Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane

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 isotop...

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Detalles Bibliográficos
Autores: Palau, Jordi, Shouakar-Stash, O., Hunkeler, D.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2014
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/163717
Acceso en línea:https://hdl.handle.net/2445/163717
Access Level:acceso abierto
Palabra clave:Isòtops de carboni
Clor
Carbon isotopes
Chlorine
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repository_id_str
spelling Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethanePalau, JordiShouakar-Stash, O.Hunkeler, D.Isòtops de carboniClorCarbon isotopesChlorineThis 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 ε_bulk^C and ε_bulk^Cl 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, ε_bulk^C<ε_bulk^Cl 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.American Chemical Society2014info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/163717Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésVersió postprint del document publicat a: https://doi.org/10.1021/es504252zEnvironmental Science & Technology, 2014, vol. 48, num. 24, p. 14400-14408https://doi.org/10.1021/es504252z(c) American Chemical Society , 2014info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1637172026-05-27T06:46:51Z
dc.title.none.fl_str_mv Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane
title Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane
spellingShingle Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane
Palau, Jordi
Isòtops de carboni
Clor
Carbon isotopes
Chlorine
title_short Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane
title_full Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane
title_fullStr Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane
title_full_unstemmed Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane
title_sort Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane
dc.creator.none.fl_str_mv Palau, Jordi
Shouakar-Stash, O.
Hunkeler, D.
author Palau, Jordi
author_facet Palau, Jordi
Shouakar-Stash, O.
Hunkeler, D.
author_role author
author2 Shouakar-Stash, O.
Hunkeler, D.
author2_role author
author
dc.subject.none.fl_str_mv Isòtops de carboni
Clor
Carbon isotopes
Chlorine
topic Isòtops de carboni
Clor
Carbon isotopes
Chlorine
description 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 ε_bulk^C and ε_bulk^Cl 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, ε_bulk^C<ε_bulk^Cl 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.
publishDate 2014
dc.date.none.fl_str_mv 2014
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/163717
url https://hdl.handle.net/2445/163717
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1021/es504252z
Environmental Science & Technology, 2014, vol. 48, num. 24, p. 14400-14408
https://doi.org/10.1021/es504252z
dc.rights.none.fl_str_mv (c) American Chemical Society , 2014
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) American Chemical Society , 2014
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.198674

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