室内空气与灰尘中典型卤代阻燃剂的污染研究进展
The Review of Typical Halogenated Flame Retardants, HFRs Pollution in Indoor Air and Dust
摘要: 卤代阻燃剂(Halogenated Flame Retardants, HFRs)是一类用于降低聚合物易燃性的功能性助剂，广泛存在于室内环境中，对人体健康有严重的负面影响。多溴联苯醚、多氯联苯、得克隆是三种典型的卤代阻燃剂(HFRs)，本文介绍了室内这三类HFRs的来源、采样方法与分析技术，并结合国内外的研究报告简要总结室内环境中这三类HFRs的污染特征及污染水平。利用暴露模型分析这三类污染物的人体暴露。
Abstract: Halogenated Flame Retardants (HFRs) used to reduce the polymer flammability are a kind of widespread typical pollutants in the indoor environment medium. They have a severe negative impact on human health. Polybrominated Biphenyl Ethers (PBDEs), Polychorinated Biphenyls (PCBs) and Dechlorane Plus (DP) are three kinds of the important Halogenated Flame Retardants. The present paper reviews the source, sampling, quantification, the pollution characteristics, pollution levels and human exposure of these HFRs in indoor environment.
文章引用：林敏. 室内空气与灰尘中典型卤代阻燃剂的污染研究进展[J]. 环境保护前沿, 2014, 4(2): 40-53. http://dx.doi.org/10.12677/AEP.2014.42007

参考文献

[1] Chow, J.C., Watson, J.G.; Pritchett, L.C., Pierson, W.R., Frazier, C.A. and Purcell, R.G. (1993) The dri thermal optical reflectance carbon analysis system—Description, evaluation and applications in United-States air-quality studies. Atmospheric Environment. Part A. General Topics, 27, 1185-1201.
[2] Chow, J.C., Watson, J.G., Crow, D., Lowenthal, D.H. and Merrifield, T. (2001) Comparison of IMPROVE and NIOSH carbon measurements. Aerosol Science and Technology, 34, 23-34.
[3] 北镇 (2004) 中国室内环境污染危害严重. 世界环境, 5, 30-45.
[4] Kierkegaard, A., Bignert, A., Sellstrom, U., Olsson, M., Asplund, L., Jansson, B. and de Wit, C.A. (2004) Polybrominated diphenyl ethers (PBDEs) and their methoxylated derivatives in pike from Swedish waters with emphasis on temporal trends, 1967-2000. Environmental Pollution, 130, 187-198.
[5] Kuriyama, S.N., Wanner, A., Fidalgo-Neto, A.A., Talsness, C.E., Koerner, W. and Chahoud, I. (2007) Developmental exposure to low-dose PBDE-99: Tissue distribution and thyroid hormone levels. Toxicology, 242, 80-90.
[6] Herbstman, J.B., Sjodin, A., Kurzon, M., Lederman, S.A., Jones, R.S., Rauh, V., Needham, L.L., Tang, D., Niedzwiecki, M., Wang, R.Y. and Perera, F. (2010) Prenatal exposure to PBDEs and neurodevelopment. Environmental Health Perspectives, 118, 712-719.
[7] Pijnenburg, A., Everts, J., De Boer, J. and Boon, J. (1995) Polybrominated biphenyl and diphenylether flame retardants: Analysis, toxicity, and environmental occurrence. In: Reviews of Environmental Contamination and Toxicology, Springer, Berlin, 1-26.
[8] Mandalakis, M., Stephanou, E.G., Horii, Y. and Kannan, K. (2008) Emerging contaminants in car interiors: Evaluating the impact of airborne PBDEs and PBDD/Fs. Environmental Science & Technology, 42, 6431-6436.
[9] Sjodin, A., Patterson, D.G. and Bergman, A. (2003) A review on human exposure to brominated flame retardants— Particularly polybrominated diphenyl ethers. Environment International, 29, 829-839.
