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.     

Consumer health risk to pesticide residues in Salvia officinalis L. and its infusions

Salvia officinalis L. is a popular herb widely used in culinary, cosmetic, and medicinal preparations, and also as an ornamental plant. Sage crops are threatened by many diseases, such as gray mold, powdery mildew, and leaf spot, by weeds, and by pests, such as aphids. Use of crop protection products may lead to presence of pesticide residues in this herb. The aim of this work was to study presence of pesticide residues in the herb, S. officinalis L., available on the retail market in Poland, to verify their compliance with the maximum residue levels (MRLs) and to assess the chronic and acute risks associated with consumption of this herb and infusions prepared from contaminated sage plants. Ninety active substances of pesticides were analyzed, including all active substances registered in Poland for protection of the sage. Five active substances were found, one fungicide – boscalid and four insecticides: chlorpyrifos, pp′-DDT, dimethoate (residue levels above MRL) and indoxacarb. The chronic and acute exposure to pesticide residues consumed with sage did not exceed 0.02% of the acceptable daily intake (ADI) and 0.1% of the acute reference dose (ARfD), respectively.     

Variability of pesticide residues in cauliflower units collected from a field trial and market places in Greece

To estimate the variability of pesticide residue levels present in cauliflower units, a total of 142 samples were collected from a field trial of a cooperative farmer, and 120 samples were collected from different market places in Thessaloniki, Greece. The collected samples were extracted using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction technique, and the residues were determined by liquid chromatography–tandem mass spectrometry. The developed method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD), and limit of quantification (LOQ). The average recoveries for all the analytes, derived from the data of control samples fortified at 0.01, 0.05, 0.1, and 0.2 mg/kg, ranged from 74 to 110% with a relative standard deviation of ≤8%. The correlation coefficient (R²) was ≥0.997 for all the analytes using matrix-matched calibration standards. The LOD values ranged from 0.001 to 0.003 mg/kg, and the LOQ was determined at 0.01 mg/kg for all the sought analytes. The matrix effect was found to be at a considerable level, especially for cypermethrin and deltamethrin, amounting to +90% and +145%, respectively. For the field samples, the unit-to-unit variability factors (VFs) calculated for cypermethrin and deltamethrin were 2.38 and 2.32, respectively, while the average VF for the market basket samples was 5.11. In the market basket samples, residues of cypermethrin, deltamethrin, chlorpyrifos, and indoxacarb were found at levels ≥LOQ and their respective VFs were 7.12, 5.67, 5.28, and 2.40.     

Development,validation of QuEChERS-based method for simultaneous determination of multiclass pesticide residue in milk,and evaluation of the matrix effect

Extraction and quantification of pesticide residue from the milk matrix at or below the established maximum residue limit (MRL) is a challenging task for both analytical chemists and the regulatory institutions to take corrective actions for the human health and safety. The main aim of the study is to develop a simple rapid and less expensive QuEChERS extraction and cleanup method for simultaneous analysis of 41 multiclass pesticide residue in milk by gas chromatography-electron capture detector (GC-ECD), followed by confirmation of the residues with gas chromatography-mass spectrometer (GC-MS). Effect of sorbent type, temperature, spiking concentration, matrix effect (ME), measurement uncertainty (MU), inter- and intra-assay repeatability, reproducibility of recovery, and trueness of the results were investigated to validate the effectiveness of the method. Limit of determination (LOD) and limit of quantitation (LOQ) for all the analytes ranged within 0.001–0.02 and 0.002–0.05 µg mL^?1, respectively. The % recovery of all the pesticides ranged between 91.38 and 117.56% with relative standard deviation (RSD) below 2.79%. The MU for all the analytes was ≤29% of respective LOQs, and except for few pesticides, the ME was largely negative. The method fulfilled all the SANTE guidelines and thus can be extended for routine analysis of multiclass pesticide residue in milk.     

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.     

