Residues of insecticides and fungicides on Ontario-grown vegetables, 1986-1988

Between 1986 and 1988, 433 composite vegetable samples representing 16 commodities were collected from farm deliveries to the marketplace in Ontario, Canada. All samples were analysed for insecticides and fungicides. The analyses included organochlorine, organophosphorus, synthetic pyrethroid, and N-methylcarbamate insecticides and dithiocarbamate, dicarboximide, and organochlorine fungicides. The commodities tested included asparagus, beans, carrots, celery, cole crops, cucumbers, lettuce, onions, peppers, potatoes, radishes, rutabagas and tomatoes. In 64% of samples, no pesticide residues were identified to the limits of detection which ranged from 0.005 to 0.05 mg/kg. A further 22% had combined insecticide and fungicide residues below 0.1 mg/kg. Most of the positive findings were a fraction of the Maximum Residue Limit permitted for each commodity under the Canadian Food and Drugs Act and Regulation. Three samples (0.7%) had residues that exceeded the MRL. These involved diazinon and parathion on celery and chlorothalonil on peppers. While some commodities had no detectable residues others had measurable residues of up to three separate pesticides. The most were found on celery, lettuce and field tomatoes.     

Occurrence of fungicide and insecticide residues in trade samples of leafy vegetables

The aim of this work was to report on a total of 23 fungicides and insecticides residues in 75 green and leafy vegetables (Swiss chards, Spinaches and Lettuces) collected from Ourense (NW Spain) by Spring 2007. The pesticides in the study samples were extracted with acetonitrile; the extracts were then cleaned-up by solid-phase extraction and concentrated before determination by PTV (Programmable Temperature Vaporization Injector) – GC-ITMS. Use of analyte protectants mixtures provided the best results in terms of effective compensation for matrix-induced enhancement effect. Pesticide residues were determined above the maxima residue limits (MRL) in 15 of the 75 analyzed samples, with a total of 18 violations of the MRL (three of the samples did not fulfil with two different pesticide MRL). The highest concentrations of fungicides were found in lettuce (procymidone, 12 mg/kg) and the highest concentrations of insecticides were found in Swiss chard (cypermethrin, 6 mg/kg). More positives for fungicides were detected and at larger concentrations than insecticides, especially for lettuces. Accumulation of pesticides in lettuces is higher than for the other leafy vegetables. The findings of this study pointed to the following recommendation: the need for a monitoring program for residues of iprodione and procymidone, together with cypermethrin, in food crops at the national level.     

Pesticide residues in grapes and wine in Italy

Two hundred and one pesticides comprising 84 fungicides, 88 insecticides and 29 herbicides are registered in Italy for use on grapes. Recently, the maximum residue limits (MRLs) for 16 fungicides and five insecticides were established for wine. However, literature data show that some MRLs for wine are not consistent with the corresponding values for grapes. In Italy, the Ministry of Health has the responsibility for checking pesticide contamination in fruit and vegetables in general distribution (i.e. grocery shops, food stores). From 1996 to 1999, out of 1532 grape samples analysed, levels of 1.0, 0.9, 1.8 and 1.9% in each year respectively were contaminated. As part of the National Residue Monitoring Programme, the Ministry of Agriculture carried out investigations of samples collected directly from the field (therefore of a known pesticide treatment history) in order to find the causes of the observed irregularities and to identify preventative measures. In 1996, 1998 and 1999, out of 481, 1195 and 1949 grape samples analysed, 7.9, 6.5 and 2.5% respectively were contaminated, while no residues were detected in 259 wine samples. The National Observatory on Pesticide Residues collects data from analyses performed by highly reliable, non-institutional laboratories on samples from farming cooperatives or individual farms, food companies, wholesale and retail markets. Of the 846 grapes samples and 190 wine samples collected in 1998 and 1999, a total of 6.1 and 2.1% respectively of grapes and 0% for all wine samples were found to contain residues.     

Baby food production chain: pesticide residues in fresh apples and products.

