Factors Controlling In Situ Biogeochemical Transformation of Trichloroethene: Column Study

In situ biogeochemical transformation involves biological formation of reactive minerals in an aquifer that can destroy chlorinated solvents such as trichloroethene (TCE) without accumulation of intermediates such as vinyl chloride. There is uncertainty regarding the materials and geochemical conditions that are required to promote biogeochemical transformation. The objective of this study was to identify amendments and biogeochemical conditions that promote in situ biogeochemical transformation. Laboratory columns constructed with plant mulch were supplemented with different amendments and were operated under varying conditions of water chemistry and hydraulic residence time. Four patterns of TCE removal were observed: (1) no removal, (2) biotic transformation of TCE to cis‐1,2‐dichloroethene (cis‐1,2‐DCE), (3) biogeochemical transformation of TCE without accumulation of reductive dechlorination products, and (4) mixed behavior where a combination of patterns was observed either simultaneously or over time. Principal coordinates analysis and analysis of variance (ANOVA) identified factors that promoted biogeochemical transformation: (1) high influent sulfate concentration, (2) relatively high hydraulic retention time, (3) supplementation of mulch with vegetable oil, and (4) addition of hematite or magnetite. The combination of the first three factors promoted complete sulfate reduction and a high volumetric sulfate consumption rate. The fourth factor provided a source of ferrous iron and/or a surface to which sulfide could react to form reactive iron sulfides. Many columns demonstrated either no TCE removal or a biotic TCE transformation pattern. Modification of column operation to include all four factors identified above promoted biogeochemical transformation in these columns. These results support the importance of the factors in biogeochemical transformation.     

Long-Term Evaluation of Mulch Biowall Performance to Treat Chlorinated Solvents

Permeable reactive barriers (PRBs), such as mulch biowalls, have been installed at numerous groundwater cleanup sites, and laboratory and field studies have demonstrated biotic and abiotic processes that degrade chlorinated volatile organic compounds (CVOCs) in groundwater passing through these engineered remedies. However, the longevity of mulch biowalls remains a fundamental research question. Soil and groundwater sampling at seven mulch biowalls at Altus Air Force Base (AFB) approximately 10 years after installation demonstrated the ongoing degradation of CVOCs. Trichloroethene was not detected in five of seven groundwater samples collected from the biowall despite upgradient detections above federal drinking water standards. Microbial sampling established the presence of key dechlorinating bacteria and the abundance of genes encoding specific enzymes for degradation, high methane concentrations, low sulfate concentrations, and negative oxidation-reduction potential, all indicative of highly reducing conditions within the biowalls and favorable conditions for CVOC destruction via microbial reductive dechlorination. High cellulose content (>79%) of the mulch, elevated total organic carbon (TOC) content in groundwater, and elevated potentially bioavailable organic carbon (PBOC) measurements in soil samples further supports an ongoing, long-lived source of carbon. These results demonstrate the ongoing and long-term efficacy of the mulch biowalls at Altus AFB. In addition, concentrations of bacteria, TOC, PBOC, and other geochemical parameters suggest a modest impact of the biowalls downgradient. The continued presence of CVOCs downgradient may be attributable to back diffusion from low-permeability shale. However, the biowalls continue to provide benefits by removing CVOCs in groundwater, thus reducing further CVOC loading to the downgradient, low-permeability strata.     

Review of Abiotic Degradation of Chlorinated Solvents by Reactive Iron Minerals in Aquifers

