海螺沟植物和积雪中有机磷酸酯的分布及来源
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摘要
为研究大气传输以及干湿沉降对偏远地区环境中有机磷酸酯(OPEs)含量及分布的影响,本研究以海螺沟景区为例,采集了海螺沟的植物和积雪样品,用气相色谱-质谱联用仪(GC-MS)定量分析了样品中7种典型有机磷酸酯[磷酸三丁酯(Tn BP)、磷酸三氯乙酯(TCEP)、磷酸三氯丙酯(TCPP)、磷酸三(2,3-二氯丙基)酯(TDCPP)、磷酸三苯酯(TPh P)、磷酸三丁氧乙酯(TBEP)和磷酸三异辛酯(TEHP)]的含量及分布特征.结果表明,海螺沟景区常见的9种植物中7种OPEs(Σ7OPEs)的含量(以DW计)水平在43. 1～1 050. 8 ng·g-1之间,其中TBEP和TPh P含量最高,分别占Σ7OPEs总含量的36%～70%和24%～80%.冰川积雪中主要污染物与植物中一致,TBEP含量最高,占Σ7OPEs总含量的47%,其次为TPh P,占24%.采用Grads、后向轨迹模型及历史风向数据分析得出海螺沟环境显著受到人类活动扰动,其OPEs主要受来自成都方向和云南昭通与宜宾、泸州、西昌交界处方向的大气传输的影响,需要进一步研究其环境行为并加强城市污染控制.
In order to study the effects of atmospheric transport and the wet/dry deposition on the content and distribution of organophosphate esters( OPEs) in remote areas,seven types of OPEs including tri-n-butyl phosphate( Tn BP),tri( 2-chloroethyl)phosphate( TCEP),trichloropropyl phosphate( TCPP),tridichloropropyl phosphate( TDCPP),triphenyl phosphate( TPh P),tributoxyethyl phosphate( TBEP),and tris( 2-ethylhexyl) phosphate( TEHP) were analyzed in plants and snow samples in Hailuogou using gas chromatography-mass spectrometry. The results showed that the pollution levels of the seven OPEs( Σ 7 OPEs) in the plant samples ranged from 43. 1 ng·g-1 to 1 050. 8 ng·g-1. TBEP and TPh P were the main pollutants,accounting for 36%-70% and 24%-80% of the Σ 7 OPEs,respectively. The main pollutants in the snow in Hailuogou were the same as those in the plants,with TBEP dominating the profile of the Σ 7 OPEs at 47%,followed by TPh P at 24%. The analysis results of the grid analysis display system( Grads),backward trajectory model,and historical wind data of Hailuogou indicate that the OPEs in this region are affected mainly by atmospheric transmission from Chengdu and the junction of Yunnan Zhaotong and Yibin,Luzhou,and Xichang. The environment of Hailuogou has obviously been disturbed by human activities. It is necessary to conduct thorough investigations of its environmental behavior and to strengthen urban pollution control measures.
In order to study the effects of atmospheric transport and the wet/dry deposition on the content and distribution of organophosphate esters( OPEs) in remote areas,seven types of OPEs including tri-n-butyl phosphate( Tn BP),tri( 2-chloroethyl)phosphate( TCEP),trichloropropyl phosphate( TCPP),tridichloropropyl phosphate( TDCPP),triphenyl phosphate( TPh P),tributoxyethyl phosphate( TBEP),and tris( 2-ethylhexyl) phosphate( TEHP) were analyzed in plants and snow samples in Hailuogou using gas chromatography-mass spectrometry. The results showed that the pollution levels of the seven OPEs( Σ 7 OPEs) in the plant samples ranged from 43. 1 ng·g-1 to 1 050. 8 ng·g-1. TBEP and TPh P were the main pollutants,accounting for 36%-70% and 24%-80% of the Σ 7 OPEs,respectively. The main pollutants in the snow in Hailuogou were the same as those in the plants,with TBEP dominating the profile of the Σ 7 OPEs at 47%,followed by TPh P at 24%. The analysis results of the grid analysis display system( Grads),backward trajectory model,and historical wind data of Hailuogou indicate that the OPEs in this region are affected mainly by atmospheric transmission from Chengdu and the junction of Yunnan Zhaotong and Yibin,Luzhou,and Xichang. The environment of Hailuogou has obviously been disturbed by human activities. It is necessary to conduct thorough investigations of its environmental behavior and to strengthen urban pollution control measures.
