塑料包装材料中内分泌干扰素邻苯二甲酸酯类物质的测定及模拟条件下溶出的研究
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摘要
本文共分三章。
第一章：文献综述,概括了塑料包装材料中内分泌干扰素邻苯二甲酸酯类物质分析方法的现状和进展情况。对邻苯二甲酸酯类内分泌干扰素进行了简要介绍,详细总结了样品前处理和检测技术的发展情况,以及这些技术在对塑料包装材料中内分泌干扰素邻苯二甲酸酯类物质分析中的应用。
第二章：本文利用固相萃取-气相色谱法对塑料包装材料中的6种内分泌干扰素邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二丁基苄基酯(BBP)、邻苯二甲酸二(2-乙基已基)酯(DEHP)和邻苯二甲酸二正辛酯(DNOP)进行了分析方法研究。采用无水乙醇超声辅助提取样品,低温处理去除杂质,结合ENVI-18固相萃取技术净化提取液,以气相色谱-氢火焰离子化检测器测定其含量。各待测组分的检出限均小于0.04μg/mL,回收率在92.8～116.7%之间。相对标准偏差小于8.2%。
第三章：将分散液液微萃取(DLLME)与气相色谱-氢火焰离子化检测器(GC-FID)技术相结合,建立了一种简单快速测定塑料包装材料在酸性模拟体系(3%乙酸水溶液)中六种邻苯二甲酸酯(PAEs)溶出的新方法。采用四氯化碳作萃取剂,乙腈为分散剂,在优化条件下,六种PAEs在1.0～100.0μg/L浓度范围内呈良好的线性关系,线性相关系数在0.9998～0.9999之间,检出限为0.15～1.5μg/L(S/N=3)。将本方法应用于塑料包装材料在酸性模拟体系下的邻苯二甲酸酯的分析检测,并且考察了自然放置时间,加热温度,加热时间对于塑料包装材料中PAEs溶出的影响,加标回收率72.9%～113.7%,相对标准偏差在1.9%～12.6%之间。
This thesis consists of four chapters.
In CHAPTER ONE, The current state and development of analytical methods of endocrine disruptors-phthalate esters in plastic packaging materials are summarized. Toxicity of phthalate esters is introduced briefly. The methods of sample pretreatment and phthalate esters determination are summarized systemically and these methods applied to analysis of phthalate esters as well.
In CHAPTER TWO, A determination method of six endocrine disruptors-phthalate esters in plastic packaging materials including Di-methylphthalate (DMP), Di-ethylphthalate (DEP), Dibutylphthalate (DBP), Butylbenzylphthalate (BBP), Di(2-ethylhexyl)p-hthalate (DEHP) and Di-n-octylphthalate (DNOP) is developed. These phthalate esters are analyzed by gas chromatography combined with solid phase extraction (SPE). The samples are prepared by ultrasonic-assisted extraction with ethanol. Then the extract is purified by removing impurity with low temperature treatment and SPE with ENVI-18 column. Finally the samples are analyzed by using gas chromatography with flame ionization detector (GC-FID). The limits of detection of the 6 pollutants were all below 0.04μg/mL. The average recoveries were between 92.8 and 116.7% with relative standard deviation (RSD) less than 8.2%.
In CHAPTER THREE, The effectual, rapid, simple and convenient method,dispersive liquid-liquid microextraction (DLLME) combination gas chromatography coupled with flame ionization detector(GC-FID), was used for the determination of six phthalate esters (PAEs) in acid simulative system(3% acetic acid liquid), Under the optimum extraction conditions (extraction solvent:carbon tetrachloride; dispersive solvent:acetonitrile), a good linear relationship was obtained in the range of 1.0～100.0μg/L, the correlation coefficients was 0.9998～0.9999 and the limits of detection was between 0.15～1.5μg/L (S/N=3). The PAEs of plastic packaging materials under acid simulative system condition was successfully analyzed by using the proposed method. The influencing factors of dissolving PAEs from plastic packaging materials, such as laying time laying time, heating temperature and heating time were researched. The recoveries, which had been spiked with different levels, fell in the range of 72.9%～113.7% and the relative standard deviations were between 1.9% and 12.6%.
第一章：文献综述,概括了塑料包装材料中内分泌干扰素邻苯二甲酸酯类物质分析方法的现状和进展情况。对邻苯二甲酸酯类内分泌干扰素进行了简要介绍,详细总结了样品前处理和检测技术的发展情况,以及这些技术在对塑料包装材料中内分泌干扰素邻苯二甲酸酯类物质分析中的应用。
第二章：本文利用固相萃取-气相色谱法对塑料包装材料中的6种内分泌干扰素邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二丁基苄基酯(BBP)、邻苯二甲酸二(2-乙基已基)酯(DEHP)和邻苯二甲酸二正辛酯(DNOP)进行了分析方法研究。采用无水乙醇超声辅助提取样品,低温处理去除杂质,结合ENVI-18固相萃取技术净化提取液,以气相色谱-氢火焰离子化检测器测定其含量。各待测组分的检出限均小于0.04μg/mL,回收率在92.8～116.7%之间。相对标准偏差小于8.2%。
第三章：将分散液液微萃取(DLLME)与气相色谱-氢火焰离子化检测器(GC-FID)技术相结合,建立了一种简单快速测定塑料包装材料在酸性模拟体系(3%乙酸水溶液)中六种邻苯二甲酸酯(PAEs)溶出的新方法。采用四氯化碳作萃取剂,乙腈为分散剂,在优化条件下,六种PAEs在1.0～100.0μg/L浓度范围内呈良好的线性关系,线性相关系数在0.9998～0.9999之间,检出限为0.15～1.5μg/L(S/N=3)。将本方法应用于塑料包装材料在酸性模拟体系下的邻苯二甲酸酯的分析检测,并且考察了自然放置时间,加热温度,加热时间对于塑料包装材料中PAEs溶出的影响,加标回收率72.9%～113.7%,相对标准偏差在1.9%～12.6%之间。
This thesis consists of four chapters.