[10] Huang, Y., Chen, L., Peng, X., Xu, Z. and Ye, Z. (2010) PBDEs in indoor dust in South-Central China: Characteristics and implications. Chemosphere, 78, 169-174.
[11] Butt, C.M., Diamond, M.L., Truong, J., Ikonomou, M.G. and Ter Schure, A.F.H. (2004) Spatial distribution of polybrominated diphenyl ethers in southern Ontario as measured in indoor and outdoor window organic films. Environmental Science & Technology, 38, 724-731.
[12] Harrad, S., Wijesekera, R., Hunter, S., Halliwell, C. and Baker, R. (2004) Preliminary assessment of UK human dietary and inhalation exposure to polybrominated diphenyl ethers. Environmental Science & Technology, 38, 2345-2350.
[13] Bjorklund, J.A., Thuresson, K., Cousins, A.P., Sellstrom, U., Emenius, G. and de Wit, C.A. (2012) Indoor air is a significant source of tri-decabrominated diphenyl ethers to outdoor air via ventilation systems. Environmental Science & Technology, 46, 5876-5884.
[14] Jones-Otazo, H.A., Clarke, J.P., Diamond, M.L., Archbold, J.A., Ferguson, G., Harner, T., Richardson, G.M., Ryan, J.J. and Wilford, B. (2005) Is house dust the missing exposure pathway for PBDEs? An analysis of the urban fate and human exposure to PBDEs. Environmental Science & Technology, 39, 5121-5130.
[15] 陈来国 (2009) 广州市大气环境中多溴联苯醚PBDEs和多氯联苯PCBs的初步研究. 博士论文, 中国科学院研究生院(广州地球化学研究所), 广州.
[16] Allen, J.G., McClean, M.D., Stapleton, H.M., Nelson, J.W. and Webster, T.F. (2007) Personal exposure to polybrominated diphenyl ethers (PBDEs) in residential indoor air. Environmental Science & Technology, 41, 4574-4579.
[17] Rose, M., Bennett, D.H., Bergman, Å., Fängström, B., Pessah, I.N. and Hertz-Picciotto, I. (2010) PBDEs in 2 5 year-old children from California and associations with diet and indoor environment. Environmental Science & Technology, 44, 2648-2653.
[18] Hale, R.C., La Guardia, M.J., Harvey, E., Gaylor, M.O. and Mainor, T.M. (2006) Brominated flame retardant concentrations and trends in abiotic media. Chemosphere, 64, 181-186.
[19] Takasuga, T., Senthilkumar, K., Matsumura, T., Shiozaki, K. and Sakai, S.-I. (2006) Isotope dilution analysis of polychlorinated biphenyls (PCBs) in transformer oil and global commercial PCB formulations by high resolution gas chromatography—High resolution mass spectrometry. Chemosphere, 62, 469-484.
[20] Herrick, R.F., McClean, M.D., Meeker, J.D., Baxter, L.K. and Weymouth, G.A. (2004) An unrecognized source of PCB contamination in schools and other buildings. Environmental Health Perspectives, 112, 1051-1053.
[21] Kohler, M., Tremp, J., Zennegg, M., Seiler, C., Minder-Kohler, S., Beck, M., Lienemann, P., Wegmann, L. and Schmidt, P. (2005) Joint sealants: An overlooked diffuse source of polychlorinated biphenyls in buildings. Environmental Science & Technology, 39, 1967-1973.
[22] Kohler, M., Zennegg, M. and Waeber, R. (2002) Coplanar polychlorinated biphenyls (PCB) in indoor air. Environmental Science & Technology, 36, 4735-4740.
[23] 张志, 李一凡, 任南琪 (2007) 室内空气中PCBs污染状况研究. 持久性有机污染物论坛2007暨第二届持久性有机污染物全国学术研讨会论文集.
[24] 刘洋, 翼秀玲, 马静 (2011) 上海市典型家庭室内空气中PCBs与PBDEs初步研究. 环境科学研究, 5, 482-488.
