蔬菜DEHP污染状况及污染成因研究
|
摘要
随着工业生产和塑料制品的使用,塑料垃圾的大量增加,邻苯二甲酸酯(PAEs)不断进入环境,已成为全球性的最普遍的污染物。邻苯二甲酸酯(2-乙基己基)酯(DEHP)是塑化剂的主要成分,它可以从塑料中释放至大气、土壤和水域中,迁移到蔬菜、水果和庄稼,通过食物链进入人体,从而对人类健康造成危害。本研究开展了主要蔬菜受DEHP污染状况的调查和污染原因分析,蔬菜吸收累积DEHP受污染源的影响及其规律,并探讨了不同种类蔬菜吸收DEHP能力的差异。主要结论如下：
(1)对不同采样点的蔬菜进行了DEHP含量分析,采于塑料厂周边农田的叶菜类蔬菜可食部分和瓜果类叶子部分均被检出DEHP,且受DEHP污染较为严重；采自农贸市场和路边小摊的叶菜类和瓜果类亦有部分检出DEHP;而采于山区的蔬菜DEHP污染极少。冬令时节采集的蔬菜样品中的DEHP含量比夏令时节相同蔬菜样品DEHP含量高。塑料厂周边瓜果类蔬菜的可食部分也均有DEHP检出,但较其叶子部分中的DEHP含量低。
(2)根据蔬菜的污染状况,分析采样点的土壤、大气和蔬菜中的DEHP含量,结果表明,蔬菜叶中累积DEHP的量与大气中DEHP含量有较好的线性关系；而其与土壤中DEHP含量的线性关系不明显。
(3)分析了地膜导致的蔬菜累积DEHP的情况。结果显示,种植在用地膜覆盖的土地上的蔬菜均能检出DEHP。同厚度条件下,黑地膜种植的蔬菜中(除了小葱)含有的DEHP高于白地膜的。地膜厚度越大,膜中释放出的DEHP越多,蔬菜累积DEHP的量亦高。除小葱外,蔬菜中DEHP含量与地膜厚度的呈线性相关(R2>0.8)。
(4)通过盆栽试验,发现不同种类蔬菜吸收DEHP的能力有较大差异,冬瓜、南瓜、黄瓜及大白菜的叶子累积较高DEHP。蔬菜不同部位中DEHP的含量顺序为叶子>茎>根。田间地膜试验中发现雪里蕻、生菜、南瓜、丝瓜和黄瓜含量较高。
(5)以大棚塑料膜为DEHP污染源,研究了DEHP在棚膜/棚内空气/棚内蔬菜的转移规律。结果显示,棚内空气中DEHP的日含量变化曲线呈峰形,与棚内温度的日变化情况基本一致。棚内青菜样品中DEHP的日含量变化呈缓慢增加趋势,与空气中DEHP含量变化趋势稍有差异。蔬菜大棚影响棚内蔬菜吸收累积DEHP,这些因素分别是塑料膜材质和厚度,大棚高度和棚龄。塑料膜中所含DEHP量越高,棚内蔬菜中DEHP含量越高；塑料膜越厚,所搭建的大棚高度越低,棚龄越短,蔬菜累积的DEHP量越高。
(6)通过在塑料厂周边农田种植蔬菜,研究了蔬菜中DEHP累积量。结果得出,试验田距塑料厂越近,气温越高,位于污染源的下风向,其大气中DEHP的含量越高,蔬菜中DEHP含量也越高。另外,试验田上方空气中DEHP的浓度水平与蔬菜累积DEHP的量呈正相关,相关系数均大于0.95,佐证了蔬菜受DEHP污染主要来自大气中的DEHP。
以上研究结果可为避免蔬菜DEHP污染、种植出符合食品安全标准的蔬菜提供科学依据。
Phthalates have being caused severe environmental and food contaminants since the use of plasterers in plastic products. Di-(2-ethylhexyl) phthalate (DEHP), the main substance in plasticizers, can be continuously released from the plastic to the atmosphere, soil and water, and then migrate to vegetables, fruits and crops, which lead to uptake of human body through food chain. Because DEHP possesses teratogenicity and carcinogenicity, the DEHP-contamination degree of vegetables, the source of the contamination, and the factors influencing the accumulation of DEHP in vegetables from different pollution sources were investigated in the present paper. The main results are summarized as follows:
(1) DEHP contents of vegetables from the different sampling sites were analyzed. The edible parts of leafy and fruit vegetables had DEHP accumulation from the farmland surrounding the plastics factory, and some of them were seriously contaminated. DEHP was also detected in part of leafy and fruit vegetables from the markets and roadside stalls. However, DEHP of vegetables from the mountains were rarely detected. The DEHP content of the vegetables in winter were higher than those in summer. The edible parts of fruits surrounding the plastic factory were also polluted by DEHP, but the DEHP contents in fruits were lower than that of in corresponding leaves.
(2) The DEHP contents in soil, atmosphere and the selected vegetables were determined. The regression analyses of the data showed that there was in good linear relationship between the content of DEHP in the leaves of vegetables and in the atmosphere while no linear relationship between the content DEHP in vegetable and in soil, which suggested that DEHP in vegetables came from air, not soil.
(3) DEHP contents in the vegetables cultivated in soil covered by mulch film were analyed. The results showed that all the vegetables was polluted by DEHP, and black film could cause more severe DEHP contamination than white film, which imply black film possesses stronger release ability of DEHP than white film. In addition, the greater the thickness of mulch film, the higher the DEHP amount released from the film to air, and caused more DEHP accumulation in the vegetables. The linear coefficients R2 between the film thickness and DEHP contents of the vegetables were more than 0.8, except for the onion samples.
(4) Pot-planting experiment with mulch film was conducted for a comparision of ability of DEHP uptake of different vegetable plants. The result showed the leaves of B. hispida, C. moschata, C. sativus and B. parachinensis possessed strong ability of DEHP uptake. Usually, leaves accumulated the highest DEHP content, followed by stem and root. The DEHP contents of vegetables planting in field with mulch film were determined. The result showed that there were high DEHP levels in B. juncea, L. sativa, C. moschata, L. cylindrical and C. sativus.
