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通过模拟太阳光揭示不同介质中十溴二苯醚(BDE-209)的光转化机制:通过化合物特异性稳定同位素分析的启示。

Disclosing phototransformation mechanisms of decabromodiphenyl ether (BDE-209) in different media by simulated sunlight: Implication by compound-specific stable isotope analysis.

机构信息

College of Environmental Science and Engineering, Dalian Maritime University, No.1 Linghai Road, 116026, Dalian, People's Republic of China.

Navigation College, Dalian Maritime University, No.1 Linghai Road, 116026, Dalian, People's Republic of China.

出版信息

Environ Sci Pollut Res Int. 2024 Feb;31(10):14980-14989. doi: 10.1007/s11356-024-32203-6. Epub 2024 Jan 29.

Abstract

As one of the typical brominated flame retardants, decabromodiphenyl ether (BDE-209) has been widely detected in environment. However, scarce information was available on BDE-209 phototransformation mechanisms in various media. In this study, compound-specific stable isotope analysis was first applied to investigate BDE-209 phototransformation in n-hexane, MeOH:HO (v:v, 8:2), and simulated seawater by simulated sunlight. BDE-209 transformation followed pseudo-first-order kinetic, with degradation rate in the following of n-hexane (2.66 × 10 min) > simulated seawater (1.83 × 10 min) > MeOH:HO (1.41 × 10 min). Pronounced carbon isotope fractionation was first observed for BDE-209 phototransformation, with carbon isotope enrichment factors (ε) of -1.01 ± 0.14‰, -1.77 ± 0.26‰, -2.94 ± 0.38‰ in n-hexane, MeOH:HO and simulated seawater, respectively. Combination analysis of products and stable carbon isotope, debromination with cleavage of C-Br bonds as rate-limiting step was the main mechanism for BDE-209 phototransformation in n-hexane, debromination and hydroxylation with cleavage of C-Br bonds as rate-limiting steps in MeOH:HO, and debromination, hydroxylation and chlorination in simulated seawater. This present study confirmed that stable carbon isotope analysis was a robust method to discovery the underlying phototransformation mechanisms of BDE-209 in various solutions.

摘要

作为典型的溴系阻燃剂之一,十溴二苯醚(BDE-209)已广泛存在于环境中。然而,关于 BDE-209 在各种介质中的光转化机制的信息却很少。在本研究中,首次应用化合物特异性稳定同位素分析方法,通过模拟太阳光研究了 BDE-209 在正己烷、甲醇:水(v:v,8:2)和模拟海水中的光转化。BDE-209 的转化遵循准一级动力学,降解速率的顺序为正己烷(2.66×10-2 min-1)>模拟海水(1.83×10-2 min-1)>甲醇:水(1.41×10-2 min-1)。首次观察到 BDE-209 光转化过程中存在明显的碳同位素分馏现象,其碳同位素富集因子(ε)分别为-1.01±0.14‰、-1.77±0.26‰和-2.94±0.38‰,在正己烷、甲醇:水和模拟海水中分别存在。产物与稳定碳同位素的综合分析表明,BDE-209 在正己烷中的光转化主要以脱溴和 C-Br 键断裂为限速步骤的脱溴化反应为主,在甲醇:水中的光转化主要以脱溴和 C-Br 键断裂以及羟基化反应为限速步骤,而在模拟海水中的光转化则以脱溴、羟基化和氯化反应为主。本研究证实,稳定碳同位素分析是一种可靠的方法,可以发现 BDE-209 在各种溶液中的潜在光转化机制。

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