Assessment of pesticide residues in fresh peach samples produced under integrated crop management in an agricultural region of northern Greece

A multi-residue method using selected ion monitoring mode GC/MS has been developed for the quantitative analysis of residue levels of 23 widely used pesticides in fresh peaches produced under integrated crop management process (ICM). The proposed methodology involved a sample extraction procedure using liquid–liquid partition with acetonitrile followed by a clean-up step based on solid-phase extraction (SPE). Fortification studies were performed at different concentration levels for various types of peaches that differ in properties, such as appearance, flavor and pit. The data showed that the different peach matrices had no significant effect on recoveries. Recoveries were greater than 80% for most of the pesticides with a RSD below 18%. The limits of quantification (LOQs) were in the range 0.002–0.050 mg kg^?1, depending on the compound. To assess method performance with real samples and determine whether pesticide concentrations in peaches exceed their maximum residue levels (MRLs), the proposed method was successfully applied to the analysis of 104 fruit samples collected under integrated pest management (IPM) production during the 2006 cultivation period. Residues detected were lower than those established by legislation for all pesticides, except diazinon, where one positive sample was detected at a level of 0.03 mg kg^?1.     

Evaluation of pesticides residues in Greek peaches during 2002–2007 after the implementation of integrated crop management

The incidence and levels of pesticide residues in peaches grown using Integrated Crop Management (ICM) methods in Pella and Imathia, districts of Macedonia, Northern Greece, are hereby presented. A total of 1150 peach samples were collected pre-harvest (June–September) and were analysed during the period of 2002–2007. Residual levels of selected insecticides, fungicides and acaricides were determined by Gas Chromatography-Mass Spectrometry following solid phase extraction. The monitoring program is extended up to 31 pesticides. Twenty-two of them were measured above detection limit, and 8 of them were found present every year. Insecticides represent the highest incidence amongst pesticide categories (654 positive samples, 56.9%) while chlorpyrifos is the most frequent within the category (491 positive samples). The incidence of pyrethrins was the highest in 2007 (26.8%) while bifenthrin was detected most frequently within this category (67 positive samples in 2007). Traceable levels of pesticides were lower than the Maximum Residues Limits (MRLs) in all peach samples. Variances in incidence and levels of pesticides are attributed to some extent to the weather conditions as well as due to abidance by the guidelines of agronomists during blowing and harvest period. Monitoring in agricultural products could be employed as the first step in a chain of biomonitoring studies in humans, and may also be proven to be a good and ample indicator of exposure.     

Exposure assessment of fruits contaminated with pesticide residues from Valencia, 2001- 03.

A total of 634 samples of oranges, tangerines, peaches, nectarines, khakis and watermelons were collected from an Agricultural Valencia Community Cooperative during the May 2001 to April 2003 campaigns and they were analysed for 15 pesticides among those recommended for pest treatment. A conventional multiresidue analytical procedure based on ethyl acetate extraction was used followed by gas chromatography coupled to a nitrogen phosphorus detector for routine analysis; and mass spectrometry was performed for confirmation. Recovery studies with spiked samples at 0.5 mg kg-1 for each pesticide ranged from 52% for acephate to 87% for fenthion with a standard deviation <20%. Limits of quantification ranged from 0.1 to 100 microg kg-1. A total of 43% of samples contained pesticide residues; and 5% exceeded the maximum residue levels (MRLs). Nine of the pesticides studied were found. Malathion, which was the most frequently detected, was found in 121 samples (19%) at 0.002-4.25 mg kg-1; followed by fenthion in 104 samples (16%) at 0.005-2.3 mg kg-1; and methidation in 68 samples (10%) at 0.008-1.3 mg kg-1. Khaki showed the highest contamination rates with 60% of contaminated samples that exceeded more often the MRLs; and fenthion was the pesticide more frequently detected in all the commodities studied at levels above the European MRLs. The estimated daily intakes of each pesticide calculated from the results obtained were much lower than the acceptable daily intakes.     

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.     

河北产区桃农药残留风险评估

目的 明确河北产区桃中农药残留水平和风险状况。方法 在河北省采集70份桃样品进行农药残留检测与分析,对检出农药残留行急性和慢性膳食摄入风险评估,并利用风险排序矩阵对农药残留风险大小进行排序。结果 70批次桃样品共检出农药残留33种,农药残留检出率为100%,个别样品存在农药残留超标现象,超标农药为多菌灵和甲氨基阿维菌素苯甲酸盐。桃中检出农药的慢性膳食摄入风险(%ADI)在0.00%～1.06%之间,急性膳食摄入风险(%ARfD )在0.00%～11.34%之间。根据农药残留风险排序结果,高风险农药共有5种,其中毒死蜱和甲氨基阿维菌素苯甲酸盐检出率较高,分别为45.7%和18.6%。结论 河北地区桃样品中农药残留检出率较高,但94.3%的样品中农药残留量符合国家限量标准,桃中农药残留急性和慢性膳食摄入风险均处于较低水平,其中,多菌灵、毒死蜱和甲氨基阿维菌素苯甲酸盐是桃中应重点关注的风险因子。     

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.     

