Bromine Radical (Br• and Br2•-) Reactivity with Dissolved Organic Matter and Brominated Organic Byproduct Formation.

Dissolved organic matter (DOM) is a major scavenger of bromine radicals (e.g., Br• and Br2•-) in sunlit surface waters and during oxidative processes used in water treatment. However, the literature lacks quantitative measurements of reaction rate constants between bromine radicals and DOM and lacks information on the extent to which these reactions form brominated organic byproducts. Based on transient kinetic analysis with different fractions and sources of DOM, we determined reaction rate constants for DOM with Br• ranging from <5.0 × 107 to (4.2 ± 1.3) × 108 MC-1 s-1, which are comparable with those of HO• but higher than those with Br2•- (k = (9.0 ± 2.0) × 104 to (12.4 ± 2.1) × 105 MC-1 s-1). Br• and Br2•- attack the aromatic and antioxidant moieties of DOM via the electron transfer mechanism, resulting in Br- release with minimal substitution of bromine into DOM. For example, the total organic bromine was less than 0.25 μM (as Br) at environmentally relevant bromine radicals' exposures of ∼10-9 M·s. The results give robust evidence that the scavenging of bromine radicals by DOM is a crucial step to prevent inorganic bromine radical chemistry from producing free bromine (HOBr/OBr-) and subsequent brominated byproducts.

[1]  Gangfeng Ouyang,et al.  Rate Constants and Mechanisms for Reactions of Bromine Radicals with Trace Organic Contaminants. , 2021, Environmental science & technology.

[2]  P. Westerhoff,et al.  Reactivity of Chlorine Radicals (Cl• and Cl2•-) with Dissolved Organic Matter and the Formation of Chlorinated Byproducts. , 2020, Environmental science & technology.

[3]  Jie Yang,et al.  Methods for total organic halogen (TOX) analysis in water: Past, present, and future , 2020 .

[4]  Woorim Lee,et al.  Mechanistic and kinetic understanding of the UV254 photolysis of chlorine and bromine species in water and formation of oxyhalides. , 2020, Environmental science & technology.

[5]  Christina K. Remucal,et al.  Molecular-level transformation of dissolved organic matter during oxidation by ozone and hydroxyl radical. , 2020, Environmental science & technology.

[6]  Christina K. Remucal,et al.  The role of reactive halogen species in disinfection by-product formation during chlorine photolysis. , 2020, Environmental science & technology.

[7]  Liping Wang,et al.  Comparative study for interactions of sulfate radical and hydroxyl radical with phenol in the presence of nitrite. , 2020, Environmental science & technology.

[8]  Shaomin Ji,et al.  Roles of bromine radicals and hydroxyl radicals in the degradation of micropollutants by the UV/bromine process. , 2020, Environmental science & technology.

[9]  Jin Jiang,et al.  Formation and control of bromate in sulfate radical-based oxidation processes for the treatment of waters containing bromide: A critical review. , 2020, Water research.

[10]  Y. Lei,et al.  Co-exposure degradation of purine derivatives in sulfate radical-mediated oxidation process. , 2019, Environmental science & technology.

[11]  W. Mitch,et al.  Pilot-scale evaluation of oxidant speciation, 1,4-dioxane degradation and disinfection byproduct formation during UV/hydrogen peroxide, UV/free chlorine and UV/chloramines advanced oxidation process treatment for potable reuse. , 2019, Water research.

[12]  T. Karanfil,et al.  Oxidation byproducts from the degradation of dissolved organic matter by advanced oxidation processes - A critical review. , 2019, Water research.

[13]  Ye Du,et al.  Disinfection byproducts and their toxicity in wastewater effluents treated by the mixing oxidant of ClO2/Cl2. , 2019, Water research.

[14]  Huaxi Zhou,et al.  Photochemical formation of carbonate radical and its reaction with dissolved organic matters. , 2019, Water research.

[15]  T. An,et al.  Rate Constants and of Mechanisms for the Reactions of Cl• and Cl2•- with Trace Organic Contaminants. , 2019, Environmental science & technology.

[16]  S. Zou,et al.  DBP alteration from NOM and model compounds after UV/persulfate treatment with post chlorination. , 2019, Water research.

