Assessing supercritical fluid extraction for the analysis of fipronil,kresoxim-methyl,acrinathrin, and pyridaben residues in melon

An analytical method, using supercritical fluid extraction (SFE), was assessed for residue analysis of the insecticides fipronil, acrinathrin and pyridaben and the fungicide kresoxim-methyl in melons. Extraction conditions were optimized on glass beads, as inert material, evaluating different pressures, temperatures, and CO₂ volumes. Also, the extractability of pesticides from hydromatrix and anhydrous magnesium sulfate was evaluated. Both adsorbents were evaluated for the preparation of SFE-spiked melon samples. Extractions of fortified samples were done using 20 mL of CO₂, 300 atm, and 50°C. Different extraction conditions, including the addition of water and methanol as a static modifier, were used to assess the extractability of these pesticides, and the addition of methanol was demonstrated to improve the extraction of all the studied pesticides.     

Persistence and dissipation kinetics of trifloxystrobin and tebuconazole in onion and soil

The persistence and dissipation kinetics of trifloxystrobin and tebuconazole on onion were studied after application of their combination formulation at a standard and double dose of 75 + 150 and 150 + 300 g a.i. ha^?1. The fungicides were extracted with acetone, cleaned-up using activated charcoal (trifloxystrobin) and neutral alumina (tebuconazole). Analysis was carried out by gas chromatograph (GC) and confirmed by gas chromatograph mass spectrometry (GC-MS). The recovery was above 80% and limit of quantification (LOQ) 0.05 mg kg^?1 for both fungicides. Initial residue deposits of trifloxystrobin were 0.68 and 1.01 mg kg^?1 and tebuconazole 0.673 and 1.95 mg kg^?1 from standard and double dose treatments, respectively. Dissipation of the fungicides followed first-order kinetics and the half life of degradation was 6–6.6 days. Matured onion bulb (and field soil) harvested after 30 days was free from fungicide residues. These findings suggest recommended safe pre-harvest interval (PHI) of 14 and 25 days for spring onion consumption after treatment of Nativo 75 WG at the standard and double doses, respectively. Matured onion bulbs at harvest were free from fungicide residues.     

A simple HPLC method for determination of permethrin residues in wine

An isocratic High Performance Liquid Chromatographic (HPLC) method was optimized for 3-phenoxybenzyl (1RS)-cis-trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate (permethrin) residues identification and quantification in wine matrix. Analytical reverse phase (RP) C-18 column was used (25 cm × 4 mm i.d., 5 μ m) with mobile phase consisting of acetonitrile and water in ratio 70 %/30 % (v v^?1), flow-rate 2.0 mL min^?1, UV-detection at 215 nm and controlled oven temperature at 25°C. The peaks of isomers were identified with the retention times as compared to standard cis-/trans- mixture and confirmed with characteristic spectra using photodiode array detector. Under these conditions, permethrin isomers were well separated with resolution 2.8 and no interference with the naturally present wine compounds was observed. The method was validated for linearity, precision, accuracy, limit of detection (LOD) and limit of quantification (LOQ). Linear regression analysis data proved a good linear relationship (correlation coefficients, r², for cis- and trans-isomer are: 0.9995 and 0.9997, respectively) between response of the detector and concentration of permethrin isomers over a wide concentration range for both isomers (0.55 mg L^?1 ?4.40 mg L^?1). Experimental data showed mean recoveries between 93.95% and 96.58% with RSD values in range: 0.89% ?3.69%. The effect of ethanol content in the solvent on permethrin isomers peak areas was also studied and 60% v v^?1 ethanol was found to be optimal for sample preparation. The method was successfully tested on 20 commercial wine samples from the market in which no permethrin was detected. Thus, it was proved that it is suitable for routine permethrin residues analysis. The proposed method is suitable for routine analysis because of the simple sample preparation, acceptable run-time, low cost and its applicability with conventional instruments.     

