Environmental Science and Pollution Research

, Volume 25, Issue 30, pp 30160–30169 | Cite as

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

  • Jiafeng Ding
  • Gaoyuan Long
  • Yang Luo
  • Runze Sun
  • Mengxia Chen
  • Yajun Li
  • Yanfang Zhou
  • Xinhua Xu
  • Weirong ZhaoEmail author
Research Article


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.


OH-PBDEs PBDD/Fs Goethite Manganese oxides Oxidative transformation Water inhibition 



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

Funding information

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

Supplementary material

11356_2018_2980_MOESM1_ESM.docx (274 kb)
ESM 1 (DOCX 220 kb)


  1. 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 46:7239–7244CrossRefGoogle Scholar
  2. 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 277:20–28CrossRefGoogle Scholar
  3. 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 47:8238–8247Google Scholar
  4. 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 148:72–78CrossRefGoogle Scholar
  5. 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 133:41–46CrossRefGoogle Scholar
  6. 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 485:497–507CrossRefGoogle Scholar
  7. Eickhoff H, Jung G, Rieker A (2001) Oxidative phenol coupling - tyrosine dimers and libraries containing tyrosyl peptide dimers. Tetrahedron 57:353–364CrossRefGoogle Scholar
  8. 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 46:8174–8180CrossRefGoogle Scholar
  9. 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 39:7940–7948CrossRefGoogle Scholar
  10. Grobelny Z (2004) Chemical methods for ether-bond cleavage by electron-transfer reagents. Eur J Org Chem 2004:2973–2982CrossRefGoogle Scholar
  11. Gu C, Li H, Teppen BJ, Boyd SA (2008) Octachlorodibenzodioxin formation on Fe (III)-montmorillonite clay. Environ Sci Technol 42:4758–4763CrossRefGoogle Scholar
  12. 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 45:3445–3451CrossRefGoogle Scholar
  13. Hites RA (2011) Dioxins: an overview and history. Environ Sci Technol 45:16–20CrossRefGoogle Scholar
  14. 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 1360:57–65CrossRefGoogle Scholar
  15. Kende AS, Decamp MK (1975) Smile rearrangements in synthesis of hexachlorodibenzo-p-dioxins. Tetrahedron Lett 33:2877–2880CrossRefGoogle Scholar
  16. 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 48:7245–7253CrossRefGoogle Scholar
  17. Li H, Lee LS, Schulze DG, Guest CA (2003) Role of soil manganese in the oxidation of aromatic amines. Environ Sci Technol 37:2686–2693CrossRefGoogle Scholar
  18. Lin KD, Gan J, Liu WP (2014a) Production of hydroxylated polybrominated diphenyl ethers (HO-PBDEs) from bromophenols by bromoperoxidase-catalyzed dimerization. Environ Sci Technol 48:11977–11983CrossRefGoogle Scholar
  19. Lin KD, Yan C, Gan J (2014b) Production of hydroxylated polybrominated diphenyl ethers (OH-PBDEs) from bromophenols by manganese dioxide. Environ Sci Technol 48:263–271CrossRefGoogle Scholar
  20. 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 138:806–813CrossRefGoogle Scholar
  21. Liu HB, Chen TH, Frost RL (2014) An overview of the role of goethite surfaces in the environment. Chemosphere 103:1–11CrossRefGoogle Scholar
  22. 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 43:7350–7356CrossRefGoogle Scholar
  23. 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):2566–2576CrossRefGoogle Scholar
  24. Marsh G, Athanasiadou M, Athanassiadis I, Sandholm A (2006) Identification of hydroxylated metabolites in 2,2′,4,4′-tetrabromodiphenyl ether exposed rats. Chemosphere 63:690–697CrossRefGoogle Scholar
  25. 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 191:31–37CrossRefGoogle Scholar
  26. Ortuno N, Conesa JA, Molto J, Font R (2014b) De novo synthesis of brominated dioxins and furans. Environ Sci Technol 48:7959–7965CrossRefGoogle Scholar
  27. Raff JD, Hites RA (2006) Gas-phase reactions of brominated diphenyl ethers with OH radicals. J Phys Chem A 110:10783–10792CrossRefGoogle Scholar
  28. Remucal CK, Ginder-Voge M (2014) A critical review of the reactivity of manganese oxides with organic contaminants. Environ Sci Proc Imp 16:1247–1266CrossRefGoogle Scholar
  29. 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 42:519–531CrossRefGoogle Scholar
  30. 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 CanadaGoogle Scholar
  31. Schmitz M, Scheeder G, Ernau S, Dohrmann R, Germann K (2011) Dioxins in primary kaolin and secondary kaolinitic clays. Environ Sci Technol 45:461–467CrossRefGoogle Scholar
  32. 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 25:1474–1479CrossRefGoogle Scholar
  33. Sovocool GW, Mitchum RK, Tondeur Y, Munslow WD, Vonnahme TL, Donnelly JR (1991) Predictions of bromo- and bromochloro-dioxin GC elution properties. Chemosphere 22:455–460CrossRefGoogle Scholar
  34. 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 43:4405–4411CrossRefGoogle Scholar
  35. Stone AT, Morgan JT (1987) Reductive dissolution of metal oxides. In: Stumm W (ed) Aquatic surface chemistry. Wiley, New York, pp 221–254Google Scholar
  36. 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 48:1508–1516CrossRefGoogle Scholar
  37. Tolosa I, Bayona JM, Albaiges J (1991) Identification and occurrence of brominated and nitrated phenols in estuarine sediments. Mar Pollut Bull 22:603–607CrossRefGoogle Scholar
  38. Truce WE, Brand WW (1970) Rearrangements of sulfones to sulfinic acids via carbanion intermediates. J Org Chem 35:1828–1836CrossRefGoogle Scholar
  39. 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 44:497–504CrossRefGoogle Scholar
  40. 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 15:785–790CrossRefGoogle Scholar
  41. 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 29:699–710CrossRefGoogle Scholar
  42. Weiss W, Zscherpel D, Schlögl R (1998) On the nature of the active site for the ethylbenzene dehydrogenation over iron oxide catalysts. Catal Lett 52:215–220CrossRefGoogle Scholar
  43. 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 212:464–471CrossRefGoogle Scholar
  44. 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 116:34–39CrossRefGoogle Scholar
  45. Zhang H, Huang CH (2007) Adsorption and oxidation of fluoroquinolone antibacterial agents and structurally related amines with goethite. Chemosphere 66:1502–1512CrossRefGoogle Scholar
  46. 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 44:3395–3403CrossRefGoogle Scholar
  47. Zhang MM, Buekens A, Li XD (2016) Brominated flame retardants and the formation of dioxins and furans in fires and combustion. J Hazard Mater 304:26–39CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Environmental EngineeringZhejiang UniversityHangzhouChina

Personalised recommendations