Pesticide residues in fruits and vegetables in Jordan using liquid chromatography/tandem mass spectrometry

A total of 158 fruit and vegetable samples produced in Jordan were examined for the presence of pesticide residues using the multi-residue analysis technique by Liquid Chromatography-tandem Mass Spectrometry (LC-MS/MS) and the QuEchERS extraction method. A total of 73 samples (46%) were free from detectable residues, while 85 samples (54%) contained residues. Among the tested samples, 34 (22%) contained residues above Maximum Residue Levels (MRLs) and 51 (32%) contained residues at or below MRLs. Most of the detected residues were found in sweet pepper, peach and apricot samples. Only watermelon samples were free from detectable residues, while tomato and melon samples exhibited residues below MRLs. Out of the 113 pesticides tested, 22 pesticides were found above the limit of detection, 9 of which (hexaconazole, propargite, propiconazole, myclobutanil, thiamethoxam, thiacloprid, clothianidin, clofentezine and pyridaben) had residues that violate MRLs according to European regulations. A continuous monitoring programme for pesticide residues in Jordanian fruits and vegetables is highly recommended.     

杨桃中化学污染物分析及农药残留暴露评估

以杨桃为研究对象,对广东、广西、海南和福建的基地收购点、批发市场和农贸市场等地点的样品进行化学污染物残留分析。结果表明：农贸市场和水果摊样品的农药残留种类少,基地收购点的农残种类最多,超标样品集中在基地收购点。检出率最高的3 种农药为氯氰菊酯、多菌灵和灭幼脲。3 份样品检出镉超标。经点评估对农药残留初步分析,杨桃中的残留风险总体较低,仅三氯杀螨醇存在潜在风险。分布点评估的结果表明,在较高的置信概率P99.5风险水平下,三氯杀螨醇暴露量在幼儿和儿童（2～10 岁）的亚群超过日允许摄入量,存在不可接受的风险。建议重点对基地收购点样品监控,制定三氯杀螨醇、多菌灵和灭幼脲在杨桃上的最大残留限量或筛选三氯杀螨醇的替代品。     

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

The effects of processing and cooking on the levels of pesticide residues in wheat samples were investigated for 13 pesticides in pre-harvest (Pre, 9 pesticides) and post-harvest (Post, 6 pesticides) samples. In the milling process, the transfer ratios (%, total pesticide residue amount in product/that in wheat grain) of wheat bran were greater than 70% and 80% for pre-harvest and post-harvest samples, respectively. The transfer ratios of flour ranged from 1.7% to 23% (Pre) and 4.0% to 11% (Post). There was no significant difference in transfer ratio among the pesticides investigated. The processing factors (Pf, the concentration (mg/kg) of pesticide in product/that in the wheat grain) of flour ranged from 0.030 to 0.40 (Pre) and 0.069 to 0.18 (Post). The values in pre-harvest samples were higher than those in post-harvest samples. 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.     

2012—2014年青岛、深圳、大连三口岸282份进口水果和蔬菜中农药残留监测

目的掌握和了解进口水果和蔬菜中农药残留污染状况,为国家制定和完善相关标准和采取相关措施提供科学依据。方法本文采用GB/T 19648—2006《水果和蔬菜中500种农药及相关化学品残留量的测定气相色谱-质谱法》和GB/T 20769—2008《水果和蔬菜中450种农药及相关化学品残留量的测定液相色谱-串联质谱法》分析方法,对2012—2014年从青岛、深圳、大连三个主要水果和蔬菜进口口岸采集的282份水果和蔬菜样品进行了666种农药残留的检测。结果对282份水果和蔬菜样品进行农药残留测定和技术分析:未检出农药残留样品31份,占11.0%;检出农药残留样品251份,占89.0%。共检测出农药52种,频次702次。结合中国、欧盟、日本的农药最大残留限量标准,对获得的数据进行了科学的分析:进口香蕉、榴莲、火龙果、草莓的农药残留水平整体处于安全水平,应加强进口龙眼、樱桃、葡萄中农药残留的检测和监管。结论进口水果和蔬菜的农药残留检出率较高,达到89.0%,但超出中国最大残留限量标准的样品较少,只占1.1%,说明进口水果和蔬菜中农药残留整体处于安全水平。     

Pesticide residues in orange fruit from citrus orchards in Nuevo Leon State,Mexico