Determination of some pesticide residues in conventional-grown and IPM-grown tomato by using QuEChERS method

The present study was conducted to determine pesticide (emamectin-benzoate, penconazole and imidacloprid) residues over tomatoes by using QuEChERS method. The method was validated by spiking tomato matrix at 0.1, 1.0, and 10.0 MRL levels of the pesticides. Tomatoes were harvested from two conventional and two Integrated Pest Management-grown fields. Laboratory samples were taken from the bulk samples. Analyses of spiked and real-field tomatoes were performed with QuEChERS procedure. Experimental samples were subjected to LC-MS/MS analysis. As indicated in “CAC/GL 40-1993,” representative sample matrix (apple) calibration was used for quantification. The overall recovery was 107.12% with a relative standard deviation of 17.96% (n?=?162). Present values were within the specified recovery ranges (60-140%) and repeatability value of (RSD ≤20%) of SANCO. Analysis of field experiment samples showed that both conventional tomato plots had trace levels (less than MRL) of emamectin-benzoate and imidacloprid, whereas there were not any pesticide residues in both IPM tomato plots     

Quantitative analysis of acetamiprid and imidacloprid residues in tomato fruits under greenhouse conditions

Abstract

A selective liquid chromatographic analytical method was studied for determination of two neonicotinoids, acetamiprid and imidacloprid, in tomato fruits under greenhouse conditions in Egypt. The fruits were extracted and cleaned up by QuEChERS method followed by HPLC determination. The method showed a good linearity with a determination coefficient (R²) of higher than 0.99 for the 0.0125–0.15 µg/mL concentration range. The method was validated using a blank tomato spiked at 5, 25 and 50 mg/kg and the recovery percentages were 83.71, 94.52 and 97.49% for acetamiprid and 88.59, 89.63 and 90.18% for imidacloprid, respectively. The rates of dissipation of both pesticides were studied and the preharvest intervals (PHIs) were calculated. Imidacloprid dissipated faster than acetamiprid and half-life periods were 1.30 and 2.07 days, respectively. Acetamiprid and imidacloprid residues were below the already established European maximum residue limits (EU MRLs) (0.5 mg/kg) 3 and 5 days after application, respectively.     

Determination of fungicide kresoxim-methyl residues in cucumber and soil by capillary gas chromatography with nitrogen-phosphorus detection

The method of residue analysis of kresoxim-methyl and its dissipation rate in cucumber and soil in a greenhouse were studied. Residues of kresoxim-methyl were extracted from cucumber and soil matrices with acetone, purified by liquid-liquid extraction and Florisil cartridges, and then determined by GC with NP-detector. The limit of detection was estimated to be 9 x 10-12 g, and the minimum determination concentration of kresoxim-methyl in the samples was 0.005 mg kg-1. The average recoveries ranged from 89.4 to 100.2% with a coefficient variation between 2.4 and 8.9%. Dissipation study showed that the half-lives of kresoxim-methyl in cucumber were approximately 6.5 days at both the recommended and double the recommended dosage. Half-lives for both the treatments were approximately 8 days in soil. The present study revealed that the residues in cucumber were below the MRL (0.05 mg kg-1, fixed by EU) after 7 days for both treatments.     

Comparison of in-house-developed ELISA with HPLC techniques for the analysis of atrazine residues

In-house developed ELISA was standardized to monitor atrazine residues in different environmental samples. The standard curve was linear, indicating an increase in log concentration with decrease in absorbance (%B/B₀ = 1.075–0.042 Log C; r = ?0.966). The middle of the test was at 75 ng/L and the lowest detection limit at 4 ng/L. ELISA significantly correlated with the high performance liquid chromatography (HPLC) (r = 0.990). Internal validation showed good accuracy and precision. Maximum atrazine residues were present in Jehlum River water/sediments and maize/sugarcane plant roots. Most of the food samples were found to be contaminated. ELISA required less clean-up steps than HPLC, but showed matrix effect in soil/colored extracts.     

