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甲氧滴滴涕在受污染含水层中的归宿与降解:来自碳 - 氯双同位素分析和异构体分馏的见解

Fate and degradation of methoxychlor in a contaminated aquifer: Insights from dual carbon-chlorine isotope analysis and isomeric fraction.

作者信息

Vinyes-Nadal Martí, Gil-Villalba Sergio, Rosell Mònica, Soler Albert, Otero Neus, Torrentó Clara

机构信息

Grup MAiMA, SGR Mineralogia Aplicada, Geoquímica i Hidrogeologia (MAGH), Departament de Mineralogia, Petrologia i Geologia Aplicada, Facultat de Ciències de la Terra, Institut de Recerca de l'Aigua (IdRA), Universitat de Barcelona (UB), Martí i Franquès s/n, Barcelona 08028, Spain.

Grup MAiMA, SGR Mineralogia Aplicada, Geoquímica i Hidrogeologia (MAGH), Departament de Mineralogia, Petrologia i Geologia Aplicada, Facultat de Ciències de la Terra, Institut de Recerca de l'Aigua (IdRA), Universitat de Barcelona (UB), Martí i Franquès s/n, Barcelona 08028, Spain.

出版信息

J Hazard Mater. 2025 May 5;488:137447. doi: 10.1016/j.jhazmat.2025.137447. Epub 2025 Jan 29.

DOI:10.1016/j.jhazmat.2025.137447
PMID:39892150
Abstract

The combined use of isomeric fraction (IF) and multi-element compound-specific isotope analysis (ME-CSIA) was evaluated for the first time to assess the fate and degradation of methoxychlor in the environment. The concentration and carbon and chlorine isotope composition of methoxychlor and its transformation products were monitored in water and solid phases of a fractured aquifer. The results from the interception trenches water samples demonstrated that induced alkaline conditions promoted alkaline hydrolysis. Natural attenuation of methoxychlor isomers was evidenced by carbon and chlorine isotopic fractionation. The field C-Cl isotope slope (Λ = 0.42 ± 0.06; R² = 0.98) was statistically indistinguishable (p > 0.05) from that obtained in a previous experiment (0.44 ± 0.14), confirming the occurrence of reductive dechlorination of methoxychlor isomers. P,p'-methoxychlor δC values in groundwater samples revealed variations linked to rainfall patterns. The extent of p,p'-methoxychlor biodegradation was calculated to be greater than 89 % across the monitoring period. The combined use of CSIA and IF evidenced that alkaline hydrolysis and reductive dechlorination did not exhibit isomeric selectivity. Differences in IF values between slurry and water samples, as well as between upstream and downstream wells, suggested variations in the environmental behaviour of the p,p' and o,p'-isomers, likely due to differing water solubilities. Overall, ME-CSIA proved to be a valuable tool for identifying, quantifying, and tracing methoxychlor degradation in this aquifer. Additionally, IF provided insights into the distinct environmental behaviour of the p,p'- and o,p'-isomers. These tools offer crucial information, valuable for decision-makers in developing remediation strategies for methoxychlor-contaminated sites.

摘要

首次评估了异构体分数(IF)和多元素化合物特定同位素分析(ME-CSIA)的联合使用,以评估甲氧滴滴涕在环境中的归宿和降解情况。在一个裂隙含水层的水相和固相相中监测了甲氧滴滴涕及其转化产物的浓度、碳和氯同位素组成。截流沟水样的结果表明,诱导碱性条件促进了碱性水解。甲氧滴滴涕异构体的自然衰减通过碳和氯同位素分馏得到证明。现场C-Cl同位素斜率(Λ = 0.42 ± 0.06;R² = 0.98)与先前实验中获得的斜率(0.44 ± 0.14)在统计学上无显著差异(p > 0.05),证实了甲氧滴滴涕异构体发生了还原脱氯。地下水样中P,p'-甲氧滴滴涕的δC值揭示了与降雨模式相关的变化。在整个监测期内,计算得出P,p'-甲氧滴滴涕的生物降解程度大于89%。CSIA和IF的联合使用证明,碱性水解和还原脱氯没有表现出异构体选择性。浆液和水样之间以及上游和下游井之间IF值的差异表明,p,p'和o,p'-异构体的环境行为存在差异,这可能是由于它们不同的水溶性所致。总体而言,ME-CSIA被证明是识别、量化和追踪该含水层中甲氧滴滴涕降解的有价值工具。此外,IF提供了关于p,p'-和o,p'-异构体不同环境行为的见解。这些工具提供了关键信息,对决策者制定甲氧滴滴涕污染场地的修复策略具有重要价值。

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