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Formation of 1,3,8-tribromodibenzo-p-dioxin and 2,4,6,8-tetrabromodibenzofuran in the oxidation of synthetic hydroxylated polybrominated diphenyl ethers by iron and manganese oxides under dry conditions

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Abstract

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are ubiquitous and highly toxic emerging endocrine disruptors found in surface and subsurface soils and clay deposits. Seriously, they could be easily transformed to the more toxic dioxins (PBDD/Fs) in photochemical processes and incineration, but the spontaneous formation of PBDD/Fs has rarely been reported. This study focused on the formation of 1,3,8-tribromodibenzo-p-dioxin (1,3,8-TrBDD) and 2,4,6,8-tetrabromodibenzofuran (2,4,6,8-TeBDF) from 2′-OH-BDE-68 and 2,2′-diOH-BB-80 under the oxidization of iron and manganese oxides (goethite and MnOx). Approximately 0.09 μmol/kg (2.33%) and 0.17 μmol/kg (4.15%) were transformed to 1,3,8-TrBDD and 2,4,6,8-TeBDF by goethite in 8 days and a higher conversion 0.15 μmol/kg (3.77%) and 0.23 μmol/kg (5.74%) were observed for MnOx in 4 days. However, the formation of PBDD/Fs, probably proceeding via Smiles rearrangements and bromine elimination processes, was greatly inhibited by the presence of water. Transformation of OH-PBDEs by goethite and MnOx was accompanied by release of Fe and Mn ions and the possible pathways for the formation of reaction products were proposed. In view of the ubiquity of OH-PBDEs and metal oxides in the environment, oxidation of OH-PBDEs mediated by goethite and MnOx is likely an abiotic route for the formation of PBDD/Fs.

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References

  • Arnoldsson K, Andersson PL, Haglund P (2012) Formation of environmentally relevant brominated dioxins from 2,4,6-tribromophenol via bromoperoxidase-catalyzed dimerization. Environ Sci Technol 46:7239–7244

    Article  CAS  Google Scholar 

  • Cao J, Lin YA, Guo LH, Zhang AQ, Wei Y, Yang Y (2010) Structure-based investigation on the binding interaction of hydroxylated polybrominated diphenyl ethers with thyroxine transport proteins. Toxicology 277:20–28

    Article  CAS  Google Scholar 

  • Cao H, He M, Han D, Li J, Li M, Wang W, Yao S (2013) OH-initiated oxidation mechanisms and kinetics of 2,4,4′-tribrominated diphenyl ether. Environ Sci Technol 47:8238–8247

    CAS  Google Scholar 

  • Chen ZJ, Liu HY, Ho KL, Huang HB, Liu Q, Man YB, Lam MHW, Du J, Wong MH, Wang HS (2016) Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) in paired maternal and neonatal samples from South China: placental transfer and potential risks. Environ Res 148:72–78

    Article  CAS  Google Scholar 

  • Ding JF, Su M, Wu CW, Lin KD (2015) Transformation of triclosan to 2,8-dichlorodibenzo-p-dioxin by iron and manganese oxides under near dry conditions. Chemosphere 133:41–46

    Article  CAS  Google Scholar 

  • Drage D, Aries E, Harrad S (2014) Studies into the formation of PBDEs and PBDD/Fs in the iron ore sintering process. Sci Total Environ 485:497–507

    Article  CAS  Google Scholar 

  • Eickhoff H, Jung G, Rieker A (2001) Oxidative phenol coupling - tyrosine dimers and libraries containing tyrosyl peptide dimers. Tetrahedron 57:353–364

    Article  CAS  Google Scholar 

  • Erickson PR, Grandbois M, Arnold WA, McNeill K (2012) Photochemical formation of brominated dioxins and other products of concern from hydroxylated polybrominated diphenyl ethers (OH-PBDEs). Environ Sci Technol 46:8174–8180

    Article  CAS  Google Scholar 

  • Evans CS, Dellinger B (2005) Formation of bromochlorodihenzo-p-dioxins and furans from the high-temperature pyrolysis of a 2-chlorophenol/2-bromophenol mixture. Environ Sci Technol 39:7940–7948

    Article  CAS  Google Scholar 

  • Grobelny Z (2004) Chemical methods for ether-bond cleavage by electron-transfer reagents. Eur J Org Chem 2004:2973–2982

    Article  CAS  Google Scholar 

  • Gu C, Li H, Teppen BJ, Boyd SA (2008) Octachlorodibenzodioxin formation on Fe (III)-montmorillonite clay. Environ Sci Technol 42:4758–4763

    Article  CAS  Google Scholar 

  • Gu C, Liu C, Ding Y, Li H, Teppen BJ, Johnston CT, Boyd SA (2011) Clay mediated route to natural formation of polychlorodibenzo-p-dioxins. Environ Sci Technol 45:3445–3451