[17]  Tanju Karanfil,et al.  Historical and Future Needs for Geospatial Iodide Occurrence in Surface and Groundwaters of the United States of America , 2019, Environmental Science & Technology Letters.

[18]  Benjamin D. Stanford,et al.  Does Granular Activated Carbon with Chlorination Produce Safer Drinking Water? From Disinfection Byproducts and Total Organic Halogen to Calculated Toxicity. , 2019, Environmental science & technology.

[19]  Liping Wang,et al.  PPCP degradation and DBP formation in the solar/free chlorine system: Effects of pH and dissolved oxygen. , 2019, Water research.

[20]  Shuwen Yan,et al.  Comparison of the UV/chlorine and UV/H2O2 processes in the degradation of PPCPs in simulated drinking water and wastewater: Kinetics, radical mechanism and energy requirements. , 2018, Water research.

[21]  Ke Zhang,et al.  Halogen Radical Oxidants in Natural and Engineered Aquatic Systems. , 2018, Environmental science & technology.

[22]  Jörg E. Drewes,et al.  Evaluation of advanced oxidation processes for water and wastewater treatment - A critical review. , 2018, Water research.

[23]  U. von Gunten.  Oxidation Processes in Water Treatment: Are We on Track? , 2018, Environmental science & technology.

[24]  Xin Yang,et al.  The Multiple Role of Bromide Ion in PPCPs Degradation under UV/Chlorine Treatment. , 2018, Environmental science & technology.

[25]  Jun Ma,et al.  Mechanistic insight into suppression of bromate formation by dissolved organic matters in sulfate radical-based advanced oxidation processes , 2018 .

[26]  W. Mitch,et al.  Drinking Water Disinfection Byproducts (DBPs) and Human Health Effects: Multidisciplinary Challenges and Opportunities. , 2017, Environmental science & technology.

[27]  Qian-Yuan Wu,et al.  Degradation of natural organic matter by UV/chlorine oxidation: Molecular decomposition, formation of oxidation byproducts and cytotoxicity. , 2017, Water research.

[28]  J. Chovelon,et al.  Reactivity of sulfate radicals with natural organic matters , 2017, Environmental Chemistry Letters.

[29]  Tianhu Chen,et al.  Photochemical reaction between triclosan and nitrous acid in the atmospheric aqueous environment , 2017 .

[30]  Shuwen Yan,et al.  Kinetic Study of Hydroxyl and Sulfate Radical-Mediated Oxidation of Pharmaceuticals in Wastewater Effluents. , 2017, Environmental science & technology.

[31]  J. Vanbriesen,et al.  Current and Potential Future Bromide Loads from Coal-Fired Power Plants in the Allegheny River Basin and Their Effects on Downstream Concentrations. , 2016, Environmental science & technology.

[32]  L. Wojnárovits,et al.  One-electron oxidation of molecules with aromatic and thioether functions: Cl2−/Br2− and OH induced oxidation of penicillins studied by pulse radiolysis , 2016 .

[33]  W. Mitch,et al.  Halogen radicals contribute to photooxidation in coastal and estuarine waters , 2016, Proceedings of the National Academy of Sciences.

[34]  Qingguo Huang,et al.  Natural Organic Matter Exposed to Sulfate Radicals Increases Its Potential to Form Halogenated Disinfection Byproducts. , 2016, Environmental science & technology.

[35]  J. Criquet,et al.  Reaction of bromine and chlorine with phenolic compounds and natural organic matter extracts--Electrophilic aromatic substitution and oxidation. , 2015, Water research.

[36]  D. Dionysiou,et al.  Bromate formation in bromide-containing water through the cobalt-mediated activation of peroxymonosulfate. , 2015, Water research.

[37]  U. Gunten,et al.  Development of Prediction Models for the Reactivity of Organic Compounds with Ozone in Aqueous Solution by Quantum Chemical Calculations: The Role of Delocalized and Localized Molecular Orbitals. , 2015, Environmental science & technology.

[38]  L. Mayer,et al.  A marine sink for chlorine in natural organic matter , 2015 .

