李成辉;张冬蕊;李胜红;朱芬芬;董仪;

• 1:中国人民大学环境学院

摘要(Abstract)：

有机磷酸酯(OPEs)作为阻燃剂和增塑剂被广泛用于建筑、电子、化学和纺织等行业中。由于有机磷酸酯大多以物理方法掺加于产品中,更易被释放进入环境中。有机磷酸酯具有神经毒性、致癌性和基因毒性,关于有机磷酸酯产生、迁徙和削减的研究受到了学界的广泛注意。污水处理厂作为地表水环境中污染物的重要来源,在有机磷酸酯进入环境的过程中发挥了重要作用。本文总结了各国污水处理厂中有机磷酸酯研究现状,随着技术的发展被监测的有机磷酸酯种类越来越多;欧洲国家污水中有机磷酸酯检出的最高浓度普遍高于其他国家和地区;极性有机磷酸酯更倾向于转移至污水中,非极性的更倾向于吸附到污泥中;氯代有机磷酸酯普遍去除率很低,有的经过污水处理工艺反而增加,烷基和芳基有机磷酸酯有较高的去除率。

关键词(KeyWords)： 有机磷酸酯;阻燃剂;污水处理厂;污水;污泥

Abstract:

Keywords:

基金项目(Foundation): 北京市自然科学基金项目(8172029)

作者(Author): 李成辉;张冬蕊;李胜红;朱芬芬;董仪;

Email:

DOI:

