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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 δ(37) Cl -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.)

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.

Compound-specific chlorine isotope analysis (CSIA-Cl) is promising as a novel and powerful method for monitoring in situ degradation of organochlorines in the environment and for source fingerprinting purposes. In order to apply CSIA-Cl in field studies of polychlorinated biphenyls (PCBs), the chlorine isotopic composition (delta(37)Cl) of individual PCB congeners in source materials must be known. In the present study, we determined delta(37)Cl of 18 congeners isolated from three widely produced technical mixtures. All congeners provided delta(37)Cl ranging between -1.9 per thousand and -3.5 per thousand. Although the comparable products Aroclor 1242 (-2.0 per thousand to -2.5 per thousand) and Clophen A30 (-1.9 per thousand to -3.0 per thousand) were synthesized by different industries, they provided similar delta(37)Cl for the same type of congeners. On the contrary, the more chlorinated congeners present in Aroclor 1254 (-2.1 to -3.5 per thousand) were more (37)Cl depleted compared to Aroclor 1242 manufactured by the same company. Overall, delta(37)Cl of PCB congeners decreased by -0.26 per thousand for each additional chlorine atom.

Polychlorinated dibenzo-p-dioxins (PCDDs) of high concentrations in a ball clay deposit from the Mississippi Embayment were found to be consistent with a natural abiotic and non-pyrogenic origin by investigation with bulk radiocarbon analysis, compound-specific chlorine isotope analysis (CSIA-delta37Cl) of octachlorodibenzo-p-dioxin (OCDD), and black carbon (BC) analysis. The conventional radiocarbon date of total organic carbon from a depth of approximately 10 m in three parallel cores ranged from 14 700 years to >48 000 years, indicating that the strata with elevated levels of PCDDs have remained isolated from recent anthropogenic input in these >40 Ma old clay sediments. The CSIA-delta37Cl of OCDD yielded a delta37Cl of -0.2 per thousandth, which is significantly higher than the postulated range for biotic chlorination by chloroperoxidase enzymes, -11 to -10 per thousandth, and falls within the known range for abiotic organochlorines, -6 to +3 per thousandth. The absence of correlations between concentrations of PCDDs and corresponding pyrogenic black carbon (BC), together with estimations of BC sorptive loadings and the absence of polychlorinated dibenzofurans (PCDFs), suggest that vegetation fires did not form these ball-clay PCDDs. Results from this study indicate that the high levels of the toxic and carcinogenic PCDDs found in kaolinite-bearing clays may result from natural abiotic formation via in situ surface-promoted reactions on the clay mineral, including a so-far unknown organic precursor, rather than being the result of anthropogenic contamination.

Compound-specific chlorine-isotope analysis (CSIA-Cl) of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (p,p′-DDT) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethene (p,p′-DDE) in blubber from Baltic Grey seal (Halichoerus grypus) was performed in order to investigate if a kinetic isotope effect (KIE) could be observed concomitant to environmental degradation of DDT. The δ37Cl of p,p′-DDT and p,p′-DDE were −0.69±0.21‰ and −2.98±0.57‰ (1σ, n =3), respectively. Both samples were enriched relative to the hypothesized initial isotope composition (−4.34‰), thus indicating a composite KIE associated with the degradation mechanisms pertaining to DDT. An isotope fractionation factor for degradation of dichloromethane, from the literature, was adapted and modified for use in the calculation of DDT degradation. A subsequent simplified Rayleigh distillation model of the DDT chlorine-isotope composition yielded an estimated fraction (f) of 7±2% of released DDT presently remaining as undegraded compound in the environment. The consistency between the result of the Rayleigh model (f ∼7%) and the use of the DDT/(DDT+DDE) ratio as a measure of DDT degradation (∼10% undegraded DDT) suggests that the KIE of DDT degradation may be significant, and that the novel approach of CSIA-Cl may be a valuable tool for degradation/persistence studies of lipophilic organochlorines in the environment. [Copyright &y& Elsevier]

Abstract: Chlorine isotope fractionation during preparative capillary gas chromatography (pcGC) was investigated using 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) as a model compound for semi-volatile organochlorine (OCl) molecules. Chlorine isotope analysis by thermal ionization mass spectrometry revealed no significant alteration of the chlorine isotope composition when the whole peaks were collected in pcGC (δ37Cl −3.2‰ versus −3.6‰ for the unprocessed DDT, ±0.5‰ SD). However, distinct isotope fractionations were measured for the front (δ37Cl −5.1‰) and tail (δ37Cl −1.8‰) segments of partially collected samples. Isolation of individual OCls by pcGC enables accurate off-line chlorine isotope analysis, and thus facilitates the investigation of naturally occurring OCls. [Copyright &y& Elsevier]