Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE) Reductive Dehalogenation
Abstract
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). Thesemore »
- Authors:
-
- 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
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER). Biological Systems Science Division; German Research Foundation (DFG)
- OSTI Identifier:
- 1628475
- Grant/Contract Number:
- AC05-00OR22725; EL 266/3-1
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Molecules
- Additional Journal Information:
- Journal Volume: 19; Journal Issue: 5; Journal ID: ISSN 1420-3049
- Publisher:
- MDPI
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 54 ENVIRONMENTAL SCIENCES; 59 BASIC BIOLOGICAL SCIENCES; Biochemistry & Molecular Biology; Chemistry; reductive dehalogenation; chlorinated ethenes; trichloroethene; biodegradation; organohalide respiration; dechlorination mechanism; regioselectivity; vitamin B12; reductive dehalogenase
Citation Formats
Cretnik, Stefan, Bernstein, Anat, Shouakar-Stash, Orfan, Löffler, Frank, and Elsner, Martin. Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE) Reductive Dehalogenation. United States: N. p., 2014.
Web. doi:10.3390/molecules19056450.
Cretnik, Stefan, Bernstein, Anat, Shouakar-Stash, Orfan, Löffler, Frank, & Elsner, Martin. Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE) Reductive Dehalogenation. United States. https://doi.org/10.3390/molecules19056450
Cretnik, Stefan, Bernstein, Anat, Shouakar-Stash, Orfan, Löffler, Frank, and Elsner, Martin. Tue .
"Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE) Reductive Dehalogenation". United States. https://doi.org/10.3390/molecules19056450. https://www.osti.gov/servlets/purl/1628475.
@article{osti_1628475,
title = {Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE) Reductive Dehalogenation},
author = {Cretnik, Stefan and Bernstein, Anat and Shouakar-Stash, Orfan and Löffler, Frank and Elsner, Martin},
abstractNote = {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.},
doi = {10.3390/molecules19056450},
journal = {Molecules},
number = 5,
volume = 19,
place = {United States},
year = {Tue May 20 00:00:00 EDT 2014},
month = {Tue May 20 00:00:00 EDT 2014}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Anaerobic Microbial Dehalogenation
journal, October 2004
- Smidt, Hauke; de Vos, Willem M.
- Annual Review of Microbiology, Vol. 58, Issue 1
Evidence for the Formation of a cis -Dichlorovinyl Anion upon Reduction of cis- 1,2-Dichlorovinyl(pyridine)cobaloxime
journal, March 2006
- Follett, Angela D.; McNeill, Kristopher
- Inorganic Chemistry, Vol. 45, Issue 6
Enhanced Degradation of Halogenated Aliphatics by Zero-Valent Iron
journal, November 1994
- Gillham, Robert W.; O'Hannesin, Stephanie F.
- Ground Water, Vol. 32, Issue 6
3D-CSIA: Carbon, Chlorine, and Hydrogen Isotope Fractionation in Transformation of TCE to Ethene by a Dehalococcoides Culture
journal, August 2013
- Kuder, Tomasz; van Breukelen, Boris M.; Vanderford, Mindy
- Environmental Science & Technology, Vol. 47, Issue 17
Bacterial dehalorespiration with chlorinated benzenes
journal, November 2000
- Adrian, Lorenz; Szewzyk, Ulrich; Wecke, Jörg
- Nature, Vol. 408, Issue 6812
A New Concept Linking Observable Stable Isotope Fractionation to Transformation Pathways of Organic Pollutants
journal, September 2005
- Elsner, Martin; Zwank, Luc; Hunkeler, Daniel
- Environmental Science & Technology, Vol. 39, Issue 18
Carbon and Chlorine Isotope Fractionation During Microbial Degradation of Tetra- and Trichloroethene
journal, May 2013
- Wiegert, Charline; Mandalakis, Manolis; Knowles, Tim
- Environmental Science & Technology, Vol. 47, Issue 12
Corrinoid-Mediated Reduction of Tetrachloroethene, Trichloroethene, and Trichlorofluoroethene in Homogeneous Aqueous Solution: Reaction Kinetics and Reaction Mechanisms
journal, January 1997
- Glod, Guy; Angst, Werner; Holliger, Christof
- Environmental Science & Technology, Vol. 31, Issue 1
Characterization of Co−C Bonding in Dichlorovinylcobaloxime Complexes
journal, March 2007
- Follett, Angela D.; McNabb, Katherine A.; Peterson, Alicia A.
