固相萃取-气相色谱-质谱联用法筛查食用菌中的农药残留

采用气相色谱-质谱联用结合NAGINATA™软件建立了筛查食用菌中多种农药残留的分析方法。采用乙腈提取,Carbon-NH2固相萃取小柱净化,气相色谱-质谱联用检测后NAGINATA™软件全智能分析,对照每个化合物的质谱质量精度以及质谱谱图的谱库给出匹配度,通过保留时间锁定对化合物作定性判断。结果表明,18 种农药在香菇中检出限为0.001～0.050 mg/kg;平均回收率为77%～110%;相对标准偏差为1.1%～6.9%。应用所建立的方法对35 个市售食用菌样品进行了筛查,检测出2 种农药残留,残留量均低于GB 2763-2014《食品中农药最大残留限量》的限量。该方法操作便捷、快速高效,适用于食用菌中农药多残留的快速筛查。     

超高效液相色谱-四级杆-飞行时间质谱法快速筛查与确证蔬菜水果中的多种农药残留

目的应用超高效液相色谱-四极杆-飞行时间质谱技术,针对GB 2763—2014《食品安全国家标准食品中农药最大残留限量》规定的农药残留,整合多种检测方法,建立无需标准品的快速筛查与确证蔬菜、水果中多种农药残留的方法。方法通过一级精确质量数据库比对样品准分子离子的精确质量数、同位素分布与丰度,对蔬菜、水果中农药残留进行初筛,通过实际测定样品的二级谱图与二级谱库中谱图进行比对或通过图谱解析方法进行确证。结果通过基质加标进行了方法验证,10.0和50.0μg/kg添加水平检出率均为100%,90%以上的农药化合物回收率在70%~120%,并且相对标准偏差(RSD)≤20%(n=5)。对30份蔬菜、水果样品进行筛查与确证,共检出27种农药残留,并依据GB 2763—2014进行了判定,共有2份样品超标。结论该方法的灵敏度、准确性和重复性良好,可以在较短的时间内,甚至在没有标准品的情况下,对GB 2763—2014中数百种农药进行筛查与确证,可为食品安全监管提供有效保障。     

非靶向快速筛查茶饮料中未知农药残留

本文建立了分散液液微萃取-高效液相色谱-四极杆-飞行时间质谱法(DLLME/HPLC-Q-TOF/MS)非靶向快速筛查茶饮料中未知农药残留的方法。根据目标化合物特征离子的精确质量数、同位素匹配、二级碎片信息进行数据库匹配,筛查可疑未知农药。依据13种农药为质控化合物优化了测定方法。结果表明,2 g N-丙基乙二胺为预净化剂,甲醇为分散剂,200 μL三氯甲烷为萃取剂,通过摇床震荡的方式提取茶饮料中的目标化合物,Xbridge BEH C18色谱柱分离的方法回收率范围为83.1%~96.8%,RSD范围在0.88%~4.82%。空白基质校准曲线的线性范围为2~400 μg/L,决定系数R2在0.9989以上,检测限为0.002~0.092 μg/kg,定量限为0.006~0.307 μg/kg。该方法无需标准品即可快速筛查茶饮料中的农药残留,能够应用于茶饮料样品的实际筛查。该方法快速、准确、分析通量高,可以为茶饮料中农药残留的快速筛查和质量控制提供重要的方法依据。     

气相色谱-四极杆/飞行时间质谱法非靶向快速筛查凉茶中的农药残留

为建立QuEChERS法净化,结合气相色谱-四极杆-飞行时间质谱法(QuEChERS/GC-Q-TOF/MS)非靶向快速筛查凉茶中农药残留的方法,将样品经乙酸乙酯提取,石墨化炭黑(GCB)和氨丙基粉(NH2)分散固相萃取净化,GC-Q-TOF/MS测定。利用20种质控化合物建立的筛查方法检出限范围为2.00~50.0 μg/kg,定量限范围5.00~150 μg/kg。3个不同加标水平(25,50,125 μg/kg)下的平均回收率为73.47%～106.3%,相对标准偏差为0.91%～9.11%(n=6)。在该定量方法基础上利用目标化合物特征离子的精确质量数、二级碎片丰度比、主要离子碎片的同位素丰度比等信息进行精确质量数据库筛查与确证,以数据库检索匹配得分≥80的最低浓度作为方法的筛查限,无标准品情况下实现了非靶向筛查凉茶中751种农药残留。方法快速、准确、分析通量高,可为凉茶中农药残留的非靶向快速筛查和质量控制提供重要依据。     