In CHAPTER ONE, The current state and development of analytical methods of endocrine disruptors-phthalate esters in plastic packaging materials are summarized. Toxicity of phthalate esters is introduced briefly. The methods of sample pretreatment and phthalate esters determination are summarized systemically and these methods applied to analysis of phthalate esters as well.
In CHAPTER TWO, A determination method of six endocrine disruptors-phthalate esters in plastic packaging materials including Di-methylphthalate (DMP), Di-ethylphthalate (DEP), Dibutylphthalate (DBP), Butylbenzylphthalate (BBP), Di(2-ethylhexyl)p-hthalate (DEHP) and Di-n-octylphthalate (DNOP) is developed. These phthalate esters are analyzed by gas chromatography combined with solid phase extraction (SPE). The samples are prepared by ultrasonic-assisted extraction with ethanol. Then the extract is purified by removing impurity with low temperature treatment and SPE with ENVI-18 column. Finally the samples are analyzed by using gas chromatography with flame ionization detector (GC-FID). The limits of detection of the 6 pollutants were all below 0.04μg/mL. The average recoveries were between 92.8 and 116.7% with relative standard deviation (RSD) less than 8.2%.
In CHAPTER THREE, The effectual, rapid, simple and convenient method,dispersive liquid-liquid microextraction (DLLME) combination gas chromatography coupled with flame ionization detector(GC-FID), was used for the determination of six phthalate esters (PAEs) in acid simulative system(3% acetic acid liquid), Under the optimum extraction conditions (extraction solvent:carbon tetrachloride; dispersive solvent:acetonitrile), a good linear relationship was obtained in the range of 1.0～100.0μg/L, the correlation coefficients was 0.9998～0.9999 and the limits of detection was between 0.15～1.5μg/L (S/N=3). The PAEs of plastic packaging materials under acid simulative system condition was successfully analyzed by using the proposed method. The influencing factors of dissolving PAEs from plastic packaging materials, such as laying time laying time, heating temperature and heating time were researched. The recoveries, which had been spiked with different levels, fell in the range of 72.9%～113.7% and the relative standard deviations were between 1.9% and 12.6%.
引文
[1]Saito I, Ueno E, Oshima H, et al. Levels of phthalates and adipates in processed foods and migration of di-isononyl adipate from polyvinyl chloride film into foods[J]. Journal of the Food Hygienic Society of Japan.2002,43(3):185-189.
[2]Balafas D, Shaw K J, Whitfield F B. Phthalate and adipate esters in Australian packaging materials[J]. Food-Chemistry.1999,65(3):279-287.
[3]Begley, T. H., Biles, J. E., Cunningham, C., Piringer, O. Migration of a UV stabilizer from Polyethylene terephthalate (PET) into food stimulant [J]. Food Additives & Contaminants,2004, 21(10):1007～1014.
[4]叶常明,田康.邻苯二甲酸酯类化合物生物降解动力学[J].环境科学学报,1989,9(1)：7-41.
[5]Toppari J, Larsen JC, ChristiansenP, et al. Male reproductive health and environmental xenoest-rogens[J]. Environ Health Perspect,1996,104(4):741-803.
[6]林兴桃,王小逸,任仁.环境内分泌干扰物邻苯二甲酸酯的研究[J].环境污染与防治,2003,25(10)：286-288.
[7]LoPez-Cervante J etal. Effects of Compression Stacking, Vacuum Packaging and Temperature on the Migration of BisPhenol A from Poly (vinylehloride) Packaging Sheeting into food simulants [J]. ChromatograPhia,2003,58(5/6):327-330.
[8]杨科峰,历曙光,蔡智鸣.食用油及其加热产物中酞酸酯类增塑剂的分析[J].环境与职业医学,2002,19(2)：32-34.
[9]Petersen J H, Breindahl T. Plasticizers in total diet samples, baby food and infant formulae[J]. Food-Additives-and-Contaminants.2000,17(2):133-141.
[10]Tsumura Y, Lshimitsu S, Nakamura, et al. Simultaneous determination of 11 phthalates and di(2-ethylhexyl)adipate in foods by GC/MS[J]. Shokuhin Eiseigaku Zasshi Journal of the Food hygienic Society of Japan,2000,41(4):254-260.
[11]Bluthgen A, Heeschen W H. Secretory and migratory contamination of cow milk with plasticizers especially phthalic acid esters[J]. Bulletin of the international Dairy Federation,1998,330:6-11.
[12]张蕴晖.邻苯二甲酸酯类的雄性生殖发育毒性及健康危险度评价[D]：[博士学位论文].上海： 复旦大学公共卫生学院,2004.
[13]陈荣祈,王建平编著.生态纺织品与环保染化料[M].北京：中国纺织出版社,2002,1：50.
[14]莫测辉,蔡全英,吴启堂等.我国城市污泥中邻苯二甲酸酯的研究[J].中国环境科学,59 2001,21(4)：362-366.
[15]Karen A, Bames, C, etal. Chemical migration and food contact materials[M]. Cambridge, Englangd:Woodhead Publishing limited,2007.
[16]俞力平,高光虎.我国增塑剂工业现状及发展[J].石油化工技术经济,1997,13(2)：26-49.
[17]韩关根,吴平谷,王惠华等.邻苯二甲酸酯对城镇供水的污染及现行水处理工艺净化效果的评价[J].环境与健康杂志,2001,18(3)：155-156.
[18]阎吉昌.环境分析[M].化学工业出版社,2002.12-15.
[19]刘振岭,刘二保.新固相微萃取-气相色谱技术快速检测水中的邻苯二甲酸酯[J].山西师范大学学报.2000,14(2)：36-41.
[20]赵贵平,蒋宏键.环境水样中酞酸酯的提取与分析[J].环境化学.2003,22(5)：520.
