凝胶渗透色谱和固相萃取净化-气相色谱分离组合法测定糙米中的残留农药

提出糙米中38种有机氯农药、拟除虫菊酯和多氯联苯残留量的同时测定方法。用乙酸乙酯提取,凝胶渗透色谱和固相萃取净化,气相色谱．电子俘获检测,外标法定量。3个添加水平的平均回收率分别为77．3、81．4和83．8％;相对标准偏差3．8％～13．9％。有机氯农药和多氯联苯检出限为0．07μg／kg;拟除虫菊酯的检出限为0．4μg／kg。检测方法简便省时,自动化程度高,稳定可靠。     

气相色谱-离子阱质谱法测定海洋贝类中多残留有机氯农药、多氯联苯和多环芳烃

本研究建立了凝胶渗透色谱和铝硅胶柱前处理,气相色谱-离子阱质谱法测定海洋贝类体内20种有机氯农药、28种多氯联苯和16种多环芳烃的多残留分析方法。通过对凝胶渗透色谱的组分收集时间和铝硅胶柱的正戊烷淋洗体积的实验条件优化,实现了样品索氏提取液的凝胶渗透色谱初步净化、铝硅胶柱色谱的组分分离和进一步去除干扰物质。结果表明,多氯联苯、有机氯农药和多环芳烃各化合物的方法检出限分别为0.01~0.14,0.02~0.17和0.52~0.81ng/g(湿重),样品的加标回收率和相对标准偏差分别为:多氯联苯84.1%~120.2%、5.6%~15.9%;多环芳烃62.3%~123.1%、8.7%~20.5%;有机氯农药77.3%~127.5%、3.1%~18.7%。本方法降低了样品的前处理成本,缩短了样品处理时间,可应用于海洋贝类体内持久性有机污染物的实际监测。     

气相色谱法测定火锅底料中的多种有机氯农药和拟除虫菊酯农药残留

建立了火锅底料中21种有机氯农药和6种拟除虫菊酯农药残留的同时测定方法.样品经乙腈超声提取,凝胶渗透色谱、弗罗里硅土固相萃取柱和N-丙基-2-乙二胺净化,毛细管气相色谱柱分离后,微电子捕获检测器检测.火锅底料中有机氯农药和拟除虫菊酯农药的检出限分别为0.082～2.3 μg/kg和1.5～13.0 μg/kg;有机氯农药的加标水平为10, 20和50 μg/kg,拟除虫菊酯农药为20, 40和100 μg/kg时,27种农药的平均回收率为70.5%～116.0%;相对标准偏差为0.2%～6.1%.本方法快速、灵敏、可靠,可用于火锅底料中多种农药残留的同时检测.     

凝胶渗透色谱技术在农药残留分析中的应用

综述了凝胶渗透色谱技术在食品农药残留分析中的应用、研究现状和存在的问题。测定的农药残留包含有机氯、有机磷、除虫菊酯和农药多残留等等。参考文献37篇。     

GPC-GC-MS对食用植物油中多种类型农药残留的同步测定

基于凝胶渗透色谱(GPC)对脂类优良的分离能力,研究了其对有机氯、有机磷、氨基甲酸酯、拟除虫菊酯等多种类型农药与油脂基体的分离行为,建立了一种可同步测定食用植物油中4种类型共29种农药残留的分析方法.样品用凝胶渗透色谱提取净化,然后用自动快速浓缩仪浓缩后直接用气相色谱-质谱法(GC-MS)测定,其在0.05、0.10、0.20 mg/kg 3个添加水平的平均回收率为82% ～119%,相对标准偏差为1.35% ～10.2%,29种农药方法检出限和定量下限分别为0.1 ～10.0 μg/kg和0.4 ～33.0 μg/kg,可以满足食用植物油中农药残留限量的检测要求.     