(5) The migration of DEHP from the cover film of greenhouse to atmosphere and vegetables was studied. The results exhibited that the daily DEHP content in air increased with the increase of the greenhouse temperature and the change curve of DEHP exhibited in peak shape. In the greenhouse, the daily DEHP content of vegetable was increased from morning to night, and the monthly DEHP content changes in vegetable were consistent with the change of DEHP levels in the greenhouse air. The factors influencing the DEHP uptake of vegetables in greenhouse included the material and thickness of the plastic membrane, the height and the age of the greenhouse. A low and young greenhouse covered with a thick film caused a higher DEHP content of vegetable than a high and old one covered with a thin film.
(6) The accumulation of DEHP in vegetables cultivating around a plastic factory was studied. The result showed that high DEHP content was detected in the vegetables cultivated the site near to the plastic factory, and temperature and wind direction were the key factors influencing the measurable DEHP concentration of the air and vegetables. A strong positive linear correlation between atmospheric DEHP concentration and DEHP content of the vegetable crops was found, and all the correlation coefficients (R2) were more than 0.95, which indirectly demonstrated that the DEHP in plants is distributed by the uptake of leaves, stem and fruits from atmosphere.
The total results of the present paper can provide scientific knowledge for avoiding DEHP contamination of vegetables to meet the requirement of food safety.
(1)对不同采样点的蔬菜进行了DEHP含量分析,采于塑料厂周边农田的叶菜类蔬菜可食部分和瓜果类叶子部分均被检出DEHP,且受DEHP污染较为严重；采自农贸市场和路边小摊的叶菜类和瓜果类亦有部分检出DEHP;而采于山区的蔬菜DEHP污染极少。冬令时节采集的蔬菜样品中的DEHP含量比夏令时节相同蔬菜样品DEHP含量高。塑料厂周边瓜果类蔬菜的可食部分也均有DEHP检出,但较其叶子部分中的DEHP含量低。
(2)根据蔬菜的污染状况,分析采样点的土壤、大气和蔬菜中的DEHP含量,结果表明,蔬菜叶中累积DEHP的量与大气中DEHP含量有较好的线性关系；而其与土壤中DEHP含量的线性关系不明显。
(3)分析了地膜导致的蔬菜累积DEHP的情况。结果显示,种植在用地膜覆盖的土地上的蔬菜均能检出DEHP。同厚度条件下,黑地膜种植的蔬菜中(除了小葱)含有的DEHP高于白地膜的。地膜厚度越大,膜中释放出的DEHP越多,蔬菜累积DEHP的量亦高。除小葱外,蔬菜中DEHP含量与地膜厚度的呈线性相关(R2>0.8)。
(4)通过盆栽试验,发现不同种类蔬菜吸收DEHP的能力有较大差异,冬瓜、南瓜、黄瓜及大白菜的叶子累积较高DEHP。蔬菜不同部位中DEHP的含量顺序为叶子>茎>根。田间地膜试验中发现雪里蕻、生菜、南瓜、丝瓜和黄瓜含量较高。
(5)以大棚塑料膜为DEHP污染源,研究了DEHP在棚膜/棚内空气/棚内蔬菜的转移规律。结果显示,棚内空气中DEHP的日含量变化曲线呈峰形,与棚内温度的日变化情况基本一致。棚内青菜样品中DEHP的日含量变化呈缓慢增加趋势,与空气中DEHP含量变化趋势稍有差异。蔬菜大棚影响棚内蔬菜吸收累积DEHP,这些因素分别是塑料膜材质和厚度,大棚高度和棚龄。塑料膜中所含DEHP量越高,棚内蔬菜中DEHP含量越高；塑料膜越厚,所搭建的大棚高度越低,棚龄越短,蔬菜累积的DEHP量越高。
(6)通过在塑料厂周边农田种植蔬菜,研究了蔬菜中DEHP累积量。结果得出,试验田距塑料厂越近,气温越高,位于污染源的下风向,其大气中DEHP的含量越高,蔬菜中DEHP含量也越高。另外,试验田上方空气中DEHP的浓度水平与蔬菜累积DEHP的量呈正相关,相关系数均大于0.95,佐证了蔬菜受DEHP污染主要来自大气中的DEHP。
以上研究结果可为避免蔬菜DEHP污染、种植出符合食品安全标准的蔬菜提供科学依据。
Phthalates have being caused severe environmental and food contaminants since the use of plasterers in plastic products. Di-(2-ethylhexyl) phthalate (DEHP), the main substance in plasticizers, can be continuously released from the plastic to the atmosphere, soil and water, and then migrate to vegetables, fruits and crops, which lead to uptake of human body through food chain. Because DEHP possesses teratogenicity and carcinogenicity, the DEHP-contamination degree of vegetables, the source of the contamination, and the factors influencing the accumulation of DEHP in vegetables from different pollution sources were investigated in the present paper. The main results are summarized as follows:
(1) DEHP contents of vegetables from the different sampling sites were analyzed. The edible parts of leafy and fruit vegetables had DEHP accumulation from the farmland surrounding the plastics factory, and some of them were seriously contaminated. DEHP was also detected in part of leafy and fruit vegetables from the markets and roadside stalls. However, DEHP of vegetables from the mountains were rarely detected. The DEHP content of the vegetables in winter were higher than those in summer. The edible parts of fruits surrounding the plastic factory were also polluted by DEHP, but the DEHP contents in fruits were lower than that of in corresponding leaves.
(2) The DEHP contents in soil, atmosphere and the selected vegetables were determined. The regression analyses of the data showed that there was in good linear relationship between the content of DEHP in the leaves of vegetables and in the atmosphere while no linear relationship between the content DEHP in vegetable and in soil, which suggested that DEHP in vegetables came from air, not soil.
(3) DEHP contents in the vegetables cultivated in soil covered by mulch film were analyed. The results showed that all the vegetables was polluted by DEHP, and black film could cause more severe DEHP contamination than white film, which imply black film possesses stronger release ability of DEHP than white film. In addition, the greater the thickness of mulch film, the higher the DEHP amount released from the film to air, and caused more DEHP accumulation in the vegetables. The linear coefficients R2 between the film thickness and DEHP contents of the vegetables were more than 0.8, except for the onion samples.