[25] Rudel, R.A. and Perovich, L.J. (2009) Endocrine disrupting chemicals in indoor and outdoor air. Atmospheric Environment, 43, 170-181.
[26] 任南琪, 李一凡 (2011) 我国得克隆(dechlorane plus)的研究进展. 2011中国环境科学学会学术年会论文集(第四卷).
[27] Ren, G.F., Yu, Z.Q., Ma, S.T., Li, H.R., Peng, P.G., Sheng, G.Y. and Fu, J.M. (2009) Determination of dechlorane plus in serum from electronics dismantling workers in South China. Environmental Science & Technology, 43, 9453-9457.
[28] Zhu, J., Feng, Y.L. and Shoeib, M. (2007) Detection of dechlorane plus in residential indoor dust in the city of Ottawa, Canada. Environmental Science & Technology, 41, 7694-7698.
[29] Levin, J.O., Andersson, K., Lindahl, R. and Nilsson, C.A. (1985) Determination of sub-part-per-million levels of formaldehyde in air using active or passive sampling on 2,4-dinitrophenylhydrazine-coated glass fiber filters and highperformance liquid chromatography. Analytical Chemistry, 57, 1032-1035.
[30] Wilford, B.H., Harner, T., Zhu, J., Shoeib, M. and Jones, K.C. (2004) Passive sampling survey of polybrominated diphenyl ether flame retardants in indoor and outdoor air in Ottawa, Canada: Implications for sources and exposure. Environmental Science & Technology, 38, 5312-5318.
[31] Harrad, S., Hazrati, S. and Ibarra, C. (2006) Concentrations of polychlorinated biphenyls in indoor air and polybrominated diphenyl ethers in indoor air and dust in Birmingham, United Kingdom: Implications for human exposure. Environmental Science & Technology, 40, 4633-4638.
[32] Ren, N.Q., Sverko, E., Li, Y.F., Zhang, Z., Harner, T., Wang, D.G., Wan, X.N. and McCarry, B.E. (2008) Levels and isomer profiles of dechlorane plus in Chinese air. Environmental Science & Technology, 42, 6476-6480.
[33] Colt, J.S., Zahm, S.H., Camann, D.E. and Hartge, P. (1998) Comparison of pesticides and other compounds in carpet dust samples collected from used vacuum cleaner bags and from a high-volume surface sampler. Environmental Health Perspectives, 106, 721-724.
[34] Simcox, N.J., Fenske, R.A., Wolz, S.A., Lee, I.C. and Kalman, D.A. (1995) Pesticides in household dust and soil: Exposure pathways for children of agricultural families. Environmental Health Perspectives, 103, 1126-1134.
[35] Zhu, J., Feng, Y.-L. and Shoeib, M. (2007) Detection of dechlorane plus in residential indoor dust in the city of Ottawa, Canada. Environmental Science & Technology, 41, 7694-7698.
[36] Rudel, R.A., Camann, D.E., Spengler, J.D., Korn, L.R. and Brody, J.G. (2003) Phthalates, alkylphenols, pesticides, polybrominated diphenyl ethers, and other endocrine-disrupting compounds in indoor air and dust. Environmental Science & Technology, 37, 4543-4553.
[37] Fromme, H., Körner, W., Shahin, N., Wanner, A., Albrecht, M., Boehmer, S., Parlar, H., Mayer, R., Liebl, B. and Bolte, G. (2009) Human exposure to polybrominated diphenyl ethers (PBDE), as evidenced by data from a duplicate diet study, indoor air, house dust, and biomonitoring in Germany. Environment International, 35, 1125-1135.
[38] 于恩平 (1994) 用超临界流体萃取方法处理多氯联苯污染物. 北京化工学院学报, 21, 11-19.