[21]Wang Xikui, Guo Weilin, Xu Guangtong, Wang Xiaomei, Meng Pingrui. Degradation of alachlor in aqueous solution by using hydrodynamic cavitation. Chinese Journal of Analytical Chemistry.1995,23(12):1425.
[22]Castillo M, BarceloD, Pereira A S, Neto F R A. Characterization of organic pollutants in industrial effluents by high-temperature gas chromatography-mass spectrometry[J]. Trends in Analytical Chemistry,1999,18(1):26—36
[23]Jaeyer R. J, Rubbin R. J.. Stir bar sorptive extraction and large volume injection gas chromatography to determination a group of endocrine disrupters in water samples[J]. New England Journal of Medicine,1972,278:1114-1118.
[24]石万聪,石志博,蒋平平.增塑剂及其应用[M].北京化学工业出版社.2002：634-638.
[25]边志忠.塑料包装食品中酞酸酯类增塑剂污染状况的检测与研究[D]：[硕士学位论文].无锡：江南大学,2008,6.
[26]BakerVA. Endocrine disrupters-testing strategies to assess human hazard[J]. Toxicol in Vitro,2001, 15(425):413-419.
[27]EN13130-1 Materials and articles in contact with foodstuffs Plastics subject to limitation-Part1:Guide to test methods for the specific migration of substances from Plasties to foods and food simulants and determination of substances in Plasties and the selection of eonditions of exposure to food stimulant.
[28]GB/T17409-1998,中华人民共和国国家标准：食品用包装材料及其制品的浸泡试验方法通则.中华人民共和国卫生部.1998,5.
[29]王琳玲,黄卫红,邵秀梅等.环境内分泌干扰素分析方法进展[J].分析科学学报,2003,19(2)：179-184.
[30]Chee.微波萃取技术萃取海洋沉积物和土壤中的邻苯二甲酸酯[J].环境化学,2003,22(5).
[31]李平波.加速溶剂萃取-高效液相色谱法测定了塑料中两种邻苯二甲酸酯[J].化工装备技术,2002,23(4)：43—45
[32]Penalver A, Pocurull E, borrull F. et al. Comparison of different fibers for the solid-phase microextraction of phthalate esters from water[J]. Journal of Chromatography A,2001,922:377-384.
[33]Cortazar E, Zuloaga O, Sanz J. et al. Multisimplex optimization of the solid-phase microextraction-gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons polychlorinated biphenyls and phthalates from water samples[J]. Journal of Chromatography A, 2002,978:165-175.
[34]王丽霞.超声波萃取测定塑料袋袋装食品中的四种邻苯二甲酸酯[J]. Journal of Chromatography A,2002,963:287-294.
[35]赵贵平,蒋宏健.环境水样中酞酸酯的提取和分析(二)[J].环境化学,2003,22(5)520-521.
[36]戴树桂,张东梅,张仁江等.环境水样中邻苯二甲酸酯固相膜萃取预富集方法[J].中国环境科学,2000,20(2)：146—149.
[37]Penalver A, Garcia V, Pocurull E. et al. Stir bar sorptive extraction and large volume injection gas chromatography to determination a group of endocrine disrupters in water samples[J]. Journal of Chromatography A,2003,1007:1—9.
[38]郑和辉,赵立文,刘玉敏等.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.
[39]Hideyuki K, Aleya B, Satoshi K. et al. Preconcentration of phthalic acid esters in water amples by Saccharomyces cerevisiae immobilized on silica gel[J]. Analytica Chimica Acta. (502):2004, 167-172.
[40]Jara S, Lysebo C, Greibrokk T. et al. Determination of phthalates in water samples using olystryrene solid-phase extraction and liquid chromatography quantification[J]. Analytical imica Acta,2000,407: 165—171.
[41]Mary T, Kelly M. Trace determination of diethyl phthalate in aqueous media by solid-phase micro-extraction liquid chromatography[J]. Chromatography. A,1999,841:177—185.
[42]龚丽雯,卫才银,李京会.顶空固相微萃取气相色谱法测定水中多种增塑剂[J].广东化工,2005,10：59—60.
[43]戴树桂,张东梅,张仁江,等.固相萃取技术预富集环境水样中邻苯二甲酸酯[J].环境科学,2000,21(2)：66—69.
[44]FATTAHI N, ASSADI Y, MILANI HOSSEINI M R, et al. Determination of chlorophenols in water samples using simultaneous dispersive liquid-liquid microextraction and derivatization followed by gas chromatography-electron-capture detection[J]. Journal of Chromatography A,2007,1157: 23—29.
[45]方亚敏.荧光分光光度法测定饮用水和食品包装材料中的酚含量[J].食品工业,2004,24(5)：35—38.
[46]印晖,蔡智鸣,赵文红等.紫外分光光度法测定一次性使用体外循环管道中的DEHP[J].同济大学学报(医学版),2003,5：395—397.
[47]王成云,余煜棉,赖子尼.傅立叶变换红外光谱法定量测定PVC玩具中的DEHP[J].茂名学院学报,2006,15(3)：12—15.
[48]印晖,蔡智鸣,赵文红等.紫外分光光度法测定一次性使用体外循环管道中的DEHP[J].同济大学学报(医学版),2003,5：395—397.
[49]刘丽,牟峻,杨左军,李英,张伟亚等.聚氯乙烯塑料中增塑剂的气相色谱/质谱法分析[J].分析化学研究简报.2002.30(3)：289—291.
[52]廖艳,余煜棉,赖子尼.固相萃取—气相色谱分析水产品中的增塑剂[J].茂名学院学报,2006,15(3)：12—15.
[53]陈海东,鲜啟鸣,邹惠仙等.固相微萃取气相色谱法测定水体中邻苯二甲酸酯[J].分析试验室, 2006,25(3)：32—37.
[54]Gabriela Prokupkova, Katerina Holadova, Jan Poustka. et al. Development of a solid-phase microextraction method for the determination of phthalic acid esters in water[J]. Analytica Chimica Acta,2002,457:211-223.