- Inorganic Chemistry, Vol. 46, Issue 5
Detoxification of vinyl chloride to ethene coupled to growth of an anaerobic bacterium
journal, July 2003
- He, Jianzhong; Ritalahti, Kirsti M.; Yang, Kun-Lin
- Nature, Vol. 424, Issue 6944
Carbon and Chlorine Isotope Fractionation during Aerobic Oxidation and Reductive Dechlorination of Vinyl Chloride and cis -1,2-Dichloroethene
journal, November 2008
- Abe, Y.; Aravena, R.; Zopfi, J.
- Environmental Science & Technology, Vol. 43, Issue 1
High-Precision Simultaneous Determination of Multiple Small Kinetic Isotope Effects at Natural Abundance
journal, September 1995
- Singleton, Daniel A.; Thomas, Allen A.
- Journal of the American Chemical Society, Vol. 117, Issue 36
Dechlorination of chloroethylenes by cob(i)alamin and cobalamin model complexes
journal, January 2008
- Kliegman, Sarah; McNeill, Kristopher
- Dalton Transactions, Issue 32
Chlorine Kinetic Isotope Effects on Enzymatic Dehalogenations
journal, February 2003
- Paneth, Piotr
- Accounts of Chemical Research, Vol. 36, Issue 2
Reductive Dechlorination of Trichloroethylene: A Computational Study
journal, September 2002
- Nonnenberg, Christel; van der Donk, Wilfred A.; Zipse, Hendrik
- The Journal of Physical Chemistry A, Vol. 106, Issue 37
Experimental Evaluation and Mathematical Modeling of Microbially Enhanced Tetrachloroethene (PCE) Dissolution
journal, February 2007
- Amos, Benjamin K.; Christ, John A.; Abriola, Linda M.
- Environmental Science & Technology, Vol. 41, Issue 3
Compound-specific chlorine isotope ratios of TCE, PCE and DCE isomers by direct injection using CF-IRMS
journal, May 2006
- Shouakar-Stash, Orfan; Drimmie, Robert J.; Zhang, Min
- Applied Geochemistry, Vol. 21, Issue 5
Synthesizing Nanoscale Iron Particles for Rapid and Complete Dechlorination of TCE and PCBs
journal, July 1997
- Wang, Chuan-Bao; Zhang, Wei-xian
- Environmental Science & Technology, Vol. 31, Issue 7
Reductive Dechlorination of TCE by Chemical Model Systems in Comparison to Dehalogenating Bacteria: Insights from Dual Element Isotope Analysis ( 13 C/ 12 C, 37 Cl/ 35 Cl)
journal, May 2013
- Cretnik, Stefan; Thoreson, Kristen A.; Bernstein, Anat
- Environmental Science & Technology, Vol. 47, Issue 13
Stable isotope fractionation to investigate natural transformation mechanisms of organic contaminants: principles, prospects and limitations
journal, January 2010
- Elsner, Martin
- Journal of Environmental Monitoring, Vol. 12, Issue 11
On the Intermediacy of Chlorinated Alkylcobalt Complexes in the Reductive Dehalogenation of Chloroalkenes. A First-Principles Molecular Dynamics Study
journal, October 2007
- Bühl, Michael; Golubnychiy, Volodymyr
- Organometallics, Vol. 26, Issue 25
Modeling Chlorine Isotope Trends during Sequential Transformation of Chlorinated Ethenes
journal, September 2009
- Hunkeler, Daniel; Van Breukelen, Boris M.; Elsner, Martin
- Environmental Science & Technology, Vol. 43, Issue 17
Direct Investigation of Covalently Bound Chlorine in Organic Compounds by Solid-State 35 Cl NMR Spectroscopy and Exact Spectral Line-Shape Simulations
journal, March 2012
- Perras, Frédéric A.; Bryce, David L.