Abiotic degradation of chlorinated solvents by reactive iron minerals such as iron sulfides, magnetite, green rust, and other Fe(II)‐containing minerals has been observed in both laboratory and field studies. These reactive iron minerals form under iron‐ and sulfate‐reducing conditions which are commonly found in permeable reactive barriers (PRBs), enhanced reductive dechlorination (ERD) treatment locations, landfills, and aquifers that are chemically reducing. The objective of this review is to synthesize current understanding of abiotic degradation of chlorinated solvents by reactive iron minerals, with special focus on how abiotic processes relate to groundwater remediation. Degradation of chlorinated solvents by reactive minerals can proceed through reductive elimination, hydrogenolysis, dehydrohalogenation, and hydrolysis reactions. Degradation products of abiotic reactions depend on degradation pathways and parent compounds. Some degradation products (e.g., acetylene) have the potential to serve as a signature product for demonstrating abiotic reactions. Laboratory and field studies show that various minerals have a range of reactivity toward chlorinated solvents. A general trend of mineral reactivity for degradation of chlorinated solvents can be approximated as follows: disordered FeS > FeS > Fe(0) > FeS₂ > sorbed Fe²⁺ > green rust = magnetite > biotite = vermiculite. Reaction kinetics are also influenced by factors such as pH, natural organic matter (NOM), coexisting metal ions, and sulfide concentration in the system. In practice, abiotic reactions can be engineered to stimulate reactive mineral formation for groundwater remediation. Under appropriate site geochemical conditions, abiotic reactions can occur naturally, and can be incorporated into remedial strategies such as monitored natural attenuation.     

A Tracer Test to Characterize Treatment of TCE in a Permeable Reactive Barrier

A tracer test was conducted to characterize the flow of groundwater across a permeable reactive barrier constructed with plant mulch (a biowall) at the OU‐1 site on Altus Air Force Base, Oklahoma. This biowall is intended to intercept and treat groundwater contaminated by trichloroethylene (TCE) in a shallow aquifer. The biowall is 139‐m long, 7.3‐m deep, and 0.5‐m wide. Bromide was injected from an upgradient well into the groundwater as a conservative tracer, and was subsequently observed breaking through in monitoring wells within and downgradient of the biowall. The bromide breakthrough data demonstrate that groundwater entering the biowall migrated across it, following the slope of the local groundwater surface. The average seepage velocity of groundwater was approximately 0.06 m/d. On the basis of the Darcy velocity of groundwater and geometry of the biowall, the average residence time of groundwater in the biowall was estimated at 10 d. Assuming all TCE removal occurred in the biowall, the reduction in TCE concentrations in groundwater across the biowall corresponds to a first‐order attenuation rate constant in the range of 0.38 to 0.15 per d. As an independent estimate of the degradation rate constant, STANMOD software was used to fit curves through data on the breakthrough of bromide and TCE in selected wells downgradient of the injection wells. Best fits to the data required a first‐order degradation rate constant for TCE removal in the range of 0.13 to 0.17 per d. The approach used in this study provides an objective evaluation of the remedial performance of the biowall that can provide a basis for design of other biowalls that are intended to remediate TCE‐contaminated groundwater.     

Chemistry and mineralogy of pyrite-enriched sediments at a passive margin sulfide brine seep: abyssal Gulf of Mexico

Pyrite is rapidly accumulating at the contact between the Cretaceous limestones of the Florida Platform and the hemipelagic sediments of the abyssal Gulf of Mexico. Sediments sampled with the submersible “Alvin” in 3266 m of water are associated with a dense community of organisms that depend on chemosynthetic primary production as a food source. Analysis of the chemistry, mineralogy, and textural composition of these sediments indicate that iron sulfide mineralization is occurring at the seafloor within an anoxic micro-habitat sustained by the advection of hydrogen sulfide-charged saline brines from the adjacent platform. The chemosynthetic bacteria that directly overlie the sediments oxidize hydrogen sulfide for energy and provide elemental sulfur that reacts with iron monosulfide to form some of the pyrite. The sediments are mixtures of pyrite ( 30 wt.%), BaSr sulfates ( 4 wt.%), clays, and locally derived biogenic carbonates and are progressively being cemented by iron sulfides. Oxidation of hydrogen sulfide produces locally acidic conditions that corrode the adjacent limestones. Potential sources of S, H₂S, Fe, Ba, and Sr are discussed.     

