杭州市地表水有机农药的污染现状及风险
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摘要
本文在评述国内外地表水有机农药污染现状、农药的多介质环境化学行为、健康风险的基础上，研究了杭州市地表水有机农药的污染现状及健康风险；基本搞清了杭州市饮用水原水、西湖、运河等地表水有机氯和有机磷农药的污染现状，探索了常规给水处理工艺对微量有机污染物的去除效果，初步评价了有机农药的健康风险，提出了地表水有机农药污染的防治措施和安全饮用水的保障技术。
研究表明，杭州市钱塘江、东苕溪、西湖、运河等地表水普遍存在有机农药的污染，其中DDT、六六六的总浓度分别为0～0.270μg／L、0～0.00625μg／L，DDT基本以代谢产物DDE的形式存在；检出的有机磷农药较多，其中以对硫磷为主，浓度为0～0.445μg／L。钱塘江和东苕溪有机氯农药含量在丰水期较枯水期高，而有机磷农药含量在枯水期较高；运河水有机农药含量在枯水期较高。常规给水处理工艺不能有效去除痕量有机农药等污染物。当前地表水有机农药污染的风险主要由有机磷农药所致。
Advances in research on pollution of organo-pesticides (OPs) in surface water, their environmental behaviors and health risks are reviewed. Pollution survey and risk assessements of organo-chlorine pesticides (OCPs) and organo-phosphorus pesticides (OPPs) in surface water of Hangzhou are conducted. It was indicated that the contamination of the OCPs exists in surface water although they had been banned for decades. Total concentrations of dichloro-diphenyl-trichloroethane (DDT) and hexachloride-benzene (BHC) in surface water were observed to be 0~0.270ug/L and 0~0.00625ug/L, respectively. DDE, as a metabolite of DDT and many species of OPPs were determined in some samples of surface water. Parathion, the main pollutant of OPPs in surface water of Hangzhou, was observed to be 0-0.445 ug/L. In the drinking water resources of Hangzhou (Qiantang Liver and East Tiao Stream), concentrations of OCPs are higher during plentiful water time while OPPs are higher during low water time. In Yun Liver, however, OCPS and O
PPs are both higher during low water time than those during plentiful time. It was also observed that microamount of organic pollutants such as OCPs and OPPs in drinking water can not be removed efficiently by traditional treatment technologies. Therefore, it is vital and necessary to develop deep treatment technologies for the drinking water.
研究表明，杭州市钱塘江、东苕溪、西湖、运河等地表水普遍存在有机农药的污染，其中DDT、六六六的总浓度分别为0～0.270μg／L、0～0.00625μg／L，DDT基本以代谢产物DDE的形式存在；检出的有机磷农药较多，其中以对硫磷为主，浓度为0～0.445μg／L。钱塘江和东苕溪有机氯农药含量在丰水期较枯水期高，而有机磷农药含量在枯水期较高；运河水有机农药含量在枯水期较高。常规给水处理工艺不能有效去除痕量有机农药等污染物。当前地表水有机农药污染的风险主要由有机磷农药所致。
Advances in research on pollution of organo-pesticides (OPs) in surface water, their environmental behaviors and health risks are reviewed. Pollution survey and risk assessements of organo-chlorine pesticides (OCPs) and organo-phosphorus pesticides (OPPs) in surface water of Hangzhou are conducted. It was indicated that the contamination of the OCPs exists in surface water although they had been banned for decades. Total concentrations of dichloro-diphenyl-trichloroethane (DDT) and hexachloride-benzene (BHC) in surface water were observed to be 0~0.270ug/L and 0~0.00625ug/L, respectively. DDE, as a metabolite of DDT and many species of OPPs were determined in some samples of surface water. Parathion, the main pollutant of OPPs in surface water of Hangzhou, was observed to be 0-0.445 ug/L. In the drinking water resources of Hangzhou (Qiantang Liver and East Tiao Stream), concentrations of OCPs are higher during plentiful water time while OPPs are higher during low water time. In Yun Liver, however, OCPS and O
PPs are both higher during low water time than those during plentiful time. It was also observed that microamount of organic pollutants such as OCPs and OPPs in drinking water can not be removed efficiently by traditional treatment technologies. Therefore, it is vital and necessary to develop deep treatment technologies for the drinking water.
