Effects of home preparation on organophosphorus pesticide residues in raw cucumber

The effects of washing with tap water and different detergent solutions, storage at different temperatures and ultrasonic cleaning on organophosphorus pesticide (trichlorfon, dimethoate, dichlorvos, fenitrothion, and chlorpyrifos) residue levels in raw cucumber was investigated. Analysis was carried out by liquid chromatography–tandem mass spectrometry. Washing with detergent solutions proved more effective than tap water. The organophosphorus pesticides reduced from 31.1% to 98.8% after washing with detergent solutions for 20 min. Among detergent solutions, 5% sodium carbonate solution caused the greatest loss in trichlorfon and dimethoate, and 5% sodium bicarbonate solution caused the greatest loss in dichlorvos, fenitrothion and chlorpyrifos. Storage at 4 °C for 48 h caused pesticides reduction by 60.9–90.2%. Ultrasonic cleaning for 20 min lowered pesticides by 49.8–84.4%. The data indicated that home preparation is effective for the reduction of organophosphorus pesticide residues in raw cucumber and it is useful for reducing the dietary exposure.     

Food safety evaluation of buprofezin, dimethoate and imidacloprid residues in pomegranate

Food safety aspects of buprofezin, dimethoate and imidacloprid residues in pomegranate are reported. The residue analysis involved extraction of samples (15 g) with 10 ml ethyl acetate, cleanup by dispersive solid phase extraction with 25 mg primary secondary amine and 25 mg C₁₈ sorbents and estimation by LC-MS/MS. The limit of quantification of each analyte was 0.001 mg kg⁻¹ with recoveries within 76-109%. The residues of buprofezin and dimethoate were confined to outer rind, which degraded to below the maximum residue limit for the European Union (EU-MRL) after 10.5 and 31.5 days at standard dose and 32.0 and 44.0 days at double dose. Residues of imidacloprid penetrated into the albedo and membrane, although at less than the MRL in all samples even at double dose. The dietary exposure of buprofezin and imidacloprid was safe on all sampling days; whereas samples with dimethoate appeared safe after 15 and 30 days of field applications at standard and double doses, respectively.     

Evaluation of cost-effective methods in the pesticide residue analysis of non-fatty baby foods

Three non-fatty ready-to-eat baby food matrices (fruits: juice, purée and cocktail plus rice flour/starch and sugar) were fortified with 0.01, 0.05, 0.1 and 0.2 mg/kg of dimethoate, chlorpyrifos, methidathion, phosalone and diazinon. Simple methods including extraction by ethyl acetate [EtAc] and acetone partition and determination by gas chromatography with Nitrogen–Phosphorus Detector (GC–NPD) were used. Acceptable pesticides recoveries (70–110%), low detection and quantification limits (0.001 to >0.1 mg/kg and 0.005 to 0.04 mg/kg, respectively) and repeatabilities (%RSDs), in 0.01 mg/kg, within 2.9–13.9% were observed. However, analytes recoveries were affected (p < 0.05) by both the baby food formulation and the extraction method used. Specifically, fruits purée and cocktail EtAc extracts gave excessively over-(dimethoate recoveries of 119.7–153.5%) or underestimation (phosalone and especially diazinon recoveries of 19.3–79.2%) in contrast to fruits juice (e.g., 61.3–87.9%). Also, EtAc extracts showed higher amount of lipophilic compounds and provided lower recoveries for non-polar analytes than those of acetone partition. Consequently, the examined methods may be successfully applied in non-fatty baby foods with the matrix-matched standards determination, following improvements of certain parameters in relation to the clean-up of samples.     

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.     

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.     

Study on antioxidant activity of certain plants in Thailand: Mechanism of antioxidant action of guava leaf extract

The ethanol extracts from 24 samples plant species commonly found in Thailand were investigated and compared on their antioxidant activity by ABTS assay. The ethanol extract from the leaves of guava (Psidium guajava) showed the highest antioxidant capacity with the TEAC value of 4.908 ± 0.050 mM/mg, followed by the fruit peels of rambutan (Nephelium lappaceum) and mangosteen (Garcinia mangostana) with the TEAC values of 3.074 ± 0.003 and 3.001 ± 0.016 mM/mg, respectively. The further investigation of guava leaf extracts from different solvents; n-hexane, ethyl acetate, n-butanol, and methanol, was examined using ABTS and FRAP assays. The total phenolic content was done by Folin–Ciocalteu reaction. The results indicated that the methanol fraction possessed the highest antioxidant activity, followed by the butanol and ethyl acetate fractions, respectively. The hexane fraction showed the lowest antioxidant activity. The results demonstrated that the mechanism of antioxidant action of guava leaf extracts was free radical scavenging and reducing of oxidized intermediates. The phenolic content in guava leaf fraction played a significant role on the antioxidant activity via reducing mechanisms.     

