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.     

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。     

微酸性电解水对溶液体系中有机磷农药的降解机制及途径分析研究

目的研究对硫磷、甲基对硫磷和乐果对微酸性电解水的敏感性,检测其降解产物并推断降解过程。方法以对硫磷、甲基对硫磷和乐果标准品单一组分为研究对象,通过调节反应时间、微酸性电解水有效氯浓度和有机磷农药的初始浓度,采用气相色谱-质谱联用法检测有机磷农药的降解产物。对有机磷农药在微酸性电解水主要活性成分次氯酸和羟自由基作用下的降解途径进行了分析。结果在反应时间30 s下,有效氯浓度为5.66 mg/L时,对硫磷、甲基对硫磷和乐果的降解率均能达到100%。并检测到对硫磷和甲基对硫磷的直接降解产物对氧磷和甲基对氧磷。结论微酸性电解水能够有效降解有机磷农药,并对HOCl和·OH共同作用于有机磷农药这一降解途径做出假设。该研究对于电解水在消除果蔬有机磷农药残留的应用具有一定的理论意义。     

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.     

Study on the method of setting limits for pesticides residues under the positive list system based on the data for pesticide residues in vegetables and fruits collected in Aichi Prefecture (Fiscal Years 2001-2005)

Based on the data for pesticide residues in vegetables and fruits collected in Aichi prefecture (fiscal years 2001-2005), we selected groups of foods and pesticides that would allow efficient and effective inspection under the positive list system. Statistical analyses were done to examine the rates of detection of pesticides and the numbers of kinds of pesticides detected in samples of domestic vegetables, domestic fruits, imported vegetables, and imported fruits. The rate of detection of pesticides has decreased gradually in domestic vegetables. The number of different kinds of pesticides detected in each sample was significant higher in domestic fruits. Data for previous years were reassessed in terms of the present maximum residue limits (MRL), and classified as relative value to the MRL. The proportion of pesticides detected at levels that exceeded the MRLs showed a decreasing tendency. In addition, we were able to identify combinations of pesticides and agricultural commodities in which the MRLs were more likely to be exceeded.     

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.     

Pesticide residues in leafy vegetables,stalk and stem vegetables from South Korea: a long-term study on safety and health risk assessment

South Korea has a unique food culture. South Koreans enjoy wrapping meat and eating or making kimchi (traditionally fermented Korean food) and eating using raw leafy vegetables, stalk and stem vegetables. Therefore, there is a high chance of being exposed to pesticide residues of vegetables. The objective of this study was to investigate pesticide residues in leafy vegetables, stalk and stem vegetables from South Korea. A total of 8496 samples were mainly collected from Gwangju and Jeonnam area (the largest production region of leafy vegetables, stalk and stem vegetables) in South Korea from 2010 to 2014. A total of 230 pesticides were used for multi-residue analysis of pesticides. Among 8496 samples, 61 different pesticides (1029 times) were detected in 890 samples, of which 118 samples (1.4%) exceeded the Korea maximum residue limits (MRLs). Samples exceeding the MRLs were mostly found in leafy vegetables (brassica lee ssp. namai, leafy lettuce, spinach, perilla leaves, crown daisy, marsh mallow, aster scaber, pimpinella brachycarpa) and Chinese chive. Procymidone, dimethomorph and azoxystrobin were the most frequently found pesticides. A risk assessment of pesticides exceeding the MRLs was evaluated by calculating the estimated daily intake (EDI) and the acceptable daily intake (ADI). The ratio of EDI to ADI was 0.003–30.4%.     

Organophosphorus pesticide residues in milled rice ( Oryza sativa ) on the Chinese market and dietary risk assessment

The present study investigates the occurrence of acetylcholinesterase (AChE)-inhibiting organophosphorus (OP) pesticide residues in milled rice samples obtained form local markets in China during the period 2004–2006 and estimates their cumulative exposure. Concentrations of OP pesticides were determined by gas chromatography with flame photometric detection (GC–FPD). The results showed that 9.3% of the samples contained detectable residues of at least one of the seven target OP pesticides (chlorpyrifos, dichlorvos, omethoate, methamidophos, parathion-methyl, parathion and triazophos) mainly used for agriculture in China, with concentrations ranging 0.011–1.756 mg kg^?1. Rice consumption data was obtained from an individual food consumption survey. Relative potency factors (RPFs) for each pesticide were calculated with methamidophos as the index compound (IC), using 1- or 2-year chronic non-observed adverse effect levels (NOAEL) for AChE inhibition, mostly in rat brain, obtained from international evaluations of pesticides. Exposure to AChE-inhibiting pesticides for the population above 7 years old at P99.9 represented 52–94.5% of the acceptable daily intake (ADI) expressed as methamidophos. Estimated exposure for children aged 2–4 and 4–7 years at P99.9 were 119 and 104.3% of the ADI level, respectively. This study suggests that a yearly monitoring program for OP pesticide residues and strict implementation of the national safety standard for milled rice is necessary.     