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection

The Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) has been validated for the extraction of 15 organochlorine pesticides (OCPs) in completely different matrices of traditional Chinese medicine (TCM). The method employed a rapid, simple and cost-effective procedure. The spiking levels for the recovery experiments were 0.1, 0.5 and 2.0 mg kg⁻¹. Mean recoveries mostly ranged between 76.0% and 114.0% (96.0% on average), and relative standard deviations (RSD) were generally below 10% (4.72% on average). Based on these results, the methodology has been proven to be highly efficient and robust and thus suitable for monitoring the MRL compliance of a wide range of commodity. The contamination status of 15 OCPs on 80 different TCMs marketed in China, and a total of 400 samples were also performed using a previously validated method. 15 OCPs were benzene hexachloride (BHC, including α-BHC, β-BHC, γ-BHC, δ-BHC), hexachlorobenzene, heptachlor, heptachlor epoxide, aldrin, p, p′-DDE, p, p′-DDD, o, p′-DDT, p, p′-DDT, mirex, endrin, dieldrin. This study indicates that the proposed method is useful for analyzing OCPs in TCM.     

Application of the QuEChERS method for the determination of organochlorine pesticide residues in Brazilian fruit pulps by GC-ECD

The Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method was applied to the extraction of 14 organochlorine pesticides (OCPs) residues from commercial fruit pulps available in supermarkets in Fortaleza, Northeastern Brazil. The analyses were carried out by gas chromatography (GC), coupled to an electron-capture detector (ECD), and were confirmed by GC-tandem mass spectrometry (MS). The parameters of the analytical method, such as accuracy, precision, linear range, limits of detection and quantification, were determined for each pesticide. The results showed good linearity (R² ≥ 0.9916) and the overall average recoveries were considered satisfactory obtaining values between 69 and 110%, RSD of 2–15 %, except for hexachlorobenzene (HCB) in açai, acerola and guava pulp samples. The OCPs were detected in guava (α–HCH; lindane) and soursop (α, β–HCH isomers) samples. The QuEChERS method and GC–ECD were successfully used to analyze OCPs in commercially available Brazilian fruit pulps and can be applied in routine analytical laboratories.     

LC-MS/MS determination of pesticide residues in fruits and vegetables

The aim of the research is to evaluate pesticide residue contamination of fresh and frozen fruits and vegetables, agricultural raw material, purchased from Polish farmers for production of frozen fruits and vegetables, and the estimation of the multiresidue method effectiveness expressed as the proportion of pesticides detected in food samples to the total number of pesticides analyzed by multiresidue methods. A total of 144 samples (of black currants, red currants, raspberries, cherries, strawberries, blackberries, cauliflowers and broccoli) were analyzed using LC-MS/MS method for the determination of 60 pesticides. QuEChERS extraction, matrix-matched calibration and dynamic multiple reaction monitoring method were used. Residues of 15 compounds, mainly fungicides and insecticides, were detected in 46 samples. The percentage of samples with residues above the maximum residue levels (MRL) was 15%, whereas samples with residues below MRL were 17%. A total of 13 samples contained more than one pesticide residue. Pesticide residues were detected most often in samples of black currants (50%), broccoli (36.4%), raspberries (29%) and red currants (21.8%). The most frequently detected pesticides were carbendazim and acetamiprid. The proportion of pesticides detected during our study to the total number of analyzed pesticides amounted to 25%. It was compared to literature findings. For three fourth of multiresidue methods, the proportion was below 50% for methods developed for the analysis of less than 100 pesticides, and below 30% for methods developed for the analysis of more than 100 pesticides. It appears that a lot of efforts and means is lost on pesticides never or rarely detected in examined samples. The workload and cost effectiveness of the development and application of multiresidue methods along with the range of pesticides covered by the method should be carefully and thoroughly considered anytime when a new method or workflow is developed. Including non-targeted screenings in pesticide residue control seems to be an alternative worth considering.     

