Study and Application of Analytical Method for Polybrominated Biphenyls and Polybrominated Diphenyl Ethers Residue in Food and Electrical and Electronic Products by Gas Chromatography-Mass Spectrometr

社会的进步使得人们越来越多地关注人类的健康，科学技术的发展也使得人们对食品安全性问题有了更多的了解。食品安全不仅影响消费者的健康，而且影响国际食品贸易的发展，甚至影响社会的稳定，因此食品安全问题已成为全世界普遍关心的热点问题。 本论文致力于食品和电子电器产品中多溴联苯(PolybrominatedBiphenyls，PBBs)和多溴联苯醚(PolybrominatedDiphenylEthers，PBDEs)残留的气相色谱－负离子化学源质谱联用(GasChromatography-NegativeChemicalIonization-MassSpectrometry，GC-NCI/MS)分析...People pay more attention to their own health because of the progress of the society, at the same time, people know more about the food security problem because of the development of science and technology. The food security not only affects the healthy of the consumer, but also affects progress of the international food trade, even affects the stabilization of the society. So the food security pr...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：X20032500

GC Determination of Decabromodiphenyl Ether in Electronic Products

提出了气相色谱法测定电子产品中十溴联苯醚的方法。样品先后用甲苯超声提取和浓硫酸提取,所得有机相经硅胶层析柱净化和二氯甲烷洗脱后,以PCb-103为内标物,采用气相色谱法,用电子捕获检测器检测。十溴联苯醚与内标峰面积的比值对十溴联苯醚与内标物质量浓度比值在0.01--10.0 Mg.l-1范围内呈线性,检出限(3S/n)为8.0μg.kg-1。方法用于电视机塑料外壳中十溴联苯醚的测定,相对标准偏差(n=5)为2.2%--8.9%,回收率在92.1%--95.3%之间。Contents of decabromodiphenyl ether(BDE-209) in electronic products was determined by GC.The sample was extracted with toluene and con.H2SO4 in succession.The organic phase was purified and concentrated on silica-gel chromatographic column and eluted with dichloromethane.The dluate was used for GC-ECD analysis after adding PCB-103 as internal standard.Linear relationship between values of peak area ratios of the BDE-209 standard to internal standard and mass concentration of BDE-209 was obtained in the range of 0.01-10.0 mg·L-1,with detection limit(3S/N) of 8.0 μg·kg-1.The proposed method was applied to the analysis of plastic shells of TV-sets,giving values of RSD′s(n=5) in the range of 2.2%-8.9% and recovery in the range of 92.1%-95.3%.国家基础科学人才培养基金(J0630429

HPCE Determination of Ephedrine Hydrochloride and Pseudo-Ephedrine Hydrochloride in Drugs with Enrichment by Electro-stacking

应用电堆积柱上富集-高效毛细管电泳法测定了6种药品中盐酸麻黄碱和盐酸伪麻黄碱含量。试验选择了以下分析条件:1检测波长205 nM;2内标物为间苯二酚;3运行液为PH9.2的40 MMOl·l-1硼砂缓冲溶液;4分离电压20 kV;5进样时间10 S;6分离温度25℃。麻黄碱及伪麻黄碱质量浓度在1--400 Mg·l-1之间与相应的相对峰面积值(即被测物与内标物的峰面积之比)呈线性关系。方法的检出限(3S/n)为0.35 Mg·l-1(麻黄碱)和0.29 Mg·l-1(伪麻黄碱)。以2种药品作基体加入标准溶液做回收试验,测得平均回收率依次为101.1%及103.6%。HPCE with electro-stacking enrichment was applied to the determination of ephedrine hydrochloride and pseudo-ephedrine hydrochloride in 6 drugs.Analytical conditions were studied and following optimized parameters were given: ① wavelength for UV-detection: 205 nm;② internal standard: resorcinol;③ electrophoretic medium: 40 mmol·L-1 borax solution(pH 9.2);④ separation voltage: 20 kV;⑤ time of sample introduction: 10 s;⑥ temperature of capillary: 25 ℃.Linear relationships between values of relative peak area(i.e.,ratio of peak area of the analyte to peak area of internal standard) and concentration of ephedrine and pseudo-ephedrine were kept in the same range of 1 to 400 mg·L-1,with detection limits(3S/N) of 0.35 mg·L-1 and 0.29 mg·L-1 respectively.Recovery was tested by standard addition method using 2 drug samples as matrixes,giving values of average recovery of 101.1%(for ephedrine) and 103.6%(for pseudo-ephedrine).龙岩学院第二批教育教学改革立项项目(岩学院教[2009]40号)资

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

Multiresidue Determination of Organophosphorus Pesticide Residues in Vegetables and Fruit by Gas Chromatography-Negative Ion Chemical Ionization-Mass Spectrometry