Assessing washing methods for reduction of pesticide residues in Capia pepper with LC-MS/MS

Abstract

The effects of washing treatments on removal rates of some pesticides residues (acetamiprid, chlorpyrifos and formetanate hydrochloride) on pepper were investigated. Method verification was conducted through spiking pepper samples at 0.1, 1.0 and 10.0 × MRL. QuEChERS method produced average recovery of 104.91% with relative standard deviation (RSD) of 13.41%. LOQ values of acetamiprid, chlorpyrifos and formetanate hydrochloride were estimated as 2, 10 and 5?µg/kg, respectively. Capia peppers grown in open fields were sprayed three times with pesticides. Peppers were harvested after 1st, 2nd and 3rd day of the treatments. Then the peppers were subjected to tap water, acetic acid and citric acid washing and ultrasonic cleaning treatments (for 2 and 5?min). Based on three different harvest times and two different washing durations, processing factors (PFs) and reduction rates were calculated for each washing treatment. The residues gradually decreased during washing treatments with increasing process duration. Similarly, a gradual reduction was noted with the progress of harvest times. This in turn corresponded to an increase in PF. Ultrasonic cleaning and citric acid (9%) washing were more effective than the others. Non-systemic pesticides (chlorpyrifos) were more readily removed than the systemic ones (acetamiprid). Similarly, highly soluble pesticides exhibited higher reduction.     

Determination of the residue dynamics and dietary risk of thiamethoxam and its metabolite clothianidin in citrus and soil by LC-MS/MS

A modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed for the determination of thiamethoxam and its metabolite clothianidin in citrus (including the whole citrus, peel and pulp) and soil samples by liquid chromatography-tandem mass spectrometry. The sample was extracted with acetonitrile and purified with octadecylsilane. The detection limits of both compounds were 0.0001–0.0002?mg kg^–1, while the limit of quantification of thiamethoxam was 0.002?mg kg^–1 and the limit of quantitation of metabolites was 0.001?mg kg^–1. The recovery was 70.37%–109.76%, with inter-day relative standard deviations (RSD) (n?=?15) values ≤9.46% for the two compounds in the four matrices. The degradation curve of thiamethoxam in whole citrus and soil was plotted using the first-order kinetic model. The half-life of the whole citrus was 1.9–6.2?days, and the half-life of the soil was 3.9–4.2?days. The terminal residue of thiamethoxam (the sum of thiamethoxam and clothianidin, expressed as thiamethoxam) was found to be concentrated on the peel. The final residual amount of thiamethoxam in the edible portion (pulp) was less than 0.061?mg kg^–1. The risk quotient values were all below 1, indicating that thiamethoxam as a citrus insecticide does not pose a health risk to humans at the recommended dosage.     

Determination of glyphosate residue in maize and rice using a fast and easy method involving liquid chromatography–mass spectrometry (LC/MS/MS)

A fast and easy method was developed for the determination of glyphosate in maize and rice by using liquid chromatography triple quadrupole mass spectrometry with a Dionex Ion Pack column and phosphate buffer mobile phase. Samples were extracted with an acidified methanol solution. An isotope-labeled internal standard was added to the sample before extraction to ensure accurate tracking and quantification. The method’s performance was evaluated through a series of assessments to determine the accuracy, precision, linearity, matrix effect, limit of detection (LOD), and limit of quantification (LOQ). The mean recoveries for both matrices were within 70–105% at three fortification levels, including the LOQ. The precision for replicates was <20% (RSD%) for both matrices. Good linearity (R²=0.9982) was obtained over the concentration range of 0.01–1.5?mg kg^?1. The LOD was determined to be 0.002?mg kg^?1 for rice and 0.004?mg kg^?1 for maize. The LOQ was 0.01?mg kg^?1 for both maize and rice. Due to its versatility, the proposed method could be considered useful for the determination of glyphosate in cereals in routine analysis.     

Development,validation and matrix effect of a QuEChERS method for the analysis of organochlorine pesticides in fish tissue

This study aims to develop and validate a method to determine OCPs in fish tissues, minimizing the consumption of sample and reagents, by using a modified QuEChERS along with ultrasound, d-SPE and gas chromatography with an electron capture detector (GC-ECD), refraining the pooling. Different factorial designs were employed to optimize the sample preparation phase. The validation method presented a recovery of around 77.3% and 110.8%, with RSD lower than 13% and the detection limits were between 0.24 and 2.88 μgkg^?1, revealing good sensitiveness and accuracy. The method was satisfactorily applied to the analysis of tissues from different species of fish and OCPs residues were detected. The proposed method was shown effective to determine OCPs low concentrations in fish tissues, using small sample mass (0.5 g), making the sample analyses viable without the need for grouping (pool).     

