基于色谱-质谱联用技术的食品中农药残留高通量非靶向检测技术研究进展

农药残留导致的食品安全事件威胁人们的健康和生命。现阶段食品中的农药残留具有品类多、残留量低且施用未知等特点,检测难度较大。因此,开发食品中农药残留高通量非靶向检测技术具有重要意义。色谱-质谱联用技术因具有高分离、高鉴别、高通量、非靶向等优点,在农药残留检测领域得到了广泛应用。本文对近10年国内外基于色谱-质谱联用技术的食品中农药残留高通量非靶向检测相关报道进行归纳和总结,简要介绍食品中多农药残留检测的现状,重点从多维色谱及高分辨质谱技术的开发、吸附材料及样品前处理技术的改进、化学计量学方法的优化等方面阐述色谱-质谱联用技术在食品中农药残留检测中的应用进展,并对其存在的问题提出相关建议,以期为色谱-质谱联用技术在食品中多农药残留检测领域的相关研究应用提供新的参考依据。     

色谱-质谱联用技术在农药残留中的应用

农药残留严重危害人类健康,需要进行有效检测和严格控制。色谱-质谱联用技术的飞速发展使其在农药残留检测中得到了广泛应用。本文概述了色谱-质谱联用技术和农药残留以及色谱-质谱联用技术在农药残留中的应用,并展望了色谱-质谱联用技术的应用前景。     

农产品中农药残留的检测技术应用及分析

本文主要对农产品中农药残留检测技术的应用进行分析,包括色谱法、色谱-质谱联用技术、毛细管电泳法、免疫分析技术、生物传感器技术、活体生物检测技术以及酶抑制法等。     

食品中菊酯类农药残留检测技术研究进展

菊酯类农药是模拟天然除虫菊酯化学结构发展而来的仿生农用药物,使用量仅次于有机磷农药。菊酯类农药对人体免疫、生殖、神经系统等多方面存在毒副作用,我国对其在食品中的残留限量作了严格的规定。随着剧毒、高毒农药禁用令的实施,加强食品中菊酯类农药残留监控显得更为重要,建立高效、快捷、准确测定食品中菊酯类农药残留的方法迫在眉睫。目前,QuEChERS法、微萃取、石墨烯技术等样品前处理技术,气相色谱-质谱联用、液相色谱-质谱联用等仪器分析技术及免疫标记法、化学分析快速检测法等快检技术成为了研究热点。本文主要综述了食品中菊酯类农药残留检测检测方法的前处理、色谱-质谱分析及快速检测技术应用的研究进展,并在此基础上结合食品安全监测的工作实际,对食品中菊酯类农药残留检测技术的发展趋势进行了展望。     

食品中残留农药检测技术的新进展

对食品中残留农药检测技术其新进展进行了综述。样品前处理中,固相萃取、超临界流体萃取、基质固相分散萃取得到了迅速发展和广泛应用。毛细管气相色谱、超临界流体色谱、液相色谱---质谱联用技术、酶免疫分析等已开始应用于食品的残留家药检测中。直接光谱技术和生物传感器的应用潜力很大。对食品中残留农药检测技术的发展进行了展望。     

气相色谱-串联质谱在食品农药残留检测中的应用进展

正气相色谱-质谱联用(GC-MS)综合气相色谱和质谱两种检测方法的特点,既具有气相色谱法分离能力较强的特点,又具有质谱检测法对化合物的结构准确鉴定的特点,能同时准确且快速地检测食品中微量的多种农药残留及其衍生物质。因此,在各国家食品检测中得到较为广泛的应用,笔者根据实际工作经验从各个层面分析现阶段我国食品农药残留检测中使用到的气相色谱-质谱联用法,并以此     

气相色谱及其联用技术在食品风味中的研究进展

我国食品风味科学近年来发展迅速,在国内已经形成了对于食品风味体系检测较为完善的检测机制和仪器分析平台,该文对气相色谱法（gas chromatography,GC）、气相色谱-闻香器（gas chromatography olfactometry,GC-O）、气相色谱-质谱联用法（gas chromatography-mass spectrometry,GC-MS）、全二维气相色谱法（gas chromatography-mass spectrometry,GC×GC）、气相色谱-嗅闻-质谱联用法（gas chromatography-olfactometry-mass spectrometry,GC-O-MS）、全二维气相色谱-质谱联用法（comprehensive two-dimensional gas chromatography-mass,GC×GC-MS）以及气相色谱-离子迁移率光谱法（gas chromatography-ion-mobility spectrometry,GC-IMS）等技术的原理、优缺点及其在食品风味中的进展进行研究,在原有技术不断发展的同时,与新技术结合共同发展,对食品的风味研究具有重要意义,为今后食品风味物质的深入研究提供相关依据。     

