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.     

Removal of imidacloprid and acetamiprid from tea infusions by microfiltration membrane

Removal of imidacloprid and acetamiprid in tea infusions by microfiltration membrane using dead‐end model was investigated in the present study. The results showed that microfiltration significantly promoted the removal of both pesticides (P < 0.05) in tea infusions. Furthermore, the extent of removal was strongly influenced by the pore size of membrane, operational pressure and the concentrations of tea infusions. The initial concentration of imidacloprid and acetamiprid showed no significant effect on their removal rates. The maximum removal rates were 79.7% for imidacloprid and 81.9% acetamiprid. The changes in major chemical components of tea infusions after microfiltration were evaluated. The results indicated that microfiltration caused no considerable changes in total polyphenols and total free amino acids, and small but statistically significant losses (6.3–18.0%) of eight catechins and three methylxanthines when filtration volume reached to 200 mL. The present study validated the application of microfiltration as a potentially feasible and promising method for the removal of imidacloprid and acetamiprid residues from tea infusions.     

Residue contents of captan and procymidone applied on tomatoes grown in greenhouses and their reduction by duration of a pre-harvest interval and post-harvest culinary applications

In this study, controlled applications of captan and procymidone were carried out on tomatoes grown in two different greenhouses at different times. The first group of samples were collected immediately after the application and the second group were collected 14 days later. Additionally, control samples were collected before application. The effects of washing, peeling and predetermined storage period, at 4 °C for 7 and 14 days, on the reduction of residue levels in the plant tissues were investigated in the two groups. A gas chromatographic method using acetone, dichloromethane and petroleum ether as extraction solvents, was used to analyse residual captan and procymidone in tomatoes, with obtained recoveries higher than 83%. Captan and procymidone were determined by gas chromatography-electron capture detection (GC-ECD), using a 5% phenylmethylpolysiloxane-coated fused-silica capillary column.

Results showed that waiting for the recommended pre-harvest intervals, indicated on the prospectuses of both pesticides, lowered the residue levels to within acceptable limits. Culinary applications, such as washing and peeling and refrigeration storage, were also effective in reducing the residue levels.     

Persistence of acetamiprid in tea and its transfer from made tea to infusion

Acetamiprid, a new-generation, highly active neonicotinoid insecticide has been used to control mites and insect pests. In the present study, the disappearance trend of acetamiprid residue in tea under field conditions was studied at two dosages for two seasons (dry and wet), and transfer of residues from made tea to infusion was also determined. Acetamiprid dissipation rate was found to be faster in the wet season. Half-life of acetamprid was found to be 1.82–2.33 days in green tea shoots and 1.84–2.25 days in made tea for both dry and wet seasons. The percent transfer of acetamiprid residues from made tea to infusion was 36.84–50.00%; however, 31.11–44.40% of the residues remained stuck to the spent leaves during both the dry and wet seasons. On the basis of transfer of residues from made tea to infusion, a waiting period of 15 days for tea plucking after pesticide application at recommended dose may be suggested.     

Residue levels and health risk of pesticide residues in bell pepper in Shandong

ABSTRACT

The purpose of this study was to investigate pesticide residues in bell peppers from Shandong Province, China. A total of 299 samples were collected from 17 cities in 2016. The concentrations of 26 pesticide residues were determined by gas chromatography with mass spectrometry (GC–MS). The results showed that there were 25 pesticides (15 OPs, 7 PYs, 3 CBs) found in 86 bell pepper samples, and the total number of positives was 120. The total frequency was 28.76%. The detection frequency for OPs, PYs and CBs was 16.39%, 12.37% and 3.01%, respectively. The most frequently detected pesticide was bifenthrin, with the frequency of 5.02%. 5.35% of samples contained pesticide residues above the maximum residue limits (MRLs) set by China. 7.36% of samples contained more than one pesticide. The values of %ADI were below 100, while the %ARfD of carbofuran and methidathion exceeded 100 for children. The cumulative risk was highest for OPs. From the public health point of view, the levels of pesticide residues in bell peppers do not pose a serious health risk to adults, but the acute health risk to children should be paid more attention.     