(4) Pot-planting experiment with mulch film was conducted for a comparision of ability of DEHP uptake of different vegetable plants. The result showed the leaves of B. hispida, C. moschata, C. sativus and B. parachinensis possessed strong ability of DEHP uptake. Usually, leaves accumulated the highest DEHP content, followed by stem and root. The DEHP contents of vegetables planting in field with mulch film were determined. The result showed that there were high DEHP levels in B. juncea, L. sativa, C. moschata, L. cylindrical and C. sativus.
(5) The migration of DEHP from the cover film of greenhouse to atmosphere and vegetables was studied. The results exhibited that the daily DEHP content in air increased with the increase of the greenhouse temperature and the change curve of DEHP exhibited in peak shape. In the greenhouse, the daily DEHP content of vegetable was increased from morning to night, and the monthly DEHP content changes in vegetable were consistent with the change of DEHP levels in the greenhouse air. The factors influencing the DEHP uptake of vegetables in greenhouse included the material and thickness of the plastic membrane, the height and the age of the greenhouse. A low and young greenhouse covered with a thick film caused a higher DEHP content of vegetable than a high and old one covered with a thin film.
(6) The accumulation of DEHP in vegetables cultivating around a plastic factory was studied. The result showed that high DEHP content was detected in the vegetables cultivated the site near to the plastic factory, and temperature and wind direction were the key factors influencing the measurable DEHP concentration of the air and vegetables. A strong positive linear correlation between atmospheric DEHP concentration and DEHP content of the vegetable crops was found, and all the correlation coefficients (R2) were more than 0.95, which indirectly demonstrated that the DEHP in plants is distributed by the uptake of leaves, stem and fruits from atmosphere.
The total results of the present paper can provide scientific knowledge for avoiding DEHP contamination of vegetables to meet the requirement of food safety.
引文
[1]Lang T, Peters G, Hoffman R, Meyer R. Experimental investigations on the toxicity of ammonia:Effection on ventilation frequency growth epidermal mucous cell, and gill structure of rainbow trout (Salmo gairdnrei) [J]. Diseases of Aquatic Organisms,1987,3(3):159-165.
[2]Petersen JH. Survey of di-ethylhexyl phthalate plasticizer contamination of Danishmilks [J]. Food Additives and Contaminants,1991, (8):701-706.
[3]Petersen JH, Naamansen ET, Nielsen PA. PVC cling film in contact with cheese:health related to global migration and specific migration of DEHA [J]. Food Control,1995(2):245-249.
[4]卞战强,田向红,黄艳,张娟.可见光催化降解水中邻苯二甲酸二异辛酯的研究[J].净水技术,2010,29(5)：30-32.
[5]Ralf P, Holger MK, Jurgen A. Biological monitoring of the five major metabolites of di-(2-ethylhexyl)phthalate (DEHP)in human urine using column switching liquid chromatography-tandem mass spectrometry [J]. Journal of Chromatography B,2005,816:269-280.
[6]Hammad KM, Jin YJ. Ozonation catalyzed by homogeneous and heterogeneous catalysts for degradation of DEHP in aqueous phase [J].Chemosphere,2008,72(4):690-696.
[7]Latini G. Monitoring phthalate exposure in humans [J]. Clinica ChimicaActa,2005,61:20-29.
[8]胡晓宇,张克荣,孙俊红,吴德生.中国环境中邻苯二甲酸酯类化合物污染的研究[J].中国卫生检验杂志,2003,13(1)：9-14.
[9]Sathyanarayana S. Current problems in pediatric and adolescent health care [J].Phthalates and children's health,2008,38,34-49.
[10]Rider CV, Furr J. A mixture of seven antiandrogens induces reproductive malformations in rats [J]. International Journal of Andrology,2008,31:249-262.
[11]Deutschle T, Reiter R, Butte W. A controlled challenge study on di(2-ethylhexyl) phthalate (DEHP) in house dust and the immune response in human nasal mucosa of allergic subjects [J]. Environmental Health Perspectives,2008,116:1487-1493.
[12]Takashima K, Ito Y, Gonzalez FJ. Different mechanisms of DEHP-induced hepatocellular adenoma tumorigenesis in wild-type and PPRA alpha-null mice [J]. Journal of Occupational Health,2008,50:169-180.
[13]Roberts R, Moffat G. Exposure to peroxisome proliferators:Reassessment of the potential carcinogenic hazard [J]. Environmental Health Perspectives,2001,109 (10):A462.
[14]曹攽,马军,李云木子,刘清辉.索氏提取—液相色谱法测定土壤中邻苯二甲酸酯类物质[J].地质学刊,2011,35(1)：73-77.
[15]陈莎,钟薿盛,王晓伟,谢亚勃.异烟酸铜吸附剂固相萃取分离水中的邻苯二甲酸酯[J].环境化学,2011,30(4)：891-892.
[16]胡银川,李明元,谢晖,邱一雯.塑料桶装食用油中邻苯二甲酸酯固相萃取方法研究[J].食品工业科技,2011,8：405-407.
[17]朱国辉,丘泰球,黄卓烈.超声波在萃取中的应用[J].声学技术,2001,20(4)：118-120.
[18]白利涛,张占恩.超声萃取-C18柱净化·GC/MS法测定士壤中邻苯二甲酸酯类污染物[J].光谱实验室,2010,27(5)：1705-1708.
[19]陈海东,鲜啟鸣,邹惠仙,刘云,孙成.超声萃取气相色谱法测定植物样中邻苯二甲酸醋[J].环境化学,2006,25(2)：228-230.
[20]许泓,佟晖.固相微萃取技术及应用[J].现代仪器,2001(4)：21-24.
[21]刘梵岩,高丽,中杰,刘薇,蔡立鹏.固相微萃取—气相色谱法测定白洋淀水样中的邻苯二甲酸酯类化合物[J].色谱,2010,28(5)：517-520.
