环甲基硅氧烷的环境分布、行为与效应研究进展The Research Progress of Environmental Distribution, Behavior and Effects of Cyclic Methylsiloxanes
张松林;吴丽华;
摘要(Abstract):
近年来,挥发性环甲基硅氧烷(cVMS)在生产和生活过程中的广泛使用导致其环境和人体暴露风险日益增加,由于其具有持久性、潜在的生物积累性和毒性而被受关注。目前,人们对cVMS在全球各种环境介质中的赋存、行为及效应有一定的了解。排入环境中的cVMS大部分进入大气,在水体、沉积物、土壤和生物体中也有一定的含量。研究表明,希腊室内空气降尘中总的环硅氧烷含量中位数最高(1 380 ng·g~(-1)),其次为中国(362 ng·g~(-1));中国污水处理厂总的硅氧烷年人均通量(10 g·y~(-1))低于英国(D4~D6 48.3 g·y~(-1))和美国(D4~D6 93.5 g·y~(-1)),其中大连市一家采用CWSBR工艺的污水处理厂进水中cVMS的总浓度(1.05μg·L~(-1))普遍低于希腊(5.14μg·L~(-1))、西班牙(9.2μg·L~(-1))、加拿大(44μg·L~(-1))和一些北欧国家(17μg·L~(-1));我国大部分废水处理厂污泥中甲基硅氧烷的含量(0.1~lμg·g~(-1)dw)比一些北欧国家(26μg·g~(-1)dw)、希腊(20μg·g~(-1)dw)和加拿大(64μg·g~(-1)dw)等要低得多。中国普通居民吸入+摄食D4~D6的PELs中位数(173 ng·d~(-1))远低于中国普通人群的皮肤暴露(中位数18.5μg·d~(-1)),更低于英国成人日暴露量(1.875 mg·d~(-1))和美国妇女对总硅氧烷的日暴露量(307 mg·d~(-1))。环境中cVMS的行为和效应取决于其理化性质和具体的环境条件。进入大气的cVMS会与·NO_3、O_3和·OH反应,而与·OH反应脱去甲基生成硅醇是其主要的消除机制。污水处理过程中,大部分cVMS被污泥吸附固定,D6吸附污泥的能力最强,其次为D5和D4。挥发、吸附和非生物降解是cVMS在土壤中主要的环境行为。D4和D5可能存在生物放大作用。评估cVMS的TMF(trophic magnification factor)研究结果相互矛盾,且与BCF、BMF和BSAF的评估结果相反。总之,国内外对污水处理过程中cVMS的赋存状态和迁移、转化行为的研究比较多,且以进、出水和剩余污泥为主,而对整个工艺流程中具体变化的细化研究很少,对其生物积累特征、降解机制和降解产物更缺乏深入研究。因此,今后需要补充对其他环境介质、尤其是和人们居住、工作密切相关环境中cVMS分布规律的研究,深入探索其在实际环境中的降解过程,包括其降解产物或中间产物的环境行为,进一步评估其生态环境效应和人类健康风险。
关键词(KeyWords): 环甲基硅氧烷;环境分布;环境行为;环境效应
基金项目(Foundation): 国家自然科学基金(51068025);; 甘肃省油气资源研究重点实验室开放课题基金(SZDKFJJ20150606)
作者(Author): 张松林;吴丽华;
Email:
DOI:
参考文献(References):
- [1]Annual Report of China Polysiloxane Market in 2009:Report of China Silicon Industry[R].CRCSI,2010
- [2]周川琪,袁涛.挥发性甲基硅氧烷的环境分布与行为归趋研究进展[J].环境化学,2014,33(3):386-396Zhou C Q,Yuan T.The environmental occurrences and behaviors of volatile methylsiloxanes:A review[J].Environmental Chemistry,2014,33(3):386-396(in Chinese)
- [3]Kierkegaard A,McL achlan M.Codetermination of linear and cyclic volatile methylsiloxanes in air at a regional background site in Sweden[J].Atmospheric Environment,2013,80:322-329
- [4]Wang R,Moody R P,Koniecki D,et al.Low molecular weight cyclic volatile methylsiloxanes in cosmetic products sold in Canada:Implication for dermal exposure[J].Environment International,2009,35(6):900-904
- [5]Horii Y,Kannan K.Survey of organosilicone compounds,including cyclic and linear siloxanes in personal-care and household products[J].Archives of Environmental Contamination and Toxicology,2008,55(4):701-710
- [6]Wang D G,Norwood W,Alaee M,et al.Review of recent advances in research on the toxicity,detection,occurrence and fate of cyclic volatile methyl siloxanes in the environment[J].Chemosphere,2013,93:711-725
- [7]王秀兰.三大有机硅中间体在加拿大受限[N].中国化工报,2008-08-29005Wang X L.The three organic silicon intermediates were limited in Canada[N].China Chemical Industry News,2008-08-29005(in Chinese)
- [8]Liu N N,Shi Y L,Li W H,et al.Concentrations and distribution of synthetic musks and siloxanes in sewage sludge of wastewater treatment plants in China[J].Science of the Total Environment,2014,476-477:65-72
- [9]Zhang Z F,Qi H,Ren N Q,et al.Survey of cyclic and linear siloxanes in sediment from the Songhua River and in sewage sludge from wastewater treatment plants,Northeastern China[J].Archives of Environmental Contamination and Toxicology,2011,60(2):204-211
- [10]Gouin T,Van Egmond R,Sparham C,et al.Simulated use and wash-off release of decamethylcyclopentasiloxane used in antiperspirant[J].Chemosphere,2013,93(5):726-734