Application of indoxacarb for managing shoot and fruit borer of eggplant (Solanum melongena L.) and its decontamination

Indoxacarb was applied at 75 and 150 g a.i. ha^{? 1} for two years to an eggplant (Solanum melongena L.) crop grown in the field plots in order to evaluate its efficacy for management of the lepidopteron pest, shoot and fruit borer. The residues of the insecticide were quantified by high-pressure liquid chromatography (HPLC). The mean initial deposits of indoxacarb on eggplant fruits were found to be 2.60–2.634 mg kg^{? 1} and 3.64–3.68 mg kg^{? 1} from the two rates of applications, respectively. They declined with time and reached to non-detectable (< 0.02 mg kg^{? 1}) after 15–20 d. Residues dissipated with a half-life of 3.0–3.8 d from both first and second-year application. A 3 d waiting period for harvest of fruits after insecticide application and processing resulted in the residue levels that were below the Codex maximum residue limit (MRL) of 0.5 mg kg^{? 1} thereby achieving a maximum safety and minimum risk to consumers. The best combination of chemicals for decontamination of indoxacarb was found to be by washing with a mixture of alkali and potassium permanganate (KMnO₄) thereby resulting in the removal of 67.5% and 59.2 % residues for 5 and 10 μ g g^{? 1} spiking doses, respectively. Major products formed on reaction of indoxacarb with alkali were identified by electron spray ionization chromatography/mass spectrometry (ESI/MS). The per cent reduction on the weight and number basis of treated eggplant plots were compared to those observed in control plots to demonstrate the effectiveness of indoxacarb treatment on shoot and fruit borer population.     

Validation of a QuEChERS-based gas chromatographic method for analysis of pesticide residues in Cassia angustifolia (senna)

A simple multi-residue method based on modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was established for the determination of 17 organochlorine (OC), 15 organophosphorous (OP) and 7 synthetic pyrethroid (SP) pesticides in an economically important medicinal plant of India, Senna (Cassia angustifolia), by gas chromatography coupled to electron capture and flame thermionic detectors (GC/ECD/FTD) and confirmation of residues was done on gas chromatograph coupled with mass spectrometry (GC-MS). The developed method was validated by testing the following parameters: linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect, accuracy–precision and measurement uncertainty; the validation study clearly demonstrated the suitability of the method for its intended application. All pesticides showed good linearity in the range 0.01–1.0 μg mL^?1 for OCs and OPs and 0.05–2.5 μg mL^?1 for SPs with correlation coefficients higher than 0.98. The method gave good recoveries for most of the pesticides (70–120%) with intra-day and inter-day precision < 20% in most of the cases. The limits of detection varied from 0.003 to 0.03 mg kg^?1, and the LOQs were determined as 0.01-0.049 mg kg^?1. The expanded uncertainties were <30%, which was distinctively less than a maximum default value of ±50%. The proposed method was successfully applied to determine pesticide residues in 12 commercial market samples obtained from different locations in India.     

Effect of processing on the disappearance of pesticide residues in fresh-cut lettuce: Bioavailability and dietary risk

The aim of this research is to establish the processing factors of six pesticides durong the preparation of fresh-cut lettuce and to assess the risk of ingestion of pesticide residues associated with the consumption of the same. A field study was carried out on the dissipation of three insecticides (imidacloprid, tebufenozide, cypermethrin) and three fungicides (metalaxyl, tebuconazole, azoxystrobin) during treatment conditions simulating those used for commercial fresh-cut lettuce. A simultaneous residue analysis method is validated using QuEChERS extraction with acetonitrile and CG-MS and LC-MS/MS analysis. The residues detected after field application never exceed the established Maximum Residue Limits. The processing factors were generally less than 1 (between 0.34 for tebufenozide and 0.53 for imidacloprid), indicating that the process, as a whole, considerably reduces residue levels in processed lettuce compared to fresh lettuce. It is confirmed that cutting, followed by washing and drying, considerably reduces the residues. A matrix effect in the dialyzation of the pesticides is observed and the in vitro study of bioavailability establishes a low percentage of stomach absorption capacity (<15%). The EDI/ADI ratios found in all cases were well below their ADI values, and the dietary exposure assessed (EDI) in fresh-cut lettuce showed no concerns for consumer health.     

