Accumulation Of Vinyl Chloride Research Articles

Subsurface Transport of Sulfidated Nano Zero Valent Iron and In Situ Biogeochemical Transformation of Chlorinated Solvents: A Field Study

In situ chemical reduction of chlorinated volatile organic compounds (cVOCs) by nano zero-valent iron (nZVI) has been widely applied in the past 20 years, but with limited effectiveness for bare nZVI due to rapid particle settling, short lifespan, and low reactivity. Stabilization and sulfidation of nZVI have improved its mobility and longevity, increased reactivity towards cVOCs, and reduced toxicity to microbes (Nunez Garcia et al. 2021). In the first-ever CMC-S-nZVI field trial, nZVI sulfidated by dithionite (S-nZVI) and stabilized by carboxymethyl cellulose (CMC) was injected into the subsurface of a site contaminated with a wide range of cVOCs. Multi-level wells were installed to monitor the transport of the CMC-S-nZVI suspension and its remedial performance for two years. Short-term (0-17 days) monitoring demonstrated a good transport of the suspension in the down- and up-gradient wells, in terms of total iron, boron, and sulfides which were major constituents of CMC-S-nZVI. Changes in concentrations of parent compounds, intermediates, and ethene showed effective dechlorination of high-chlorinated VOCs such as tetrachloroethene (PCE) and carbon tetrachloride (Nunez Garcia et al. 2020a, Nunez Garcia et al. 2020b). Long-term (157-729 days) performance was evaluated through temporal analyses of microbial communities, total iron, boron, and cVOCs in groundwater samples. Microbial populations, including organohalide-respiring bacteria, increased by >1 order of magnitude; with Geobacter being the most abundant. This long-term enrichment can be attributed to the low toxicity of CMC-S-nZVI and biostimulation by CMC and perhaps Fe3+. Non-metric multidimensional scaling analysis was carried out on microbial data grouped by depth range and proximity to the injection well. At locations that clearly received CMC-S-nZVI, there was a significant shift in microbial communities that was sustained for the long term. Iron concentrations increased substantially in long-term samples while boron concentrations decreased, suggesting that this iron did not come from CMC-S-nZVI. Microbial dissolution of iron minerals might have contributed to the increased iron content (Jones et al. 2006). Excess dithionite in CMC-S-nZVI would also have reductively dissolved native iron from the soil, as successfully demonstrated in the in situ redox manipulation (ISRM) technology wherein subsurface Fe3+ in soil was reduced to Fe2+ for long-term remedial purposes (Vermeul et al. 2000). Long-term changes in concentrations of lesser-chlorinated VOCs and hydrocarbons suggest that PCE was degraded via both the microbially-mediated sequential hydrogenolysis as well as the abiotic β-elimination. The intermediate vinyl chloride (VC) surprisingly did not accumulate in the current study, in contrast to the significant VC accumulation in a previous un-sulfidated CMC-nZVI trial at the same location (Kocur et al. 2016). Excess dithionite injected in this study might have avoided VC accumulation, as previously reported for ISRM treatment of a cVOCs-contaminated site (Vermeul et al. 2000). Additionally, the identified bacterial populations might have utilized sulfur species (from dithionite decomposition) and iron to form iron sulfides, which could dechlorinate cVOCs via in situ biogeochemical transformation (Kennedy et al. 2006). In summary, this study has demonstrated the long-term efficiency of CMC-S-nZVI for cVOCs removal through a combination of abiotic, biotic, and biostimulatory processes in the subsurface.

The effects of arsenic on dechlorination of trichloroethene by consortium DH: Microbial response and resistance

Inorganic arsenic and organochlorines are frequently co-occurring contaminants in anoxic groundwater environments, and the bioremediation of their composite pollution has long been a rigorous predicament. Currently, the dechlorination behaviors and stress responses of microbial dechlorination consortia to arsenic are not yet fully understood. This study assessed the reductive dechlorination performance of a Dehalococcoides-bearing microcosm DH under gradient concentrations of arsenate [As(V)] or arsenite [As(III)] and investigated the response patterns of different functional microorganisms. Our results demonstrated that although the dechlorination rates declined with increasing arsenic concentrations in both As(III/V) scenarios, the inhibitory impact was more pronounced in As(III)-amended groups compared to As(V)-amended groups. Moreover, the vinyl chloride (VC)-to-ethene step was more susceptible to arsenic exposure compared to the trichloroethene (TCE)-to-dichloroethane (DCE) step, while high levels of arsenic exposure [e.g. As(III) > 75 μM] can induce significant accumulation of VC. Functional gene variations and microbial community analyses revealed that As(III/V) affected reductive dechlorination by directly inhibiting organohalide-respiring bacteria (OHRB) and indirectly inhibiting synergistic populations such as acetogens. Metagenomic results indicated that arsenic metabolic and efflux mechanisms were identical among different Dhc strains, and variations in arsenic uptake pathways were possibly responsible for their differential responses to arsenic exposures. By comparison, fermentative bacteria showed high potential for arsenic resistance due to their inherent advantages in arsenic detoxification and efflux mechanisms. Collectively, our findings expanded the understanding of the response patterns of different functional populations to arsenic stress in the dechlorinating consortium and provided insights into modifying bioremediation strategies at co-contaminated sites for furtherance.