[22]赵汝松,徐晓白,刘秀芬.液相微萃取技术的研究进展[J].分析化学,2004,32(9)：1246-1251.
[23]李敏霞,胡京洪,曾玮,马志玲.液相微萃取-气相色谱法测定水样中邻苯二甲酸酯[J].分析化学,2006,34(8)：1172-1174.
[24]楼佳.快速溶剂萃取—气相色谱／质谱联用测定塑料桌布中的邻苯二甲酸酯[J].化学研究,2011,22(2)：65-67.
[25]朱九群,兰婉,张罗红.HPLC测定PVC输液袋中的邻苯二甲酸二(2-乙基己基)酯[J].华西药学杂志,2009,24(3)：318-319.
[26]李波平,林勤保,宋欢,李莉莉.快速溶剂萃取-高效液相色谱测定塑料中邻苯二甲酸酯类化合物[J].应用化学,2008,25(1)：63-66.
[27]费斐,李亚玲,张坤,陈强,李玉玲.高效液相色谱测定啤酒瓶盖内衬垫DEHP的含量[J].包装工程,2011,32(5)：32-35.
[28]邓琳,陈鹏宇,涂建峰,吴峰,邓南圣.固相微萃取-高效液相色谱法测定水中的酞酸二(2-乙基己基)酯[J].分析科学学报,2005,21(1)：27-29.
[29]Wang L, Jiang G B. Cloud Point Extraction Coupled with HPLC/UV for the Determination of Phthalate Esters in Environmental Water Samples [J]. Journal of Environmental Sciences,2007, 19:874-878.
[30]刘祥萍,黄薇,吴秀兰,唐世树.高效液相色谱法测定化妆品中邻苯二甲酸二丁酯和邻苯二甲酸二(2-乙基己基)酯的含量[J].中国卫生检验杂志,2009,17(9)：1563-1564.
[31]张双灵,徐仰丽,王世清.食品塑料袋中DEHP气相色谱检测方法的建立[J].食品科学,2007,28(8)：341-344.
[32]刘伟红,杨丹华,欧阳少伦,高小兰.快速溶剂萃取-气相色谱法测定PVC中增塑剂含 量[J].科技资讯,2008,17：92-94.
[33]杨左军,张伟亚,潘坤永,江丽媛,余建新,吴采樱.SPME-GC法测定塑料玩具制品在模拟汗液浸泡液中DEHP[J].检验检疫科学,2002,12(4)：8-10.
[34]郑和辉,赵立文,刘玉敏,周香玉.饮用水中邻苯二甲酸酯的气相色谱-质谱测定法[J].环境与健康杂志,2005,22(5)：377-378.
[35]曹艳平,王大威,张霞.气相色谱-质谱联用法测定饮用水中邻苯二甲酸酯类物质[J].预防医学论坛,2007,13(5)：441-442.
[36]Brossa L, Mare M, Borrul F. Application of on-line solid phase extraction gas chromatography massspectrometry to the determination of endocrine disruptor in water sample [J]. Chromatogram A,2002,963:287-294.
[37]蔡智鸣,张前龙,赵文红.色谱-质谱测定塑料食品袋溶出的酞酸酯DBP和DEHP[J].理化检验,2003,39(9)：529-531.
[38]王明林,寇立娟,张玉倩,史衍玺.基质固相分散-气相色谱／质谱法测定蔬菜中的邻苯二甲酸酯[J].色谱,2007,25(4)：577-580.
[39]孙若男,陈美瑜,林竹光.气相色谱口质谱联用同时测定蔬菜中16种邻苯二甲酸酯残留[J].分析试验室,2010,29(12)：73-76.
[40]王硕,王琨,朱华平,方国臻,陈静.气相色谱-质谱法检测食用油中的邻苯二甲酸酯[J].食品研究与开发,2010,31(9)：127-130.
[41]黄永辉.SPE-GC-MS法同时测定奶粉中18种邻苯二甲酸酯迁移量[J].食品研究与开发,2010,31(11)：167-171.
[42]王东辉,李懿睿,田玉平,郭卫荣,吴建军.食品包装用塑料中八种邻苯二甲酸酯的检测方法[J].氨基酸和生物资源,2010,34(3)：83-86.
[43]张晶,何士龙,张昱,陈雪梅,杨敏.液相色谱串联质谱法同时测定垃圾渗滤液中的邻苯二甲酸酯和烷基酚[J].分析化学,2007,35(12)：1706-1710.
[44]王丽霞,寇立娟,潘峰云,王明林.基质固相分散-液相色谱-质谱法测定蔬菜中的邻苯二甲酸酯[J].分析化学,2007,35(11)：1559-1564.
[45]庄惠生,张明翠.兔抗邻苯二甲酸二甲酯的多克隆抗体制备及特性分析[J].化学试剂,2006,28(10)：577-580.
[46]郎庆,张明翠.双抗体夹心荧光免疫法测定水中的邻苯二甲酸环己二酯[J].中国环境监测,2006,22(4)：13-15.
[47]张明翠,庄惠生.邻苯二甲酸二丁酯免疫检测Ⅰ.人工抗原的制备及表征[J].应用化学,2006,23(8)：850-853.
[48]国伟林,王西奎.城区大气和塑料大棚空气中酞酸酯的分析[J].环境化学,1997,16(4)：382-385.
[49]邵龙义,牛红亚,贺桃娥,李红,方家虎.北京市西北城区大气PM10中酞酸酯的分布特征[J].环境工程,2009,27,增刊,300-303.
[50]史坚,徐鸿.杭州市大气总悬浮颗粒物中酞酸酯的污染[J].环境污染与防治,2000,22(6)：44-45.
[51]于涵,胡建英,金晓辉,何文杰,韩宏大.北方某水厂原水和处理过程中邻苯二甲酸酯类的监测[J].给水排水,2005,31(6)：20-23.
[52]吴平谷,韩关根,黄惠华,赵莹.饮用水中邻苯二甲酸酯类的调查[J].环境与健康杂志,1999,16(6)：338-339.
