污水处理厂进出水中环状挥发性甲基硅氧烷(cVMS)浓度季节性变化
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摘要
环状挥发性甲基硅氧烷(cVMS)具有高挥发性和高亲脂性,被确认为潜在全球性污染物.本文采用液-液微萃取法,对大连市内8座污水处理厂进出水中3种环状挥发性甲基硅氧烷(D4、D5、D6)浓度水平进行为期一年监测,探究了进出水中cVMS浓度季节性变化规律.污水厂进出水中cVMS年平均浓度分别为830.2 ng·L~(-1)和234.8 ng·L~(-1),进水cVMS中D4、D5、D6年平均浓度分别为471.9、1.565×10~3、453.6 ng·L~(-1),出水cVMS中D4、D5、D6年平均浓度分别为249.3、244.1、210.9 ng·L~(-1),cVMS去除率范围为47.2%—84.4%.进水中D4、D5、D6浓度均高于出水,其中D5占比为62.2%.污水厂中进出水中cVMS浓度水平有明显的季节变化规律,冬季较高,春秋较低,冬季进水中cVMS年均浓度是春季的1.57倍,是秋季的2.26倍,冬季出水是春季的1.95倍,是秋季的4.24倍.相比曝气生物滤池(BAF)和循环式活性污泥法(CAST)两种处理工艺,恒水位序批式反应器(CWSBR)工艺对cVMS具有较高的去除率.
Cyclic volatile methylsiloxanes(cVMS) have high volatility and high lipophilicity and they are identified as potential global pollutants that are widely distributed in the environment. In this paper, the concentrations of three cyclic volatile methylsiloxanes(D4, D5, D6) were investigated using liquid-liquid microextraction method in the influents and effluents of eight wastewater treatment plants(WWTPs) in Dalian, China. For a period of one year, the seasonal variation of cVMS concentrations in the influents and effluents was investigated. The annual average concentrations of total siloxanes in the influents and effluents were 830.2 ng·L~(-1) and 234.8 ng·L~(-1) in WWTPs, respectively. The average concentrations of D4, D5, and D6 in the influents were 471.9 ng·L~(-1), 1.565×10~3 ng·L~(-1) and 453.6 ng·L~(-1), respectively. The average concentrations of D4, D5, and D6 in the effluents were 249.3 ng·L~(-1), 244.1 ng·L~(-1), and 210.9 ng·L~(-1), respectively. In general, the range of cVMS removal efficiency was 47.2%—84.4%. Concentrations of D4、D5、D6 in the influents were higher than those found in the effluents. The percentage ratio of D5 is 62.2%. The concentration of cVMS in the influents and effluents of WWTPs showed obvious seasonal variations, with higher concentration in the winter and lower in the spring and autumn. The average concentration of cVMS in the influents in the winter was 1.57 times that of spring, and 2.26 times that of autumn. And the average concentration in the effluents in the winter was 1.95 times that of spring and 4.24 times that of autumn. Compared to biological aerated filter(BAF) and cyclic activated sludge technology(CAST) processes, constant water level sequencing batch reactor(CWSBR) had higher removal rate for cVMS.
Cyclic volatile methylsiloxanes(cVMS) have high volatility and high lipophilicity and they are identified as potential global pollutants that are widely distributed in the environment. In this paper, the concentrations of three cyclic volatile methylsiloxanes(D4, D5, D6) were investigated using liquid-liquid microextraction method in the influents and effluents of eight wastewater treatment plants(WWTPs) in Dalian, China. For a period of one year, the seasonal variation of cVMS concentrations in the influents and effluents was investigated. The annual average concentrations of total siloxanes in the influents and effluents were 830.2 ng·L~(-1) and 234.8 ng·L~(-1) in WWTPs, respectively. The average concentrations of D4, D5, and D6 in the influents were 471.9 ng·L~(-1), 1.565×10~3 ng·L~(-1) and 453.6 ng·L~(-1), respectively. The average concentrations of D4, D5, and D6 in the effluents were 249.3 ng·L~(-1), 244.1 ng·L~(-1), and 210.9 ng·L~(-1), respectively. In general, the range of cVMS removal efficiency was 47.2%—84.4%. Concentrations of D4、D5、D6 in the influents were higher than those found in the effluents. The percentage ratio of D5 is 62.2%. The concentration of cVMS in the influents and effluents of WWTPs showed obvious seasonal variations, with higher concentration in the winter and lower in the spring and autumn. The average concentration of cVMS in the influents in the winter was 1.57 times that of spring, and 2.26 times that of autumn. And the average concentration in the effluents in the winter was 1.95 times that of spring and 4.24 times that of autumn. Compared to biological aerated filter(BAF) and cyclic activated sludge technology(CAST) processes, constant water level sequencing batch reactor(CWSBR) had higher removal rate for cVMS.
