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
Copyright © 2014 American Chemical Society
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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

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  12. Patrick Höhener, Gwenaël Imfeld. Quantification of Lambda (Λ) in multi-elemental compound-specific isotope analysis. Chemosphere 2021, 267 , 129232.
  13. Berhane Abrha Asfaw, Kaori Sakaguchi‐Söder, Anat Bernstein, Hagar Siebner, Christoph Schüth. Optimization of compound‐specific chlorine stable isotope analysis of chloroform using the Taguchi design of experiments. Rapid Communications in Mass Spectrometry 2020, 34 (23)
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  16. Jeremy Zimmermann, Landon J.S. Halloran, Daniel Hunkeler. Tracking chlorinated contaminants in the subsurface using compound-specific chlorine isotope analysis: A review of principles, current challenges and applications. Chemosphere 2020, 244 , 125476.
  17. Ann Sullivan Ojeda, Elizabeth Phillips, Barbara Sherwood Lollar. Multi-element (C, H, Cl, Br) stable isotope fractionation as a tool to investigate transformation processes for halogenated hydrocarbons. Environmental Science: Processes & Impacts 2020, 22 (3) , 567-582.
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  19. Wenbing Wang, Yanqing Wu. Sequential coupling of bio-augmented permeable reactive barriers for remediation of 1,1,1-trichloroethane contaminated groundwater. Environmental Science and Pollution Research 2019, 26 (12) , 12042-12054.
  20. Dan Zhang, Langping Wu, Jun Yao, Carsten Vogt, Hans-Hermann Richnow. Carbon and hydrogen isotopic fractionation during abiotic hydrolysis and aerobic biodegradation of phthalate esters. Science of The Total Environment 2019, 660 , 559-566.
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  22. Felipe M. Solano, Massimo Marchesi, Neil R. Thomson, Daniel Bouchard, Ramon Aravena. Carbon and Hydrogen Isotope Fractionation of Benzene, Toluene, and o ‐Xylene during Chemical Oxidation by Persulfate. Groundwater Monitoring & Remediation 2018, 38 (4) , 62-72.
  23. Shuai Chen, Jorge Bedia, Hui Li, Lu Yao Ren, Fauzia Naluswata, Carolina Belver. Nanoscale zero-valent [email protected] hydrated silica core-shell particles with enhanced dispersibility, transportability and degradation of chlorinated aliphatic hydrocarbons. Chemical Engineering Journal 2018, 343 , 619-628.
  24. Massimo Marchesi, Luca Alberti, Orfan Shouakar-Stash, Ilaria Pietrini, Francesca de Ferra, Giovanna Carpani, Ramon Aravena, Andrea Franzetti, Tatiana Stella. 37Cl-compound specific isotope analysis and assessment of functional genes for monitoring monochlorobenzene (MCB) biodegradation under aerobic conditions. Science of The Total Environment 2018, 619-620 , 784-793.
  25. Jie Yang, Liang Meng, Lin Guo. In situ remediation of chlorinated solvent-contaminated groundwater using ZVI/organic carbon amendment in China: field pilot test and full-scale application. Environmental Science and Pollution Research 2018, 25 (6) , 5051-5062.
  26. Daniel Bouchard, Philipp Wanner, Hong Luo, Patrick W. McLoughlin, James K. Henderson, Robert J. Pirkle, Daniel Hunkeler. Optimization of the solvent-based dissolution method to sample volatile organic compound vapors for compound-specific isotope analysis. Journal of Chromatography A 2017, 1520 , 23-34.
  27. Wenbing Wang, Yanqing Wu. Combination of zero-valent iron and anaerobic microorganisms immobilized in luffa sponge for degrading 1,1,1-trichloroethane and the relevant microbial community analysis. Applied Microbiology and Biotechnology 2017, 101 (2) , 783-796.
  28. Patrick Höhener. Simulating stable carbon and chlorine isotope ratios in dissolved chlorinated groundwater pollutants with BIOCHLOR-ISO. Journal of Contaminant Hydrology 2016, 195 , 52-61.
  29. Ivonne Nijenhuis, Hans H Richnow. Stable isotope fractionation concepts for characterizing biotransformation of organohalides. Current Opinion in Biotechnology 2016, 41 , 108-113.
  30. Yevgeni Zakon, Ludwik Halicz, Ovadia Lev, Faina Gelman. Compound-specific bromine isotope ratio analysis using gas chromatography/quadrupole mass spectrometry. Rapid Communications in Mass Spectrometry 2016, 30 (17) , 1951-1956.
  31. Dugin Kaown, Seong-Chun Jun, Rak-Hyeon Kim, Shin Woosik, Kang-Kun Lee. Characterization of a site contaminated by chlorinated ethenes and ethanes using multi-analysis. Environmental Earth Sciences 2016, 75 (9)
  32. Bradley M. Patterson, Matthew Lee, Trevor P. Bastow, John T. Wilson, Michael J. Donn, Andrew Furness, Bryan Goodwin, Mike Manefield. Concentration effects on biotic and abiotic processes in the removal of 1,1,2-trichloroethane and vinyl chloride using carbon-amended ZVI. Journal of Contaminant Hydrology 2016, 188 , 1-11.
  33. Jordi Palau, Pierre Jamin, Alice Badin, Nicolas Vanhecke, Bruno Haerens, Serge Brouyère, Daniel Hunkeler. Use of dual carbon–chlorine isotope analysis to assess the degradation pathways of 1,1,1-trichloroethane in groundwater. Water Research 2016, 92 , 235-243.
  34. Biao Jin, Massimo Rolle. Position-specific isotope modeling of organic micropollutants transformation through different reaction pathways. Environmental Pollution 2016, 210 , 94-103.
  35. Daniel Hunkeler. Use of Compound-Specific Isotope Analysis (CSIA) to Assess the Origin and Fate of Chlorinated Hydrocarbons. 2016,,, 587-617.