Treatment Technologies for Removal of Polybrominated Diphenyl Ethers (PBDEs) from Wastewater

하·폐수내 브롬화 디페닐 에테르(Polybrominated Diphenyl Ether, PBDEs)의 분포 및 제거기술 동향

  • Kim, Minhee (Korea University Institute of Environment and Ecology, Korea University) ;
  • Hyun, Seunghun (Department of Environmental Science and Ecological Engineering, Korea University) ;
  • Lee, Won-Seok (Water Supply and Sewerage Research Division, National Institute of Environmental Research)
  • 김민희 (고려대학교 환경생태연구소) ;
  • 현승훈 (고려대학교 환경생태공학과) ;
  • 이원석 (국립환경과학원 상하수도연구과)
  • Received : 2017.08.24
  • Accepted : 2017.10.17
  • Published : 2017.11.30


Polybrominated diphenyl ethers (PBDEs) are a group of industrial aromatic organobromine chemicals that have been used since the 1970s as flame retardants in a wide range of consumer products and articles, including plastics, computers, textiles and upholstery. Commercial PBDEs were added to Annex A of the Stockholm Convention as persistent organic pollutants in May 2009. PBDEs are still frequently found in sludge and effluent from wastewater treatment plants, even though commercial PBDEs were prohibited or voluntarily phased out several years ago. Conventional wastewater treatment processes are not designed to effectively remove PBDEs. This indicates that there is an urgent need for new developments and improvements to enhance upon the treatment techniques which are currently available. Several studies have suggested the potential removal and degradation technologies for PBDEs in wastewater. In this study, the concentrations and compositional profiles of PBDE congeners in sludge and effluent are investigated by analyzing the relevant literature data in relation to their usage patterns in commercial products in North America and South Korea. The strengths and weaknesses of the current PBDEs removal techniques (i.e., biodegradation, zero-valent iron, photolysis, sorption, etc.) are discussed critically. In addition, future research direction regarding the treatment and removal of PBDEs from wastewater is also suggested, based on the literature review.


Supported by : National Research Foundation of Korea (NRF)


  1. Anderson, T. D. and MacRae, J. D. (2006). Polybrominated Diphenyl Ethers in Fish and Wastewater Samples from an Area of the Penobscot River in Central Maine, Chemosphere, 62, 1153-1160.
  2. Andrade, N. A., McConnell, L. L., Torrents, A., and Ramirez, M. (2010). Persistence of Polybrominated Diphenyl Ethers in Agricultural Soils after Biosolids Applications, Journal of Agricultural and Food Chemistry, 58, 3077-3084.
  3. Arnold, R. G., Teske, S., Tomanek, M., Engstrom, J., Leung, C., Zhang, J., Banihani, Q., Quanrud, D., Ela, W. P., and Saez, A. E. (2008). Fate of Polybrominated Diphenyl Ethers during Wastewater Treatment/Polishing and Sludge Stabilization/Disposal. Environmental Challenges in the Pacific Basin, Carpenter, D. O., ed., Blackwell Publishing, Oxford, 394-411.
  4. Bezares-Cruz, J., Jafvert, C. T., and Hua, I. (2004). Solar Photodecomposition of Decabromodiphenyl Ether: Products and Quantum Yield, Environmental Science and Technology, 38(15), 4149-4156.
  5. Breivik, K., Armitage, J. M., Wania, F., Sweetman, A. J., and Jones, K. C. (2016). Tracking the Global Distribution of Persistent Organic Pollutants Accounting for E-waste Exports to Developing Regions, Environmental Science and Technology, 50, 798-805.
  6. Bromine Science and Environmental Forum (BSEF). (2003). Major Brominated Flame Retardants Volume Estimates, Total Market Demand by Region in 2001, Bromine Science Environmental Forum.
  7. Cai, Y., Liang, B., Fang, Z., Xie, Y., and Tsang, E. (2015). Effect of Humic Acid and Metal Ions on the Debromination of BDE209 by nZVM prepared from Steel Pickling Waste Liquor, Front, Environmental Science and Engineering,
  8. Ciblak, A. (2011). Chemical Changes and Performance of Iron-Electrolysis for Groundwater Remediation, MSc thesis, Northeastern University, Boston-Massachusetts, USA.