芹菜农药残留风险评估

目的 评估芹菜样品的农药残留风险, 为生产上安全合理使用农药及制订农药最大残留限量标准提供参考依据。方法 随机抽取基地30份芹菜样品, 检测68种农药残留, 分别运用风险系数法、慢性膳食摄入风险(acceptable daily intake, ADI)评估法、急性膳食摄入风险(acute reference dose, ARfD)评估法、风险矩阵排序法进行芹菜农药残留风险评估。结果 芹菜农药残留合格率为70.00%, 超标农药为甲拌磷、二甲戊灵、阿维菌素、对硫磷。甲拌磷、对硫磷、阿维菌素和二甲戊灵的风险系数R﹥2.5, 为高风险农药, 其余农药为低风险。慢性膳食摄入风险及急性膳食摄入风险均在可接受范围内。风险矩阵排序位于前五位的分别是甲拌磷、对硫磷、阿维菌素、异丙威、联苯菊酯。结论 芹菜种植中农药残留超标率较高, 其中甲拌磷风险最大, 其次为对流磷和阿维菌素等, 应重点监控芹菜种植中这些农药的使用。     

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.     

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。     

芦笋中农药最大残留限量及检测方法研究进展

总结了芦笋中常用农药及欧盟、日本、美国和我国对其最大残留限量规定,并对农药残留相关检测方法在芦笋等果蔬中的应用进行综述,以期为我国芦笋中农药残留检测和控制提供参考。     

果蔬加工过程农药残留行为研究及加工因子在风险评估中的应用

食品安全问题一直是社会关注的焦点,而果蔬中农药残留是影响食品安全的重要因素之一。果蔬产品大部分需要经过加工处理,残留在果蔬中的农药在加工过程中受到不同程度的影响,如清洗、去皮等加工对于果 蔬表面的非内吸性农药有显著的去除效果,而热处理过程对某些农药存在蓄积作用,在某些情况下也会加快分解或形成有毒的代谢产物。随着加工工艺水平不断提升,新型的加工方式在果蔬加工过程中应用越来越广泛,对农药残留影响也越发复杂。因此,本文对果蔬加工过程中农药残留行为影响进行系统综述,并总结农药残留加工因子在膳食暴露评估中的应用,以期为农药残留进行精准膳食风险评估和农药合理使用提供依据。     

Pesticide residues survey in citrus fruits

The use of pesticides is widespread in citrus fruits production for pre- and post-harvest protection and many chemical substances may be applied in order to control undesirable moulds or insects. A survey was carried out to evaluate levels of pesticide residues in citrus fruits. Two multiresidue analytical methods were used to screen samples for more than 200 different fungicides, insecticides and acaricides. A total of 240 samples of citrus fruits including lemon, orange, mandarin, grapefruit, lime, pomelo and kumquat were taken in various markets in the Geneva area during the year 2003. Ninety-five percent of the 164 samples issued from classical agriculture contained pesticides and 38 different compounds have been identified. This high percentage of positive samples was mainly due to the presence of two post-harvest fungicides, imazalil and thiabendazole, detected in 70% and 36% of samples respectively. Only three samples exceeded the Swiss maximum residue limits (MRLs). Fifty-three samples sold with the written indication “without post-harvest treatment” were also controlled. Among theses samples, three exceeded the Swiss MRLs for penconazole or chlorpyrifos and 18 (34%) did not respect the written indication since we found large amounts of post-harvest fungicides. Finally, 23 samples coming from certified organic production were analysed. Among theses samples, three contained small amounts of pesticides and the others were pesticides free.     

