title: Bromination of Marine Dissolved Organic Matter following Full Scale Electrochemical Ballast Water Disinfection.
abstract: An extensively diverse array of brominated disinfection byproducts (DBPs) were generated following electrochemical disinfection of natural coastal/estuarine water, which is one of the main treatment methods currently under consideration for ballast water treatment. Ultra-high-resolution mass spectrometry revealed 462 distinct brominated DBPs at a relative abundance in the mass spectra of more than 1%. A brominated DBP with a relative abundance of almost 22% was identified as 2,2,4-tribromo-5-hydroxy-4-cyclopentene-1,3-dione, which is an analogue to several previously described 2,2,4-trihalo-5-hydroxy-4-cyclopentene-1,3-diones in drinking water. Several other brominated molecular formulas matched those of other known brominated DBPs, such as dibromomethane, which could be generated by decarboxylation of dibromoacetic acid during ionization, dibromophenol, dibromopropanoic acid, dibromobutanoic acid, bromohydroxybenzoic acid, bromophenylacetic acid, bromooxopentenoic acid, and dibromopentenedioic acid. Via comparison to previously described chlorine-containing analogues, bromophenylacetic acid, dibromooxopentenoic acid, and dibromopentenedioic acid were also identified. A novel compound at a 4% relative abundance was identified as tribromoethenesulfonate. This compound has not been previously described as a DBP, and its core structure of tribromoethene has been demonstrated to show toxicological implications. Here we show that electrochemical disinfection, suggested as a candidate for successful ballast water treatment, caused considerable production of some previously characterized DBPs in addition to novel brominated DBPs, although several hundred compounds remain structurally uncharacterized. Our results clearly demonstrate that electrochemical and potentially direct chlorination of ballast water in estuarine and marine systems should be approached with caution and the concentrations, fate, and toxicity of DBP need to be further characterized.
authors.affiliation: †Chesapeake Biological Laboratory, University of Maryland Center for Environmental Science, Solomons, Maryland 20688, United States.
authors.forename: Michael
authors.initials: M
authors.lastname: Gonsior
authors.affiliation: †Chesapeake Biological Laboratory, University of Maryland Center for Environmental Science, Solomons, Maryland 20688, United States.
authors.forename: Carys
authors.initials: C
authors.lastname: Mitchelmore
authors.affiliation: †Chesapeake Biological Laboratory, University of Maryland Center for Environmental Science, Solomons, Maryland 20688, United States.
authors.forename: Andrew
authors.initials: A
authors.lastname: Heyes
authors.affiliation: ‡Helmholtz Zentrum München, Analytical BioGeoChemistry, D-85764 Neuherberg, Germany.
authors.forename: Mourad
authors.initials: M
authors.lastname: Harir
authors.affiliation: §Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States.
authors.forename: Susan D
authors.initials: SD
authors.lastname: Richardson
authors.affiliation: §Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States.
authors.forename: William Tyler
authors.initials: WT
authors.lastname: Petty
authors.affiliation: †Chesapeake Biological Laboratory, University of Maryland Center for Environmental Science, Solomons, Maryland 20688, United States.|⊥Environmental Research Services, Baltimore, Maryland 21231, United States.
authors.forename: David A
authors.initials: DA
authors.lastname: Wright
authors.affiliation: ‡Helmholtz Zentrum München, Analytical BioGeoChemistry, D-85764 Neuherberg, Germany.|∥Technische Universität München, Analytical Food Chemistry, D-85354 Freising-Weihenstephan, Germany.
authors.forename: Philippe
authors.initials: P
authors.lastname: Schmitt-Kopplin
mesh_terms: D004203:Disinfection / Q000379:methods*; D004563:Electrochemistry / Q000379:methods*; D054879:Halogenation; D007554:Isotopes; D013058:Mass Spectrometry; D009930:Organic Chemicals / Q000032:analysis*; D012623:Seawater / Q000737:chemistry*; D012995:Solubility; D014874:Water Pollutants, Chemical / Q000032:analysis*; D018508:Water Purification / Q000379:methods*
chemical_list: D007554:Isotopes; D009930:Organic Chemicals; D014874:Water Pollutants, Chemical