参考文献(References)：

• [1]David M D, Seiber J N. Analysis of organophosphate hydraulic fluids in U.S. Air Force base soils[J]. Archives of Environmental Contamination&Toxicology, 1999, 36(3):235-241
• [2]Apostoluk W, Robak W. Analysis of liquid-liquid distribution constants of organophospohorus based extractants[J]. Analytica Chimica Acta, 2005, 548(1):116-133
• [3]Lamouroux C, Virelizier H, Moulin C, et al. Direct determination of dibutyl and monobutyl phosphate in a tributyl phosphate/nitric aqueous-phase system by electrospray mass spectrometry[J]. Analytical Chemistry, 2000, 72(6):1186-1191
• [4]Dodi A, Verda G. Improved determination of tributyl phosphate degradation products(mono-and dibutyl phosphates)by ion chromatography[J]. Journal of Chromatography A, 2001, 920(1):275-281
• [5]Stevens R, van Es D S, Bezemer R, et al. The structureactivity relationship of fire retardant phosphorus compounds in wood[J]. Polymer Degradation&Stability,2006, 91(4):832-841
• [6]Kannan S, Kishore K. Absolute viscosity and density of trisubstituted phosphoric esters[J]. Journal of Chemical&Engineering Data, 1999, 44(4):649-655
• [7]Aresta M, Caramuscio P, De Stefano L, et al. Solid state dehalogenation of PCBs in contaminated soil using Na BH4[J]. Waste Management, 2003, 23(4):315-319
• [8]Official Journal of the European Union. Directive 2003/11/EC of the European Parliament and of the Council of 6February 2003 amending for the 24th time Council Directive 76/769/EEC relating to restrictions on the marketing and use of certain dangerous substances and preparations(pentabromodiphenyl ether, octabromodiphenyl ether)[EB/OL].[2018-04-18]. http://eur-lex.europa.eu/legal-content/EN/TXT/? uri=OJ:L:2003:042:TOC
• [9]Betts K. Does a key PBDE break down in the environment?[J]. Environmental Science&Technology, 2008, 42(18):6781
• [10]Ceresana. Market Study Flame Retardants. 2nd ed.[R].Konstanz:Ceresana, 2014
• [11]Ceresana. Market Study Flame Retardants. 3rd ed.[R].Konstanz:Ceresana, 2015
• [12]Federal Environmental Agency. Substituting environmentally relevant flame retardants:Assessment fundamental[R]. Dessau:Federal Environmental Agency, 2001
• [13]Meyer J, Bester K. Organophosphate flame retardants and plasticisers in wastewater treatment plants[J]. Journal of Environmental Monitoring, 2004, 6(7):599-605
• [14]Scientific Committee on Health and Environmental Risks(SCHER). Risk assessment report on tris[2-chloro-1-(chloromethyl)ethyl]phosphate(TDCP)Environmental Part[R]. Brussels:SCHER, 2007
• [15]Scientific Committee on Health and Environmental Risks(SCHER). Risk assessment report on 2,2-bis(chloromethyl)trimethylene bis[bis(2-chloroethyl)phosphate](V6)Environmental Part[R]. Brussels:SCHER, 2007
• [16]Andresen J A, Grundmann A, Bester K. Organophosphorus flame retardants and plasticisers in surface waters[J].Science of the Total Environment, 2004, 332(1):155-166
• [17]Dishaw L V, Powers C M, Ryde I T, et al. Is the penta BDE replacement, tris(1,3-dichloro-2-propyl)phosphate(TDCPP), a developmental neurotoxicant? Studies in PC12 cells[J]. Toxicology and Applied Pharmacology,2011, 256(3):281-289
• [18]Word Health Organization(WHO). Flame retardants:Tris(chloropropyl)phosphate and tris(2-chloroethyl)phosphate[R]. Geneva:WHO, 1998
• [19]Ni Y, Kumagai K, Yanagisawa Y. Measuring emissions of organophosphate flame retardants using a passive flux sampler[J]. Atmospheric Environment, 2007, 41(15):3235-3240
• [20]Word Health Organization. Flame retardants:Tricresyl phosphate[R]. Geneva:WHO, 1990
• [21]Chapin R E, Sloane R A, Haseman J K. The relationships among reproductive endpoints in Swiss mice, using the reproductive assessment by Continuous Breeding database[J]. Fundamental&Applied Toxicology, 1997, 38(2):129-142
• [22]Illinois Environmental Protection Agency. Report on alternatives to the flame retardant Deca BDE:Evaluation of toxicity, availability, affordability, and fire safety issues[R]. Springfield:Illinois EPA, 2007
• [23]Washington State Department of Ecology&Washington State Department of Health(WSDOE&WSDOH). Polybrominated diphenyl ether(PBDE)chemical action plan:Final plan[R]. Washington D C:WSDOE&WSDOH,2006
• [24]Clean Production Agency(CPA). Brominated flame retardants in dust on computers:The case for safer chemicals and better computer design[R]. CPA, 2004
• [25]Word Health Organization(WHO). Flame retardants:A general introduction[R]. Geneva:WHO, 1997
• [26]Le Bel G L, Williams D T, Benoit F M. Gas chromatographic determination of trialkyl/aryl phosphates in drinking water, following isolation using macroreticular resin[J]. Journal of the Association of Official Analytical Chemists, 1981, 64(4):991-998
• [27]Ishikawa S, Taketomi M, Shinohara R. Determination of trialkyl and triaryl phosphates in environmental samples[J]. Water Research, 1985, 19(1):119-125
• [28]Fukushima M, Kawai S, Yamaguchi Y. Behavior of organophosphoric acid triesters in Japanese riverine and coastal environment[J]. Water Science&Technology,1992, 25(11):271-278