ABSTRACT

Some international organisations established maximum residue limits (MRLs) in food to protect human health. Mexico lacks regulations in this matter, affecting national and international trade from agroindustry. The aim of this study was to diagnose pesticide residues in oranges from Nuevo Leon, México, in citrus orchards. In May 2014, 100 orange fruit samples were taken randomly from orchards and subjected to analysis for 93 pesticides at residual level by GC/QQQ-MS and LCQ-TOF-MS. Results showed the presence of 15 pesticide residues in the samples. The comparison of the residual levels of pesticides found in orange samples among the MRLs allowed by USA, EU and Japanese regulations demonstrated that all samples were below MRLs issued by USA and Japan. Some orange samples were above MRLs issued by the EU. This provides a basis to establish strategies in order to satisfy International Standards to protect human health and encourage Food Safety in Mexico.     

Unit-to-unit variability of pesticide residues in fruit and vegetables.

Pesticide residue levels (36 pesticides and some of their metabolites) were determined in the individual units taken from large samples of apples, bananas, celery, kiwi fruit, oranges, peaches and nectarines, pears, plums, potatoes, and tomatoes. The 65 large samples (generally about 100-110 units, but only 45 units of celery) were purchased at retail or wholesale outlets in the UK. The lots from which the samples were drawn originated from 17 different countries. Average concentrations in the samples were in the approximate range 0.002-2 mg kg(-1). Unit-to-unit variability factors (97.5th percentile mg kg(-1)/average mg kg(-1)), for the pesticide/product combination data sets in which >10% of samples contained measurable residues (n = 106), were in the range 1.4-9.6 (11.1 based on a value of zero for data below reporting limits). Analytical variance contributed only a small proportion (up to 11%) to the overall variance of the 106 data sets. There was no evidence of a relationship between the variability factor and the commodity, country of origin, residue concentration or the physicochemical characteristics of the pesticide. The extent of variability appears to be determined at or about the time of pesticide application. Taking non-detectable residues as half the reporting limits, the frequency distribution of variability factors was approximately log-normal, with a geometric mean of 3.4. The corresponding 95% probability limits of the variability factors were calculated to be 1.6 and 7.6.     

Pesticide residues determination in China vegetables in 2010–2013 applying gas chromatography with mass spectrometry

The levels of multi-pesticide residues in highly consumed types of vegetables in western regions of China were investigated in this study. Vegetable samples (506) were collected from local markets from 2010 to 2013, and the concentrations of 21 types of organophosphorus (OP) and pyrethroid (PYR) pesticides from the samples were determined by gas chromatography–mass spectrometry (GC–MS). Ten OP pesticides were found in concentrations ranging from 0.0008 to 4.0544 mg/kg. Five types of PYR pesticides were determined to have concentrations in the range of 0.0009 to 6.0827 mg/kg. There were no residues in 69.76% of the samples. A portion (25.49%) of the samples contained pesticide residues less than or equal to the maximum residue limits (MRLs), and 4.94% of samples contained pesticide residues greater than their MRLs. This study provides useful information on the current contamination status of a key agricultural area in China from 2010 to 2013 and highlights the need for regular monitoring of pesticide residues in a greater number of vegetable samples and for longer periods, especially in leafy vegetables, to protect consumers.     

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。     

Pesticide residues in apples grown under a conventional and integrated pest management system

This paper describes method validation for determination of more than 40 pesticides in apples using a GC technique. Target compounds belonged to the organochlorine, organophosphorus, carbamates, pyrethroids, triazoles, dicarboximides and strobilurins groups, among others. Sample preparation consisted of acetone extraction and subsequent cleanup/concentration by SPE with a polymer-based sorbent. Single quadrupole GC–MS operating in SIM mode and electron impact ionization was used for identification and quantification of the pesticides. Average recoveries for analytes ranged between 70 and 110% at three fortification levels – 0.01, 0.1 and 0.2 mg kg^?1. Relative standard deviations were lower than 20% for all tested compounds. Calculated limits of detection and limits of quantification were below 0.01 mg kg^?1, which were sufficiently low compared to the maximum residue levels (MRLs) established by European legislation. The proposed method was applied for determination of pesticide residue in four selected apple varieties after harvesting. Whole and processed fruits (peel and peeled fruits) were analyzed from different treatment systems: two conventional, one based on integrated pest management (IPM) and two variants based on organic production (controls). Higher levels of pesticide residues were found in apple fruits under conventional conditions. Fenitrothion and chlorpyrifos residues were detected frequently in apple peel at concentrations up to 0.45 and 0.77 mg kg^?1, respectively. The levels found in the whole fruits of the same samples were much lower than in peel and below the respective MRLs (0.5 mg kg^?1 for both pesticides). Measurable residues of triadimenol only, up to 0.05 mg kg^?1, concentrated in the peel, were found in the apples from IPM.     

