Residues of insecticides, and fungicides in fruit produced in Ontario, Canada, 1986-1988

Between 1986 and 1988, 306 composite samples of fruit representing eight commodities were collected from farm deliveries to the marketplace in Ontario, Canada. All samples were analysed for insecticides and fungicides. The analysis procedure included tests for organochlorine, organophosphorus, synthetic pyrethroid and methylcarbamate insecticides and dithiocarbamate, dicarboximide and organochlorine fungicides. The commodities tested included apples, blueberries, cherries, grapes, peaches, pears, raspberries and strawberries. In 14% of all fruit samples, pesticide residues were below the detection limits, which ranged between 0.005 and 0.02 mg/kg. A further 14% had total combined pesticide residues below 0.1 mg/kg. Total combined fungicide and insecticide residues ranged from 0.1 to 11 mg/kg in 72% of samples. Six different pesticides were in violation of maximum residue limits (MRL) on 11 (3.6%) of fruit samples. Captan exceeded the 5 mg/kg MRL in five samples and EBDC exceeded the 7 mg/kg MRL in two. Other violations included single fruit samples with dicofol, endosulphan, phosalone and iprodione above the MRL. Raw grapes harvested for wine contained residues of 10 pesticides and the number changed little following the crushing of the grapes; however, fermentation into wine significantly reduced residues. Six insecticides and four fungicides were present on the raw grapes and 4/105 were above the MRL. Following crushing, four insecticides and five fungicides were identified and 4/40 were above the MRL. In wine only three insecticides were identified and all were well below the MRL. Carbaryl appeared to be the most persistent, declining very little between raw grapes and wine.     

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).     

Dissipation rates of iprodione and thiacloprid during tomato production in greenhouse

The behaviour of the insecticide thiacloprid and the fungicide iprodione was investigated in greenhouse tomato fruits, when both pesticides were applied in two different rates (normal dose-ND, and double dose-DD). Thiacloprid residues were below the already established EU MRLs (0.5 mg/kg) 2 and 7 days after ND and DD application, respectively. Iprodione residues were always below EU MRLs (5 mg/kg) in both application rates. The impact of storage on pesticide residues in tomatoes was also assessed. Significantly higher iprodione residue levels were observed during post harvest storage compared with those determined in fresh harvested tomatoes. Mean residue levels determined in fresh harvested tomatoes 12 days after iprodione application were 0.69 mg/kg whereas, in post harvest tomatoes stored for the same period was 0.86 mg/kg. On the contrary, no differences were noticed in thiacloprid residues between post harvest stored and fresh harvested tomatoes. Model equations that best describe the dissipation curves obtained from the experimental data of iprodione and thiacloprid in tomatoes showing different behaviour of the two pesticides. Half-life period of iprodione in ND treatment, calculated by the best fitted experimental data, (2nd order model) was 6.8 days, whilst for thiacloprid the best fitted to experimental data, model equation (R.F. 1st order model) gave a half-life of 1.9 days.     

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.     

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.     

Analysis of pesticide residues in bananas harvested in the Canary Islands (Spain)

In this work, 11 pesticides (ethoprofos, dimethoate, diazinon, malaoxon, chlorpyrifos-methyl, fenitrothion, malathion, chlorpyrifos, fenamiphos, buprofezin and phosmet) were analysed in 57 banana samples taken from the local markets of the Canary Islands (Spain). Analyses were carried out by the QuEChERS approach developed for pesticide residue analysis in food, using gas chromatography (GC) with nitrogen–phosphorus detection (NPD). Triphenylphosphate (TPP) was used as internal standard. Recoveries ranged between 67% and 118% with RSD values below 16%. Typical limits of quantification (LOQs) of the method were 0.01–0.14 mg/kg, which are below the EU maximum residue limits (MRLs) established for these compounds in bananas. Chlorpyrifos was detected in 50 samples (88%) in the concentration range 0.03–0.65 mg/kg, malathion in five samples (8.8%) in the concentration range 0.16–0.17 mg/kg, fenitrothion in four samples (7.0%) in the concentration range 0.02–0.10 mg/kg and buprofezin in one sample (1.8%) at 0.15 mg/kg. All these values are below the MRLs established for these compounds except for two samples containing fenitrothion. Among the studied pesticides only chlorpyrifos has a high occurrence in the samples. However, the levels of these residues cannot be considered a serious public health problem according to EU regulations. Because of the high occurrence of chlorpyrifos, its distribution between the pulp and the peel was also investigated. Results show that most of the pesticide remains in the peel and that only amounts between 0.07 and 0.12 mg/kg occur in the pulp even at concentrations in the peel as high as 0.87 mg/kg.     

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.     

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.     

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.     

6种杀虫剂在上海青中的残留消解动态及膳食风险评估

目的 评价蔬菜生产中6种常用杀虫剂5％啶虫脒乳油、15％哒螨灵水乳剂、20％溴氰虫酰胺可分散油悬浮剂、30％唑虫酰胺悬浮剂、22％氟啶虫胺腈悬浮剂和60 g/L乙基多杀菌素悬浮剂在十字花科蔬菜上海青中的残留消解动态,评估其膳食摄入风险.方法 于2018年4～10月在福州采用喷雾的施药方法进行了6种药剂在上海青上的残留试...     