Dissipation of pendimethalin in the soil of field pea (Pisum sativum L.) and detection of terminal residues in plants

Dissipation of pendimethalin in the soil of field peas (Pisum sativum L.) at 0 to 110 days, and terminal residues in green and mature pea were studied under field conditions. Pendimethalin was applied as pre-emergence herbicide at 750, to 185 g a.i. ha^?1 in winter, in field peas. Dissipation of pendimethalin in the soil at 0 to 110 days followed first-order kinetics showing a half-life of 19.83 days averaged over all doses. Low pendimethalin residues were found in mature pea grain (0.004, 0.003, <0.001 μg g^?1), and straw (0.007, 0.002, <0.001 μg g^?1) at 750, 350 and 185 g a.i. ha^?1 treatments, respectively. The study indicated that residues of pendimethalin in green and mature pea were within the prescribed MRL limits.     

Dissipation,residues, and risk assessment of imidacloprid in Zizania latifolia and purple sweet potato under field conditions using LC-MS/MS

A shortened version of Quick, Easy, Cheap, Effective, Rugged, and Safe method (QuEChERS) for determining the dissipation and residue of imidacloprid present in Zizania latifolia and purple sweet potato was established by using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The average recoveries of imidacloprid in the two crops ranged from 82.12 to 113.79%, with relative standard deviation (RSD) of <7.32%. The dissipation dynamics of imidacloprid in Z. latifolia plants and purple sweet potato plants followed first-order kinetics, with half-lives of 3.2–5.5?days in each of sampling locations. The terminal imidacloprid residues in Z. latifolia and purple sweet potato at each of location were <0.005–0.120?mg kg^?1. According to the risk assessment results, both the acute dietary risk quotient and chronic dietary risk quotient values were <1, indicating that imidacloprid is unlikely to pose health risks to humans with normal recommended use. The present study may serve as a valuable reference for the safe and reasonable use of imidacloprid in Z. latifolia and purple sweet potato fields.     

Determination of sulfosulfuron residues in soil under wheat crop by a novel and cost-effective method and evaluation of its carryover effect

A novel and cost-effective method of sulfosulfuron extraction has been developed using distilled water as an extraction solvent. Using this method, the environmental fate of sulfosulfuron was investigated in soil under wheat crop. Studies were conducted under natural field conditions in randomized block design and herbicide (75% water dispersible granules (WG)) was applied after 24 days of sowing. The rates of applications were 25 and 50 g of active ingredient (a.i.) per hectare. Soil samples were collected at predetermined intervals and analyzed by high performance liquid chromatography (HPLC). The minimum detection limit was found to be 0.001 μ g g^{? 1}. The dissipation of sulfosulfuron followed first-order rate kinetics and dissipated with a half-life of 5.4–6.3 days. After harvest, field soil was used for conducting a pot experiment with bottle gourd (Lagenaria siceraria) as test plants to study the carry over effect of sulfosulfuron. No phytotoxicity was observed to bottle gourd in pot experiment with harvest soil.     

Application of an enzyme-linked immunosorbent assay for the detection of clenbuterol residues in swine urine and feeds

The present study outlines applications of an enzyme-linked immunosorbent assay (ELISA) for the analysis of clenbuterol residues. Antisera were raised from rabbits immunized with diazotized clenbuterol-bovine serum albumin (BSA) conjugate. The assay was specific to clenbuterol with a half-maximum inhibition concentration (IC₅₀) of 1.8 ng/mL and 2.5 ng/mL in blank swine urine and phosphate buffer solution, respectively. The assay had high cross-reactivity (86%) with mabuterol, but low with other adrenergic agonists and antagonists. The average recovery of clenbuterol, as measured with the ELISA, ranged from 90% to 112% in swine urine samples and from 86% to 95% in feeds, respectively. This new assay was compared with commercial ELISA test kits. An excellent correlation (r ² = 0.98) between the two methods and satisfactory recoveries suggest that the new assay can be suitable for the determination of clenbuterol residues in real samples. The assay was used to analyze clenbuterol residues in 103 swine urine samples and 68 feed samples collected from northern China. Approximately 50% of the urine samples and 25% of the feed samples analyzed were found positive (concentration of clenbuterol ≥ 1 ppb). The results indicate that clenbuterol was misused in some of the areas surveyed.     

