Use of Hydrochloric Acid for Determining Solid-Phase Arsenic Partitioning in Sulfidic Sediments

We examined the use of room-temperature hydrochloric acid (1−6 M) and salt solutions of magnesium chloride, sodium carbonate, and sodium sulfide for the removal of arsenic from synthetic iron monosulfides and contaminated sediments containing acid-volatile sulfides (AVS). Results indicate that acid-soluble arsenic reacts with H2S released from AVS phases and precipitates at low pH as disordered orpiment or alacranite. Arsenic sulfide precipitation is consistent with geochemical modeling in that conditions during acid extraction are predicted to be oversaturated with respect to orpiment, realgar, or both. Binding of arsenic with sulfide at low pH is sufficiently strong that 6 M HCl will not keep spiked arsenic in the dissolved fraction. Over a wide range of AVS concentrations and molar [As]/[AVS] ratios, acid extraction of arsenic from sulfide-bearing sediments will give biased results that overestimate the stability or underestimate the bioavailability of sediment-bound arsenic. Alkaline solutions of sodium sulfide and sodium carbonate are efficient in removing arsenic from arsenic sulfides and mixed iron−arsenic sulfides because of the high solubility of arsenic at alkaline pH, the formation of stable arsenic complexes with sulfide or carbonate, or both

Evidence of Sulfate-Dependent Anaerobic Methane Oxidation within an Area Impacted by Coalbed Methane-Related Gas Migration

We evaluated water quality characteristics in the northern Raton Basin of Colorado and documented the response of the Poison Canyon aquifer system several years after upward migration of methane gas occurred from the deeper Vermejo Formation coalbed production zone. Results show persistent secondary water quality impacts related to the biodegradation of methane. We identify four distinct characteristics of groundwater–methane attenuation in the Poison Canyon aquifer: (i) consumption of methane and sulfate and production of sulfide and bicarbonate, (ii) methane loss coupled to production of higher molecular weight (C₂₊) gaseous hydrocarbons, (iii) patterns of ¹³C enrichment and depletion in methane and dissolved inorganic carbon, and (iv) a systematic shift in sulfur and oxygen isotope ratios of sulfate, indicative of microbial sulfate reduction. We also show that the biogeochemical response of the aquifer system has not mobilized naturally occurring trace metals, including arsenic, chromium, cobalt, nickel, and lead, likely due to the microbial production of hydrogen sulfide which favors stabilization of metals in aquifer solids

Geochemical Impacts to Groundwater from Geologic Carbon Sequestration: Controls on pH and Inorganic Carbon Concentrations from Reaction Path and Kinetic Modeling

Geologic carbon sequestration has the potential to cause long-term reductions in global emissions of carbon dioxide to the atmosphere. Safe and effective application of carbon sequestration technology requires an understanding of the potential risks to the quality of underground sources of drinking water. In particular, concern is warranted regarding the potential for CO2 leakage through geological features and abandoned wells that may result in detrimental perturbations to subsurface geochemistry. Reaction path and kinetic models indicate that geochemical shifts caused by CO2 leakage are closely linked to mineralogical properties of the receiving aquifer. CO2 gas dissolution into groundwater and subsequent reaction with aquifer minerals will control the evolution of pH−bicarbonate envelopes. These parameters provide geochemical context for predicting how regulated contaminants associated with aquifer solids will respond via various mineral−water reaction processes. The distribution and abundance of carbonate, silicate, oxide, and phyllosilicate minerals are identified as key variables in controlling changes in groundwater geochemistry. Site-specific risk assessments may require characterization of aquifer geology, mineralogy, and groundwater chemistry prior to CO2 injection. Model results also provide a frame of reference for developing indicative measurement, monitoring, and verification (MMV) protocols for groundwater protection

Transformation of Reactive Iron Minerals in a Permeable Reactive Barrier (Biowall) Used to Treat TCE in Groundwater