引文
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[18]杨博.城市典型植物叶片中PAHs的时空分布特征及迁移转化机理[D].上海:华东师范大学,2017.Yang B. The spatial-temporal distribution and transport process of polycyclic aromatic hydrocarbons in leaves of urban typical tree species[D]. Shanghai:East China Normal University,2017.
[19] Wild E,Dent J,Thomas G O,et al. Visualizing the air-to-leaf transfer and within-leaf movement and distribution of phenanthrene:further studies utilizing two-photon excitation microscopy[J]. Environmental Science&Technology,2006,40(3):907-916.
[20] Reemtsma T,Quintana J B,Rodil R,et al. Organophosphorus flame retardants and plasticizers in water and air I. Occurrence and fate[J]. Tr AC Trends in Analytical Chemistry,2008,27(9):727-737.
[21]秦宏兵,范苓,顾海东.固相萃取-气相色谱/质谱法测定水中6种有机磷酸酯类阻燃剂和增塑剂[J].分析科学学报,2014,30(2):259-262.Qin H B,Fan L,Gu H D. Determination of organophosphorus flame retardants and plasticizers in environmental water by solid phase extraction coupled with gas chromatography/mass spectrometry[J]. Journal of Analytical Science,2014,30(2):259-262.
[22] Wang X W,Liu J F,Yin Y G. Development of an ultra-highperformance liquid chromatography-tandem mass spectrometry method for high throughput determination of organophosphorus flame retardants in environmental water[J]. Journal of Chromatography A,2011,1218(38):6705-6711.
[23]印红玲,李世平,叶芝祥,等.成都市大气PM2. 5中有机磷阻燃剂的污染水平及来源[J].环境科学,2015,36(10):3566-3572.Yin H L,Li S P,Ye Z X,et al. Pollution level and sources of organic phosphorus esters in airborne PM2. 5in Chengdu City[J].Environmental Science,2015,36(10):3566-3572.
[24] Shi Y L,Gao L H,Li W H,et al. Occurrence,distribution and seasonal variation of organophosphate flame retardants and plasticizers in urban surface water in Beijing, China[J].Environmental Pollution,2016,209:1-10.
[25] Regnery J, Püttmann W. Seasonal fluctuations of organophosphate concentrations in precipitation and storm water runoff[J]. Chemosphere,2010,78(8):958-964.
[26] Lai S C,Xie Z Y,Song T L,et al. Occurrence and dry deposition of organophosphate esters in atmospheric particles over the northern South China Sea[J]. Chemosphere,2015,127:195-200.
[27] Li J,Xie Z Y,Mi W Y,et al. Organophosphate Esters in air,snow,and seawater in the North Atlantic and the Arctic[J].Environmental Science&Technology,2017,51(12):6887-6896.
[28] Cheng W H,Xie Z Q,Blais J M,et al. Organophosphorus esters in the oceans and possible relation with ocean gyres[J].Environmental Pollution,2013,180:159-164.
[29] Castro-Jimenez J, Berrojalbiz N, Pizarro M, et al.Organophosphate ester(OPE)flame retardants and plasticizers in the Open Mediterranean and Black Seas Atmosphere[J].Environmental Science&Technology,2014,48(6):3203-3209.
[30] Li J,Tang J H,Mi W Y,et al. Spatial distribution and seasonal variation of organophosphate esters in air above the Bohai and Yellow Seas,China[J]. Environmental Science&Technology,2018,52(1):89-97.
[31]吴迪,印红玲,李世平,等.成都市锦江表层水和沉积物中有机磷酸酯的污染特征[J].环境科学,2019,40(3):1245-1251.Wu D,Yin H L,Li S P,et al. Pollution characteristics of OPEs in the surface water and sediment of the Jinjiang River in Chengdu city[J]. Environmental Science,2019,40(3):1245-1251.
