珠江三角洲含N-亚硝胺地下水与地区性癌症
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摘要
肆虐我国南方局部区数百年以鼻咽癌和肝癌为主的恶性肿瘤病,为典型的地区性癌症。本文以珠江三角洲为例,应用流行病学与生态地球化学相结合的调查方法,检出了病区环境水和饮水中存在致癌物质N-亚硝胺,研究了癌病区生态系统由地质构造背景、气候、水文和生态条件制约,自然形成水体N-亚硝胺的机理。实验改进、优化了环境-饮水微量亚硝胺测定方法,新建立的固相萃取-气相色谱-串联质谱(GC/El-MS/MS)测定纳克级N-亚硝胺方法一次可测9种N-亚硝胺化合物,检出限达到0.34～2.19ng/L。在珠江三角洲癌病区环境-饮水中首次发现9种亚硝胺化合物,含量为307～0.34ng/L,总检出率为40%。四会等较低工业污染区古井水、手压井水和自来水的亚硝胺有相近似的含量统计特点:亚硝基二甲胺和亚硝基二正丁胺的均值和峰值为不高的超标值,均值分别为21.77和15.54ng/L。这批水样大多采自0～20m深度井水,属本区代表性特殊地质构造和气候生态环境中形成的地下水,也是研究区生产和生活开发最多的水源层;所含超标亚硝胺可能是本区数百年高发癌症的主因。近年工业发展带来的亚硝胺污染源的叠加,增高了该区环境-饮水亚硝胺超标率及癌症发病率。文中分析了珠江三角洲土壤和地下水富氮营养化现象和区域氮的来源。
Localized/regional nasopharyngeal and hepatocellular carcinoma in South China are the typical cancer types by regional malignant tumor,ravaging public health in the area for hundreds of years.In this paper,taking the centuries old regional carcinoma epidemic in the Pearl River Delta as an example,applying epidemiology and ecogeochemical methodology,we determined that both environmental and drinking waters contained N-nitrosamine,a known carcinogen.We investigated the formation mechanism of N-nitrosamines compounds in natural waters under the constraints of regional geological,climate,hydrologic and ecological conditions. We developed a solid-phase extraction method(SPE) adaptable to gas chromatography-mass spectrometric(GC-MS)analysis to detect nine trace N-nitrosamine compounds in environmental and drinking waters.The detection limit ranged from 0.34 to 2.19 ng/L.In two representative cancer high-risk areas,Shunde and Sihui,we performed for the first time quantitive analysis of nine trace Nnitrosamines in different water occurrences.The results showed that the N-nitrosamine concentrations in local waters ranged from 0.34 to 307 ng/L.And the detection rate of 40% was much higher than the 15%rate set by healthy drinking water standard for N-nitrosamines at 10 ng/L.The testing results indicated NDMA and NDBA were the main pollutants,while other nitrosamines were detected at lower concentrations.In the less industrialized Sihui area,nitrosamine concentrations share the same statistical characteristics for different water occurrences such as well,tap,underground and spring waters:the average and peak values of NDMA and NDBA barely exceeded the standards at 21.77 and 15.54 ng/L,respectively,higher than other nitrosamines.This was a typical nitrosamine composition profile for the natural regional underground water.The water samples were taken from wells at 0-20 mdepths.The underground water is ammonium-rich and contains nitrosamines formed under unique regional ecogeological and climate conditions,and it may be the original culprit of the regional carcinoma.Among the five endemic regions studied,the industrialized Shunde area has highest nitrosamine content,with nitrosamine concentration correlating positively with hepatocellular carcinoma morbidity.Our study confirmed that cumulative effect of industrial pollution can increase cancer morbidity.