引文
[1] 贺红武，刘钊杰．有机磷农药的发展趋势与低毒有机磷杀虫剂的开发与利用(上)，世界农药，2001，23(3)：1-5
[2] 贺红武，刘钊杰．有机磷农药的发展趋势与低毒有机磷杀虫剂的开发与利用(下)，世界农药，2001，23(4)：26-49
[3] 王占生，刘文君．微污染水源饮用水处理，北京：中国建筑工业出版社，1999
[4] El-Kabbany S., Rashed M.M., Zayed M.A.. Monitoring of the pesticide levels in some water supplies and agricultural land, in El-Haram, Giza, J. Hazardous Materials A, 1999,72:11-21
[5] Hu J.Y., Aizawa T., Asami M.and Magara Y.. Analysis of thermolable and polar pesticides in environmental water with capillary chromatography-frit fast atom bombardment mass spectrometry, Wat.Sci. Tech, 1998,38(7): 169-177
[6] Ollers S., Singer H. P., Fassler P., Muller S. R.. Simultaneous quantification of neutral acidic pharmaceuticals and peticides at the low-ng/1 level in surface and waste water, J. Chromatography A, 2001,911:225-234
[7] Sun C., Dong Y., Xu S., Yao S., Dai J., Han S., Wang L.. Trace analysis of dissolved poly chlorinate organic compounds in the water of the Yangtse River (Nanjing China), Environmental Pollution,2002,117:9-14
[8] 张祖麟，洪华生等．厦门港表层水体中有机氯农药和多氯联苯的研究，海洋环境科学，2000，19(3)：48-51
[9] 张祖麟，陈伟琪等．九龙江口水体中有机氯农药分布特征及归宿，环境科学，2001，22(3)：88-92
[10] 徐伟．高效液相色谱法测定环境水体中8种农药残留量，环境与健康杂志，2000，17(6)：362-363
[11] 齐文启，阿里木·阿不拉都，王晓慧，孙宗光．二恶英等环境激素类污染物的来源调查，中国环境监测，2002，18(4)：15-19
[12] 宋宏宇，王捷．环境内分泌干扰物与农药，农药科学与管理，2001，22(2)：23-25
[13] 胡青燕编译．有机磷杀虫剂的安全性究竟如何，农药译丛，1999，21(3)：44-46
[14] 华小梅，江希流．我国农药环境优先控制品种的筛选，环境保护，2001，6：35-39
[15] Tomkins B. A., Barnard A. R.. Determination of organochlorine pesticides in ground water using solid-phase microextraction followed by dual-column gas chromatographywith electron-capture detection, J. Chromatography A, 2002,964:21-23
[16] 中国城市供水水质监测网水质检测实施细则，北京，1993，p109-113
[17] 中华人民共和国城镇建设行业标准,CJ／T 141～150—2001：18-21
[18] Mahara B. M., Borossay J., Torkos K.. Liquid-liquid extaction for sample prior to gas chromatograph and chromatography-and chromatography-mass spectrometry determination of herbicide and pesticide compounds, Microchemical journal, 1998, 58:31-38
[19] 张全争，谢建荣．水中低残留有机物萃取过程的盐析作用及色谱分析，环境化学，2001，20(3)：286-289
[20] 康跃惠，张于，盛国英，傅家谟．固相萃取法测定水源水中的有机磷农药，中国环境科学，2000，20(1)：1-4
[21] Colume A., Cardenas S., Gallego M., Valcarcel M.. Evaluation of an automated solid-phase extraction system for the enrichment of organochlorine pesticides from waters, Talanta,2001,54:943-951
[22] Quayle W.C., Jepson I., Fowlis I. A.. Simultaneous quantitationof sixteen organochlorine pesticides in drinking waters using automated solid-phase extraction, high-volume ingection, high-resolution gas chromatography, J. Chromatography A, 1997,773:271-276
[23] Perez-Trujillo J.P., Frias S., Conde J.E., Rodriguez-Delgado M.A.. Comparison of different coatings in solid-phase microextrction for the determination of organochlorine pesticides in ground water, J. Chromatography A,2002,963:95-105
[24] Sampledro M.C., Martin O., Armentia C.L., Goicolea M.A., Rodriguez E., Balugera Z.G., CostaMoreira J., Barrio R.J.. Solid phase microextaction for the determination of systemic and nonvolatile pesticides in river water using gas chromatography with nitrogen-phosphorous nand electron-capture detection,J. Chromatography A,2000,893:347-358