[39]  Junhe Lu,et al.  Transformation of bromide in thermo activated persulfate oxidation processes. , 2015, Water research.

[40]  J. Thornton,et al.  Tropospheric Halogen Chemistry: Sources, Cycling, and Impacts , 2015, Chemical Reviews.

[41]  J. Croué,et al.  Formation of brominated disinfection byproducts from natural organic matter isolates and model compounds in a sulfate radical-based oxidation process. , 2014, Environmental science & technology.

[42]  Jing Ma,et al.  Sunlight-driven photochemical halogenation of dissolved organic matter in seawater: a natural abiotic source of organobromine and organoiodine. , 2014, Environmental science & technology.

[43]  T. Schmidt,et al.  Formation of bromate in sulfate radical based oxidation: mechanistic aspects and suppression by dissolved organic matter. , 2014, Water research.

[44]  K. Linden,et al.  Identifying the factors that influence the reactivity of effluent organic matter with hydroxyl radicals. , 2014, Water research.

[45]  K. McNeill,et al.  Photooxidation-induced changes in optical, electrochemical, and photochemical properties of humic substances. , 2014, Environmental science & technology.

[46]  S. Canonica,et al.  Chemical oxidation of dissolved organic matter by chlorine dioxide, chlorine, and ozone: effects on its optical and antioxidant properties. , 2013, Environmental science & technology.

[47]  P. Pernot,et al.  Oxidation of bromide ions by hydroxyl radicals: spectral characterization of the intermediate BrOH•-. , 2013, The journal of physical chemistry. A.

[48]  U. von Gunten,et al.  Quantitative structure-activity relationships (QSARs) for the transformation of organic micropollutants during oxidative water treatment. , 2012, Water research.

[49]  G. Mailhot,et al.  Assessing the occurrence of the dibromide radical (Br₂⁻•) in natural waters: measures of triplet-sensitised formation, reactivity, and modelling. , 2012, The Science of the total environment.

[50]  C. Shang,et al.  Bromate formation from bromide oxidation by the UV/persulfate process. , 2012, Environmental science & technology.

[51]  S. Mezyk,et al.  Temperature dependence of the reaction between the hydroxyl radical and organic matter. , 2011, Environmental Science and Technology.

[52]  Xin Yang,et al.  Characterization of algal organic matter and formation of DBPs from chlor(am)ination. , 2010, Water research.

[53]  J. Pignatello,et al.  Effect of halide ions and carbonates on organic contaminant degradation by hydroxyl radical-based advanced oxidation processes in saline waters. , 2010, Environmental science & technology.

[54]  S. Mezyk,et al.  Reactivity of effluent organic matter (EfOM) with hydroxyl radical as a function of molecular weight. , 2010, Environmental science & technology.

[55]  Jun Ma,et al.  Formation of carbonaceous and nitrogenous disinfection by-products from the chlorination of Microcystis aeruginosa. , 2010, Water research.

[56]  Matthew P. Miller,et al.  Effect of instrument‐specific response on the analysis of fulvic acid fluorescence spectra , 2010 .

[57]  B. d'Anna,et al.  Photoinduced oxidation of sea salt halides by aromatic ketones: a source of halogenated radicals , 2009 .

[58]  I. Fábián,et al.  One- versus two-electron oxidation with peroxomonosulfate ion: reactions with iron(II), vanadium(IV), halide ions, and photoreaction with cerium(III). , 2009, Inorganic chemistry.

[59]  Devin F R Doud,et al.  Quantitative correlation of absolute hydroxyl radical rate constants with non-isolated effluent organic matter bulk properties in water. , 2008, Environmental science & technology.

[60]  B. Xing,et al.  Dissolved organic matter conformation and its interaction with pyrene as affected by water chemistry and concentration. , 2008, Environmental science & technology.

[61]  D. DeMarini,et al.  Occurrence, genotoxicity, and carcinogenicity of regulated and emerging disinfection by-products in drinking water: a review and roadmap for research. , 2007, Mutation research.

[62]  W. J. Cooper,et al.  Electron pulse radiolysis determination of hydroxyl radical rate constants with Suwannee River fulvic acid and other dissolved organic matter isolates. , 2007, Environmental science & technology.