[55]Luks B, Popp P, Janoszka B. Paschke H. Solid-phase microextraction phthalates from ater[J]. Chromatography. A,2001,938:93—101.
[56]贾宁,许恒智,胡亚丽等.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—22.
[57]赵利剑,杨亚玲,夏静.固相萃取技术的研究[J].四川化工,2005.
[58]王轩.固相萃取技术对样品进行预处理的注意事项[J].甘肃科技,2005,21(9)：94.
[59]SZymskiA., Rykowskal., WasiakW. NewKetoimine Sorbenisin Solid Phase EXtraction for HPLC Analysis of BisPhenolAandOther Endoerine DisruPting, Residuesin Drinking Water[J]. Polish Joumal of Environmental Studies,2006,15(3):479—483.
[60]胡睿,王琳玲,陆晓华.固相萃取-气相色谱法测定水中的酚类污染物[J].环境科学与技术,2005,28(1)：56—65.
[61]刘红河,黄晓群,王晖等.食品中邻苯二甲酸的二极管阵列检测高效液相色谱法[J].职业与健康,2006,22(11)：801—804.
[63]S Jara, Lysebo C, Greibrokk T. et al. Determination of phthalates in water samples using olystryrene solid-phase extraction and liquid chromatography quantification[J]. Analytical imica Acta,2000, 407:165—171.
[64]尤志杰.微量液—液萃取气相色谱法测定水中的苯系物[J].环境与开发,1999,14(1)：48～49.
[65]马继平,陈令新,丁明玉.微液相色谱分离的在线样品预处理技术-固相微萃取和膜萃取[J].分析测试学报,2005,24(4)：116—121.
[66]王立,王继宗.膜萃取—微扑集/气相色谱—质谱测定小体积水样中痕量苯系物的方法[J].环境科学,1999,20(4)：89—92.
[67]王玉,刘菲,孙玉梅等.固相膜萃取与GC-MS联用测定地下水中痕量半挥发性有机物的野外采样方法研究[J].分析试验室,2006,25(4)：25—28.
[68]陈猛,袁东星,许鹏翔.微波萃取法研究进展[J].分析测试学报,1999,18(2)：82—86.
[69]李娟,赵永刚,周春宏.微波萃取高效液相色谱法测定环境空气总悬浮颗粒物中16种多环芳烃[J].环境监测管理与技术,2004,16(6)：24—26.
[70]张银华,李植生,雷志洪,等.湖泊沉积物中邻苯二甲酸酯类的GC/MS分析[J].分析测试学报,1995,14(5)：17—21.
[71]曾锋,陈丽旋,崔昆燕,等.硅胶-氧化铝层析柱-气相色谱法测定沉积物中邻苯二甲酸酯类有机物[J].分析化学,2005,33(8):1063—1067.
[72]Penalver A, Pocurull E. Determination of phthalate esters in water samples by solid-phase micro-extraction and gas chromatography with mass spectrometric detection[J]. Chromatography. A, 2000,872:191—201.
[73]周益奇,许宜平,马梅,等.柱前衍生/气相色谱-质谱法同时测定水中壬基酚和邻苯二甲酸酯[J].分析测试报,2005,24(1)：49—52.
[74]刘振岭,刘二保.新固相微萃取气相色谱技术快速检测水中的邻苯二甲酸酯[J].山西师范大学学报：自然科学版,2000,14(2)：36—41.
[75]刘振岭,肖春华,吴采樱,等.固相微萃取-气相色谱法测定水相中邻苯二甲酸二酯[J].色谱,2000,18(6)：568—570.
[76]赵明桥,李攻科.SPME-GC-MS法测定海水中PAEs及与赤潮关系[J].中山大学学报：自然科学版,2000,39(3)：54.
[77]BROSSA L, M AREeR M, BORRUL F. Application of on2line solid-phase extraction-gas Chromatography-mass spectrometry o the Dtermination of endo rcrine disruptor in water sample[J]. J. Chromatogr. A,2002,963:287—294.
[77]A. Penalver, E. Pocurull, F. Borrull, R. M. Marce. Determination of phthalate esters in water samples by solid-phase microextraction and gas chromatography with mass spectrometric[J]. Journal of Chromatography A,872(2000)191—201.
[78]J. D. Carrillo, C. Salazar, C. Moreta, M. T. Tena. Determination of phthalates in wine by headspace solid-phase microextraction followed by gaschromatography mass spectrometry:Fibre comparison and selection[J]. Journal of Chromatography A,1164(2007)248—261.
[79]中国环境监测总站译.美国EPA标准方法.城市和工业排水中有机化合物的分析方法[J].环境监测资料,1986：3—4.
[80]关根,吴平谷,王惠华,等.邻苯二甲酸酯对城镇供水的污染及现行水处理工艺净化效果的评价[J].环境与健康杂志,2001,18(3)：155—156.
[81]金朝晖,黄国兰,李红亮,等.水中邻苯二甲酸酯类化合物的预富集[J].环境科学,1998,19(1)：30—33.
[82]吴平谷,韩关根.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.
[83]韩关根,吴平谷.邻苯二甲酸脂对城镇供水的污染及现行水处理工艺净化效果的评价[J].环境与健康杂志,2001,18(3)：155—156.
[84]张晓峰.反相高效液相色谱法测定废水中的邻苯二甲酸酯类化合物[J].石化技术,2001,8(4)：225—228.
[85]赵振华,许征帆.北京市大气飘尘和土壤样品中邻苯二甲酸酯的分离鉴定[J].环境化学,1982,1(6)：461466.
[86]孟平蕊,王西奎.土壤中邻苯二甲酸酯的净化分离方法研究[J].山东建材学院学报,1996,10(2)：15—18.
[87]王西奎,王筱梅.大气样品中酞酸酯的分离与测定研究[J].环境科学研究,1995,8(6)：25—28.