[53]贾宁,许恒睿,胡亚丽,林兴桃,陈明,张淑芬.固相萃取-气相色谱法测定北京市水样中的邻苯二甲酸酯[J].分析试验室,2005,24(11)：18-21.
[54]金维光.光降解地膜的农业效果与降解过程[J].农业环境保护,1995,14(4)：162-165.
[55]孟平蕊,王西奎.济南市土壤中酞酸酯的分布与分析[J].环境化学,1996,15(5)：427-432.
[56]张中华,金士威.台州电子废物拆解地区表层土壤中酞酸酯的污染水平[J].武汉工程大学学报,2010,32(7)：28-32.
[57]王家文,杜琪珍,宋英琦.塑料工业区附近农田蔬菜DEHP的浓度水平及评价[J].环境科学,2010,31(10)：2450-2455.
[58]李米.绿色食品和有机食品蔬菜基地土壤和蔬菜中邻苯二甲酸酯的分布特征[J].安徽农业科学,2010,38(19)：10189-10191.
[59]张茂生.东莞市蔬菜基地邻苯二甲酸酯的污染特征研究[J].广东农业科学,2009,6：172-180.
[60]Yin R, Lin XG, Wang SG. Effect of DBP/DEHP in vegetable planted soil on the quality of capsicum fruit [J]. Chemosphere,2003,50 (6):801-805.
[61]曾巧云,莫测辉,蔡全英,王伯光.菜心对邻苯二甲酸酯(PAEs)吸收途径的初步研究[J].农业工程学报,2005,21(8)：137-141.
[62]曾巧云,莫测辉,蔡全英,吴启堂.萝卜对邻苯二甲酸酯(PAEs)吸收累积特征及途径的初步研究[J].环境科学学报,2006,26(1)：10-16.
[63]王家文.塑料工业区DEHP污染及蔬菜安全评价[D],浙江工商大学生工食品学院,2011：23-33.
[64]Du Q, Shen L. Di-2-ethylhexyl phthalate in the fruits of Benincasa hispid [J]. Food additives & contaminants,2006,23(6):527-531.
[65]吴杰民.聚烯烃类农膜及酞酸脂类(PAES)在环境中的残留及生物降解前景[J].环境科学,1995,15(2)：77-80.
[66]代平,安瞳昕,吴伯志,字淑慧,牛华林.云南通海蔬菜区土壤和蔬菜中重金属及农药 残留分析[J].安徽农业科学,2012,1：29-33.
[67]王连珠,周昱,陈泳,王瑞龙,林子旭,郑少惠.QuEChERS样品前处理-液相色谱-串联质谱法测定蔬菜中66种有机磷农药残留量方法评估[J].色谱,2012.2：56-63.
[68]姜俊,李培武,谢立华,丁小霞.李英,王秀瑸,王雪芳,管笛.固相萃取-全二维气相色谱/飞行时间质谱同步快速检测蔬菜中64种农药残留[J].分析化学,2011,1：61-68.
[69]Schmitzer JL, Scheunert I, Korte F. Fate of bis (2-ethylhexyl) [14C] phthalate in laboratory and outdoor soil-plant systems [J]. Agricultural and Food Chemistry,1988,36(24):210-215.
[70]Du Q, Fu X, Xia H. Uptake of di-(2-ethyIhexyl)phthalate from plastic mulch film by vegetable plants [J]. Food additives & contaminants,2009,26:1325-1329.
[71]王绪强.植物累积有机污染物物DEHP能力及其特异性研究[D].浙江工商大学生工食品学院,2009：52-70
[72]Collins SC, Fryer M, Grosso A. Plant uptake of non-Ionic orgnic chemicals [J]. Environmental Science Technology,2006,40:45-52.
[73]Howsam M, Jones KC. PAHs associated with the leaves of three deciduous tree species I-Concentrations and profiles [J]. Environmental Pollution,2000,108:413-424.
[74]蔡全英,莫测辉,曾巧云,李云辉,肖凯恩,李海琴,徐国生,王伯光,吴清柱.邻苯二甲酸酯在不同品种通菜-士壤系统中的累积效应研究[J].应用生态学报,2004,15：1455-1458.
[75]Mental AM, Monoli E, Manoli C. Bioconcentration of polycyclic aromatic hydrocarbons in vegetables growen in an industrial area [J]. Environmental Pollution,1999,369-380.
[76]Sinmnich SL, Hites RA. Organic pollutant accumulation in vegetation [J]. Environmental Science and Technology,1995.29:2905-2914.
[77]王明林.蔬菜大棚中邻苯二甲酸酯分析方法及环境行为的研究[D].山东：山东农业大学环境与资源学院,2007：45-55.
[78]郑文芝,周勇强,张霖霖.PVC塑料制品中增塑剂PAEs在水环境中迁移规律的研究[J].广东化工,2006,33(3)：29-30.
[79]曾巧云,莫测辉,文荣联,蔡全英.2种基因型菜心根系解剖结构差异及其对DEHP吸收累积的影响[J].环境科学,2010,31(8)：1981-1986.
[80]曾巧云,莫测辉,蔡全英,文荣联.两种基因型菜心根系形态和生理特性差异对其吸收累积DEHP影响的初步研究[J].环境科学学报,2010,30(6)：1280-1285.
[81]曾巧云,莫测辉,文荣联,蔡全英.2种基因型菜心根系分泌物对水稻土中DEHP解吸效应的初步研究[J].农业环境科学学报,2010,29(8)：1466-1470.
[82]宋广宇,代静玉,胡锋.邻苯二甲酸酯在不同类型土壤-植物系统中的累积特征研究[J].农业环境科学学报,2010,29(8)：1502-1508.
[83]王诗嘉,和月强,叶珊,常青,李韧,丁书茂.邻苯二甲酸二乙基己酯对蚕豆幼苗茎和叶POD活性和MDA含量的影响[J].生态毒理学报,2010,5(4)：587-591.
[84]Adibi JJ, Whyatt RM, Williams PL, Calafat AM, Camann D, Herrick R, Nelson H, Bhat HK, Perera FP, Silva MJ, Hauser R. Characterization of phthalate exposure among pregnant women assessed by repeat air and urine samples [J]. Environmental Health Perspectives,2008,116: 467-473.