[2] Cristale J,Quintana J,Chaler R,et al. Gas chromatography/mass spectrometry comprehensive analysis of organophosphorus,brominated flame retardants, by-products and formulation intermediates in water[J]. Journal of Chromatography A,2012,1241:1-12.
[3] Yan X J, Huan H E, Peng Y, et al. Determination of organophosphorus flame retardants in surface water by solid phase extraction coupled with gas chromatography-mass spectrometry[J]. Chinese Journal of Analytical Chemistry,2012,40(11):1693-1697.
[4]李闯修,赵晓丽,高立红,等.高效液相色谱-串联质谱法测定地表水样品中5种有机磷酸酯代谢物[J].分析测试学报,2016,35(2):194-199.Li C X,Zhao X L,Gao L H,et al. Determination of five organophosphate ester metabolites in surface water samples by LC-MS/MS[J]. Journal of Instrumental Analysis,2016,35(2):194-199.
[5] 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(1-2):9-15.
[6] Bollmann U E,Mller A,Xie Z Y,et al. Occurrence and fate of organophosphorus flame retardants and plasticizers in coastal and marine surface waters[J]. Water Research,2012,46(2):531-538.
[7] Bacaloni A, Cucci F, Guarino C, et al. Occurrence of organophosphorus flame retardant and plasticizers in three volcanic lakes of central Italy[J]. Environmental Science&Technology,2008,42(6):1898-1903.
[8] Carlsson H,Nilsson U,Becker G,et al. Organophosphate ester flame retardants and plasticizers in the indoor environment:analytical methodology and occurrence[J]. Environmental Science&Technology,2014,31(10):2931-2936.
[9] Hartmann P C,Bürgi D,Giger W. Organophosphate flame retardants and plasticizers in indoor air[J]. Chemosphere,2004,57(8):781-787.
[10] Ma Y Q,Cui K Y,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,2013,786:47-53.
[11] Kim J W,Ramaswamy B R,Chang K H,et al. Multiresidue analytical method for the determination of antimicrobials,preservatives,benzotriazole UV stabilizers,flame retardants and plasticizers in fish using ultra high performance liquid chromatography coupled with tandem mass spectrometry[J].Journal of Chromatography A,2011,1218(22):3511-3520.
[12] Sundkvist A M,Olofsson U,Haglund P. Organophosphorus flame retardants and plasticizers in marine and fresh water biota and in human milk[J]. Journal of Environmental Monitoring,2010,12(4):943-951.
[13]高宇航,那广水,李瑞婧,等. C18膜萃取/液相色谱-质谱联用法测定极地水体中有机磷酸酯[J].分析测试学报,2017,36(12):1464-1468.Gao Y H,Na G S,Li R J. Determination of organophosphate esters in polar waters by liquid chromatography-mass spectrometry with C18 membrane disk extraction[J]. Journal of Instrumental Analysis,2017,36(12):1464-1468.
[14]程文瀚.有机磷酸酯在南大洋海洋边界层和东南极冰盖的分布及意义[D].合肥:中国科学技术大学,2013.Cheng W H. Distribution and significance of organophosphate esters in the boundary layer of the Southern Ocean and on the East Antarctic Ice Sheet[D]. Hefei:University of Science and Technology of China,2013.
[15] Dishaw L V,Powers C M,Ryde I T,et al. Is the PentaBDE 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.
[16]尹观,王小丹,高志友,等.贡嘎山海螺沟冰川径流水文规律的同位素示踪研究[J].冰川冻土,2008,30(3):365-372.Yin G,Wang X D,Gao Z Y,et al. Study of the hydrology of glacial runoff in Hailuogou Valley,Gongga Mountain by means of isotopic tracing[J]. Journal of Glaciology and Geocryology,2008,30(3):365-372.
