液相色谱串联质谱法同时测定饲料中6种代表性霉菌毒素

目的建立液相色谱-串联质谱法(liquidchromatography-tandemmassspectrometry,LC-MS/MS)同时检测4种代表性饲料(猪、鸡配合饲料、玉米和麸皮)中黄曲霉毒素B1(alatoxinB1,AFB1)、呕吐毒素(deoxynivalenol, DON)、T-2毒素(T-2 toxin, T-2)、赭曲霉毒素A(ochratoxin A, OTA)、玉米赤霉烯酮(zearalenone,ZEN)、伏马毒素B1(fumonisin B1, FB1)6种霉菌毒素的方法。方法样品经乙腈-水-甲酸(80:19:1, V:V:V)震荡和超声提取,取上清液经由七水硫酸镁和C18组成的混合型吸附剂-稀释净化,采用HR-ODS色谱柱分离,以0.1%甲酸-水和5mmol/L乙酸铵-0.1%甲酸甲醇溶液作为流动相进行梯度洗脱,采用ESI正负模式转换多反应监测模式测量,基质匹配标准曲线外标法进行定量。结果在高、中、低3种添加浓度水平下, 6种霉菌毒素的平均回收率为83%～113%,相对标准偏差为3.1%～18%。结论该方法灵敏度高、精密度好、经济、环保,适用于饲料中6种代表性霉菌毒素的测定。     

气相色谱-串联质谱法测定原料类果酱中百菌清残留量

建立了原料类果酱中百菌清农药残留的气相色谱-串联质谱（GC-MS/MS）测定方法。通过对关键步骤进行优化,样品经乙腈提取,氟罗里硅土固相萃取柱净化,气相色谱-串联质谱仪测定,外标法定量。结果表明：百菌清的定量限为0.01 mg/kg;标准曲线在5~250 ng/mL范围内线性良好,相关系数＞0.99;在0.01~0.1 mg/kg浓度范围的加标实验中,回收率为83.0%~111.0%,精密度为3.7%~10.3%,符合方法学验证要求。该方法操作简便,结果准确,可适用于不同种类的原料类果酱中百菌清残留的测定。     

气相色谱-串联质谱法测定韭菜中的氯氟氰菊酯残留

目的建立气相色谱-串联质谱法(gas chromatography-tandem mass spectrometry,GC-MS/MS)测定韭菜中氯氟氰菊酯残留量的分析方法。方法将韭菜样品的乙腈提取物经石墨化碳黑/氨基混合型固相萃取柱净化、乙腈-甲苯(3:1,V:V)洗脱以及浓缩定容后进行检测。目标化合物经SLB-5MS(30 m×0.25 mm,0.25μm)色谱柱分离后,通过三重串联四级杆多反应监测模式对其进行定性定量分析。结果在添加水平为0.05~0.50mg/L(n=5)时,氯氟氰菊酯的回收率在81.7%~99.1%之间,相对标准差(RSD)在2.5%~8.7%之间。该方法的线性范围为0.05~0.50 mg/L,相关系数r~20.990,检出限为0.001 mg/kg,定量限为0.01 mg/kg。结论该方法能满足韭菜中氯氟氰菊酯残留检测的要求。     

气相色谱-串联质谱测定韭菜中的氟氯氰菊酯残留量

目的建立了韭菜中测定氟氯氰菊酯的气相色谱-串联质谱(gas chromatography-tandem mass spectrometry,GC-MS/MS)分析方法。方法样品用乙腈匀浆提取、盐析、石墨化碳黑/氨基混合型固相萃取柱净化、乙腈/甲苯(3:1,v:v)洗脱,浓缩定容后检测。目标化合物经SLB-5MS(30 m×0.25 mm×0.25μm)色谱柱分离,采用三重串联四级杆多反应监测模式(multiple reaction monitoring,MRM)进行定性定量分析。结果在0.05~0.50mg/L添加水平时(n=5),氟氯氰菊酯的回收率在78.5%~98.0%之间,相对标准差在3.4%~8.3%之间。方法的线性范围为0.05~0.50 mg/L,决定系数R~20.99,该方法对氟氯氰菊酯的定量限为0.05 mg/kg。,结论该方法能满足韭菜中氟氯氰菊酯残留检测的要求。     

