Study of Phthalic Acid Esters in Food and Plastics rubber by GC-EI/MS and CG-MS/MS

酞酸酯类化合物（Phthalicacidesters，简称PAEs）是塑料制品中不可缺少的一种改性添加剂。过去人们一直认为PAEs的毒性低，因而毫无限制地生产，但近年来的研究结果表明，尽管它们在环境中的残留量不大，急性毒性不明显，但具有致突变、致癌和致畸性，并可混合在食物、空气和其它物质中，通过消化、呼吸器官和皮肤进入人体，已对人体健康构成了潜在危害，故PAEs被称为“第二个全球性PCBs污染物”。 本学位论文致力于动物内脏，蔬菜以及塑料橡胶中十几种PAEs残留分析的方法研究，针对不同的样品体系，建立了以不同溶剂为提取剂的超声提取、Florisil硅土净化预分离、GC-EI/MS定性定量分析...Phthalic acid esters ( PAEs ) are widely used as plasticizers all over the world. In the past year, people had thougt that they were less toxic, but recently, more and more investigations have shown that PAEs are Environmental Incretion. Usually，they combine with the food, the air and other things, coming into body through digestion, respiration or skin and leading to the instability of internal s...学位：理学硕士院系专业：化学化工学院化学系_分析化学学号：2005130181

气相色谱-质谱联用同时测定蔬菜中16种邻苯二甲酸酯残留

研究了蔬菜中16种邻苯二甲酸酯(PAEs)环境激素残留的气相色谱-电子轰击离子源质谱(GC-EI/MS)分析方法。优化了样品的前处理条件,以苯甲酸苄酯(BB)为内标物,采用GC-EI/MS的选择离子检测方式(SIM)进行定性和定量分析。当蔬菜样品的加标浓度水平分别为100和200μg/kg时,加标回收率为70.9%~123.0%,相对标准偏差为1.6%~15%。除邻苯二甲酸二甲氧基已酯(DMEP)外,其它15种PAEs的方法检测限(MDL)均为0.11~2.77μg/kg。在50.0~800.0μg/kg浓度范围内16种PAEs都呈现良好的线性关系,r为0.99623~0.99998。方法已用于5种蔬菜中16种痕量PAEs残留的分析

基质固相分散-气相色谱-离子阱串联质谱法分析牛奶中有机磷农药

将改进的基质固相分散法与GC-MS/MS分析方法结合应用于牛奶中13种有机磷农药残留的同时分析。优化各样品前处理参数后,样品与分散剂中性氧化铝研磨后,采用乙腈超声提取。过滤浓缩后以灭线磷为内标物,采用GC-MS/MS进行定性与定量分析。从样品前处理到分析约需1 h,当样品的加标水平为50、200μg/kg时,平均加标回收率为70.4%~117.6%,相对标准偏差为0.8%~19%;除倍硫磷和毒死蜱的检测限分别为5.60和9.35μg/kg外,其它11种有机磷农药的检测限均在0.37~3.77μg/kg之间;线性范围为25~500μg/kg,相关系数均大于0.9949

Determination of 19 Organophosphorous Pesticides Residues in Milk Drink and Milk Powder by Gas Chromatography-Negative Chemical Ionization-Mass Spectrometry