采用GC-MS/MS对酿酒原料中农残测量可靠性的探讨

GB 23200.113-2018《食品安全国家标准植物源性食品中208种农药及其代谢物残留量的测定气相色谱-质谱联用法》规定了植物源性食品中208种农药及其代谢物残留量的气相色谱-质谱联用测定方法,本实验室对其中10种农药及其代谢物残留量进行测定,为了酿酒原料中农药及其代谢物残留量测定方法在本化验室的适宜性和可靠性,在方法使用前对此方法进行方法验证。从方法的专属性、精密度和回收率几个指标对酿酒原料中农药及其代谢物残留量测定方法进行验证,结果表明此方法适用于酿酒原料中农药及其代谢物残留量的测定。     

蜂产品中氯霉素残留检测方法的研究进展

本文综述了近年来蜂产品中氯霉素残留的主要检测方法及其研究进展, 包括微生物法、免疫分析法、色谱分析法和生物传感器法。其中, 免疫分析法着重介绍了酶联免疫法, 色谱分析法则主要介绍了高压液相色谱和色谱-质谱联用技术。最后, 对现有检测方法进行了比较分析。     

食品的化学性风险专题点评

正化学性污染物在食品供应链中广泛存在,包含从重金属、农业生产外部投入品残留、及加工过程产生的有害物等各个方面。本期有22篇优秀学术论文被收录入"食品的化学性风险"专题,涉及内容包括:食品中金属元素、重金属、抗生素、添加剂、农药、抗菌和抗病毒药物残留等分布情况;液质联用、气质联用、微波消解-电感耦合等离子体质谱和同位素稀释离子色谱-串联质谱等检测方法在特定食品中化学污染物检测中的应用及方法     

Fast selective detection of polar brominated disinfection byproducts in drinking water using precursor ion scans

Brominated disinfection byproducts (DBPs), formed from the reaction of disinfectant(s) with natural organic matter and bromide in raw water, are generally more cytotoxic and genotoxic than their chlorinated analogues. Brominated DBPs have been intensively studied over the past 35 years, yet only a fraction of the total organic bromine formed during disinfection has been identified. A significant portion of the unaccounted total organic bromine may be attributed to polar/highly polar brominated DBPs. In this work, a method for fast selective detection of polar/ highly polar brominated DBPs in drinking water was developed using negative ion electrospray ionization-triple quadrupole mass spectrometry (ESI-tqMS) by setting precursor ion scans of m/z 79 and 81. This method was conducted without liquid chromatography separation. The results demonstrate that the ESI-tqMS precursor ion scan is an effective tool for the selective detection of electrospray ionizable bromine-containing compounds in a complex mixture. Many polar/ highly polar bromine-containing DBPs were tentatively found in two drinking water samples, and some of them may be new brominated DBPs that have not been previously reported. This method was also extended for the selective detection of polar bromine-containing compounds/contaminants in groundwater, surface water and wastewater.     

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.     

食品中有机磷农药残留检测方法的研究进展

近年来,食品质量安全问题频繁发生,有机磷农药(organophosphorus pesticides,OPs)残留是食品安全问题的主要来源之一。OPs与其他种类杀虫剂相比,具有杀虫广谱、价格低廉、残效期较短以及抗药性不显著等优点,广泛用于农作物的病虫害防治。但是,OPs的长期不合理使用,微量或痕量残留在蔬菜、水果和粮食上,对人、动植物以及环境造成了危害。因此,建立快速便捷,灵敏高效的OPs残留检测方法已刻不容缓。本文简要介绍了OPs的毒性、残留现状和管理措施,对仪器检测法如气相色谱法、气相色谱-质谱法、高效液相色谱法、液相色谱-串联质谱法等以及快速检测法如酶抑制法、免疫法和生物传感器法等在OPs残留检测中的应用进行阐述,为进一步研究OPs的残留提供基础。     

QuEChERs-超高效液相色谱三重四级杆线性 离子阱串联质谱法测定果蔬中64种农药残留量

目的建立QuEChERs-超高效液相色谱三重四级杆线性离子阱串联质谱法测定果蔬中64种农药的残留量。方法通过优化传统的QuEChERS前处理方法,解决了传统QuEChERS法中前处理试样结块、农药回收率偏低及重现性差的问题;采用超高效液相色谱三重四级杆线性离子阱串联质谱法对果蔬中64种农残进行检测,通过增加切换阀步骤,减少质谱仪不必要的污染,保护质谱系统。结果仪器在10.00min之内完成64种目标物的定量测定。使用外标法绘制64种农药的校准曲线,线性良好,相关系数绝大部分在0.9990以上。方法检出限低,可用于对痕量农药残留的检测。对64农药进行不同基质的加标回收实验,回收率在70%～111%之间。结论该方法前处理简便,分析速度快、灵敏度高,适合于蔬菜、水果中多种残留物的初筛、痕量检测和定量检测分析。     

Screening method for the determination of 199 pesticides in agricultural products by gas chromatography/ion trap mass spectrometry (GC/MS/MS)