- Angewandte Chemie International Edition, Vol. 51, Issue 17
Chloroform respiration to dichloromethane by a Dehalobacter population: Growth-linked reductive dechlorination of chloroform
journal, January 2010
- Grostern, Ariel; Duhamel, Melanie; Dworatzek, Sandra
- Environmental Microbiology, Vol. 12, Issue 4
Evaluating Chlorine Isotope Effects from Isotope Ratios and Mass Spectra of Polychlorinated Molecules
journal, May 2008
- Elsner, Martin; Hunkeler, Daniel
- Analytical Chemistry, Vol. 80, Issue 12
Reductive dechlorination in the energy metabolism of anaerobic bacteria
journal, December 1998
- Holliger, Christof; Wohlfarth, Gert; Diekert, Gabriele
- FEMS Microbiology Reviews, Vol. 22, Issue 5
Reductive Transformation of Trichloroethene by Cobalamin: Reactivities of the Intermediates Acetylene, Chloroacetylene, and the DCE Isomers
journal, May 1998
- Semadeni, Marco; Chiu, Pei-Chun; Reinhard, Martin
- Environmental Science & Technology, Vol. 32, Issue 9
Naturally Occurring Organohalogen Compounds †
journal, March 1998
- Gribble, Gordon W.
- Accounts of Chemical Research, Vol. 31, Issue 3
Synthesis and Characterization of Chlorinated Alkenylcobaloximes To Probe the Mechanism of Vitamin B 12 -Catalyzed Dechlorination of Priority Pollutants
journal, January 2002
- McCauley, Kevin M.; Wilson, Scott R.; van der Donk, Wilfred A.
- Inorganic Chemistry, Vol. 41, Issue 2
On the role of alkylcobalamins in the vitamin B 12 -catalyzed reductive dehalogenation of perchloroethylene and trichloroethylene
journal, January 2006
- Pratt, Derek A.; van der Donk, Wilfred A.
- Chem. Commun., Issue 5
Geobacter lovleyi sp. nov. Strain SZ, a Novel Metal-Reducing and Tetrachloroethene-Dechlorinating Bacterium
journal, April 2006
- Sung, Y.; Fletcher, K. E.; Ritalahti, K. M.
- Applied and Environmental Microbiology, Vol. 72, Issue 4
Reduction of Trichloroethylene by Outer-Sphere Electron-Transfer Agents
journal, January 2005
- Follett, Angela D.; McNeill, Kristopher
- Journal of the American Chemical Society, Vol. 127, Issue 3
Reconciling Disparate Models of the Involvement of Vinyl Radicals in Cobalamin-Mediated Dechlorination Reactions
journal, October 2009
- Kliegman, Sarah; McNeill, Kristopher
- Environmental Science & Technology, Vol. 43, Issue 23
Anaerobic Microbial Reductive Dechlorination of Tetrachloroethene to Predominately trans -1,2-Dichloroethene
journal, August 2004
- Griffin, Benjamin M.; Tiedje, James M.; Löffler, Frank E.
- Environmental Science & Technology, Vol. 38, Issue 16
Direct Investigation of Covalently Bound Chlorine in Organic Compounds by Solid-State 35 Cl NMR Spectroscopy and Exact Spectral Line-Shape Simulations
journal, March 2012
- Perras, Frédéric A.; Bryce, David L.
- Angewandte Chemie, Vol. 124, Issue 17
Compound-specific chlorine isotope ratios of TCE, PCE and DCE isomers by direct injection using CF-IRMS
journal, May 2006
- Shouakar-Stash, Orfan; Drimmie, Robert J.; Zhang, Min
- Applied Geochemistry, Vol. 21, Issue 5
Redox chemistry of cobalamin and iron-sulfur cofactors in the tetrachloroethene reductase of Dehalobacter restrictus
journal, June 1997
- Schumacher, Wolfram; Holliger, Christof; Zehnder, Alexander J. B.