固相萃取-在线凝胶渗透色谱-气相色谱/质谱法测定松子仁中的28种有机氯农药和拟除虫菊酯农药

建立了松子仁中28种有机氯农药和拟除虫菊酯农药多残留的在线凝胶渗透色谱-气相色谱/质谱（GPC-GC/MS）分析方法。样品以乙腈-水(体积比为4∶1)为提取剂高速匀浆提取,提取液经Aluminium-N固相萃取柱净化,除去样品中大部分的脂肪和甾醇等干扰基质,再经在线GPC进一步除去样液中的色素和脂肪等大分子干扰物质,有效地降低了样品复杂基质带来的背景干扰。加标水平为0.05 mg/kg时,大部分农药的回收率为70%～120%,相对标准偏差小于15%。28种农药的检出限为0.002～0.05 mg/kg。采用外标法定量,方法的线性关系和回收率结果均令人满意。实验证明,该方法是一种快速、准确、灵敏度高的同时检测松子仁中农药多残留的检测方法。     

气相色谱法同时测定山药和葛根中27种有机氯及拟除虫菊酯农药残留量

建立了山药和葛根中20种有机氯和7种拟除虫菊酯农药残留的提取、净化及其残留量测定的方法。样品采用丙酮-正己烷(4:3,V/V)提取,经凝胶渗透色谱净化后,采用气相色谱-电子捕获检测器检测。结果表明山药和葛根样品基质4水平添加条件下,27种农药的回收率(n=7)为80.1%～103.7%,相对标准偏差为1.9%～11%,最低检测限为0.09～1.82μg/kg,符合农药多残留检测要求。方法可用于山药和葛根中多种有机氯及拟除虫菊酯农药残留量的检测。     

微波萃取-全自动凝胶色谱净化-气相色谱法同时测定太湖沉积物中多氯联苯和有机氯

建立了沉积物中多氯联苯和有机氯农药等39种持久性有机污染物的同时测定方法。样品用正己烷和丙酮(体积比为1∶1)进行微波提取,提取溶液经凝胶色谱和弗罗里硅土净化,浓缩后采用气相色谱法测定。回收率在68.8%~84.2%,检出限为0.05~0.25ng/g。方法适用于沉积物样品中多种多氯联苯和有机氯农药含量的同时测定。     

应用搅拌棒吸附萃取-热脱附-气相色谱-质谱测定烟叶和茶叶中拟除虫菊酯类农药残留

应用搅拌棒吸附萃取(SBSE)技术分别萃取烟叶和茶叶中的5种拟除虫菊酯,并利用热脱附系统将萃取到的物质进行热脱附,然后通过气相色谱-质谱联用仪(GC-MS)进行分析测定。实验过程中对影响SBSE的因素及影响热脱附的条件进行了优化。在优化条件下,采用外标法分别对烟叶和茶叶中的5种拟除虫菊酯类农药残留进行了定量分析。结果表明,烟叶中5种拟除虫菊酯的检出限范围为3.3~11.4 ng,加标回收率为94.8%~103.4%,6次测定的相对标准偏差（RSD）为5.3%~8.6%;茶叶中5种拟除虫菊酯的检出限范围为4.2~10.5 ng,加标回收率为98.2%~110.1%,6次测定的RSD为5.0%~9.6%。实验证明该法具有较高的准确度、灵敏度和较好的重现性,可用于烟叶和茶叶中拟除虫菊酯类农药残留的快速分析测定。     

加速溶剂萃取/凝胶渗透色谱－固相萃取净化、气相色谱－质谱法测定茶叶中残留的33种农药

建立了茶叶中有机磷、有机氯、拟除虫菊酯类共33种农药残留的分析方法。样品以丙酮-二氯甲烷(体积比为1:1)为提取剂经加速溶剂方法萃取,提取液用凝胶渗透色谱净化除去大部分的色素、脂类和蜡质,再用Carb-NH2小柱和Florisil小柱净化。采用气相色谱法分析、外标法定量、气相色谱-质谱法（GC-MS）定性。加标水平为0.05 mg/kg时,大部分农药的回收率为70%~120%,相对标准偏差小于20%。方法的检测限为0.005～0.05 mg/kg (以10倍信噪比计)。该方法的提取效率高,准确灵敏,目前已应用于出口茶叶中农药残留的日常检测。大量实际样品的检测结果表明,此方法适于出口茶叶中农药残留检测实际工作的需要。     

Simultaneous determination of 109 pesticides in unpolished rice by a combination of gel permeation chromatography and Florisil column purification, and gas chromatography/mass spectrometry