Carbon Isotope Analysis to Evaluate Nanoscale Fe(O) Treatment at a Chlorohydrocarbon Contaminated Site

Remediation of groundwater contaminated by chlorinated hydrocarbons via in situ technologies such as direct injection of nanoscale zero valent iron (ZVI, Fe(O)) particles is increasingly common. However, assessing target compound degradation by abiotic processes is difficult because (1) the injection may displace the contaminant plume so that concentration measurements alone are often inconclusive and (2) biodegradation may also occur, making it challenging to identify and evaluate the abiotic degradation component. In this study, trichloroethylene (TCE) and 1,1,1-trichloroethane (1,1,1-TCA) were treated in a highly heterogeneous hydrogeologic setting. The purpose of this study was to evaluate the potential for compound-specific stable isotope analysis (CSIA) to monitor the effectiveness of ZVI injection by assessing TCE and 1,1,1-TCA degradation. Prior to ZVI injection, carbon isotope measurements demonstrated biodegradation of TCE by native microorganisms. This in situ biodegradation was quantified by measuring the enrichment of ¹³C in TCE samples downstream of the suspected source. When ZVI was injected through only two injection wells, no changes in TCE and 1,1,1-TCA isotope signatures were detected compared to preinjection values. In contrast, when ZVI was injected through 11 wells covering a greater portion of the contaminated area, 5 out of 10 monitoring wells showed further enrichment of ¹³C in either TCE or 1,1,1-TCA, indicating additional target compound transformation. The abiotic nature of this TCE transformation was confirmed through temporal trends in carbon isotope values of the putative transformation products cis-dichloroethylene (cis-DCE), ethene and ethane. This demonstrates the usefulness of CSIA in distinguishing abiotic vs. biotic transformation in the field.     

Magnetic minerals in sediments at the Cretaceous/Paleogene boundary (the Gams Section,Eastern Alps)

The paper presents results of detailed magnetomineralogical and microprobe studies of sediments at the Cretaceous/Paleogene (K/T) boundary in two epicontinental sections in the Eastern Alps (Austria), where deposits, including the K/T boundary, outcrop along the Gams River and its tributaries. K/T boundary layers in these sections are similar in the set of such magnetic minerals as iron hydroxides, ferrospinels, hemoilmenite, titanomagnetite, magnetite, hematite, and metallic iron. However, the boundary layer in the Gams-1 section is distinguished by the presence of metallic nickel and its alloy with iron and by the absence of iron sulfides, whereas nickel has not been discovered in the Gams-2 section, which, however, contains iron sulfides of the pyrite type. Therefore, these minerals occur locally. It is suggested that enrichment in iron hydroxides of a common origin can be regarded as a global phenomenon inherent in the K/T boundary and unrelated to an impact event.     

Remediation of DNAPL source zones with granular iron: laboratory and field tests

Degradation of dissolved chlorinated solvents using granular iron is an established in situ technology. This paper reports on investigations into mixing iron and bentonite with contaminated soil for in situ containment and degradation of dense nonaqueous phase liquid source zones. In the laboratory, hypovials containing soil, water, bentonite, iron, and free-phase trichloroethene (TCE) were assembled. Periodic measurement of TCE, chloride, and degradation products showed progressive degradation of TCE to nondetectable levels. Subsequently, a demonstration was conducted at Canadian Forces Base Borden near Alliston, Ontario, Canada, where, in 1991, a portion of the surficial aquifer was isolated and free-phase tetrachloroethene (PCE) was introduced. Using a drill rig equipped with large-diameter mixing blades, three mixed zones were prepared containing 0%, 5%, and 10% granular iron by volume. The bentonite was added to serve as a lubricant to facilitate injection of the iron and to isolate the contaminated zone. Analysis of core samples showed reasonably uniform distributions of iron through the mixed zones. Monitoring over a 13-month period following installation showed, relative to the control, a decline in PCE concentrations to virtually nondetectable values. Reaction rates in the laboratory tests were similar to those reported in the literature, while the rate in the field test was substantially lower. The lower rate may be a consequence of mass transfer limitations under the static conditions of the field test. Results indicate that mixing iron and bentonite into source zones may be an effective means of source-zone remediation, with the particular advantage of being relatively immune to effects of geologic heterogeneity.     

