Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE) Reductive Dehalogenation

Cretnik, Stefan; Bernstein, Anat; Shouakar-Stash, Orfan; Löffler, Frank; Elsner, Martin

doi:10.3390/molecules19056450

Title: Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE) Reductive Dehalogenation

Journal Article · Tue May 20 00:00:00 EDT 2014 · Molecules

DOI:https://doi.org/10.3390/molecules19056450· OSTI ID:1628475

Cretnik, Stefan ^[1]; Bernstein, Anat ^[1]; Shouakar-Stash, Orfan ^[2]; Löffler, Frank ^[3]; Elsner, Martin ^[1]

Helmholtz Zentrum München, Neuherberg (Germany). Inst. of Groundwater Ecology
Univ. of Waterloo, ON (Canada). Dept. of Earth and Environmental Sciences
Univ. of Tennessee, Knoxville, TN (United States). Center for Environmental Biotechnology. Dept. of Microbiology; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Civil and Environmental Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Inst. for Biological Sciences (JIBS) and Bioscience Division

Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER). Biological Systems Science Division; German Research Foundation (DFG)

Grant/Contract Number:: AC05-00OR22725; EL 266/3-1

OSTI ID:: 1628475

Journal Information:: Molecules, Vol. 19, Issue 5; ISSN 1420-3049

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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Use of Compound-Specific Isotope Analysis (CSIA) to Assess the Origin and Fate of Chlorinated Hydrocarbons Hunkeler, Daniel Organohalide-Respiring Bacteria https://doi.org/10.1007/978-3-662-49875-0_25	book	January 2016
Multi-element (C, H, Cl, Br) stable isotope fractionation as a tool to investigate transformation processes for halogenated hydrocarbons Ojeda, Ann Sullivan; Phillips, Elizabeth; Sherwood Lollar, Barbara Environmental Science: Processes & Impacts, Vol. 22, Issue 3 https://doi.org/10.1039/c9em00498j	journal	January 2020
Evaluation of the Microbial Reductive Dehalogenation Reaction Using Compound-Specific Stable Isotope Analysis (CSIA) Renpenning, Julian; Nijenhuis, Ivonne Organohalide-Respiring Bacteria https://doi.org/10.1007/978-3-662-49875-0_18	book	January 2016
Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene Van Breukelen, Boris M.; Thouement, Héloïse A. A.; Stack, Philip E. Journal of Contaminant Hydrology, Vol. 204 https://doi.org/10.1016/j.jconhyd.2017.07.003	journal	September 2017
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54 ENVIRONMENTAL SCIENCES
59 BASIC BIOLOGICAL SCIENCES
Biochemistry & Molecular Biology
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reductive dehalogenation
chlorinated ethenes
trichloroethene
biodegradation
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dechlorination mechanism
regioselectivity
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reductive dehalogenase

Title: Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE) Reductive Dehalogenation

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