Microbiome Reengineering by Heat Selection for Rapid Biodegradation of Trichloroethylene with Minimal Vinyl Chloride Formation

Trichloroethylene (TCE) was a widely used industrial solvent but is now regarded as a notorious groundwater contaminant. Both physicochemical and biological methods have been applied to remediate groundwater contaminated by TCE. For medium to low level of TCE contamination, bioremediation could be more cost-effective. However, bioremediation approaches suffer from slow degradation rates and accumulation of vinyl chloride (VC). In addition, bioaugmentation is often highly encouraged but may introduce foreign genes and increase the pace of microbial evolution. In this study, a microbiome reengineering strategy by heat selection is applied to solve these problems. Out of eight heat-treated mixed cultures, two showed a much-improved TCE degradation rate, more than 70 times higher than the untreated. The biodegradation half-life (t1/2) of TCE was 0.0627 d or shorter. No VC was detected by a gas chromatography equipped with flame ionization detector (GC-FID) and only a minimal amount by a GC-mass spectrometer (GC-MS). Ethene achieved a fairly good mass balance. Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) and next-generation sequencing (NGS) results showed that the heating process did not kill most bacteria, but Dehalococcoides were either not present or very scarce. Acetoanaerobium and Methanosarcina could be the most important species in this reductive dechlorination process. Kinetic study results showed that the maximum specific TCE degradation rate was approximately 1,271 nmole/min/mg cell protein, which are two orders of magnitude higher than that of the mixed cultures reported in literature. These results suggest that apart from biostimulation and bioaugmentation, microbiome reengineering could be a promising approach for rapid bioremediation of TCE-contaminated aquifers.

Sustained Dechlorination of Vinyl Chloride to Ethene in Dehalococcoides-Enriched Cultures Grown without Addition of Exogenous Vitamins and at Low pH.

Trichloroethene (TCE) bioremediation has been demonstrated at field sites using microbial cultures harboring TCE-respiring Dehalococcoides whose growth is cobalamin (vitamin B12)-dependent. Bioaugmentation cultures grown ex situ with ample exogenous vitamins and at neutral pH may become vitamin-limited or inhibited by acidic pH once injected into field sites, resulting in incomplete TCE dechlorination and accumulation of vinyl chloride (VC). Here, we report growth of the Dehalococcoides-containing bioaugmentation culture KB-1 in a TCE-amended mineral medium devoid of vitamins and in a VC-amended mineral medium at low pH (6.0 and 5.5). In these cultures, Acetobacterium, which can synthesize 5,6-dimethylbenzimidazole (DMB), the lower ligand of cobalamin, and Sporomusa are dominant acetogens. At neutral pH, Acetobacterium supports complete TCE dechlorination by Dehalococcoides at millimolar levels with a substantial increase in cobalamin (∼20-fold). Sustained dechlorination of VC to ethene was achieved at pH as low as 5.5. Below pH 5.0, dechlorination was not stimulated by DMB supplementation but was restored by raising pH to neutral. Cell-extract assays revealed that vinyl chloride reductase activity declines significantly below pH 6.0 and is undetectable below pH 5.0. This study highlights the importance of cobamide-producing populations and pH in microbial dechlorinating communities for successful bioremediation at field sites.

Remediation of chlorinated ethenes in fractured sandstone by natural and enhanced biotic and abiotic processes: A crushed rock microcosm study