Iron and sulfur reducing conditions generally develop in permeable reactive barrier systems (PRB) constructed to treat contaminated groundwater. These conditions allow formation of FeS mineral phases. FeS readily degrades TCE, but a transformation of FeS to FeS2 could dramatically slow the rate of TCE degradation in the PRB. This study uses acid volatile sulfide (AVS) and chromium reducible sulfur (CRS) as probes for FeS and FeS2 to investigate iron sulfide formation and transformation in a column study and PRB field study dealing with TCE degradation. Solid phase iron speciation shows that most of the iron is reduced and sulfur partitioning measurements show that AVS and CRS coexist in all samples, with the conversion of AVS to CRS being most significant in locations with potential oxidants available. In the column study, 54% of FeS was transformed to FeS2 after 2.4 years. In the field scale PRB, 43% was transformed after 5.2 years. Microscopy reveals FeS, Fe3S4 and FeS2 formation in the column system; however, only pyrite formation was confirmed by X-ray diffraction. The polysulfide pathway is most likely the primary mechanism of FeS transformation in the system, with S0 as an intermediate species formed through H2S oxidation

Perchlorate Behavior in a Municipal Lake Following Fireworks Displays

Perchlorate salts of potassium and ammonium are the primary oxidants in pyrotechnic mixtures, yet insufficient information is available regarding the relationship between fireworks displays and the environmental occurrence of perchlorate. Here we document changes in perchlorate concentrations in surface water adjacent to a site of fireworks displays from 2004 to 2006. Preceding fireworks displays, perchlorate concentrations in surface water ranged from 0.005 to 0.081 μg/L, with a mean value of 0.043 μg/L. Within 14 h after the fireworks, perchlorate concentrations spiked to values ranging from 24 to 1028× the mean baseline value. A maximum perchlorate concentration of 44.2 μg/L was determined following the July 4th event in 2006. After the fireworks displays, perchlorate concentrations decreased toward the background level within 20 to 80 days, with the rate of attenuation correlating to surface water temperature. Adsorption tests indicate that sediments underlying the water column have limited (<100 nmol/g) capacity to remove perchlorate via chemical adsorption. Microcosms showed comparatively rapid intrinsic perchlorate degradation in the absence of nitrate consistent with the observed disappearance of perchlorate from the study site. This suggests that at sites with appropriate biogeochemical conditions, natural attenuation may be an important factor affecting the fate of perchlorate following fireworks displays

Examination of Arsenic Speciation in Sulfidic Solutions Using X-ray Absorption Spectroscopy

Both thioarsenites and thioarsenates have been demonstrated to exist in sulfidic waters, yet there is uncertainty regarding the geochemical conditions that govern the formation of these arsenic species. The purpose of this research was to use advanced spectroscopy techniques, speciation modeling, and chromatography to elucidate the chemical speciation of arsenic in sulfidic solutions initially containing arsenite and sulfide. Results of X-ray absorption spectroscopy (XAS) show that experimental solutions contained mixtures of arsenite and thioarsenites with increasing substitution of sulfur for oxygen on arsenic as the sulfide concentration increased. Experimental samples showed no evidence of polymeric arsenic species, or transformation of thioarsenites to thioarsenates. The arsenic speciation measured using XAS was similar to predictions obtained from a thermodynamic model for arsenic speciation, excluding thioarsenate species in sulfidic systems. Our data cast some doubt on the application of chromatographic methods for determining thioarsenates and thioarsenites (or mixtures) in natural waters in cases where the arsenic oxidation state cannot be independently verified. The same chromatographic peak positions proposed for thioarsenates can be explained by thioarsenite species. Furthermore, sample dilution was shown to change the species distribution and care should be taken to avoid sample dilution prior to chromatographic analysis

Chromium-Removal Processes during Groundwater Remediation by a Zerovalent Iron Permeable Reactive Barrier