- FEBS Letters, Vol. 409, Issue 3
Evaluating Chlorine Isotope Effects from Isotope Ratios and Mass Spectra of Polychlorinated Molecules
journal, May 2008
- Elsner, Martin; Hunkeler, Daniel
- Analytical Chemistry, Vol. 80, Issue 12
Chlorine Kinetic Isotope Effects on Enzymatic Dehalogenations
journal, February 2003
- Paneth, Piotr
- Accounts of Chemical Research, Vol. 36, Issue 2
Naturally Occurring Organohalogen Compounds †
journal, March 1998
- Gribble, Gordon W.
- Accounts of Chemical Research, Vol. 31, Issue 3
A New Concept Linking Observable Stable Isotope Fractionation to Transformation Pathways of Organic Pollutants
journal, September 2005
- Elsner, Martin; Zwank, Luc; Hunkeler, Daniel
- Environmental Science & Technology, Vol. 39, Issue 18
Experimental Evaluation and Mathematical Modeling of Microbially Enhanced Tetrachloroethene (PCE) Dissolution
journal, February 2007
- Amos, Benjamin K.; Christ, John A.; Abriola, Linda M.
- Environmental Science & Technology, Vol. 41, Issue 3
Carbon and Chlorine Isotope Fractionation During Microbial Degradation of Tetra- and Trichloroethene
journal, May 2013
- Wiegert, Charline; Mandalakis, Manolis; Knowles, Tim
- Environmental Science & Technology, Vol. 47, Issue 12
Reductive Dechlorination of TCE by Chemical Model Systems in Comparison to Dehalogenating Bacteria: Insights from Dual Element Isotope Analysis ( 13 C/ 12 C, 37 Cl/ 35 Cl)
journal, May 2013
- Cretnik, Stefan; Thoreson, Kristen A.; Bernstein, Anat
- Environmental Science & Technology, Vol. 47, Issue 13
Carbon and Chlorine Isotope Fractionation during Aerobic Oxidation and Reductive Dechlorination of Vinyl Chloride and cis -1,2-Dichloroethene
journal, November 2008
- Abe, Y.; Aravena, R.; Zopfi, J.
- Environmental Science & Technology, Vol. 43, Issue 1
Modeling Chlorine Isotope Trends during Sequential Transformation of Chlorinated Ethenes
journal, September 2009
- Hunkeler, Daniel; Van Breukelen, Boris M.; Elsner, Martin
- Environmental Science & Technology, Vol. 43, Issue 17
Reconciling Disparate Models of the Involvement of Vinyl Radicals in Cobalamin-Mediated Dechlorination Reactions
journal, October 2009
- Kliegman, Sarah; McNeill, Kristopher
- Environmental Science & Technology, Vol. 43, Issue 23
Corrinoid-Mediated Reduction of Tetrachloroethene, Trichloroethene, and Trichlorofluoroethene in Homogeneous Aqueous Solution: Reaction Kinetics and Reaction Mechanisms
journal, January 1997
- Glod, Guy; Angst, Werner; Holliger, Christof
- Environmental Science & Technology, Vol. 31, Issue 1
Reductive Transformation of Trichloroethene by Cobalamin: Reactivities of the Intermediates Acetylene, Chloroacetylene, and the DCE Isomers
journal, May 1998
- Semadeni, Marco; Chiu, Pei-Chun; Reinhard, Martin
- Environmental Science & Technology, Vol. 32, Issue 9
Synthesis and Characterization of Chlorinated Alkenylcobaloximes To Probe the Mechanism of Vitamin B 12 -Catalyzed Dechlorination of Priority Pollutants
journal, January 2002
- McCauley, Kevin M.; Wilson, Scott R.; van der Donk, Wilfred A.
