Rapid screening of 420 pesticide residues in fruits and vegetables using ultra high performance liquid chromatography combined with quadrupole-time of flight mass spectrometry

A new method for screening and identification 420 pesticide residues in fruits and vegetables by ultra-performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry(UPLC-Q-TOF/MS)were developed.The samples were extracted with acetonitrile/acetic acid(99:1,V/V),and clean-up by SinChERS-Nano(single-step,cheap,effective,rugged,safe,nano)column,determined by UPLC-Q-TOF/MS.The accurate mass database and MS/MS database which contains 420 pesticides were established,the automatic retrieval of detection results was carried on according to the accurate mass,retention time,isotope ratio,ion fragment information,and so on.Method verification was performed on leeks samples.The results showed that 420 pesticides had good linearity in the range of 0.1-100μg/L,and the correlation coeffificients(R2)was greater than 0.990.The limits of detections(LODs)and limits of quantifications(LOQs)of 420 pesticides were in range of 0.05-2.0 and 0.1-5.0μg/L,respectively.The average spike recoveries at 3 levels were 70.1%to 119.7%,and the relative standard deviations(RSD)were lower than 20%(n=6).With this method,a survey of pesticide residues was conducted for 110 samples of 10 different fruits and vegetables,which provided scientific data for ensuring pesticide residue safety of the fruits and vegetables consumed daily by the public.This method was simple,sensitive and accurate,and could be used for rapid screening of 420 pesticide residues in fruits and vegetables.

Pesticide Residues and Government Regulation in China─Evidence from Pesticide Residues in Fruits and Vegetables

China is a big producer and exporter of fruits and vegetables,and pesticide residues are an important factor affecting the quality and safety of fruits and vegetables and their export trade.In this paper,we analyzed the pesticide residue data on fruits and vegetables in 32 major Chinese cities between 2012—2019,the export data of Chinese fruits and vegetables and the role of pesticides in foodborne diseases.The results showed that pesticide residues in fruits and vegetables(PRFV)partial excess of maximum residue standard(MRL)and residues of banned pesticide were still widespread in China.By comparing the standards of pesticide residues in the European Union and China and addressing the agricultural situation in China,this paper analyzed the main causes of PRFV in China and put forward some policy suggestions for strengthening government regulation of pesticide application in agricultural products.

Determination of Pesticides Residues in Some Fruits and Vegetables Imported to Iraq

A study was carried out in the laboratories of the National Center for Pesticides Control/State Board for Plant Protection / Ministry of Agriculture in 2010-2011. The aim was to determine the residues of some pesticides in fruits and vegetables imported to Iraq from neighboring countries （Jordan, Syria, Turkey and Iran）. Two types of fruits （apples and oranges） and two types of vegetables （tomatoes and cucumber） were selected for the purpose of this study. These fruits and vegetables are the most agricultural products imported for human consumption in Iraq. Samples were taken from different border points and from local markets. Extraction, clean up and analysis were then processed. The results indicated the presence of small amounts of residues of certain pesticides such as Deltamethrin and Abamectin and Thiamethoxam in some samples. However, these amounts were less than the limit allowed internationally. No indication was observed for the presence of other pesticides residues such as Bifenthrin Trticonazol and Imidacloprid ... etc. in the samples analyzed. Therefore, there is a need to continuity of inspection on pesticides residues in agricultural products imported to Iraq in order to prevent the entry of contaminating materials and secure human safety.

Effect of low-temperature plasma on the degradation of omethoate residue and quality of apple and spinach

Dielectric barrier corona discharge was developed to generate low-temperature plasma(LTP) to treat apple and spinach samples contaminated with omethoate. Experimental results showed that,after 20 min exposure, the degradation rate of omethoate residue in apple and spinach was(94.55± 0.01)% and(95.55 ± 0.01)%, respectively. When the treatment time was shorter than 20 min,the contents of moisture, vitamin C and beta-carotene were not affected by LTP. Exploration of related mechanisms suggested that LTP might destroy unsaturated double bonds of omethoate and produce phosphate ion, eventually leading to omethoate destruction. It is concluded that appropriate dosage of LTP can effectively degrade omethoate residue in fruits and vegetables without affecting their quality.

