新疆不同品种红枣农药残留风险评估与排序

为了评估新疆不同品种红枣中农药残留的危害,探明不同品种红枣(冬枣、灰枣和骏枣)中农药残留的高风险危害因子及其风险等级。利用液相色谱-质谱法和气相色谱-质谱法测定红枣中的93种农药,比较不同品种红枣的农药残留差异,并进行风险评估,对红枣中的农药残留风险和样品风险进行排序。85份红枣共检出农药16种,不同品种的红枣农药残留检出率和检出种类不同,冬枣的农药残留检出率93.33%、检出农药种类15种,明显高于灰枣和骏枣农药残留检出率和农药种类。红枣检出农药的慢性膳食摄入风险和急性膳食摄入风险远小于100%,风险在可接受范围。冬枣中高风险农药是甲氨基阿维菌素苯甲酸盐和中风险农药哒螨灵、联苯菊酯、辛硫磷、啶虫脒、甲氰菊酯。灰枣和骏枣中风险农药为:辛硫磷、丙溴磷和啶虫脒。冬枣样品中存在高风险和中等风险的样品,灰枣和骏枣样品为中风险和低风险样品。新疆红枣的质量安全状况整体良好,但冬枣农药残留风险整体偏高,应引起重视。     

Method Development,Optimization and Validation of Matrix Hydration Effect on Pesticide Residues in Cocoa Beans Using Modified QuEChERS Method and Gas Chromatography Tandem Mass Spectrometry

Modified QuEChERS method combined with gas chromatography tandem mass spectrometry (GC-MS/MS) was developed and validated to determine pesticide residues in dried cocoa beans. Extraction efficiency of matrix hydration effect on 19 pesticide residues was studied and optimized using 2³ full factorial design with percentage recoveries as the response variable. The optimized hydration method was validated for 24 pesticides, and recoveries obtained were in the range of 70–120% with relative standard deviations of less than 20% for most pesticides. Limit of quantification was obtained at 10 μg/kg for all pesticides, and this value was lower than national maximum residue levels (MRLs). Finally, the developed and optimized method was applied to real cocoa bean samples and the results from incurred residues were compared between method with and without matrix hydration. These results suggest that the addition of water to the dry and high-fat cocoa bean samples is crucial in pesticide residue analysis.     

红外光谱技术在红枣农药残留检测中的研究进展

红枣是新疆特色林果的支柱产业,随着栽培面积的不断扩大,由于栽培生态的不同和病虫害的增加,致使农药的使用也越来越多,农药的滥用、误用、超量使用等不规范使用会导致红枣质量安全问题逐渐增多。基于红枣质量安全的关注及红枣中农药残留快速检测的需求,因红外光谱技术简单、快捷、经济、无损的特点,近年来国内外学者利用红外光谱技术对农产品中农药残留检测的可行性进行研究,验证红外光谱技术可用于农产品中农药残留检测分析,结合数据处理方法,化学计量学方法等可建立定性、定量分析检测模型。本文概述近年来红枣中农药的残留和检测现状以及红外光谱技术在农药残留检测相关领域的研究进展,并对红外光谱技术在农药残留检测中的应用发展进行展望。     

Household vegetable processing practices influencing occurrence of pesticide residues in ready-to-eat vegetables

Influence of vegetable processing on pesticide residues in ready-to-eat vegetables studied at the experimental level does not necessarily reflect actual situation at household level. This study assessed influence of household vegetable processing practices on pesticide residues in ready-to-eat vegetables at household level in Arusha, Tanzania. Data on vegetable handling practices were collected through observations and physical interviews in 70 households. Samples of raw and ready-to-eat vegetables were collected from the households for pesticide residues analysis. Detectable pesticide levels were found in 46% of raw and 14% of ready-to-eat vegetable samples. Pesticide residues detected were in the groups of organophosphates (22.8%), pyrethroids (14.3%), organochlorines (7.14%), benzoic acids (7.14%), and carbamates (5.71%). Unauthorized pesticides (dichlorvos, tetramethrin, and bendiocarb) and environmentally persistent pesticide (dieldrin) were found at levels above their respective maximum residue levels. Washing of vegetables twice or more (p = .01) or peeling (p = .008) was significantly associated with reduction of pesticide residues. There was a significant association between occurrence of pesticide residues in ready-to-eat vegetables and washing of minor ingredients with the water used to wash major ingredients (p = .001). Household practices of washing of vegetables with portable water followed with peeling can reduce pesticide residue levels significantly.     