气相色谱-质谱法测定茶叶中12种农药残留的方法

用气相色谱-质谱仪研究同时测定茶叶中12种农药残留的测定方法。分析样品经粉碎、浸泡，用丙酮-正己烷(1：4，V／V)AA，经活性炭柱和弗罗里硅土柱净化，乙醚-丙酮-正己烷(4：4：2，V／V／V)洗脱后，以环氧七氯为内标，GC／MS测定。经过对茶叶加标的回收实验，证实具有快速灵敏简便的优点，适用于多种农药残留分析。其平均回收率在75%-110％，变异系数下于21％，最低检测限为0．01-0．5mg／kg。     

Novel approach to fast determination of multiple pesticide residues using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)

A rapid, high-throughput method employing ultra-performance liquid chromatography with tandem quadrupole mass spectrometry (UPLC-MS/MS) was developed and optimized for simultaneous quantification and confirmation of 64 pesticide residues and their toxic metabolites in fruit extracts prepared by a buffered QuEChERS procedure. The total time required for UPLC-MS/MS analysis was 8 min plus 2 min for re-equilibration to the initial UPLC conditions. Performance characteristics were determined for apple extracts spiked at 10 microg kg(-1). The repeatability of measurements expressed as relative standard deviations was in the range 1.5-13% at this level for most analytes. Thanks to very low limits of quantification (<10 microg kg(-1)for the majority of pesticides), an optimized method allows for the reliable control of not only common maximum residue limits (MRLs) set by European Union regulation for various pesticides/fruit combinations, but also of a uniform MRL of 10 microg kg(-1)endorsed for baby food.     

Multiresidue method for pesticides and veterinary drugs in bovine milk using GC/MS and LC/MS/MS

A simple, sensitive and selective method with gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS) has been developed to detect 342 pesticides and veterinary drugs contaminating bovine milk at the maximum residue limits (MRLs) defined in the "positive list system". Sample preparation was performed by extracting the analytes with acetonitrile, followed by salting-out with sodium chloride. For some pesticides, the extract was further cleaned up by n-hexane partitioning and PSA cartridge column chromatography. GC/MS-EI or -NCI was used to determine pesticide residues, while LC/MS/MS-ESI was applicable to the determination of pesticide and veterinary drug residues. The variation of the recoveries of these drugs at MRL was relatively wide; however the relative standard deviations of the recovery of each drug were within 28%, suggesting that the present method is good enough for use as a screening test for contaminants at the MRLs. These results show that this method is useful for multiresidue analysis of numerous pesticides and veterinary drugs in bovine milk.     

Degradation of organophosphorus pesticides in wheat during cookie processing

For investigating carryover of some organophosphorus pesticide residues in the cereal food chain from grain to consumer, a study was set up on wheat bran, flour and cookies, with and without bran. Special emphasis was given to malathion and chlorpyrifos-methyl residues in cookies for better protection of consumers. Pesticide-free wheat was placed in a small-scale model of a commercial storage vessel and treated with these pesticides. The residue levels of insecticides were determined in wheat, as well as in bran, flour and cookies produced from stored wheat at various time intervals during storage. A multiresidue analysis was performed using GC–NPD and GC–MS. Malathion and chlorpyrifos-methyl residue levels were higher than the maximum residue limits (MRLs) in wheat after 240 days of storage. MRLs established by the EC for malathion and chlorpyrifos-methyl in wheat are 8 and 3 mg kg⁻¹, respectively. The residue levels of insecticides in flour samples also exceeded the MRL (2 mg kg⁻¹ for both insecticides). Eight months of storage were not effective for reducing the residues in wheat to the levels below MRLs. Although, considerable amounts of the insecticides remained in the bran and flour, the cookie processing significantly reduced the concentrations in general. Chlorpyrifos-methyl was more persistent than was malathion and comparatively less degradation occurred during milling and cookie processing due to its physicochemical properties.     

Novel approach to fast determination of multiple pesticide residues using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS).

A rapid, high-throughput method employing ultra-performance liquid chromatography with tandem quadrupole mass spectrometry (UPLC-MS/MS) was developed and optimized for simultaneous quantification and confirmation of 64 pesticide residues and their toxic metabolites in fruit extracts prepared by a buffered QuEChERS procedure. The total time required for UPLC-MS/MS analysis was 8 min plus 2 min for re-equilibration to the initial UPLC conditions. Performance characteristics were determined for apple extracts spiked at 10 microg kg(-1). The repeatability of measurements expressed as relative standard deviations was in the range 1.5-13% at this level for most analytes. Thanks to very low limits of quantification (<10 microg kg(-1)for the majority of pesticides), an optimized method allows for the reliable control of not only common maximum residue limits (MRLs) set by European Union regulation for various pesticides/fruit combinations, but also of a uniform MRL of 10 microg kg(-1)endorsed for baby food.     

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.     

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 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.     

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%).     

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%).