Biostimulation was identified as a potential technology to treat a fractured sandstone aquifer contaminated with trichloroethene (TCE) and cis-1,2-dichloroethene (cis-DCE). Most of the mass of TCE and cis-DCE resides within the rock matrix and strategies to restore groundwater to pre-existing conditions are severely limited by back diffusion. A microcosm study using crushed rock and groundwater from the site was performed to assess biostimulation and natural attenuation. Lactate, hydrogen release compound® (HRC), and emulsified vegetable oil (EVO) significantly increased the rate of TCE reduction to cis-DCE. Lactate also stimulated dechlorination of cis-DCE to vinyl chloride (VC) and ethene, suggesting the presence of indigenous Dehalococcoides. Illumina sequencing and qPCR analyses suggest that reductive dechlorination of TCE to cis-DCE is mediated by Geobacter spp. while Dehalococcoides spp. perform reduction of cis-DCE to VC and ethene. The rate of VC reduction to ethene was much slower than the reduction of TCE to cis-DCE and cis-DCE to VC, indicating the indigenous Dehalococcoides perform the final step co-metabolically. This was confirmed in enrichment cultures fed with only VC. Consequently, biostimulation may create an elevated risk due to transient accumulation of VC. Abiotic transformation of TCE and cis-DCE was observed based on accumulation of 14C-labeled products from 14C-TCE and 14C-cis-DCE, as well as enrichment in δ13C-cis-DCE in the absence of reductive dechlorination. Based on accumulation rates for 14C-products in unamended microcosms, pseudo-first-order rates for abiotic transformation were 0.038 yr−1 for TCE and 0.044 yr−1 for cis-DCE. These rates within the rock matrix may be sufficient to support natural attenuation in this diffusion controlled system.

Migration of chlorinated hydrocarbons in multilayer unconsolidated porous media: a case study from the Po Plain, Italy

Chlorinated solvents are the most ubiquitous organic contaminants found in groundwater since the last six decades. Due to their high degree of carcinogenicity/toxicity and the relatively high mobility and persistence, they represent a serious threat against the human health and the environment. These contaminants generally reach groundwater as Dense Non-Aqueous Phase Liquid (DNAPL) that can migrate through aquifers easier than aqueous contaminants. The complex phase partitioning to which chlorinated solvent DNAPLs can undergo (i.e. to the dissolved, vapor or sorbed phase), as well as their transformations (e.g. degradation), depend on the physico-chemical properties of the contaminants and on the features of the hydrogeological system in which they migrate. The hydrogeologic setting below the city of Ferrara (Po plain, northern Italy), which is affected by scattered contamination by chlorinated solvents, has been investigated. In particular, a limited-inspace high-resolution investigation was performed in one selected contaminated test-site, known as “Caretti site”. Here, high-resolution vertical profiling of different kind of data (i.e. stratigraphic data, hydraulic heads, hydrochemical composition of water, stable isotopes of water and contaminants) were collected by means of multilevel monitoring systems and other innovative sampling and analytical techniques. The main goals of the research were to assess the intrinsic vulnerability of the aquifers and to identify the dynamics of migration and transformation of the chloroethene contaminants in relationship to the features of the hosting porous medium. The confined aquifers turned out to be more vulnerable to DNAPLs than aqueous contaminants due to the occurrence of microfractures in the overlying clayey aquitards. The presence of organic-rich deposits in the local stratigraphy enhanced the biodegradation of chloroethenes causing accumulation of Vinyl Chloride. The results are useful at the local scale, e.g. to interpret the origin of contamination in other sites of the Ferrara area, and also at the global scale, to better address future remediation and protection actions in similar settings.

The dechlorination of TCE by a perchlorate reducing consortium

We enriched a trichloroethene (TCE)-dechlorinating consortium from a perchlorate-reducing bacterial culture (PRB) with a very low initial abundance of Dehalococcoides by feeding the culture lactate and TCE; named the novel culture perchlorate-reducing dechlorinating bacteria (PRTB). Short batch tests showed that the PRTB consortium reduced up to 0.45mmol/L of TCE to non-toxic ethene in eight days after two additions of TCE and simultaneously reduced up to 0.15mmol/L of ClO4− to Cl−. TCE reduction by PRTB was sensitive to oxygen: 0.2mg/L of oxygen delayed reduction of TCE to ethene from 5 to 15days, while ⩾0.5mg/L of oxygen significantly inhibited TCE reduction, causing vinyl chloride accumulation. After the consortium was enriched twice with TCE, the Dhc gene (reflecting the abundance of Dehalococcoides) increased from 1.14×104 to 3.25×108 copies/mL. The original PRB culture was dominated by Proteobacteria (78.4%), but the enriched PRTB culture was dominated by Chloroflexi (57.7%). The relative abundance of Dehalococcoides increased from 0.02% to 57.4%. Other presumptive dechlorinators Desulfuromonas and Geobacter were enriched as well. Possible acetogens (Spirochaetes) and putative fermenters (Bacteroidetes and Desulfovibrio) were also present in the culture, providing Dehalococcoides with acetate as the carbon source, hydrogen gas as the electron donor, and Vitamin B12 as a growth factor.

Geochemical and microbial community determinants of reductive dechlorination at a site biostimulated with glycerol.