• [29]Carlsson H, Nilsson U, Gerhard Becker A, et al. Organophosphate ester flame retardants and plasticizers in the indoor environment:Analytical methodology and occurrence[J]. Environmental Science&Technology, 1997, 31(10):2931-2936
• [30]Ingerowski G, Friedle A, Thumulla J. Chlorinated ethyl and isopropyl phosphoric acid triesters in the indoor environment—An inter-laboratory exposure study[J]. Indoor Air-International Journal of Indoor Air Quality and Climate, 2001, 11(3):145-149
• [31]Otake T, Jun Yoshinaga A, Yanagisawa Y. Analysis of organic esters of plasticizer in indoor air by GC-MS and GC-FPD[J]. Environmental Science&Technology, 2001,35(15):3099-3102
• [32]Kim J W, Isobe T, Chang K H, et al. Levels and distribution of organophosphorus flame retardants and plasticizers in fishes from Manila Bay, the Philippines[J]. Environmental Pollution, 2011, 159(12):3653-3659
• [33]Ma Y, Cui K, Zeng F, et al. Microwave-assisted extraction combined with gel permeation chromatography and silica gel cleanup followed by gas chromatography-mass spectrometry for the determination of organophosphorus flame retardants and plasticizers in biological samples[J]. Analytica Chimica Acta, 2013, 786(13):47-53
• [34]Gao Z, Deng Y, Yuan W, et al. Determination of organophosphorus flame retardants in fish by pressurized liquid extraction using aqueous solutions and solid-phase microextraction coupled with gas chromatography-flame photometric detector[J]. Journal of Chromatography A, 2014,1366:31-37
• [35]Papachlimitzou A, Barber J L, Losada S, et al. Organophosphorus flame retardants(PFRs)and plasticisers in harbour porpoises(Phocoena phocoena)stranded or bycaught in the UK during 2012[J]. Marine Pollution Bulletin, 2015, 98(1-2):328-334
• [36]Malarvannan G, Belpaire C, Geeraerts C, et al. Organophosphorus flame retardants in the European eel in Flanders, Belgium:Occurrence, fate and human health risk[J].Environmental Research, 2015, 140:604-610
• [37]Petropoulou S S E, Petreas M, Park J S. Analytical methodology using ion-pair liquid chromatography-tandem mass spectrometry for the determination of four di-ester metabolites of organophosphate flame retardants in California human urine[J]. Journal of Chromatography A,2016, 1434:70-80
• [38]Jonsson O B, Dyremark E, Nilsson U L. Development of a microporous membrane liquid-liquid extractor for organophosphate esters in human blood plasma:Identification of triphenyl phosphate and octyl diphenyl phosphate in donor plasma[J]. Journal of Chromatography B:Biomedical Sciences&Applications, 2001, 755(1):157-164
• [39]Li P, Li Q X, Ma Y L, et al. Determination of organophosphate esters in human serum using gel permeation chromatograph and solid phase extraction coupled with gas chromatography-mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2015, 43(7):1033-1039
• [40]Kim J W, Isobe T, Muto M, et al. Organophosphorus flame retardants(PFRs)in human breast milk from several Asian countries[J]. Chemosphere, 2014, 116:91-97
• [41]Ding J, Xu Z, Wei H, et al. Organophosphate ester flame retardants and plasticizers in human placenta in Eastern China[J]. Science of the Total Environment, 2016, 554-555:211-217
• [42]Fries E, Püttmann W. Occurrence of organophosphate esters in surface water and ground water in Germany[J].Journal of Environmental Monitoring, 2001, 3(6):621-626
• [43]Bester K. Comparison of TCPP concentrations in sludge and wastewater in a typical German sewage treatment plant-comparison of sewage sludge from 20 plants[J].Journal of Environmental Monitoring, 2005, 7(5):509-513
• [44]Fries E, Püttmann W. Monitoring of the three organophosphate esters TBP, TCEP and TBEP in river water and ground water(Oder, Germany)[J]. Journal of Environmental Monitoring, 2003, 5(2):346-352
• [45]Rodil R, Quintana J B, Reemtsma T. Liquid chromatography-tandem mass spectrometry determination of nonionic organophosphorus flame retardants and plasticizers in wastewater samples[J]. Analytical Chemistry, 2005, 77(10):3083-3089
• [46]Rodríguez I, Calvo F, Quintana J B, et al. Suitability of solid-phase microextraction for the determination of organophosphate flame retardants and plasticizers in water samples[J]. Journal of Chromatography A, 2006, 1108(2):158-165
• [47]Rodil R, Quintana J B, Concha-Gra?a E, et al. Emerging pollutants in sewage, surface and drinking water in Galicia(NW Spain)[J]. Chemosphere, 2012, 86(10):1040-1049
• [48]Cristale J, Ramos D D, Dantas R F, et al. Can activated sludge treatments and advanced oxidation processes remove organophosphorus flame retardants?[J]. Environmental Research, 2016, 144(Pt A):11-18
• [49]García-López M, Rodríguez I, Cela R. Development of a dispersive liquid-liquid microextraction method for organophosphorus flame retardants and plasticizers determination in water samples[J]. Journal of Chromatography A,2007, 1166(1):9-15
