链长和官能团对全氟有机酸降解路径的影响

顾玉蓉, 李旭, 朱佳, 董紫君, 李娴丽

中国环境科学 ›› 2020, Vol. 40 ›› Issue (7) : 2952-2959.

PDF(446 KB)
PDF(446 KB)
中国环境科学 ›› 2020, Vol. 40 ›› Issue (7) : 2952-2959.
水污染与控制

链长和官能团对全氟有机酸降解路径的影响

  • 顾玉蓉1, 李旭2, 朱佳1, 董紫君1, 李娴丽1
作者信息 +

Effect of carbon chain length and functional group on decomposition pathway of perfluorinated organic acids

  • GU Yu-rong1, LI Xu2, ZHU Jia1, DONG Zi-jun1, LI Xian-li1
Author information +
文章历史 +

摘要

考察了碳链长度和官能团对高强UV/SO32-体系降解全氟有机酸的影响,选取典型全氟有机酸PFOA和PFOS,探明其降解机制.结果表明,高强UV/SO32-体系可高效降解5种全氟有机酸.全氟有机酸的降解速率随着碳链长度的增加而增加.官能团对全氟有机酸的降解有重要影响,全氟羧酸在体系中的降解速率显著快于全氟磺酸.全氟羧酸是从与羧基相连的α碳上的氟原子开始,通过逐步脱CF2单元的形式生成短链全氟羧酸进行降解.全氟磺酸主要有三条降解路径:脱磺酸基、α位脱氟以及中心C—C键断裂.

Abstract

Effect of carbon chain length and functional group on decomposition of perfluorinated organic acids by the high intensity UV/sulfite system was investigated in this study. Typical perfluorinated organic acids, such as PFOA and PFOS, were selected to reveal their decomposition mechanisms. The results showed five kinds of perfluorinated organic acids were efficiently decomposed in this system, and their decomposition rate increased with increase of carbon chain length. Functional group played an important role in decomposition of perfluorinated organic acids. Decomposition rate of perfluorocarboxylic acids was obviously faster than perfluorosulfonic acids. Decomposition of perfluorocarboxylic acids started from the fluorine atom at α-position bonding with carboxyl, and then underwent decomposition with stepwise elimination of CF2 to form short chain perfluorocarboxylic acids. Desulfonation, defluorination at α position and centermost C-C bond scission were three main decomposition pathways of perfluorosulfonic acids.

关键词

UV/SO32- / 官能团 / 全氟有机酸 / 水合电子 / 碳链长度

Key words

carbon chain length / functional group / hydrated electron / perfluorinated organic acids / UV/sulfite

引用本文

导出引用
顾玉蓉, 李旭, 朱佳, 董紫君, 李娴丽. 链长和官能团对全氟有机酸降解路径的影响[J]. 中国环境科学. 2020, 40(7): 2952-2959
GU Yu-rong, LI Xu, ZHU Jia, DONG Zi-jun, LI Xian-li. Effect of carbon chain length and functional group on decomposition pathway of perfluorinated organic acids[J]. China Environmental Science. 2020, 40(7): 2952-2959
中图分类号: X703   