A screening method is described for determining 200 pesticides, except dimethipin, divided into four groups by means of gas chromatography/tandem mass spectrometry (GC/MS/MS) using an ion trap mass spectrometer equipped with automated gain control (AGC). The quantitation limit for 194 pesticides was 0.01 mg/kg on a crop basis, except for allidochlor, dimethoate, hexythiazox, methamidophos and triadimenol. The calibration curve of each pesticide was linear in the range of 0.04-5.0 microg/mL. One hundred and ninety-nine pesticides were added to matrix of potato, spinach, cabbage, apple, orange, soybean and unpolished rice at twice the limits of quantitation. The recoveries of 194 pesticides from all crops were satisfactory (50-150%) for screening purposes. Although some pesticides in apple and orange were not determined by selected ion monitoring (SIM) analysis at the limits of quantitation, all of them were identified by ion-trap GC/MS/MS at the same concentration. Thus, the ion trap GC/MS/MS technique is useful for the screening of residual pesticides present at low levels in agricultural products.     

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。     

A review of extraction,analytical and advanced methods for determination of pesticides in environment and foodstuffs

Pesticides are widely applied to prevent unwanted pests from attacking crops and livestock which led to their access into the environment. Overuses of pesticides in environment are presence of pesticide residues and their metabolites that are causing serious detrimental effects on human health and all other living organisms. Several severe diseases (Cancer, chronic obstructive pulmonary disease, birth defects, infertility) and more damages of human health are associated with the exposure of pesticides. The maximum residue limits for pesticides have been regulated by the Codex Alimentarius Commission and European Union to protect human health. Thus, monitoring these compounds is extremely important to ensure that only permitted levels of pesticide are consumed. To date, several techniques have been developed for pesticide detection, from conventional analytical to advanced detection techniques. The conventional analytical methods are gas chromatography and high performance liquid chromatography coupled with various detectors involved a sample preparation step prior to further analysis. Advanced detection methods refer to the sensors development such as electrochemical, optical, piezoelectric and molecular imprinted polymer. In this review, we summarized and explained the available analytical and advanced methods for determination of pesticides compound in environment and foodstuffs. Also, pesticides classification and its toxicity, and available extraction methods are briefly discussed.     

食品中速灭威农药残留检测方法研究进展

速灭威是目前使用较为广泛的氨基甲酸酯类农药,主要用于水稻、棉花和果树的虫害防治。如果长期或不正当用药,极易在食品中残留损害人体健康,速灭威农药残留问题引起人们的极度关注。本文综述了毛细管电泳、高效液相色谱、气相色谱、色谱-质谱联用、免疫分析方法等速灭威农药残留检测方法的研究进展,并对检测方法进行了展望,以期为保证食品安全和提高我国速灭威农药残留的检测能力提供技术支持。     

Multiresidue method for detection of pesticides in beef meat using liquid chromatography coupled to mass spectrometry detection (LC-MS) after QuEChERS extraction

Beef meat is an important food that can be contaminated by pesticides. This study aimed to optimize a multiresidue method for identification and quantification of pesticides in beef meat by liquid chromatography coupled to mass spectrometry detection (LC-MS). The extraction and clean-up procedures were adapted from the QuECHERS method. From the 188 analytes tested, the method was validated as qualitative method for 19 compounds and as quantitative method for 152 compounds. The results were satisfactory, yielding coefficients of variation of less than 20% and recoveries ranging from 70% to 120% and expanded uncertainty of less than 50%. The quantification limit was typically 10 µg kg^?1 (but 25 µg kg^?1 for 12 of the compounds) and the detection limit was 5.0 µg kg^?1. Thirty-two real samples of commercialized beef meat were analyzed without any residual pesticide being found. Thus, the results showed that the multiresidue method for detecting 171 pesticides, using adapted QuECHERS for extraction and LC-MS for detection, is suitable for analyzing beef meat.     

气相色谱-三重四极杆质谱法测定稻米中27种持久性有机污染物

目的建立气相色谱-三重四极杆质谱法测定稻米样品中多氯联苯、有机氯农药和多溴联苯醚等27种持久性有机污染物的分析方法。方法糙米粉样品经水化后,采用乙酸乙酯进行2次直接提取,采用5 g酸性硅胶(44%,m:m)固相净化柱进行净化后采用气相色谱-三重四极杆质谱在动态多反应离子监测模式进行分析,内标法定量。结果27种持久性有机污染物中,4-溴联苯醚的回收率较低,其他7种多氯联苯、7种有机氯农药和12种多溴联苯醚具有较好定量范围,其中高取代溴联苯醚呈二次曲线,回归系数均大于0.996;方法检出限为0.002~1.543 ng/g之间,高取代溴联苯醚的检测灵敏度略差;方法回收率为59.3%~132.7%,相对标准偏差为0.7%~10.8%(n=6)。结论本方法样品前处理操作简单,具有较好的灵敏度、准确度和精密度,适用于稻米中极低含量持久性有机污染物的检测分析。