[25] Beltran J., Lopez F.J., Cepria O., Hernandenz F.. Solid-phase microextraction for puantitative analysis of organophosphorus pesticides in environmental water samples, J. Chromatography A, 1998,808:257-263
[26] Su P.G., Huang S,D.. Determination of organophosphorus pesticides in water by solid-phase microextraction, Talanta,1999,49:393-402
[27] Hwang B.H., Lee M.R.. Solid-phase microextraction for organochlorine pesticide resides analysis in Chinese herbal formulations, J. Chromatography A, 2000, 898:245-256
[28] Nerin C., Batlle R., Cacho J.. Determination of pesticides in high-water-content samples by offline supercritical fluid extraction-gase chromatography-electron-capture detection, J. Chromatography A, 1998,795:117-124
[29] Sabik H., Jeannot R.. Determination of organonitrongen pesticides in large volumes of surface water by liquid-liquid and solid-phase extraction using gas chromatography with nitrogenphosphorus detection and liquid chromatography with atomospheric pressure chemical ionization mass spectrometery, J. Chromatography A, 1998, 818:197-207
[30] Lopez F.J., Beltran J., Forcada M., Hernandez F.. Comparison of simplified methods for pesticide residue analysis use of large-volume injection in capillary gas chlomatograph, J.
Chromatography A, 1998, 823:25-23
[31] Jover E., Bayona J.M., Trace level determination of organochlorine organophosphorus and pyrethroid pesticides in lanolin using gel permeation chromatography followed by dual gas chromatography ang gas chromatography-negative chemical ionization mass spectrometric confirmation, J. Chromatography A, 2002,950:213-220
[32] 朱利中，松下秀鹤．空气中多环芳烃的研究现状，环境科学进展，1997，5(1)：18-19
[33] Lopez F.J., Pitarch E., Egea S., Beltran J., Hernandez F.. Gas chromatographic determination of organochlorine and organophosphorus pestecides in human fluids using solid phase microextraction, Analytica Chimica Acta,2001, 433 :217-226
[34] Veningerova M., Prachar V., Kovacicova J., Uhnak J.. Analytical method for the determination of organochlorine compounds application to environmental samples in the Slovak Republic, J. Chromatography A, 1997,774:333-347
[35] Franko M.. Recent applications of thermal lens spectrometry in food analysis and envioronmental research, Talanta, 2001,54:1-13
[36] Colume A., Cardenas S., Gallego M., Valcarcel M.. Semiautomatic method for the screening and determination of 23 organochlorine pesticides in horticultural samples by gas chlomatograph with electon-capture detection, J. Chromatography A, 1999,849:235-243
[37] 中国生活饮用水卫生标准GB3838-2002
[38] 中国生活饮用水卫生规范，卫生部，2001．6，1-10
[39] EPA. Supplement Risk Assessment Part 1.Guidance For Public health Risk Assessment.1989,EPA/601/5-89-001
[40] EPA. Superfund Public Health Evaluation Manual. 1996, EPA/504/1-86-060
[41] 曾光明等．水环境健康风险评价模型，水科学进展，1998，9(3)：212-216
[42] EPA. Development and use of risk-based consumotion limits. Table3-1, P3-3,3-4
[43] 潘科，黄炳球．昆虫对有机磷类抗性机制研究进展，世界农药，2001，23(2)：49-50
[44] 赖以飞编译．农药允许残留极限与发展中国家。世界农药，2002，22(6)：45-49
[45] 荆海强．美国对食品中农药残留的监管，世界农药，2000，22(6)：50-12
[46] 蒋木庚，杨春龙等．手性有机磷农药的研究与展望，世界农药，2000，22(2)：16-21
[47] 王忠和．地下水污染与环境健康，城市环境与城市健康，1998，11(23)：19～22