  9. Cincinelli, A., Martellini, T., Misuri, L., Lanciotti, E., Sweetman, A., Laschi, S., and Palchetti, I. (2012). PBDEs in Italian Sewage Sludge and Environmental Risk of using Sewage Sludge for Land Application, Environmental Pollution, 161, 229-234.
  10. Ciparis, S. and Hale, R. C. (2005). Bioavailability of Polybrominated Diphenyl Ether Flame Retardants in Biosolids and Spiked Sediment to the Aquatic Oligochaete, Lumbriculus Variegatus, Environmental Toxicology and Chemistry, 24, 916-925.
  11. Daso, A. P., Fatoki, O. S., Odendaal, J. P., and Olujimi, O. O. (2012). Occurrence of Selected Polybrominated Diphenyl Ethers and 2,2',4,4',5,5'-hexabromobiphenyl (BB-153) in Sewage Sludge and Effluent Samples of a Wastewater Treatment Plant in Cape Town, South Africa, Archives of Environmental Contamination and Toxicology, 62, 391-402.
  12. Davis, E. F., Klosterhaus, S. L., and Stapleton, H. M. (2012). Measurement of Flame Retardants and Triclosan in Municipal Sewage Sludge and Biosolids, Environment International, 40, 1-7.
  13. Davis, E. F. and Stapleton, H. M. (2009). Photodegradation Pathways of Nonabrominated Diphenyl Ethers, 2-Ethylhexyltetrabromobenzoate and Di(2-ethylhexyl)tetrabromophthalate: Identifying Potential Markers of Photodegradation, Environmental Science and Technology, 43(15), 5739-5746.
  14. Deng, D., Chen, H., and Tam, N. F. Y. (2015). Temporal and Spatial Contamination of Polybrominated Diphenyl Ethers (PBDEs) in Wastewater Treatment Plants in Hong Kong, Science of the Total Environment, 502, 133-142.
  15. Deplanche, K., Snape, T. J., Hazrati, S., Harrad, S., and Macaskie, L. E. (2009). Versatility of a New Bioinorganic Catalyst: Palladized Cells of Desulfovibrio Desulfuricans and Application to Dehalogenation of Flame Retardant Materials, Environmental Technology, 30, 681-692.
  16. ENVIRON. (2003). Voluntary Children's Chemical Evaluation Program Pilot. Tier 1 Assessment of the Potential Health Risks to Children Associated with Exposure to the Commercial Penta-Bromodiphenyl Ether Product, Emeryville, California, ENVIRON Int. Corp.
  17. Eriksson, J., Green, N., Marsh, G., and Bergman, A. (2004). Photochemical Decomposition of 15 Polybrominated Diphenyl Ether Congeners in Methanol/Water, Environmental Science and Technology, 38, 3119-3125.
  18. European Union (EU). (2003). Directive 2002/95/EC of 27 January 2003 of the European Parliament and of the Council on the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment, Official Journal of the European Union. L37/19-L37/23.
  19. Fang, L., Huang, J., Yu, G., and Wang, L. (2008). Photochemical Degradation of Six Polybrominated Diphenyl Ether Congeners under Ultraviolet Irradiation in Hexane, Chemosphere, 71 (2), 258-267.
  20. Fang, Z., Qiu, X., and Chen, J. (2011a). Debromination of Polybrominated Diphenyl Ethers by Ni/Fe Bimetallic Nanoparticles: Influencing Factors, Kinetics, and Mechanism, Journal of Hazardous Materials, 185(2-3), 958-969.
  21. Fang, Z., Qiu, X., and Chen, J. (2011b). Degradation of the Polybrominated Diphenyl Ethers by Nanoscale Zero-Valent Metallic Particles prepared from Steel Pickling Waste liquor, Desalination, 267(1), 34-41.
  22. Gardner, M., Comber, S., Scrimshaw, M. D., Cartmell, E., Lester, J., and Ellor, B. (2012). The Significance of Hazardous Chemicals in Wastewater Treatment Works Effluents, Science of the Total Environment, 437, 363-372.
  23. Gereke, A., Hartmann, P., Heeb, N., Kohler, H. P., Giger, W., Schmid, P., Zennegg, M., and Kohler, M. (2005). Anaerobic Degradation of Decabromodiphenyl Ether, Environmental Science and Technology, 39, 1078-1083.
