PMID- 36680820 OWN - NLM STAT- MEDLINE DCOM- 20230210 LR - 20230210 IS - 1879-2448 (Electronic) IS - 0043-1354 (Linking) VI - 231 DP - 2023 Mar 1 TI - Photoinduced transformation of ferrihydrite in the presence of aqueous sulfite and its influence on the repartitioning of Cd. PG - 119607 LID - S0043-1354(23)00042-8 [pii] LID - 10.1016/j.watres.2023.119607 [doi] AB - The photoinduced transformation of ferrihydrite is an important process that can predict the geochemical cycle of Fe in anoxic environments as well as the fate of trace elements bonded to Fe minerals. We report that the photooxidation of sulfite by UV irradiation produces hydrated electrons (super-reductants), which significantly promote ferrihydrite reduction to Fe(II), and SO(3)(*-) (a moderate oxidant), enabling its further oxidation to more crystalline Fe(III) products. The experimental results show that the concentration of sulfite was key in influencing the rate and extent of surface-bound Fe(II) formation, which ultimately determined the distribution of individual products. For example, fitting of the Mossbauer spectroscopy data revealed that the relative abundances of mineral species after 8 h of treatment in the UV/sulfite systems were 41.9% lepidocrocite and 58.1% ferrihydrite at 2 mM SO(3)(2-); 41.8% goethite, 28.2% lepidocrocite, and 29.1% ferrihydrite at 5 mM SO(3)(2-); and 100% goethite at 10 mM SO(3)(2-). The combined results of the chemical speciation analysis and the Cd K-edge EXAFS characterization provided compelling evidence that Cd was firmly incorporated into the structure of newly formed minerals, particularly at high sulfite concentrations. These findings provide an understanding of the role of UV/sulfite in facilitating ferrihydrite transformation and promoting Cd stabilization in oxygen-deficit soils and aquatic environments. CI - Copyright (c) 2023 Elsevier Ltd. All rights reserved. FAU - Qiu, Jinwen AU - Qiu J AD - The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, School of Environment and Energy, South China University of Technology, Guangzhou 510006, PR China. FAU - Hou, Xiaokang AU - Hou X AD - The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, School of Environment and Energy, South China University of Technology, Guangzhou 510006, PR China. FAU - Ren, Yuan AU - Ren Y AD - The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, School of Environment and Energy, South China University of Technology, Guangzhou 510006, PR China. FAU - Liu, Chengshuai AU - Liu C AD - State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, PR China. FAU - Meng, Fangyuan AU - Meng F AD - State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, PR China. FAU - Lee, Jyh-Fu AU - Lee JF AD - National Synchrotron Radiation Research Center, Hsinchu, Taiwan 30076, ROC. FAU - Lin, Yu-Jung AU - Lin YJ AD - National Synchrotron Radiation Research Center, Hsinchu, Taiwan 30076, ROC. FAU - Huang, Ziyuan AU - Huang Z AD - The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, School of Environment and Energy, South China University of Technology, Guangzhou 510006, PR China. FAU - Ma, Huanxin AU - Ma H AD - The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, School of Environment and Energy, South China University of Technology, Guangzhou 510006, PR China. FAU - Shi, Zhenqing AU - Shi Z AD - The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, School of Environment and Energy, South China University of Technology, Guangzhou 510006, PR China. FAU - Feng, Chunhua AU - Feng C AD - The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, School of Environment and Energy, South China University of Technology, Guangzhou 510006, PR China. Electronic address: chfeng@scut.edu.cn. LA - eng PT - Journal Article DEP - 20230112 PL - England TA - Water Res JT - Water research JID - 0105072 RN - 87PZU03K0K (ferric oxyhydroxide) RN - 1K09F3G675 (ferric oxide) RN - 0 (Ferric Compounds) RN - 1310-14-1 (goethite) RN - E1UOL152H7 (Iron) RN - 00BH33GNGH (Cadmium) RN - 0 (Minerals) RN - 059QF0KO0R (Water) RN - 0 (Ferrous Compounds) SB - IM MH - *Ferric Compounds/chemistry MH - *Iron/chemistry MH - Cadmium MH - Minerals/chemistry MH - Water MH - Oxidation-Reduction MH - Ferrous Compounds OTO - NOTNLM OT - Advanced reduction process OT - Cd immobilization OT - Fe cycle OT - Fe(II) catalysis OT - Ferrihydrite transformation OT - Photoinduced reactive species 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- 2023/01/22 06:00 MHDA- 2023/02/11 06:00 CRDT- 2023/01/21 18:04 PHST- 2022/10/30 00:00 [received] PHST- 2023/01/10 00:00 [revised] PHST- 2023/01/11 00:00 [accepted] PHST- 2023/01/22 06:00 [pubmed] PHST- 2023/02/11 06:00 [medline] PHST- 2023/01/21 18:04 [entrez] AID - S0043-1354(23)00042-8 [pii] AID - 10.1016/j.watres.2023.119607 [doi] PST - ppublish SO - Water Res. 2023 Mar 1;231:119607. doi: 10.1016/j.watres.2023.119607. Epub 2023 Jan 12.