Quantitative analysis of pesticide residues in vegetables and fruits by liquid chromatography quadrupole time-of-flight mass spectrometry

The applicability of liquid chromatography coupled to hybrid quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) for the quantitative analysis of pesticide residues in vegetables and fruits was demonstrated. The LC-QTOF-MS parameters, such as cone voltage, capillary voltage, collision energy and mass extraction window, were carefully optimised for the analysis of pesticide residues. The LC-QTOF-MS method was validated for 149 pesticides in four vegetables and fruits, i.e. apple, potato, cabbage and spinach, at a spiking level of 0.01 mg kg^?1. The samples were prepared according to the Japanese official multi-residue method with a modification to the column clean-up procedure. Of the 149 pesticides, recoveries in the range of 70–120% were achieved for 147 pesticides in apple, 145 in potato, 141 in cabbage and 131 in spinach, with intra-day precisions (RSDs) of < 25% and inter-day precisions (RSDs) of < 30%, which are within the acceptable range given in the Japanese method validation guideline. Matrix effects were negligible for the majority of the target pesticides. Except for spiroxamine in spinach, no interfering peaks were observed in the blank samples. The target pesticides, except those with low sensitivity, achieved calibration curves with satisfactory linearity, with correlation coefficients (r) greater than 0.995 in the concentration range of 0.002–0.1 μg ml^?1. Furthermore, the majority of the target pesticides provided more than one fragment ion or isotope ion that could be used for confirmation. The overall results suggest that LC-QTOF-MS is a powerful tool for the quantification of pesticide residues in vegetables and fruits at the level of 0.01 mg kg^?1.     

Occurrence of pesticide residues and transformation products in different types of dietary supplements

The purpose of this study was to evaluate the presence of pesticide residues and transformation products in dietary supplement products. Thirty-two samples were analysed to determine 177 pesticides by gas chromatography–tandem mass spectrometry (GC-MS/MS) and 333 pesticides by liquid chromatography–high-resolution mass spectrometry (LC-HRMS). Pesticides were extracted from different kinds of dietary supplements by the use of a modified QuEChERS extraction method. Six samples contained pesticide residues at concentration up to 92.7 µg kg^?1, but only butralin exceeded the maximum residue limits set for raw material. In addition to target compounds, LC-HRMS enables the simultaneous detection of non-target pesticides. In this case, transformation products of pesticides were detected in the analysed samples using HRMS analyser (Exactive-Orbitrap). These compounds were not included in the original method, and they were monitored as post-target compounds, knowing their molecular formula and exact mass. Mass accuracy was always < 2 ppm, corresponding to a maximum mass error. The positive findings endorse the idea that a deeper and continuous investigation of pesticide residues and transformation products in dietary supplement products is necessary in order to guaranty consumer’s safety.     

新疆红枣农药残留风险评估与排序

为明确残留农药对新疆红枣质量安全的危害水平及其排序,本文以新疆10县市产出的124份红枣样品为研究对象,并对37种农药残留进行了测定,在此基础上,通过急性、慢性膳食摄入风险分析,探讨了残留农药对红枣质量安全的危害水平;并采用风险矩阵,对残留农药进行了风险排序。结果显示,样品中残留11种农药;残留农药的% ADI(慢性膳食摄入风险)值远小于100%;10种农药的% ARfD值(急性膳食摄入风险)也远低于100%;较其他残留农药,哒螨灵、毒死蜱、苯醚甲环唑、氯氟氰菊酯、氯氰菊酯、甲氰菊酯6种残留农药风险值相对较高,均大于12.05。结论:新疆红枣残留农药的膳食风险较低,哒螨灵、毒死蜱、苯醚甲环唑、氯氟氰菊酯、氯氰菊酯、甲氰菊酯为需重点关注的农药。     