超高效液相色谱-串联质谱法测定果蔬中氟啶虫胺腈、Pyrifluquinazon和螺虫乙酯残留量

建立超高效液相色谱-串联质谱同时测定蔬菜和水果中氟啶虫胺腈、Pyrifluquinazon和螺虫乙酯残留量的分析方法。样品经乙腈均质提取,混合使用乙二胺-N-丙基硅烷和十八烷基硅烷基质分散净化剂净化,以C18色谱柱分离待测物,采用电喷雾离子化,正离子扫描和动态多反应监测模式检测,基质匹配标准溶液外标法定量。氟啶虫胺腈在0.2～100μg/L之间,Pyrifluquinazon在0.02～10μg/L之间,螺虫乙酯在0.1～10μg/L之间的范围内线性关系良好,相关系数均大于0.999 0。在4个添加水平进行氟啶虫胺腈、Pyrifluquinazon和螺虫乙酯添加回收率实验,平均添加回收率在79.9%～103.9%之间,相对标准偏差在3.3%～8.8%之间。氟啶虫胺腈、Pyrifluquinazon和螺虫乙酯的方法定量限分别为0.334、0.040 5μg/kg和0.378μg/kg,检出限分别为0.100、0.012 2μg/kg和0.133μg/kg。该方法快速简便、定量准确,可满足多种蔬菜和水果中氟啶虫胺腈、Pyrifluquinazon和螺虫乙酯3种杀虫剂的残留检测要求。

Pesticide residue elimination for fruits and vegetables:the mechanisms,applications,and future trends of thermal and non-thermal technologies

Pesticide residues on food are threatening human health and wellbeing,ecological security.Food processing is one of the necessary ways to eliminate residues to guarantee the safety and sustainable development of the environment.This review outlines the mechanisms,applications,and factors influencing the efficiency as well as their limitations of pesticide residue elimination technologies.Conventional thermal processing technologies like drying,blanching,baking,and roasting have been proved to reduce pesticides extensively whereas sometimes concentration effects occur,and more toxic metabolites or by-products are generated.Additionally,the negative effects on quality attributes of fruits and vegetables(F&V)should be considered.Several innovative non-thermal processing technologies like ultrasound,cold plasma,high-pressure processing,and pulsed electric fields have flourished currently,which show great ability to eliminate pesticide residues significantly with minimal impact on the quality of F&V.In particular,heat-sensitive nutrients like ascorbic acid,phenolics,and carotenoids would retain to a great extent.Similarly,these technologies have their limitations.Furthermore,there is much information about combined processing technology affecting the pesticide behaviors of F&V.Finally,the future developments for pesticide elimination of these technologies are identified and discussed.

柠檬汁还原法制备AgNPs用于果蔬农药残留的SERS快速检测

[目的/意义]为满足目前市场上对农产品农药残留的快速灵敏检测需求,报道一种基于柠檬汁还原制备银纳米粒子(AgNPs)的方法。[方法]首先将新鲜柠檬汁经滤纸过滤,稀释成2%的柠檬汁水溶液,再配制一定浓度的AgNO3溶液、50 mM的NaOH溶液,放置室温保存。然后在室温下,将10 mL的ddH2O、2mL的NaOH、2mL的2%柠檬汁和5 mL的AgNO3溶液混合,待溶液颜色变为澄清的黄色时,溶液离心即可获得AgNPs。[结果和讨论]该方法制备的AgNPs,其颗粒形貌大小基本均一,约为20 nm,具有很好的表面增强拉曼散射(Surface Enhancement of Raman Scattering,SERS)增强效应,即良好的SERS信号稳定性,较强的SERS增强性能。该胶体中AgNPs分散较均匀,并且具有较长时间储存的稳定性,因此可用于微量农残检测。柠檬汁中主要还原成分抗坏血酸、葡萄糖和果糖,其含量分别为395.76μg/mL、5.95 mg/mL和5.90 mg/mL。将柠檬汁还原法制备的AgNPs用于果蔬表面农残检测,对于百草枯、多菌灵的检出限分别最低至3.90 ng/kg及0.22μg/kg。[结论]这项工作为果蔬农残快检提供了一种绿色、便捷的SERS材料制备方法,为实现农产品农药残留的快速、灵敏检测提供一种新的途径。