Biostimulation is widely used to enhance reductive dechlorination of chlorinated ethenes in contaminated aquifers. However, the knowledge on corresponding biogeochemical responses is limited. In this study, glycerol was injected in an aquifer contaminated with cis-dichloroethene (cDCE), and geochemical and microbial shifts were followed for 265 days. Consistent with anoxic conditions and sulfate reduction after biostimulation, MiSeq 16S rRNA gene sequencing revealed temporarily increased relative abundance of Firmicutes, Bacteriodetes and sulfate reducing Deltaproteobacteria. In line with 13 C cDCE enrichment and increased Dehalococcoides mccartyi (Dcm) numbers, dechlorination was observed toward the end of the field experiment, albeit being incomplete with accumulation of vinyl chloride. This was concurrent with (i) decreased concentrations of dissolved organic carbon (DOC), reduced relative abundances of fermenting and sulfate reducing bacteria that have been suggested to promote Dcm growth by providing electron donor (H2 ) and essential corrinoid cofactors, (ii) increased sulfate concentration and increased relative abundance of Epsilonproteobacteria and Deferribacteres as putative oxidizers of reduced sulfur compounds. Strong correlations of DOC, relative abundance of fermenters and sulfate reducers, and dechlorination imply the importance of syntrophic interactions to sustain robust dechlorination. Tracking microbial and environmental parameters that promote/preclude enhanced reductive dechlorination should aid development of sustainable bioremediation strategies.

Origin of VC-only plumes from naturally enhanced dechlorination in a peat-rich hydrogeologic setting

The occurrence of vinyl chloride (VC) is often a main concern at sites contaminated with chlorinated solvents due to its high degree of toxicity and carcinogenicity. VC occurrence in aquifers is most often related to the degradation of higher chlorinated ethenes or ethanes and it is generally detected in plumes along with parent contaminants. However, specific combination of stratigraphic, hydrogeologic and geochemical conditions can enhance the degradation of parents and lead to the formation of plumes almost entirely composed of VC (i.e. VC-only plumes). This paper investigates the causes of VC-only plumes in the aquifers below the city of Ferrara (northern Italy) by combining multiple lines of evidence. The City of Ferrara is located on an alluvial lowland, built by the River Po, and is made up of alternating unconsolidated sandy aquifer and silt-clay aquitard deposits of fluvial origin. This region has been strongly impacted by prior industrial activities, with the occurrence of chlorinated compounds at several sites. VC-only plumes with uncertain source location were found at two contaminated sites. The source zone of a third plume composed of chloroethenes from PCE to VC was investigated for high resolution depositional facies architecture and contaminant distribution (contaminant concentration and Compound Specific Isotope Analysis – CSIA). The investigation suggested that degradation of PCE and TCE takes place during contaminant migration through peat-rich (swamp) layers related to the Holocene transgression, which locally act as a “reactor” for stimulating degradation with the accumulation of VC in the strongly reducing environment of the peat. Regional-scale stratigraphic architecture showed the ubiquitous occurrence of swamp layers at distinct stratigraphic levels in the investigated system and their apparent linkage to the in situ creation of the VC-only plumes.

Concentration effects on biotic and abiotic processes in the removal of 1,1,2-trichloroethane and vinyl chloride using carbon-amended ZVI

A permeable reactive barrier, consisting of both zero valent iron (ZVI) and a biodegradable organic carbon, was evaluated for the remediation of 1,1,2-trichloroethane (1,1,2-TCA) contaminated groundwater. During an 888day laboratory column study, degradation rates initially stabilized with a degradation half-life of 4.4±0.4days. Based on the accumulation of vinyl chloride (VC) and limited production of 1,1-dichloroethene (1,1-DCE) and 1,2-dichloroethane (1,2-DCA), the dominant degradation pathway was likely abiotic dichloroelimination to form VC. Degradation of VC was not observed based on the accumulation of VC and limited ethene production.After a step reduction in the influent concentration of 1,1,2-TCA from 170±20mgL−1 to 39±11mgL−1, the degradation half-life decreased 5-fold to 0.83±0.17days. The isotopic enrichment factor of 1,1,2-TCA also changed after the step reduction from −14.6±0.7‰ to −0.72±0.12‰, suggesting a possible change in the degradation mechanism from abiotic reductive degradation to biodegradation. Microbiological data suggested a co-culture of Desulfitobacterium and Dehalococcoides was responsible for the biodegradation of 1,1,2-TCA to ethene.