Multi-residual Pesticide Monitoring in Commercial Chinese Herbal Medicines by Gas Chromatography–Triple Quadrupole Tandem Mass Spectrometry

To investigate multi-residual pesticide monitoring data in commercial Chinese herbal medicines on major markets, an easy, rapid, and selective gas chromatography with mass spectrometry (GC/MS/MS) method was established for simultaneously determining multi-residual pesticides including organochlorine, pyrethroid, carbamate, and organophosphorus pesticides in Chinese herbal medicines. The analytical method was based on an efficient extraction procedure and further cleanup steps by solid-phase extraction columns, yielding recovery rates in the range of 70.0–120.0 % for the majority of pesticides, except for hexachlorobenze, diazinon, β-HCH, δ-HCH, and omethoate, with precision values expressed as relative standard deviation of 0.1–14.7 %. The limits of detection of the established GC/MS/MS method for all investigated pesticides ranged from 0.01 to 3.6 μg kg^?1 and limits of quantification from 0.03 to 11.88 μg kg^?1. With this validated method, multi-residual pesticides of 132 Chinese herbal medicine samples were analyzed. The monitoring results indicated that pesticide residue was found in 74 samples. In total, 51 pesticides were found with detection rate ranging from 0.76 to 18.94 %. An 82.3 % of positive pesticides were found in less than 6 % of samples. Hexachlorobenzene was found in 25 samples, quintozene in 15 samples, and acephate and simazine in 13 samples. Concentrations of pesticide residue from monitoring data obtained ranged from 0.5 to 203.5 μg kg^?1. The simple and rapid method can be used as routine analysis method in multi-residual pesticide monitoring of Chinese herbal medicines.     

QuEChERS-Based Methods for the Determination of Pesticide Residues in a Dill Using Gas Chromatography with Electron Capture and Nitrogen Phosphorus Detection

In this study, three QuEChERS-based methods of improving sample extract preparation through reduction of unwanted matrix background for pesticide residue analysis in dill (a chlorophyll-containing matrix) were developed and compared. These methods involved the use of (1) dispersive solid-phase extraction (dispersive-SPE), (2) dispersive-SPE combined with liquid–liquid extraction (LLE), and (3) only LLE. Samples were analyzed by gas chromatography with electron capture and nitrogen phosphorus detection (GC-ECD/NPD). The results indicated that cleanup with primary secondary amine (PSA) and graphitized carbon black (GCB) sorbents followed by final solvent exchange from acetonitrile to petroleum ether was the best alternative of the tested methods, resulting in the cleanest extracts. The matrix effect of dill on the most favorable method herein was not significant, and the calibration performed well, with R ²?≥?0.99. The overall recoveries at three spiking levels of 0.01, 0.1, and 1.0 mg kg^?1 fell in the range between 73 and 110 % (95 % on average) with relative standard deviation (RSD) values equal to or lower than 12 % (5 % on average). Uncertainty for the studied pesticides ranged from 7 to 14 % (with the overall average uncertainty of 11 %). Analyses of real samples revealed the presence of pesticides unapproved for use on dill, as well as exceedances of the maximum residue levels (MRLs) for some pesticides. The samples with residue violation results were also confirmed by gas chromatography–tandem mass spectrometry (GC-MS/MS). The proposed method of sample preparation and chromatographic analysis is sufficient and can be applied with all certainty to determine pesticide residues in dill and other plants of high pigment content, i.e., chlorophyll.     

Evaluation of pesticide residues in fruits and vegetables from Algeria

ABSTRACT

A total of 160 samples of 13 types of fresh fruits and vegetables from domestic production and import were analysed to detect the presence of pesticide residues. Analysis was performed by multi-residual extraction followed by gas chromatography–mass spectrometry. In 42.5% of the tested samples, no residues were found and 12.5% of samples contained pesticide residues above maximum residue limits. Risk assessment for long-term exposure was done for all pesticides detected in this study. Except chlorpyrifos and lambda-cyhalothrin, exposure to pesticides from vegetables and fruits was below 1% of the acceptable daily intake. Short-term exposure assessment revealed that in seven pesticide/commodity combinations, including three pesticides (chlorpyrifos, deltamethrin and lambda-cyhalothrin), the acute reference dose had been exceeded.     