A multi-residue method is described for the simultaneous analysis of 109 pesticides with different properties in unpolished rice. The range covers organophosphorus, organochlorine, carbamate, and synthetic pyrethroid pesticides. The pesticides were extracted from the sample using ethyl acetate. Most higher molecular weight components such as lipids in the co-extractives were removed by gel permeation chromatography (GPC) with a Bio-bead SX-3 column. A Florisil column with ethyl acetate/hexane as the eluting solvents was used for further cleanup. The pesticides were finally simultaneously determined by gas chromatography/mass spectrometry (GC/MS) in selective ion monitoring (SIM) mode. The average recoveries for most pesticides (spiked level 0.02, 0.1 and 1 microg/g) ranged from 70% to 110%, the relative standard deviation (RSD) was below 20% in every case, and the limit of detection (LOD) varied from 1 to 20 ng/g.     

凝胶渗透色谱-气相色谱质谱法测定：花生中6种除草剂农药残留

建立了凝胶渗透色谱一气相色谱质谱（GPC～GC=MS）法测定花生中6种除草剂（氟乐灵、异恶草酮、甲草胺、二甲戊乐灵、乙氧氟草醚、喹禾灵）农药残留的方法。样品经乙腈提取,氨基固相萃取柱和凝胶渗透色谱净化,在选择离子扫描（SIM）模式下进行气相色谱质谱法测定,外标法定量。6种除草剂浓度在0．02-1．00mg／L范围内与色谱峰面积呈良好的线性,线性相关系数为O．9949～0．9998,添加回收率为77．8％-101．6％,测定结果的相对标准偏差为4．4％～11．4％（月=5）,方法的检出限为0．1～1．3μg／kg。     

Qualitative screening and quantitative determination of pesticides and contaminants in animal feed using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry

A method has been developed for the target analysis of over 100 pesticides and contaminants in a complex feed matrix. The method is based on extraction with ethyl acetate, cleanup by gel permeation chromatography (GPC) and dispersive solid-phase extraction (SPE) with primary secondary amine phase (PSA), and analysis by comprehensive two-dimensional gas chromatography with full scan time-of-flight mass spectrometric detection (GC x GC-TOF-MS). Parameters studied during method development included a dispersive SPE cleanup step after GPC, large volume injection into the GC system and the GC x GC separation. Qualitative and quantitative performance of the GC x GC system was evaluated by analyzing spiked extracts in the range equivalent to 1-100 microg/kg in feed. At levels of 50 microg/kg and higher, all compounds targeted for could be identified fully automatically by the software based on their mass spectra. At lower levels the hit rate decreased with the concentration. System linearity was excellent in solvent and only slightly affected by matrix (correlation coefficients r>or=0.995 for 90% of the compounds). Limits of quantification were in the 1-20 microg/kg range for most compounds. The overall method was validated for 106 compounds at the 10 and 100 microg/kg level. Recoveries between 70% and 110% and RSDs below 20% were obtained for the majority of the compounds.     

大口径毛细管气相色谱法测定糙米中异丙威残留量

介绍一种用气相色谱氮磷检测器（ＧＣ－ＮＰＤ）测定糙米中异丙威残留量的简便方法，其检出限为：０．２ｍｇ／ｋｇ．     

Validation study on 660 pesticide residues in animal tissues by gel permeation chromatography cleanup/gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry

A new method using gel permeation chromatography (GPC) cleanup followed by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS-MS) has been established for quantitative determination of 437 pesticide residues in animal tissues such as beef, mutton, pork, chicken, and rabbit. Based on an appraisal of the characteristics of both GC-MS and LC-MS-MS, validation experiments were conducted for 660 pesticides. In the method, 10 g animal samples were mixed with 20 g sodium sulfate and extracted with 35 mL of cyclohexane+ethyl acetate (1+1) twice by blender homogenization, centrifugation, and filtration. Evaporation was conducted and an equivalent of 5 g sample was injected into a 400 mm x 25 mm S-X3 GPC column, with cyclohexane+ethyl acetate (1+1) as the mobile phase at a flow rate of 5 mL/min. The 22-40 min fraction was collected for subsequent analysis. For the 368 pesticides determined by GC-MS, the portions collected from GPC were concentrated to 0.5 mL and exchanged with 5 mL hexane twice. For the 69 pesticides by LC-MS-MS, the portions collected from GPC were dissolved with acetonitrile+water (60+40) after taking the extract to dryness with nitrogen gas. In the linear range of each pesticide, the correlation coefficient was r > or = 0.98, exceptions being dinobuton, linuron, and fenamiphos sulfoxide. At the low, medium and high three fortification levels of 0.2-4800 microg/kg, recoveries fell within 40-120%, among which 417 pesticides recoveries between 60% and 120%, accounting for 95%, 20 analytes between 40% and 60%, accounting for 5%. The relative standard deviation was below 28% for all 437 pesticides. The limits of detection for the method were 0.2-600 microg/kg, depending on each pesticide.     