Localized/regional nasopharyngeal and hepatocellular carcinoma in South China are the typical cancer types by regional malignant tumor,ravaging public health in the area for hundreds of years.In this paper,taking the centuries old regional carcinoma epidemic in the Pearl River Delta as an example,applying epidemiology and ecogeochemical methodology,we determined that both environmental and drinking waters contained N-nitrosamine,a known carcinogen.We investigated the formation mechanism of N-nitrosamines compounds in natural waters under the constraints of regional geological,climate,hydrologic and ecological conditions. We developed a solid-phase extraction method(SPE) adaptable to gas chromatography-mass spectrometric(GC-MS)analysis to detect nine trace N-nitrosamine compounds in environmental and drinking waters.The detection limit ranged from 0.34 to 2.19 ng/L.In two representative cancer high-risk areas,Shunde and Sihui,we performed for the first time quantitive analysis of nine trace Nnitrosamines in different water occurrences.The results showed that the N-nitrosamine concentrations in local waters ranged from 0.34 to 307 ng/L.And the detection rate of 40% was much higher than the 15%rate set by healthy drinking water standard for N-nitrosamines at 10 ng/L.The testing results indicated NDMA and NDBA were the main pollutants,while other nitrosamines were detected at lower concentrations.In the less industrialized Sihui area,nitrosamine concentrations share the same statistical characteristics for different water occurrences such as well,tap,underground and spring waters:the average and peak values of NDMA and NDBA barely exceeded the standards at 21.77 and 15.54 ng/L,respectively,higher than other nitrosamines.This was a typical nitrosamine composition profile for the natural regional underground water.The water samples were taken from wells at 0-20 mdepths.The underground water is ammonium-rich and contains nitrosamines formed under unique regional ecogeological and climate conditions,and it may be the original culprit of the regional carcinoma.Among the five endemic regions studied,the industrialized Shunde area has highest nitrosamine content,with nitrosamine concentration correlating positively with hepatocellular carcinoma morbidity.Our study confirmed that cumulative effect of industrial pollution can increase cancer morbidity.
引文
[1]郝捷,陈万青.中国肿瘤登记年报(2012)[M].北京:军事医学科学出版社,2012:96-126.
[2]国家癌症中心.中国肿瘤登记工作报告2014[R].北京:卫生计生委疾病预防控制局,2015:11-26.
[3]曾水泉,罗毓珍,廖洪涛.珠江三角洲基塘生态系统物质循环与原发性肝癌[M].北京:中国环境科学出版社,1991:74-93.
[4]赫捷,陈万青.2015中国肿瘤登31记年报[M].北京:清华大学出版社,2017:200-236.
[5]SCHREIBER I M,MITCH W A.Nitrosamine formation pathway revisited:the importance of chloramine speciation and dissolved oxygen[J].Environmental Science&Technology,2006,40(19):6007-6014.
[6]CHARROIS J W A,BOYD J M,FROESE K L,et al.Occurrence of N-nitrosamines in Alberta public drinking-water distribution systems[J].Journal of Environmental Engineering and Science,2007,6(1):103-114.
[7]汤洁,林年丰.扶绥肝癌高发与饮水有机污染关系的研究[J].环境与健康杂志,1995,12(5):193-195.
[8]刘晓琳,韦霄,屈卫东.饮用水中亚硝胺类消毒副产物的识别、遗传毒性和致癌性研究进展[J].卫生研究,2012,41(1):163-168.
[9]奚小环.生态地球化学:从调查实践到应用理论的系统工程[J].地学前缘,2008,15(5):1-8.
[10]李家熙,吴功健,黄怀曾,等.区域地球化学与农业和健康[M].北京:人民卫生出版社,2000:87-217.
[11]郑宝山,肖唐付,李社红,等.医学地质学:自然环境对公共健康的影响[M].北京:科学出版社,2009:17-365.
[12]LIU X L,CEN K,ZHAO L S,et al.N-nitrodimethlyamine in natural and drinking water of high cancer incidence regions of Guangdong,China[J].Applied Geochemistry,2016,74:157-164.
[13]黄腾波,闵华庆.鼻咽癌20年发病与死亡动态[M].广州:广东科技出版社,1998:6-12.
[14]张振农,李景廉,凌启南,等.广东省四会县操广州和客家方言人群鼻咽癌发病情况分析[J].癌症,1987(2):135-136.
[15]邓熙,林秋奇,顾继光.广州市饮用水源中硝酸盐亚硝酸盐含量与癌症死亡率联系[J].生态科学,2004,23(1):38-41.
[16]林杰藩,赖启宏.广东省顺德肝癌多发区病因探讨[J].物探与化探,2004,28(3):268-272.