[88]王西奎,国伟林,徐广通,等.环境样品中痕量邻苯二甲酸酯的分离与测定[J].分析化学,1995,23(12)：1425—1428.
[89]DESIDERI P G, LEP RIL, CHECCHINIL, et al. Determination of phthalate Eters in air sample[J]. Intern. J. Environ. Anal. Chem.,1995,61(2):319—330.
[90]马玲玲,劳文剑,王学彤,等.北京近郊土壤中痕量半挥发性有机污染物的分析方法研究[J].分析化学,2003,31(9)：1025—1029.
[91]林兴桃,王小逸,陈明,等.固相萃取高效液相色谱法测定水中邻苯二甲酸酯类环境激素[J].环境科学研究,2004,17(5)：71—74.
[92]于涵,胡建英,金晓辉,等.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.
[93]韩素琴,肖春华,吴采樱,等.利用新型聚硅氧烷富勒烯涂层分析水中酞酸酯[J].分析科学学报,2002,18(3)：177—181.
[94]Francisco Jose Lopez-Jimenez, Soledad Rubio, Dolores Perez-Bendi to. Determination of phthalate esters in sewage by hemimi celles-based solid-phase extraction and liquid chromatography-mass spectrometry[J]. Analytical Chimica Acta 551(2005)142—149.
[95]刘红河,黄晓群,王晖等.高效液相色谱-串联质谱法测定食品中邻苯二甲酸酯[J].现代预防医学,2008,35(1)：119—121.
[96]Bao-Yuan Guo, Bei Wen. Xiao-Quan Shan,et al. Separation and determination of phthalates by micellar electrokinetic chromatography. Journal of Chromatography A[J],1095(2005):189-192.
[97]张月琴,吴淑琪.水中有机污染物前处理方法进展[J].分析测试学报,2003,22(3)：106—109.
[98]Jidong Li, Yaqi Cai, Yali Shi, et al. Analysis of phthalates via HPLC-UV in environmental water samples after concentration by solid-phase extraction using ionic liquid mixed hemimicelles[J]. Talanta,2008,74(4):498-504.
[99]Xiujuan Li, Zhaorui Zeng, Yin Chen, et al. Determination of phthalate acid esters plasticizers in plastic by ultrasonic solvent extraction combined with solid-phase microextraction using calix arene fiber[J]. Talanta,2004,63:1013-1019.
[100]Xiang Li, Ming Zhong, Shifen Xu, et al. Determination of phthalates in water samples using polyaniline-based solid-phase microextraction coupled with gas chromatography[J]. Journal of Chromatography A,2006,1135:101-108.
[101]杨丽莉,胡恩宇,母应锋.水中酞酸酯类化合物的测定[J].环境监测管理与技术,2008,20(4)：46～48.
[102]刘慧杰,舒为群.邻苯二甲酸酯类化合物的毒理学效应及对人群健康的危害[J].第三军医大学学报,2004,26(19)：1778～1781.
[103]REZAEE M, ASSADI Y, MILANI HOSSEINI M R, et al. Determination of organic compounds in water using dispersive liquid-liquid microextraction[J]. Journal of Chromatography A,2006, 1116:1-9.
[104]ZHOU Q X, XIE G H, PANG L. Rapid determination of atrazine in environmental water samples by a novel liquid phase microextraction[J]. Chinese Chemical Letters,2008,19:89～91.
[105]ZHAO E C, ZHAO W T, HAN L J, et al. Application of dispersive liquid-liquid microextraction for the analysis of organophosphorus pesticides in watermelon and cucumber[J]. Journal of Chromatography A,2007,1175:137～140.
[106]FATTAHI N, ASSADI Y, MILANI HOSSEINI M R, et al. Determination of chlorophenols in water samples using simultaneous dispersive liquid-liquid microextraction and derivatization followed by gas chromatography-electron-capture detection[J]. Journal of Chromatography A, 2007,1157:23～29.
[107]LI Y Y, WEI G H, HU J, et al. Dispersive liquid-liquid microextraction followed by reversed phase-high performance liquid chromatography for the determination of polybrominated diphenyl ethers at trace levels in landfill leachate and environmental water samples[J]. Analytica Chimica Acta,2008,615:96～103.
[2]Balafas D, Shaw K J, Whitfield F B. Phthalate and adipate esters in Australian packaging materials[J]. Food-Chemistry.1999,65(3):279-287.
[3]Begley, T. H., Biles, J. E., Cunningham, C., Piringer, O. Migration of a UV stabilizer from Polyethylene terephthalate (PET) into food stimulant [J]. Food Additives & Contaminants,2004, 21(10):1007～1014.
[4]叶常明,田康.邻苯二甲酸酯类化合物生物降解动力学[J].环境科学学报,1989,9(1)：7-41.
[5]Toppari J, Larsen JC, ChristiansenP, et al. Male reproductive health and environmental xenoest-rogens[J]. Environ Health Perspect,1996,104(4):741-803.
[6]林兴桃,王小逸,任仁.环境内分泌干扰物邻苯二甲酸酯的研究[J].环境污染与防治,2003,25(10)：286-288.
[7]LoPez-Cervante J etal. Effects of Compression Stacking, Vacuum Packaging and Temperature on the Migration of BisPhenol A from Poly (vinylehloride) Packaging Sheeting into food simulants [J]. ChromatograPhia,2003,58(5/6):327-330.
[8]杨科峰,历曙光,蔡智鸣.食用油及其加热产物中酞酸酯类增塑剂的分析[J].环境与职业医学,2002,19(2)：32-34.
[9]Petersen J H, Breindahl T. Plasticizers in total diet samples, baby food and infant formulae[J]. Food-Additives-and-Contaminants.2000,17(2):133-141.
[10]Tsumura Y, Lshimitsu S, Nakamura, et al. Simultaneous determination of 11 phthalates and di(2-ethylhexyl)adipate in foods by GC/MS[J]. Shokuhin Eiseigaku Zasshi Journal of the Food hygienic Society of Japan,2000,41(4):254-260.