气相色谱-串联质谱法检测新疆地区水稻及其产地环境中咪鲜胺残留量

采用气相色谱-三重四级杆串联质谱(GC-MS/MS)仪器对新疆阿克苏地区的水稻及种植地的环境样品(水和土壤)中咪鲜胺的残留量进行检测与分析。不同样品采用相应的有机溶剂提取、固相萃取柱净化,氮吹浓缩后上机测定,不同样品的质控添加回收率在78.4～108.1%之间,相对标准偏差(RSD)范围在4.9～8.3%之间,在0.05~2.00 mg/L浓度范围内工作曲线的线性关系良好(r²>0.999)。结果表明,该方法的灵敏度、精密度和准确度均满足农药残留的检测分析要求,适用于不同类型的样品中咪鲜胺残留的筛查与定性、定量分析。     

气相色谱-串联质谱法同时分析葡萄基质中 196种农药残留

目的建立同时分析葡萄基质中196种农药残留的气相色谱-串联质谱(GC-MS/MS)方法。方法葡萄样品经乙腈提取,QuEChERS方法净化,加入内标环氧七氯,采用GC-MS/MS在多反应监测模式(MRM)下分析,38 min内即可完成196种农药的分离,内标法定量。结果 196种农药在10~1000μg/L的浓度范围内线性关系良好,相关系数(r~2)大于0.99,各农药的检出限(S/N=3)为0.1~2.5μg/kg,各农药的定量限(S/N=10)为0.3~8.3μg/kg,在10.0μg/kg和50.0μg/kg 2个水平的添加浓度下,回收率在60.5%~126.2%之间,相对标准偏差0.2%~16.1%(n=6)。结论该方法准确可靠,灵敏度高,可用于葡萄基质中196种农药残留的同时检测。     

液质联用法检测粮谷制品中4种单端孢霉烯类真菌毒素

建立粮谷制品中4种单端孢霉烯类真菌毒素的液相色谱—质谱联用分析方法。样品经乙腈/水溶液（84︰16,v/v）提取后用MycoSep?226多功能柱净化,Agilent ZORBAX Bonus-RP色谱柱分离,液相色谱—质谱联用（LC-MS/MS）测定。结果表明,样品中4种单端孢霉烯类真菌毒素在各自的线性范围内线性关系良好,相关系数均不低于0.995,检出限为2~5 μg/kg,3个加标水平下平均回收率为73.19%~107.39%,相对标准偏差为1.46%~13.24%。表明该方法净化效果好、灵敏度高,适用于同时检测单种粮谷制品中4种单端孢霉烯类真菌毒素的残留量。     

基于QuEChERS-气相色谱-串联质谱法测定鸡蛋中48种农药残留

目的建立基于QuEChERS前处理方法结合气相色谱-串联质谱测定鸡蛋中48种农药残留的检测方法。方法样品用1%乙酸乙腈、MgSO4和NaOAC混合盐包脱水提取,经MgSO4、PSA、GCB和C18混合净化管净化,净化液经氮吹浓缩后乙酸乙酯定容,利用气相色谱分离,MRM模式测定,内标校正,外标法定量。结果 48种农药在线性范围为5～100 ng/mL内关系良好, r2均在0.995以上。方法检出限在0.03～5.00μg/kg之间,方法定量限在0.12～17.00μg/kg之间。48种农药在5、10和50μg/kg 3个加标水平上,平均回收率在70%～120%的占比分别为97.92%、97.92%、95.83%。相对标准偏差(relative standard deviation, RSD, n=6)为2.12%～12.28%。结论该方法基本能够满足应用于实际样品的分析检测,较传统检测方法更加简便快捷,使用试剂少,灵敏度高。     

