New insights into the degradation mechanism and risk assessment of HFPO-DA by advanced oxidation processes based on activated persulfate in aqueous solutions
Hexafluoropropylene oxide dimer acid (HFPO-DA) is widely used as a substitute for perfluorooctanoic acid (PFOA). HFPO-DA exhibits high water solubility and low adsorption potential, conferring significant fluidity in aquatic environments. Given that the toxicity of HFPO-DA is similar to PFOA, it is...
| Main Authors: | , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Elsevier
2023-09-01
|
| Series: | Ecotoxicology and Environmental Safety |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S0147651323008023 |
| _version_ | 1797683218566086656 |
|---|---|
| author | Chenxi Zhang Youxin Xu Wenyan Liu Huaiyu Zhou Ningning Zhang Zhihao Fang Junping Gao Xiaoan Sun Di Feng Xiaomin Sun |
| author_facet | Chenxi Zhang Youxin Xu Wenyan Liu Huaiyu Zhou Ningning Zhang Zhihao Fang Junping Gao Xiaoan Sun Di Feng Xiaomin Sun |
| author_sort | Chenxi Zhang |
| collection | DOAJ |
| description | Hexafluoropropylene oxide dimer acid (HFPO-DA) is widely used as a substitute for perfluorooctanoic acid (PFOA). HFPO-DA exhibits high water solubility and low adsorption potential, conferring significant fluidity in aquatic environments. Given that the toxicity of HFPO-DA is similar to PFOA, it is necessary to control its content in aquatic environments. Electrochemical and thermally-activated persulfates have been successfully used to degrade HFPO-DA, but UV-activated persulfates cannot degrade the compound. Given that research on degradation mechanisms is still incomplete and lacks kinetic research, the mechanism and kinetic calculations of oxidative degradation were studied in detail using DFT calculations. And the toxicity of HFPO-DA degradation intermediates and products was evaluated to reveal the feasibility of using advanced oxidation process (AOP) technology based on persulfate to degrade HFPO-DA in wastewater. The results showed that the committed step of HFPO-DA degradation was initiated by the electron transfer reaction of SO4•- radicals. This reaction is not spontaneous at room temperature and requires sufficient electrical or thermal energy to be absorbed from the external environment. The perfluoroalcohol produced during this reaction can subsequently undergo four possible reactions: H atom abstraction from alcohol groups by an OH radical; H atom abstraction by SO4•-; direct HF removal; and HF removal with water as the catalyst. The final degradation products of HFPO-DA mainly include CO2, CF3CF2COOH, CF3COOH, FCOOH and HF, which has been identified through previous experimental analysis. Ecotoxicity assessment indicates that degradation does not produce highly toxic intermediates, and that the final products are non-toxic, supporting the feasibility of persulfate-based AOP technologies. |
| first_indexed | 2024-03-12T00:11:22Z |
| format | Article |
| id | doaj.art-b84d351679794286ad055cc735b6dd6f |
| institution | Directory Open Access Journal |
| issn | 0147-6513 |
| language | English |
| last_indexed | 2024-03-12T00:11:22Z |
| publishDate | 2023-09-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Ecotoxicology and Environmental Safety |
| spelling | doaj.art-b84d351679794286ad055cc735b6dd6f2023-09-16T05:28:28ZengElsevierEcotoxicology and Environmental Safety0147-65132023-09-01263115298New insights into the degradation mechanism and risk assessment of HFPO-DA by advanced oxidation processes based on activated persulfate in aqueous solutionsChenxi Zhang0Youxin Xu1Wenyan Liu2Huaiyu Zhou3Ningning Zhang4Zhihao Fang5Junping Gao6Xiaoan Sun7Di Feng8Xiaomin Sun9Shandong Facility Horticulture Bioengineering Research Center, Weifang University of Science and Technology, Weifang 262700, China; Environment Research Institute, Shandong University, Qingdao 266237, ChinaShandong Facility Horticulture Bioengineering Research Center, Weifang University of Science and Technology, Weifang 262700, China; Environment Research Institute, Shandong University, Qingdao 266237, ChinaSchool of agriculture, Ludong University, Yantai 264025, ChinaShandong Facility Horticulture Bioengineering Research Center, Weifang University of Science and Technology, Weifang 262700, ChinaShandong Facility Horticulture Bioengineering Research Center, Weifang University of Science and Technology, Weifang 262700, ChinaShandong Facility Horticulture Bioengineering Research Center, Weifang University of Science and Technology, Weifang 262700, ChinaShandong Facility Horticulture Bioengineering Research Center, Weifang University of Science and Technology, Weifang 262700, ChinaShandong Facility Horticulture Bioengineering Research Center, Weifang University of Science and Technology, Weifang 262700, ChinaShandong Facility Horticulture Bioengineering Research Center, Weifang University of Science and Technology, Weifang 262700, China; Corresponding authors.Environment Research Institute, Shandong University, Qingdao 266237, China; Corresponding authors.Hexafluoropropylene oxide dimer acid (HFPO-DA) is widely used as a substitute