[11]Bluthgen A, Heeschen W H. Secretory and migratory contamination of cow milk with plasticizers especially phthalic acid esters[J]. Bulletin of the international Dairy Federation,1998,330:6-11.
[12]张蕴晖.邻苯二甲酸酯类的雄性生殖发育毒性及健康危险度评价[D]：[博士学位论文].上海： 复旦大学公共卫生学院,2004.
[13]陈荣祈,王建平编著.生态纺织品与环保染化料[M].北京：中国纺织出版社,2002,1：50.
[14]莫测辉,蔡全英,吴启堂等.我国城市污泥中邻苯二甲酸酯的研究[J].中国环境科学,59 2001,21(4)：362-366.
[15]Karen A, Bames, C, etal. Chemical migration and food contact materials[M]. Cambridge, Englangd:Woodhead Publishing limited,2007.
[16]俞力平,高光虎.我国增塑剂工业现状及发展[J].石油化工技术经济,1997,13(2)：26-49.
[17]韩关根,吴平谷,王惠华等.邻苯二甲酸酯对城镇供水的污染及现行水处理工艺净化效果的评价[J].环境与健康杂志,2001,18(3)：155-156.
[18]阎吉昌.环境分析[M].化学工业出版社,2002.12-15.
[19]刘振岭,刘二保.新固相微萃取-气相色谱技术快速检测水中的邻苯二甲酸酯[J].山西师范大学学报.2000,14(2)：36-41.
[20]赵贵平,蒋宏键.环境水样中酞酸酯的提取与分析[J].环境化学.2003,22(5)：520.
[21]Wang Xikui, Guo Weilin, Xu Guangtong, Wang Xiaomei, Meng Pingrui. Degradation of alachlor in aqueous solution by using hydrodynamic cavitation. Chinese Journal of Analytical Chemistry.1995,23(12):1425.
[22]Castillo M, BarceloD, Pereira A S, Neto F R A. Characterization of organic pollutants in industrial effluents by high-temperature gas chromatography-mass spectrometry[J]. Trends in Analytical Chemistry,1999,18(1):26—36
[23]Jaeyer R. J, Rubbin R. J.. Stir bar sorptive extraction and large volume injection gas chromatography to determination a group of endocrine disrupters in water samples[J]. New England Journal of Medicine,1972,278:1114-1118.
[24]石万聪,石志博,蒋平平.增塑剂及其应用[M].北京化学工业出版社.2002：634-638.
[25]边志忠.塑料包装食品中酞酸酯类增塑剂污染状况的检测与研究[D]：[硕士学位论文].无锡：江南大学,2008,6.
[26]BakerVA. Endocrine disrupters-testing strategies to assess human hazard[J]. Toxicol in Vitro,2001, 15(425):413-419.
[27]EN13130-1 Materials and articles in contact with foodstuffs Plastics subject to limitation-Part1:Guide to test methods for the specific migration of substances from Plasties to foods and food simulants and determination of substances in Plasties and the selection of eonditions of exposure to food stimulant.
[28]GB/T17409-1998,中华人民共和国国家标准：食品用包装材料及其制品的浸泡试验方法通则.中华人民共和国卫生部.1998,5.
[29]王琳玲,黄卫红,邵秀梅等.环境内分泌干扰素分析方法进展[J].分析科学学报,2003,19(2)：179-184.
[30]Chee.微波萃取技术萃取海洋沉积物和土壤中的邻苯二甲酸酯[J].环境化学,2003,22(5).
[31]李平波.加速溶剂萃取-高效液相色谱法测定了塑料中两种邻苯二甲酸酯[J].化工装备技术,2002,23(4)：43—45
[32]Penalver A, Pocurull E, borrull F. et al. Comparison of different fibers for the solid-phase microextraction of phthalate esters from water[J]. Journal of Chromatography A,2001,922:377-384.
[33]Cortazar E, Zuloaga O, Sanz J. et al. Multisimplex optimization of the solid-phase microextraction-gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons polychlorinated biphenyls and phthalates from water samples[J]. Journal of Chromatography A, 2002,978:165-175.
[34]王丽霞.超声波萃取测定塑料袋袋装食品中的四种邻苯二甲酸酯[J]. Journal of Chromatography A,2002,963:287-294.
[35]赵贵平,蒋宏健.环境水样中酞酸酯的提取和分析(二)[J].环境化学,2003,22(5)520-521.
[36]戴树桂,张东梅,张仁江等.环境水样中邻苯二甲酸酯固相膜萃取预富集方法[J].中国环境科学,2000,20(2)：146—149.
[37]Penalver A, Garcia V, Pocurull E. et al. Stir bar sorptive extraction and large volume injection gas chromatography to determination a group of endocrine disrupters in water samples[J]. Journal of Chromatography A,2003,1007:1—9.
[38]郑和辉,赵立文,刘玉敏等.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.
[39]Hideyuki K, Aleya B, Satoshi K. et al. Preconcentration of phthalic acid esters in water amples by Saccharomyces cerevisiae immobilized on silica gel[J]. Analytica Chimica Acta. (502):2004, 167-172.
[40]Jara S, Lysebo C, Greibrokk T. et al. Determination of phthalates in water samples using olystryrene solid-phase extraction and liquid chromatography quantification[J]. Analytical imica Acta,2000,407: 165—171.
[41]Mary T, Kelly M. Trace determination of diethyl phthalate in aqueous media by solid-phase micro-extraction liquid chromatography[J]. Chromatography. A,1999,841:177—185.
[42]龚丽雯,卫才银,李京会.顶空固相微萃取气相色谱法测定水中多种增塑剂[J].广东化工,2005,10：59—60.
[43]戴树桂,张东梅,张仁江,等.固相萃取技术预富集环境水样中邻苯二甲酸酯[J].环境科学,2000,21(2)：66—69.