将气相色谱-负离子化学源质谱法(GC-NCIMS)应用于牛奶饮品和奶粉中19种有机磷农药残留的同时分析。牛奶饮品和奶粉经乙腈提取剂超声提取、Florisil硅藻土和中性氧化铝双净化剂同时净化及正己烷-乙酸乙酯(体积比1∶1)混合洗脱剂洗脱后,以三苯基磷酸酯为内标物,采用GC-NCI MS的选择离子监测方式(SIM)定性与定量分析。当牛奶饮品和奶粉的加标浓度水平为20、100、500μg/kg时,平均加标回收率为64.5%~129%,相对标准偏差为2%~20%;除喹硫磷的方法检出限(MDL)为2.4μg/kg外,其余18种有机磷农药的MDL均小于1.0μg/kg;线性范围为10~500μg/kg,相关系数均大于0.9988,此分析方法成功地应用于牛奶饮品和奶粉中多种痕量有机磷农药残留的分析。A rapid method was developed for the determination of 19 organophosphorous pesticides residues in commercial milk drink and milk powder.Under optimized conditions,the pesticides were extracted from milk drink or milk powder with acetonitrile in an ultrasonic bath and cleaned up on a Florisil and neutral alumina column,and were determined by gas chromatography with negative chemical ionization mass spectrometric detection in the selected ion monitoring mode with triphenyl phosphate as internal standard.The recoveries for all the pesticides studied ranged from 64.5% to 129% with a relative standard deviation range of 2%-20%.The detection limit of the method was less than 1.0 μg/kg for most of the pesticides except for the quinolphos.The linear ranges of the calibration curves ranged from 10 μg/kg to 500 μg/kg with correlation coefficients of 0.998 8.The proposed method was successfully applied to the analysis of these compounds in milk drink and milk powder

Simultaneous determination of 14 phthalate ester residues in animal innards by gas chromatography-mass spectrometry with electron impact ionization

开展了动物内脏中14种酞酸酯类(PAEs)环境激素残留的气相色谱-电子轰击离子源质谱(GC-EI/MS)分析方法的研究,优化与选择了动物内脏样品的前处理条件。动物内脏样品经正己烷-二氯甲烷(体积比为1∶1)混合提取剂超声提取、Florisil硅土固相萃取柱净化与乙酸乙酯-正己烷(体积比为2∶3)混合洗脱剂洗脱和浓缩后,以邻苯二甲酸二苯基酯(DPhP)为内标物,采用GC-EI/MS的选择离子检测方式(SIM)进行定性和定量分析。当猪肝样品的加标浓度水平为100,200,400μg/kg时,加标回收率为60%~110%,相对标准偏差为0.8%~10.3%。除邻苯二甲酸二甲氧基乙酯(DMEP)与邻苯二甲酸二(2-乙氧基乙基)酯(DEEP)的方法检出限(MDL)分别为3.30μg/kg与2.25μg/kg外,其余12种PAEs的MDL均不大于1.74μg/kg;线性范围为50.0~800.0μg/kg,相关系数均大于0.9994。该分析方法已成功地应用于6种动物内脏中14种痕量PAEs残留的分析。An analytical multiresidue method was developed for the simultaneous determination of 14 phthalate esters (PAEs) in animal innards by gas chromatography-mass spectrometry with electron impact ionization (GC-EI/MS). After the optimization of different parameters such as the extraction solvent, PAEs were extracted from animal innards with hexane-dichloromethane (1∶1, v/v) in an ultrasonic bath and cleaned up on a Florisil column, then were determined by GC-EI/MS in selected ion monitoring mode with diphenyl phthalate (DPhP) as internal standard. The recovery studies were performed at 100, 200 and 400 μg/kg levels for each PAE, and the recoveries ranged from 60%-110% with the relative standard deviations between 0.8% and 10.3% for different PAEs. The detection limit of the method was less than 1.74 μg/kg for most of PAEs except dimethoxyethyl phthalate (DMEP) and di(2-ethoxyethyl) phthalate (DEEP). The method was linear over the range of 50.0-800.0 μg/kg with the correlation coefficients larger than 0.999 4. The method has been successfully applied to the determination of 14 PAEs in six animal innards.国家基础科学人才培养基金(J0630429)项目资

Determination of Five Polybrominated Diphenyl Ether Residues in Deep-Sea Fish Oil Using Gas Chromatography-Negative Chemical Ionization/Mass Spectrometry