QuEChERS结合GC-MS/MS检测果蔬中13种农药残留

目的:基于QuEChERS方法结合气相色谱串联质谱(Gas Chromatography-Tandem Mass Spectrometry,GC-MS/MS)技术,建立一种简单、快速检测果蔬中农药残留的方法。方法:果蔬样品匀浆后,先用乙腈和乙酸缓冲盐包提取,再用m-PFC小柱净化,最后用GC-MS/MS测定,外标法定量。结果:13种农药在10~500μg·L^(-1)浓度范围内线性关系良好,相关系数(R^(2))均大于0.994,检出限为0.35~0.92μg·kg^(-1),定量限为1.0~2.8μg·kg^(-1);13种农药在3个水平下的加标回收率为82.4%~110.1%,相对标准偏差为2.9%~9.3%。结论:所建立的方法可操作性强,具有较高的精密度和准确度,可用于果蔬中农药残留的定性和定量检测。

QuEChERS-超高效液相色谱-串联质谱法检测果蔬中ipfentrifluconazole残留量

建立一种QuEChERS-超高效液相色谱-串联质谱法测定果蔬中ipfentrifluconazole残留的分析方法。样品经乙腈提取,无水硫酸镁、PSA、GCB净化,滤膜过滤后采用UPLC-MS/MS测定,外标法定量。结果表明,在质量浓度0.005~0.5 mg/L,方法线性关系良好,相关系数大于0.995,定量限均为0.01 mg/kg。在3个添加水平(0.01、0.1、0.5 mg/kg)下,ipfentrifluconazole在5种果蔬中的平均添加回收率为84.0%~102.1%,相对标准偏差为2.1%~12.7%。该方法简单、灵敏、高效,可用于果蔬中ipfentrifluconazole残留检测。

用于检测果蔬中农药残留的柔性表面增强拉曼散射基底的设计策略和应用进展

随着人口增长和生活水平的提高,果蔬中的农药残留已成为关注焦点。表面增强拉曼散射(surface-enhanced Raman scattering,SERS)技术因其快速、无损和指纹识别特性,被认为是食品安全检测的有效方法之一。引入柔性SERS基底为非平面果蔬表面的原位检测带来了新机遇,相比于传统的刚性基底,柔性基底通过“粘贴-剥离”或拭子取样方法,提供了更大的灵活性和适应性。尽管柔性基底在农药残留检测中显示出巨大潜力,但设计和制备高灵敏度、高稳定性且信号重现性好的柔性基底仍是一个挑战。本文深入探讨了柔性基底的构建策略,包括柔性基底材料的选择和柔性基底的制备方法。此外,文章还总结了柔性基底在果蔬农药残留检测中的应用实例,展示了其在实际应用中的效果。文章最后提出了针对这些挑战的可能解决方案,并对未来的研究方向进行了展望。这些解决方案和展望旨在推动柔性SERS基底的进一步研究和应用,为提高果蔬农药残留检测的准确性和效率提供支持。

果蔬农药残留快速检测技术研究进展

果蔬是居民日常生活中不可缺少的食物,农药残留是影响果蔬质量安全的关键因素,农药残留超标会对人体健康造成威胁,严重的会导致中毒、诱发消化系统疾病,甚至癌变。新鲜度是影响果蔬品质的关键因素,直接影响果蔬的口感、营养价值和商品性等,因此农药残留快速检测技术对于保障果蔬质量安全具有十分重要的意义。本文概述了果蔬农药残留的原因与危害,系统梳理了果蔬中农药残留常见的快速检测技术,如酶抑制法、酶联免疫法、生物传感器法、光谱法、胶体金法、质谱法等,并通过分析总结果蔬中农药残留常见快检技术的优缺点及适宜应用场景,以期促进农残分析更加快捷、精确、标准。