[17]徐致祥,谭家驹,陈凤兰,等.农家肥料污染水源诱发鸡咽食管癌胃癌和肝癌[J].中华肿瘤杂志,2003,25(4):344-347.
[18]徐致祥,谭家驹,韩建英,等.“食管癌、胃癌、肝癌氮循环”病因假说的检验进展[J].前沿科学,2008(3):61-74.
[19]窦磊,周永章,李勇,等.珠江三角洲典型肝癌高发区土壤锰形态及其生态效应[J].应用生态学报,2008,19(6):1362-1368.
[20]马瑾,周永章,窦磊,等.广东省若干典型地方病环境地球化学病因分析[J].生态环境,2007.16(4):1318-1323.
[21]刘子宁,朱鑫,窦磊,等.珠江三角洲典型肝癌发病区土壤重金属富集特征分析及生态风险测度[J].土壤通报,2011:471-476.
[22]黄启洪,凌启南,李艳华,等.四会市恶性肿瘤发病动态分析[J].中国肿瘤,2005,14(4):241-243.
[23]韦忠亮,梁任祥,汪凯波,等.扶绥县1974-2003年肝癌发病率变化趋势分析[J].中国肿瘤,2007,16(9):679-680.
[24]林年丰.医学环境地球化学[M].长春:吉林科学技术出版社,1991:242-256.
[25]梅全喜.鼻咽癌的最新研究与对策[M].北京:中国中医药出版社,2010:13-26.
[26]苏德龙.饮水与肝癌[J].中华预防医学杂志,1980,14(2):65-73.
[27]WOLFF I A,WASSERMAN A E.Nitrates,nitrites,and nitrosamines[J].Science,1972,177(4043):15-19.
[28]BROWN J L.N-nitrosamines[J].Occupational Medicine(Philadelphia,Pa.),1999,14(4):839-848.
[29]涂文升,刘宗河,黎远冬,等.广西某肝癌高发区食物及饮用水中二甲基亚硝胺的调查[J].广西医学,1995,17(2):174-175.
[30]孟瑞琳,许燕君,林立丰,等.广东省2012年恶性肿瘤发病与死亡[J].中国肿瘤,2016,25(12):933-941.
[31]JOBB D B,HUNSINGER R B,MERESZ O,et al.A study of the occurrence and inhibition of formation of N-nitrosodimethylamine(NDMA)in the Ohsweken water supply[C]∥Proceedings of the fifth national conference on drinking water.Winnipeg,Manitoba,Canada.Denver,Colorado:American Water Works Association,1993:241-252.
[32]MITCH W A,SHARP J O,TRUSSELL R R,et al.N-nitrosodimethylamine(NDMA)as a drinking water contaminant:a review[J].Environmental Engineering Science,2003,20(5):389-404.
[33]RIPOLLES C,PITARCH E,SANCHO J V,et al.Determination of eight nitrosamines in water at the ng/L levels by liquid chromatography coupled to atmospheric pressure chemical ionization tandem mass spectrometry[J].Analytica Chimica Acta,2011,702(1):62-71.
[34]JURADO-SANCHEZ B,BALLESTEROS E,GALLEGOM.Screening of N:nitrosamines in tap and swimming pool waters using fast gas chromatography[J].Journal of Separation Science,2010,33(4/5):610-616.
[35]GREBEL J E,YOUNG C C,SUFFET I H M.Solid-phase microextraction of N-nitrosamines[J].Journal of Chromatography A,2006,1117(1):11-18.
[36]KRAUSS M,HOLLENDER J.Analysis of nitrosamines in wastewater:exploring the trace level quantification capabilities of a hybrid linear ion trap/orbitrap mass spectrometer[J].Analytical Chemistry,2008,80(3):834-842.
[37]TOPUZ E,AYDIN E,PEHLIVANOGLU-MANTAS E.Apractical LC-MS/MS method for the detection of NDMA at nanogram per liter concentrations in multiple water matrices[J].Water,Air,&Soil Pollution,2012,223(9):5793-5802.
[38]陈文文,张原,李小水,等.水中N-亚硝胺的富集及色谱分析测试技术[J].环境化学,2016,35(10):2117-2126.