建立了气相色谱-负离子化学电离质谱法(GC-NCI/MS)同时分析深海鱼油食品中5种多溴联苯醚残留的分析方法。深海鱼油食品用正己烷超声提取、中性与酸性硅胶色谱柱净化和正己烷洗脱后,以PCB103为内标物,采用GC-NCI/MS的选择离子监测方式(SIM)分析;同时探讨了5种多溴联苯醚的NCI/MS特征离子的断裂机理。当空白深海鱼油食品的加标浓度为20.0和100.0μg/kg时,加标回收率为88.6%-111.3%,相对标准偏差为3.8%-13.5%,方法的检测限为0.77-1.34μg/kg,线性范围为1.0-500.0μg/kg,相关系数均大于0.999 2。此方法已成功地应用于深海鱼油食品中5种痕量多溴联苯醚残留的同时分析。Polybrominated diphenyl ethers(PBDEs) are a kind of brominated flame retardants(BFRs),which refer to compounds used in some plastics to impede or even suppress the combustion process.As the emission or disposal of plastics,PBDE residues have been found in both environment and biota.In this work,an analytical method was developed for the simultaneous determination of 5 PBDE residues in deep-sea fish oil.PBDEs were extracted from deep-sea fish oil with n-hexane,cleaned up on a silical gel column,and determined by using gas chromatography-negative chemical ionization/mass spectrometry(GC-NCI/MS) in the selected ion-monitoring(SIM) mode,with PCB103 as the internal standard.Meanwhile,the characteristic ion and fragmentation mechanism of some PBDEs in NCI/MS were evaluated.Recovery studies were performed at 20.0 and 100.0 μg/kg fortification levels for each PBDE,and the recoveries ranged from 88.6% to 111.3% with relative standard deviations between 3.8% and 13.5% for different PBDEs.The limits of detection(LOD) were from 0.77 to 1.34 μg/kg for different PBDEs.The developed method was linear over the range assayed,1.0-500.0 μg/kg,with correlation coefficients larger than 0.999 2.The developed method has also been successfully applied to the determination of PBDEs in several deep-sea fish oil samples and the three most abundant PBDEs(PBDE-47,PBDE-99 and PBDE-100) were found

Determination of nine polybrominated diphenyl ethers residues in animal liver by gas chromatography-negative chemical ionization/mass spectrometry

建立了动物肝脏中9种PBDEs残留量的气相色谱-负化学离子源/质谱(GC-NCI/MS)的分析方法。动物肝脏样品经V(正己烷)∶V(丙酮)=1∶1超声辅助提取,中性与酸性硅胶层析柱净化和V(正已烷)∶V(CH2Cl2)=1∶1洗脱和浓缩后,以PCB-103为内标物,采用GC-NCI/MS的选择离子监测方式(SIM)对其中的9种PBDEs残留量进行了定性与定量分析。当动物肝脏空白样品的加标质量浓度为5.0、20.0μg/kg(PBDE-183为6.0、24.0μg/kg)时,9种PBDEs的平均加标回收率为75.1%~88.2%,相对标准偏差为3.3%~7.9%,方法检出限均小于0.07μg/kg;线性范围除PBDE-183为0.12~600.0μg/kg外,其余8种PBDEs为0.1~500.0μg/kg,相关系数都大于0.9993。所建立的分析方法已用于5种动物肝脏的8个样品中9种PBDEs残留量的分析。An analytical method for the determination of nine polybrominated diphenyl ethers(PBDEs) residue in animal liver is described based on gas chromatography coupled with negative chemical ionization mass spectrometry(GC-NCI/MS).In this paper,hexane/acetone(1/1,V/V) and hexane/dichloromethane(1/1,V/V) were used as the extraction and elution solvents.After the extraction was cleaned by silica and acid silica,the analysis of nine PBDEs in samples was accomplished using GC-NCI/MS in the selected ion monitoring mode(SIM) with PCB-103 as the internal standard(IS).This method performs well: the average recoveries of spiked samples range from 75.1% to 88.2% with relative standard deviations between 3.3% and 7.9%,method detection limit is lower than 0.07 μg/kg,the range of linearity is from 0.1 to 500.0 μg/kg for the other eight PBDEs except 0.12 to 600.0 μg/kg for PBDE-183,with correlation coefficients larger than 0.9993.The method has been applied successfully to the determination of nine polybrominated diphenyl ethers residues in eight samples of five animal livers.国家基础科学人才培养基金(J0630429)项目资

