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.

Simultaneous Screening of 733 Pesticide Residues in Fruits and Vegetables by a GC/LC-Q-TOFMS Combination Technique

In this paper,we report the construction of two accurate mass databases and the development of a combination detection method that simultaneously screens for 733 pesticide and chemical contaminant multi-residues via high-throughput liquid chromatography(LC)-and gas chromatography(GC)-quadru pole-time-of-flight mass spectrometry(Q-TOFMS).This work demonstrates that electronic mass spectral standards may replace chemical-source standard materials as references through one sample preparation and the combination of GC/LC-Q-TOFMS screening.This cutting-edge technique has also replaced multiresidue determination using targeted detection with non-targeted screening.The pesticide residue types,sensitivity,recovery,and reproducibility of this combination technique are evaluated in eight fruit and vegetable matrices.This technique shows three advantages:①In comparison with the discovery capability of a single technique,the combination technique shows an improvement of 51.1%(GC-QTOFMS)and 39.6%(LC-Q-TOFMS),respectively;②the combination technique can satisfy a screening limit lower than 10μg·kg^-1 and meet the requirements of“uniform standards,”although some of the pesticide residues could be optimized to further improve screening sensitivity;③over 488 pesticides with recoveries between 60%-120%and relative standard deviation(RSD)<20%at a spiked level of 10μg·kg^-1 were detected with the combination technique in eight different matrices.From 2012 to 2017,this combination technique was applied in an investigation to screen pesticide residues from 1384 sampling locations for 38138 batched samples covering 18 categories and 134 types of fruits and vegetables obtained from across the mainland of China.After statistical analysis,533 pesticides in 115891 determinations were detected,and the regularity of pesticides in the fruits and vegetables sold on the Chinese market was shown.

Statistical Analysis of Regularity of Pesticide Residues in Vegetables Produced in Inner Mongoli

[Objective]The paper was to study regularity of pesticide residues in vegetables produced in Inner Mongolia.[Method]Mathematical statistic analysis was carried out on 6 800 samples of veggies,fruits,leguminous vegetables,nuts and seeds produced in Inner Mongolia.[Result]The dominated vegetables in Inner Mongolia were green leafy vegetables,solanaceous vegetables and melon vegetables,and their yields accounted for 70%of the total vegetables production.Since 2003,with the rapid increase of detected vegetable numbers,the status of vegetable quality safety had entered into a new stage of sustainable steady after a rapid decline or periodic fluctuation,and the differences in safety levels were obvious,of which the range of exceeding standard rate of pesticide residues in solanaceous vegetables,melon vegetables and leguminous vegetables(about 55%of the total vegetables)was under 2%,with average values of 1.1%,1.6%and 3.1%,respectively.They belonged to stable type.The exceeding standard rate of pesticide residues in green leafy vegetables and Chinese cabbage group(about 30%of total vegetables)presented a decreasing trend year by year,wondering in the range of 7%-10%.They belonged to main risk type.The time period of exceeding standard of pesticide residues in root vegetables and cole vegetables was under predictable,and its exceeding standard rate in some years was over 5%(amplitude variation is over 15percentage points).They belonged to random risk type.The kinds of pesticides,which exceeding standard rate in vegetables were relatively intensive,presented variance in different vegetable species.70%of the pesticides belonged to intermittent over-limits and the probability was below 5%.About 20%tradition pesticides often exceeded standard and their probabilities were over 30%.The exceeding standard of organophosphorus and carbamates pesticides in vegetables presented a decreasing tend,while the risk of some new pesticides containing nitrogen element and high effective pyrethroids showed an increasing tendency.[Conclusion]The paper provided decision making services for agricultural management departments.

Monitoring of Pesticide Residues in Commonly Used Fruits in Hyderabad Region, Pakistan

A market based survey was carried out to evaluate the level of 26 pesticides in some commonly used fruits in Hyderabad region, Pakistan. Gas chromatography coupled with micro electron capture detector was used to assess the levels of pesticide residues. Gas chromatography-mass spectrometry (GC-MS) was also applied for the confirmation of results. Out of total 131 analyzed samples, 53 (40%) were found contaminated with pesticide residues while only 3 (2%) samples were exceeded the MRLs of some pesticides. Chlorpyrifos and dieldrin were detected in almost all analyzed samples. Residues of chlorpyrifos (1256 μg/kg) and endosulfan sulfate (1236 μg/kg) were found higher in orange and apple samples, respectively. The findings of this study provided important data about contamination of pesticide residue in some fruits sold in Hyderabad, Pakistan, and recommended that monitoring studies should be expanded to other fruits grown in different agro climatic regions, which may serve as basis for future policy about the standards and quality control of pesticides.

