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Rationale The environmental occurrence of chlorinated acetic acids (CAAs) has been extensively studied, but the sources and transport are still not yet fully understood. A promising approach for source apportionment and process studies is the isotopic characterization of target compounds. We present the first on-line stable chlorine isotope analysis of CAAs by use of gas chromatography/quadrupole mass spectrometry (GC/qMS). Methods Following approved procedures for concentration analysis, CAAs extracted into MTBE were methylated to GC-amenable methyl esters (mCAAs). These mCAAs were then analyzed by GC/qMS for their stable chlorine isotope composition using a sample/standard-bracketing approach (CAA standards in the range δ37Cl −6.3 to −0.2 ‰, Standard Mean Ocean Chloride). Results Cross-calibration of the herein presented method with off-line reference methods (thermal ionization and continuous-flow GC isotope ratio mass spectrometry; TI-MS and CF-GC/IRMS, respectively) shows good agreement between the methods (regression slope for GC/qMS vs reference method data sets: 0.92 ± 0.29). Sample amounts as small as 10 pmol Cl can herewith be analyzed with a precision of 0.1 to 0.4 ‰. Conclusions This method should be useful for environmental studies of CAAs at ambient concentrations in precipitations (<0.06 to 100 nmol L-1), surface waters (<0.2 to 5 nmol L-1) and soil (<0.6 to 2000 nmol kg-1 dry soil) where conventional off-line methods cannot be applied. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Two-dimensional compound-specific isotope analysis (2D-CSIA), combining stable carbon and chlorine isotopes, holds potential for monitoring of natural attenuation of chlorinated ethenes (CEs) in contaminated soil and groundwater. However, interpretation of 2D-CSIA data sets is challenged by a shortage of experimental Cl isotope enrichment factors. Here, isotope enrichments factors for C and Cl (i.e., εC and εCl) were determined for biodegradation of tetrachloroethene (PCE) and trichloroethene (TCE) using microbial enrichment cultures from a heavily CE-contaminated aquifer. The obtained values were εC = -5.6 ± 0.7‰ (95% CI) and εCl = -2.0 ± 0.5‰ for PCE degradation and εC = -8.8 ± 0.2‰ and εCl = -3.5 ± 0.5‰ for TCE degradation. Combining the values for both εC and εCl yielded mechanism-diagnostic εCl/εC ratios of 0.35 ± 0.11 and 0.37 ± 0.11 for the degradation of PCE and TCE, respectively. Application of the obtained εC and εCl values to a previously investigated field site gave similar estimates for the fraction of degraded contaminant as in the previous study, but with a reduced uncertainty in assessment of the natural attenuation. Furthermore, 16S rRNA gene clone library analyses were performed on three samples from the PCE degradation experiments. A species closely related to Desulfitobacterium aromaticivorans UKTL dominated the reductive dechlorination process. This study contributes to the development of 2D-CSIA as a tool for evaluating remediation strategies of CEs at contaminated sites. [ABSTRACT FROM AUTHOR]

Chlorinated ethenes (CEs) are ubiquitous groundwater contaminants, yet there remains a need for a method to efficiently monitor their in situ degradation. We report here the first field application of combined stable carbon and chlorine isotope analysis of tetrachloroethene (PCE) and trichloroethene (TCE) to investigate their biodegradation in a heavily contaminated aquifer. The two-dimensional Compound Specific Isotope Analysis (2D-CSIA) approach was facilitated by a recently developed gas chromatography-quadrupole mass spectrometry (GCqMS) method for δ37Cl determination. Both C and Cl isotopes showed evidence of ongoing PCE transformation. Applying published C isotope enrichment factors (ϵC) enabled evaluation of the extent of in situ PCE degradation (11-78%). We interpreted C and Cl isotopes using a numerical reactive transport model along a 60-m flow path. It revealed that combined PCE and TCE mass load was dechlorinated by less than 10%, and that cis-dichloroethene was not further dechlorinated. Furthermore, the 2D-CSIA approach allowed estimation of Cl isotope enrichment factors ϵCl (-7.8 to -0.8‰) and characteristic ϵCl/ϵC values (0.42-1.12) for reductive PCE dechlorination at this field site. This investigation demonstrates the benefit of 2D-CSIA to assess in situ degradation of CEs and the applicability of Cl isotope fractionation to evaluate PCE and TCE dechlorination. [ABSTRACT FROM AUTHOR]