[39]周树伟,李鸿龙.促进广东先进制造业发展的思考:以广东省佛山市顺德区为例[J].发展改革理论与实践,2018(1):55-59.
[40]国土资源部中国地质调查局.中华人民共和国多目标区域地球化学图集:广东省珠江三角洲经济区[CM].北京:地质出版社,2011:52-53.
[41]广东省地质调查院水工环组.珠江三角洲地区地下水污染调查评价[R].广州:广东省地质调查院,2008:76-154.
[42]ПЕРЕЛЬМАНАИ,КАСИМОВИС.Геохимияландшафта[M].Moсква:ИздательствоЦентра“Интеграция”,1999:64-70.
[43]丁平,沈承德,王宁,等.广东四会古森林地下生态系统碳同位素组成及其古气候意义[J].中国科学:D辑,2009(1):70-78.
[2]国家癌症中心.中国肿瘤登记工作报告2014[R].北京:卫生计生委疾病预防控制局,2015:11-26.
[3]曾水泉,罗毓珍,廖洪涛.珠江三角洲基塘生态系统物质循环与原发性肝癌[M].北京:中国环境科学出版社,1991:74-93.
[4]赫捷,陈万青.2015中国肿瘤登31记年报[M].北京:清华大学出版社,2017:200-236.
[5]SCHREIBER I M,MITCH W A.Nitrosamine formation pathway revisited:the importance of chloramine speciation and dissolved oxygen[J].Environmental Science&Technology,2006,40(19):6007-6014.
[6]CHARROIS J W A,BOYD J M,FROESE K L,et al.Occurrence of N-nitrosamines in Alberta public drinking-water distribution systems[J].Journal of Environmental Engineering and Science,2007,6(1):103-114.
[7]汤洁,林年丰.扶绥肝癌高发与饮水有机污染关系的研究[J].环境与健康杂志,1995,12(5):193-195.
[8]刘晓琳,韦霄,屈卫东.饮用水中亚硝胺类消毒副产物的识别、遗传毒性和致癌性研究进展[J].卫生研究,2012,41(1):163-168.
[9]奚小环.生态地球化学:从调查实践到应用理论的系统工程[J].地学前缘,2008,15(5):1-8.
[10]李家熙,吴功健,黄怀曾,等.区域地球化学与农业和健康[M].北京:人民卫生出版社,2000:87-217.
[11]郑宝山,肖唐付,李社红,等.医学地质学:自然环境对公共健康的影响[M].北京:科学出版社,2009:17-365.
[12]LIU X L,CEN K,ZHAO L S,et al.N-nitrodimethlyamine in natural and drinking water of high cancer incidence regions of Guangdong,China[J].Applied Geochemistry,2016,74:157-164.
[13]黄腾波,闵华庆.鼻咽癌20年发病与死亡动态[M].广州:广东科技出版社,1998:6-12.
[14]张振农,李景廉,凌启南,等.广东省四会县操广州和客家方言人群鼻咽癌发病情况分析[J].癌症,1987(2):135-136.
[15]邓熙,林秋奇,顾继光.广州市饮用水源中硝酸盐亚硝酸盐含量与癌症死亡率联系[J].生态科学,2004,23(1):38-41.
[16]林杰藩,赖启宏.广东省顺德肝癌多发区病因探讨[J].物探与化探,2004,28(3):268-272.
[17]徐致祥,谭家驹,陈凤兰,等.农家肥料污染水源诱发鸡咽食管癌胃癌和肝癌[J].中华肿瘤杂志,2003,25(4):344-347.
[18]徐致祥,谭家驹,韩建英,等.“食管癌、胃癌、肝癌氮循环”病因假说的检验进展[J].前沿科学,2008(3):61-74.
[19]窦磊,周永章,李勇,等.珠江三角洲典型肝癌高发区土壤锰形态及其生态效应[J].应用生态学报,2008,19(6):1362-1368.
[20]马瑾,周永章,窦磊,等.广东省若干典型地方病环境地球化学病因分析[J].生态环境,2007.16(4):1318-1323.
[21]刘子宁,朱鑫,窦磊,等.珠江三角洲典型肝癌发病区土壤重金属富集特征分析及生态风险测度[J].土壤通报,2011:471-476.