Evaluation of the QuEChERS Method with GC-MS Detection for the Determination of Organochlorine Pesticides in Food of Animal Origin

This paper reports the evaluation of the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for the determination of organochlorine pesticide residues in food of animal origin with gas chromatography–mass spectrometry detection. There is a very little information about sample preparation method for the determination of pesticide residues in food of animal origin in the literature. Moreover, any example of application of the QuEChERS method for the determination of pesticide residues in food of animal origin has not been reported as yet. The results showed that the best recovery ratios from 75 to 112 % were obtained for the method with primary secondary amine, C₁₈ sorbents and evaporation to dryness and dissolving the residues in hexane with relative standard deviation lower than 10 % for most compounds. The limit of quantification ranged from 0.0015 to 0.0071 mg kg^?1. This method was also used for the determination of pesticide residues in 15 samples of pork ham. In 12 samples, low concentrations of DDT or its metabolites and isomers of hexachlorocyclohexane were detected. Heptachlor epoxide and α-chlordane were determined in one sample and HCB in two samples. There were no exceedances of maximum residue levels (MRLs) for the determined pesticides in any of the analysed samples.     

初加工过程对党参中5种农药残留的影响

[目的] 明确党参初加工过程中多菌灵、三唑酮、戊唑醇、咪鲜胺和苯醚甲环唑5种农药残留变化情况。[方法] 通过实验室浸泡法模拟农药污染试验,采用超高效液相色谱-串联质谱法(UHPLC-MS/MS)检测经过清洗、水煮和干燥3种初加工过程后,多菌灵、三唑酮、戊唑醇、咪鲜胺和苯醚甲环唑在党参中的残留量。[结果] 结果表明,清洗后党参中农药残留量降低至0.04~0.76 mg/kg,去除率达18.0%~87.9%,加工因子（PF）在0.12~0.79之间,以2%的小苏打水清洗效果最佳。水煮后残留浓度降低至0.069~0.64 mg/kg,去除率达18.6%~67.1%,PF在0.35~0.84之间,以水煮3 min处理对5种农药残留去除效果较好。党参中5种农药残留量在经干燥后残留量在0.27~1.22 mg/kg之间,PF值范围为1.86~4.10,比干燥前增加了44.3%~74.7%,不同温度下的农药残留量大小顺序为50 ℃＞40 ℃＞60 ℃。不同加工过程对5种农药的去除效果强弱顺序依次为：清洗>水煮>干燥。[结论]党参以2%小苏打水清洗,水煮时间为3 min,烘干温度为60 ℃进行加工,农药残留去除效果最佳;实验结果为有效预防农药残留对生产的影响提供技术支撑,对保障食品安全具有重要意义。     

Effect of household and industrial processing on the levels of pesticide residues and degradation products in melons

Two varieties of melons (Cucumis melo) were treated with two fungicides (carbendazim and maneb) and four insecticides (acetamiprid, cyromazin, imazalil and thiamethoxam) to quantify the effect of household processing on the pesticide residues. To ensure sufficiently high levels of residues in flesh and peel, the most concentrated formulations were applied observing good agricultural practice. The peeling step decreased the concentration of pesticide residues for maneb, imazalil and acetamiprid by more than 90%. Cyromazin, carbendazim and thiamethoxam were reduced by approximately 50%. The reduction of the pesticides could not be fully explained by the systemic character of the pesticides. However, the agricultural practices (time of application), solubility and mode of action (systemic versus contact pesticide) of the pesticides could be used to explain the difference in processing factors for the studied pesticides. Degradation products (melamine and ethylenethiourea) were also investigated in this study, but were not detected.     