Solid-phase associations of chromium were examined in core materials collected from a full-scale, zerovalent iron permeable reactive barrier (PRB) at the U.S. Coast Guard Support Center located near Elizabeth City, NC. The PRB was installed in 1996 to treat groundwater contaminated with hexavalent chromium. After eight years of operation, the PRB remains effective at reducing concentrations of Cr from average values >1500 μg L-1 in groundwater hydraulically upgradient of the PRB to values -1 in groundwater within and hydraulically downgradient of the PRB. Chromium removal from groundwater occurs at the leading edge of the PRB and also within the aquifer immediately upgradient of the PRB. These regions also witness the greatest amount of secondary mineral formation due to steep geochemical gradients that result from the corrosion of zerovalent iron. X-ray absorption near-edge structure (XANES) spectroscopy indicated that chromium is predominantly in the trivalent oxidation state, confirming that reductive processes are responsible for Cr sequestration. XANES spectra and microscopy results suggest that Cr is, in part, associated with iron sulfide grains formed as a consequence of microbially mediated sulfate reduction in and around the PRB. Results of this study provide evidence that secondary iron-bearing mineral products may enhance the capacity of zerovalent iron systems to remediate Cr in groundwater, either through redox reactions at the mineral−water interface or by the release of Fe(II) to solution via mineral dissolution and/or metal corrosion

Nonbiological Removal of <i>cis</i>-Dichloroethylene and 1,1-Dichloroethylene in Aquifer Sediment Containing Magnetite

The U.S. EPA Technical Protocol for Evaluating Natural Attenuation of Chlorinated Solvents in Groundwater emphasizes biological reductive dechlorination as the primary mechanism for destruction of chlorinated solvents. However, biological reductive dechlorination could not explain the removal of cis-dichloroethylene (cis-DCE) and 1,1-DCE from a plume of contaminated groundwater in Minnesota. Several recent laboratory studies have demonstrated that common iron minerals such as magnetite can also transform chlorinated alkenes. Laboratory microcosms were constructed with sediment from three depth intervals in the aquifer near the source of the plume. The microcosms were autoclaved to prevent biological transformations. In these autoclaved sediments, the rates of removal of cis-DCE in samples from the shallow, intermediate, and deeper depth intervals in the aquifer were 0.58 ± 0.09, 2.29 ± 0.26, and 0.31 ± 0.08 per year at 95% confidence. The rate of removal of 1,1-DCE in sediment from the shallow interval was 1.37 ± 0.50 per year. The rates of removal in the microcosms are similar to the rates of attenuation observed in the field. Magnetite was identified in the sediment by X-ray diffraction and optical microscopy. Published rates of transformation of cis-DCE by magnetite are consistent with the rates of removal in the microcosm study

In Situ Chemical Reduction of Cr(VI) in Groundwater Using a Combination of Ferrous Sulfate and Sodium Dithionite: A Field Investigation

A field study was conducted to evaluate the performance of a ferrous iron based in situ redox zone for the treatment of a dissolved phase Cr(VI) plume at a former industrial site. The ferrous iron based in situ redox zone was created by injecting a blend of 0.2 M ferrous sulfate and 0.2 M sodium dithionite into the path of a dissolved Cr(VI) plume within a shallow medium to fine sand unconfined aquifer formation. Monitoring data collected over a period of 1020 days after more than 100 m of linear groundwater flow through the treatment zone indicated sustained treatment of dissolved phase Cr(VI) from initial concentrations between 4 and 8 mg/L to less than 0.015 mg/L. Sustained treatment is assumed to be primarily due to the reduction of Cr(VI) to Cr(III) by ferrous iron adsorbed to, precipitated on, and/or incorporated into aquifer iron (hydr)oxide solid surfaces within the treatment zone. Precipitated phases likely include FeCO3 and FeS based on saturation index considerations and SEM/EDS analysis. The detection of solid phase sulfites and thiosulfates in aquifer sediments collected from the treatment zone more than 2 years following injection suggests dithionite decomposition products may also play a significant role in the long-term treatment of the dissolved phase Cr(VI)