Maria Prieto-Espinoza, Laure Malleret, Amandine Durand, Patrick Höhener
{"title":"阐明有机氯农药十氯酮在非生物还原和氧化过程中的去向:动力学、转化产物和 C 与 Cl 同位素分馏","authors":"Maria Prieto-Espinoza, Laure Malleret, Amandine Durand, Patrick Höhener","doi":"10.1021/acs.est.4c04912","DOIUrl":null,"url":null,"abstract":"Pollution of French West Indies (FWI) soils by the organochlorine pesticide chlordecone poses environmental and societal concerns due to its long-term persistence. Assessing chlordecone degradation remains challenging due to analytical constraints to identify transformation products. Here, multielement compound-specific isotope analysis (ME-CSIA) was used to identify changes in stable isotope signatures of chlordecone produced during abiotic transformation reactions under reducing and oxidative conditions. Effective chlordecone transformation was shown in reactions with zerovalent iron (ZVI), vitamin B<sub>12</sub> and sodium sulfide (VSS), alkaline ascorbic acid (AA), and sodium persulfate activated by microwave irradiation (MWPS). Significant enrichment of <sup>13</sup>C and <sup>37</sup>Cl was observed in all abiotic reactions, with ε<sub>C,bulk</sub> and ε<sub>Cl,bulk</sub> values ranging from −4.3 ± 0.4‰ to −2.3 ± 0.2‰ and from −2.6 ± 0.4‰ to −1.3 ± 0.3‰, respectively. Distinct mechanisms were evidenced in dual isotope plots, resulting in Λ values of 1.17 ± 0.28 for ZVI, 1.26 ± 0.50 for VSS, 2.06 ± 0.30 for AA, and 2.90 ± 0.50 for MWPS. Two major products were formed, 10-monohydrochlordecone and 8-monohydrochlordecone. Cl-CSIA data suggested that the first Cl substitution at the C<sub>10</sub>-position likely produced secondary Cl isotope effects (via nucleophilic substitution). Overall, results suggest that ME-CSIA can help quantify <i>in situ</i> chlordecone degradation, distinguishing between different ongoing degradation mechanisms and fingerprinting pollutant sources from chlordecone formulations (Curlone).","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":null,"pages":null},"PeriodicalIF":10.8000,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Elucidating the Fate of the Organochlorine Pesticide Chlordecone under Abiotic Reductive and Oxidative Processes: Kinetics, Transformation Products, and C vs Cl Isotope Fractionation\",\"authors\":\"Maria Prieto-Espinoza, Laure Malleret, Amandine Durand, Patrick Höhener\",\"doi\":\"10.1021/acs.est.4c04912\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Pollution of French West Indies (FWI) soils by the organochlorine pesticide chlordecone poses environmental and societal concerns due to its long-term persistence. Assessing chlordecone degradation remains challenging due to analytical constraints to identify transformation products. Here, multielement compound-specific isotope analysis (ME-CSIA) was used to identify changes in stable isotope signatures of chlordecone produced during abiotic transformation reactions under reducing and oxidative conditions. Effective chlordecone transformation was shown in reactions with zerovalent iron (ZVI), vitamin B<sub>12</sub> and sodium sulfide (VSS), alkaline ascorbic acid (AA), and sodium persulfate activated by microwave irradiation (MWPS). Significant enrichment of <sup>13</sup>C and <sup>37</sup>Cl was observed in all abiotic reactions, with ε<sub>C,bulk</sub> and ε<sub>Cl,bulk</sub> values ranging from −4.3 ± 0.4‰ to −2.3 ± 0.2‰ and from −2.6 ± 0.4‰ to −1.3 ± 0.3‰, respectively. Distinct mechanisms were evidenced in dual isotope plots, resulting in Λ values of 1.17 ± 0.28 for ZVI, 1.26 ± 0.50 for VSS, 2.06 ± 0.30 for AA, and 2.90 ± 0.50 for MWPS. Two major products were formed, 10-monohydrochlordecone and 8-monohydrochlordecone. Cl-CSIA data suggested that the first Cl substitution at the C<sub>10</sub>-position likely produced secondary Cl isotope effects (via nucleophilic substitution). 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Elucidating the Fate of the Organochlorine Pesticide Chlordecone under Abiotic Reductive and Oxidative Processes: Kinetics, Transformation Products, and C vs Cl Isotope Fractionation
Pollution of French West Indies (FWI) soils by the organochlorine pesticide chlordecone poses environmental and societal concerns due to its long-term persistence. Assessing chlordecone degradation remains challenging due to analytical constraints to identify transformation products. Here, multielement compound-specific isotope analysis (ME-CSIA) was used to identify changes in stable isotope signatures of chlordecone produced during abiotic transformation reactions under reducing and oxidative conditions. Effective chlordecone transformation was shown in reactions with zerovalent iron (ZVI), vitamin B12 and sodium sulfide (VSS), alkaline ascorbic acid (AA), and sodium persulfate activated by microwave irradiation (MWPS). Significant enrichment of 13C and 37Cl was observed in all abiotic reactions, with εC,bulk and εCl,bulk values ranging from −4.3 ± 0.4‰ to −2.3 ± 0.2‰ and from −2.6 ± 0.4‰ to −1.3 ± 0.3‰, respectively. Distinct mechanisms were evidenced in dual isotope plots, resulting in Λ values of 1.17 ± 0.28 for ZVI, 1.26 ± 0.50 for VSS, 2.06 ± 0.30 for AA, and 2.90 ± 0.50 for MWPS. Two major products were formed, 10-monohydrochlordecone and 8-monohydrochlordecone. Cl-CSIA data suggested that the first Cl substitution at the C10-position likely produced secondary Cl isotope effects (via nucleophilic substitution). Overall, results suggest that ME-CSIA can help quantify in situ chlordecone degradation, distinguishing between different ongoing degradation mechanisms and fingerprinting pollutant sources from chlordecone formulations (Curlone).
期刊介绍:
Environmental Science & Technology (ES&T) is a co-sponsored academic and technical magazine by the Hubei Provincial Environmental Protection Bureau and the Hubei Provincial Academy of Environmental Sciences.
Environmental Science & Technology (ES&T) holds the status of Chinese core journals, scientific papers source journals of China, Chinese Science Citation Database source journals, and Chinese Academic Journal Comprehensive Evaluation Database source journals. This publication focuses on the academic field of environmental protection, featuring articles related to environmental protection and technical advancements.