食品农药残留检测技术的分析及展望

随着我国农产品贸易的快速发展,人民群众的物质生活得到了极大的丰富。在农产品贸易发展过程中,大量的农药残留不仅会导致农产品质量不符合要求,还会对人体造成损伤,所以必须要积极加强食品农药残留检测。本文通过对当前食品农药残留检测技术进行分析,为今后农药残留检测技术的发展提供重要的建议。     

超高效液相色谱-高分辨质谱法快速筛查土豆中的农药残留

农药残留严重影响农产品的品质,对人们的食用安全非常不利,所以需要对农产品当中的农药残留进行快速的检测和筛查。土豆是现阶段人们生活中食用的一种重要农产品,其农药残留对人体健康有着重要的影响,所以做好土豆当中的农药残留检测,控制残留超标的土豆流入市场可以有效的减轻其对人体健康的影响。从具体分析来看,超高效液相色谱-高分辨质谱法能够对土豆当中的农药残留进行快速的筛查,所以本文就其具体的利用进行分析和讨论。     

高分辨质谱在食品检测分析中的应用进展

高分辨质谱技术在食品检测分析领域的应用日益广泛。本文对高分辨质谱的特点进行了阐述,并对近十年发表的相关文献进行了总结和分析。以兽药、农药残留,生物毒素,持久性有机污染物的应用为例进行综述,并对高分辨质谱在食品检测分析领域的应用进行了展望。高分辨质谱可用于定向和非定向化合物的筛查,其参数设定简单,且不需要标准品,可同时测定上百种化合物,极大的提高了检测效率。     

农产品安全快速筛查检测技术的展望

正农产品的安全是国计民生的大事,中国有关农产品的安全规划中明确指出必须加大对农产品安全检测的投入,建设职业化农产品的检查员队伍,加强对农产品安全的各项保障,大力发展相关的安全快速筛查和检测技术。农产品的快筛检测体系的现状简介农产品安全快筛检测现状目前,实验室配备快检设备,可快速检测食用农产品中农药残留、兽药残留、重金属、食品添加剂、真菌毒素、致病微生物等7大类。其中,主要以农药残留为主。本     

食品农药残留检测中的化学计量学研究进展

现阶段食品农药残留的检测主要依靠色谱法,但针对日趋复杂的食品农药残留分析,色谱信号中不可避免地出现背景基线和多组分重叠干扰。光谱法近年来凭借其快速无损的优势逐渐受到研究者的青睐,但常用的拉曼光谱和近红外光谱信号不仅容易受到高频噪声和背景基线的干扰,且信号中常出现谱峰重叠的干扰,因此大多需要建立多元校正模型才能实现定量分析;荧光光谱检测信号中也常常出现其它组分信号的干扰,同样较难实现对农药残留的准确分析。化学计量学方法利用"数学分离"的思想,能为食品中农药残留分析提供强大助力。因此,利用化学计量学方法可以用于信号中噪声的消除、背景基线的校正、多元校正模型的建立以及重叠信号的解析。文章总结评述了近十年相关化学计量学方法在食品农药残留分析中的应用研究,旨在为食品农药残留的分析方法和途径提供参考,同时思考了化学计量学方法在食品分析中的研究现状并对其进行了前景展望。     

食品中农药残留筛查系统的构建

对常见农药的种类、农药残留的危害及有关农药残留的最新检测技术和复杂基质样品的前处理技术进行概述,主要总结固相萃取、凝胶渗透色谱、微波辅助消解以及分散固相萃取技术。农药残留检测主要使用色谱学方法,文中重点概述气相色谱、液相色谱方法以及相应的质谱联用技术,高分辨质谱技术的发展可以为农药残留筛查系统的建立提供有力支撑。在此基础上提出基于粮油食品中重点关注的农药残留种类并建立农药残留的监测系统、软件系统及数据库,进而建立农药残留的风险筛查系统,为政府部门及产业部门掌握农产品农药污染情况提出切实可行的解决方案。     