Analysis of Nine Polybrominated Diphenyl Ethers Residue in Marine Samples by Gas Chromatography-Negative Chemical Ionization/Mass Spectrometry

建立了海产品中九种多溴联苯醚(PBDEs)残留的气相色谱-负化学离子源/质谱(GC-NCI/MS)分析方法。采用正己烷提取剂超声提取、Florisil硅藻土净化柱净化和正己烷洗脱剂洗脱的样品前处理方法,以PCB-103作为内标物,以GC-NCI/MS的选择离子监测方式(SIM)对海产品中九种PBDEs残留进行了定性与定量分析。分析方法的线性相关系数均≥0.9988,九种PBDEs两种添加浓度水平时的平均加标回收率为88.1%~97.3%,相对标准偏差为2.0%~6.6%,方法检出限均小于0.106 ng/g。线性范围除PBDE-183为0.60~300.0 ng/g外,其余八种PBDEs为0.50~250.0 ng/g。同时分析了紫菜、海带、鲜海带、鱼干和花蛤干等海产品,在这些海产品干货中都检出了较多种的PBDEs残留。In this paper,gas chromatography coupled with negative chemical ionization mass spectrometric(GC-NCI/MS) was described to detect the residue of nine polybrominated diphenyl ethers in marine samples.Samples was extracted by hexane and cleaned up on a Florisil column,then were determined by GC-NCI/MS in the selected ion monitoring mode and with PCB-103 as the internal standard.The recovery studies were performed at 10.0 and 25.0 ng/g fortification levels for eight PBDEs(12.0 and 30.0 ng/g for PBDE-183),and the recoveries ranged from 88.1%~97.3% with a relative standard deviation between 2.0%~6.6%.The developed method was linear over the range of 0.50~250.0 μg/L(for PBDE-183: 0.60~300.0 μg/L) with correlation coefficient in the range of 0.9988~0.9999,and the detection limits are lower than 0.106 ng/g.The method was successfully applied to the determination of nine polybrominated diphenyl ethers residue in five marine samples.国家基础科学人才培养基金(No.J0630429

Determination of five polybrominated diphenyl ethers in tea leaves by gas chromatography-mass spectrometry-negative chemical ionization

将气相色谱-负离子化学源-质谱法(GC-NCI-MS)应用于快速分析茶叶中5种多溴联苯醚残留量。茶叶样品以正己烷作为提取剂,采用超声辅助提取法,提取液经中性氧化铝和Florisil硅藻土层析柱净化和正己烷洗脱后,以PCB-103为内标物和GC-NCI-MS的选择离子监测方式(SIM)进行定性与定量分析。5种多溴联苯醚的平均加标回收率为70.9%~81.7%,相对标准偏差为6.9%~11.0%,方法检出限小于0.12μg/kg,线性范围为0.1~500μg/kg,相关系数都大于0.9990。所分析的8种茶叶样品中6种含有微量的PBDE-47,1种茶叶样品含有微量的PBDE-99。A rapid method based on ultrasonic extraction was developed for the determination of five polybrominated diphenyl ethers in tea leaves.Hexane was used as the extraction solvent and elution solvent,after the extraction was cleaned by the cartridge filling with alumina and Florisil,the analysis of samples was accomplished using gas chromatography with negative chemical ionization mass spectrometric detection(GC-NCI-MS) in the selected ion monitoring mode(SIM),and with PCB-103 as internal standard(IS).The average recoveries of the standard samples spiked ranged from 70.9% to 81.7% with relative standard deviation between 6.9 and 11.0% for the five different polybrominated diphenyl ethers(PBDEs),and the detection limit of the method was smaller than 0.12 μg/kg.The lineer range is from 0.1 to 500 μg/kg,and the correlation coefficients were larger than 0.9990.Six out of the eight determinated tea leaves had PBDE-47,and one had PBDE99