title: Formation of brominated phenolic contaminants from natural manganese oxides-catalyzed oxidation of phenol in the presence of Br(.).
abstract: Brominated phenolic compounds (BPCs) are a class of persistent and potentially toxic compounds ubiquitously present in the aquatic environment. However, the origin of BPCs is not clearly understood. In this study, we investigated the formation of BPCs from natural manganese oxides (MnOx)-catalyzed oxidation of phenol in the presence of Br(-). Experiments at ambient temperature clearly demonstrated that BPCs were readily produced via the oxidation of phenol by MnOx in the presence of Br(-). In the reaction of MnOx sand with 0.213 μmol/L phenol and 0.34 mmol/L Br(-) for 10 min, more than 60% of phenol and 56% of Br(-) were consumed to form BPCs. The yield of BPCs increased with increasing concentrations of phenol and Br(-). Overall, a total of 14 BPCs including simple bromophenols (4-bromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol), hydroxylated polybrominated diphenyl ethers (OH-PBDEs), and hydroxylated polybrominated biphenyls (OH-PBBs) were identified. The production of BPCs increased with increasing concentrations of Br(-) or phenol. It was deduced that Br(-) was first oxidized to form active bromine, leading to the subsequent bromination of phenol to form bromophenols. The further oxidation of bromophenols by MnOx resulted in the formation of OH-PBDEs and OH-PBBs. In view of the ubiquity of phenol, Br(-), and MnOx in the environment, MnOx-mediated oxidation may play a role on the natural production of BPCs.
authors.affiliation: State Key Laboratory of Marine Environmental Science, Key Laboratory of the Ministry of Education for Coastal and Wetland Ecosystem, College of the Environment and Ecology, Xiamen University, Xiamen 361005, China; College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032, China. Electronic address: link@xmu.edu.cn.
authors.forename: Kunde
authors.initials: K
authors.lastname: Lin
authors.affiliation: College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032, China.
authors.forename: Lianghui
authors.initials: L
authors.lastname: Song
authors.affiliation: College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032, China.
authors.forename: Shiyang
authors.initials: S
authors.lastname: Zhou
authors.affiliation: Cooperative Wildlife Research Laboratory and Department of Zoology, Southern Illinois University, Carbondale, IL 62901, USA.
authors.forename: Da
authors.initials: D
authors.lastname: Chen
authors.affiliation: Department of Environmental Sciences, University of California, Riverside, CA 92521, USA.
authors.forename: Jay
authors.initials: J
authors.lastname: Gan
mesh_terms: D001966:Bromine; D002384:Catalysis; D055768:Halogenated Diphenyl Ethers; D054879:Halogenation; D006900:Hydroxylation; D017895:Manganese Compounds / Q000737:chemistry*; D008956:Models, Chemical; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry*; D019800:Phenol / Q000737:chemistry*; D010636:Phenols; D011075:Polybrominated Biphenyls
chemical_list: D055768:Halogenated Diphenyl Ethers; D017895:Manganese Compounds; D010087:Oxides; D010636:Phenols; D011075:Polybrominated Biphenyls; D019800:Phenol; C027424:manganese oxide; C013930:2,4-dibromophenol; C032037:4-bromophenol; D001966:Bromine; C004554:2,4,6-tribromophenol
keywords: Brominated phenolic compounds; Emerging contaminants; Manganese dioxide; OH-PBDEs; Persistent organic pollutants