参考文献

[1] 方淑红,李成,卞玉霞,等.岷江流域全氟化合物的污染特征及排放通量[J]. 中国环境科学, 2019,39(7):2983-2989. Fang S H, Li C, Bian Y X, et al. Pollution characteristics and flux of perfluoroalkyl substances in Minjiang River[J]. China Environmental Science, 2019,39(7):2983-2989.
[2] Sun Z Y, Zhang C J, Chen P, et al. Impact of humic acid on the photoreductive degradation of perfluorooctane sulfonate (PFOS) by UV/Iodide process[J]. Water Research, 2017,127:50-58.
[3] Zhang Y Z, Wang B, Wang W, et al. Occurrence and source apportionment of Per-and poly-fluorinated compounds (PFCs) in North Canal Basin, Beijing[J]. Scientific Report, 2016,6:36683.
[4] Merino N, Qu Y, Deeb R A, et al. Degradation and removal methods for perfluoroalkyl and polyfluoroalkyl substances in water[J]. Environmental Engineering Science, 2016,33:615-649.
[5] Bentel M J, Yu Y C, Xu L H, et al. Defluorination of per-and polyfluoroalkyl substances (PFASs) with hydrated electrons:structural dependence and implications to PFAS remediation an management[J]. Environmental Science & Technology, 2019,53:3718-3728.
[6] GuY R, Dong W Y, Luo C, et al. Efficient reductive decomposition of perfluorooctanesulfonate in a high photon flux UV/sulfite system[J]. Environmental Science & Technology, 2016,50(19):10554-10561.
[7] 顾玉蓉,董文艺,董紫君,等.高强UV/SO32-体系高效降解一氯乙酸[J]. 中国环境科学, 2019,39(11):4772-4729. Gu Y R, Dong W Y, Dong Z J, et al. Efficient decomposition of monochloroaceticaid in the high intensity UV/sulfite system[J]. China Environmental Science, 2019,39(11):4772-4729.
[8] Park H, Vecitis C, Cheng J, et al. Reductive defluorination of aqueous perfluorinated alkyl surfactants:effects of ionic headgroup and chain length[J]. The Journal of Physical Chemistry A, 2009,113(4):690-696.
[9] Zhuo Q F, Deng S B, Yang B, et al. Degradation of perfluorinated compounds on a boron-doped diamond electrode[J]. Electrochim. Acta, 2012,77:17-22.
[10] Syracuse Research Corporation, Interactive PhysProp Database[EB/OL]. http://www.syrres.com/esc/physdemo.htm, 2006.
[11] Qu Y, Zhang C, Chen P, et al. Effect of initial solution pH on photo-induced reductive decomposition of perfluorooctanoic acid[J]. Chemosphere, 2014,107:218-223.
[12] Song Z, Tang H, Wang N, et al. Reductive defluorination of perfluorooctanoic acid by hydrated electrons in a sulfite-mediated UV photochemical system[J]. Journal of Hazardous Materials, 2013,262:332-338.
[13] Bentel M J, Yu Y C, Xu L H, et al. Defluorination of per-and polyfluoroalkyl substances (PFASs) with hydrated electrons:structural dependence and implications to PFAs remediation and management[J]. Environmental Science & Technology, 2019,53:3718-3728.
[14] Hori H, Hayakawa E, Einaga H, et al. Decomposition of environmentally persistent perfluorooctanoic acid in water by photochemical approaches[J]. Environmental Science & Technology, 2004,38(22):6118-6124.
[15] Song Z, Dong X, Wang N, et al. Efficient photocatalytic defluorination of perfluorooctanoic acid over BiOCl nanosheets via a hole direct oxidation mechanism[J]. Chemical Engineering Journal, 2017,317:925-934.
[16] Blondel C, Cacciani P, Delsart C, et al. High-resolution determination of the electron affinity of fluorine and bromine using crossed ion and laser beams[J]. Physical Review A, 1989,40(7):3698-3701.
[17] Combellas C, Kanoufi F, Thiébault A. Reduction of polyfluorinated compounds[J]. The Journal of Physical Chemistry B, 2003,107(39):10894-10905.
[18] Qu Y, Zhang C, Li F, et al. Photo-reductive defluorination of perfluorooctanoic acid in water[J]. Water Research, 2010,44(9):2939-2947.
[19] Paul A, Wannere C, Schaefer H. Do linear-chain perfluoroalkanes bind an electron?[J]. The Journal of Physical Chemistry A, 2004, 108(43):9428-9434.
[20] Lyu X, Li W, Lam P, et al. Insights into perfluorooctane sulfonate photodegradation in a catalyst-free aqueous solution[J]. Scientific Reports, 2015,5:9353.
[21] Yamamoto T, Noma Y, Sakai S, et al. Photodegradation of perfluorooctane sulfonate by UV irradiation in water and alkaline 2-propanol[J]. Environmental Science & Technology, 2007,41(16):5660-5665.

基金

广东省基础与应用基础研究基金(2020A1515011545);广东省攀登计划(pdjh2019b0856);深圳职业技术学院项目(6019310013K0);深圳水务集团项目(2019-131-F)

PDF(446 KB)

Accesses

Citation

Detail

段落导航
相关文章

/