引文
[1] 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.
[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):386-396.ZHOU 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,MCLACHLAN M.Determination of linear and cyclic volatile methylsiloxanes in air at a regional background site in Sweden[J].Atmospheric Environment,2013,80(6):322-329.
[4] HORII Y,KANNAN K.Survey of organosiloxane compounds,including cyclic and linear siloxanes,in personal-care and household products[J].Archives of Environmental Contamination and Toxicology,2008,55(10):701-710.
[5] 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(5):711-725.
[6] DODSON R E,NISHIOKA M,STANDLEY L J,et al.Endocrine disruptors and asthma-associated chemicals in consumer products[J].Environmental Health Perspectives,2012,120(7):935-943.
[7] HASSEN L,WARNER N A,BRAATHEN T,et al.Plasma concentrations of cyclic volatile methylsiloxanes(VMS) in pregnant and postmenopausal Norwegian women and self-reported use of personal care products (PCPs)[J].Environment International,2013(51):82-87.
[8] HARVEY P W,EVERETT D J.Regulation of endocrine-disrupting chemicals:Critical overview and deficiencies in toxicology and risk assessment for human health[J].Best Practice& Research Clinical Endocrinology& Metabolism,2005,20(1):145-165.
[9] 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(3):254-261.
[10] KROGSETH I S,KIERKEGAARD A,MCLACHLAN M S,et al.Occurrence and seasonality of cyclic volatile methyl siloxanes in arctic air[J].Environmental Science & Technology,2013,47(1):502-509.
[11] MCLACHLAN M S,KIERKEGAARD A,HANSEN K J,et al.Concentrations and fate of demathylcyclopentasiloxane (D5) in the atmosphere[J].Environmental Science & Technology,2010,44(22):5365-5370.
[12] QUINN A L,REGAN J M,TOBIN J M,et al.In vitro and in vivo evaluation of the estrogenic,androgenic,and progestagenic potential of two cyclic siloxanes[J].Toxicological Sciences An Official Journal of the Society of Toxicology,2007,96(1):145-152.
[13] XU S,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(5):835-843.
[14] WAMER N A,EVENSET A,CHRISTENSEN G,et al.Volatile siloxanes in the European arctic:Assessment of sources and spatial distribution[J].Environmental Science & Technology,2017,44(19):7705-7710.
[15] LINDA H,NICHOLAS A W,TONJE B,et al.Plasma concentrations of cyclic volatile methylsiloxanes (cVMS) in pregnant and postmenopausal norwegian women and self-reported use of personal care products (PCPs)[J].Environment International,2013,51(1):82-87.
[16] GENUALDI S,HARNER T,CHENG Y,et al.Global distribution of linear and cyclic volatile methyl siloxanes in air[J].Environmental Science& Technology,2011,45(8):3349-3354.
[17] CHENG Y,MAHIBA S,LUTZ A,et al.Wastewater treatment plants and landfills emit volatile methyl siloxanes (VMSs) to the atmosphere:Investigations using a new passive air sampler[J].Environmental Pollution,2011,159(10):2380-2386.
[18] WANGD 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.
[19] 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.
[20] BLETSOU A A,ASIMAKOPOULOS A G,STASINAKIS A S,et al.Mass loading and fate of linear and cyclic siloxanes in a wastewater treatment plant in Greece[J].Environmental Science& Technology,2013,47(4):1824-1832.
[21] LI B,LI W L,SUN S J,et al.The occurrence and fate of siloxanes in wastewater treatment plant in Harbin,China[J].Environmental Science & Pollution Research,2016,23(13):13200-13209.
[22] 吴婧娴.市政污水与厂区空气中cVMS浓度与排放研究[D].辽宁:大连海事大学,2016.WU J X.Emission research of cVMS and concentration level in municipal wastewater and air[D].Liaoning:Dalian Maritime University,2016 (in Chinese).
[23] CORTADA C,LUCIANA C D R,VIDAL L,et al.Determination of cyclic and linear siloxanes in wastewater samples by ultrasound-assissted dispersive liquid-liquid microextrstion followed by gas chromatography-mass spectrometry[J].Talanta,2014,120(2):191-197.
