH range of 7.7–8.0. Within this narrow pH range, a green rust (GR) precipitated. The dechlorination reactivity of the resulting GR precipitates increased with the dissolved Fe(II) concentration remaining in solution after precipitation. Controls run using only the dissolved Fe(II) supernatant were not reactive, suggesting the relative amount of Fe(II) on the surface of precipitated GRs was the causative agent in the relative reactivity. To test this, a series of GR batches with varying dissolved Fe(II) concentrations were prepared by acid-base titration and examined for cis-DCE and VC dechlorination kinetics under reducing conditions. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses of these batches were performed to characterize the bulk mineralogy and the excess surface Fe(II), respectively. Cis-DCE and VC dechlorination results along with solid phase characterization show that different surface Fe(II)/Fe(III) compositions are responsible for the different reactivity of GRs formed within the GR precipitation zone.

Reaction of aqueous uranium(VI) with iron(II) monosulfide mackinawite in an O(2) and CO(2) free model system was studied by batch uptake measurements, equilibrium modeling, and L(III) edge U X-ray absorption spectroscopy (XAS). Batch uptake measurements showed that U(VI) removal was almost complete over the wide pH range between 5 and 11 at the initial U(VI) concentration of 5 × 10(-5) M. Extraction by a carbonate/bicarbonate solution indicated that most of the U(VI) removed from solution was reduced to nonextractable U(IV). Equilibrium modeling using Visual MINTEQ suggested that U was in equilibrium with uraninite under the experimental conditions. X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy showed that the U(IV) phase associated with mackinawite was uraninite. Oxidation experiments with dissolved O(2) were performed by injecting air into the sealed reaction bottles containing mackinawite samples reacted with U(VI). Dissolved U measurement and XAS confirmed that the uraninite formed from the U(VI) reduction by mackinawite did not oxidize or dissolve under the experimental conditions. This study shows that redox reactions between U(VI) and mackinawite may occur to a significant extent, implying an important role of the ferrous sulfide mineral in the redox cycling of U under sulfate reducing conditions. This study also shows that the presence of mackinawite protects uraninite from oxidation by dissolved O(2). The findings of this study suggest that uraninite formation by abiotic reduction by the iron sulfide mineral under low temperature conditions is an important process in the redistribution and sequestration of U in the subsurface environments at U contaminated sites.

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using2 mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 x 10(-8) to 10(-5) M in [U(VI)](tot), 7.2 to 8.0 in pH, 3.0 x 10(-3) to 6.0 x 10(-3) M in [Ca(2+)], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption K(d) values for the sand and2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters.

As(III) uptake from solution by synthetic mackinawite is examined as a function of pH and initial As(III) concentration using X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD). XAS data indicate that when mackinawite is reacted at pH 5, 7, and 9 with 5 x 10(-4) M As(III), arsenic is reduced from its original +3 valence state and is primarily coordinated as As-S (approximately 2.26 angstroms) and As-As (approximately 2.54 angstroms), which is consistent with the formation of a realgar-like phase in agreement with XRD data. At 5 x 10(-5) M As(III), samples are markedly different from those collected at an order of magnitude higher concentration and differ at each pH value. The XAS analysis of mackinawite samples reacted with 5 x 10(-5) M As(III) shows a transition from As-O coordination to As-S coordination as pH decreases, with the sample reacted at pH 5 resembling realgar. Under alkaline conditions, arsenic retains its original valence state of +3 and is primarily coordinated to oxygen at a distance of 1.75 angstroms. This may be attributed to uptake by adsorption as an As(III) oxyanion. These results provide the basis for selecting the reactions needed for modeling and are beneficial in understanding the mechanisms of arsenite uptake by mackinawite under anoxic sulfidic conditions.