Determination of trichothecenes in cereals and cereal-based products by liquid chromatography-tandem mass spectrometry

A sensitive, accurate and precise method for the simultaneous determination of nivalenol (NIV), deoxynivalenol (DON), T-2 toxin (T-2) and HT-2 toxin (HT-2) in different food matrices, including wheat, maize, barley, cereal-based infant foods, snacks, biscuits and wafers, has been developed. The method, using liquid chromatography coupled with atmospheric pressure chemical ionization triple quadrupole mass spectrometry (LC-APCI-MS/MS), allowed unambiguous identification of the selected trichothecenes at low µg per kg levels in such complex food matrices. A clean-up procedure, based on reversed phase SPE Oasis® HLB columns, was used, allowing good recoveries for all studied trichothecenes. In particular, NIV recoveries significantly improved compared to those obtained by using Mycosep® #227 columns for clean-up of the extracts. Limits of detection in the various investigated matrices ranged 2.5-4.0 µg kg^-1 for NIV, 2.8-5.3 µg kg^-1 for DON, 0.4-1.7 µg kg^-1 for HT-2 and 0.4-1.0 µg kg^-1 for T-2. Mean recovery values, obtained from cereals and cereal products spiked with NIV, DON, HT-2 and T-2 toxins at levels from 10 to 1000 µg kg^-1, ranged from 72 to 110% with mean relative standard deviation lower than 10%. A systematic investigation of matrix effects in different cereals and cereal products was also carried out by statistically comparing the slopes of standard calibration curve with matrix-matched calibration curve for each of the four toxins and the eight matrices tested. For seven of the eight matrices tested, statistically significant matrix effects were observed, indicating that, for accurate quantitative analysis, matrix-matched calibration was necessary. The method was applied to the analysis of 57 samples of ground wheat originated from South Italy and nine cereal food samples collected from retail markets.     

QuEChERS-GC-MS/MS法测定淡水鱼中6种拟除虫菊酯的残留量

建立了气相色谱-串联质谱法（GC-MS/MS）结合QuEChERS前处理技术检测淡水鱼（鲤鱼、鲟鱼、鲢鱼）中6种拟除虫菊酯（氯氰菊酯、溴氰菊酯、氰戊菊酯、氯氟氰菊酯、甲氰菊酯、联苯菊酯）的残留量。样品经乙腈提取,N-丙基乙二胺（PSA）和十八烷基键合硅胶（C18）粉末分散固相萃取（SPE）净化浓缩后,采用GC-MS/MS选择反应监测（SRM）模式测定,内标法定量。结果表明,6种拟除虫菊酯在3～300 μg/L的质量浓度范围内,各农药峰面积与进样质量浓度间线性关系良好,决定系数＞0.999 5,检出限（LOD）低于0.9 μg/kg,定量限（LOQ）低于3 μg/kg,在添加水平分别为3 μg/kg、30 μg/kg及300 μg/kg时,6种拟除虫菊酯的平均回收率在83%～102%之间,相对标准偏差（RSDs）在0.9%～4.9%之间。该方法简便、快速,灵敏度高,能够满足市场上淡水鱼中6种拟除虫菊酯的检测。     

Gas chromatography-tandem mass spectrometry multi-residual analysis of contaminants in Italian honey samples

ABSTRACT

Contaminants belonging to various classes, including polychlorobiphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs), pyrethroid insecticides (PYRs), fungicides (Fs), herbicides (Hs), synergists (SYNs) and insect growth regulators (IGRs) were analysed simultaneously in honey samples using a new simultaneous, easy and rapid method based on a liquid–liquid extraction with a mixture of n-hexane and ethyl acetate. It allowed recoveries in the range 80–137%, with limits of detection (LODs) between 0.10 and 5.21 ng g^–1, showing a good sensitivity and accuracy. All the analysed Italian honeys showed the presence of residues of OPPs; PAHs were in 46.8% of the samples and PCBs were always below the LODs; 53.2% of the samples were contaminated by OCPs, PYRs, SYNs and IGRs. In addition, 46.8% of the samples exceeded the maximum residue limits (MRLs) established by the European Community in honey for chlorfenvinphos (cis + trans), TPP, γ-HCH, tebuconazole, coumaphos and τ-fluvalinate (cis + trans).     