- [11]Surita S C,Tansel B.Emergence and fate of cyclic volatile polydimethylsiloxanes(D4,D5)in municipal waste streams:Release mechanisms,partitioning and persistence in air,water,soil and sediments[J].Science of the Total Environment,2014,468-469:46-52
- [12]Sparham C,Van Egmond R,O’Connor S,et al.Determination of decamethylcyclopentasiloxane in river water and final effluent by headspace gas chromatography/mass spectrometry[J].Chromatography A,2008,1212(1-2):124-129
- [13]Sanchís J,Martínez E,Ginebreda A,et al.Occurrence of linear and cyclic volatile methylsiloxanes in wastewater,surface water and sediments from Catalonia[J].Science of the Total Environment,2013,443:530-538
- [14]Lee S,Moon H B,Song G J,et al.A nationwide survey and emission estimates of cyclic and linear siloxanes through sludge from wastewater treatment plants in Korea[J].Science of the Total Environment,2014,497-498:106-112
- [15]Sánchez-Brunete C,Miguel E,Albero B,et al.Determination of cyclic and linear siloxanes in soil samples by ultrasonic-assisted extraction and gas chromatography-mass spectrometry[J].Chromatography A,2010,1217(45):7024-7030
- [16]Companioni-Damas E Y,Santos F J,Galceran M T.Analysis of linear and cyclic methylsiloxanes in sewage sludges and urban soils by concurrent solvent recondensation-large volume injection-gas chromatography-mass spectrometry[J].Chromatography A,2012,1268:150-156
- [17]McL achlan M S,Kierkegaard A,Hansen K M,et al.Concentrations and fate of decamethylcyclopentasiloxane(D5)in the atmosphere[J].Environmental Science and Toxicology,2010,4(14):5365-5370
- [18]Whelan M J,Sanders D,Van Egmond R.Effect of Aldrich humic acid on water-atmosphere transfer of decamethylcyclopentasiloxane[J].Chemosphere,2009,74(8):1111-1116
- [19]Environment Canada and Health Canada.Screening Assessment for the Challenge Decamethylcyclopentasiloxane(D5)[R].Canada,2008
- [20]Kierkegaard A,Van Egmond R,McL achlan M S.Cyclic volatile methylsiloxane bioaccumulation in flounder and ragworm in the Humber Estuary[J].Environmental Science and Technology,2011,45(14):5936-5942
- [21]Hayden J F,Barlow S A.Structure-activity relationships of organosiloxanes and the female reproductive system[J].Toxicology and Applied Pharmacology,1972,21(1):68-79
- [22]Granchi D,Cavedagna D,Ciapetti G,et al.Silicone breast implants:The role of immune-system on capsular contracture formation[J].Biomedical Materials Research,1995,29:197-202
- [23]Lieberman M W,Lykissa E D,Barrios R,et al.Cyclosiloxanes produce fatal liver and lung damage in mice[J].Environmental Health Perspectives,1999,107(2):161-165
- [24]He B,Rhodes-Brower S,Miller M R,et al.Octamethylcyclotetrasiloxane exhibits estrogenic activity in mice via ERalpha[J].Toxicology and Applied Pharmacology,2003,192:54-261
- [25]Quinn A L,Regan J M,Tobin J,et al.In vitro and in vivo evaluation of the estrogenic,androgenic,and progestagenic potential of two cyclic siloxanes[J].Toxicological Sciences,2007,96(1):145-153
- [26]Genualdi S,Harner T,Yu C,et.al.Global distribution of linear and cyclic volatile methyl siloxanes in air[J].Environmental Science and Technology,2011,45:3349-3354
- [27]Muir D C G,Howard P H.Are there other persistent organic pollutants?A challenge for environmental chemists[J].Environmental Science and Technology,2006,40(23):7157-7166
- [28]Howard P H,Muir D C G.Identifying new persistent and bioaccumulative organics among chemicals in commerce[J].Environmental Science and Technology,2010,44(7):2277-2285