[44]FATTAHI N, ASSADI Y, MILANI HOSSEINI M R, et al. Determination of chlorophenols in water samples using simultaneous dispersive liquid-liquid microextraction and derivatization followed by gas chromatography-electron-capture detection[J]. Journal of Chromatography A,2007,1157: 23—29.
[45]方亚敏.荧光分光光度法测定饮用水和食品包装材料中的酚含量[J].食品工业,2004,24(5)：35—38.
[46]印晖,蔡智鸣,赵文红等.紫外分光光度法测定一次性使用体外循环管道中的DEHP[J].同济大学学报(医学版),2003,5：395—397.
[47]王成云,余煜棉,赖子尼.傅立叶变换红外光谱法定量测定PVC玩具中的DEHP[J].茂名学院学报,2006,15(3)：12—15.
[48]印晖,蔡智鸣,赵文红等.紫外分光光度法测定一次性使用体外循环管道中的DEHP[J].同济大学学报(医学版),2003,5：395—397.
[49]刘丽,牟峻,杨左军,李英,张伟亚等.聚氯乙烯塑料中增塑剂的气相色谱/质谱法分析[J].分析化学研究简报.2002.30(3)：289—291.
[52]廖艳,余煜棉,赖子尼.固相萃取—气相色谱分析水产品中的增塑剂[J].茂名学院学报,2006,15(3)：12—15.
[53]陈海东,鲜啟鸣,邹惠仙等.固相微萃取气相色谱法测定水体中邻苯二甲酸酯[J].分析试验室, 2006,25(3)：32—37.
[54]Gabriela Prokupkova, Katerina Holadova, Jan Poustka. et al. Development of a solid-phase microextraction method for the determination of phthalic acid esters in water[J]. Analytica Chimica Acta,2002,457:211-223.
[55]Luks B, Popp P, Janoszka B. Paschke H. Solid-phase microextraction phthalates from ater[J]. Chromatography. A,2001,938:93—101.
[56]贾宁,许恒智,胡亚丽等.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—22.
[57]赵利剑,杨亚玲,夏静.固相萃取技术的研究[J].四川化工,2005.
[58]王轩.固相萃取技术对样品进行预处理的注意事项[J].甘肃科技,2005,21(9)：94.
[59]SZymskiA., Rykowskal., WasiakW. NewKetoimine Sorbenisin Solid Phase EXtraction for HPLC Analysis of BisPhenolAandOther Endoerine DisruPting, Residuesin Drinking Water[J]. Polish Joumal of Environmental Studies,2006,15(3):479—483.
[60]胡睿,王琳玲,陆晓华.固相萃取-气相色谱法测定水中的酚类污染物[J].环境科学与技术,2005,28(1)：56—65.
[61]刘红河,黄晓群,王晖等.食品中邻苯二甲酸的二极管阵列检测高效液相色谱法[J].职业与健康,2006,22(11)：801—804.
[63]S Jara, Lysebo C, Greibrokk T. et al. Determination of phthalates in water samples using olystryrene solid-phase extraction and liquid chromatography quantification[J]. Analytical imica Acta,2000, 407:165—171.
[64]尤志杰.微量液—液萃取气相色谱法测定水中的苯系物[J].环境与开发,1999,14(1)：48～49.
[65]马继平,陈令新,丁明玉.微液相色谱分离的在线样品预处理技术-固相微萃取和膜萃取[J].分析测试学报,2005,24(4)：116—121.
[66]王立,王继宗.膜萃取—微扑集/气相色谱—质谱测定小体积水样中痕量苯系物的方法[J].环境科学,1999,20(4)：89—92.
[67]王玉,刘菲,孙玉梅等.固相膜萃取与GC-MS联用测定地下水中痕量半挥发性有机物的野外采样方法研究[J].分析试验室,2006,25(4)：25—28.
[68]陈猛,袁东星,许鹏翔.微波萃取法研究进展[J].分析测试学报,1999,18(2)：82—86.
[69]李娟,赵永刚,周春宏.微波萃取高效液相色谱法测定环境空气总悬浮颗粒物中16种多环芳烃[J].环境监测管理与技术,2004,16(6)：24—26.
[70]张银华,李植生,雷志洪,等.湖泊沉积物中邻苯二甲酸酯类的GC/MS分析[J].分析测试学报,1995,14(5)：17—21.
[71]曾锋,陈丽旋,崔昆燕,等.硅胶-氧化铝层析柱-气相色谱法测定沉积物中邻苯二甲酸酯类有机物[J].分析化学,2005,33(8):1063—1067.
[72]Penalver A, Pocurull E. Determination of phthalate esters in water samples by solid-phase micro-extraction and gas chromatography with mass spectrometric detection[J]. Chromatography. A, 2000,872:191—201.
[73]周益奇,许宜平,马梅,等.柱前衍生/气相色谱-质谱法同时测定水中壬基酚和邻苯二甲酸酯[J].分析测试报,2005,24(1)：49—52.
[74]刘振岭,刘二保.新固相微萃取气相色谱技术快速检测水中的邻苯二甲酸酯[J].山西师范大学学报：自然科学版,2000,14(2)：36—41.
[75]刘振岭,肖春华,吴采樱,等.固相微萃取-气相色谱法测定水相中邻苯二甲酸二酯[J].色谱,2000,18(6)：568—570.
[76]赵明桥,李攻科.SPME-GC-MS法测定海水中PAEs及与赤潮关系[J].中山大学学报：自然科学版,2000,39(3)：54.
[77]BROSSA L, M AREeR M, BORRUL F. Application of on2line solid-phase extraction-gas Chromatography-mass spectrometry o the Dtermination of endo rcrine disruptor in water sample[J]. J. Chromatogr. A,2002,963:287—294.
[77]A. Penalver, E. Pocurull, F. Borrull, R. M. Marce. Determination of phthalate esters in water samples by solid-phase microextraction and gas chromatography with mass spectrometric[J]. Journal of Chromatography A,872(2000)191—201.