Determination of Chlorantraniliprole Residues in Grape by High-Performance Liquid Chromatography

An effective analytical method for the residue analysis of a novel insecticide chlorantraniliprole and its dissipation in grape were studied. Chlorantraniliprole residues were extracted from grape samples with ethyl acetate. The extract was cleaned up with QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method and determined by high-performance liquid chromatography with photodiode array detector (HPLC-DAD). At fortification levels of 0.06, 0.5, and 1.0 mg kg^?1 in grape, it was shown that recoveries ranged from 95.11 to 102 % with relative standard deviation (RSD) of 6 to 11 %. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 0.02 and 0.06 mg kg^?1, respectively. The dissipation half-life time of chlorantraniliprole residues in grape was 2.70 days. According to maximum residue limit (MRL), the preharvest interval (PHI) of chlorantraniliprole on grape was 4 days after the treatment. Based on the results of this study and the relevant residue regulation, chlorantraniliprole residue levels will be acceptable when applied to grape in Egypt.     

Dissipation of imidacloprid in Orthodox tea and its transfer from made tea to infusion

Imidacloprid is a systemic insecticide used widely in controlling mites, mealy bugs and other related pests in fruits, vegetables and tea. The dissipation behaviour of imidacloprid residues in green tea shoots, made tea and its transfer potential from made tea to infusion in hot water was studied. Analysis in tea matrices of imidacloprid was carried out using high-performance liquid chromatography with diode array detection. Under field conditions, imidacloprid dissipation rate was found to be faster in the wet season than the dry season. Half lives in green shoots were in the range 1.14–1.23 and 1.03–1.09 days, and 1.14–1.25, 1.04–1.07 days in made tea, for the dry and wet season, respectively. The percent transfer of imidacloprid residue from made tea to infusion was in the range of 29.2–42.0% during the dry and wet season; however, 38.2% and 57.9% of the residues remained stuck to the spent leaves during the dry and wet seasons, respectively. On the basis of transfer of residues from made tea to hot water infusion, a waiting period of 7 days after pesticide application at a recommended dose for tea plucking is suggested.     

Optimization of gas chromatography–single quadrupole mass spectrometry conditions for multiresidue analysis of pesticides in grapes in compliance to EU-MRLs

A single quadrupole GC–MS method was optimized for multiresidue determination of 47 pesticides in grapes with limit of quantifications of each compound in compliance with the EU-MRL requirements. Sample preparation involved extraction of 10 g sample with 10 ml ethyl acetate (+10 g sodium sulphate) by homogenization at 15,000 rpm followed by centrifugation at 3000 rpm. The supernatant was cleaned by dispersive solid phase extraction with primary secondary amine and acidified with 0.1% formic acid. Residues were estimated in selected ion monitoring mode with programmable temperature vaporizer-large volume injection (8 μl). All the GC and MS parameters were thoroughly optimized to achieve satisfactory linearity (R² > 0.99) within 0.01–0.25 mg kg⁻¹ with minimum matrix interferences. Recoveries at 0.01 and 0.02 mg kg⁻¹ were within 67–120% with associated precision RSD below 19%. The method was successfully applied for analysis of the real world samples for incurred residues.     

Validation of a headspace solid-phase microextraction procedure with gas chromatography-electron capture detection of pesticide residues in fruits and vegetables

Headspace solid-phase microextraction (HS-SPME) was evaluated for the determination of pesticide residues in fruits and vegetables by gas chromatography with an electron capture detector (GC-ECD). The fibre used was coated with polydimethylsiloxane (100 μm thickness) and the analytical conditions employed have been developed and optimised in a previous work [Chai, M. K., Tan, G. H., & Asha, L. (2008). Optimisation of headspace solid-phase microextraction for the determination of pesticide residues in vegetables and fruits. Analytical Sciences, 24 (2), 273–276]. The results show that the HS-SPME procedure gave a better linear range, accuracy, precision, detection and quantification limits and is adequate for analysing pesticide residues in fruits and vegetables. The average recoveries obtained for each pesticide ranged between 71% and 98% at three fortification levels with the relative standard deviation of less than 5%. Repeatability (0.3–3.7%) and intermediate precision (0.8–2.5%) were shown to be satisfactory. The limits of detection (0.01–1 μg L⁻¹) and the limits of quantification (0.05–5 μg L⁻¹) of these pesticides were much lower than the maximum residue levels (MRL), allowed for fruits and vegetables in Malaysia.     