A novel method for the determination of some pesticides in vegetable oils based on dissociation extraction followed by gas chromatography-mass spectrometry

The distribution of 40 pesticides of basic nature in different extraction systems was studied at 20 ± 1°C. The distribution constants (P) and distribution ratios (D) between n-hexane and polar phases are calculated. It was found that the studied pesticides are most fully and selectively extracted from hexane and vegetable oils by solutions of perchloric acid in acetonitrile. In particular, the acidification of acetonitrile decreases the D-value of fenpropimorph by 29,000 times. This phenomenon was used for the development of an improved technique for the quantitative analysis of widely used pesticides of basic nature in rapeseed, linseed, sunflower and olive oils by GC-MS. The proposed approach allows obtaining much purer sample extracts, compared with the use of standard solvent extraction with further purification by the freezing-out technique. This approach expands the range of pesticides (flutriafol, fenpropidine, metazachlor, cyprodinil and others) that can be determined by GC-MS. The recovery values of the studied pesticides from vegetable oils were between 85% and 115% with RSD values below 10%. The obtained limits of detection ranged from 0.001 to 0.1 mg kg^–1, and are below or equal to the maximum residue levels (MRLs) set by the European Union for the corresponding pesticides.     

Pesticide residues and estrogenic activity in fruit and vegetables sampled from major fresh produce markets in South Africa

Food is likely to be one of the major pathways through which people are exposed to endocrine-disrupting chemicals. With the exception of residual effects, there are concerns that a number of naturally occurring and synthetic chemicals exert adverse effects upon endocrine systems in wildlife and humans. The current study reports selected pesticide concentrations and the total estrogenic activity of fruit and vegetables using the recombinant yeast oestrogen screen (YES) and T47D-KBluc reporter gene assays. A total of 53 food samples (27 fruit and 26 vegetables) from Johannesburg and Tshwane fresh produce markets (in South Africa) were analysed. Of these, 17 contained one to three different pesticide residues with concentrations ranging between 0.01 and 0.68 mg kg^–1, whereas in the rest of the samples no residues were detected. All pesticides detected except in one sample were below the maximum residue level (MRL), but others were unauthorised for use in specified fruit and vegetables. Estrogenic activity was detected in 26.4% (14 samples) of the samples tested, and the estradiol equivalents ranged from 0.007 to 2 pg g^–1. Although the estrogenic activity was low, it may contribute to adverse health effects. Continuous monitoring for pesticides in fruit and vegetables is important in view of the unauthorised pesticides detected in produce from South Africa and the endocrine-disrupting chemical activity found.     

Effects of processing and cooking on the levels of pesticide residues in rice samples

The effects of processing and cooking on the levels of pesticide residues in rice samples were investigated for 11 pesticides in pre-harvest (9 pesticides) and post-harvest (4 pesticides) samples. In the polishing process, the transfer ratio (%, total pesticide residue amount in product/that in brown rice) of rice bran ranged from 40% to 106%, and the transfer ratio of polished rice ranged from 9% to 65% in pre-harvest samples. These values varied from pesticide to pesticide. The processing factor (the concentration (mg/kg) of pesticide in product/that in the brown rice) of polished rice ranged from 0.11 to 0.73. The loss of pesticides during processing and/or cooking did not correlate to any single physical or chemical property. Investigation of changes of pesticide residues during processing and/or cooking is useful not only to establish MRLs, but also to recognize actual levels of pesticide residues in food.     