[39] Langenfeld, J.J., Hawthorne, S.B., Miller, D.J. and Pawliszyn, J. (1993) Effects of temperature and pressure on supercritical fluid extraction efficiencies of polycyclic aromatic hydrocarbons and polychlorinated biphenyls. Analytical Chemistry, 65, 338-344.
[40] Alothman, Z.A., Khan, M.R., Wabaidur, S.M. and Siddiqui, M.R. (2012) Persistent organic pollutants: Overview of their extraction and estimation. Sensor Letters, 10, 698-704.
[41] 董亮, 张秀蓝, 史双昕, 许鹏军, 周丽, 杨文龙, 张利飞, 张烃, 黄业茹 (2013) 新型持久性有机污染物分析方法研究进展. 中国科学: 化学, 3, 010.
[42] Guvenius, D.M., Aronsson, A., Ekman-Ordeberg, G., Bergman, A. and Norén, K. (2003) Human prenatal and postnatal exposure to polybrominated diphenyl ethers, polychlorinated biphenyls, polychlorobiphenylols, and pentachlorophenol. Environmental Health Perspectives, 111, 1235.
[43] Sverko, E., Tomy, G.T., Reiner, E.J., Li, Y.F., McCarry, B.E., Arnot, J.A., Law, R.J. and Hites, R.A. (2011) Dechlorane plus and related compounds in the environment: A review. Environmental Science & Technology, 45, 5088-5098.
[44] Stapleton, H.M. (2006) Instrumental methods and challenges in quantifying polybrominated diphenyl ethers in environmental extracts: A review. Analytical and Bioanalytical Chemistry, 386, 807-817.
[45] Bjorklund, J., Tollback, P., Hiarne, C., Dyremark, E. and Ostman, C. (2004) Influence of the injection technique and the column system on gas chromatographic determination of polybrominated diphenyl ethers. Journal of Chromatography A, 1041, 201-210.
[46] Covaci, A., Voorspoels, S. and de Boer, J. (2003) Determination of brominated flame retardants, with emphasis on polybrominated diphenyl ethers (PBDEs) in environmental and human samples—A review. Environment International, 29, 735-756.
[47] Allen, J.G., McClean, M.D., Stapleton, H.M. and Webstert, T.F. (2008) Linking PBDEs in house dust to consumer products using X-ray fluorescence. Environmental Science & Technology, 42, 4222-4228.
[48] Imm, P., Knobeloch, L., Buelow, C. and Anderson, H.A. (2009) Household exposures to polybrominated diphenyl ethers (PBDEs) in a Wisconsin cohort. Environmental Health Perspectives, 117, 1890-1895.
[49] Wilford, B.H., Shoeib, M., Harner, T., Zhu, J. and Jones, K.C. (2005) Polybrominated diphenyl ethers in indoor dust in Ottawa, Canada: Implications for sources and exposure. Environmental Science & Technology, 39, 7027-7035.
[50] Bohlin, P., Jones, K.C., Tovalin, H. and Strandberg, B. (2008) Observations on persistent organic pollutants in indoor and outdoor air using passive polyurethane foam samplers. Atmospheric Environment, 42, 7234-7241.
[51] Sjodin, A., Carlsson, H., Thuresson, K., Sjolin, S., Bergman, A. and Ostman, C. (2001) Flame retardants in indoor air at an electronics recycling plant and at other work environments. Environmental Science & Technology, 35, 448-454.
[52] Toms, L.M.L., Bartkow, M.E., Symons, R., Paepke, O. and Mueller, J.F. (2009) Assessment of polybrominated diphenyl ethers (PBDEs) in samples collected from indoor environments in South East Queensland, Australia. Chemosphere, 76, 173-178.
[53] Besis, A. and Samara, C. (2012) Polybrominated diphenyl ethers (PBDEs) in the indoor and outdoor environments—A review on occurrence and human exposure. Environmental Pollution, 169, 217-229.