    Article  CAS  Google Scholar 

  • Hites RA (2011) Dioxins: an overview and history. Environ Sci Technol 45:16–20

    Article  CAS  Google Scholar 

  • Iparraguirre A, Rodil R, Quintana JB, Bizkarguenaga E, Prieto A, Zuloaga O, Cela R, Fernandez LA (2014) Matrix solid-phase dispersion of polybrominated diphenyl ethers and their hydroxylated and methoxylated analogues in lettuce, carrot and soil. J chrom A 1360:57–65

    Article  CAS  Google Scholar 

  • Kende AS, Decamp MK (1975) Smile rearrangements in synthesis of hexachlorodibenzo-p-dioxins. Tetrahedron Lett 33:2877–2880

    Article  Google Scholar 

  • Kim UJ, Yen NT, Oh JE (2014) Hydroxylated, methoxylated and parent polybrominated diphenyl ethers (PBDEs) in the inland environment, Korea, and potential OH- and MeO-BDE source. Environ Sci Technol 48:7245–7253

    Article  CAS  Google Scholar 

  • Li H, Lee LS, Schulze DG, Guest CA (2003) Role of soil manganese in the oxidation of aromatic amines. Environ Sci Technol 37:2686–2693

    Article  CAS  Google Scholar 

  • Lin KD, Gan J, Liu WP (2014a) Production of hydroxylated polybrominated diphenyl ethers (HO-PBDEs) from bromophenols by bromoperoxidase-catalyzed dimerization. Environ Sci Technol 48:11977–11983

    Article  CAS  Google Scholar 

  • Lin KD, Yan C, Gan J (2014b) Production of hydroxylated polybrominated diphenyl ethers (OH-PBDEs) from bromophenols by manganese dioxide. Environ Sci Technol 48:263–271

    Article  CAS  Google Scholar 

  • Lin KD, Zhou SY, Chen X, Ding JF, Kong XY, Gan J (2015) Formation of hydroxylated polybrominated diphenyl ethers from laccase-catalyzed oxidation of bromophenols. Chemosphere 138:806–813

    Article  CAS  Google Scholar 

  • Liu HB, Chen TH, Frost RL (2014) An overview of the role of goethite surfaces in the environment. Chemosphere 103:1–11

    Article  CAS  Google Scholar 

  • Ma J, Addink R, Yun SH, Cheng JP, Wang WH, Kannan K (2009) Polybrominated dibenzo-p-dioxins/dibenzofurans and polybrominated diphenyl ethers in soil, vegetation, workshop-floor dust, and electronic shredder residue from an electronic waste recycling facility and in soils from a chemical industrial complex in eastern China. Environ Sci Technol 43:7350–7356

    Article  CAS  Google Scholar 

  • Marsh G, Stenutz R, Bergman A (2003) Synthesis of hydroxylated and methoxylated polybrominated diphenyl ethers-natural products and potential polybrominated diphenyl ether metabolites. Eur J Org Chem 2003(14):2566–2576

    Article  CAS  Google Scholar 

  • Marsh G, Athanasiadou M, Athanassiadis I, Sandholm A (2006) Identification of hydroxylated metabolites in 2,2′,4,4′-tetrabromodiphenyl ether exposed rats. Chemosphere 63:690–697

    Article  CAS  Google Scholar 

  • Ortuno N, Molto J, Conesa JA, Font R (2014a) Formation of brominated pollutants during the pyrolysis and combustion of tetrabromobisphenol A at different temperatures. Environ Pollut 191:31–37

    Article  CAS  Google Scholar 

  • Ortuno N, Conesa JA, Molto J, Font R (2014b) De novo synthesis of brominated dioxins and furans. Environ Sci Technol 48:7959–7965

    Article  CAS  Google Scholar 

  • Raff JD, Hites RA (2006) Gas-phase reactions of brominated diphenyl ethers with OH radicals. J Phys Chem A 110:10783–10792

    Article  CAS  Google Scholar 

  • Remucal CK, Ginder-Voge M (2014) A critical review of the reactivity of manganese oxides with organic contaminants. Environ Sci Proc Imp 16:1247–1266

    Article  CAS  Google Scholar 

  • Sakai S, Watanabe J, Honda Y, Takatsuki H, Aoki I, Futamatsu M, Shiozaki K (2001) Combustion of brominated flame retardants and behavior of its byproducts. Chemosphere 42:519–531

    Article  CAS  Google Scholar 

  • Sandau CD (2000) Analytical chemistry of hydroxylated metabolites of PCBs and other halogenated phenolic compounds in blood and their relationship to thyroid hormone and retinol homeostasis in humans and polar bears. Ph.D. Dissertation Carleton University Ottawa Ontario Canada

  • Schmitz M, Scheeder G, Ernau S, Dohrmann R, Germann K (2011) Dioxins in primary kaolin and secondary kaolinitic clays. Environ Sci Technol 45:461–467

    Article  CAS  Google Scholar 

  • Smith BA, Siems WF, Teel AL, Watts RJ (2006) Pyrolusite (β-MnO2)-mediated, near dry-phase oxidation of 2,4,6-trichlorophenol. Environ Toxicol Chem 25:1474–1479