液相色谱-串联质谱法与离子色谱-串联质谱法测定食品中氯酸盐和高氯酸盐方法比较研究

目的 考察离子色谱-串联质谱法（ion chromatography-tandem mass spectrometry,IC-MS/MS）和液相色谱-串联质谱法（liquid chromatography-tandem mass spectrometry,LC-MS/MS）在测定不同食品中氯酸盐和高氯酸盐的一致性。方法 利用乙腈/水（3:2, V:V）提取鸡蛋、奶粉和菠菜中的目标物,经石墨化炭黑（graphitized carbon black, GCB）小柱净化,以IonPacTM AS20离子色谱柱和CSHTM Fluoro-Phenyl液相色谱柱为分析柱,三重四极杆质谱仪检测,内标法定量。对两种方法测得的数据进行正态性检验和差异性分析。比较两种方法的保留时间漂移,考察色谱稳定性。对两种方法测得的浓度进行线性回归和B-AbBland -aAltman（B-A）图可视化考察方法一致性。结果 两种方法测得氯酸盐（高氯酸盐）的浓度在1~500（0.1~50.0） ?g/L范围内线性良好（r2＞0.999）。IC-MS/MS与LC-MS/MS测定高氯酸盐的定量限均为0.5 ?g/kg,氯酸盐的定量限分别为5.7 ?g/kg和4.2 ?g/kg。回收率范围分别为82.3%~107.4%和94.8%~109.4%,相对标准偏差分别为1.5%~13.6%和1.2%~9.6%。IC-MS/MS（LC-MS/MS）测得鸡蛋、奶粉、菠菜中氯酸盐和高氯酸盐的基质效应分别为12.1%（22.1%）、9.0%（27.4%）、-11.8%（-24.0%）和-16.8%（-18.5%）、-18.6%（-28.4%）、-20.2%（-21.1%）。线性回归法显示两种方法测定氯酸盐和高氯酸盐浓度的回归曲线斜率分别为1.0144和1.0908。B-A图显示绝大多数数据点位于平均值±1.96标准偏差范围。结论 两种方法的准确度和精密度均符合化学检验方法验证通则的要求,两种方法测得的氯酸盐、高氯酸盐浓度结果基本一致,但氯酸盐在LC-MS/MS系统中的保留时间稳定性更好,IC-MS/MS在测定食品中氯酸盐、高氯酸盐时的抗基质干扰能力更强。     

固相萃取-气相色谱-串联质谱法测定蔬菜中的 16种多环芳烃

目的建立固相萃取-气相色谱-串联质谱法测定蔬菜中16种多环芳烃(polycyclic aromatic hydrocarbons,PAHs)的分析方法。方法样品经正己烷-二氯甲烷匀浆提取,经中性硅胶-中性氧化铝复合固相萃取柱净化后,用多反应监测(multiple-reaction monitoring,MRM)正离子扫描方式进行检测,气相色谱-串联质谱法测定,内标法定量。结果 16种目标物在2~250 ng/m L范围内呈线性关系良好,方法的检出限(S/N=3)为0.09~0.51μg/kg,定量限(S/N=10)为0.31~1.68μg/kg。在2、5、20μg/kg 3个加标水平下的平均回收率为添加平均回收率范围为70.6%~109.2%,相对标准偏差(RSD)为1.95%~10.4%。结论该方法选择性好、抗干扰能力强,能满足国内外法规的要求,可用于蔬菜中多环芳烃残留的日常检测。     

QuEChERS技术结合气相色谱-串联质谱法同时测定水产品中10种亚硝胺

目的 建立QuEChERS技术结合气相色谱-串联质谱法(gas chromatography-tandem mass spectrometry,GC-MS/MS)同时测定水产品中10种亚硝胺含量的分析方法.方法 样品经过乙腈-水溶液(1:1,V:V)提取后,利用QuEChERS分散吸附剂净化基质,随后采用多反应监测(m...     