The solubility of a metallic mineral with other coexisting minerals and the ore-forming processes of metallic sulfides

Most metallic minerals in ore deposits are sulfides. When a sulfide mineral coexists with rock-forming minerals, its solubility is distinctly different from itself alone. The change in dissolution character of a mineral with coexisting rock-forming minerals leads to particular geochemical behavior. The concept of solubility of a metallic mineral with coexisting rock-forming minerals and its theory and model of calculation are put forward. Taking Tianmashan Cu-Au ore deposit of sulfide minerals in Tongling district as an example, solubilities of some metallic minerals with other coexisting minerals, such as pyrite or chalcopyrite with quartz (representing sandstone) or calcite (representing limestone), are calculated. The results show the mechanism of ore-forming processes. As the ore-forming fluid flows through sandstone, it dissolves pyrite in the sandstone at first, then transports the iron and sulfur to the interface between sandstone and limestone and eventually precipitates them on the interface.     

Injection of Zero‐Valent Iron into an Unconfined Aquifer Using Shear‐Thinning Fluids

Approximately 190 kg of 2 μm‐diameter zero‐valent iron (ZVI) particles were injected into a test zone in the top 2 m of an unconfined aquifer within a trichloroethene (TCE) source area. A shear‐thinning fluid was used to enhance ZVI delivery in the subsurface to a radial distance of up to 4 m from a single injection well. The ZVI particles were mixed in‐line with the injection water, shear‐thinning fluid, and a low concentration of surfactant. ZVI was observed at each of the seven monitoring wells within the targeted radius of influence during injection. Additionally, all wells within the targeted zone showed low TCE concentrations and primarily dechlorination products present 44 d after injection. These results suggest that ZVI can be directly injected into an aquifer with shear‐thinning fluids to induce dechlorination and extends the applicability of ZVI to situations where other emplacement methods may not be viable.     

Back diffusion of chlorinated solvent contaminants from a natural aquitard to a remediated aquifer under well-controlled field conditions: predictions and measurements

Vertical profiles of tetrachloroethene (or perchloroethylene, PCE) and trichloroethene (TCE) were used to validate a diffusion process in a natural aquitard at Dover Air Force Base, Delaware. PCE and TCE distributions in the aquitard underlying an unconfined aquifer were sampled from core tubes obtained at four times over the course of a 35-month field investigation within "test cells" that were isolated from the surrounding ground water by means of grout-sealed steel sheetpile barriers (Mackay et al. 2000). For the final 23 months of this period, boundary conditions at the aquifer/aquitard interface were such that a "back diffusion" of contaminants from the aquitard was induced. Modeling predictions of concentration changes were made on the basis of the earliest coring results and an assumption of sorption-retarded diffusion and using laboratory information about sorption and diffusion characteristics of the media. The predictive modeling was complicated by the fact that "initial" and "final" PCE and TCE distributions in the aquitard were measured at different (albeit proximate) coring locations, such that results reflect spatial variations in aquitard characteristics. This problem was solved by means of an inverse interpretation that involved spatial "translation" of observed profiles on the basis of the laboratory characterizations and assuming a common aquifer-side contaminant history. Predictions indicated substantial change in PCE and TCE concentrations within the upper aquitard (near the aquifer/aquitard interface) and the development of a back-diffusion profile up into the aquifer. Modeling also predicted comparatively minor profile changes in the deeper aquitard, and especially in the deep layer where sorption was strongest. All of these predicted effects were observed in the coring results. Although not exact, the agreement between predictions and observations was sufficiently good to justify the basic tenets of the diffusion model and to support a conclusion that major processes of advection and/or transformation were unimportant within the 35-month time scale of this work.     