Residues and dissipation kinetic of abamectin,chlorfenapyr and pyridaben acaricides in green beans (Phaseolus vulgaris L.) under field conditions using QuEChERS method and HPLC

Abstract

The current study estimated the dissipation rates of abamectin, chlorfenapyr and pyridaben acaricides in pods of green beans (Phaseolus vulgaris L.) under field conditions in Egypt. Pesticides were extracted and cleaned-up by QuEChERS method and were analyzed by HPLC. The dissipation of these acaricides followed the first order kinetics model with half-life (t_1/2) values 1.00, 3.50 and 1.50?days for abamectin, chlorfenapyr and pyridaben, respectively. The lowest residues, at different time intervals of field application rate of each pesticide, were observed with abamectin followed by pyridaben and then chlorfenapyr. Pre-harvest intervals (PHIs) were 10.00, 13.50 and 6.00?days for abamectin, chlorfenapyr and pyridaben, respectively and were below the established European maximum residue limits (EU MRLs) 10–14, 14–21 and 7–10?days after application, respectively. If the fresh pods will be consumed after harvest, it is expected that the presence of these pesticides in the food will have a negative impact on human health. Therefore, the elimination of the residues of these harmful pesticides must be carried out.     

Determination of etoxazole residues in fruits and vegetables by SPE clean-up and HPLC-DAD

A method for determination of etoxazole residues in apples, strawberries and green beans was developed and validated. The analyte was extracted with acetonitrile from foodstuff and a charcoal-celite cartridge was used for clean-up of raw extracts. Reversed phase high performance liquid chromatography with photodiode array detector (HPLC-DAD) was used for the determination and quantification of etoxazole residues in the studied samples. The calibration graphs of etoxazole in a solvent or three blank matrixes were linear within the tested intervals 0.01–2 mg L^?1, with correlation coefficient of determination >0.999. The combined solid phase extraction (SPE) clean-up and the chromatographic method steps were sensitive and reliable for simultaneous determination of etoxazole residues in the studied samples. The average recoveries of etoxazole in the tested foodstuffs were between 93.4 to 102% at spiking levels of 0.01, 0.10, and 0.50 mg kg^?1, with relative standard deviations ranging from 2.8 to 4.7%, in agreement with directives for method validation in residue analyses. The limit of detection (LOD) of the HPLC-DAD system was 100 pg. The limit of quantification of the entire method was 0.01 mg kg^?1.     

Determination of Fungicide Kresoxim-Methyl Residues in Cucumber and Soil by Capillary Gas Chromatography with Nitrogen-Phosphorus Detection

The method of residue analysis of kresoxim-methyl and its dissipation rate in cucumber and soil in a greenhouse were studied. Residues of kresoxim-methyl were extracted from cucumber and soil matrices with acetone, purified by liquid-liquid extraction and Florisil cartridges, and then determined by GC with NP-detector. The limit of detection was estimated to be 9× 10^?12 g, and the minimum determination concentration of kresoxim-methyl in the samples was 0.005 mg kg^?1. The average recoveries ranged from 89.4 to 100.2% with a coefficient variation between 2.4 and 8.9%. Dissipation study showed that the half-lives of kresoxim-methyl in cucumber were approximately 6.5 days at both the recommended and double the recommended dosage. Half-lives for both the treatments were approximately 8 days in soil. The present study revealed that the residues in cucumber were below the MRL (0.05 mg kg^?1, fixed by EU) after 7 days for both treatments.     