Determination of Organochlorine Pesticide Residues in Pumpkin, Spinach and Sorrel Leaves Grown in Akwanga, Nasarawa State, Nigeria

Three green leafy vegetable samples of pumpkin leaves, spinach leaves, and sorrel leaves were collected from a farm in Akwanga and were tested for the presence of residues of organochlorine pesticides. The concentrations of all the pesticide residues in the vegetable samples were determined using GC/MS. Among the organochlorine pesticide p,p’-DDT was detected in pumpkin (0.75 mg/kg), spinach (0.319 mg/kg) and sorrel (0.219 mg/kg). θ-BHC and γ-BHC were detected only in pumpkin leaves (0.359 mg/kg and 0.647 mg/kg respectively). Dieldrin was detected in spinach and sorrel (0.124 mg/kg and 0.053 mg/kg respectively). Endrin was detected in pumpkin (0.732 mg/kg) and Aldrin in sorrel (0.095 mg/kg). All these values were above the maximum residue limit (MRL) value of the pesticides. Endosulfan II was detected in sorrel (0.306 mg/kg) below the MRL. The levels of most of the pesticide residues found in vegetables were above the maximum residue limits (MRLs) that call for laws to regulate the use and circulation of such chemicals. Routine monitoring of pesticide residues in this study area is necessary for the prevention, control and reduction of environmental pollution, to minimize health risks.

A Device for Rapid Detection of Dithiocarbamate Pesticide Residues in Fruits

Based on the chemical properties of dithiocarbamate pesticides,a device for rapid detection was developed in the paper,and the experimental conditions were optimized. Dithiocarbamate residues in fruits were successfully detected using molecular absorption spectro-photometry,and the recovery rate was over 80%.The rapid detection method was simple to operate with low cost,and was conducive to application in basic level and enterprise laboratories.

Pesticide Residue Content in Vegetable Bases of Lhasa City

[Objectives]To understand the quality safety of vegetables produced in vegetable planting bases around Lhasa City.[Methods]Four vegetable planting bases in the east,west,south,and north of Lhasa City were randomly selected for testing using rapid measuring instrument for agricultural residues and solid-phase microextraction-gas chromatography-mass spectrometer,with 120 vegetable samples selected.The testing samples included seven categories:green leafy vegetables,eggplants,melons,onions and garlic,root vegetables,beans,and fungi,totaling 29 types of vegetables.The samples were tested for 8 common prohibited and restricted pesticides in organic phosphorus and carbamate esters,including methamidophos,parathion,methyl parathion,monocrotophos,isocarbophos,methamidophos,aldicarb,and carbofuran.[Results]The pesticide inhibition rate of 6 kinds of vegetables detected by the rapid measuring instrument for agricultural residues was relatively high,with green leafy vegetables being the majority,reaching over 25%.By further establishing a solid-phase microextraction-gas chromatography-tandem mass spectrometry method,the accuracy of the data was verified experimentally.The experimental results indicated that the inhibition rate of vegetable samples in this experiment did not exceed 15%,and it was determined as a pollution-free vegetable.[Conclusions]According to the restriction standard of national pesticide use,the inhibition rate of vegetable samples was less than or equal to 40%,indicating that the quality of vegetables was qualified.

Matrix Effects of Fourteen Organophosphorus Pesticides Residues in Nine Kinds of Vegetable Matrices

The matrix effects of 14 organophosphorus pesticides in 9 kinds of vegetables matrices were preliminarily studied by gas chromatography/flame photomet- ric detection（FPD） in the paper. The matrix effects of 14 organophosphoms pesticides in 9 kinds of vegetable matrices at 0.05, 0.1 and 0.2 mg/L were compared, respectively. The results showed that matrix enhancement effect and matrix attenuation effect existed in all cases, while matrix effects did not have strong correlation with concentrations of pesticides, but were related to species of vegetables and structure and polarity of pesticides.