Effect of household and commercial processing on acetamiprid,azoxystrobin and methidathion residues during crude rapeseed oil production

Rape crops with residues of acetamiprid, azoxystrobin and methidathion incurred from field trials were used to evaluate the effect of household and commercial crude rapeseed oil processing on the transfer of pesticide residues. The pesticides were applied at exaggerated dosage to quantify residue levels in processed samples. The processing procedure was conducted as closely as possible to the actual conditions in practice. The conditioning step removed at least 30% of pesticides, while azoxystrobin and methidathion were concentrated by at least 15% at the single pressing step. The residue level of methidathion was concentrated with a processing factor (PF) of 1.07, while azoxystrobin and acetamiprid decreased with PFs of 0.67 and 0.04, respectively, after all processing procedures. The overall magnitudes of acetamiprid, azoxystrobin and methidathion in rapeseed oil and meal were all decreased after processing compared with the magnitude of those in raw rapeseed.     

Reduction in residues of deltamethrin and fenitrothion on stored wheat grains by ozone gas

The effectiveness of ozone gas treatment in the removal of residues of organophosphate (fenitrothion) and pyrethroid (deltamethrin) pesticides in wheat grains by ozone gas was evaluated. The fenitrothion content was decreased following (60 μmol/mol) treatment after 180 min of exposure (a 66.7% reduction). At 20% mc (water activity a_w = 0.9). Similarly deltamethrin residues were reduced by 67.5, 88.1 and 89.8% after 60, 120 and 180 min of O₃ exposure, respectively. At the lowest mc and a_w (12% and 0.6) wheat grains had deltamethrin reductions of 80.6% and 85.7% after exposure for 120 and 180 min, respectively. The use of O₃ may be a potentially effective method of reducing pesticide residues in stored grains.     

Results from the monitoring of pesticide residues in fruit and vegetables on the Danish market, 1998?99

The objective of the Danish pesticide monitoring programme for fruit and vegetables was to check for compliance with the maximum residue levels in foods and to monitor the residue levels to assess the pesticide exposure of the Danish population. Sampling plans were designed based on previous findings and on food consumption data. Approximately 60% of the samples were selected on the basis of positive findings in samples from the previous 5 years. The remaining samples reflected the pattern of food consumption in Denmark. In addition, a rolling programme is maintained for commodities with a low consumption and no detected residues. Within each commodity, the sampling was random. Samples (n = 4150) of mainly fresh, conventionally grown fruit and vegetables were taken throughout the chain of suppliers including foodprocessing companies. Of the samples, 3% were frozen products and 2% were organically grown. Of the samples, 35% were of Danish origin, with 65% originating from other countries. Three accredited laboratories performed analyses of the samples using capillary gas chromatography, liquid chromatography and spectrophotometric methods. Results were registered online into a central database. Residues were found in 54% of the samples of fruit but only in 13% of the vegetables. Residues above the MRL were found in 4% of all samples of fruit and in 1% of vegetables.     

Results from the monitoring of pesticide residues in fruit and vegetables on the Danish market, 2000-01

To check compliance with the maximum residue levels in foods and to monitor the residue levels to enable an evaluation of the exposure of the Danish population to pesticides, a monitoring programme for pesticides residues in fruit and vegetables was performed. Sampling plans were designed based on previous findings and on consumption data. Samples (n = 4404) of mainly fresh conventionally and organically grown fruit and vegetables were collected at wholesalers and importers and at food processing companies. Of the samples, 3% were frozen products and 5% organically grown. Of the samples, 34% were of Danish origin, with 66% from other countries. Two accredited laboratories performed analyses of the samples using capillary gas chromatography, liquid chromatography and a spectrophotometric method. Reporting levels were set at the lowest calibration level or at the limit of determination. Residues were found in 60% of the samples of fruit but in only 18% of the vegetable samples. Residues above the maximum residue levels were found in 6% of all samples of fruit and in 2% of the vegetable samples.     

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.     

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.     

Properties of a protein-based film from round scad (Decapterus maruadsi) as affected by muscle types and washing

The effects of muscle types and washing on the properties of a protein-based film from round scad (Decapterus maruadsi) mince were investigated. Washing resulted in an increase in the protein content with a coincidental decrease in the fat content of mince, especially from whole muscle and dark muscle. Among all types of muscle (ordinary, dark and whole muscle), the ordinary muscle rendered the film with the highest tensile strength (TS) (p < 0.05). TS of films from washed mince was greater than that of films prepared from unwashed mince for the same type of muscle used (p < 0.05). Nevertheless, the water vapour permeability (WVP) of films from unwashed mince was higher than that of films prepared from washed mince (p < 0.05). Films from washed mince had higher solubility but lower protein solubility than those from unwashed mince (p < 0.05). Regardless of washing, films from ordinary muscle showed the highest L^∗-value (p < 0.05). However, films prepared from dark muscle were more yellowish than those prepared from other muscles, as evidenced by the greater b^∗-value. Films from round scad mince and washed mince had excellent barrier properties to UV light at the wavelength of 200–280 nm. Generally, films from round scad mince had a lower preventive effect on visible light transmission than had those from unwashed mince. Among films from all muscles, those prepared from dark muscle exhibited the highest barrier to visible light transmission (p < 0.05). Therefore, the properties of films from round scad meat were governed by muscle type as well as by washing.     