[24] 周鸿艳,叶朝霞,谭军,等.分散液液微萃取-气相色谱法测定水样中甲基环硅氧烷[J].分析试验室,2011,30(2):66-69.ZHOU H Y,YE Z X,TAN J.Determination of methyl siloxane in water samples by liquid-liquid microextraction-gas chromatography[J].Chinese Journal of Analysis Laboratory,2011,30(2):66-69(in Chinese).
[25] 国家环境保护局.环境监测技术规范.第四册,生物监测(水环境)部分[M].国家环境保护局,1986.National Environmental Protection Agency.Technical specifications for environmental monitoring.Volume IV[M],Biological Monitoring (Water Environment) Section.National Environmental Protection Agency,1986(in Chinese).
[26] LU Y,YUAN T,WANG W,et al.Concentrations and assessment of exposure to exposure to siloxanes and synthetic musks in personal care products from China[J].Environmental Pollution,2011,159(12):3522-3528.
[27] KAJ L,ANDERSSON J,COUSINS A P,et al.Results from the Swedish national screening programme 2004 subreport 4:Siloxanes[R].IVL Swedish Environmental Research Institute Ltd,2005.
[28] SANCHIS J,MARTINEZ 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(3):530-538.
[29] SURITA S C,TANSEL B.A multiphase analysis of partitioning and hazard index characteristics of siloxanes in biosolids[J].Ecotoxicology and Environmental Safety,2014,102(1):79-83.
[30] 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(5):757-765.
[31] 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(2):209-217.
[32] KNOERR S M,DURHAM J A,MCNETT D A.Development of collection,storage and analysis procedures for the quantification of cyclic volatile methylsiloxanes in wastewater treatment plant effluent and influent[J].Chemosphere,2107,182(2):114-121.
[33] XU S,KROPSCOTT B.Method for simultaneous determination of partition coefficients for cyclic volatile methylsiloxanes and dimethylsilanediol[J].Analytical Chemistry,2012,84(4):1948-1955.
[34] XU S.Fate of cyclic methylsilocanes in soils.1.The degradation pathway[J].Environmental Science and Technology,1999,33(3):603-608.
[35] 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,2005.
[36] KAJ L,SCHLABACH M,ANDERSSON J,et al.Siloxanes in the Nordic environment [C].Copenhagen:Nordic council of ministers,2005.
[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):386-396.ZHOU 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,MCLACHLAN M.Determination of linear and cyclic volatile methylsiloxanes in air at a regional background site in Sweden[J].Atmospheric Environment,2013,80(6):322-329.
[4] HORII Y,KANNAN K.Survey of organosiloxane compounds,including cyclic and linear siloxanes,in personal-care and household products[J].Archives of Environmental Contamination and Toxicology,2008,55(10):701-710.
[5] 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(5):711-725.
[6] DODSON R E,NISHIOKA M,STANDLEY L J,et al.Endocrine disruptors and asthma-associated chemicals in consumer products[J].Environmental Health Perspectives,2012,120(7):935-943.
[7] HASSEN L,WARNER N A,BRAATHEN T,et al.Plasma concentrations of cyclic volatile methylsiloxanes(VMS) in pregnant and postmenopausal Norwegian women and self-reported use of personal care products (PCPs)[J].Environment International,2013(51):82-87.
[8] HARVEY P W,EVERETT D J.Regulation of endocrine-disrupting chemicals:Critical overview and deficiencies in toxicology and risk assessment for human health[J].Best Practice& Research Clinical Endocrinology& Metabolism,2005,20(1):145-165.
[9] 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(3):254-261.
[10] KROGSETH I S,KIERKEGAARD A,MCLACHLAN M S,et al.Occurrence and seasonality of cyclic volatile methyl siloxanes in arctic air[J].Environmental Science & Technology,2013,47(1):502-509.
[11] MCLACHLAN M S,KIERKEGAARD A,HANSEN K J,et al.Concentrations and fate of demathylcyclopentasiloxane (D5) in the atmosphere[J].Environmental Science & Technology,2010,44(22):5365-5370.
[12] QUINN A L,REGAN J M,TOBIN J M,et al.In vitro and in vivo evaluation of the estrogenic,androgenic,and progestagenic potential of two cyclic siloxanes[J].Toxicological Sciences An Official Journal of the Society of Toxicology,2007,96(1):145-152.