[48] 朱光爽，朱光译．臭氧技术及应用手册，北京：中国建筑工业出版社，1991，216-217
[2] 贺红武，刘钊杰．有机磷农药的发展趋势与低毒有机磷杀虫剂的开发与利用(下)，世界农药，2001，23(4)：26-49
[3] 王占生，刘文君．微污染水源饮用水处理，北京：中国建筑工业出版社，1999
[4] El-Kabbany S., Rashed M.M., Zayed M.A.. Monitoring of the pesticide levels in some water supplies and agricultural land, in El-Haram, Giza, J. Hazardous Materials A, 1999,72:11-21
[5] Hu J.Y., Aizawa T., Asami M.and Magara Y.. Analysis of thermolable and polar pesticides in environmental water with capillary chromatography-frit fast atom bombardment mass spectrometry, Wat.Sci. Tech, 1998,38(7): 169-177
[6] Ollers S., Singer H. P., Fassler P., Muller S. R.. Simultaneous quantification of neutral acidic pharmaceuticals and peticides at the low-ng/1 level in surface and waste water, J. Chromatography A, 2001,911:225-234
[7] Sun C., Dong Y., Xu S., Yao S., Dai J., Han S., Wang L.. Trace analysis of dissolved poly chlorinate organic compounds in the water of the Yangtse River (Nanjing China), Environmental Pollution,2002,117:9-14
[8] 张祖麟，洪华生等．厦门港表层水体中有机氯农药和多氯联苯的研究，海洋环境科学，2000，19(3)：48-51
[9] 张祖麟，陈伟琪等．九龙江口水体中有机氯农药分布特征及归宿，环境科学，2001，22(3)：88-92
[10] 徐伟．高效液相色谱法测定环境水体中8种农药残留量，环境与健康杂志，2000，17(6)：362-363
[11] 齐文启，阿里木·阿不拉都，王晓慧，孙宗光．二恶英等环境激素类污染物的来源调查，中国环境监测，2002，18(4)：15-19
[12] 宋宏宇，王捷．环境内分泌干扰物与农药，农药科学与管理，2001，22(2)：23-25
[13] 胡青燕编译．有机磷杀虫剂的安全性究竟如何，农药译丛，1999，21(3)：44-46
[14] 华小梅，江希流．我国农药环境优先控制品种的筛选，环境保护，2001，6：35-39
[15] Tomkins B. A., Barnard A. R.. Determination of organochlorine pesticides in ground water using solid-phase microextraction followed by dual-column gas chromatographywith electron-capture detection, J. Chromatography A, 2002,964:21-23
[16] 中国城市供水水质监测网水质检测实施细则，北京，1993，p109-113
[17] 中华人民共和国城镇建设行业标准,CJ／T 141～150—2001：18-21
[18] Mahara B. M., Borossay J., Torkos K.. Liquid-liquid extaction for sample prior to gas chromatograph and chromatography-and chromatography-mass spectrometry determination of herbicide and pesticide compounds, Microchemical journal, 1998, 58:31-38
[19] 张全争，谢建荣．水中低残留有机物萃取过程的盐析作用及色谱分析，环境化学，2001，20(3)：286-289
[20] 康跃惠，张于，盛国英，傅家谟．固相萃取法测定水源水中的有机磷农药，中国环境科学，2000，20(1)：1-4
[21] Colume A., Cardenas S., Gallego M., Valcarcel M.. Evaluation of an automated solid-phase extraction system for the enrichment of organochlorine pesticides from waters, Talanta,2001,54:943-951
[22] Quayle W.C., Jepson I., Fowlis I. A.. Simultaneous quantitationof sixteen organochlorine pesticides in drinking waters using automated solid-phase extraction, high-volume ingection, high-resolution gas chromatography, J. Chromatography A, 1997,773:271-276
[23] Perez-Trujillo J.P., Frias S., Conde J.E., Rodriguez-Delgado M.A.. Comparison of different coatings in solid-phase microextrction for the determination of organochlorine pesticides in ground water, J. Chromatography A,2002,963:95-105
[24] Sampledro M.C., Martin O., Armentia C.L., Goicolea M.A., Rodriguez E., Balugera Z.G., CostaMoreira J., Barrio R.J.. Solid phase microextaction for the determination of systemic and nonvolatile pesticides in river water using gas chromatography with nitrogen-phosphorous nand electron-capture detection,J. Chromatography A,2000,893:347-358
