直链全氟己磺酸(L-PFHxS)仿生降解特性

陈铃心; 杨志敏; 刘淑坡; 周真明; 李飞

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中国环境科学 ›› 2025, Vol. 45 ›› Issue (8) : 4620-4627.

新污染物与毒理

直链全氟己磺酸(L-PFHxS)仿生降解特性

陈铃心¹, 杨志敏², 刘淑坡¹, 周真明¹, 李飞¹

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Biomimetic degradation characteristics of linear perfluorohexanesulfonate (L-PFHxS)

CHEN Ling-xin¹, YANG Zhi-min², LIU Shu-po¹, ZHOU Zhen-ming¹, LI Fei¹

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摘要

在确定直链全氟己磺酸(L-PFHxS)可仿生降解脱氟的基础上,定性分析了同位素(¹³C)标记L-PFHxS(MPFHxS)的降解产物,以明确L-PFHxS仿生降解机理.研究结果表明,仿生降解MPFHxS可生成两种¹³C标记全氟羧酸类(PFCAs,即¹³C₃-全氟己酸和¹³C₃-全氟壬酸)、8种非¹³C标记PFCAs类 (全氟碳链长度C1~C8)和7种非¹³C标记全氟磺酸类(全氟碳链长度C3~C8,含两种PFHxS异构体,即直链和支链PFHxS)降解产物.L-PFHxS降解途径如下:L-PFHxS分子中的C-S键首先断裂生成C₆F₁₃•,C₆F₁₃•自由基经一系列水解生成PFHxA;然后,C₆F₁₃•自由基或L-PFHxS分子在不同位置断裂C-C键生成C_nF_2n+1•自由基(n = 1,2或3),C_nF_2n+1•自由基(n = 1,2或3)逐步增加0~2个C₃F₆基团,后经一些列水解生成不同全氟链长PFCAs或与•SO₃H自由基结合生成不同全氟链长PFSAs.

Abstract

Based on confirming that the linear perfluorohexanesulfonate (L-PFHxS) could be degraded and defluorinated in a biomimetic system, the degradation products of isotope-labelled (¹³C) L-PFHxS (MPFHxS) were qualitatively analyzed, and the degradation mechanisms of L-PFHxS were then clarified. Two ¹³C-labeled perfluorocarboxylates (PFCAs, i.e. ¹³C₃-perfluorohexanoate and ¹³C₃-perfluorononanoate), eight native PFCAs (perfluorocarbon chain length ranged from C1 to C8), and seven native perfluoroalkylsulfonates (PFSAs, perfluorocarbon chain length ranging from C3 to C8, including linear and branched PFHxS), had been identified as the biomimetic degradation products of MPFHxS. The degradation pathways of L-PFHxS were proposed as follows: L-PFHxS were firstly reduced to C₆F₁₃• radical by cleavage of C-S bond, and then transformed to perfluorohexanoate through a series of hydrolysis. C₆F₁₃• radical or/and L-PFHxS were further reduced to form C_nF_2n+1• (n = 1, 2or 3) radicals, and these radicals were chain-lengthened by stepwise addition of 0 ~ 2C₃F₆ moieties and eventually transformed to various degradation products with different perfluorocarbon chain length via a series of hydrolysis (PFCAs) or combination reaction with sulfonyl hydroxide radical (PFSAs).

导出引用

陈铃心, 杨志敏, 刘淑坡, 周真明, 李飞. 直链全氟己磺酸(L-PFHxS)仿生降解特性[J]. 中国环境科学. 2025, 45(8): 4620-4627

CHEN Ling-xin, YANG Zhi-min, LIU Shu-po, ZHOU Zhen-ming, LI Fei. Biomimetic degradation characteristics of linear perfluorohexanesulfonate (L-PFHxS)[J]. China Environmental Science. 2025, 45(8): 4620-4627

中图分类号： X131

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