  24. Gorgy, T., Li, L. Y., Grace, J. R., and Ikonomou, M. G. (2010). Polybrominated Diphenyl Ether Leachability from Biosolids and their Partitioning Characteristics in the Leachate, Water Air and Soil Pollution, 209, 109-121.
  25. Gottschall, N., Topp, E., Edwards, M., Russell, P., Payne, M., Kleywegt, S., Curnoe, W., and Lapen, D. R. (2010). Polybrominated Diphenyl Ethers, Perfluorinated Alkylated Substances, and Metals in Tile Drainage and Groundwater following Applications of Municipal Biosolids to Agricultural Fields, Science of the Total Environment, 408, 873-883.
  26. Habekost, A. and Aristov, N. (2012). Heterogeneous Reductive Dehalogenation of PCB Contaminated Transformer Oil and Brominated Diphenyl Ethers with Zero Valent Iron, Chemosphere, 88, 1283-1286.
  27. Hale, R. C., Alaee, M., Manchester-Neesvig, J. B., Stapleton, H., and Ikonomou, M. G. (2003). Polybrominated Diphenyl Ether Flame Retardants in the North American Environment, Environment International, 29, 771-779.
  28. Hale, R. C., La Guardia, M. J., Harvey, E., and Mainor, T. M. (2002). Potential Role of Fire Retardant-Treated Polyurethane Foam as a Source of Brominated Diphenyl Ethers to the US Environment, Chemosphere, 46, 729-735.
  29. He, J., Robrock, K., and Alvarez-Cohen, L. (2006). Microbial Reductive Debromination of Polybrominated Diphenyl Ethers (PBDEs), Environmental Science and Technology, 40, 4429-4434.
  30. Hu, J. W., Zhuang, Y., Luo, J., Wei, X. H., and Huang, X. F. (2012). A Theoretical Study on Reductive Debromination of Polybrominated Diphenyl Ethers, International Journal of Molecular Sciences, 13(7), 9332-9342.
  31. Hwang, I., Kang, H., Lee, I., and Oh, J. (2012). Assessment of Characteristic Distribution of PCDD/Fs and BFRs in Sludge Generated at Municipal and Industrial Wastewater Treatment Plants, Chemosphere, 88, 888-894.
  32. Keum, Y. S. and Li, Q. X. (2005). Reductive Debromination of Polybrominated Diphenyl ethers by Zero Valent Iron, Environmental Science and Technology, 39(7), 2280-2286.
  33. Kim, M., Guerra, P., Theocharides, M., Barclay, K., Smyth, S. A., and Alaee, M. (2013). Polybrominated Diphenyl Ethers in Sewage Sludge and Treated Biosolids: Effect Factors and Mass Balance, Water Research, 47, 6496-6505.
  34. Kim, M., Li, L. Y., Gorgy, T., and Grace, J. R. (2017). Review of Contamination of Sewage Sludge and Amended Soils by Polybrominated Diphenyl Ethers based on Meta-Analysis, Environmental Pollution, 220, 753-765.
  35. Kim, U. J., Lee, I. S., and Oh, J. E. (2016). Occurrence, Removal and Release Characteristics of Dissolved Brominated Flame Retardants and Their Potential Metabolites in Various Kinds of Wastewater, Environmental Pollution, 218, 551-557.
  36. Kim, Y. J., Lee, D. H., and Song, J. T. (2011). Discharge Characteristics of PBDEs from MSW Landfills and Sewage Treatment Plants, Journal of Korean Society of Urban Environment, 11(3), 261-267.
  37. Kim, Y. M., Murugesan, K., Chang, Y. Y., Kim, E. J., and Chang, Y. S. (2012). Degradation of Polybrominated Diphenyl Ethers by a Sequential Treatment with Nanoscale Zero Valent Iron and Aerobic Biodegradation, Journal of Chemical Technology and Biotechnology, 87, 216-224.
  38. Kim, Y. J. and Osako, M. (2004). Effect of Adsorption Capacity of Dissolved Humic Matter on Leachability of Dioxins from Raw and Treated Fly Ashes of Municipal Solid Waste Incinerators, Archives of Environmental Contamination Toxicology, 46, 8-16.