[54] 黄玉妹, 陈来国, 许振成, 彭晓春, 曾敏, 叶芝祥 (2009) 室内尘土中PBDEs的含量, 分布, 来源和人体暴露水平. 中国环境科学学会 2009年学术年会论文集(第四卷).
[55] 张娴, 高亚杰, 颜昌宙 (2009) 多溴联苯醚在环境中迁移转化的研究进展. 生态环境学报, 2, 761-770.
[56] Zhang, X., Diamond, M.L., Robson, M. and Harrad, S. (2011) Sources, emissions, and fate of polybrominated diphenyl ethers and polychlorinated biphenyls indoors in Toronto, Canada. Environmental Science & Technology, 45, 32683274.
[57] Fitzgerald, E.F., Shrestha, S., Palmer, P.M., Wilson, L.R., Belanger, E.E., Gomez, M.I., Cayo, M.R. and Hwang, S.A. (2011) Polychlorinated biphenyls (PCBs) in indoor air and in serum among older residents of upper Hudson River communities. Chemosphere, 85, 225-231.
[58] Pentamwa, P. and Oanh, N.T.K. (2008) Levels of pesticides and polychlorinated biphenyls in selected homes in the Bangkok metropolitan region, Thailand. Annals of the New York Academy of Sciences, 1140, 91-112.
[59] Wilson, N.K., Chuang, J.C. and Lyu, C. (2001) Levels of persistent organic pollutants in several child day care centers. Journal of Exposure Analysis and Environmental Epidemiology, 11, 449-458.
[60] Frederiksen, M., Meyer, H.W., Ebbehøj, N.E. and Gunnarsen, L. (2012) Polychlorinated biphenyls (PCBs) in indoor air originating from sealants in contaminated and uncontaminated apartments within the same housing estate. Chemosphere, 89, 473-479.
[61] Menichini, E., Lacovella, N., Monfredini, F. and Turrio-Baldassarri, L. (2007) Relationships between indoor and outdoor air pollution by carcinogenic PAHs and PCBs. Atmospheric Environment, 41, 9518-9529.
[62] Cupr, P., Skarek, M., Bartos, T., Ciganek, M. and Holoubek, I. (2005) Assessment of human health risk due to inhalation exposure in cattle and pig farms in south Moravia. Acta Veterinaria Brno, 74, 305-312.
[63] Takigami, H., Suzuki, G., Hirai, Y. and Sakai, S. (2009) Brominated flame retardants and other polyhalogenated compounds in indoor air and dust from two houses in Japan. Chemosphere, 76, 270-277.
[64] Hwang, H.M., Park, E.K., Young, T.M. and Hammock, B.D. (2008) Occurrence of endocrine-disrupting chemicals in indoor dust. Science of the Total Environment, 404, 26-35.
[65] Vorhees, D.J., Cullen, A.C. and Altshul, L.M. (1999) Polychlorinated biphenyls in house dust and yard soil near a Superfund site. Environmental Science & Technology, 33, 2151-2156.
[66] Roosens, L., Abdallah, M.A.-E., Harrad, S., Neels, H. and Covaci, A. (2009) Current exposure to persistent polychlorinated biphenyls (PCBs) and dichlorodiphenyldichloroethylene (p,p’-DDE) of Belgian students from food and dust. Environmental Science & Technology, 44, 2870-2875.
[67] Andersson, M., Ottesen, R. and Volden, T. (2004) Building materials as a source of PCB pollution in Bergen, Norway. Science of the Total Environment, 325, 139-144.
[68] Colt, J.S., Severson, R.K., Lubin, J., Rothman, N., Camann, D., Davis, S., Cerhan, J.R., Cozen, W. and Hartge, P. (2005) Organochlorines in carpet dust and non-Hodgkin lymphoma. Epidemiology, 16, 516-525.
[69] Ali, N., Eede, V.d., Neels, H. and Covaci, A. (2012) Country specific comparison for profile of chlorinated, brominated and phosphate organic contaminants in indoor dust. Case study for Eastern Romania, 2010. Environmental International, 49, 1-8.