Microparticles of native metals,sulfides, and oxides in andesitic ashes of Karymskii Volcano

New data on accessory mineral phases found in ashes of the erupting Karymskii Volcano as micro-dispersed particles of native metals (Al, Fe, and Zn), intermetallic compounds, sulfides and oxides of iron, and carbonaceous substances are presented. Dominating submicron particles of native Al and Fe are largely confined to coarse-grained ash fractions; this is supported by extensive observations. The co-occurrence of iron oxide and sulfide particles of the same size possibly indicates extremely heterogeneous conditions of gas transport reactions during the eruption. The presence of native metals and carbonaceous compounds may attest to periods of a highly reducing environment in the fluid system supplying Karymskii Volcano.     

Long‐Term Impacts on Groundwater and Reductive Dechlorination Following Bioremediation in a Highly Characterized Trichloroethene DNAPL Source Area

High‐resolution soil and groundwater monitoring was performed to assess the long‐term impacts of bioremediation using bioaugmentation with a dechlorinating microbial consortium (and sodium lactate as the electron donor) in a well‐characterized trichloroethene (TCE) dense nonaqueous phase liquid (DNAPL) source area. Monitoring was performed up to 3.7 years following active bioremediation using a high‐density monitoring network that included several discrete interval multi‐level sampling wells. Results showed that despite the absence of lactate, lactate fermentation transformation products, or hydrogen, biogeochemical conditions remained favorable for the reductive dechlorination of chlorinated ethenes. In locations where soil data showed that TCE DNAPL sources persisted, local contaminant rebound was observed in groundwater, whereas no rebound or continuous decreases in chlorinated ethenes were observed in locations where DNAPL sources were treated. While ethene levels measured 3.7 years after active treatment suggested relatively low (2 to 30%) dechlorination of the parent TCE and daughter products, carbon stable isotope analysis showed that the extent of complete dechlorination was much greater than indicated by ethene generation and that the estimated first‐order rate constant describing the complete dechlorination of TCE at 3.7 years following active bioremediation was approximately 3.6 y–1. Overall, results of this study suggest that biological processes may persist to treat TCE for years after cessation of active bioremediation, thereby serving as an important component of remedial treatment design and long‐term attenuation.     

Hot spring deposits on the East Pacific Rise at 21°N: preliminary description of mineralogy and genesis

Hydrothermal sulfide-sulfate deposits were sampled from eight active and inactive vent sites along the East Pacific Rise at 21°N during the RISE expedition of April, 1979. The mineralogy of the samples has been determined by X-ray diffractometry, scanning electron microscopy, and X-ray energy dispersive analysis. Mounds of Zn, Fe, and Cu sulfides, dominated by sphalerite, pyrite, and lesser chalcopyrite, are topped by inactive and active chimneys, spouting fluids ≤350°C. The outer zones of active chimneys bear abundant anhydrite precipitated from heated ambient seawater, in addition to hydrothermal pyrite and sphalerite. Mg-hydroxysulfate-hydrate, a phase identified in seawater heating experiments, but previously not observed in nature, is intimately intergrown with anhydrite. Hottest chimneys contain massive chalcopyrite±bornite in their interior zones and belch fluids blackened by a presumably non-equilibrium assemblage of pyrrhotite plus minor sphalerite and pyrite. The early, outer walls of chimneys form from sulfates and the sulfide minerals in black smoke, but metastable pyrrhotite in outer zones is rapidly recrystallized to pyrite or marcasite. Reduction in the permeability of the outer walls permits a high-temperature (>～250°C), low-pH environment within chimneys that enhances precipitation of Cu-Fe sulfides in the central zones. Cooler, worm-covered chimneys emit white fluids bearing particulates of amorphous silica, barite, and pyrite. Amorphous silica and barite are also widely associated with fossilized worm-tubes. Two inactive chimneys are filled with sphalerite, wurtzite, sulfur, pyrite, and marcasite. Anhydrite has been dissolved from these dead chimneys, and the sulfate assemblage is dominated by barite and alteration products such as jarosite and natrojarosite. Silicates other than amorphous silica are not abundant in these deposits, although talc forms in hot chimneys from seawater Mg and hydrothermal silica, and nontronite is found in sediments on the crest of the East Pacific Rise. Other accessory phases identified include copper-rich sulfides such as cubanite, chalcocite, covellite, and digenite; galena; Fe-oxyhydroxides, including goethite; and gypsum. Chimney debris accumulates to form basal mounds, and the mineralogical differences between mounds and chimneys are attributable to weathering of mounds. Mn-oxyhydroxides form crusts within a few meters of the vents, but are not coprecipitating with the sulfide/sulfate minerals.     