  39. La Guardia, M. J., Hale, R. C., and Harvey, E. (2006). Detailed Polybrominated Diphenyl Ether (PBDE) Congener Composition of the Widely Used Penta-, Octa-, and Deca-PBDE Technical Flame-Retardant Mixtures, Environmental Science and Technology, 40, 6247-6254.
  40. Lee, H. and Kim, G. B. (2014). Removal Rate and Mass Loading of Polybrominated Diphenyl Ethers in Sewage Treatment Plants (STP) in Tongyeong and Jinhae, Korea, The Korean Society for Marine Environment and Energy, 93-93.
  41. Lee, H. J., Kim, C. J., Hong, G. H., Hong, S. H., Shim, W. J., and Kim, K. B. (2014). Congener-Specific Accumulation and Environmental Risk Assessment of Polybrominated Diphenyl Ethers in Diverse Korean Sewage Sludge Types, Environmental Science and Pollution Research, 21, 7480-7488.
  42. Lee, L. K. and He, J. (2010). Reductive Debromination of Polybrominated Diphenyl Ethers by Anaerobic Bacteria from Soils and Sediments, Applied and Environmental Microbiology, 76, 794-802.
  43. Leal, J. F., Esteves, V. I., and Santos, E. B. H. (2013). BDE-209: Kinetic Studies and Effect of Humic Substances on Photodegradation in Water, Environmental Science and Technology, 47(24), 14010-14017.
  44. Li, W. H. (2015). The Influence of Dissolved Organic Matter on the Fate of Polybrominated Diphenyl Ethers (PBDEs) in the Environment, The Ohio State University B. A. Dissertation.
  45. Luo, S., Yang, S., Sun, C., and Gu, J. D. (2012). Improved Debromination of Polybrominated Diphenyl Ethers by Bimetallic Ironesilver Nanoparticles Coupled with Microwave Energy, Science of the Total Environment, 429, 300-308.
  46. Lyman, W. J. (1990). Handbook of Chemical Estimation Methods, 1-29, in HSDB, 2006-03-04.
  47. Matheson, L. J. and Tratnyek, P. G. (1994). Reductive Dehalogenation of Chlorinated Methanes by Iron Metal, Environmental Science and Technology, 28(12), 2045-2053.
  48. Ministry of environment (ME). (2005). International Restrictions and Counterplans of Brominated Flame Retardants, Ministry of Environment.
  49. Ministry of Environment (ME). (2010). Toxic Chemicals Control Act, Ministry of Environment.
  50. Ni, S. Q., Cui, Q.. and Zheng, Z. (2014). Interaction of Polybrominated Diphenyl Ethers and Aerobic Granular Sludge: Biosorption and Microbial Degradation, BioMed Research International, 2014, 1-10.
  51. North, K. D. (2004). Tracking Polybrominated Diphenyl Ether Releases in a Wastewater Treatment Plant Effluent, Palo Alto, California, Environmental Science and Technology, 38, 4484-4488.
  52. Nyholm, J. R., Grabic, R., Arp, H. P. H., Moskeland, T., and Andersson, P. L. (2013). Environmental Occurrence of Emerging and Legacy Brominated Flame Retardants Near Suspected Sources in Norway, Science of the Total Environment, 443, 307-314.
  53. Peng, X. Z., Tang, C. M., Yu, Y. Y., Tan, J. H., Huang, Q. X., Wu, J. P., Chena, S., and Mai, B. (2009). Concentrations, Transport, Fate, and Releases of Polybrominated Diphenyl Ethers in Sewage Treatment Plants in the Pearl River Delta, South China, Environment International, 35, 303-309.
  54. Peng, Y. H., Chen, M. K., and Shih, Y. H. (2013). Adsorption and Sequential Degradation of Polybrominated Diphenyl Ethers with Zerovalent Iron, Journal of Hazardous Materials, 260, 844-850.
  55. Rashed, M. N. (2013). Adsorption Technique for the Removal of Organic Pollutants from Water and Wastewater, Organic Pollutants - Monitoring, Risk and Treatment, Chapter 7.
  56. Rayne, S. and Ikonomou, M. G. (2005a). Polybrominated Diphenyl Ethers in an Advanced Wastewater Treatment Plant. Part 1: Concentrations, Patterns, and Influence of Treatment Processes, Journal of Environmental Engineering and Science, 4, 353-367.