农产品中50余种农药LC/MS-MS质谱数据库的建立及应用

为评价和维护农产品的质量安全,采用离子阱质谱建立50 余种农药的液相色谱- 质谱数据库,通过谱库检索技术可以实现农产品中未知农药组分的快速筛选及定性。在对未知组分进行谱库检索后,通过LC-DAD-MS/MS 方法比较未知组分与标准样品的保留时间、二级质谱的萃取离子流色谱图(EIC)以及紫外光谱图,得到确认结果。采用本实验所建立的未知组分定性方法对实际样品中的未知污染物进行快速筛选,确认了实际样品中所残留的农药污染物。     

Simultaneous determination of pesticides in agricultural products by LC/MS/MS using clean-up with ultrafiltration

A method for simultaneous determination of multiple pesticide residues in agricultural products was developed by using a pretreatment with ultrafiltration, followed by liquid chromatography-tandem mass spectrometry (LC/MS/MS). The pretreatment process (extraction of pesticides from agricultural products with methanol, dilution of the extract with water, and ultrafiltration) gave recoveries in the range of 50-150% for 63 of 83 pesticides spiked at 0.25 microg/ g into 6 agricultural products. The detection limits of pesticides by LC/MS/MS were below 0.0005-0.05 micro/g. This method is useful for screening purposes and for multiresidue analysis of pesticides in agricultural products. Pesticide residues in 50 domestic crops were investigated by this method, and residues of 14 pesticides were detected in 30 crops.     

Multiresidue analysis of pesticides in agricultural products by GC/MS coupled with database software

We evaluated a multiresidue method for determination of pesticides in agricultural products by SCAN mode GC/MS coupled with three kinds of database for 253 pesticides: relative retention time, mass spectra and calibration curve (SCAN method). Twenty-six pesticides, a total of 131 pesticides were detected in samples by the SCAN method. The detection results agreed closely with those of the SIM mode GC/MS method using calibration standards (SIM method). The ratios of the SCAN method to the SIM method ranged from 0.3 to 3.1 with SD values of 0.63. It was judged that the SCAN method could be applied to the screening analysis of pesticide residues in agricultural products, provided that the sample preparation method makes it possible to effectively remove sample matrixes with minimal loss of analytes.     

Multiresidue analysis of pesticides in agricultural products by GC/MS,GC-ECD and GC-FTD using acetonitrile extraction and clean-up with mini-columns

An analytical method was developed for determination of organochlorine, pyrethroid and nitrogen-containing pesticide residues in agricultural products by GC/MS, GC-ECD and GC-FTD. Pesticides were extracted with acetonitrile, and the organic layer was cleaned up on C18 and ENVI-Carb/LC-NH2 cartridges. Pesticides were determined by GC/MS, GC-ECD and GC-FTD. Detection limits of pesticides by GC/MS and GC were below 1-30 ng/g and 1-3 ng/g, respectively. Recoveries of 27 out of 53 pesticides determined by GC/MS and 47 out of 53 determined by GC were 70-120%. This method was useful for the multiresidue analysis of pesticides in agricultural products. Pesticide residues in 81 domestic crops were investigated from April 2001 to March 2002. Residues of 31 pesticides were detected from 21 crops.     

凝胶渗透色谱净化系统与气相色谱-串联质谱法检测5种食品中14种有机磷和7种拟除虫菊酯类农药残留

建立GPC与GC-MS/MS测定5种食品中14种有机磷和7种拟除虫菊酯类农药残留的方法,初步分析GPC净化技术及MS/MS分析技术在食品农药多残留分析的优势。方法 用GPC作为样品前处理方法,处理韭菜、大白菜、辣椒、猪肉、鱼肉五种食品,用 GC-MS/MS检测并进行定性、定量分析。结果 GPC与GC-MS-MS检测食品中14种有机磷和7种拟除虫菊酯类农药方法的线性相关系数r＞0.995,定量限为0.002～0.034 mg/kg,对韭菜、猪肉样品按0.05、0.10、0.20 mg/kg三组水平加标测试,方法精密度RSD%为2.9～10.2%,回收率为78.6～108.3%。结论 本方法检测样品范围广、灵敏度高、定性可靠、定量准确,适合多种类食品中农药多残留分析。     