Residual pattern of fenhexamid on pepper fruits grown under greenhouse conditions using HPLC and confirmation via tandem mass spectrometry

Fenhexamid (25%, SC) was sprayed on pepper fruits grown under greenhouse conditions at the recommended dose rate of 20 g/20 L water. Fruit samples were collected randomly at 0 (2 h after application), 1, 2, 4, 6, 8, 11, and 14 days post-application. The samples were extracted with acetonitrile, partitioned with water, passed through a cleanup procedure, and analysed via HPLC. Residues were confirmed via LC–tandem mass spectrometry (LC–MS/MS) in positive-ion electrospray ionisation (ESI+) mode. The rate of disappearance of fenhexamid on pepper fruits was described as first-order kinetics (r² = 0.992) with a half-life of 4.7-day. Based on the pattern of decline of the fungicide residues in relation to the estimated maximum residue limits (MRL = 5 mg/kg), a safety pre-harvest interval of 1 day is suggested for peppers at the recommended dosage.     

Residue levels of captan and trichlorfon in field-treated kaki fruits, individual versus composite samples, and after household processing.

The dissipation of residue levels of captan and trichlorfon in field-treated kaki crops was studied according to good laboratory practices to propose maximum residue limits (MRLs). Residue levels of captan and trichlorfon were analysed by GC/MS and LC-MS/MS, respectively. Residue levels of captan and trichlorfon permitted one to propose MRLs in kaki of 3 and 5 mg kg(-1), respectively. The behaviour of these residues was also studied after peeling and cooking, and in individual fruits versus composite samples. Residue levels of these compounds for individual fruits suggested that a variability factor up to three could be set for the acute risk assessment. Levels of captan decreased by more than 90% after peeling and completely after cooking. Trichlorfon penetrates into the flesh in a proportion of 70% of the residue at the pre-harvest interval. Cooking resulted in a decrease of 27% of residue levels of trichlorfon.     

Dissipation kinetics of forchlorfenuron, 6-benzyl aminopurine,gibberellic acid and ethephon residues in table grapes (Vitis vinifera)

The residue dynamics of plant growth regulators (PGR) forchlorfenuron (CPPU), 6-benzylaminopurine (6-BA), gibberellic acid (GA₃) and ethephon in grape are presented, corresponding to their field applications at recommended and double doses. Random samples were collected from each treated and control plot at regular time intervals. The optimised sample preparation technique involves extraction of 10 g homogenised sample with 20 ml methanol (+1% formic acid) and measurement by LC–MS/MS multiple reaction monitoring, offering limit of quantification ?0.0025 μg/g for all except ethephon with LOQ of 0.005 μg/g. The recoveries at LOQ and above were 84.8–109.5%. Residue dissipation of all the PGRs followed non-linear two-compartment first + first-order kinetics. CPPU, 6-BA and ethephon residues dissipated with preharvest intervals (PHIs) of 33.5, 12 and 32 days at recommended dose with no PHI applicable for GA₃. The PHIs successfully minimised residue problems as observed from survey results of traceable field samples.     

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.     

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.     

Behaviour of some organophosphorus pesticide residues in peppermint tea during the infusion process

In order to investigate dissipation behaviour of malathion, fenitrothion, dimethoate, chlorpyrifos and pirimiphos-ethyl during the infusion process, pesticide-free dried peppermint leaves were spiked with the pesticides. Infusions were prepared according to the usual process of infusion preparation. The effect of the infusion process on the transfer of the pesticides from the spiked peppermint leaves into brew was examined at intervals of 5, 10, 15 and 20 min. Residues were determined using a gas chromatograph equipped with a flame ionisation detector (FID). The decrease in pesticide levels during infusion was found to be statistically significant (p < 0.05). Transfer of residues decreased significantly with infusion time. The carryover of the residues of dimethoate, which has the highest water solubility, into the infusion was the highest. Satisfactory relationships were found between water-solubility (Ws), partition coefficient (K_ow) and Henry’s law constant (H) of the pesticides with the transfer of pesticides to brewed tea. It was observed that not only water solubility or K_ow but also H controls the dissipation of the pesticides from water or their air–water partitioning.     