- [29]杨尚源,李鑫,杨佳,等.二甲基硅油的环境行为与生态效应研究进展[J].应用生态学报,2012,23(8):2319-2324Yang S Y,Li X,Yang J,et al.Environmental behavior and ecological effect of polydimethylsiloxane:A review[J].Chinese Journal of Applied Ecology,2012,23(8):2319-2324(in Chinese)
- [30]Wang X M,Lee S C,Sheng G Y,et al.Cyclic organosilicon compounds in ambient air in Guangzhou,Macau and Nanhai,Pearl River Delta[J].Applied Geochemistry,2001,16:1447-1454
- [31]Allen R B,Kochs P,Chandra G.The Handbook of Environmental Chemistry,Part H:Organosilicon Materials,vol.3[M].Berlin:Springer-Verlag,1997:1-25
- [32]Tran T M,Abualnaja K O,Asimakopoulos A G,et al.A survey of cyclic and linear siloxanes in indoor dust and their implications for human exposures in twelve countries[J].Environment International,2015,78:39-44
- [33]Dudzina T,Goetz N V,Bogdal C,et al.Concentrations of cyclic volatile methylsiloxanes in European cosmetics and personal care products:Prerequisite for human and environmental exposure assessment[J].Environment International,2014,62:86-94
- [34]Xu L,Shi Y L,Cai Y Q.Occurrence and fate of volatile siloxanes in a municipal Wastewater Treatment Plant of Beijing,China[J].Water Research,2013,47(2):715-724
- [35]Wang D G,Steer H,Tait T,et al.Concentrations of cyclic volatile methylsiloxanes in biosolid amended soil,influent,effluent,receiving water,and sediment of wastewater treatment plants in Canada[J].Chemosphere,2013,93(5):766-773
- [36]Griessbach E F,Lehmann R G.Degradation of polydimethylsiloxane fluids in the environment--A review[J].Chemosphere,1999,38(6):1461-1468
- [37]Xu S.Fate of cyclic methylsiloxanes in soils.1.The degradation pathway[J].Environmental Science and Technology,1999,33:603-608
- [38]McG oldrick D J,Chan C,Drouillard K G,et al.Concentrations and trophic magnification of cyclic siloxanes in aquatic biota from the Western Basin of Lake Erie,Canada[J].Environmental Pollution,2014,86:141-148
- [39]Kierkegaard A,Bignert A,McL achlan M S.Cyclic volatile methylsiloxanes in fish from the Baltic Sea[J].Chemosphere,2013,93(5):774-778
- [40]Pieri F,Katsoyiannis A,Martellini T,et al.Occurrence of linear and cyclic volatile methyl siloxanes in indoor air samples(UK and Italy)and their isotopic characterization[J].Environment International,2013,59:363-371
- [41]Lu Y,Yuan T,Yun S H,et al.Occurrence of synthetic musks in indoor dust from China and implications for human exposure[J].Archives of Environmental Contamination and Toxicology,2011,60(1):182-189
- [42]Lu Y,Yuan T,Yun S H,et al.Occurrence of cyclic and linear siloxanes in indoor dust from China,and implications for human exposures[J].Environmental Science and Toxicology,2010,44(16):6081-6087
- [43]Xu L,Shi Y L,Liu N N,et al.Methyl siloxanes in environmental matrices and human plasma/fat from both general industries and residential areas in China[J].Science of the Total Environment,2015,505:454-463
- [44]Whelan M J,Estrada E,Van Egmond R.A modeling assessment of the atmospheric fate of volatile methyl siloxanes and their reaction products[J].Chemosphere,2004,57:1427-1437
- [45]Atkinson R.Kinetics of the gas phase reactions of a series of organosilicon compounds with OH and NO3radicals and O3at 297±2K[J].Environmental Science and Toxicology,1991,25:863-866
- [46]Xu S H,Wania F.Chemical fate,latitudinal distribution and long-range transport of cyclic volatile methylsiloxanes in the global environment:A modeling assessment[J].Chemosphere,2013,93:835-843
- [47]Wang D G,Aggarwal M,Tait T,et al.Fate of anthropogenic cyclic volatile methylsiloxanes in a wastewater treatment plant[J].Water Research,2015,72:209-217