植物源性食品中农药残留筛选平台研究

目的针对植物源性食品中的未知农药残留,在原农药残留筛选平台的基础上,采用气相色谱-三重四极杆质谱联用仪和UPLC-Q-Orbitrap两种色质技术并配合商业和自建农药筛查库建立共1200多个农药及其降解产物的筛选平台,满足未知农残的快速筛选要求。方法建立筛选平台相关筛选方法和准则,并通过两次欧盟国际比对(EUPT)对该平台进行验证评估。结果该平台在24 h内可完成农残筛选,筛选方法基于农药数据库和空白基质,两次能力验证中阳性化合物的检出率均在90%以上且结果无假阳性。结论该平台利用串联质谱和高分辨质谱的高选择性,结合农药数据库和智能筛选软件,在无标准参考物质的情况下实现非靶向农药的快速筛查。     

食品中拟除虫菊酯类农药残留检测前处理技术研究进展

拟除虫菊酯类农药是一类高效、低毒、广谱杀虫剂, 大量用于农业生产, 其残留广泛分布于食物链中, 对人类的食品安全构成威胁。随着人类生活水平的提高, 人们对食品质量安全愈加重视。因此, 建立各种食品基质中拟除虫菊酯类农药残留量可靠的分析测定方法十分必要。而在整个样品分析过程中, 前处理环节是瓶颈。本文重点对近年来不同基质源食品中拟除虫菊酯类农药残留分析的样品前处理技术和方法进行综述, 主要总结了植物源食品(水果、蔬菜和食用油等)和动物源食品(肉、蛋、奶以及水产品等)基质中菊酯类农药残留提取、净化和富集等前处理步骤, 同时, 对常用的前处理方法的优点和限制因素进行了比较, 并对具有发展前景的前处理技术进行了展望。     

Multiresidue analysis of pesticides in agricultural products by GC-ECD after GPC and graphitized carbon column cleanup

A multiresidue method that enables determination of many pesticides in agricultural products by GC-ECD was studied. First, 63 pesticides were selected as agrochemicals commonly used in crop protection in this country, and/or found in agricultural products over the past 6 years (April 1996-March 2002) in Aichi Prefecture. A sample was extracted with acetonitrile and the acetonitrile layer was separated by salting-out. The extract was purified on a GPC system with a graphitized carbon columns, and then by a Florisil mini-column fractionation. The test solution was subjected to one-injection, dual-column GC with dual ECD (column: Stx-CLPesticides and Stx-CLPesticides2). The detection limits of the pesticides were in a suitable range (0.0001-0.01 microg/g) for monitoring pesticide residues in agricultural products. The method was applied to 203 commercial agricultural products to demonstrate its suitability for routine analysis.     

Feasibility of LC/TOFMS and elemental database searching as a spectral library for pesticides in food

Traditionally, the screening of unknown pesticides in food has been accomplished by GC/MS methods using conventional library-searching routines. However, many of the new polar and thermally labile pesticides are more readily and easily analysed by LC/MS methods and no searchable libraries currently exist (with the exception of some user libraries, which are limited). Therefore, there is a need for LC/MS libraries that can detect pesticides and their degradation products. This paper reports an identification scheme using a combination of LC/MS time-of-flight (accurate mass) and an Access database of 350 pesticides that are amenable to positive ion electrospray. The approach differs from conventional library searching of fragment ions. The concept consists of three parts: (1) initial screening of possible pesticides in actual market-place fruit extracts (apple and orange) using accurate mass and generating an accurate mass via an automatic ion-extraction routine, (2) searching the Access database manually for screening identification of a pesticide, and (3) identification of the suspected compound by accurate mass of at least one fragment ion and comparison of retention time with an actual standard. Imazalil and iprodione were identified in apples and thiabendazole in oranges using this database approach.     

Marine-derived bioactive materials for neuroprotection

A sensitive and specific liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed for the determination of 56 residual pesticides from commercial crops. For a validation of the method, the recoveries, linearities, limits of detection (LOD), and limits of quantitation (LOQ) of the 56 pesticides were investigated. The linearities, LOD, and mean recoveries of the pesticides ranged 0.9686–0.9999, 0.00–11.54 μg/kg, and 65–82%, respectively. This method was evaluated by its application to monitor 345 agricultural products collected from 9 provinces in Korea 2011. Fifteen pesticides were detected from 39 samples and 2 or more residual pesticides were found in 7 samples. However, none of the compounds were observed above the corresponding maximum residue level. The results reflect that the detected pesticide residues were in a safe range and that residual pesticides in the agricultural products in Korea were properly controlled.