During 3 years of a monitoring programme, 522 samples of fresh apples, six brands of fruit purées and various types of fruit baby food prepared from these materials were analysed. Each sample was examined for the presence of 86 GC amenable pesticide residues. The reporting limits of the procedure employed for sample analyses were in the range 0.003-0.01 mg kg(-1). Pesticide residues were detected in 59.5% of the samples of fresh apples. However, maximum residue levels (European Union MRLs) were exceeded only in 1.4% of samples. The levels of residues in 'positive' fruit purées were substantially lower, overall with residues detected in 33% of samples. Fruit baby food represented the commodity with the lowest incidence of residues being detected in only 16% of samples. The 0.01 mg kg(-1) MRL was exceeded in 9% of these products. Multiple residues were found in 25% of fresh apples and in 10% of fruit purées. None of fruit baby food samples contained more than a single residue. Organophosphorus insecticides and fungicides representing phtalimides, sulphamides and dicarboximides were the most frequently found residues. To obtain more knowledge on the fate of residues during fruit baby food production, processing experiments employing apples with incurred residues (fenitrothion, phosalone and tolylfluanid) were conducted. Washing of apples did not significantly reduce the content of pesticides. Steam boiling followed by removal of peels/stems was identified as the most efficient steps in terms of residues decrease (phosalone) or complete elimination (fenitrothion and tolylfluanid).     

Organochlorine pesticide residues in poultry feed,chicken muscle and eggs at a poultry farm in Punjab,India

Animals intended for human food may absorb pesticides from residues in their feed, water or during direct/indirect exposure in the course of pest control. The objective of the present investigation was to monitor organochlorine pesticide residues in poultry feed, chicken muscle and eggs at a selected poultry farm. The samples were Soxhlet extracted for 8 h in 200 mL hexane–acetone (1:1, v/v) mixture. The clean‐up of the samples was performed by silica gel column chromatography and analysis was done on a gas chromatograph equipped with an electron capture detector. The mean total hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT), endosulfan sulfate and heptachlor epoxide residues were 0.65, 0.91, 0.42 and 0.02 mg kg^?1, respectively, in feed while respective values for chicken muscle were 0.11, 0.24, 0.10 and 0.07 mg kg^?1. Higher residues were encountered in eggs as compared to muscle. None of the muscle samples exceeded maximum residue limits (MRL) for organochlorine pesticides, while all egg samples had values above the MRL for HCH and heptachlor epoxide and seven egg samples exceeded MRL for DDT residues. The results indicated that poultry feed could be one of the major sources of contamination for chicken and eggs. These residues are present despite complete ban on the use of technical HCH and DDT for agricultural purposes in India. Copyright © 2005 Society of Chemical Industry     

Pesticide residues in grapes from vineyards included in integrated pest management in Slovenia

Although the list of pesticides used in integrated pest management (IPM) in grape growing and their annual application rates are limited, we are still confronted with the problem of pesticide residues in grapes. This paper presents the results of pesticide monitoring of 47 samples of wine grapes (Vitis vinifera L.) from the 2006 vintage from vineyards included in IPM. The grape samples were analysed for the presence of 67 pesticides. Among them 20 were allowed in IPM in 2006. Grapes were sampled at harvest. Two internal analytical methods were used for the determination of pesticides: gas chromatography-mass spectrometry (GC-MS) method for the determination of dithiocarbamates and a multi-residue GC-MS method. One grape sample (2.1%) contained no residues or they were below the limit of detection, 28 samples (59.6%) contained residues lower or equal than maximum residue levels (MRLs), and 18 samples (38.3%) exceeded national MRLs for cyprodinil (the concentration range was 0.03-0.40 mg kg^-1 of cyprodinil) and fludioxonil (concentration was 0.03 mg kg^-1 of fludioxonil). Multiple residues were found in 41 samples (87.2%). The highest number of pesticides detected per sample was seven. No violation of pesticides allowed in IPM was observed. Folpet (97.9%), cyprodinil (51.1%), dithiocarbamates (44.7%), chlorothalonil (23.4%), chlorpyriphos (19.1%) and pyrimethanil (14.9%) were the most frequently found pesticides in grapes. Risk assessment showed that the exceeded concentrations of cyprodinil and fludioxonil did not represent any risk for consumer's health (the national estimate of short-term intake as a percentage of the acceptable daily intake was below 100%).     

Monitoring Ontario-grown apples for pest control chemicals used in their production, 1978-86

Between 1978 and 1986, 305 samples of apples were monitored for the residues of a wide range of pesticides used in their production. Three (1%) contained residues above the maximum residue limits (MRL) permitted under the Canadian Food and Drug Act and regulations; two involved phosalone at 5.9 and 6.2 mg/kg respectively and one involved diphenylamine at 6.7 mg/kg when the MRL was 5.0 mg/kg for both compounds. Low residues of dicofol, endosulfan, phosalone, phosmet, captan, daminozide and diphenylamine were frequently found; however they were well below the MRLs. These residue levels were correlated with survey data on the areas of the apple crop treated with specific pesticides. Residues of carbaryl, diazinon, ethion, azinophosmethyl, parathion, and dithiocarbamate fungicides were found occasionally; all were well below the MRLs and correlated with the pattern of use. No residues of PCB were found to a limit of detection of 0.01 mg/kg.     