[22]黄启洪,凌启南,李艳华,等.四会市恶性肿瘤发病动态分析[J].中国肿瘤,2005,14(4):241-243.
[23]韦忠亮,梁任祥,汪凯波,等.扶绥县1974-2003年肝癌发病率变化趋势分析[J].中国肿瘤,2007,16(9):679-680.
[24]林年丰.医学环境地球化学[M].长春:吉林科学技术出版社,1991:242-256.
[25]梅全喜.鼻咽癌的最新研究与对策[M].北京:中国中医药出版社,2010:13-26.
[26]苏德龙.饮水与肝癌[J].中华预防医学杂志,1980,14(2):65-73.
[27]WOLFF I A,WASSERMAN A E.Nitrates,nitrites,and nitrosamines[J].Science,1972,177(4043):15-19.
[28]BROWN J L.N-nitrosamines[J].Occupational Medicine(Philadelphia,Pa.),1999,14(4):839-848.
[29]涂文升,刘宗河,黎远冬,等.广西某肝癌高发区食物及饮用水中二甲基亚硝胺的调查[J].广西医学,1995,17(2):174-175.
[30]孟瑞琳,许燕君,林立丰,等.广东省2012年恶性肿瘤发病与死亡[J].中国肿瘤,2016,25(12):933-941.
[31]JOBB D B,HUNSINGER R B,MERESZ O,et al.A study of the occurrence and inhibition of formation of N-nitrosodimethylamine(NDMA)in the Ohsweken water supply[C]∥Proceedings of the fifth national conference on drinking water.Winnipeg,Manitoba,Canada.Denver,Colorado:American Water Works Association,1993:241-252.
[32]MITCH W A,SHARP J O,TRUSSELL R R,et al.N-nitrosodimethylamine(NDMA)as a drinking water contaminant:a review[J].Environmental Engineering Science,2003,20(5):389-404.
[33]RIPOLLES C,PITARCH E,SANCHO J V,et al.Determination of eight nitrosamines in water at the ng/L levels by liquid chromatography coupled to atmospheric pressure chemical ionization tandem mass spectrometry[J].Analytica Chimica Acta,2011,702(1):62-71.
[34]JURADO-SANCHEZ B,BALLESTEROS E,GALLEGOM.Screening of N:nitrosamines in tap and swimming pool waters using fast gas chromatography[J].Journal of Separation Science,2010,33(4/5):610-616.
[35]GREBEL J E,YOUNG C C,SUFFET I H M.Solid-phase microextraction of N-nitrosamines[J].Journal of Chromatography A,2006,1117(1):11-18.
[36]KRAUSS M,HOLLENDER J.Analysis of nitrosamines in wastewater:exploring the trace level quantification capabilities of a hybrid linear ion trap/orbitrap mass spectrometer[J].Analytical Chemistry,2008,80(3):834-842.
[37]TOPUZ E,AYDIN E,PEHLIVANOGLU-MANTAS E.Apractical LC-MS/MS method for the detection of NDMA at nanogram per liter concentrations in multiple water matrices[J].Water,Air,&Soil Pollution,2012,223(9):5793-5802.
[38]陈文文,张原,李小水,等.水中N-亚硝胺的富集及色谱分析测试技术[J].环境化学,2016,35(10):2117-2126.
[39]周树伟,李鸿龙.促进广东先进制造业发展的思考:以广东省佛山市顺德区为例[J].发展改革理论与实践,2018(1):55-59.
[40]国土资源部中国地质调查局.中华人民共和国多目标区域地球化学图集:广东省珠江三角洲经济区[CM].北京:地质出版社,2011:52-53.
[41]广东省地质调查院水工环组.珠江三角洲地区地下水污染调查评价[R].广州:广东省地质调查院,2008:76-154.
[42]ПЕРЕЛЬМАНАИ,КАСИМОВИС.Геохимияландшафта[M].Moсква:ИздательствоЦентра“Интеграция”,1999:64-70.
[43]丁平,沈承德,王宁,等.广东四会古森林地下生态系统碳同位素组成及其古气候意义[J].中国科学:D辑,2009(1):70-78.