Analysis of polybrominated diphenyl ethers(PBDEs) and polybromodiphenyls(PBBs) in halobios in marine organisms

将气相色谱-负离子化学源/质谱法(gC-nCI/MS)应用于分析海洋生物中五种多溴联苯醚(PbdES)和五种多溴联苯(PbbS)残留。样品以正己烷/丙酮(1∶1,V/V)作为提取剂,采用超声萃取法,提取液经酸性硅胶和中性硅胶层析柱净化和正己烷洗脱后,以PCb-103为内标物和gC-nCI/M的选择离子监测方式(SIM)进行定性与定量分析。平均加标回收率为82.7%~101.0%,相对标准偏差小于5.6%,方法检测限都小于0.20x10-9,PbdES的线性范围是(0.1~500)x10-9,PbbS的线性范围是(0.35~350)x10-9,相关系数都大于0.9999。所分析生物样品中PbdE-47是最主要检出目标物。A rapid method based on ultrasonic extraction was developed for the determination of five polybrominated diphenyl ethers(PBDEs) and five polybromodiphenyls(PBBs) in fish and mussel.Hexane/acetone(1/1) was used as the extraction solvent,and hexane was elution solvent,after the extraction was cleaned by the cartridge filled with silica gel and acidic silica gel,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 spiked standard samples ranged from 82.7% to 101.0% with a relative standard deviation that was less than 5.6%,and the detection limit of the method was lower than 0.20×10-9 for all PBDEs and PBBs,the range of linearity was from 0.1×10-9 to 500×10-9 for PBDEs,and 0.35×10-9 to 350×10-9 for PBBs,with determination coefficients>0.9999.PBDE-47 was the main in all studied samples

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 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

热轴自动判别系统的分析

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红外探测轴温的信号分析

本文对运行列车轴温信号的波形进行分析。给出红外线探头的光学系统扫描轴箱不同部位时,滑动轴承和滚动轴承的轴温信号波形。叙述了轴温信号脉冲序列能量谱的确定。最后介绍利用轴温信号波形的不同特征和能量谱公式,解决几个实际问题

Analysis of polybrominated diphenyl ethers(PBDEs) and polybromodiphenyls(PBBs) in fish and shellfish 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)应用于分析鱼类和贝类样品中5种多溴联苯醚(PbdES)和5种多溴联苯(PbbS)残留。鱼类和贝类样品以正己烷/丙酮(1∶1,V/V)作为提取剂,采用超声萃取法,提取液经酸性硅胶和中性硅胶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。平均加标回收率为82.7%~101.4%,相对标准偏差为0.9%~5.9%,方法检测限(Mdl=3S/n)都小于0.20μg/kg,PbdES的线性范围是0.1~500μg/kg,PbbS的线性范围是0.35~350μg/kg,相关系数都大于0.9999。所分析生物样品中PbdE-47是最主要检出目标物。A method based on ultrasonic extraction was developed for the determination of five polybrominated diphenyl ethers(PBDEs) and five Polybromodiphenyls(PBBs) in fish and mussel.Hexane/acetone(1/1) was used as the extraction solvent,and hexane was elution solvent,after the extraction was cleaned by the cartridge filled with silica gel and acidic silica gel,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 spiked standard samples ranged from 82.7% to 101.4% with relative standard deviations between 0.9% and 5.9%,and the method detection limits(MDL=3S/N) are lower than 0.20 μg/kg for all PBDEs and PBBs,the range of linearity was from 0.1μg/kg to 500 μg/kg for PBDEs,and from 0.35μg/kg to 350μg/kg for PBBs,with correlation coefficients > 0.9999.PBDE-47 is the main in all studied samples

Determination of polybrominated diphenyl ethers and polybrominated biphenyls in sediment from Xiamen sea by gas chromatography-mass spectrometry-negative chemical ionization and gas chromatography-electron capture detector

将气相色谱-负离子化学源-质谱法(gC-nCI/MS)和气相色谱-电子捕获检测法(gC-ECd)应用于分析沉积物中6种多溴联苯醚(PbdES)和5种多溴联苯(PbbS)残留。沉积物样品以V(正己烷)∶V(丙酮)=1∶1作为提取剂,采用索式提取法,提取液经酸性硅胶和中性硅胶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,PbdE-209则采用gC-ECd法分析。平均加标回收率为93.3%--110.8%,相对标准偏差为1.2%--8.6%,方法检测限均小于0.20μg/kg(PbdE-209的方法检测限是7.74μg/kg),相关系数都大于0.9990。所分析沉积物样品中均含有微量的PbdE-99、Pbb-49和PbdE-209。Soxhlet extraction was developed for the determination of six polybrominated diphenyl ethers and five polybrominated biphenyls in sediment.Hexane/actone(1∶1, V/V) was used as the extraction solvent and hexane as elution solvent,after the extraction was cleaned by the cartridge filling with acidic and neutral silica gel,the analysis of samples was accomplished by using gas chromatography with negative chemical ionization mass spectrometric detection(GC-NCI/MS) in the selected ion monitoring mode(SIM) and gas chromatography-electron capture detector,and with PCB-103 as internal standard(IS).The average recoveries of the spiked-samples ranged from 93.3% to 110.8% with relative standard deviations between 1.2% and 8.6%,the detection limit(MDL) was smaller than 0.20 μg/kg (the MDL was 7.74 μg/kg for PBDE-209),and the correlation coefficients were larger than 0.9990.PBDE-99、 PBB-49 and PBDE-209 were detected in all sediments