国内外大蒜农药残留限量对比分析

目的 掌握国内外大蒜中农药最大残留限量(Maximum residue limits,MRLs)标准现状,以便降低大蒜出口贸易风险,并在此基础上对完善我国大蒜农残限量标准提出建议。方法 收集我国与欧盟、国际食品法典委员会(Codex Alimentarius Commission, CAC)、日本和韩国等5个组织或国家的大蒜农药MRLs标准并进行对比分析。 结果 我国大蒜农药MRLs标准有129项,欧盟、日本、韩国和CAC分别有510、252、173和23项。欧盟、日本、韩国和CAC标准中与我国相同的农药种类数量分别有93、67、56和18项,其中限量值低于中国标准的分别占49、19、22和4项。结论 由于各国膳食结构不同及登记使用的农药情况不同,我国与欧盟、CAC、日本和韩国大蒜MRLs标准指标总数及指标要求差异明显,建议结合我国大蒜生产实际及膳食需求,完善我国相关标准。     

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.     

Study of pesticide residues in agricultural products for the "Positive List" system

During a 3-year monitoring survey (April 2002-March 2005) of pesticide residues in agricultural products, 592 samples (324 domestic; 268 imported) collected in Hyogo prefecture, Japan were analyzed. The number of pesticides tested increased from 232 in FY 2002 to 323 in FY 2004. The purpose of the study was to clarify the residue status by accumulating information about pesticides detected frequently, to allow effective and efficient regulation under the new "Positive List" legislation to be implemented in FY 2006. Overall, 47% of domestic and 61% of imported samples contained detectable residues and ca. 60% of positive samples contained multiple residues. The limit of quantitation was set at 0.01 microg/g and the limit of detection was 0.001-0.003 microg/ g. Most of the residues were present at low concentrations: 80% of the detections in samples excluding imported citrus fruits were < 0.05 microg/g. More than 5 different pesticides (> 0.01 microg/g) were detected simultaneously in 13 samples. The sum of the ratios of residues to MRLs was calculated as one of the indexes to represent the risk of multiple residues, and they exceeded 100% in 3 imported frozen vegetables; baby kidney bean, spinach, Welsh onion. Samples in violation of the Food Sanitation Law were not found in our survey, but 1.9% of the samples might be in conflict with the new "Positive List" legislation.     

芒果果实中农药残留分布及慢性膳食摄入风险

为掌握常用农药在芒果果实中的残留分布情况及其对慢性膳食摄入风险的贡献大小。采用气相色谱和超高效液相色谱-串联质谱法测定样品中42个常用农药残留。采用点评估方法计算检出农药对儿童和成人的慢性膳食摄入风险的贡献份额,采用相对效能因子法计算农药的累积风险。44.1%的全果样品和35.5%的果肉样品中检出农药残留。吡虫啉在全果和果肉中的检出率最高,分别为21.6%和19.6%。按照我国制定的最大残留限量标准(MRL),吡唑醚菌酯、噻虫胺、吡虫啉和苯醚甲环唑在全果和果肉中均存在超标现象,在全果和果肉中的超标率分别是6.9%/1.0%、5.9%/1.0%、3.0%/2.0%、2.0%/2.0%。不套袋品种(台农和贵妃)农药检出率和超标率高于套袋品种(金煌)。所有检出农药的残留水平基本符合全果的残留量高于果肉的残留量。对于内吸性较强的农药(如新烟碱类农药和三唑类农药等),少部分芒果样品果肉中的残留量高于全果或者只在果肉中有检出。果肉中同时检出4种及以上农药的样品比例为7.9%,小于全果中的比例(20.6%)。所有检出农药对成人和儿童的%ADI均远远小于100%,且三唑类和新烟碱类农药的累积风险也极小。通过芒果摄入的农药残留对慢性膳食摄入风险的贡献极低。     

Survey of pesticide residues in baby foods (1996.4-1998.6)

Between April 1996 to June 1998, 133 samples of 9 food commodities were analyzed for pesticide residues. In 8 samples of 5 commodities, 5 kinds of pesticides residues were detected. The baby foods in which the pesticides were detected were produced from vegetables and fruits. In our investigations, pesticide residues have been frequently detected in the raw materials. For the baby foods containing pesticides, intake amounts of the pesticides calculated from the daily feeding volume and the ADI were compared. Residual pesticide levels in baby food commodities are low, and it was concluded that they are not likely to present any problem in normal usage.     

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.