  57. Rayne, S. and Ikonomou, M. G. (2005b). Polybrominated Diphenyl Ethers in an Advanced Wastewater Treatment Plant. Part 2: Potential Effects on a Unique Aquatic System, Journal of Environmental Engineering and Science, 4, 369-383.
  58. Rayne, S., Wan, P., and Ikonomou, M. (2006). Photochemistry of a Major Commercial Polybrominated Diphenyl Ether Flame Retardant Congener: 2,2',4,4',5,5'-Hexabromodiphenyl Ether (BDE153), Environment International, 32(5), 575-585.
  59. Reick, R. H. (2004). Polybrominated Diphenyl Ethers Analysis in Fish Tissue and Other Matrices by GC-ECD, LC GC North America, 22, 914-925.
  60. Robrock, K. R., Korytar, P., and Alvarez-Cohen, L. (2008). Pathways for the Anaerobic Microbial Denomination of Polybrominated Diphenyl Ethers, Environmental Science and Technology, 42, 2845-2852.
  61. Sanchez-Prado, L., Kalafata, K., Risticevic, S., Pawliszyn, J., Lores, M., Llompart, M., Kalogerakis, N., and Psillakis, E. (2012). Ice Photolysis of 2,2',4,4',6-Pentabromodiphenyl Ether (BDE-100): Laboratory Investigations using Solid Phase Microextraction, Analytica Chimica Acta, 742, 90-96.
  62. Santos, M. S. F., Alves, A., and Madeira, L. M. (2016). Chemical and Photochemical Degradation of Polybrominated Diphenyl Ethers in Liquid Systems-A Review, Water Research, 88, 39-59.
  63. Schwarzenbach, R. P., Gschwend, P. M., and Imboden, D. M. (2005). Environmental Organic Chemistry, John Wiley & Sons, New Jersey, USA.
  64. Shih, Y. H. and Tai, Y. T. (2010). Reaction of Decabrominated Diphenyl Ether by Zerovalent Iron Nanoparticles, Chemosphere, 78, 1200-1206.
  65. Shih, Y. H. and Wang, C. K. (2009). Photolytic Degradation of Polybromodiphenyl Ethers under UV-Lamp and Solar Irradiations, Journal of Hazardous Materials, 165 (1-3), 34-38.
  66. Song, M., Chu, S. G., Letcher, R. J., and Seth, R. (2006). Fate, Partitioning, and Mass Loading of Polybrominated Diphenyl Ethers (PBDEs) during the Treatment Processing of Municipal Sewage, Environmental Science and Technology, 40, 6241-6246.
  67. Sun, C., Chang, W., Ma, W., Chen, C., and Zhao, J. (2013). Photoreductive Debromination of Decabromodiphenyl Ethers in the Presence of Carboxylates under Visible Light Irradiation, Environmental Science and Technology, 47(5), 2370-2377.
  68. Tan, L., Liang, B., Fang, Z., Xie, Y., and Tsang, E. (2014). Effect of Humic Acid and Transition Metal Ions on the Debromination of Decabromodiphenyl by Nano Zero-valent Iron: Kinetics and Mechanisms, Journal of Nanoparticle Research, 16(12), 1-13.
  69. Ter Laak, T. L., Van Eijkeren, J. C. H., Busser, F. J. M., Van Leeuwen, H. P., and Hermens, J. L. M. (2009). Facilitated Transport of Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers by Dissolved Organic Matter, Environmental Science and Technology, 43, 1379-1385.
  70. United Nations Environment Programme (UNEP). (2007). Report of the Persistent Organic Pollutants Review Committee on the Work of its Third Meeting-Addendum, Risk Management Evaluation on Commercial Pentabromodiphenylether UNEP/POPS/POPRC.3/20/Add1.
  71. United Nations Environment Programme (UNEP). (2014). Risk Profile on Decabromodiphenyl Ether (Commercial Mixture, c-decaBDE), Report of the Persistent Organic Pollutants Review Committee on the Work of its Tenth Meeting, Addendum. United Nations, Stockholm Convention on Persistent Organic Pollutants.
  72. U. S. Environmental Protection Agency (U. S. EPA). (2009). Targeted National Sewage Sludge Survey Sampling and Analysis Technical Report, U. S. Environmental Protection Agency.