Characterization of Health and Environmental Risks of Pesticide Use in Market-Gardening in the Rural City of Tori-Bossito in Benin, West Africa

A study on the use of pesticides in market-gardening production was carried out on 108 market-gardeners in the rural city of Tori-Bossito in Southern Benin. The objective of the study was to characterize the potential risks of pesticides usage by farmers and the impacts on their health and on the environment. Two risk indexes were calculated for each pesticide: an environmental risk index (ERI) and a health risk index (HRI). First stage larva of the mosquito Aedes aegypti were used as bio-indicator for detecting insecticide residue in vegetable before their harvesting on the farms. The highest ERI were obtained for carbofuran, chlorpyriphos ethyl and endosulfan. Pesticide residues were found in 42% of the samples of leaves of eggplant, cucumber, amaranth and solanum. Vegetables growers used pesticides that may be highly hazardous and which were not registered in most cases. These situations could have unexpected consequences including the exposure of consumers to health hazards.

Assessment of Organochlorine Pesticide Residues in Vegetable Samples from Some Agricultural Areas in Togo

The study was conducted to monitor the concentration of pesticide residues in three staple vegetables (tomato, cabbage, lettuce) collected from 12 prefectures belonging to 4 agro-ecological regions of Togo. A total of 150 samples of ripe tomato, cabbage and lettuce were collected from the study areas and analyzed for 20 OCPs (organochlorine pesticides) residues, which can be grouped into DDTs, Drins, Heptachlors, Chlordanes and HCHs. The data revealed that 100% of the analyzed vegetable samples were contaminated by one or more pesticide residues;83.32% and 100% were below the maximum residue limits (MRLs) set par European Union and FAO/WHO respectively whereas 16.68% were above the EU (MRLs) adopted values. Overall, cabbage contained the highest number of samples with pesticide residues above the MRLs followed by tomato, whilst none of lettuce samples contained pesticide residues above the MRLs. It is therefore proposed to perform continuous monitoring studies of pesticide residues in vegetables cultivated in Togo.

Multi-Residue Levels of Persistent Organochlorine Pesticides in Edible Vegetables: A Human Health Risk Assessment

Background: This study evaluates the quantitative assessment of persistent organochorine pesticide (OCPs) residues in vegetables (Senecio biafrae) from four selected cocoa plantations in Ekiti State, Nigeria. Methods: The pesticides were extracted from the vegetable samples by using USEPA 3500C method and later clean-up on activated silica gel. The pesticides residues in the samples were determined using Gas Chromatography coupled with Electron Capture Detector (GC-ECD). Results: The results showed that the analyzed samples were contaminated with ten OCPs. The mean OCPs concentration ranged from ND—0.399 mg/kg to ND—0.379 mg/kg during the wet and dry seasons respectively. α-BHC, β-BHC, p, p’-DDE, dieldrin, endrin, endosulfan sulphate and methoxychlor were not detected in the samples. Pesticides such as aldrin, endosulfan II, endrin aldehyde and heptachlor slightly exceeded their maximum residue limit. Conclusion: The hazard indices (HI) of heptachlor, endosulfan I, endosulfan II, aldrin, heptachlor-epoxide and p, p’-DDT exceeded 1 and thus pose likely potential non-carcinogenic health risk.

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.

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。

SPS监管差异对中国果蔬类农产品出口贸易的影响——基于农药最大残留限量标准视角

利用2022年中国对157个国家(地区)出口50种果蔬类农产品贸易数据,采用Heckman两阶段模型,基于农药最大残留限量(MRLs)视角,实证分析SPS监管差异对中国果蔬类农产品出口贸易的影响。结果表明:SPS监管差异抑制中国果蔬类农产品出口的二元边际,即贸易成本效应大于竞争优势效应,贸易成本效应抑制扩展边际和集约边际,而竞争优势效应仅促进集约边际;SPS监管差异对中国向发达国家出口以及对蔬菜农产品出口的抑制作用更大;杀菌剂监管差异对集约边际和扩展边际均具有抑制作用,而杀虫剂监管差异仅抑制集约边际。据此,提出对标国际高标准SPS措施、帮助中小型企业克服技术难关、宣传食品安全理念等政策建议。

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.

TurboFlow在线净化/液相色谱-串联质谱法测定水果蔬菜中多菌灵、吡虫啉、啶虫脒与甲基硫菌灵的残留量

建立了TurboFlow在线净化/液相色谱-串联质谱同时测定水果蔬菜中多菌灵、吡虫啉、啶虫脒和甲基硫菌灵残留的方法.样品用乙腈提取,经Cyclone-p在线净化柱净化后,将富集的分析物洗脱转至Betasil Phenyl-hexyl C18分析柱,经色谱分离后,电喷雾串联质谱检测.结果表明,4种农药在1～50 ng/mL范围内呈良好线性,相关系数均大于0.999 7.方法的定量下限（LOQ）为10 μg/kg.4种农药在3个水平的加标回收率为80.3％～109.9％,相对标准偏差为1.5％ ～7.8％.