for perfluorooctanoic acid (PFOA). HFPO-DA exhibits high water solubility and low adsorption potential, conferring significant fluidity in aquatic environments. Given that the toxicity of HFPO-DA is similar to PFOA, it is necessary to control its content in aquatic environments. Electrochemical and thermally-activated persulfates have been successfully used to degrade HFPO-DA, but UV-activated persulfates cannot degrade the compound. Given that research on degradation mechanisms is still incomplete and lacks kinetic research, the mechanism and kinetic calculations of oxidative degradation were studied in detail using DFT calculations. And the toxicity of HFPO-DA degradation intermediates and products was evaluated to reveal the feasibility of using advanced oxidation process (AOP) technology based on persulfate to degrade HFPO-DA in wastewater. The results showed that the committed step of HFPO-DA degradation was initiated by the electron transfer reaction of SO4•- radicals. This reaction is not spontaneous at room temperature and requires sufficient electrical or thermal energy to be absorbed from the external environment. The perfluoroalcohol produced during this reaction can subsequently undergo four possible reactions: H atom abstraction from alcohol groups by an OH radical; H atom abstraction by SO4•-; direct HF removal; and HF removal with water as the catalyst. The final degradation products of HFPO-DA mainly include CO2, CF3CF2COOH, CF3COOH, FCOOH and HF, which has been identified through previous experimental analysis. Ecotoxicity assessment indicates that degradation does not produce highly toxic intermediates, and that the final products are non-toxic, supporting the feasibility of persulfate-based AOP technologies.http://www.sciencedirect.com/science/article/pii/S0147651323008023HFPO-DAPersulfate-based AOP technologySO4•- and OH radicalsReaction mechanismEcotoxicity assessment |
| spellingShingle | Chenxi Zhang Youxin Xu Wenyan Liu Huaiyu Zhou Ningning Zhang Zhihao Fang Junping Gao Xiaoan Sun Di Feng Xiaomin Sun New insights into the degradation mechanism and risk assessment of HFPO-DA by advanced oxidation processes based on activated persulfate in aqueous solutions Ecotoxicology and Environmental Safety HFPO-DA Persulfate-based AOP technology SO4•- and OH radicals Reaction mechanism Ecotoxicity assessment |
| title | New insights into the degradation mechanism and risk assessment of HFPO-DA by advanced oxidation processes based on activated persulfate in aqueous solutions |
| title_full | New insights into the degradation mechanism and risk assessment of HFPO-DA by advanced oxidation processes based on activated persulfate in aqueous solutions |
| title_fullStr | New insights into the degradation mechanism and risk assessment of HFPO-DA by advanced oxidation processes based on activated persulfate in aqueous solutions |
| title_full_unstemmed | New insights into the degradation mechanism and risk assessment of HFPO-DA by advanced oxidation processes based on activated persulfate in aqueous solutions |
| title_short | New insights into the degradation mechanism and risk assessment of HFPO-DA by advanced oxidation processes based on activated persulfate in aqueous solutions |
| title_sort | new insights into the degradation mechanism and risk assessment of hfpo da by advanced oxidation processes based on activated persulfate in aqueous solutions |
| topic | HFPO-DA Persulfate-based AOP technology SO4•- and OH radicals Reaction mechanism Ecotoxicity assessment |
| url | http://www.sciencedirect.com/science/article/pii/S0147651323008023 |
| work_keys_str_mv | AT chenxizhang newinsightsintothedegradationmechanismandriskassessmentofhfpodabyadvancedoxidationprocessesbasedonactivatedpersulfateinaqueoussolutions AT youxinxu newinsightsintothedegradationmechanismandriskassessmentofhfpodabyadvancedoxidationprocessesbasedonactivatedpersulfateinaqueoussolutions AT wenyanliu newinsightsintothedegradationmechanismandriskassessmentofhfpodabyadvancedoxidationprocessesbasedonactivatedpersulfateinaqueoussolutions AT huaiyuzhou newinsightsintothedegradationmechanismandriskassessmentofhfpodabyadvancedoxidationprocessesbasedonactivatedpersulfateinaqueoussolutions AT ningningzhang newinsightsintothedegradationmechanismandriskassessmentofhfpodabyadvancedoxidationprocessesbasedonactivatedpersulfateinaqueoussolutions AT zhihaofang newinsightsintothedegradationmechanismandriskassessmentofhfpodabyadvancedoxidationprocessesbasedonactivatedpersulfateinaqueoussolutions AT junpinggao newinsightsintothedegradationmechanismandriskassessmentofhfpodabyadvancedoxidationprocessesbasedonactivatedpersulfateinaqueoussolutions AT xiaoansun newinsightsintothedegradationmechanismandriskassessmentofhfpodabyadvancedoxidationprocessesbasedonactivatedpersulfateinaqueoussolutions AT difeng newinsightsintothedegradationmechanismandriskassessmentofhfpodabyadvancedoxidationprocessesbasedonactivatedpersulfateinaqueoussolutions AT xiaominsun newinsightsintothedegradationmechanismandriskassessmentofhfpodabyadvancedoxidationprocessesbasedonactivatedpersulfateinaqueoussolutions |