Carbon and Chlorine Isotope Analysis to Identify Abiotic Degradation Pathways of 1,1,1-Trichloroethane

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Centre for Hydrogeology and Geothermics, University of Neuchâtel, Neuchâtel CH-2000, Switzerland
Department of Earth and Environmental Sciences, University of Waterloo, Waterloo N2L 3G1, Canada
§ Isotope Tracer Technologies Inc., Waterloo, Ontario, Canada N2V 1Z5
*Jordi Palau. Address: Centre d’Hydrogéologie et de Géothermie, Université de Neuchâtel, Rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland. E-mail: [email protected]
Cite this: Environ. Sci. Technol. 2014, 48, 24, 14400–14408
Publication Date (Web):November 7, 2014
https://doi.org/10.1021/es504252z
Copyright © 2014 American Chemical Society
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Abstract

This study investigates dual C–Cl isotope fractionation during 1,1,1-TCA transformation by heat-activated persulfate (PS), hydrolysis/dehydrohalogenation (HY/DH) and Fe(0). Compound-specific chlorine isotope analysis of 1,1,1-TCA was performed for the first time, and transformation-associated isotope fractionation εbulkC and εbulkCl values were −4.0 ± 0.2‰ and no chlorine isotope fractionation with PS, −1.6 ± 0.2‰ and −4.7 ± 0.1‰ for HY/DH, −7.8 ± 0.4‰ and −5.2 ± 0.2‰ with Fe(0). Distinctly different dual isotope slopes (Δδ13C/Δδ37Cl): ∞ with PS, 0.33 ± 0.04 for HY/DH and 1.5 ± 0.1 with Fe(0) highlight the potential of this approach to identify abiotic degradation pathways of 1,1,1-TCA in the field. The trend observed with PS agreed with a C–H bond oxidation mechanism in the first reaction step. For HY/DH and Fe(0) pathways, different slopes were obtained although both pathways involve cleavage of a C–Cl bond in their initial reaction step. In contrast to the expected larger primary carbon isotope effects relative to chlorine for C–Cl bond cleavage, εbulkC < εbulkCl was observed for HY/DH and in a similar range for reduction by Fe(0), suggesting the contribution of secondary chlorine isotope effects. Therefore, different magnitude of secondary chlorine isotope effects could at least be partly responsible for the distinct slopes between HY/DH and Fe(0) pathways. Following this dual isotope approach, abiotic transformation processes can unambiguously be identified and quantified.

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Further information about experiment setup details, analytical methods, reaction kinetics, Rayleigh isotope plots (Figure S1), calculation of product carbon isotope fractionation trends and AKIEs (Tables S1 and S2), estimation of 13C-AKIE for HY/DH of 1,1,1-TCA via SN2/E2 mechanisms and degradation pathway for reaction of 1,1,1-TCA with Fe(0) (Scheme S1). This material is available free of charge via the Internet at http://pubs.acs.org.

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