Dual Carbon–Chlorine Stable Isotope Investigation of Sources and Fate of Chlorinated Ethenes in Contaminated Groundwater

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 (ε_C) 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 <i>cis</i>-dichloroethene was not further dechlorinated. Furthermore, the 2D-CSIA approach allowed estimation of Cl isotope enrichment factors ε_Cl (−7.8 to −0.8‰) and characteristic ε_Cl/ε_C 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