无锡市市售蔬菜中新烟碱类杀虫剂残留分析及膳食风险评估

目的调查无锡市市售蔬菜中新烟碱类杀虫剂残留情况,评估其膳食暴露风险。方法采集2023年无锡市共7类20种74份市售蔬菜样品,采用超高效液相色谱-串联质谱法检测12种新烟碱类杀虫剂残留量,依据GB 2763—2021《食品安全国家标准食品中农药最大残留限量》分析检出和超标情况,通过相对效能因子模型、食品安全指数法、危害物风险系数进行膳食风险评估。结果新烟碱类杀虫剂检出率为39.19%,超标率为1.35%。检出5种新烟碱类杀虫剂,分别为吡虫啉、啶虫脒、呋虫胺、噻虫胺、噻虫嗪,检出率最高为噻虫嗪(21.62%)。7大类蔬菜均检出新烟碱类杀虫剂残留。平均总暴露浓度(IMIRPF)为0.980 mg/kg。相对效能因子模型中联合暴露浓度小于健康指导值,所有检出单一安全指数和总体安全指数均值均小于1,危害物风险系数R值中噻虫嗪为2.45,呈中度风险,其余杀虫剂R值均小于1.5,呈低度风险。结论本研究中发现无锡市市售蔬菜存在新烟碱类杀虫剂残留污染,尽管总体膳食风险较低,不会对一般人群造成不可接受的健康风险,仍需继续监测蔬菜新烟碱类杀虫剂。

植物性样品中二硫代氨基甲酸酯类农药残留检测方法比较研究

目的建立准确且适用于植物性样品中二硫代氨基甲酸酯类(DTCs)农药残留的检测方法并进行比较。方法研究检测植物性样品中DTCs农药残留的气相色谱-火焰光度检测器法(GC-FPD)和气相色谱质谱法(GC-MS)的特异性、灵敏度、准确度、精密度和转化率并进行比较,并对2015~2021年镇江市售104份植物性样本中DTCs农药残留监测结果进行分析。结果GC-MS法检出限更低(0.003mg·kg^(-1)),GC-FPD法和GC-MS法在检测浓度范围内线性关系良好(r>0.999),在低、中、高3个加标水平下的加标回收率为87.6%~103.4%,相对标准偏差(RSD)为5.6%~8.9%,转化率良好且稳定;104份样品中有10类29份样品检出,检出率为27.9%,检出值为0.030~1.54mg·kg^(-1)。结论GC-FPD法和GC-MS法准确度高、精密度好,均满足植物性样品中DTCs农药残留的检测需求,GC-FPD法操作简便、快捷,而GC-MS法灵敏度更高,具有更佳的抗干扰能力。

6种非标农药的改进QuEChERS结合GC-MS/MS技术检测方法的建立与应用

针对6种欧盟及日本进出口果蔬中重点检测,但在我国食品安全国家标准中暂无检测标准的农药物质进行研究,建立一种改进的QuEChERS(Quick,Easy,Cheap,Effective,Rugged and Safe)提取净化方法结合气相色谱-串联质谱技术(Gas Chromatography-tandem Mass Spectrometry,GC-MS/MS)检测方法,能快速检测叶菜类蔬菜基质中邻苯基苯酚钠、二甲基敌草索等6种农药多残留。样品采用乙腈提取、无水MgSO4与NaCl盐析除水后,经N-丙基乙二胺(PSA)固相材料净化,使用GC-MS/MS在多反应监测模式(Multi Reaction Monitoring,MRM)下分析检测。结果表明:6种农药物质在0.002~0.5μg/mL范围内线性关系良好,相关系数R均大于0.998,方法检出限(RSN=3)为0.15~2.32μg/kg,平均回收率为84.50%~106.23%,相对标准偏差为0.96%~8.35%,此结果均符合欧盟农药残留分析质量控制程序要求与日本和欧盟对农残“一律标准”中农药限量要求。将建立的检测方法应用于其他蔬菜中高发农药物质的检测,检测效果良好。该方法重复性好、耗时短、易操作,为邻苯基苯酚钠、二甲基敌草索等多种农药残留的检测提供了新的检测技术和依据。