Pesticide residues in grapes from vineyards included in integrated pest management in Slovenia

Although the list of pesticides used in integrated pest management (IPM) in grape growing and their annual application rates are limited, we are still confronted with the problem of pesticide residues in grapes. This paper presents the results of pesticide monitoring of 47 samples of wine grapes (Vitis vinifera L.) from the 2006 vintage from vineyards included in IPM. The grape samples were analysed for the presence of 67 pesticides. Among them 20 were allowed in IPM in 2006. Grapes were sampled at harvest. Two internal analytical methods were used for the determination of pesticides: gas chromatography-mass spectrometry (GC-MS) method for the determination of dithiocarbamates and a multi-residue GC-MS method. One grape sample (2.1%) contained no residues or they were below the limit of detection, 28 samples (59.6%) contained residues lower or equal than maximum residue levels (MRLs), and 18 samples (38.3%) exceeded national MRLs for cyprodinil (the concentration range was 0.03–0.40 mg kg^?1 of cyprodinil) and fludioxonil (concentration was 0.03 mg kg^?1 of fludioxonil). Multiple residues were found in 41 samples (87.2%). The highest number of pesticides detected per sample was seven. No violation of pesticides allowed in IPM was observed. Folpet (97.9%), cyprodinil (51.1%), dithiocarbamates (44.7%), chlorothalonil (23.4%), chlorpyriphos (19.1%) and pyrimethanil (14.9%) were the most frequently found pesticides in grapes. Risk assessment showed that the exceeded concentrations of cyprodinil and fludioxonil did not represent any risk for consumer's health (the national estimate of short-term intake as a percentage of the acceptable daily intake was below 100%).     

水果中26种有机氯及拟除虫菊酯农药残留GC-ECD测定

利用气相色谱(GC)建立了水果中26种有机氯农药同时测定的方法。试样中农药残留在超声波振荡条件下用乙腈提取,经PSA、C18净化,GC-电子捕获检测器(ECD)检测。方法的检出限为0.001～0.005mg/kg,回收率为84.5%～104.5%,相对标准偏差为1.1%～6.7%。该方法的灵敏度、准确度和精密度均符合农药残留测定的技术要求。     

中国输东盟葡萄农残风险分析及对策研究

葡萄是中国向东盟出口量较大的农产品之一。葡萄在生产过程中极易发生病虫害,会使用到多种农药,影响着葡萄质量安全,中国及东盟国家均制定了葡萄上的农药最大残留限量（maximum residue limit,MRL）。本文比较了中国和泰国、越南、印度尼西亚、菲律宾、新加坡、马来西亚和缅甸葡萄上的农药MRL,分析葡萄出口时的农残违规风险。结论显示,代森锰锌、福美双、嘧菌酯和烯酰吗啉这4种国内葡萄上登记使用的杀菌剂和甲氰菊酯、氰戊菊酯、氟虫腈、马拉硫磷、溴氰菊酯、敌百虫这6种国内葡萄上未登记的杀虫剂出口时农残违规风险较高。此外,泰国和马来西亚都制定了默认限量0.01 mg/kg,对于这两个国家法规和国际食品法典委员会（Codex Alimentarius Commission,CAC）都没有制定限量标准且我国在葡萄上有登记的农药,出口时同样应引起关注。     

Pesticide residues in oranges from Valencia (Spain)

One hundred and fifty citrus samples from an agricultural co-operative of the Valencian Community (Spain) were analysed for pre- and post-harvest pesticide residues using high performance liquid chromatography and gas chromatography. Among the residues from post-harvest treatments, imazalil was detected in 112 (74.7%) samples at a mean level of 1.2mg/kg, thiabendazole in 21 (14.0%) samples at a mean level of 0.47mg/kg and carbendazim in 5 (3.3%) samples at a mean level of 1.05mg/kg. Among the residues from preharvest treatment, dicofol was detected in 28 (18.7%) samples at a mean level of 0.28mg/kg, chlorpyriphos in 19 (12.7%) samples at a mean level of 0.16mg/kg and endosulfan in 11 (7.3%) at a mean level of 0.27mg/kg. Most of the samples contained residues of various pesticides and six samples (4.0%) exceeded the European Union Maximum Residue Limit (MRL). The pesticides that surpassed the MRLs were chlorpyriphos in five samples and dicofol in one.     