- [48]Whelan M J,Sanders D,Van Egmond R.Effect of Aldrich humic acid on water-atmosphere transfer of decamethylcyclopentasiloxane[J].Chemosphere,2009,74(8):1111-1116
- [49]David M D,Fendinger N J,Hand V C.Determination of Henry's law constants for organosilicones in actual and simulated wastewater[J].Environmental Science and Technology,2000,34(21):4554-4559
- [50]Bletsou A,Asimakopoulos A,Stasinakis A,et al.Mass loading and fate of linear and cyclic siloxanes in a wastewater treatment plant in Greece[J].Environmental Science and Technology,2013,47:1824-1832
- [51]Society of Environmental Toxicology and Chemistry.Kinetics and mechanism of the abiotic hydrolysis reactions of permethylated cyclosiloxanes in aqueous solution:Report of SETAC Northern America 27 th Annual Meeting[R].Montreal,Quebec,Canada:SETAC,2009
- [52]Whelan M J,Van Egmond R,Gore D,et al.Dynamic multi-phase partitioning of decamethylcyclopentasiloxane(D5)in river water[J].Water Research,2010,44(12):3679-3686
- [53]Silicones Environment,Health and Safety Council.Hydrolysis of Octamethylcyclotetrasiloxane(D4):Report of the Assessment for D4 by Environment Canada and Health Canada[R].Canada:SEHSC,2005a
- [54]Silicones Environment,Health and Safety Council.Hydrolysis of Octamethylcyclotetrasiloxane(D5):Report of the Assessment for D5 by Environment Canada and Health Canada[R].Canada:SEHSC,2006
- [55]Xu S,Chandra G.Fate of cyclic methylsiloxanes in soils.2.Rates of degradation and volatilization[J].Environmental Science and Technology,1999,33:4034-4039
- [56]Silicones Environment,Health and Safety Council.Hydrolysis of Octamethylcyclotetrasiloxane(D4):Report of the Assessment for D4 by Environment Canada and Health Canada[R].Canada:SEHSC,2005b
- [57]Health and Environmental Sciences,Dow Corning Corporation.Estimation of degradation rates of cV MS in soils[R].HES,2007
- [58]Kent D J,McN amara P C,Putt A E,et al.Octamethylcyclotetrasiloxane in aquatic sediments:Toxicity and risk assessment[J].Ecotoxicology and Environmental Safety,1994,29(3):372-389
- [59]Sousa J V,McN amara P C,Putt A E,et al.Effects of octamethylcyclotetrasiloxane(OMCTS)on freshwater and marine organisms[J].Environmental Toxicology and Chemistry,1995,14:1639-1647
- [60]European Commission.Amending Regulation(EC)No1907/2006 of the European Parliament and of the Council on the Registration,Evaluation,Authorisation and Restriction of Chemicals(REACH)as Regards Annex XIII[S].2010
- [61]Silicones Environment,Health and Safety Council.Decamethylcyclopentasiloxane-14-day prolonged acute toxicity to rainbow trout(Oncorhynchus mykiss)under flow-through conditions:Report of the Assessment for D5 by Environment Canada and Health Canada[R].Canada:SEHSC,2000
- [62]Parrott J,Alaee M,Wang D,et al.Fathead minnow(Pimephales promelas)egg-to-juvenile exposure to decamethylcyclopentasiloxane(D5)[J].Chemosphere,2013,93(5):813-818
- [63]Dow Corning Corporation,Silicones Environment,Health and Safety Council.Drottar K R.14C-Dodecamethylcyclohexasiloxane(14C-D6):Bioconcentration in the fathead minnow(Pimephales promelas)under flowthrough test conditions:Report of the Assessment for D6by Environment Canada and Health Canada[R].Canada:SEHSC,2005b
- [64]Annelin R B,Frye C L.The piscine bioconcentration characteristics of cyclic and linear oligomeric permethylsiloxanes[J].The Science of the Total Environment,1989,83(1-2):1-11