[85]Sathyanarayana S. Phthalates and children's health Current Problems in Pediatric and Adolescent Health [J]. Care,2008,38:34-49.
[86]Swan SH. Environmental phthalate exposure in relation to reproductive outcomes and other health endpoints in humans [J]. Environmental Research,2008,108:177-84.
[87]Rider CV, Furr J, Wilson VS, Gray LE. A mixture of seven antiandrogens induces reproductive malformations in rats [J]. International Journal of Andrology,2008,31:249-62.
[88]Deutschle T, Reiter R, Butte W, Heinzow B, Keck T, Riechelmann H. A controlled challenge study on di(2-ethylhexyl) phthalate (DEHP) in house dust and the immune response in human nasal mucosa of allergic subjects [J]. Environmental Health Perspectives,2008,116:1487-1493.
[89]Takashima K, Ito Y, Gonzalez FJ, Nakajima T. Different mechanisms of DEHP-induced hepatocellular adenoma tumorigenesis in wild-type and PPRA alpha-null mice [J]. Journal of Occupational Health,2008,50:169-80.
[2]Petersen JH. Survey of di-ethylhexyl phthalate plasticizer contamination of Danishmilks [J]. Food Additives and Contaminants,1991, (8):701-706.
[3]Petersen JH, Naamansen ET, Nielsen PA. PVC cling film in contact with cheese:health related to global migration and specific migration of DEHA [J]. Food Control,1995(2):245-249.
[4]卞战强,田向红,黄艳,张娟.可见光催化降解水中邻苯二甲酸二异辛酯的研究[J].净水技术,2010,29(5)：30-32.
[5]Ralf P, Holger MK, Jurgen A. Biological monitoring of the five major metabolites of di-(2-ethylhexyl)phthalate (DEHP)in human urine using column switching liquid chromatography-tandem mass spectrometry [J]. Journal of Chromatography B,2005,816:269-280.
[6]Hammad KM, Jin YJ. Ozonation catalyzed by homogeneous and heterogeneous catalysts for degradation of DEHP in aqueous phase [J].Chemosphere,2008,72(4):690-696.
[7]Latini G. Monitoring phthalate exposure in humans [J]. Clinica ChimicaActa,2005,61:20-29.
[8]胡晓宇,张克荣,孙俊红,吴德生.中国环境中邻苯二甲酸酯类化合物污染的研究[J].中国卫生检验杂志,2003,13(1)：9-14.
[9]Sathyanarayana S. Current problems in pediatric and adolescent health care [J].Phthalates and children's health,2008,38,34-49.
[10]Rider CV, Furr J. A mixture of seven antiandrogens induces reproductive malformations in rats [J]. International Journal of Andrology,2008,31:249-262.
[11]Deutschle T, Reiter R, Butte W. A controlled challenge study on di(2-ethylhexyl) phthalate (DEHP) in house dust and the immune response in human nasal mucosa of allergic subjects [J]. Environmental Health Perspectives,2008,116:1487-1493.
[12]Takashima K, Ito Y, Gonzalez FJ. Different mechanisms of DEHP-induced hepatocellular adenoma tumorigenesis in wild-type and PPRA alpha-null mice [J]. Journal of Occupational Health,2008,50:169-180.
[13]Roberts R, Moffat G. Exposure to peroxisome proliferators:Reassessment of the potential carcinogenic hazard [J]. Environmental Health Perspectives,2001,109 (10):A462.
[14]曹攽,马军,李云木子,刘清辉.索氏提取—液相色谱法测定土壤中邻苯二甲酸酯类物质[J].地质学刊,2011,35(1)：73-77.
[15]陈莎,钟薿盛,王晓伟,谢亚勃.异烟酸铜吸附剂固相萃取分离水中的邻苯二甲酸酯[J].环境化学,2011,30(4)：891-892.
[16]胡银川,李明元,谢晖,邱一雯.塑料桶装食用油中邻苯二甲酸酯固相萃取方法研究[J].食品工业科技,2011,8：405-407.
[17]朱国辉,丘泰球,黄卓烈.超声波在萃取中的应用[J].声学技术,2001,20(4)：118-120.
[18]白利涛,张占恩.超声萃取-C18柱净化·GC/MS法测定士壤中邻苯二甲酸酯类污染物[J].光谱实验室,2010,27(5)：1705-1708.
[19]陈海东,鲜啟鸣,邹惠仙,刘云,孙成.超声萃取气相色谱法测定植物样中邻苯二甲酸醋[J].环境化学,2006,25(2)：228-230.
[20]许泓,佟晖.固相微萃取技术及应用[J].现代仪器,2001(4)：21-24.
[21]刘梵岩,高丽,中杰,刘薇,蔡立鹏.固相微萃取—气相色谱法测定白洋淀水样中的邻苯二甲酸酯类化合物[J].色谱,2010,28(5)：517-520.
[22]赵汝松,徐晓白,刘秀芬.液相微萃取技术的研究进展[J].分析化学,2004,32(9)：1246-1251.
[23]李敏霞,胡京洪,曾玮,马志玲.液相微萃取-气相色谱法测定水样中邻苯二甲酸酯[J].分析化学,2006,34(8)：1172-1174.
[24]楼佳.快速溶剂萃取—气相色谱／质谱联用测定塑料桌布中的邻苯二甲酸酯[J].化学研究,2011,22(2)：65-67.
[25]朱九群,兰婉,张罗红.HPLC测定PVC输液袋中的邻苯二甲酸二(2-乙基己基)酯[J].华西药学杂志,2009,24(3)：318-319.
[26]李波平,林勤保,宋欢,李莉莉.快速溶剂萃取-高效液相色谱测定塑料中邻苯二甲酸酯类化合物[J].应用化学,2008,25(1)：63-66.
[27]费斐,李亚玲,张坤,陈强,李玉玲.高效液相色谱测定啤酒瓶盖内衬垫DEHP的含量[J].包装工程,2011,32(5)：32-35.