Die Entstehung von Pyrit in rezenten Sedimenten des Piburger Sees

The occurrence of pyrite (FeS₂) and iron sulfide in surficial sediments of Piburger See was compared with thermodynamic calculations based on chemical analyses of iron and hydrogen sulfide in the interstitial water. The area below 17 m, where black spots were found in the sediments, showed ion products (log K_FeS=a_Fe2·a_HS/a_H+) between?3.11 and ?4.01. In areas with no visible FeS concretions logK_FeS values were in the range of ?4.74 to ?5.77, thus thermodynamic calculations seem to be in accordance with the appearance of iron sulfide. Nevertheless pyrite framboids, composed by more than 1,000 single crystals, coul be found even in shallow parts of the lake. Therefore the formation of pyrite is assumed to occur in microniches (diatom frustules, testacean shells). Inside these microcompartments high concentrations of hydrogen sulfide are reached due to the anaerobic decomposition of organic matter, whereas iron and additional sulfur are supplied by the diffusion of ferrous iron and sulfate from the anoxic environment.     

Effect of iron type on kinetics and carbon isotopic enrichment of chlorinated ethylenes during abiotic reduction on Fe(0)

Four samples of two commercially available iron brands used as substrate for iron permeable reactive barriers (PRBs) were tested for suitability for remediation of perchloroethylene (PCE), trichloroethylene (TCE), cis-dichloroethylene (cDCE) and vinyl chloride (VC). Kinetic studies indicate that rates of reaction are enhanced for cDCE and VC on Connelly iron (2.8 x 10(-4) to 6.9 x 10(-4) L/m2/hr and 2.0 x 10(-4) to 9.0 x 10(-4) L/m2/hr, for cDCE and VC, respectively) vs. Peerless iron (3.1 x 10(-5) to 4.6 x 10(-5) L/m2/hr and 2.4 x 10(-5) to 4.1 x 10(-5) L/m2/hr, for cDCE and VC, respectively). Carbon isotopic analyses of the residual chlorinated ethylene (CE) during degradation indicate significant fractionation occurs during reductive dechlorination, with, for example, up to 70% enrichment in carbon isotopic values observed when VC is more than 99% degraded. Comparison of fractionation factors (epsilon) indicates significant differences in carbon isotopic fractionation for different iron types and for different CEs. For the lower CEs (cDCE and VC) in particular, both slower reaction rates and larger fractionation are observed for degradation on Peerless vs. Connelly iron. This is the first study to establish a correlation between the rate of abiotic degradation on Fe(0) and the extent of isotopic fractionation, and the first to confirm consistent differences in these two parameters as a function of iron type. The possibility that these differences in kinetics and carbon isotopic fractionation for cDCE and VC are related to differences in branching ratios between competing hydrogenolysis and beta-elimination reactions during reductive dechlorination on the iron surfaces is discussed.     

Volatile Organic Sulfur Compounds in a Meromictic Alpine Lake

The full spectrum of volatile sulfur compounds was detected in the water column of the permanently stratified meromictic Lake Cadagno. Besides hydrogen sulfide it included methanethiol, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and dimethyl disulfide. Their distribution in the water column suggests that these compounds are of biogenic origin. Except for carbon disulfide which is present in all layers of Lake Cadagno, these volatile organic sulfur compounds are restricted to the anoxic part of the lake. For methanethiol, dimethyl sulfide, and carbon disulfide maximum concentrations were observed in the redox transition zone and in the sediment porewater. Carbon disulfide is the most abundant volatile organic sulfur compound with concentrations of up to 60 μmol L^–1. The concentrations of the methylated sulfides are in the nmolar range. Although their concentrations varied during the summer months, seasonal trends of the concentrations of volatile organic sulfur compounds did not follow a consistent pattern. The restriction of most sulfur species to the anoxic layers of the lake indicates that their production originates from anaerobic microbial degradation of biomass and not from its release from a specific precursor like dimethylsulfoniumpropionate as in marine environments.     