桃加工过程中3种噻二唑类农药残留动态

目的 研究清洗和去皮对桃中噻唑锌、噻菌铜和噻森铜残留的影响及榨汁和罐头加工过程中3种农药的残留变化规律。方法 采用室内模拟桃加工方式, 通过高效液相色谱-串联质谱法(high performance liquid chromatography-tandem mass spectrometry, HPLC-MS/MS)检测噻唑锌、噻菌铜和噻森铜在桃中的残留。结果 清洗和去皮对降低桃中噻唑锌、噻菌铜和噻森铜的残留效果显著, 清洗对3种农药的去除率分别为62%、60%和83%, 去皮对3种农药的去除率分别为80%、64%和91%。榨汁后, 噻唑锌、噻菌铜和噻森铜在果汁中的转移率分别为17%、18%和24%, 在果渣中的转移率分别为63%、58%和54%。罐头加工过程中, KMnO4消毒和去皮对3种农药残留去除率较高, 分别为58%~65%和30%~75%; 漂烫和加入糖水对3种农药的去除率较低, 分别为5%~13%和8%~19%。桃果汁和罐头加工后3种农药的加工因子小于1, 桃果渣加工后3种农药的加工因子大于1。结论 清洗和去皮可大量减少桃中噻唑锌、噻菌铜和噻森铜残留, 桃果汁和罐头加工使3种农药残留水平降低, 果渣加工使三种农药残留水平升高。此研究可为桃饮品和桃罐头的膳食风险评估以及加工过程中农药残留消减提供数据参考。     

北方地区枣果农药残留风险评估

目的围绕我国北方地区枣果农药残留问题,开展膳食暴露风险评估研究。方法采集北方地区枣果主产省份(河北、山东、河南、陕西和山西)的102份枣果样品,对82种常用农药和23种禁限用农药进行检测,分别利用急性参考剂量(ARf D)和每日允许摄入量(ADI)进行急性和慢性膳食暴露风险评估,并利用风险排序矩阵对检出农药进行风险大小的排序。结果 102份样品中89份样品检出了农药残留,共检出37种农药,其中2个样品检出农药残留超标,超标农药分别为多菌灵和氰戊菊酯。枣果中检出农药的急性膳食暴露风险(用%ARf D表示)介于0.00%~6.01%之间,平均值为1.82%;慢性膳食暴露风险(用%ADI表示)介于0.00%~0.21%之间,平均值为0.03%。根据农药残留风险得分,检出残留的37种农药可划分为4类,即高风险农药(2种)、中风险农药(3种)、低风险农药(13种)和极低风险农药(19种)。结论我国北方地区枣果中农药残留检出率较高,98%的样品农药残留量符合国家限量标准,枣果中农药急性膳食和慢性膳食暴露风险均处于较低水平,地虫硫磷、克百威、毒死蜱、联苯菊酯和唑螨酯是枣果中应重点关注的农药风险因子。     

Investigation of pesticide residues in vegetables and fruits grown in various regions of Hatay,Turkey

In this study, 175 pesticide residues in various vegetable and fruit samples grown in different regions of Hatay, Turkey, were investigated. Residue analyses were performed using liquid chromatography–tandem mass spectrometry with the QuEChERS method. In tomato, plum and apricot samples, pesticide residues were below the limits of detection. In other samples, at least one pesticide residue was detected. Twelve pesticides (acetamiprid, carbendazim, chlorpyrifos, fenarimol, fludioxonil, hexythiazox, imidacloprid, metalaxyl, pyridaben, pyriproxyfen, thiabendozole, triadimenol) were found at levels between 0.003 and 0.759?mg?kg^?1. Only in cucumber samples, acetamiprid residues were found at levels greater than the maximum acceptable limit in Turkish Food Codex and European Union maximum residue limits (EU MRLs). In other samples, the detected residue amounts are less than the MRLs declared in the Turkish Food Codex and EU MRLs.     

Monitoring and risk assessment of 74 pesticide residues in Pu-erh tea produced in Yunnan,China

A number of 100 Pu-erh tea samples from the 2013 harvest in Yunnan Province (China) were analysed for 74 pesticides. A total of 11 pesticides were detected. At least one pesticide was detected in 56% of the samples. None of these samples contained the 74 monitored pesticides at concentrations above the Chinese maximum residual levels. Imidacloprid, bifenthrin and acetamiprid were most frequently found, with percentages of 53%, 46% and 31%, respectively. These were also the top three pesticides with maximum concentrations of 140, 246 and 672 μg kg^?1, respectively. Residual levels of the monitored pesticides showed no significant correlation with the production time or area of Pu-erh tea. Whereas a high incidence of pesticide residues was detected in Pu-erh tea, the contamination levels observed do not pose any serious health risks.