Natural populations of lactic acid bacteria isolated from vegetable residues and silage fermentation

Natural populations of lactic acid bacteria (LAB) and silage fermentation of vegetable residues were studied. Fifty-two strains of LAB isolated from cabbage, Chinese cabbage, and lettuce residues were identified and characterized. The LAB strains were gram-positive and catalase-negative bacteria, which were divided into 6 groups (A to F) according to morphological and biochemical characteristics. The strains in group A were rods that did not produce gas from glucose and formed the d and l isomers of lactate. Groups B and C were homofermentative cocci that formed l-lactic acid. Groups D, E, and F were heterofermentative cocci that formed d-lactic acid. Based on 16S rDNA gene sequence analysis, group A to F strains were identified as Lactobacillus plantarum, Lactococcus piscium, Lactococcus lactis, Leuconostoc citreum, Weissella soli and Leuconostoc gelidum, respectively. The prevalent LAB, predominantly homofermentative lactobacilli, consisted of Lactobacillus plantarum (34.6%), Weissella soli (19.2%), Leuconostoc gelidum (15.4%), Leuconostoc citreum (13.5%), Lactococcus lactis (9.6%), and Lactococcus piscium (7.7%). Lactobacillus plantarum was the dominant member of the LAB population in 3 types of vegetable residues. These vegetable residues contained a high level of crude protein (20.2 to 28.4% of dry matter). These silages prepared by using a small-scale fermentation system were well preserved, with low pH and a relatively high content of lactate. This study suggests that the vegetable residues contain abundant LAB species and nutrients, and that they could be well preserved by making silage, which is a potentially good vegetable protein source for livestock diets.     

LC/ESI–MS/MS method for the identification and quantification of spinosad residues in olive oils

This paper reports the use of liquid chromatography/electrospray ionisation tandem mass spectrometry (LC/ESI-MS/MS) method for the identification and quantification of residues of the natural insect control agent Spinosad in olive oils. The method determines the active ingredients Spinosyns A and D and two minor metabolites Spinosyns B and K without laborious sample treatment. All four analytes are determined simultaneously in a single injection using positive electrospray ionisation LC–MS with multiple reaction monitoring (MRM). For the quantitative analysis of samples an external calibration curve was built. The calibration curves for each analyte were linear in the concentration range 20–500 ng/mL with a correlation coefficient ranging between 0.995 and 0.999. Results from spike and recovery experiments at levels of 100 and 200 ng/mL gave mean recoveries ranging from 87–116% with satisfactory precision (relative standard deviation (RSD) from 1–8%). The excellent selectivity and sensitivity allows quantification and identification of low levels of Spinosad in olive oils (limits of quantification (LOQs) 0.004–0.073).     

Analysis of non-cleaned QuEChERS extracts for the determination of pesticide residues in fruit,vegetables and cereals by gas chromatography-tandem mass spectrometry

This paper investigated the possibility of leaving out the traditional clean-up step in the QuEChERS procedure and analysing non-cleaned extracts from fruit, vegetables and cereals with a combination of gas chromatography-tandem mass spectrometry (GC-MS/MS), back-flush technology and large-volume injection. By using calibration standards in cucumber matrix, recovery and precision were calculated in lettuce, orange and wheat for 109 pesticides at 0.01 and 0.1 mg kg^?1 in two sets of samples: one with and one without clean-up. For both spiking levels, 80–82% of the pesticides in the non-cleaned extracts and 80–84% of the pesticides in the cleaned extracts were within the acceptable recovery range of 70–120%. Precision data for both levels showed that 95% of the pesticides in the non-cleaned extracts and 93–95% of the pesticides in the cleaned extracts had RSDs below 20%. Recovery and precision data were determined using a two tailed t-test (p = 0.05). By using calibration standards in the respective matrix, we studied if the non-cleaned calibration standards gave an extra matrix effect compared with the cleaned standards by using the slope from calibration graphs and plotting the calculated extra matrix effect minus 100 for each compound. The results showed that for 79% of the pesticides, the extra matrix effect minus 100 was within the acceptable range of ?20% to 20%. Five European Union proficiency tests on rye, mandarin, rice, pear and barley, respectively, from 2010 to 2012 were reanalysed omitting the clean-up step and showed satisfactory results. At least 70 injections of non-cleaned extracts were made without detecting any increased need for maintenance during the experimental period. Analysing non-cleaned QuEChERS extracts of lettuce, orange and wheat are possible under the conditions described in this paper because recovery, precision and specificity showed satisfactory results compared with samples subjected to traditional dispersive clean-up.     