[13] XU S,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(5):835-843.
[14] WAMER N A,EVENSET A,CHRISTENSEN G,et al.Volatile siloxanes in the European arctic:Assessment of sources and spatial distribution[J].Environmental Science & Technology,2017,44(19):7705-7710.
[15] LINDA H,NICHOLAS A W,TONJE B,et al.Plasma concentrations of cyclic volatile methylsiloxanes (cVMS) in pregnant and postmenopausal norwegian women and self-reported use of personal care products (PCPs)[J].Environment International,2013,51(1):82-87.
[16] GENUALDI S,HARNER T,CHENG Y,et al.Global distribution of linear and cyclic volatile methyl siloxanes in air[J].Environmental Science& Technology,2011,45(8):3349-3354.
[17] CHENG Y,MAHIBA S,LUTZ A,et al.Wastewater treatment plants and landfills emit volatile methyl siloxanes (VMSs) to the atmosphere:Investigations using a new passive air sampler[J].Environmental Pollution,2011,159(10):2380-2386.
[18] WANGD 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.
[19] 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.
[20] BLETSOU A A,ASIMAKOPOULOS A G,STASINAKIS A S,et al.Mass loading and fate of linear and cyclic siloxanes in a wastewater treatment plant in Greece[J].Environmental Science& Technology,2013,47(4):1824-1832.
[21] LI B,LI W L,SUN S J,et al.The occurrence and fate of siloxanes in wastewater treatment plant in Harbin,China[J].Environmental Science & Pollution Research,2016,23(13):13200-13209.
[22] 吴婧娴.市政污水与厂区空气中cVMS浓度与排放研究[D].辽宁:大连海事大学,2016.WU J X.Emission research of cVMS and concentration level in municipal wastewater and air[D].Liaoning:Dalian Maritime University,2016 (in Chinese).
[23] CORTADA C,LUCIANA C D R,VIDAL L,et al.Determination of cyclic and linear siloxanes in wastewater samples by ultrasound-assissted dispersive liquid-liquid microextrstion followed by gas chromatography-mass spectrometry[J].Talanta,2014,120(2):191-197.
[24] 周鸿艳,叶朝霞,谭军,等.分散液液微萃取-气相色谱法测定水样中甲基环硅氧烷[J].分析试验室,2011,30(2):66-69.ZHOU H Y,YE Z X,TAN J.Determination of methyl siloxane in water samples by liquid-liquid microextraction-gas chromatography[J].Chinese Journal of Analysis Laboratory,2011,30(2):66-69(in Chinese).
[25] 国家环境保护局.环境监测技术规范.第四册,生物监测(水环境)部分[M].国家环境保护局,1986.National Environmental Protection Agency.Technical specifications for environmental monitoring.Volume IV[M],Biological Monitoring (Water Environment) Section.National Environmental Protection Agency,1986(in Chinese).
[26] LU Y,YUAN T,WANG W,et al.Concentrations and assessment of exposure to exposure to siloxanes and synthetic musks in personal care products from China[J].Environmental Pollution,2011,159(12):3522-3528.
[27] KAJ L,ANDERSSON J,COUSINS A P,et al.Results from the Swedish national screening programme 2004 subreport 4:Siloxanes[R].IVL Swedish Environmental Research Institute Ltd,2005.
[28] SANCHIS J,MARTINEZ 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(3):530-538.
[29] SURITA S C,TANSEL B.A multiphase analysis of partitioning and hazard index characteristics of siloxanes in biosolids[J].Ecotoxicology and Environmental Safety,2014,102(1):79-83.
[30] 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(5):757-765.
[31] 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(2):209-217.
[32] KNOERR S M,DURHAM J A,MCNETT D A.Development of collection,storage and analysis procedures for the quantification of cyclic volatile methylsiloxanes in wastewater treatment plant effluent and influent[J].Chemosphere,2107,182(2):114-121.
[33] XU S,KROPSCOTT B.Method for simultaneous determination of partition coefficients for cyclic volatile methylsiloxanes and dimethylsilanediol[J].Analytical Chemistry,2012,84(4):1948-1955.
[34] XU S.Fate of cyclic methylsilocanes in soils.1.The degradation pathway[J].Environmental Science and Technology,1999,33(3):603-608.
[35] 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,2005.
[36] KAJ L,SCHLABACH M,ANDERSSON J,et al.Siloxanes in the Nordic environment [C].Copenhagen:Nordic council of ministers,2005.