Application of gas chromatography-triple quadrupole mass spectrometry in the quantification-confirmation of pesticides and polychlorinated biphenyls in eggs at trace levels

A new multiresidue method has been developed and validated for the simultaneous analysis of 57 compounds, including organochlorine and organophosphorus pesticide residues (OCPs and OPPs) and polychlorinated biphenyls (PCBs), in eggs at trace levels by gas chromatography coupled to triple quadrupole mass spectrometry (GC-QqQ-MS/MS). Egg samples were extracted by a simple and fast matrix solid phase dispersion (MSPD) procedure using C18 as sorbent, and ethyl acetate and acetonitrile saturated in n-hexane (85:15, v/v) as elution solvent with a simultaneous clean up with Florisil in-line. The QqQ analyzer acquired data in selected reaction monitoring (SRM) mode, permitting both quantification and confirmation in a single injection with a running time reduced up to 17.70 min. Recovery was in the range of 70-110% and 70-106% at 15 and 50 microg/kg, respectively. Precision values expressed as relative standard deviation (RSD) were lower than 20%. Linearity in the range of 10-150 microg/kg provided determination coefficients (R(2)) higher than 0.98 for all compounds. Limits of detection (LODs) for pesticides were < or =2.25 microg/kg and limits of quantification (LOQs) ranged from 0.02 to 7.78 microg/kg. LODs for PCBs were < or =0.41 microg/kg and LOQ were < or =0.71 microg/kg. The method was applied to real samples. Endosulfan sulphate and p,p'-DDE were found in two samples at concentrations below the first calibration level.     

凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中的36种农药残留

建立了用凝胶渗透色谱净化-气相色谱/串联质谱分析蘑菇中36种农药残留的方法。蘑菇中的待测农药组分在30 ℃条件下用乙酸乙酯提取,高速匀浆后通过凝胶渗透色谱净化;选用填料为中性多孔的聚苯乙烯二乙烯基苯微球体的S-X3玻璃柱(22 g,19 cm×2 cm)作为凝胶渗透色谱净化柱,流动相为乙酸乙酯-环己烷(体积比为1∶1)溶液,流速5 mL/min;收集第7~15 min流出的液体用气相色谱-三重四极杆串联质谱仪测定。在0.01~1.0 mg/L的质量浓度范围内,各种农药标准溶液的线性相关系数均大于0.99。在样品中添加36种农药(添加水平为0.01,0.05,0.10 mg/kg)的混合标准溶液,平均回收率为72.6%~117.1%,相对标准偏差为2.0%~10.8%(n=5),最低检出限为 0.1~0.7 μg/kg,最低定量限为 0.2~2 μg/kg。     

Multiresidue determination of pesticides in honey by matrix solid-phase dispersion and gas chromatography with electron-capture detection

A multiresidue method was developed for the determination of 15 pesticides (organochlorines, organophosphorus compounds, pyrethroids, and other acaricides) in various commercial honeys (eucalyptus, lavender, orange, rosemary, and multifloral). The analytical procedure is based on the matrix solid-phase dispersion of honey in a mixture of Florisil and anhydrous sodium sulfate; the mixture is placed in small plastic columns and extracted with hexane-ethyl acetate (90 + 10, v/v). The pesticide residues are determined by capillary gas chromatography with electron-capture detection. Recoveries with the method at concentrations between 0.15 and 1.5 microg/g ranged from 80 to 113%, and relative standard deviations were <10% for all the pesticides studied. The pesticide detection limits were within the range 0.5-5 microg/kg for organochlorines, around 3 microg/kg for the chlorinated organophosphorus pesticides studied, near 15 microg/kg for fluvalinate, and about 3 microg/kg for the other pyrethroids.