Evaluation of QuEChERS method for the determination of organochlorine pesticide residues in selected groups of fruits

This paper reports a method for organochlorine pesticide determination in selected fruit species where pesticide residues were extracted and cleaned using a buffered QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method, followed by GC–MS analysis. The method results showed the matrix-matched calibration curve linearity was >0.99 for all target analytes. With pesticide recovery rates (spiked at 0.008 mg kg⁻¹) ranging from 70% to 120%, and RSD values <17% for most compounds, the limit of quantification ranged from 0.001–0.013 mg kg⁻¹. Finally, the method ruggedness was further demonstrated by analysis of actual commercial fruits and baby food samples.     

Analysis of pesticide residues in seaweeds using matrix solid-phase dispersion and gas chromatography–mass spectrometry detection

Products containing organophosphates, carbamates and pyrethroids pesticides, employed as chemotherapeutants in aquaculture, can remain as residues in the marine environment. Matrix solid-phase dispersion (MSPD) was developed to extract seventeen pesticides from seaweed samples using Florisil and graphitized carbon black as clean-up adsorbents prior to gas chromatography–mass spectrometry (GC–MS) determination. The extraction has been optimised by a Box–Behnken design. The optimal conditions were 1 g of seaweed sample, 4 g of anhydrous sodium sulphate as dispersant, 3.6 g of Florisil and 0.4 g of GCB and an elution volume of 14 mL of a hexane:ethyl acetate mixture containing 40% ethyl acetate. The recoveries ranged from 81.6% to 113.2% with relative standard deviations (RSDs) ranging from 1.6% to 13.2%. The limits of detection (LOD) ranged from 0.5 to 2.9 ngg⁻¹. Internal quality control was successfully carried out to verify the quality of the data obtained in the analysis of these pesticides in seaweed samples.     

Cloud point extraction coupled with ultrasonic-assisted back-extraction for the determination of organophosphorus pesticides in concentrated fruit juice by gas chromatography with flame photometric detection

A new method for the determination of nine organophosphorus pesticides (OPPs): Dichlorvos, methamidophos, acephate, diazinon, dimethoate, chlorpyrifos, parathion-methyl, malathion and parathion-ethyl in concentrated fruit juice was developed using the cloud point extraction coupled with ultrasonic-assisted back-extraction prior to gas chromatography with flame photometric detection (GC-FPD) analysis. The parameters and variables that affect the extraction were investigated. Under optimum conditions: a solution containing 6% (W/V) polyethylene glycol 6000 (PEG 6000) and 20% (W/V) Na₂SO₄ for the extraction of the OPPs. The coacervation phase obtained was back extracted with ethyl acetate. The upper ethyl acetate solution was centrifugated simply for further cleanup for the sake of automatic injection. A preconcentration factor of 50 was obtained for these nine pesticides. Using this method, the limits of detection (LOD) and limits of quantification (LOQ) were in the range of 0.5–3.0 and 1.5–9.0 μg kg⁻¹ in concentrated fruit juice, respectively; the relative standard deviations (RSD) were <9%.     

Validation of an ultra-performance liquid chromatography-tandem mass spectrometry method for determination of ractopamine: Application to residue depletion study in swine

A sensitive and reliable method was developed and validated for the analysis of ractopamine in swine tissues. The sample preparation procedure was based on hydrolysis overnight, extraction with ethyl acetate, and solid-phase extraction cleanup. The target compound was determined by ultra-performance liquid chromatography coupled with tandem mass spectrometry. The average recoveries ranged between 93.3% and 106.5%, with relative standard deviations of 7.2–12.8%. The detection and quantification limits were 0.2 and 0.5 μg/kg, respectively. The depletion profile of ractopamine was studied in healthy pigs after oral administration of feed containing 20 mg/kg ractopamine for 30 consecutive days. Ractopamine residues were still detected 11 days post-medication in all tissues examined with the exception of muscle. The highest ractopamine level was found in lung tissue. The developed method has been successfully applied to the depletion study of ractopamine in swine tissues.