液相色谱-串联质谱法测定猪肉及组织中沙丁胺醇的含量不确定度评定

目的分析液相色谱一串联质谱法检测猪肉及组织中沙丁胺醇的不确定度,探讨各因素对检验结果的影响。方法依据JJG1059.1-2012《测量不确定度评定与表示》和CNAS-GL06《化学分析中不确定度的评估指南》规定的方法和程序,分析影响测量不确定的来源,并对各不确定度分量进行了评估。结果合成各变量的不确定度,最终得到测定结果的扩展不确定度:(11.05±0.77)μg/kg(k=2)。结论影响检测结果不确定度的主要因素为回收率和标准曲线拟合,在实际测量过程严格控制实验条件可提高检测的准确性和可靠性。     

气相色谱-串联质谱法测定30种果蔬中61种农药的基质效应及其克服方式

目的 以气相色谱-串联质谱(gas chromatography tandem mass spectrometry, GC-MS/MS)为检测条件, 考察61种农药在30种常见蔬果中的基质效应, 探索利用替代基质配制标准溶液进行定量分析的可行性。方法 利用乙腈分别提取30种供试基质, 经分散固相萃取净化后, 配制基质标准工作曲线和溶剂标准工作曲线, 经GC-MS/MS测试, 分析基质效应。结果 所有供试农药在10~200 μg/L线性范围良好, 线性相关系数(r2)＞0.99。在未净化基质中, 绝大多数农药表现为较强的基质增强效应, 仅有14种农药表现为可忽略的弱基质效应。QuEChERS净化可减小农药在供试基质中的基质效应, 但水胺硫磷、p,p’-DDT、氟虫腈、莠灭净、氟啶脲、异菌脲在各供试基质中仍然表现为强基质增强效应。以西葫芦作为代表基质分析其他供试基质的基质效应, 95%以上数量的农药均表现为中、弱基质效应, 且在25种供试基质中, 80%以上数量的农药表现为可忽略的弱基质效应。采用添加回收的方式对本研究结果进行验证, 当添加水平为0.08 mg/kg时, 利用西葫芦基质配制标准溶液进行定量, 水胺硫磷、氟虫腈、莠灭净的回收率为73.8%~115.8%。结论 在利用GC-MS/MS结合QuEChERS法检测蔬菜水果中的农药残留过程中, 以西葫芦作为代表基质配制基质标准曲线可以有效校正待测农药在其他基质中的基质效应。     

EMR-Lipid dSPE结合气相色谱-串联质谱法同时测定玉米油中218种农药残留

目的 建立一种同时测定玉米油中218种农药残留的快速检测方法。方法 本文采用乙腈提取并经冷冻离心初次除油后用EMR-Lipid dSPE分散固相萃取净化,气相色谱-质谱联用仪（Gas chromatography-triple quadrupole mass spectrometry , GC-MS/MS）多反应监测（multi reaction monitoring , MRM）模式检测,采用基质匹配标准溶液内标法定量。结果 结果表明,218种农药在5~200 ng/mL范围内线性关系良好,相关系数均大于0.995, 在0.05、0.1、0.5 mg/kg 三个添加水平的回收率为65.7%~119.9%, 相对标准偏差(relative standard deviations, RSD)为0.78%~18.10%, 定量限(limits of the quantitation, LOQ)为10~20 μg/kg。结论 该方法前处理简单、高效,灵敏度、准确度和精密度高,能满足玉米油中218种农药多残留的分析要求。     