Fungicides in red wines produced in South America

ABSTRACT

Although recent research has shown that pesticides can remain in wine, there is only legislation regarding the level of pesticides in grapes; no such regulations exist for wine. Therefore, the objective of this work was to evaluate the presence of fungicides in 190 wines produced in southern South America, as well as to present a new method for the quantification of dithiocarbamates. The fungicides were analysed by LC-MS/MS and GC/MS using validated methods according to the SANTE recommendations. The results for dithiocarbamates are expressed in mancozeb equivalents and are reported herein for the first time. Of the 190 wines analysed, 40% had residues from at least one fungicide detected above the LOQ, and 16.3% of the wines contained levels of fungicides above the MRL for grapes. The fungicides most commonly found were dithiocarbamates, azoxystrobin, carbendazim, difenoconazole, dimethomorph and cyprodinil. The new method for quantification of dithiocarbamates presented high accuracy (89.8–108.1%) and precision (HorRat values between: 0.5 – 1.1).     

农药在葡萄酒酿造过程中残留变化及干扰风味品质研究进展

葡萄种植过程中普遍使用杀虫剂、杀菌剂等化学农药进行病虫害防治,不可避免造成酿酒葡萄中有害物质残留,从而进一步对酿造葡萄酒品质与安全带来隐患.本文综述葡萄酒酿造过程中农药残留对葡萄酒风味品质的影响,重点讨论葡萄酒酿造过程中除梗破碎、浸渍、发酵、澄清、过滤等工艺对常见农药残留迁移、降解和代谢的影响,并分析农药残留对葡萄酒中...     

Determination of organochlorine and pyrethroid pesticides in fruit and vegetables using SAX/PSA clean-up column

A study was conducted to investigate the organochlorine and pyrethroid pesticide residues in fruit and vegetables from market in Malaysia. Gas chromatography with electron capture detector (GC-ECD) was used to determine the concentrations of pesticide residues and SAX/PSA was used as a clean-up. Cypermethrin was detected in 38 of 302 vegetable samples with a mean value of 0.47 mg/kg. The mean value of cypermethrin for tomato, chinese parsley, chinese celery, chilli, brinjal, french beans, green mustard and capsicum ranged from 0.16 to 1.48 mg/kg. The mean values for all samples were below the maximum residue limits (MRLs) allowed by the Malaysian Food Regulations except for brinjal. None of the 206 fruit samples tested showed any pesticide residue.     

The fate of fungicide and insecticide residues in Australian wine grape by-products following field application

Pesticides applied to grape vines before harvest may concentrate in the grape seed due to their high oil solubility. Twenty-four samples of grape marc, representing a range of red and white wine grape varieties, were collected and analysed for selected fungicides and insecticides. Fifteen of the 24 samples were matched with insecticide and fungicide application diaries. Residue concentrations of the fungicides, procymidone, iprodione, cyprodinil, fenhexamid, fludioxinil, pyrimethanil and trifloxystrobin, and the insecticides, indoxacarb and tebufenozide, were higher in grape seed oil and grape seed meal than in the fruit and the marc. The relative concentrations were approximately proportional to the octanol to water partition coefficients, log K_ow. A range of other fungicides and insecticides were detected but were not significantly concentrated in the oil and seed meal relative to fruit and marc. The presence of pesticide residues in grape seed oil and grape seed meal will impact on the possibility of producing these wine by-products.     