Pressurised liquid extraction and capillary electrophoresis–mass spectrometry for the analysis of pesticide residues in fruits from Valencian markets,Spain

A procedure based in capillary electrophoresis–mass spectrometry (CE–MS) for the analysis of seven pesticides (flutolanil, simazine, haloxyfop, acifluorfen, dinoseb, picloram, and ioxynil) in four Mediterranean summer fruits with high water content (peaches, melon, watermelon, and apricot) is developed. Several conditions were studied for the optimisation of both, the separation and the electrospray (ESI) connection. The best results were obtained using 35 mM ammonium formiate (pH 9.7) as separation buffer, 20 °C as capillary temperature and 23 kV as applied voltage in an uncoated fused-silica capillary with 50 cm total length, 25 cm thermostated length, 25 cm at room temperature length, connected to an MS detector by an ESI sprayer kit. The appropriate sheath liquid was ammonium formiate with 10% of formic acid at 5 μL min⁻¹. Separation time for all pesticides was achieved in 12 min. Extraction was carried out by pressurised liquid extraction (PLE) in an ASE® 200 system from Dionex using hot water at 60 °C and 1500 psi, followed by a solid-phase extraction (SPE) clean-up step using StrataX cartridges. Recoveries ranged from 58% to 88% and the relative standard deviations (RSDs) were 9–19%. The limits of detection (LODs) and quantification (LOQs) were in all cases lower than the MRLs, 0.01 and 0.05 mg kg⁻¹, respectively. The potential of the method was demonstrated by analysing summer fruits taken from agricultural Mediterranean zone cooperatives.     

2018—2021年陕西省市售水果中农药残留状况调查及膳食摄入风险评估

目的 调查分析陕西省市售水果中杀虫剂和杀菌剂类农药残留情况,评估当地居民通过摄入水果的农药残留暴露风险。方法 采集2018—2021年陕西省10个地市共6大类486份市售水果样品,依据国家风险监测工作手册《植物性样品中农药多组分残留的气相色谱-串联质谱（GC-MS）法测定的标准操作程序》和《植物性样品（含食用菌）中农药多组分残留的液相色谱质谱-串联质谱（LC-MS）法测定标准操作程序》对水果中13种杀虫剂和15种杀菌剂残留水平进行检测,依据GB 2763—2021《食品安全国家标准 食品中农药最大残留限量》评价多组分农药残留的检出和超标状况。采用点评估法对各类农药残留进行急性、慢性膳食暴露风险评估,通过食品安全指数模型对检出农药开展总体风险判定。结果 本次监测的28种农药除吡唑醚菌酯、恶霜灵、腈菌唑、异菌脲4种杀菌剂和灭线磷、灭蝇胺、氟氯氰菊酯3种杀虫剂未检出,其余21种农药均有不同程度的检出,检出率在0.77%~21.54%,共7份样品4种农药残留超标,超标率在0.28%~1.27%,且有禁用的高毒农药检出。核果类（39.24%）、热带及亚热带水果（28.33%）、柑橘类（26.47%）及仁果类（25.96%）水果的农药残留检出率较高,浆果类（2.54%）的超标率较高,且均存在多种农药联合使用的情况。各类农药的急性和慢性膳食暴露量均低于其健康指导值,单项农药的食品安全指数均小于1,水果总体食品安全指数小于1。结论 陕西省市售水果中农药残留检出率较高,但超标率较低,本次监测的水果膳食摄入风险在可接受范围内,整体安全质量良好。     

Investigation of the migration of triclabendazole residues to milk products manufactured from bovine milk,and stability therein,following lactating cow treatment