- Inorganic Chemistry, Vol. 41, Issue 2
Evidence for the Formation of a cis -Dichlorovinyl Anion upon Reduction of cis- 1,2-Dichlorovinyl(pyridine)cobaloxime
journal, March 2006
- Follett, Angela D.; McNeill, Kristopher
- Inorganic Chemistry, Vol. 45, Issue 6
Characterization of Co−C Bonding in Dichlorovinylcobaloxime Complexes
journal, March 2007
- Follett, Angela D.; McNabb, Katherine A.; Peterson, Alicia A.
- Inorganic Chemistry, Vol. 46, Issue 5
High-Precision Simultaneous Determination of Multiple Small Kinetic Isotope Effects at Natural Abundance
journal, September 1995
- Singleton, Daniel A.; Thomas, Allen A.
- Journal of the American Chemical Society, Vol. 117, Issue 36
Reduction of Trichloroethylene by Outer-Sphere Electron-Transfer Agents
journal, January 2005
- Follett, Angela D.; McNeill, Kristopher
- Journal of the American Chemical Society, Vol. 127, Issue 3
Reductive Dechlorination of Trichloroethylene: A Computational Study
journal, September 2002
- Nonnenberg, Christel; van der Donk, Wilfred A.; Zipse, Hendrik
- The Journal of Physical Chemistry A, Vol. 106, Issue 37
On the Intermediacy of Chlorinated Alkylcobalt Complexes in the Reductive Dehalogenation of Chloroalkenes. A First-Principles Molecular Dynamics Study
journal, October 2007
- Bühl, Michael; Golubnychiy, Volodymyr
- Organometallics, Vol. 26, Issue 25
Bacterial dehalorespiration with chlorinated benzenes
journal, November 2000
- Adrian, Lorenz; Szewzyk, Ulrich; Wecke, Jörg
- Nature, Vol. 408, Issue 6812
Detoxification of vinyl chloride to ethene coupled to growth of an anaerobic bacterium
journal, July 2003
- He, Jianzhong; Ritalahti, Kirsti M.; Yang, Kun-Lin
- Nature, Vol. 424, Issue 6944
On the role of alkylcobalamins in the vitamin B 12 -catalyzed reductive dehalogenation of perchloroethylene and trichloroethylene
journal, January 2006
- Pratt, Derek A.; van der Donk, Wilfred A.
- Chem. Commun., Issue 5
Dechlorination of chloroethylenes by cob(i)alamin and cobalamin model complexes
journal, January 2008
- Kliegman, Sarah; McNeill, Kristopher
- Dalton Transactions, Issue 32
Stable isotope fractionation to investigate natural transformation mechanisms of organic contaminants: principles, prospects and limitations
journal, January 2010
- Elsner, Martin
- Journal of Environmental Monitoring, Vol. 12, Issue 11
Enhanced Degradation of Halogenated Aliphatics by Zero-Valent Iron
journal, November 1994
- Gillham, Robert W.; O'Hannesin, Stephanie F.
- Ground Water, Vol. 32, Issue 6
Works referencing / citing this record:
Use of Compound-Specific Isotope Analysis (CSIA) to Assess the Origin and Fate of Chlorinated Hydrocarbons
book, January 2016
- Hunkeler, Daniel
- Organohalide-Respiring Bacteria
Multi-element (C, H, Cl, Br) stable isotope fractionation as a tool to investigate transformation processes for halogenated hydrocarbons
journal, January 2020
- Ojeda, Ann Sullivan; Phillips, Elizabeth; Sherwood Lollar, Barbara
- Environmental Science: Processes & Impacts, Vol. 22, Issue 3
Evaluation of the Microbial Reductive Dehalogenation Reaction Using Compound-Specific Stable Isotope Analysis (CSIA)
book, January 2016
- Renpenning, Julian; Nijenhuis, Ivonne
- Organohalide-Respiring Bacteria
Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene
journal, September 2017
- Van Breukelen, Boris M.; Thouement, Héloïse A. A.; Stack, Philip E.
- Journal of Contaminant Hydrology, Vol. 204
Expanded uncertainty associated with determination of isotope enrichment factors: Comparison of two point calculation and Rayleigh-plot
journal, January 2018
- Julien, Maxime; Gilbert, Alexis; Yamada, Keita
- Talanta, Vol. 176