Pesticide content of infant formulae and weaning foods available in New Zealand

A survey of the pesticide content of 25 commercially available infant formulae and 30 weaning foods available in New Zealand was undertaken in 1996. It included a representative mixture of imported and New Zealand manufactured infant foods. Three different pesticide screening techniques were used: a high-sensitivity organochlorine screen was carried out on all infant formulae, while a multiresidue screen (organochlorine and organophosphorus pesticides, synthetic pyrethroids, carbamate pesticides, fungicides and herbicides), and a specific screen for dithiocarbamate fungicides were both carried out on all weaning foods and on soy-based infant formulae. All results are expressed on a ready-to-feed basis. Extremely low levels of residues of three organochlorine compounds (p,p'-DDE, p,p'-DDT and dieldrin) were detected in infant formulae samples. Residues of p,p'-DDE were found in seven of 20 milk-based infant formulae at concentrations ranging from 0.03 to 0.5 μg kg^-1. Residues of p,p'-DDT were found in one imported milk-based infant formula at 0.7 μg kg^-1, and dieldrin residues were detected in four of five soy-based infant formulae at concentrations ranging from 0.05 to 0.08 μg kg^-1. The multiresidue pesticide screen detected low levels of residues of two organophosphorus pesticides; azinphos-methyl in one soy-based infant formula at a level of 22 μg kg^-1 and pirimiphos-methyl in two cereal-based weaning foods at concentrations of 5 and 14 μg kg^-1. None of the other approximately 140 pesticides (including fungicides and herbicides) included in the multiresidue screen were detected in any weaning foods or soy-based infant formulae, at a detection limit of 10 μg kg^-1. No residues of dithiocarbamate fungicides were detected in any product analysed, at a detection limit of 100 μg kg^-1.     

西安市猕猴桃主产区农药残留水平及累积急性膳食摄入风险评估

目的评估西安市猕猴桃农药残留水平及累积急性膳食摄入风险。方法对2018～2019年西安市周至县14个猕猴桃主产乡镇共400批次样品进行农药残留定量检测分析,用相对效能因子法进行累积急性膳食摄入风险评估。结果对400个猕猴桃样品经检测分析,共有280个猕猴桃样品检出了不同程度的农药残留,检出率为70%,农药多残留样品(检出2种以上农药残留)占样品总数50.25%,检出超标农药氯氟氰菊酯1个,禁用和限用农药均未检出。从检出农药毒性分析, 22种已检出的农药中包括14种低毒农药, 7种中毒农药和1种高毒农药,根据相同毒性机制分组为有机磷类、菊酯类、有机氯类、烟碱类农药,且累积急性膳食摄入风险评估中风险系数分别为34.64%、7.20%、3.90%和2.52%,均处于低风险水平。结论西安市周至县猕猴桃有机磷类、菊酯类、有机氯类、烟碱类农药累积性急性风险较小,急性中毒情况基本不会发生。     

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.     

Analysis of contaminated milk with organochlorine pesticide residues using gas chromatography

Milk and milk products are considered to have tremendous nutritional values as they contain a good proportion of protein, fats, and important minerals. However, the nutritional value of the milk produced in Pakistan is not up to the mark as extensive use of pesticides on crops resulted in contamination of milk. Consumption of contaminated food such as milk, meat, fish, eggs can induce increased proportion of organochlorine pesticides in the body. The purpose of this study is to determine organochlorine pesticide residues in milk and their toxicity level by Maximum Residues Level (MRL) values. In the current study, organochlorines such as Dichlorodiphenyltrichloroethane (DDT), Dichlorodiphenyldichloroethane (DDE), Dieldrin, Gamma-hexachlorocyclohexane (?-HCH) also known as Lindane, α-Endosulphan, β-Endosulphan and Endosulphan sulphate were detected with the help of gas chromatograph equipped with electron detector. These pesticides were confirmed by using gas chromatography-mass spectrometry (GC-MS). Analysis of variance is applied (ANOVA) to determine variations of pesticides in all milk samples. Analysis showed non-significant results (p > 0.05) with large variation among all milk samples regarding pesticide residues. The mean values of DDT, DDE were found to be below the MRL value. The mean values of Dieldrin, ?-HCH were also below MRL value. On the other hand mean values of α-Endosulphan, β-Endosulphan, and Endosulphan sulphate were slightly higher than MRL in few milk points. The present study showed large variations of pesticides residues present in milk samples.     

Headspace solid-phase microextraction for the evaluation of pesticide residue contents in cucumber and strawberry after washing treatment

The headspace solid-phase microextraction was developed to examine the organophosphorus (diazinon, malathion, chloropyrifos, quinalphos, profenofos) and organochlorine (chlorothalonil, α-endosulfan and β-endosulfan) pesticide residues in vegetable (cucumber) and fruit (strawberry) samples. The effects of washing by different solutions were evaluated for the reduction of organophosphorus and organochlorine pesticide residues contents. Gas chromatography with electron capture detection was used to analysis the investigated pesticides. The results showed that washing by a non-toxic solution can decrease the concentration of pesticide residues in the fruit and vegetable samples. The data further indicated that acetic acid was the most effective solution in removing the residues of the investigated pesticides from the fruit and vegetable samples when compared to sodium carbonate, sodium chloride and tap water. The amount of pesticides removed by solution washing is related to their water solubility and vapour pressure properties.