- [65]Fackler P H,Dionne E,Hartley D A,et al.Bioconcentration by fish of a highly volatile silicone compound in a totally enclosed aquatic exposure system[J].Environmental Toxicology and Chemistry,1995,14:1649-1656
- [66]Dow Corning Corporation,Silicones Environment,Health and Safety Council.Drottar K R.14C-Decamethyl-cyclopentasiloxane(14C-D5):Bioconcentration in the fathead minnow(Pimphales promelas)under flowthrough test conditions:Report of the Assessment for D5by Environment Canada and Health Canada[R].Canada:SEHSC,2005a
- [67]Woodburn K,Drottar K,Domoradzki J Y,et al.Determination of the dietary biomagnification of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane with the rainbow trout(Oncorhynchus mykiss)[J].Chemosphere,2013,93(5):779-788
- [68]Silicones Environmental,Health and Safety Council.Aprolonged sediment toxicity test with Chironomus riparius using spiked sediment.Wildlife International,LTD:Report of the Assessment for D4 by Environment Canada and Health Canada[R].Canada:SEHSC,2008
- [69]Silicones Environment,Health and Safety Council.Decamethylcyclopentasiloxane(D5)-the full life-cycle toxicity to Midge(Chironomous riparius)under static conditions:Report of the Assessment for D5 by Environment Canada and Health Canada[R].Canada:SEH-SC,2003
- [70]Velicogna J,Ritchie E,Princz J,et al.Ecotoxicity of siloxane D5 in soil[J].Chemosphere,2012,87(1):77-83
- [71]Health and Environmental Sciences.Trophic dilution of cyclic volatile methylsiloxane(cV MS)materials in a temperate freshwater lake:Report of Centre Européen des Sililcones[R].HES,2009
- [72]Kierkegaard A,Van Egmond R,McL achlan M S.Cyclic volatile methylsiloxane bioaccumulation in flounder and ragworm in the Humber Estuary[J].Environmental Science and Technology,2011,45(14):5936-5942
- [73]Health and Environmental Sciences.Bioaccumulation and trophic transfer of cyclic volatile methylsiloxane(cV MS)materials in the aquatic marine food webs of the Inner and Outer Oslofjord,Norway:Report of Centre Européen des Sililcones[R].HES,2010
- [74]Gobas F A P C,De Wolf W,Burkhard L P,et al.Revisiting bioaccumulation criteria for POPs and PBT assessments[J].Integrated Environmental Assessment and Management,2009,5:624-637
- [75]Siloxane D5 Board of Review:Report of the Board of Review for Decamethylcyclopentasiloxane(D5)[R].Ottawa,ON,Canada,2011
- [76]Van Egmond R,Sparham C,Hastie C,et al.Monitoring and modelling of siloxanes in a sewage treatment plant in the UK[J].Chemosphere,2013,93:757-765
- [77]王艺,陈川,张子峰,等.甲基硅氧烷在污水处理厂中的环境行为[J].化工学报,2016,67(1):83-88Wang Y,Chen C,Zhang Z F,et al.Environmental behavior of siloxane in wastewater treatment plants[J].CIESC Journal,2016,67(1):83-88(in Chinese)
- [78]高鹏园.市政污水中甲基硅氧烷赋存形态的研究[D].大连:大连海事大学,2013Gao P Y.Occurrence of siloxanes in municipal wastewater treatment plant[D].Dalian:Dalian Maritime University,2013(in Chinese)
- [79]申凯.有机硅氧烷在市政废水处理厂的归趋研究[D].大连:大连海事大学,2014Shen K.Fate of volatile methylsiloxanes in a wastewater treatment plant[D].Dalian:Dalian Maritime University,2014(in Chinese)
- [80]吴倩.挥发性硅氧烷在恒水位序批式活性污泥法市政废水处理厂的归趋及生态风险评估[D].大连:大连海事大学,2015Wu Q.Fate and ecological risk assessment of volatile methylsiloxanes in a wastewater treatment plant using the process of constant water level sequencing batch reactors[D].Dalian:Dalian Maritime University,2015(in Chinese)
- [81]Sousa J V,McN amara P C,Putt A E,et al.Effects of octamethylcyclotetrasiloxane(OMCTS)on freshwater and marine organisms[J].Environmental Toxicology and Chemistry,1995,14(10):1640-1647