[28]邓琳,陈鹏宇,涂建峰,吴峰,邓南圣.固相微萃取-高效液相色谱法测定水中的酞酸二(2-乙基己基)酯[J].分析科学学报,2005,21(1)：27-29.
[29]Wang L, Jiang G B. Cloud Point Extraction Coupled with HPLC/UV for the Determination of Phthalate Esters in Environmental Water Samples [J]. Journal of Environmental Sciences,2007, 19:874-878.
[30]刘祥萍,黄薇,吴秀兰,唐世树.高效液相色谱法测定化妆品中邻苯二甲酸二丁酯和邻苯二甲酸二(2-乙基己基)酯的含量[J].中国卫生检验杂志,2009,17(9)：1563-1564.
[31]张双灵,徐仰丽,王世清.食品塑料袋中DEHP气相色谱检测方法的建立[J].食品科学,2007,28(8)：341-344.
[32]刘伟红,杨丹华,欧阳少伦,高小兰.快速溶剂萃取-气相色谱法测定PVC中增塑剂含 量[J].科技资讯,2008,17：92-94.
[33]杨左军,张伟亚,潘坤永,江丽媛,余建新,吴采樱.SPME-GC法测定塑料玩具制品在模拟汗液浸泡液中DEHP[J].检验检疫科学,2002,12(4)：8-10.
[34]郑和辉,赵立文,刘玉敏,周香玉.饮用水中邻苯二甲酸酯的气相色谱-质谱测定法[J].环境与健康杂志,2005,22(5)：377-378.
[35]曹艳平,王大威,张霞.气相色谱-质谱联用法测定饮用水中邻苯二甲酸酯类物质[J].预防医学论坛,2007,13(5)：441-442.
[36]Brossa L, Mare M, Borrul F. Application of on-line solid phase extraction gas chromatography massspectrometry to the determination of endocrine disruptor in water sample [J]. Chromatogram A,2002,963:287-294.
[37]蔡智鸣,张前龙,赵文红.色谱-质谱测定塑料食品袋溶出的酞酸酯DBP和DEHP[J].理化检验,2003,39(9)：529-531.
[38]王明林,寇立娟,张玉倩,史衍玺.基质固相分散-气相色谱／质谱法测定蔬菜中的邻苯二甲酸酯[J].色谱,2007,25(4)：577-580.
[39]孙若男,陈美瑜,林竹光.气相色谱口质谱联用同时测定蔬菜中16种邻苯二甲酸酯残留[J].分析试验室,2010,29(12)：73-76.
[40]王硕,王琨,朱华平,方国臻,陈静.气相色谱-质谱法检测食用油中的邻苯二甲酸酯[J].食品研究与开发,2010,31(9)：127-130.
[41]黄永辉.SPE-GC-MS法同时测定奶粉中18种邻苯二甲酸酯迁移量[J].食品研究与开发,2010,31(11)：167-171.
[42]王东辉,李懿睿,田玉平,郭卫荣,吴建军.食品包装用塑料中八种邻苯二甲酸酯的检测方法[J].氨基酸和生物资源,2010,34(3)：83-86.
[43]张晶,何士龙,张昱,陈雪梅,杨敏.液相色谱串联质谱法同时测定垃圾渗滤液中的邻苯二甲酸酯和烷基酚[J].分析化学,2007,35(12)：1706-1710.
[44]王丽霞,寇立娟,潘峰云,王明林.基质固相分散-液相色谱-质谱法测定蔬菜中的邻苯二甲酸酯[J].分析化学,2007,35(11)：1559-1564.
[45]庄惠生,张明翠.兔抗邻苯二甲酸二甲酯的多克隆抗体制备及特性分析[J].化学试剂,2006,28(10)：577-580.
[46]郎庆,张明翠.双抗体夹心荧光免疫法测定水中的邻苯二甲酸环己二酯[J].中国环境监测,2006,22(4)：13-15.
[47]张明翠,庄惠生.邻苯二甲酸二丁酯免疫检测Ⅰ.人工抗原的制备及表征[J].应用化学,2006,23(8)：850-853.
[48]国伟林,王西奎.城区大气和塑料大棚空气中酞酸酯的分析[J].环境化学,1997,16(4)：382-385.
[49]邵龙义,牛红亚,贺桃娥,李红,方家虎.北京市西北城区大气PM10中酞酸酯的分布特征[J].环境工程,2009,27,增刊,300-303.
[50]史坚,徐鸿.杭州市大气总悬浮颗粒物中酞酸酯的污染[J].环境污染与防治,2000,22(6)：44-45.
[51]于涵,胡建英,金晓辉,何文杰,韩宏大.北方某水厂原水和处理过程中邻苯二甲酸酯类的监测[J].给水排水,2005,31(6)：20-23.
[52]吴平谷,韩关根,黄惠华,赵莹.饮用水中邻苯二甲酸酯类的调查[J].环境与健康杂志,1999,16(6)：338-339.
[53]贾宁,许恒睿,胡亚丽,林兴桃,陈明,张淑芬.固相萃取-气相色谱法测定北京市水样中的邻苯二甲酸酯[J].分析试验室,2005,24(11)：18-21.
[54]金维光.光降解地膜的农业效果与降解过程[J].农业环境保护,1995,14(4)：162-165.
[55]孟平蕊,王西奎.济南市土壤中酞酸酯的分布与分析[J].环境化学,1996,15(5)：427-432.
[56]张中华,金士威.台州电子废物拆解地区表层土壤中酞酸酯的污染水平[J].武汉工程大学学报,2010,32(7)：28-32.
[57]王家文,杜琪珍,宋英琦.塑料工业区附近农田蔬菜DEHP的浓度水平及评价[J].环境科学,2010,31(10)：2450-2455.
[58]李米.绿色食品和有机食品蔬菜基地土壤和蔬菜中邻苯二甲酸酯的分布特征[J].安徽农业科学,2010,38(19)：10189-10191.
[59]张茂生.东莞市蔬菜基地邻苯二甲酸酯的污染特征研究[J].广东农业科学,2009,6：172-180.
