4.6 Article

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

期刊

MOLECULES
卷 19, 期 5, 页码 6450-6473

出版社

MDPI AG
DOI: 10.3390/molecules19056450

关键词

reductive dehalogenation; chlorinated ethenes; trichloroethene; biodegradation; organohalide respiration; dechlorination mechanism; regioselectivity; vitamin B-12; reductive dehalogenase

资金

  1. German Research Foundation (DFG) [EL 266/3-1]
  2. Initiative and Networking Fund of the Helmholtz Association
  3. Minerva Foundation, Max-Planck-Gesellschaft

向作者/读者索取更多资源

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 parts per thousand +/- 0.9 parts per thousand (PCE) and -12.2 parts per thousand +/- 1.0 parts per thousand (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 parts per thousand +/- 0.1 parts per thousand) and TCE (-3.6 parts per thousand +/- 0.2 parts per thousand). 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 parts per thousand +/- 1.4 parts per thousand (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4 parts per thousand +/- 0.3 parts per thousand and the product chloride an isotope effect of -6.5 parts per thousand +/- 2.5 parts per thousand, 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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