  73. Venkatesan, A. K. and Halden, R. U. (2014). Brominated Flame Retardants in U.S. Biosolids from the EPA National Sewage Sludge Survey and Chemical Persistence in Outdoor Soil Mesocosms, Water Research, 55, 133-142.
  74. Wang, J. Z., Hou, Y., Zhang, J., Zhu, J., and Feng, Y. L. (2013). Transformation of 2,2',4,4'-tetrabromodiphenyl Ether under UV Irradiation: Potential Sources of the Secondary Pollutants, Journal of Hazardous Materials, 263, Part 2, 778-783.
  75. Wang, L., Ni, S.Q., Guo, C. and Qian, Y. (2013). One Pot Synthesis of Ultrathin Boron Nitride Nanosheet-Supported Nanoscale Zerovalent Iron for Rapid Debromination of Polybrominated Diphenyl Ethers, Journal of Materials Chemistry A, 1(21), 6379-6387.
  76. Wang, M., Wang, H., Zhang, R., Ma, M., Mei, K., Fang, F., and Wang, X. (2015). Photolysis of Low-Brominated Diphenyl Ethers and Their Reactive Oxygen Species-Related Reaction Mechanisms in an Aqueous System, PLoS One, Aug 14,10(8): e0135400. doi: 10.1371/journal.pone.0135400.
  77. Wei, H., Zou, Y., Li, A., Christensen, E. R., and Rockne, K. J. (2013). Photolytic Debromination Pathway of Polybrominated Diphenyl Ethers in Hexane by Sunlight, Environmental Pollution, 174, 194-200.
  78. Xia, K., Hundal, L. S., Kumar, K., Armbrust, K., Cox, A. E., and Granato, T. C. (2010). Triclocarban, Triclosan, Polybrominated Diphenyl Ethers, and 4-Nonylphenol in Biosolids and in Soil Receiving 33-year Biosolids Application, Environmental Toxicology and Chemistry, 29, 597-605.
  79. Xiang, N., Zhao, X., Meng, X. Z., and Chen, L. (2013). Polybrominated Diphenyl Ethers (PBDEs) in a Conventional Wastewater Treatment Plant (WWTP) from Shanghai, the Yangtze River Delta: Implication for Input Source and Mass Loading, Science of the Total Environment, 461-462, 391-396.
  80. Xie, Q., Chen, J., Shao, J., Chen, C. E, Zhao, H., and Hao, C. (2009). Important Role of Reaction Field in Photodegradation of Deca-bromodiphenyl Ether: Theoretical and Experimental Investigations of Solvent Effects, Chemosphere, 76(11), 1486-1490.
  81. Yoon, J., Eom, I., Lee, B., Cho, C., Lee, D., and Kim. P. (2010). Environmental Exposure Level of PBDEs (III)-Focused on the Inter-Ministerial Joint Project, Ministry of Environment NIER NO. 2010-54-1229.
  82. Zeng, X., Massey Simonich, S. L., Robrock, K. R., Korytar, P., Alvarez-Cohen, L., and Barofsky, D. F. (2008). Development and Validation of a Congener-Specific Photodegradation Model for Polybrominated Diphenyl Ethers, Environmental Toxicology and Chemistry, 27(12), 2427-2435.
  83. Zhuang, Y., Ahn, S., and Luthy, R. G. (2010). Debromination of Polybrominated Diphenyl Ethers by Nanoscale Zerovalent Iron: Pathways, Kinetics, and Reactivity, Environmental Science and Technology, 44(21), 8236-8242.
  84. Zhuang, Y., Ahn, S., Seyfferth, A. L., Masue-Slowey, Y., Fendorf, S., and Luthy, R. G. (2011). Dehalogenation of Polybrominated Diphenyl Ethers and Polychlorinated Biphenyl by Bimetallic, Impregnated, and Nanoscale Zerovalent Iron, Environmental Science and Technology, 45(11), 4896-4903.
  85. Zhuang, Y., Jin, L., and Luthy, R. G. (2012). Kinetics and Pathways for the Debromination of Polybrominated Diphenyl Ethers by Bimetallic and Nanoscale Zerovalent Iron: Effects of Particle Properties and Catalyst, Chemosphere, 89(4), 426-432.