[63]  E. Ainsworth,et al.  Estimation of total phenolic content and other oxidation substrates in plant tissues using Folin–Ciocalteu reagent , 2007, Nature Protocols.

[64]  S. Canonica,et al.  Photosensitizer method to determine rate constants for the reaction of carbonate radical with organic compounds. , 2005, Environmental science & technology.

[65]  P. Neta,et al.  Rate Constants for Reactions of Phenoxyl Radicals in Solution , 2005 .

[66]  P. Westerhoff,et al.  Reactivity of natural organic matter with aqueous chlorine and bromine. , 2004, Water research.

[67]  K. Booksh,et al.  Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter. , 2003, Environmental science & technology.

[68]  H. Gallard,et al.  Chlorination of phenols: kinetics and formation of chloroform. , 2002, Environmental science & technology.

[69]  G. L. Roux,et al.  Kinetic Study of the Reactions of Chlorine Atoms and Cl2•- Radical Anions in Aqueous Solutions. II. Toluene, Benzoic Acid, and Chlorobenzene† , 2001 .

[70]  A. Braun,et al.  Kinetic Study of the Reactions of Chlorine Atoms and Cl2•- Radical Anions in Aqueous Solutions. 1. Reaction with Benzene , 2000 .

[71]  Smith,et al.  pi-Complexes as "Modulators" of Bromine Atom Reactivity in Solution. , 2000, The Journal of organic chemistry.

[72]  R. H. Schuler,et al.  Reduction Potentials and Kinetics of Electron Transfer Reactions of Phenylthiyl Radicals: Comparisons with Phenoxyl Radicals1 , 1996 .

[73]  E. O’Loughlin,et al.  Molecular weight, polydispersity, and spectroscopic properties of aquatic humic substances. , 1994, Environmental science & technology.

[74]  J. Lind,et al.  Reaction Mechanism of Hydrogen Abstraction by the Bromine Atom in Water , 1994 .

[75]  M. Krzywinski,et al.  Laser flash photolysis determination of absolute rate constants for reactions of bromine atoms in solution , 1993 .

[76]  P. Wardman,et al.  Reduction Potentials of One-Electron Couples Involving Free Radicals in Aqueous Solution , 1989 .

[77]  G. Buxton,et al.  Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O− in Aqueous Solution , 1988 .

[78]  Z. Alfassi,et al.  Substituent effects on rates of one-electron oxidation of phenols by the radicals chlorine dioxide, nitrogen dioxide, and trioxosulfate(1-) , 1986 .

[79]  S. D. Boyce,et al.  Reaction pathways of trihalomethane formation from the halogenation of dihydroxyaromatic model compounds for humic acid. , 1983, Environmental science & technology.

[80]  M. Jekel,et al.  Total organic halogen as a parameter for the characterization of reclaimed waters: measurement, occurrence, formation, and removal. , 1980, Environmental science & technology.

[81]  Y. Lei,et al.  Radical chemistry of diethyl phthalate oxidation via UV/peroxymonosulfate process: Roles of primary and secondary radicals , 2020 .

[82]  J. Criquet,et al.  Oxidative treatment of bromide-containing waters: formation of bromine and its reactions with inorganic and organic compounds--a critical review. , 2014, Water research.

[83]  U. von Gunten,et al.  Reactions of chlorine with inorganic and organic compounds during water treatment-Kinetics and mechanisms: a critical review. , 2008, Water research.

[84]  C. Anastasio,et al.  A chemical probe technique for the determination of reactive halogen species in aqueous solution: Part 1 – bromide solutions , 2006 .

[85]  U. Gunten,et al.  Advanced Oxidation of Bromide-Containing Waters: Bromate Formation Mechanisms , 1998 .

[86]  E. Land.  Preparation of unstable quinones in aqueous solution via pulse radiolytic one-electron oxidation of dihydroxybenzenes , 1993 .

[87]  P. Neta,et al.  Rate Constants for Reactions of Inorganic Radicals in Aqueous Solution , 1979 .

[88]  J. Rabani,et al.  Oxidation of aqueous bromide ions by hydroxyl radicals. Pulse radiolytic investigation , 1972 .