[60]Yin R, Lin XG, Wang SG. Effect of DBP/DEHP in vegetable planted soil on the quality of capsicum fruit [J]. Chemosphere,2003,50 (6):801-805.
[61]曾巧云,莫测辉,蔡全英,王伯光.菜心对邻苯二甲酸酯(PAEs)吸收途径的初步研究[J].农业工程学报,2005,21(8)：137-141.
[62]曾巧云,莫测辉,蔡全英,吴启堂.萝卜对邻苯二甲酸酯(PAEs)吸收累积特征及途径的初步研究[J].环境科学学报,2006,26(1)：10-16.
[63]王家文.塑料工业区DEHP污染及蔬菜安全评价[D],浙江工商大学生工食品学院,2011：23-33.
[64]Du Q, Shen L. Di-2-ethylhexyl phthalate in the fruits of Benincasa hispid [J]. Food additives & contaminants,2006,23(6):527-531.
[65]吴杰民.聚烯烃类农膜及酞酸脂类(PAES)在环境中的残留及生物降解前景[J].环境科学,1995,15(2)：77-80.
[66]代平,安瞳昕,吴伯志,字淑慧,牛华林.云南通海蔬菜区土壤和蔬菜中重金属及农药 残留分析[J].安徽农业科学,2012,1：29-33.
[67]王连珠,周昱,陈泳,王瑞龙,林子旭,郑少惠.QuEChERS样品前处理-液相色谱-串联质谱法测定蔬菜中66种有机磷农药残留量方法评估[J].色谱,2012.2：56-63.
[68]姜俊,李培武,谢立华,丁小霞.李英,王秀瑸,王雪芳,管笛.固相萃取-全二维气相色谱/飞行时间质谱同步快速检测蔬菜中64种农药残留[J].分析化学,2011,1：61-68.
[69]Schmitzer JL, Scheunert I, Korte F. Fate of bis (2-ethylhexyl) [14C] phthalate in laboratory and outdoor soil-plant systems [J]. Agricultural and Food Chemistry,1988,36(24):210-215.
[70]Du Q, Fu X, Xia H. Uptake of di-(2-ethyIhexyl)phthalate from plastic mulch film by vegetable plants [J]. Food additives & contaminants,2009,26:1325-1329.
[71]王绪强.植物累积有机污染物物DEHP能力及其特异性研究[D].浙江工商大学生工食品学院,2009：52-70
[72]Collins SC, Fryer M, Grosso A. Plant uptake of non-Ionic orgnic chemicals [J]. Environmental Science Technology,2006,40:45-52.
[73]Howsam M, Jones KC. PAHs associated with the leaves of three deciduous tree species I-Concentrations and profiles [J]. Environmental Pollution,2000,108:413-424.
[74]蔡全英,莫测辉,曾巧云,李云辉,肖凯恩,李海琴,徐国生,王伯光,吴清柱.邻苯二甲酸酯在不同品种通菜-士壤系统中的累积效应研究[J].应用生态学报,2004,15：1455-1458.
[75]Mental AM, Monoli E, Manoli C. Bioconcentration of polycyclic aromatic hydrocarbons in vegetables growen in an industrial area [J]. Environmental Pollution,1999,369-380.
[76]Sinmnich SL, Hites RA. Organic pollutant accumulation in vegetation [J]. Environmental Science and Technology,1995.29:2905-2914.
[77]王明林.蔬菜大棚中邻苯二甲酸酯分析方法及环境行为的研究[D].山东：山东农业大学环境与资源学院,2007：45-55.
[78]郑文芝,周勇强,张霖霖.PVC塑料制品中增塑剂PAEs在水环境中迁移规律的研究[J].广东化工,2006,33(3)：29-30.
[79]曾巧云,莫测辉,文荣联,蔡全英.2种基因型菜心根系解剖结构差异及其对DEHP吸收累积的影响[J].环境科学,2010,31(8)：1981-1986.
[80]曾巧云,莫测辉,蔡全英,文荣联.两种基因型菜心根系形态和生理特性差异对其吸收累积DEHP影响的初步研究[J].环境科学学报,2010,30(6)：1280-1285.
[81]曾巧云,莫测辉,文荣联,蔡全英.2种基因型菜心根系分泌物对水稻土中DEHP解吸效应的初步研究[J].农业环境科学学报,2010,29(8)：1466-1470.
[82]宋广宇,代静玉,胡锋.邻苯二甲酸酯在不同类型土壤-植物系统中的累积特征研究[J].农业环境科学学报,2010,29(8)：1502-1508.
[83]王诗嘉,和月强,叶珊,常青,李韧,丁书茂.邻苯二甲酸二乙基己酯对蚕豆幼苗茎和叶POD活性和MDA含量的影响[J].生态毒理学报,2010,5(4)：587-591.
[84]Adibi JJ, Whyatt RM, Williams PL, Calafat AM, Camann D, Herrick R, Nelson H, Bhat HK, Perera FP, Silva MJ, Hauser R. Characterization of phthalate exposure among pregnant women assessed by repeat air and urine samples [J]. Environmental Health Perspectives,2008,116: 467-473.
[85]Sathyanarayana S. Phthalates and children's health Current Problems in Pediatric and Adolescent Health [J]. Care,2008,38:34-49.
[86]Swan SH. Environmental phthalate exposure in relation to reproductive outcomes and other health endpoints in humans [J]. Environmental Research,2008,108:177-84.
[87]Rider CV, Furr J, Wilson VS, Gray LE. A mixture of seven antiandrogens induces reproductive malformations in rats [J]. International Journal of Andrology,2008,31:249-62.
[88]Deutschle T, Reiter R, Butte W, Heinzow B, Keck T, Riechelmann H. A controlled challenge study on di(2-ethylhexyl) phthalate (DEHP) in house dust and the immune response in human nasal mucosa of allergic subjects [J]. Environmental Health Perspectives,2008,116:1487-1493.
[89]Takashima K, Ito Y, Gonzalez FJ, Nakajima T. Different mechanisms of DEHP-induced hepatocellular adenoma tumorigenesis in wild-type and PPRA alpha-null mice [J]. Journal of Occupational Health,2008,50:169-80.