[78]J. D. Carrillo, C. Salazar, C. Moreta, M. T. Tena. Determination of phthalates in wine by headspace solid-phase microextraction followed by gaschromatography mass spectrometry:Fibre comparison and selection[J]. Journal of Chromatography A,1164(2007)248—261.
[79]中国环境监测总站译.美国EPA标准方法.城市和工业排水中有机化合物的分析方法[J].环境监测资料,1986：3—4.
[80]关根,吴平谷,王惠华,等.邻苯二甲酸酯对城镇供水的污染及现行水处理工艺净化效果的评价[J].环境与健康杂志,2001,18(3)：155—156.
[81]金朝晖,黄国兰,李红亮,等.水中邻苯二甲酸酯类化合物的预富集[J].环境科学,1998,19(1)：30—33.
[82]吴平谷,韩关根.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.
[83]韩关根,吴平谷.邻苯二甲酸脂对城镇供水的污染及现行水处理工艺净化效果的评价[J].环境与健康杂志,2001,18(3)：155—156.
[84]张晓峰.反相高效液相色谱法测定废水中的邻苯二甲酸酯类化合物[J].石化技术,2001,8(4)：225—228.
[85]赵振华,许征帆.北京市大气飘尘和土壤样品中邻苯二甲酸酯的分离鉴定[J].环境化学,1982,1(6)：461466.
[86]孟平蕊,王西奎.土壤中邻苯二甲酸酯的净化分离方法研究[J].山东建材学院学报,1996,10(2)：15—18.
[87]王西奎,王筱梅.大气样品中酞酸酯的分离与测定研究[J].环境科学研究,1995,8(6)：25—28.
[88]王西奎,国伟林,徐广通,等.环境样品中痕量邻苯二甲酸酯的分离与测定[J].分析化学,1995,23(12)：1425—1428.
[89]DESIDERI P G, LEP RIL, CHECCHINIL, et al. Determination of phthalate Eters in air sample[J]. Intern. J. Environ. Anal. Chem.,1995,61(2):319—330.
[90]马玲玲,劳文剑,王学彤,等.北京近郊土壤中痕量半挥发性有机污染物的分析方法研究[J].分析化学,2003,31(9)：1025—1029.
[91]林兴桃,王小逸,陈明,等.固相萃取高效液相色谱法测定水中邻苯二甲酸酯类环境激素[J].环境科学研究,2004,17(5)：71—74.
[92]于涵,胡建英,金晓辉,等.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.
[93]韩素琴,肖春华,吴采樱,等.利用新型聚硅氧烷富勒烯涂层分析水中酞酸酯[J].分析科学学报,2002,18(3)：177—181.
[94]Francisco Jose Lopez-Jimenez, Soledad Rubio, Dolores Perez-Bendi to. Determination of phthalate esters in sewage by hemimi celles-based solid-phase extraction and liquid chromatography-mass spectrometry[J]. Analytical Chimica Acta 551(2005)142—149.
[95]刘红河,黄晓群,王晖等.高效液相色谱-串联质谱法测定食品中邻苯二甲酸酯[J].现代预防医学,2008,35(1)：119—121.
[96]Bao-Yuan Guo, Bei Wen. Xiao-Quan Shan,et al. Separation and determination of phthalates by micellar electrokinetic chromatography. Journal of Chromatography A[J],1095(2005):189-192.
[97]张月琴,吴淑琪.水中有机污染物前处理方法进展[J].分析测试学报,2003,22(3)：106—109.
[98]Jidong Li, Yaqi Cai, Yali Shi, et al. Analysis of phthalates via HPLC-UV in environmental water samples after concentration by solid-phase extraction using ionic liquid mixed hemimicelles[J]. Talanta,2008,74(4):498-504.
[99]Xiujuan Li, Zhaorui Zeng, Yin Chen, et al. Determination of phthalate acid esters plasticizers in plastic by ultrasonic solvent extraction combined with solid-phase microextraction using calix arene fiber[J]. Talanta,2004,63:1013-1019.
[100]Xiang Li, Ming Zhong, Shifen Xu, et al. Determination of phthalates in water samples using polyaniline-based solid-phase microextraction coupled with gas chromatography[J]. Journal of Chromatography A,2006,1135:101-108.
[101]杨丽莉,胡恩宇,母应锋.水中酞酸酯类化合物的测定[J].环境监测管理与技术,2008,20(4)：46～48.
[102]刘慧杰,舒为群.邻苯二甲酸酯类化合物的毒理学效应及对人群健康的危害[J].第三军医大学学报,2004,26(19)：1778～1781.
[103]REZAEE M, ASSADI Y, MILANI HOSSEINI M R, et al. Determination of organic compounds in water using dispersive liquid-liquid microextraction[J]. Journal of Chromatography A,2006, 1116:1-9.
[104]ZHOU Q X, XIE G H, PANG L. Rapid determination of atrazine in environmental water samples by a novel liquid phase microextraction[J]. Chinese Chemical Letters,2008,19:89～91.
[105]ZHAO E C, ZHAO W T, HAN L J, et al. Application of dispersive liquid-liquid microextraction for the analysis of organophosphorus pesticides in watermelon and cucumber[J]. Journal of Chromatography A,2007,1175:137～140.
[106]FATTAHI N, ASSADI Y, MILANI HOSSEINI M R, et al. Determination of chlorophenols in water samples using simultaneous dispersive liquid-liquid microextraction and derivatization followed by gas chromatography-electron-capture detection[J]. Journal of Chromatography A, 2007,1157:23～29.
[107]LI Y Y, WEI G H, HU J, et al. Dispersive liquid-liquid microextraction followed by reversed phase-high performance liquid chromatography for the determination of polybrominated diphenyl ethers at trace levels in landfill leachate and environmental water samples[J]. Analytica Chimica Acta,2008,615:96～103.