• [50]García-López M, Rodríguez I, Cela R. Evaluation of liquid-liquid microextraction using polypropylene microporous membranes for the determination of organophosphorus flame retardants and plasticizers in water samples[J]. Analytica Chimica Acta, 2008, 625(2):145-153
• [51]林亚英,陈弘丽,曹美苑,等.城市市政污水A2O处理过程中有机磷酸酯阻燃剂的行为研究[C].北京:全国环境化学大会暨环境科学仪器与分析仪器展览会,2011:311Lin Y Y, Chen H L, Cao M Y, et al. Study on the behavior of organic phosphate flame retardants in A2O treatment process of municipal wastewater treatment plant[C].Beijing:The 6th National Conference on Environmental Chemistry, 2011:311(in Chinese)
• [52]庞龙,张肖静,庞榕,等.城市污水处理工艺对有机磷酸酯类化合物的去除[J].河南师范大学学报:自然版,2016, 44(3):98-103Pang L, Zhang X J, Pang R, et al. Removal of organophosphate esters in municipal wastewater treatment process[J]. Journal of Henan Normal University:Natural Science Edition, 2016, 44(3):98-103(in Chinese)
• [53]Gao Z, Deng Y, Hu X, et al. Determination of organophosphate esters in water samples using an ionic liquidbased sol-gel fiber for headspace solid-phase microextraction coupled to gas chromatography-flame photometric detector[J]. Journal of Chromatography A, 2013, 1300(14):141-150
• [54]梁钪,牛宇敏,刘景富.超高效液相色谱-串联质谱法测定污水中14种有机磷酸酯阻燃剂[J].环境化学, 2014,33(10):1681-1685Liang K, Niu Y M, Liu J F. Determination of 14 organophosphate ester flame retardants in wastewater by UPLCMS/MS[J]. Environmental Chemistry, 2014, 33(10):1681-1685(in Chinese)
• [55]Shi F, Liu J, Liang K, et al. Tris(pentafluoroethyl)trifluorophosphate-basd ionic liquids as advantageous solidphase micro-extraction coatings for the extraction of organophosphate esters in environmental waters[J]. Journal of Chromatography A, 2016, 1447:9-16
• [56]何丽雄,曹曙霞,曾祥英.固相萃取/气相色谱-质谱联用技术快速测定水中有机磷酸酯阻燃剂与增塑剂[J].分析测试学报, 2013, 32(4):437-441He L X, Cao S X, Zeng X Y, et al. Determination of organophosphate flame retardants and plasticizers in water using solid phase extraction coupled with GC-MS[J].Journal of Instrumental Analysis, 2013, 32(4):437-441(in Chinese)
• [57]Liang K, Liu J. Understanding the distribution, degradation and fate of organophosphate esters in an advanced municipal sewage treatment plant based on mass flow and mass balance analysis[J]. Science of the Total Environment, 2016, 544:262-270
• [58]Tsao Y C, Wang Y C, Wu S F, et al. Microwave-assisted headspace solid-phase microextraction for the rapid determination of organophosphate esters in aqueous samples by gas chromatography-mass spectrometry[J]. Talanta,2011, 84(2):406-410
• [59]Zeng X, He L, Cao S, et al. Occurrence and distribution of organophosphate flame retardants/plasticizers in wastewater treatment plant sludges from the Pearl River Delta, China[J]. Environmental Toxicology&Chemistry,2014, 33(8):1720-1725
• [60]Clark L B, Rosen R T, Hartman T G, et al. Determination of nonregulated pollutants in three New Jersey Publicly Owned Treatment Works(POTWs)[J]. Research Journal of the Water Pollution Control Federation, 1991, 63(2):104-113
• [61]Paxéus N. Organic pollutants in the effluents of large wastewater treatment plants in Sweden[J]. Water Research, 1996, 30(5):1115-1122
• [62]Norwegian Institute for Water(NIVA). Research screening of selected metals and new organic contaminants 2007[R]. Oslo:NIVA, 2008
• [63]Marklund A, Andersson B, Haglund P. Organophosphorus flame retardants and plasticizers in Swedish sewage treatment plants[J]. Environmental Science&Technology,2005, 39(19):7423-7429
• [64]Reemtsma T, Weiss S, Mueller J, et al. Polar pollutants entry into the water cycle by municipal wastewater:A European perspective[J]. Environmental Science&Technology, 2006, 40(17):5451-5458
• [65]Kim S D, Cho J, Kim I S, et al. Occurrence and removal of pharmaceuticals and endocrine disruptors in South Korean surface, drinking, and waste waters[J]. Water Research, 2007, 41(5):1013-1021
• [66]Jurgens S S, Helmus R, Waaijers S L, et al. Mineralisation and primary biodegradation of aromatic organophosphorus flame retardants in activated sludge[J]. Chemosphere,2014, 111:238-242
• [67]O’Brien J W, Thai P K, Brandsma S H, et al. Wastewater analysis of Census day samples to investigate per capita input of organophosphorus flame retardants and plasticizers into wastewater[J]. Chemosphere, 2015, 138:328-334
• [68]Woudneh M B, Benskin J P, Wang G, et al. Quantitative determination of 13 organophosphorous flame retardants and plasticizers in a wastewater treatment system by high performance liquid chromatography tandem mass spectrometry[J]. Journal of Chromatography A, 2015, 1400:149-155
• [69]Cristale J, Lacorte S. Development and validation of a multiresidue method for the analysis of polybrominated diphenyl ethers, new brominated and organophosphorus flame retardants in sediment, sludge and dust[J]. Journal of Chromatography A, 2013, 1305(1):267-275
• [70]Quintana J B, Rodil R, Reemtsma T. Determination of phosphoric acid mono-and diesters in municipal wastewater by solid-phase extraction and ion-pair liquid chromatography-tandem mass spectrometry[J]. Analytical Chemistry, 2006, 78(5):1644-1650