Carbon and Chlorine Isotope Fractionation Patterns Associated with Different Engineered Chloroform Transformation Reactions

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Centre for Hydrogeology and Geothermics, Université de Neuchâtel, 2000 Neuchâtel, Switzerland
Grup de Mineralogia Aplicada i Geoquímica de Fluids, Departament de Mineralogia, Petrologia i Geologia Aplicada, Facultat de Ciències de la Terra, Martí Franques s/n, Universitat de Barcelona (UB), 08028 Barcelona, Spain
§ Institute of Groundwater Ecology, Helmholtz Zentrum München, 85764 Neuherberg, Germany
Chair of Analytical Chemistry and Water Chemistry, Technical University of Munich, Marchioninistrasse 17, D-81377 Munich, Germany
*Phone: +41 32 718 26 49; fax: +41 32 718 26 03; e-mail: [email protected]
Cite this: Environ. Sci. Technol. 2017, 51, 11, 6174–6184
Publication Date (Web):May 9, 2017
https://doi.org/10.1021/acs.est.7b00679
Copyright © 2017 American Chemical Society
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Abstract

To use compound-specific isotope analysis for confidently assessing organic contaminant attenuation in the environment, isotope fractionation patterns associated with different transformation mechanisms must first be explored in laboratory experiments. To deliver this information for the common groundwater contaminant chloroform (CF), this study investigated for the first time both carbon and chlorine isotope fractionation for three different engineered reactions: oxidative C–H bond cleavage using heat-activated persulfate, transformation under alkaline conditions (pH ∼ 12) and reductive C–Cl bond cleavage by cast zerovalent iron, Fe(0). Carbon and chlorine isotope fractionation values were −8 ± 1‰ and −0.44 ± 0.06‰ for oxidation, −57 ± 5‰ and −4.4 ± 0.4‰ for alkaline hydrolysis (pH 11.84 ± 0.03), and −33 ± 11‰ and −3 ± 1‰ for dechlorination, respectively. Carbon and chlorine apparent kinetic isotope effects (AKIEs) were in general agreement with expected mechanisms (C–H bond cleavage in oxidation by persulfate, C–Cl bond cleavage in Fe(0)-mediated reductive dechlorination and E1CB elimination mechanism during alkaline hydrolysis) where a secondary AKIECl (1.00045 ± 0.00004) was observed for oxidation. The different dual carbon-chlorine (Δδ13C vs Δδ37Cl) isotope patterns for oxidation by thermally activated persulfate and alkaline hydrolysis (17 ± 2 and 13.0 ± 0.8, respectively) vs reductive dechlorination by Fe(0) (8 ± 2) establish a base to identify and quantify these CF degradation mechanisms in the field.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.7b00679.

  • Chemicals; analytical methods; further discussion in kinetics; calculation of AKIE values; calculation of isotope trend for DCM in the Fe(0) experiment; carbon and chlorine isotope fractionation patterns; further discussion in reaction pathways; comparison of ε and AKIE values for C and Cl isotopes in different studies (PDF)

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