将气相色谱-负离子化学电离质谱法(GC-NC I-M S)应用于蔬菜水果中9种有机磷农药残留的分析测定,初步解析了这些农药的NC I-M S特征阴离子结构和断裂机理,并初步探讨了GC-NC I-M S分析蔬菜水果中有机磷农药残留时基体效应的影响。采用空白样品基体匹配校准曲线法(M C)进行定量分析,有效地降低了基体效应的影响。蔬菜水果样品用乙酸乙酯超声提取,以乙硫磷为内标物,采用GC-NC I-M S的选择离子监测方式(S IM)进行定性和定量分析。9种有机磷农药的方法检测限为0.12~1.0μg/kg。在方法的检测限与1 000μg/kg范围内,线性相关系数都大于0.999 3。当空白蔬菜水果(西红柿)样品的加标水平为100,400,800μg/kg时,平均加标回收率为78%~126%,相对标准偏差为0.58%~14.7%。An analytical method of gas chromatography coupled with negative ion chemical ionization-mass spectrometry for simultaneous determination of nine organophosphorus pesticide residues in vegetables and fruit has been developed,and the negative ions structure and partition mechanism of the nine organophosphorus pesticides were interpreted.Meanwhile,the matrix effect for sample analysis was discussed,and matrix-matched calibration for quantification was introduced to reduce the matrix effect in this method.Pesticides were extracted from sample with ethyl acetate in an ultrasonic bath,then determined by gas chromatography-mass spectrometry operated in negative chemical ionization mode and quantified in selective ion monitoring mode,and ethion was used as an internal standard.The detection limits of the method were 0.12-1.0 μg/kg for the nine organophosphorus pesticides,and the relative coefficients were higher than(0.9993).A blank sample(tomato) was spiked at 100,400,800 μg/kg for each pesticide,and the recoveries were determined to be from 78% to 126% with relative standard deviations from 0.58% to 14.7% for the pesticides

Determination of Multiple Pesticide Residues in Honey Using Gas Chromatography-Mass Spectrometry

开展了蜂蜜中23种农药残留的气相色谱-电子轰击离子源质谱(GC-E I/M S)分析方法的研究,并对其中3种农药的E I/M S碎片离子的断裂机理与结构进行了初步解析。探讨了蜂蜜试样前处理条件的优化与选择。将蜂蜜试样用乙酸乙酯提取剂超声提取、F lo ris il硅藻土色谱柱净化和正己烷-乙酸乙酯(体积比为7∶3)混合洗脱剂洗脱后,以PCB103为内标物,采用选择离子监测(S IM)方式下的GC-E I/M S分析。当试样的加标浓度为50,100和200μg/kg时,加标回收率为82%~120%,相对标准偏差小于11.0%。23种农药的检测限都小于10.0μg/kg,线性范围为10~500μg/kg,相关系数都大于0.995。此分析方法已成功地应用于蜂蜜中23种痕量农药残留的分析。An analytical method was developed for the simultaneous determination of 23 pesticide residues in various commercial honeys.Meanwhile,the characteristic ions and fragmentation mechanism of three pesticides in the process of electron ionization mass spectrometry(EI/MS) were evaluated.After the optimization of different parameters such as the extraction solvent,pesticides were extracted from honey with ethyl acetate in an ultrasonic bath,cleaned up on a Florisil column by an elution of mixture of hexane and ethyl acetate(7∶ 3,v/v), and analyzed by gas chromatography-electron ionization mass spectrometry(GCEI/MS) in the selected ion monitoring mode(SIM) with PCB103 as internal standard.Recovery studies were performed at 50,100 and 200 μg/kg fortification levels for each pesticide,and the recoveries ranged from 82% to 120% with relative standard deviations between 1.8% and 11.0% for different pesticides.The limit of detection was less than 10.0 μg/kg for all the pesticides.The developed method was linear in the range of 10-500 μg/kg,with correlation coefficients larger than 0.995.Finally,the developed analytical method has been successfully applied to the determination of pesticide residues in several honey samples

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

Composition Analysis of Bentonite Deposited in Longyan City and Effect Appraisal of Na-modified Bentonite

建立了酸溶和碱熔融主称样快速分析系统,获得了福建龙岩膨润土矿物的组成。探讨了用XRD衍射分析、膨胀容、吸蓝量和CEC等指标来检验和评价钠化改型后膨润土质量的方法。In this paper,bentonite deposited in Longyan City,Fujian Province is tested and analyzed through sample digestion techniques of alkali fusion and acid dissolution.Through XRD,expansive capacity,the measurements of cation exchange capacity(CEC) and the amount of methylene blue absorption,the quality of the Na-modified bentonite is determined and evaluated.福建省教育厅B类科技计划面上资助项目(JB03248

Studies on Na-modification of Ca-bentonite by suspensoid

对福建龙岩钙基膨润土进行钠化改型,探索了钠化剂及相关钠化条件对膨润土钠化效果的影响。较佳的钠化剂为氟化钠;较佳的钠化条件为:钠化温度70℃、钠化剂用量4.2%、矿浆浓度10%,搅拌时间90min。在上述条件下,钙基膨润土经钠化改型后的膨胀容(VB)为33.5ml/g,阳离子交换容量(CEC)为1.140mmol/1g;经X射线衍射分析,d(001)值为1.27145nm,完全达到制备优良有机膨润土的质量要求。Using a low-grade Ca-bentonite produced from Longyan city,Fujian province as raw material,the test of Na-modification by suspensoid was carried out.Main technical conditions for the modification of Ca-bentonite such as modifying agent types and its dosage,pulp density and agitating time were discussed.The best reaction conditions are as following : the conversion agent is NaF;its dosage is 4.2%;pulp density is 10%;conversion time is 90min;conversion temperature is 70℃.The bentonite with high V_B of 33.5ml/g and high CEC of(1.140)mmol/g could obtained at the best experiment conditions.X-ray diffraction shows that d(001) is(1.27145)nm;The converted bentonite have been improved the properties to produce high quality organo-bentonite.福建省教育厅B类科技计划面上资助项目(JB03248