PMID- 32559882 OWN - NLM STAT- MEDLINE DCOM- 20200710 LR - 20200710 IS - 1873-6424 (Electronic) IS - 0269-7491 (Linking) VI - 264 DP - 2020 Sep TI - Mechanochemical degradation of perfluorohexane sulfonate: Synergistic effect of ferrate(VI) and zero-valent iron. PG - 114789 LID - S0269-7491(20)30772-7 [pii] LID - 10.1016/j.envpol.2020.114789 [doi] AB - Perfluorohexane sulfonate (PFHxS) has been newly recommended to be added into the Stockholm Convention on persistent organic pollutants (POPs). As one of the major perfluoroalkyl pollutants, its long half-time in human serum and neurotoxicity are cause for significant concern. Although mechanochemical degradation has been evaluated as a promising ecofriendly technology to treat pollutants, the extraordinary stability of poly- and perfluoroalkyl substances (PFASs) raises harsh requirements for co-milling reagents. In the present study, zero-valent iron (ZVI) and ferrate(VI) were for the first time used as the co-milling reagents to degrade PFHxS. When ZVI and ferrate(VI) were used alone, both the degradation and defluorination efficiencies were low. However, after milling at the optimum ratio (ferrate(VI):ZVI = 1:2) for 4 h, the synergistic effect of ZVI and ferrate(VI) resulted in almost complete degradation (100%) and defluorination (95%). Two points can account for this excellent performance: (1) the mechanochemical energy input in the system initiates and prominently promotes related reactions; and (2) the active species generated from the reactions among ZVI, ferrate(VI) and other high-valent iron species will accelerate the process of electron transfer. The sulfonate group comprises the favorable attack sites, as corroborated by both the identified intermediates and quantum chemical calculations. The homolysis of the C-S bond is not only the triggering step, but also the rate-limiting step. In summary, the present work confirms the feasibility and underlying mechanism of the ZVI-ferrate(VI) co-milling system to defluorinate PFHxS, which might be a promising technology to treat PFASs in solid wastes. CI - Copyright (c) 2020 Elsevier Ltd. All rights reserved. FAU - Deng, Shanshan AU - Deng S AD - State Key Joint Laboratory of Environmental Simulation and Pollution Control (SKLESPC), Beijing Key Laboratory for Emerging Organic Contaminants Control (BKLEOC), School of Environment, Tsinghua University, Beijing, 100084, China. FAU - Bao, Yixiang AU - Bao Y AD - State Key Joint Laboratory of Environmental Simulation and Pollution Control (SKLESPC), Beijing Key Laboratory for Emerging Organic Contaminants Control (BKLEOC), School of Environment, Tsinghua University, Beijing, 100084, China. FAU - Cagnetta, Giovanni AU - Cagnetta G AD - State Key Joint Laboratory of Environmental Simulation and Pollution Control (SKLESPC), Beijing Key Laboratory for Emerging Organic Contaminants Control (BKLEOC), School of Environment, Tsinghua University, Beijing, 100084, China. FAU - Huang, Jun AU - Huang J AD - State Key Joint Laboratory of Environmental Simulation and Pollution Control (SKLESPC), Beijing Key Laboratory for Emerging Organic Contaminants Control (BKLEOC), School of Environment, Tsinghua University, Beijing, 100084, China. Electronic address: huangjun@tsinghua.edu.cn. FAU - Yu, Gang AU - Yu G AD - State Key Joint Laboratory of Environmental Simulation and Pollution Control (SKLESPC), Beijing Key Laboratory for Emerging Organic Contaminants Control (BKLEOC), School of Environment, Tsinghua University, Beijing, 100084, China. LA - eng PT - Journal Article DEP - 20200519 PL - England TA - Environ Pollut JT - Environmental pollution (Barking, Essex : 1987) JID - 8804476 RN - 0 (Fluorocarbons) RN - 0 (Water Pollutants, Chemical) RN - 16836-06-9 (ferrate ion) RN - E1UOL152H7 (Iron) RN - FX3WJ41CMX (perflexane) SB - IM MH - *Fluorocarbons MH - Iron/analysis MH - Oxidation-Reduction MH - Water Pollutants, Chemical/*analysis OTO - NOTNLM OT - Ball milling OT - Defluorination OT - Ferrate(VI) OT - Mechanism elucidation OT - PFHxS COIS- Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. EDAT- 2020/06/21 06:00 MHDA- 2020/07/11 06:00 CRDT- 2020/06/21 06:00 PHST- 2020/02/02 00:00 [received] PHST- 2020/04/08 00:00 [revised] PHST- 2020/05/08 00:00 [accepted] PHST- 2020/06/21 06:00 [entrez] PHST- 2020/06/21 06:00 [pubmed] PHST- 2020/07/11 06:00 [medline] AID - S0269-7491(20)30772-7 [pii] AID - 10.1016/j.envpol.2020.114789 [doi] PST - ppublish SO - Environ Pollut. 2020 Sep;264:114789. doi: 10.1016/j.envpol.2020.114789. Epub 2020 May 19.