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首页> 外文期刊>Environmental Science & Technology >Carbon And Chlorine Isotope Fractionation During Aerobic Oxidation And Reductive Dechlorination Of Vinyl Chloride And Cis-1,2-dichloroethene
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Carbon And Chlorine Isotope Fractionation During Aerobic Oxidation And Reductive Dechlorination Of Vinyl Chloride And Cis-1,2-dichloroethene

机译：氯乙烯和顺式1,2-二氯乙烯的有氧氧化和还原脱氯过程中的碳和氯同位素分馏

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摘要

The study investigated carbon and chlorine isotope fractionation during aerobic oxidation and reductive dechlorination of vinyl chloride (VC) and cis-1,2-dichloroethene (cDCE). The experimental data followed a Rayleigh trend. For aerobic oxidation, the average carbon isotope enrichment factors were -7.2‰ and -8.5‰ for VC and cDCE, respectively, while average chlorine isotope enrichment factors were only -0.3‰ for both compounds. These values are consistent with an initial transformation by epoxidation for which a significant primary carbon isotope effect and only a small secondary chlorine isotope effect is expected. For reductive dechlorination, larger carbon isotope enrichment factors of -25.2‰ for VC and -18.5‰ for cDCE were observed consistent with previous studies. Although the average chlorine isotope enrichment factors were larger than those of aerobic oxidation (-1.8‰ for VC, -1.5‰ for cDCE), they were not as large as typically expected for a primary chlorine isotope effect suggesting that no cleavage of C-CI bonds takes place during the initial rate-limiting step. The ratio of isotope enrichment factors for chlorine and carbon were substantially different for the two reaction mechanisms suggesting that the reaction mechanisms can be differentiated at the field scale using a dual isotope approach.
机译：该研究调查了氯乙烯（VC）和顺式1,2-二氯乙烯（cDCE）的需氧氧化和还原脱氯过程中的碳和氯同位素分馏。实验数据遵循瑞利趋势。对于好氧氧化，VC和cDCE的平均碳同位素富集因子分别为-7.2‰和-8.5‰，而两种化合物的平均氯同位素富集因子仅为-0.3‰。这些值与环氧化的初始转化相一致，对于环氧化的初始转化，预期其具有显着的初级碳同位素效应而仅具有较小的次级氯同位素效应。对于还原性脱氯，观察到较大的碳同位素富集因子，VC为-25.2‰，cDCE为-18.5‰，与先前的研究一致。尽管平均氯同位素富集因子大于有氧氧化富集因子（VC为-1.8‰，cDCE为-1.5‰），但它们不如通常的主要氯同位素效应预期的大，这表明C-CI没有裂解在最初的限速步骤中发生债券。对于这两种反应机理，氯和碳的同位素富集因子之比基本不同，这表明可以使用双同位素方法在现场规模上区分反应机理。

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