市面上果蔬净化器和果蔬洗涤剂去除农药残留效果对比研究

农药可用于防治病虫害及调节植物生长,但我国滥用农药的现象普遍存在,市面上的果蔬大多都存在农药残留甚至部分超标。市面上果蔬净化器和果蔬洗涤剂多种多样,为了更好地了解其性能及对比果蔬净化器与果蔬洗涤剂去除农药残留的效果,分别研究了使用果蔬净化器和果蔬洗涤剂前后农药残留的对比、净化器和洗涤剂清洁同一果蔬农药残留的对比。结果表明,净化器与洗涤剂均能使果蔬农药残留降低,但洗涤剂的效果比净化器的效果好。

气相色谱-串联质谱法快速定量测定蔬果及食用菌中126种农药及代谢物残留量

[目的]建立快速定量测定蔬果及食用菌中虫螨腈等126种农药残留的气相色谱-串联质谱法。[方法]样品匀浆后,称取10.0 g样品加入10.0 mL乙腈,冷冻10 min,加入萃取盐高速振荡提取3 min,提取液用分散固相萃取净化离心后取上清液过微孔滤膜上气相色谱-串联质谱仪测定,基质匹配标准外标法定量。[结果]该方法的线性范围在0.005~0.500 mg/L,相关系数为0.991 2~0.999 7;定量限、低、中、高4个加标浓度,蔬菜、水果和食用菌加标回收率为81.1%~107.2%,RSD(n=6)为1.0%~12.3%。[结论]该方法的前处理方法节省检测时间和溶剂,并筛选出适合农药残留检测的高效能高寿命色谱柱(检测样品数量是通用色谱柱的3倍),大大节约成本和提高检测效率。该方法准确、快速简便、环保、经济,满足大批量实际样品的检测需求。

果蔬中有机磷农药残留快速检测方法的比较分析

为筛选出适用于基层市场监管部门监管水果蔬菜等农产品中有机磷农药残留的快速检测方法,本文对酶抑制率法与胶体金免疫层析法进行比较验证,并采用气相色谱法定量检测结果作为准确性判定依据,对两种快检方法检测白菜、黄瓜、胡萝卜等10种蔬菜共30批次样品的结果进行评判。结果表明,酶抑制率法检出限较高,易出现假阴性、假阳性风险,仅适用于果蔬中大剂量有机磷与氨基甲酸酯类农残检测;胶体金免疫层析法灵敏度较高,与气相色谱法检测结果基本相符,可进行单项农药残留的检测,操作简便,检测时间短,适用于基层市场监管部门对果蔬产品中农药残留的快速检测。

ZnO光消解辣椒表面三唑磷的农药试验

以小米椒为研究对象,利用农药残留检测仪器,探索ZnO材料在光催化中高效、环保地净化农药残留物的应用。研究了多组小米椒表面三唑磷农药(TAP)的残留量、清洗后的残留量以及ZnO光催化下TAP在随机小米椒表面的光消解效果。结果表明,多组小米椒表面喷洒TAP后,残留明显;清洗后,能有效降低残留,但仍有一定含量;经过240 min光照,ZnO催化下随机小米椒表面TAP的降解率达89.01%。同时,ZnO对TAP的光降解速率随时间增加而下降,表明为一级反应。ZnO材料具有良好的光催化降解性能,为农产品中的农药残留治理提供了有效方式。研究成果可为食品生产企业和农业部门提供技术支持,保障人们的饮食安全。将推广到各类农产品及农残检测与消解中。

2022—2023年度广州市市售蔬菜水果农药残留调查分析

目的了解2022—2023年度广州市市售蔬菜水果的农药残留情况,保障居民食品安全。方法利用液相色谱-串联质谱法和气相色谱-串联质谱法对采集的14类共2246份蔬菜水果样品进行农药残留筛查,检测项目一共256种,依据GB2763—2021《食品安全国家标准食品中农药最大残留限量》对检测结果进行评价,超过最大残留限量即为不合格。结果2246份样品中检出率为62.11%,其中蔬菜、水果的检出率分别为59.62%、70.80%,蔬菜中检出率排名前三的是茄果类、豆类和叶菜类,水果中排名前三的是柑橘类、核果类、浆果和其他小型水果类;不合格率为2.94%,蔬菜中豆类、鳞茎类、根茎薯芋类不合格率排名前三,水果中柑橘类、浆果和其他小型水果类、热带和亚热带水果类的不合格率位居前三,禁限用农药超标导致的不合格占不合格样品的2/3。结论筛查发现大部分蔬菜水果样品的农药残留均在GB 2763—2021规定的最大残留限量范围之内,但禁限用农药不合格的情况依然存在,应加强宣传引导和监管力度。