Triclabendazole (TCB) is a flukicide used in the treatment of liver fluke in cattle; however, its use is currently prohibited in lactating dairy cows. In this study, following administration of 10% Fasinex (triclabendazole, Novartis Animal Health UK Ltd., Camberley, UK) the milk of 6 animals was used to manufacture dairy products, to ascertain if TCB residues in milk migrate into dairy products. The detection limit of the ultra-high-performance liquid chromatography-tandem mass spectrometry method used was 0.67 μg/kg. The highest concentrations of TCB residue measured, within the individual cow milk yield, was 1,529 ± 244 µg/kg (n = 6), on d 2 posttreatment. Days 2 and 23 posttreatment represented high and low residue concentrations, respectively. At each of these 2 time points, the milk was pooled into 2 independent aliquots and refrigerated. Milk products, including cheese, butter, and skim milk powder were manufactured using pasteurized and unpasteurized milk from each aliquot. The results for high residue milks demonstrated that TCB residues concentrated in the cheese by a factor of 5 (5,372 vs. 918 µg/kg for cheese vs. milk) compared with the starting milk. Residue concentrations are the sum of TCB and its metabolites, expressed as keto-TCB. Residues were concentrated in the butter by a factor of 9 (9,177 vs. 1,082 μg/kg for butter vs. milk) compared with the starting milk. For milk, which was separated to skim milk and cream fractions, the residues were concentrated in the cream. Once skim milk powder was manufactured from the skim milk fraction, the residue in powder was concentrated 15-fold compared with the starting skim milk (7,252 vs. 423 µg/kg for powder vs. skim milk), despite the high temperature (185°C) required during powder manufacture. For products manufactured from milk with low residue concentrations at d 23 posttreatment, TCB residues were detected in butter, cheese, and skim milk powder, even though there was no detectable residue in the milk used to manufacture these products. Triclabendazole residues were concentrated in some milk products (despite manufacturing treatments), exceeding residue levels in the starting milk and, depending on the storage conditions, may be relatively stable over time.     

2018—2019年浙江省养殖水产品中6种喹诺酮类药物残留分析及风险评估

目的评估2018—2019年浙江省养殖水产品中6种喹诺酮类药物残留分析及风险。方法 2018—2019年随机抽检浙江省11个地市658家养殖场的养殖水产品,采用液相色谱-串联质谱法对水产品中恩诺沙星、环丙沙星、氧氟沙星、诺氟沙星、培氟沙星、洛美沙星6种喹诺酮类药物残留进行分析,同位素内标法定量计算得到喹诺酮类药物残留量范围,并通过查阅文献与每日允许摄入量对比,得到人体实际每日摄入量范围。结果 6种喹诺酮类药物检出率为0~24.2%,残留量范围为0~964μg/kg;其中鱼类样品检出残留量值最高,达964μg/kg;龟鳖类样品检出药物种类最多,达4种;蛙类超标率最高达18.2%;地市中湖州市养殖场6种药物的检出率最高,达29.6%。食用风险评价以每人日摄入75g水产品为例,恩诺沙星摄入量范围为0.58~115.73μg,占每日最大允许摄入量的0.16%~31.11%。结论浙江省养殖水产品中喹诺酮类药物有一定量的检出,以限用药恩诺沙星、环丙沙星为主,健康风险较小,处于相对安全水平;氧氟沙星、诺氟沙星、培氟沙星和洛美沙星4种禁用药物检出率较低,但在个别样品中残留含量较高,其每日最大允许摄入量尚不明确,存在潜在危害性。     

Yield and composition of cell wall residues isolated from various feedstuffs used for non-ruminant farm animals

The contents of cell wall residue were measured in 14 common feedstuffs used for non-ruminant farm animals by utilising a technique involving pronase and α-amylase treatments. Comparison with the contents of neutral detergent fibre (NDF) revealed that the NDF procedure underestimated cell wall contents in the dicotyledonous plant materials. The losses of cell wall material due to the neutral detergent solution were correlated (r=0.931, P<0.01) with the amount of pectic substances present in the cell wall residues of the dicotyledonous plant materials. Cell wall residues were analysed for starch, crude protein, polysaccharides, condensed tannins, sulphuric acid lignin, acetyl bromide lignin, and ash. Condensed tannins in the cell wall residues of sorghum, rapeseed meal and field bean resulted in a large protein contamination (11.3–26.6%) of these residues and to an overestimation of their lignin content. Compositions of polysaccharides are discussed from chemical and nutritonal viewpoints.