Validation of QuEChERS method for the determination of 36 pesticide residues in fruits and vegetables from Ghana,using gas chromatography with electron capture and pulsed flame photometric detectors

In this study, “Quick, Easy, Cheap, Effective, Rugged and Safe” ‘QuEChERS’ method was modified for the determination of 36 pesticides fortified at (0.01–1.0) mg kg^?1 in three vegetables and a fruit (lettuce, carrot, tomatoes and pineapples respectively) from Ghana. The method involved extraction with acetonitrile, phase separation with primary secondary amine and magnesium sulfate; the final injection solution was reconstituted in ethyl acetate. Organochlorine and synthetic pyrethroids residues were detected with electron capture detector whereas organophosphorus, pulsed flame photometric detector was used. The recoveries at different concentration levels (0.01, 0.1 and 1.0 mg kg^?1) were in the range of 83% and 93% with relative standard deviation ranging from 2% to 10% (n = 5) and the coefficient of determination (R²) was greater than 0.99 for all the 36 pesticides. The method was successfully tested on 120 real samples from Accra markets and this proved to be useful for monitoring purposes particularly in laboratories that have no gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry.     

Simultaneous determination of fenitrothion and aminocarb in blueberry foliage and fruits: Application to the analysis of residues in field samples

Abstract

Samples of blueberry foliage and fruits were collected from spray blocks in Ontario after aerial application of fenitrothion and aminocarb at dosage rates of 210 g active ingredient (AI)/ha and 70 g AI/ha respectively. Residues were extracted from the samples by homogenizing with ethyl acetate, cleaned up by microcolumn chromatography using alumina as adsorbent, and analyzed by GLC‐AFID with a glass column packed with 1.5% OV‐17 and 1.95% OV‐210 on 80–100 mesh Chromosorb W‐HP. Average recoveries for fenitrothion and aminocarb from foliage at three fortification levels (1.0, 0.10 and 0.01 ppm) were respectively 99 and 96%. The corresponding values for the fruits were 99 and 95%. Foliage samples collected 1 h post‐spray contained on average 1.13 ppm of fe‐nitrothion and 1.14 ppm of aminocarb. However, residue levels reached below the detection limit (<0.01 ppm) in foliage collected 15 d after treatment. In addition, the fruit samples collected after 15 d post‐spray contained extremely low levels (0.03 ppm for fenitrothion and 0.02 ppm for aminocarb) of residues, and were barely above the detection limit.     

Effect of organic amendment on degradation and formation of bound residues of methabenzthiazuron in soil under constant climatic conditions

Abstract

The degradation of [phenyl‐U‐¹⁴C]methabenzthiazuron (MBT) and formation of bound residues in the surface soil of an orthic luvisol were studied under constant climatic conditions (20°C, 40 % of maximum water holding capacity). In two treatments (with and without preincubation in the soil) maize straw was amended at a rate of 1.5 g/100 g dry soil in addition to the application of MBT. The mineralization of uniformly labeled maize straw was studied simultaneously. In additional flasks, MBT was incubated at 0, 10 and 30°C with and without addition of maize straw.

The turnover of the amended maize straw led to an enhanced dissipation of MBT which was mainly due to the formation of bound residues. This corresponded to a higher microbial activity in the soil after straw amendment and the intensive mineralization of the radiolabeled maize straw. About 2–3 % of the applied radioactivity from the radiolabeled maize straw was measured in the soil microbial biomass 10 and 40 days after application whereas ¹⁴C from MBT was only incorporated into soil microbial biomass in the treatments with straw amendment.

Within the bound residue fractions relatively more radioactivity was measured in fulvic and humic acids after straw amendment. Increasing temperatures promoted the dissipation of MBT and the formation of bound residues in both treatments, but without amendment of maize straw these effects were far less pronounced. The laboratory scale degradation experiment led to similar results as were found in a corresponding lysimeter study. Differences that were observed could be explained by different temperature regimes of the experiments and time of aging in soil.