[25] Beltran J., Lopez F.J., Cepria O., Hernandenz F.. Solid-phase microextraction for puantitative analysis of organophosphorus pesticides in environmental water samples, J. Chromatography A, 1998,808:257-263
[26] Su P.G., Huang S,D.. Determination of organophosphorus pesticides in water by solid-phase microextraction, Talanta,1999,49:393-402
[27] Hwang B.H., Lee M.R.. Solid-phase microextraction for organochlorine pesticide resides analysis in Chinese herbal formulations, J. Chromatography A, 2000, 898:245-256
[28] Nerin C., Batlle R., Cacho J.. Determination of pesticides in high-water-content samples by offline supercritical fluid extraction-gase chromatography-electron-capture detection, J. Chromatography A, 1998,795:117-124
[29] Sabik H., Jeannot R.. Determination of organonitrongen pesticides in large volumes of surface water by liquid-liquid and solid-phase extraction using gas chromatography with nitrogenphosphorus detection and liquid chromatography with atomospheric pressure chemical ionization mass spectrometery, J. Chromatography A, 1998, 818:197-207
[30] Lopez F.J., Beltran J., Forcada M., Hernandez F.. Comparison of simplified methods for pesticide residue analysis use of large-volume injection in capillary gas chlomatograph, J.
Chromatography A, 1998, 823:25-23
[31] Jover E., Bayona J.M., Trace level determination of organochlorine organophosphorus and pyrethroid pesticides in lanolin using gel permeation chromatography followed by dual gas chromatography ang gas chromatography-negative chemical ionization mass spectrometric confirmation, J. Chromatography A, 2002,950:213-220
[32] 朱利中，松下秀鹤．空气中多环芳烃的研究现状，环境科学进展，1997，5(1)：18-19
[33] Lopez F.J., Pitarch E., Egea S., Beltran J., Hernandez F.. Gas chromatographic determination of organochlorine and organophosphorus pestecides in human fluids using solid phase microextraction, Analytica Chimica Acta,2001, 433 :217-226
[34] Veningerova M., Prachar V., Kovacicova J., Uhnak J.. Analytical method for the determination of organochlorine compounds application to environmental samples in the Slovak Republic, J. Chromatography A, 1997,774:333-347
[35] Franko M.. Recent applications of thermal lens spectrometry in food analysis and envioronmental research, Talanta, 2001,54:1-13
[36] Colume A., Cardenas S., Gallego M., Valcarcel M.. Semiautomatic method for the screening and determination of 23 organochlorine pesticides in horticultural samples by gas chlomatograph with electon-capture detection, J. Chromatography A, 1999,849:235-243
[37] 中国生活饮用水卫生标准GB3838-2002
[38] 中国生活饮用水卫生规范，卫生部，2001．6，1-10
[39] EPA. Supplement Risk Assessment Part 1.Guidance For Public health Risk Assessment.1989,EPA/601/5-89-001
[40] EPA. Superfund Public Health Evaluation Manual. 1996, EPA/504/1-86-060
[41] 曾光明等．水环境健康风险评价模型，水科学进展，1998，9(3)：212-216
[42] EPA. Development and use of risk-based consumotion limits. Table3-1, P3-3,3-4
[43] 潘科，黄炳球．昆虫对有机磷类抗性机制研究进展，世界农药，2001，23(2)：49-50
[44] 赖以飞编译．农药允许残留极限与发展中国家。世界农药，2002，22(6)：45-49
[45] 荆海强．美国对食品中农药残留的监管，世界农药，2000，22(6)：50-12
[46] 蒋木庚，杨春龙等．手性有机磷农药的研究与展望，世界农药，2000，22(2)：16-21
[47] 王忠和．地下水污染与环境健康，城市环境与城市健康，1998，11(23)：19～22
[48] 朱光爽，朱光译．臭氧技术及应用手册，北京：中国建筑工业出版社，1991，216-217