[17]王萌,刘一超,梁琼,等.北京城市森林公园不同树种吸附大气颗粒物能力[J].北京农学院学报,2018,33(1):79-83.Wang M,Liu Y C,Liang Q,et al. Study on the atmospheric particulate matters adsorption capacity of different tree species in urban forest park of Beijing[J]. Journal of Beijing University of Agriculture,2018,33(1):79-83.
[18]杨博.城市典型植物叶片中PAHs的时空分布特征及迁移转化机理[D].上海:华东师范大学,2017.Yang B. The spatial-temporal distribution and transport process of polycyclic aromatic hydrocarbons in leaves of urban typical tree species[D]. Shanghai:East China Normal University,2017.
[19] Wild E,Dent J,Thomas G O,et al. Visualizing the air-to-leaf transfer and within-leaf movement and distribution of phenanthrene:further studies utilizing two-photon excitation microscopy[J]. Environmental Science&Technology,2006,40(3):907-916.
[20] Reemtsma T,Quintana J B,Rodil R,et al. Organophosphorus flame retardants and plasticizers in water and air I. Occurrence and fate[J]. Tr AC Trends in Analytical Chemistry,2008,27(9):727-737.
[21]秦宏兵,范苓,顾海东.固相萃取-气相色谱/质谱法测定水中6种有机磷酸酯类阻燃剂和增塑剂[J].分析科学学报,2014,30(2):259-262.Qin H B,Fan L,Gu H D. Determination of organophosphorus flame retardants and plasticizers in environmental water by solid phase extraction coupled with gas chromatography/mass spectrometry[J]. Journal of Analytical Science,2014,30(2):259-262.
[22] Wang X W,Liu J F,Yin Y G. Development of an ultra-highperformance liquid chromatography-tandem mass spectrometry method for high throughput determination of organophosphorus flame retardants in environmental water[J]. Journal of Chromatography A,2011,1218(38):6705-6711.
[23]印红玲,李世平,叶芝祥,等.成都市大气PM2. 5中有机磷阻燃剂的污染水平及来源[J].环境科学,2015,36(10):3566-3572.Yin H L,Li S P,Ye Z X,et al. Pollution level and sources of organic phosphorus esters in airborne PM2. 5in Chengdu City[J].Environmental Science,2015,36(10):3566-3572.
[24] Shi Y L,Gao L H,Li W H,et al. Occurrence,distribution and seasonal variation of organophosphate flame retardants and plasticizers in urban surface water in Beijing, China[J].Environmental Pollution,2016,209:1-10.
[25] Regnery J, Püttmann W. Seasonal fluctuations of organophosphate concentrations in precipitation and storm water runoff[J]. Chemosphere,2010,78(8):958-964.
[26] Lai S C,Xie Z Y,Song T L,et al. Occurrence and dry deposition of organophosphate esters in atmospheric particles over the northern South China Sea[J]. Chemosphere,2015,127:195-200.
[27] Li J,Xie Z Y,Mi W Y,et al. Organophosphate Esters in air,snow,and seawater in the North Atlantic and the Arctic[J].Environmental Science&Technology,2017,51(12):6887-6896.
[28] Cheng W H,Xie Z Q,Blais J M,et al. Organophosphorus esters in the oceans and possible relation with ocean gyres[J].Environmental Pollution,2013,180:159-164.
[29] Castro-Jimenez J, Berrojalbiz N, Pizarro M, et al.Organophosphate ester(OPE)flame retardants and plasticizers in the Open Mediterranean and Black Seas Atmosphere[J].Environmental Science&Technology,2014,48(6):3203-3209.
[30] Li J,Tang J H,Mi W Y,et al. Spatial distribution and seasonal variation of organophosphate esters in air above the Bohai and Yellow Seas,China[J]. Environmental Science&Technology,2018,52(1):89-97.
[31]吴迪,印红玲,李世平,等.成都市锦江表层水和沉积物中有机磷酸酯的污染特征[J].环境科学,2019,40(3):1245-1251.Wu D,Yin H L,Li S P,et al. Pollution characteristics of OPEs in the surface water and sediment of the Jinjiang River in Chengdu city[J]. Environmental Science,2019,40(3):1245-1251.