[70] Abb, M., Breuer, J.V., Zeitz, C. and Lorenz, W. (2010) Analysis of pesticides and PCBs in waste wood and house dust. Chemosphere, 81, 488-493.
[71] 李琛, 余应新, 张东平, 冯加良, 吴明红, 盛国英, 傅家谟 (2010) 上海室内外灰尘中多氯联苯及其人体暴露评估. 中国环境科学, 4, 433-441.
[72] Fabrellas, B., Martinez, A., Ramos, B., Ruiz, M.L., Navarro, I. and de la Torre, A. (2005) Results of an European survey based on pbdes analysis in household dust. Organohalogen Compound, 67, 452-454.
[73] Harrad, S., Ibarra, C., Diamond, M., Melymuk, L., Robson, M., Douwes, J., Roosens, L., Dirtu, A.C. and Covaci, A. (2008) Polybrominated diphenyl ethers in domestic indoor dust from Canada, New Zealand, United Kingdom and United States. Environment International, 34, 232-238.
[74] Ali, N., Ali, L., Mehdi, T., Dirtu, A.C., Al-Shammari, F., Neels, H. and Covaci, A. (2013) Levels and profiles of organochlorines and flame retardants in car and house dust from Kuwait and Pakistan: Implication for human exposure via dust ingestion. Environment International, 55, 62-70.
[75] Xian, Q., Siddique, S., Li, T., Feng, Y.-l., Takser, L. and Zhu, J. (2011) Sources and environmental behavior of Dechlorane plus—A review. Environment International, 37, 1273-1284.
[76] Shoeib, M., Harner, T., Webster, G.M., Sverko, E. and Cheng, Y. (2012) Legacy and current-use flame retardants in house dust from Vancouver, Canada. Environmental Pollution, 169, 175-182.
[77] Wang, J., Tian, M., Chen, S.J., Zheng, J., Luo, X.J., An, T.C. and Mai, B.X. (2011) Dechlorane plus in house dust from E-waste recycling and urban areas in South China: Sources, degradation, and human exposure. Environmental Toxicology and Chemistry, 30, 1965-1972.
[78] Zheng, J., Wang, J., Luo, X.J., Tian, M., He, L.Y., Yuan, J.G., Mai, B.X. and Yang, Z.Y. (2010) Dechlorane plus in human hair from an e-waste recycling area in South China: Comparison with dust. Environmental Science & Technology, 44, 9298-9303.
[79] Hearn, L.K., Hawker, D.W., Toms, L.M.L. and Mueller, J.F. (2013) Assessing exposure to polybrominated diphenyl ethers (PBDEs) for workers in the vicinity of a large recycling facility. Ecotoxicology and Environmental Safety, 92, 222-228.
[80] Johnson-Restrepo, B. and Kannan, K. (2009) An assessment of sources and pathways of human exposure to polybrominated diphenyl ethers in the United States. Chemosphere, 76, 542-548.
[81] Gevao, B., Al-Bahloul, M., Al-Ghadban, A.N., Ali, L., Al-Omair, A., Helaleh, M., Al-Matrouk, K. and Zafar, J. (2006) Polybrominated diphenyl ethers in indoor air in Kuwait: Implications for human exposure. Atmospheric Environment, 40, 1419-1426.
[82] Dellarco, V.L. and Wiltse, J.A. (1998) US Environmental Protection Agency’s revised guidelines for carcinogen risk assessment: Incorporating mode of action data. Mutation Research-Fundamental and Molecular Mechanisms of Mutagenesis, 405, 273-277.
[83] Harrad, S., Ibarra, C., Robson, M., Melymuk, L., Zhang, X., Diamond, M. and Douwes, J. (2009) Polychlorinated biphenyls in domestic dust from Canada, New Zealand, United Kingdom and United States: Implications for human exposure. Chemosphere, 76, 232-238.