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.     

Polyphenoloxidase activity and polyphenol levels in organically and conventionally grown peach (Prunus persica L., cv. Regina bianca) and pear (Pyrus communis L., cv. Williams)

Polyphenoloxidase (PPO) activity and total polyphenol content were tested in organically and conventionally grown whole fruits, peach (Prunus persica L., cv. Regina bianca) and pear (Pyrus communis L., cv. Williams), in order to evaluate the existence of a relationship between these parameters and of differences between fruits obtained with the two cultivation practices. Organic fruits were obtained on three different grounds: subterranean clover (sample A), spontaneous weed cover (sample B) and tilled (sample C). From the latter soil, the conventionally grown fruits were produced. All organic peach samples showed a highly significant (P<0.001) increase in polyphenols (mg equivalents of tannic acid/100 g fresh sample) compared with conventional peaches, while, of the three organic pear samples, samples B and C displayed an increased polyphenol content with respect to the conventionally grown sample (P<0.05). Activity of PPO (U.E./100 g fresh sample), extracted in appropriate conditions and tested towards 1 mM chlorogenic and caffeic acid, was significantly higher in most of the organic peach and pear samples analyzed with respect to the conventional samples.     

慈溪市葡萄农药残留膳食摄入风险评估

目的开展葡萄农药残留膳食摄入风险评估工作,为葡萄食用、农药残留监管和农药最大残留限量提供科学依据。方法在2008~2013年对慈溪市生产的169批次葡萄样品进行了23种农药残留定量检测分析,分别用%ADI和%ARf D进行农药残留慢性膳食摄入风险评估和急性膳食摄入风险评估,用ADI值、大份餐和体重等参数计算最大残留限量估计值(eMRL)。结果近6年葡萄农药检出率为24.85%,超标率为0.59%。检出的7种农药慢性膳食摄入风险(%ADI)为0.010%~1.34%,平均值为0.23%;急性膳食摄入风险(%ARf D)为0.98~28.30%,平均值为8.90%。葡萄农药残留慢性膳食摄入风险和急性膳食摄入风险均很低。结论检出的7种农药最大残留限量(MRLs)均过严,建议将敌敌畏、乙酰甲胺磷、百菌清、氯氟氰菊酯、氯氰菊酯、氰戊菊酯、腐霉利等7种农药的最大残留限量分别定为0.5、3.5、2.5、2.5、2.5、2.5、11 mg/kg。     

Organophosphorus pesticide residues in market foods in Shaanxi area,China

The aim of this study was to investigate the organophosphorus (OP) pesticide residues in market foods (cereals, vegetables, and fruits) in the Shaanxi area of China. The concentrations of eight OP pesticides were determined by gas chromatography with flame photometric detection (GC-FPD). In 18 of 200 samples, five OP pesticides, including dichlorvos, dimethoate, parathion-methyl, pirimiphos-methyl and parathion, were found in concentrations ranging from 0.004 to 0.257 mg/kg. The mean levels of dimethoate in fruits and parathion in vegetables exceeded the maximum residue limits (MRLs) allowed by the Ministry of Health, of China. Other detectable OP pesticide residues levels were below their MRLs. Demeton, diazinon and sumithion were not found in any sample. The results provide important information on the current contamination status of a key agricultural area in China, and point to the need for urgent action to control the use of some excessively applied and potentially persistent OP pesticides, such as dimethoate and parathion.     

Monitoring of pesticide residues in Egyptian fruits and vegetables during 1997

A total of 2318 domestic samples of different types of fruits and vegetables were collected from eight Egyptian local markets in six different regions of the country. All samples were examined for residues of 54 pesticides, including organophosphorus, organonitrogen, organohalogen and certain pyrethroides. However, dithiocarbamates were analysed in only 318 samples. Overall, 81.5% of the samples had no detectable pesticide residues. Of the contaminated samples, 18.5% contained detectable residues and 1.9% exceeded their maximum residue limits (MRLs). Root and leafy vegetables showed the lowest contamination rates (1.9 and 4.7%, respectively), slightly exceeding the MRLs in leafy vegetables. However, fruit samples showed a slightly higher proportion of contamination than vegetables (29 and 14.3%, respectively). Fruit also exhibited a higher level of violation than vegetables (2.3 and 1.9%, respectively). The contamination and violation rates were lower than the percentages recorded in previous years' monitoring studies. Dicofol and dimethoate were the most frequently occurring pesticide residues at 5.1 and 5.0%, respectively. Dimethoate showed higher violation levels (0.69%). However, dicofol showed a slight violation rate (0.09%) which indicates good agricultural practices for dicofol use. Dithiocarbamates residues were found in 21 of the 318 samples analysed, which when expressed as a percentage contamination was 6.6%, and only one sample exceeded the MRL.