液相色谱串联三重四极杆复合线性离子阱质谱法测定水果和蔬菜中43种杀菌剂残留量

[目的]实现蔬菜、水果中多种杀菌剂残留的同时测定。[方法]建立液相色谱串联三重四极杆复合线性离子阱质谱法(LC-QTRAP-MS/MS)同时测定水果和蔬菜中多种杀菌剂残留量。样品以含0.1%乙酸的乙腈溶液为溶剂,乙酸钠和无水硫酸镁进行盐析,使用无水硫酸镁、乙二胺-N-丙基硅烷化硅胶(PSA)、十八烷基硅烷键合硅胶(HC-C 18)、多壁碳纳米管(MWCNTs)进行净化处理,质谱采用增强子离子扫描模式(MRM-IDA-EPI)及谱库检索技术,通过对化合物保留时间、离子对及EPI谱库检索对比,外标法定量。[结果]43种杀菌剂在0.2~5.0,2.5~50.0μg/L质量浓度范围内线性关系良好(R^(2)>0.99);方法检出限为0.1~5.0μg/kg,定量限为0.4~10.0μg/kg;在3个质量浓度添加水平下,43种杀菌剂的回收率为65.1%~119.8%,相对标准偏差为0.8%~13.0%。[结论]该方法适用于水果和蔬菜中43种杀菌剂的筛查确证和定量检测。

QuEChERS与SPE前处理方法结合GC-MS/MS同时测定8种果蔬中21种农药残留的对比研究

利用气相色谱-三重四极杆质谱法(GC-MS/MS)对比研究固相萃取(SPE)和QuEChERS 2种前处理方法在果蔬中21种农药残留的检测效果。以番茄、黄瓜、胡萝卜、油麦菜、橙、梨、桃、西瓜为基质,分别从定量限、线性关系、回收率、精密度等方面进行比较。结果表明:SPE法和QuEChERS法的21种农药残留基质标准曲线:在0.1~2.0μg/mL范围内线性关系良好(r>0.999),定量限均为0.009 mg/kg。在0.009~0.09 mg/kg加标水平下,SPE法回收率为88.7%~91.9%,相对标准偏差为1.56%~3.72%;QuEChERS法回收率为94.9%~97.4%,相对标准偏差为1.54%~4.17%。QuEChERS法可针对不同果蔬的特性添加不同的净化物质,净化过程具有更高的灵活性,且回收率均优于SPE法。

果蔬产品中多组分有机磷农药残留测定新方法研究与应用

建立了QuEChERS-气相色谱仪测定蔬菜水果中20种有机磷农药残留的检测方法。净化包用阳离子交换树脂,代替PSA、GCB,在色谱柱前面加2米保护柱,20种有机磷农药残留的线性范围均为10~400g·L-1,线性相关系数(r2)均大于0.998,方法的检出限为0.01mg·kg-1。在3个不同添加水平下的加标回收率为70.0%~120%,RSD为1.2%~10%。该法操作简单、成本较低,可对蔬菜水果中多农药残留进行快速筛查。成本由一个样品50元降为5元。

2023年宝鸡市市售果蔬农药残留监测结果分析

目的:全面了解陕西省宝鸡市2023年市售水果蔬菜农药使用情况,为市场监管提供参考依据。方法:2023年度在宝鸡市12个县区超市及农贸市场随机抽取216份时令水果蔬菜,采用气相色谱法检测果蔬中毒死蜱、氧乐果、水胺硫磷、三唑磷、灭线磷、丙溴磷、甲胺磷共7种有机磷农药残留情况。结果:2023年度共有39份样品检出农药残留,检出率为18.06%(39/216),共有4批样品超标使用农药,超标率为1.86%(4/216)。其中毒死蜱超标率最高(1.39%),其次是氧乐果(0.46%),其他5种农药未有不合格样品。结论:宝鸡市果蔬安全状况较好,但仍存在部分农药残留超标情况,相关部门需要对农药的生产、销售、使用环节加强监督。