Validation of an Integrative Methodology to Assess and Monitor Reductive Dechlorination of Chlorinated Ethenes in Contaminated Aquifers

Bioremediation of tetra-and trichloroethene-contaminated aquifers is frequently hampered due to incomplete dechlorination to the more toxic dichloroethene (DCE) and vinyl chloride (VC), indicating insufficient knowledge about the biological mechanisms related to aquifer functioning. A methodology based on the joint analysis of geochemical and microbiological datasets was developed to assess the presence of the biochemical potential for complete reductive dechlorination to harmless ethene and to explain the reasons for which degradation often stalls at the more toxic intermediates. This methodology is composed of three successive steps, with i) the acquisition of geochemical data including chlorinated ethenes, ii) the detailed analysis of the bacterial community structures as well as the biochemical potential for complete dechlorination using microcosms and molecular detection of organohalide-respiring bacteria and key reductive dehalogenases, and iii) a statistical Multiple Factor Analysis combining the above mentioned abiotic and biotic variables in a functional modelling of the contaminated aquifer. The methodology was validated by analyzing two chlorinated ethenes-contaminated sites. Results from the first site showed that the full biochemical potential for ethene production was present in situ. However, redox potential was overall too high and locally manganese reduction out-competed chlorinated ethenes reduction, explaining the reasons for the local accumulation of DCE and VC to a lesser extent. The second contaminated aquifer was under bioremediation by successive cheese whey injections. Analysis demonstrated that cheese whey additions led to increasingly reduced redox conditions and that hampered reductive dechlorination was not due to competition with other anaerobic respiration processes. Complete reductive dechlorination to ethene was preferentially occurring under methanogenic conditions. DCE and VC accumulation was probably induced first by low pH resulting from whey fermentation and at a later stage by phosphate limitation. In conclusions, the proposed methodology successfully allowed the identification of biogeochemical processes limiting or supporting complete dechlorination in both aquifers. The integrative approach provided fundamental information about the functional heterogeneity of the contaminated aquifers in time and space, and can be used as a reliable tool to support corrective decision-making in the development of remediation strategies based on natural attenuation of chlorinated ethenes.

Correlations between Environmental Variables and Bacterial Community Structures Suggest Fe(III) and Vinyl Chloride Reduction As Antagonistic Terminal Electron-Accepting Processes

Natural attenuation of anaerobic aquifers contaminated with tetrachloroethene (PCE) often results in the accumulation of the intermediates cis-dichloroethene and vinyl chloride (VC) which are even more toxic than the parent compound. Reasons for this accumulation were investigated in a PCE-contaminated aquifer in which VC accumulation has previously been shown to occur using stable isotope techniques. Multifactorial analysis of bacterial community structure data and environmental variables showed that in general terminal electron-accepting processes were shaping the bacterial community structures. Both VC and Fe(III) reduction were key but antagonistic terminal electron-accepting processes. The phylogenetic affiliation of terminal restriction fragments (T-RFs), together with correlation analyses, showed that T-RFs having significant correlation with VC reduction were closely affiliated to the genus Dehalococcoides and to uncultured bacteria belonging to the "Lahn Cluster" within the class Dehalococcoidetes. A T-RF that negatively correlated with a "Lahn Cluster" T-RF was affiliated to the genus Rhodoferax that contains members identified as iron-reducing bacteria. The higher affinity of Fe(III)-reducing bacteria for hydrogen compared with VC-reducing bacteria might explain why VC accumulated locally at the studied site. In conclusion, the combination of molecular and numerical ecology approaches was helpful to identify reasons for the accumulation of toxic dechlorination intermediates and could become a useful tool for characterizing contaminated sites in general.

Sequential application of electron donors and humic acids for the anaerobic bioremediation of chlorinated aliphatic hydrocarbons

In situ anaerobic bioremediation of chlorinated solvents such as perchloroethene (PCE) frequently faces the problem of accumulating toxic, lower chlorinated compounds such as dichloroethene (cis-DCE) and vinyl chloride (VC). In the present study, the efficacy of the sequential application of electron donors, supporting reductive dechlorination, and of humic acids, acting as extracellular electron shuttles facilitating the anaerobic oxidation of recalcitrant intermediates, was explored in microcosm studies. Upon one initial dose of lactose, supplied in a 1000-fold superstoichiometric electron equivalent ratio, PCE was completely converted into cis-DCE within 35 days. Repeated electron donor additions did not entail exhaustive cis-DCE degradation over incubation time (120 days). Although the electron donor was quickly converted into fatty acids, about 30% of added reducing equivalents were recovered as acetate after four months of operation, indicating the inhibition of acetoclastic methanogenesis. In the next step, the substoichiometric addition of anthraquinone-2,6-disulfonate, a humic acid model compound, effected the complete removal of the accumulated cis-DCE within 15 days, probably as a result of the participation of the quinone in the biotic or abiotic anaerobic oxidation of cis-DCE. Cis-DCE degradation was not connected to the accumulation of VC, rendering the proposed two-step treatment an efficient and environmentally compliant remedy for anaerobic groundwater bodies contaminated with chlorinated solvents.