Determination of polycyclic aromatic hydrocarbons in edible seafood by QuEChERS-based extraction and gas chromatography-tandem mass spectrometry

A high-throughput analysis of polycyclic aromatic hydrocarbons (PAHs) in edible seafood using QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) based extraction and gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed and validated in 4 seafood matrices--crab, finfish, oyster, and shrimp. The extraction employs QuEChERS with dispersive solid phase extraction (dSPE) using cleanup sorbent that includes C18. The acetonitrile extract is partitioned into hexane and analyzed by GC-MS/MS. The procedure was validated by spike recovery experiments of 15 parent and 5 substituted PAHs at 5ppb and 25 ppb levels in the 4 matrices. Recoveries were 71%-130% with RSDs less than 14%. The limit of quantitation (LOQ) for benzo[a]pyrene are 0.4-2.5 ppb depending on matrix. For all 15 parent PAHs the LOQs are less than 10% of the Levels of Concern established by the U.S. Food and Drug Administration. Good recoveries were also achieved in aged spikes at 5 ppb level in oyster and shrimp. Method accuracy was further evaluated by analyzing NIST Standard Reference Material 1974b. Ten of 14 incurred PAHs corresponding to the parent compounds in the present study fell within the control limits established by the National Oceanic and Atmospheric Administration. Using the present method approximately 20 samples every 24 h can be analyzed with confirmation. PRACTICAL APPLICATION: The presented analytical method could be used for seafood safety assessments to examine petroleum contaminant levels in edible seafood after an oil spill. The method is fast and sensitive.     

气相色谱串联质谱法测定植物油中壬基酚

采用气相色谱—串联质谱(GC-MS/MS)研究植物油中壬基酚的测定方法。乙腈作为提取溶剂,通过涡旋提取和分散基质固相萃取净化。测定结果表明,该方法壬基酚含量在0.02~1 mg/L范围内呈良好线性关系,相关系数为0.999 2,在0.02、0.06和0.2 mg/kg三个水平上做加标回收实验,结果回收率为82.3%~94.7%。方法检出限为0.02 mg/kg。     

Analysis of non-cleaned QuEChERS extracts for the determination of pesticide residues in fruit,vegetables and cereals by gas chromatography-tandem mass spectrometry

This paper investigated the possibility of leaving out the traditional clean-up step in the QuEChERS procedure and analysing non-cleaned extracts from fruit, vegetables and cereals with a combination of gas chromatography-tandem mass spectrometry (GC-MS/MS), back-flush technology and large-volume injection. By using calibration standards in cucumber matrix, recovery and precision were calculated in lettuce, orange and wheat for 109 pesticides at 0.01 and 0.1 mg kg^?1 in two sets of samples: one with and one without clean-up. For both spiking levels, 80–82% of the pesticides in the non-cleaned extracts and 80–84% of the pesticides in the cleaned extracts were within the acceptable recovery range of 70–120%. Precision data for both levels showed that 95% of the pesticides in the non-cleaned extracts and 93–95% of the pesticides in the cleaned extracts had RSDs below 20%. Recovery and precision data were determined using a two tailed t-test (p = 0.05). By using calibration standards in the respective matrix, we studied if the non-cleaned calibration standards gave an extra matrix effect compared with the cleaned standards by using the slope from calibration graphs and plotting the calculated extra matrix effect minus 100 for each compound. The results showed that for 79% of the pesticides, the extra matrix effect minus 100 was within the acceptable range of ?20% to 20%. Five European Union proficiency tests on rye, mandarin, rice, pear and barley, respectively, from 2010 to 2012 were reanalysed omitting the clean-up step and showed satisfactory results. At least 70 injections of non-cleaned extracts were made without detecting any increased need for maintenance during the experimental period. Analysing non-cleaned QuEChERS extracts of lettuce, orange and wheat are possible under the conditions described in this paper because recovery, precision and specificity showed satisfactory results compared with samples subjected to traditional dispersive clean-up.