    Article  CAS  Google Scholar 

  • Sovocool GW, Mitchum RK, Tondeur Y, Munslow WD, Vonnahme TL, Donnelly JR (1991) Predictions of bromo- and bromochloro-dioxin GC elution properties. Chemosphere 22:455–460

    Article  Google Scholar 

  • Steen PO, Grandbois M, McNeill K, Arnold WA (2009) Photochemical formation of halogenated dioxins from hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and chlorinated derivatives (OH-PBCDEs). Environ Sci Technol 43:4405–4411

    Article  CAS  Google Scholar 

  • Stone AT, Morgan JT (1987) Reductive dissolution of metal oxides. In: Stumm W (ed) Aquatic surface chemistry. Wiley, New York, pp 221–254

    Google Scholar 

  • Tang ZW, Huang QF, Cheng JL, Yang YF, Yang J, Guo W, Nie ZQ, Zeng N, Jin L (2014) Polybrominated diphenyl ethers in soils, sediments, and human hair in a plastic waste recycling area: a neglected heavily polluted area. Environ Sci Technol 48:1508–1516

    Article  CAS  Google Scholar 

  • Tolosa I, Bayona JM, Albaiges J (1991) Identification and occurrence of brominated and nitrated phenols in estuarine sediments. Mar Pollut Bull 22:603–607

    Article  CAS  Google Scholar 

  • Truce WE, Brand WW (1970) Rearrangements of sulfones to sulfinic acids via carbanion intermediates. J Org Chem 35:1828–1836

    Article  Google Scholar 

  • Ucan-Marin F, Arukwe A, Mortensen AS, Gabrielsen GW, Letcher RJ (2010) Recombinant albumin and transthyretin transport proteins from two gull species and human: chlorinated and brominated contaminant binding and thyroid hormones. Environ Sci Technol 44:497–504

    Article  CAS  Google Scholar 

  • Viollier E, Inglett PW, Hunter K, Roychoudhury AN, Van Cappellen P (2000) The ferrozine method revisited: Fe(II)/Fe(III) determination in natural waters. Appl Geochem 15:785–790

    Article  CAS  Google Scholar 

  • Weber R, Kuch B (2003) Relevance of BFRs and thermal conditions on the formation pathways of brominated and brominated-chlorinated dibenzodioxins and dibenzofurans. Environ Int 29:699–710

    Article  CAS  Google Scholar 

  • Weiss W, Zscherpel D, Schlögl R (1998) On the nature of the active site for the ethylbenzene dehydrogenation over iron oxide catalysts. Catal Lett 52:215–220

    Article  CAS  Google Scholar 

  • Xiao X, Hu JF, Peng PA, Chen DY, Bi XH (2011) Characterization of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDDs/Fs) in environmental matrices from an intensive electronic waste recycling site, South China. Environ Pollut 212:464–471

    Article  CAS  Google Scholar 

  • Zennegg M, Schluep M, Streicher-Porte M, Lienemann P, Haag R, Gerecke AC (2014) Formation of PBDD/F from PBDE in electronic waste in recycling processes and under simulated extruding conditions. Chemosphere 116:34–39

    Article  CAS  Google Scholar 

  • Zhang H, Huang CH (2007) Adsorption and oxidation of fluoroquinolone antibacterial agents and structurally related amines with goethite. Chemosphere 66:1502–1512

    Article  CAS  Google Scholar 

  • Zhang QZ, Yu WN, Zhang RX, Zhou Q, Gao R, Wang WX (2010) Quantum chemical and kinetic study on dioxin formation from the 2,4,6-TCP and 2,4-DCP precursors. Environ Sci Technol 44:3395–3403

    Article  CAS  Google Scholar 

  • Zhang MM, Buekens A, Li XD (2016) Brominated flame retardants and the formation of dioxins and furans in fires and combustion. J Hazard Mater 304:26–39

    Article  CAS  Google Scholar 

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Acknowledgments

The authors highly appreciate the assistance of instruments and expert analysis by Prof. Lin Kunde in Zhejiang University of Technology.

Funding

This work was supported by the National Natural Science Foundation of China (Grant Nos. 51278456 and 51778564).

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Authors and Affiliations

  1. Department of Environmental Engineering, Zhejiang University, 866 Yu Hang Tang Road, Hangzhou, 310058, China

    Jiafeng Ding, Gaoyuan Long, Yang Luo, Runze Sun, Mengxia Chen, Yajun Li, Yanfang Zhou, Xinhua Xu & Weirong Zhao

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  1. Jiafeng Ding
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  2. Gaoyuan Long
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  3. Yang Luo
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  4. Runze Sun
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  7. Yanfang Zhou
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  8. Xinhua Xu
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Correspondence to Weirong Zhao.

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Responsible editor: Philippe Garrigues

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Ding, J., Long, G., Luo, Y. et al. Formation of 1,3,8-tribromodibenzo-p-dioxin and 2,4,6,8-tetrabromodibenzofuran in the oxidation of synthetic hydroxylated polybrominated diphenyl ethers by iron and manganese oxides under dry conditions. Environ Sci Pollut Res 25, 30160–30169 (2018). https://doi.org/10.1007/s11356-018-2980-4

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