Investigation of factors affecting the accumulation of vinyl chloride in polyvinyl chloride piping used in drinking water distribution systems

Plastic piping made of polyvinyl chloride (PVC), and chlorinated PVC (CPVC), is being increasingly used for drinking water distribution lines. Given the formulation of the material from vinyl chloride (VC), there has been concern that the VC (a confirmed human carcinogen) can leach from the plastic piping into drinking water. PVC/CPVC pipe reactors in the laboratory and tap samples collected from consumers homes ( n = 15) revealed vinyl chloride accumulation in the tens of ng/L range after a few days and hundreds of ng/L after two years. While these levels did not exceed the EPA’s maximum contaminant level (MCL) of 2 μg/L, many readings that simulated stagnation times in homes (overnight) exceeded the MCL-Goal of 0 μg/L. Considerable differences in VC levels were seen across different manufacturers, while aging and biofilm effects were generally small. Preliminary evidence suggests that VC may accumulate not only via chemical leaching from the plastic piping, but also as a disinfection byproduct (DBP) via a chlorine-dependent reaction. This is supported from studies with CPVC pipe reactors where chlorinated reactors accumulated more VC than dechlorinated reactors, copper pipe reactors that accumulated VC in chlorinated reactors and not in dechlorinated reactors, and field samples where VC levels were the same before and after flushing the lines where PVC/CPVC fittings were contributing. Free chlorine residual tests suggest that VC may be formed as a secondary, rather than primary, DBP. Further research and additional studies need to be conducted in order to elucidate reaction mechanisms and tease apart relative contributions of VC accumulation from PVC/CPVC piping and chlorine-dependent reactions.

Assessing chlorinated ethene degradation in a large scale contaminant plume by dual carbon–chlorine isotope analysis and quantitative PCR

The fate of chlorinated ethenes in a large contaminant plume originating from a tetrachloroethene (PCE) source in a sandy aquifer in Denmark was investigated using novel methods including compound-specific carbon and chlorine isotope analysis and quantitative real-time polymerase chain reaction (qPCR) methods targeting Dehaloccocoides sp. and vcrA genes. Redox conditions were characterized as well based on concentrations of dissolved redox sensitive compounds and sulfur isotopes in SO 4 2−. In the first 400 m downgradient of the source, the plume was confined to the upper 20 m of the aquifer. Further downgradient it widened in vertical direction due to diverging groundwater flow reaching a depth of up to 50 m. As the plume dipped downward and moved away from the source, O 2 and NO 3 − decreased to below detection levels, while dissolved Fe 2+ and SO 4 2− increased above detectable concentrations, likely due to pyrite oxidation as confirmed by the depleted sulfur isotope signature of SO 4 2−. In the same zone, PCE and trichloroethene (TCE) disappeared and cis-1,2-dichloroethene (cDCE) became the dominant chlorinated ethene. PCE and TCE were likely transformed by reductive dechlorination rather than abiotic reduction by pyrite as indicated by the formation of cDCE and stable carbon isotope data. TCE and cDCE showed carbon isotope trends typical for reductive dechlorination with an initial depletion of 13C in the daughter products followed by an enrichment of 13C as degradation proceeded. At 1000 m downgradient of the source, cDCE was the dominant chlorinated ethene and had reached the source δ 13C value confirming that cDCE was not affected by abiotic or biotic degradation. Further downgradient (up to 1900 m), cDCE became enriched in 13C by up to 8‰ demonstrating its further transformation while vinylchloride (VC) concentrations remained low (< 1 μg/L) and ethene was not observed. The correlated shift of carbon and chlorine isotope ratios of cDCE by 8 and 3.9‰, respectively, the detection of Dehaloccocides sp genes, and strongly reducing conditions in this zone provide strong evidence for reductive dechlorination of cDCE. The significant enrichment of 13C in VC indicates that VC was transformed further, although the mechanism could not be determined. The transformation of cDCE was the rate limiting step as no accumulation of VC occurred. In summary, the study demonstrates that carbon–chlorine isotope analysis and qPCR combined with traditional approaches can be used to gain detailed insight into the processes that control the fate of chlorinated ethenes in large scale plumes.