Compound‐Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis‐DCE compound‐specific isotope analysis of carbon and chlorine collected over a 16‐month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis‐DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ³⁷Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis‐DCE. Carbon isotopic values range between ?28.9 and ?20.7‰ VPDB for TCE, and ?26.5 and ?11.8‰ VPDB for cis‐DCE. In most wells, isotopic values remained steady over the 15‐month study. Isotopic enrichment from TCE to cis‐DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine‐carbon isotopic enrichment ratios (?_Cl/?_C) were 0.18 for TCE and 0.69 for cis‐DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume.     

The mineralogy and the isotopic composition of sulfur in hydrothermal sulfide/sulfate deposits on the East Pacific Rise, 21°N latitude

The mineralogy of five groups of hydrothermal chimneys from the East Pacific Rise has been examined. Three of the chimneys, where the exit temperature of the hydrothermal fluids was close to 350°C, are rich in copper sulfides. Exit temperatures from the other two chimneys were less than 300°C; in these, the chimney walls are rich in zinc sulfide. The major sulfides in the chimneys as a whole were found to be wurtzite, chalcopyrite, pyrite, and cubanite. Anhydrite is always the dominant sulfate, and is present in all the deposits. Silicates are also present but in relatively minor amounts. There are considerable differences in the mineralogy of sulfides, sulfates, and silicates between the active and inactive vent deposits.The isotopic composition of sulfur in anhydrites from active vents is close to that of seawater; the δ³⁴S values of the sulfides range from +1.3 to +4.1‰. The isotopic composition of sulfur in the anhydrites is consistent with a derivation predominantly from seawater sulfate. The sulfur in the sulfides must have a complex origin including contributions from both sulfur in basalts and sulfide produced by reduction of sulfate in seawater. Mixing of H₂S-dominated hydrothermal fluids with cold seawater near the seafloor resulted in the precipitation of non-equilibrium assemblages of sulfides and sulfates.     

Identification of Multiple Sources of Groundwater Contamination by Dual Isotopes

Chlorinated solvents are one of the most commonly detected groundwater contaminants in industrial areas. Identification of polluters and allocation of contaminant sources are important concerns in the evaluation of complex subsurface contamination with multiple sources. In recent years, compound‐specific isotope analyses (CSIA) have been employed to discriminate among different contaminant sources and to better understand the fate of contaminants in field‐site studies. In this study, the usefulness of dual isotopes (carbon and chlorine) was shown in assessments of groundwater contamination at an industrial complex in Wonju, Korea, where groundwater contamination with chlorinated solvents such as trichloroethene (TCE) and carbon tetrachloride (CT) was observed. In November 2009, the detected TCE concentrations at the study site ranged between nondetected and 10,066 µg/L, and the CT concentrations ranged between nondetected and 985 µg/L. In the upgradient area, TCE and CT metabolites were detected, whereas only TCE metabolites were detected in the downgradient area. The study revealed the presence of separate small but concentrated TCE pockets in the downgradient area, suggesting the possibility of multiple contaminant sources that created multiple comingling plumes. Furthermore, the variation of the isotopic (δ¹³C and δ³⁷Cl) TCE values between the upgradient and downgradient areas lends support to the idea of multiple contamination sources even in the presence of detectable biodegradation. This case study found it useful to apply a spatial distribution of contaminants coupled with their dual isotopic values for evaluation of the contaminated sites and identification of the presence of multiple sources in the study area.