Assessment of a groundwater contamination with vinyl chloride (VC) and precursor volatile organic compounds (VOC) by use of a geographical information system (GIS)

Regarding the health effects of volatile organic compounds (VOC) and their decomposition products (particularly vinyl chloride (VC)) under chronic low-dose exposure, VOC groundwater contaminations are seen to be an ongoing public health issue. This article presents results of a long-term investigation surveying VOC and VC groundwater contamination upstream of a large groundwater works in Cologne, Germany. For 10 years a contaminated aquifer has been monitored for different VOC and for VC. In total, 255 samples have been taken to assess both the 3-dimensional distribution and the temporal dynamics of the contaminants. VOC and VC precursor substances have been measured by means of pentane-liquid-liquid-extraction, GC and ECD, VC by means of derivatisation to 1,2 dibromochloroethane, GC, ECD, and by purge and trap technique and GC-MS-coupling. For spatial analysis all test results and additional hydrogeological attribute data have been transferred to a GIS. The spatial VOC distribution has been assessed by use of kriging interpolation indicating a decrease of the initial contaminants in time. A cluster analysis allowed to distinguish several independent contaminations within the large contamination area. The VC contamination was increasing. Anaerobic microbial dechlorination of VOC and subsequent VC accumulation were seen to be as credible from several indications (VC presence, downstream change of tetra/trichloroethylene-ratio and anaerobic conditions in the aquifer, high Fe(2+)- and Mn(2+)-concentrations). There was no statistically significant vertical differentiation of VOC and VC concentrations. The VOC load within the different water protection zones of the waterworks could be assessed.

Reductive Dechlorination of the Vinyl Chloride Surrogate Chlorofluoroethene in TCE-Contaminated Groundwater

At many trichloroethene (TCE)-contaminated field sites, microbial transformation of TCE results in the accumulation of vinyl chloride (VC), a known carcinogen and neurotoxin. Quantitative tools are needed to determine the in situ rates of VC transformation to ethene in contaminated groundwater. For this study, E-/Z-chlorofluoroethene (E-/Z-CFE) was evaluated as a surrogate for VC in laboratory microcosm and field push-pull tests. Single-well push-pull tests were conducted at a TCE-contaminated field site by injecting E-/Z-CFE and monitoring for the formation of fluoroethene (FE) over a period of up to 80 days. The rates for VC transformation to ethene and E-CFE transformation to FE were within a factor of 2.7 for laboratory microcosm systems and all preferentiallytransformed E-CFE over Z-CFE. In the field, the in situ rates of FE production from injected E-CFE ranged from 0.0018 to 1.15 microM/day, while the in situ rates of E-CFE disappearance ranged from 0.17 to 0.99 microM/day. No significant Z-CFE transformation was observed in field tests, which indicated preferential utilization of E-CFE over Z-CFE under in situ field conditions. The results of this study indicate E-CFE as a potential surrogate for estimating the in situ rates of VC transformation.

Remedial options for chlorinated volatile organics in a partially anaerobic aquifer

AbstractA laboratory study was conducted for the selection of appropriate remedial technologies for a partially anaerobic aquifer contaminated with chlorinated volatile organics (VOCs). Evaluation of in situ bioremediation demonstrated that the addition of electron donors to anaerobic microcosms enhanced biological reductive dechlorination of tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA) with half‐lives of 20, 22, and 41 days, respectively. Nearly complete reductions of PCE, TCE, 1,1,1‐TCA, and the derivative cis‐dichloroethene were accompanied by a corresponding increase in chloride concentrations. Accumulation of vinyl chloride, ethene, and ethane was not observed; however, elevated levels of 14CO2 (from 14C‐TCE spiked) were recovered, indicating the occurrence of anaerobic oxidation. In contrast, very little degradation of 1,2‐dichloropropane (1,2‐DCP) and 1,1‐dichlorethane (1,1‐DCA) was observed in the anaerobic microcosms, but nutrient addition enhanced their degradation in the aerobic biotic microcosms. The aerobic degradation half‐lives for 1,2‐DCP and 1,1‐DCA were 63 and 56 days, respectively. Evaluation of in situ chemical oxidation (ISCO) demonstrated that chelate‐modified Fenton's reagent was effective in degrading aqueous‐phase PCE, TCE, 1,1,1‐TCA, 1,2‐DCP, etc.; however, this approach had minimal effects on solid‐phase contaminants. The observed oxidant demand was 16 g‐H2O2/L‐groundwater. The oxidation reaction rates were not highly sensitive to the molar ratio of H2O2:Fe2+:citrate. A ratio of 60:1:1 resulted in slightly faster removal of chemicals of concern (COCs) than those of 12:1:1 and 300:1:1. This treatment resulted in increases in dissolved metals (Ca, Cr, Mg, K, and Mn) and a minor increase of vinyl chloride. Treatment with zero‐valent iron (ZVI) resulted in complete dechlorination of PCE, and TCE to ethene and ethane. ZVI treatment reduced 1,1,1‐TCA only to 1,1‐DCA and chloroethane (CA) but had little effect on reducing the levels of 1,2‐DCP, 1,1‐DCA, and CA. The longevity test showed that one gram of 325‐mesh iron powder was exhausted in reaction with &gt; 22 mL of groundwater. The short life of ZVI may be a barrier to implementation. The ZVI surface reaction rates (ksa) were 1.2 × 10−2 Lm−2h−1, 2 × 10−3 Lm−2h−1, and 1.2 × 10−3 Lm−2h−1 for 1,1,1‐TCA, TCE, and PCE, respectively. Based upon the results of this study, in situ bioremediation appeared to be more suitable than ISCO and ZVI for effectively treating the groundwater contamination at the site. © 2004 Wiley Periodicals, Inc.

Anaerobic Degradation of cis-1,2-Dichloroethylene and Vinyl Chloride by Clostridium sp. Strain DC1 Isolated from Landfill Leachate Sediment

The bacterial community structure of anaerobic enrichment cultures that are capable of degrading both cis -1,2-dichloroethylene ( cis -DCE) and vinyl chloride (VC) and isolation of the organism responsible for the degradation were investigated. Denaturing gradient gel electrophoresis (DGGE) of a PCR-amplified 16S rRNA gene from the cultures showed the possible predominance of Clostridium species. One isolate, designated strain DC1, was closely related to members of Clostridiaceae, based on 16S rRNA gene analysis, and the highest sequence similarity (98.9%) was obtained for Clostridium saccarobutylicum . In culture experiments, strain DC1 was shown to degrade cis -DCE and VC during the stationary phase of growth without accumulation of VC and/or ethene. The bacterial growth was not linked to the degradation of cis -DCE and VC. Stoichiometric analysis revealed that two moles of chloride ions as released from one mole of cis -DCE during the incubation period, indicating that cis -DCE was fully dechlorinated. The results appear consistent with the presence of a mechanism of oxidative dechlorination rather than respiratory reductive dechlorination; the latter is accompanied by transient formation of dechlorinated ethenes from cis -DCE and VC.

Degradation of 1,1,2,2-tetrachloroethane and accumulation of vinyl chloride in wetland sediment microcosms and in situ porewater: biogeochemical controls and associations with microbial communities

The biodegradation pathways of 1,1,2,2-tetrachloroethane (TeCA) and 1,1,2-trichloroethane (112TCA) and the associated microbial communities in anaerobic wetland sediments were evaluated using concurrent geochemical and genetic analyses over time in laboratory microcosm experiments. Experimental results were compared to in situ porewater data in the wetland to better understand the factors controlling daughter product distributions in a chlorinated solvent plume discharging to a freshwater tidal wetland at Aberdeen Proving Ground, Maryland. Microcosms constructed with wetland sediment from two sites showed little difference in the initial degradation steps of TeCA, which included simultaneous hydrogenolysis to 112TCA and dichloroelimination to 1,2-dichloroethene (12DCE). The microcosms from the two sites showed a substantial difference, however, in the relative dominance of subsequent dichloroelimination of 112TCA. A greater dominance of 112TCA dichloroelimination in microcosms constructed with sediment that was initially iron-reducing and subsequently simultaneously iron-reducing and methanogenic caused approximately twice as much vinyl chloride (VC) production as microcosms constructed with sediment that was methanogenic only throughout the incubation. The microcosms with higher VC production also showed substantially more rapid VC degradation. Field measurements of redox-sensitive constituents, TeCA, and its anaerobic degradation products along flowpaths in the wetland porewater also showed greater production and degradation of VC with concurrent methanogenesis and iron reduction. Molecular fingerprinting indicated that bacterial species [represented by a peak at a fragment size of 198 base pairs (bp) by MnlI digest] are associated with VC production from 112TCA dichloroelimination, whereas methanogens (190 and 307 bp) from the Methanococcales or Methanobacteriales family are associated with VC production from 12DCE hydrogenolysis. Acetate-utilizing methanogens (acetotrophs) appear to be involved in the biodegradation of VC. The relative abundance of Methanosarcinaceae, the only methanogen group with acetotrophic members, doubled in microcosms in which degradation of VC was observed. In addition, molecular analyses using primers specific for known dehalorespiring bacteria in the Dehalococcoides and Desulfuromonas groups showed the presence of these bacteria in microcosm slurry from the site that showed the highest VC production and degradation. Determination of biogeochemical controls and microbial consortia involved in TeCA degradation is leading to a better understanding of the heterogeneity in biodegradation rates and daughter product distribution in the wetland, improving capabilities for developing remediation and monitoring plans.