A simple spectroscopic method to determine dimethoate in water samples by complex formation

Abstract

A simple and rapid method for the determination of dimethoate in water was developed based on the monitoring of the complex formation between bis 5-phenyldipyrrinate of nickel (II) and the herbicide dimethoate. The method showed a short response time (10?s), high selectivity (very low interference from other sulfate and salts), high sensitivity (limit of detection (LOD) 0.45?µM, limit of quantitation (LOQ) of 1.39?µM), and a K_d of 2.4?µM. Stoichiometry experiments showed that complex formation occurred with a 1:1 relation. The method was applied to different environmental water samples such as lagoon, stream, urban, and groundwater samples. The results indicated that independently from the water source, the method exhibited high precision (0.25–2.47% variation coefficient) and accuracy (84.42–115.68% recovery). In addition, the method was also tested using an effluent from a wastewater treatment plant from Mexico; however, the results indicated that the presence of organic matter had a pronounced effect on the detection.     

Determination of three cresol isomers in sewage sludge by solid-liquid extraction with low temperature purification and gas chromatography-mass spectrometry

Abstract

Cresols are chemical contaminants derivative from phenol which can be found in sewage sludge. However, little attention has been given to monitoring these compounds in environmental matrices in the literature. Thus, the objective of this study was to develop a simple method based on solid-liquid extraction with low temperature purification for determining three cresol isomers in sludge. The quantification of these compounds was performed by gas chromatography coupled to mass spectrometry with a previous derivatization step. After a detailed study, the cresol recovery was higher than 91%, with relative standard deviation lower than 12% and a limit of quantification of 20?μg kg^?1. Linearity was achieved between 10 and 90?μg L^?1 (R² > 0.98) with the standard solutions prepared in matrix extracts due to the trouble caused by the matrix effect. The proposed method was applied with success for monitoring cresols in sewage sludge samples coming from six different wastewater treatment plants. All samples showed contamination by cresols, mainly p-cresol with values between 32.3 and 516.9?μg kg^?1. The majority of the analyzed samples showed a total sum of the isomers higher than the maximum residue limit established by Brazilian legislation (160?μg kg^?1).     

Bioefficacy, dissipation kinetics and safety evaluation of selected insecticides in Allium cepa L

This paper reports the bioefficacy of selected insecticides against thrips and their pre-harvest intervals (PHI) in onion pertaining to their recommended application rates and maximum residue limits. Profenophos, methomyl and imidacloprid showed comparatively higher bioefficacy against thrips. GC-MS and LC-MS/MS-based residue analysis methods in onion bulbs and composite matrix of bulbs+leaves were thoroughly validated. The residue data for bulb+leaves was assessed with reference to the EU-MRLs applicable for spring onion. Dimethoate was the most stable chemical with PHI of 52.5 days, followed by monocrotophos (24 days) and carbofuran (20.5 days). The PHIs of profenophos, chlorpyrifos, methomyl and cypermethrin were similar and within the range of 10-13 days. Imidacloprid and λ-cyhalothrin had similar PHI of 4.5 days. Spinosad was the fastest-degrading chemical with PHI of 2 days. The combined bioefficacy and residue dynamics information will support label-claim of these insecticides for the management of thrips in onion, help in scheduling their applications in pest management program as per relative PHIs and minimize the residue accumulations at harvest. The dietary exposure was less than the maximum permissible intake for most of the insecticides on all sampling days except for dimethoate and monocrotophos.     

Bioefficacy,dissipation kinetics and safety evaluation of selected insecticides in Allium cepa L

This paper reports the bioefficacy of selected insecticides against thrips and their pre-harvest intervals (PHI) in onion pertaining to their recommended application rates and maximum residue limits. Profenophos, methomyl and imidacloprid showed comparatively higher bioefficacy against thrips. GC-MS and LC-MS/MS-based residue analysis methods in onion bulbs and composite matrix of bulbs+leaves were thoroughly validated. The residue data for bulb+leaves was assessed with reference to the EU-MRLs applicable for spring onion. Dimethoate was the most stable chemical with PHI of 52.5 days, followed by monocrotophos (24 days) and carbofuran (20.5 days). The PHIs of profenophos, chlorpyrifos, methomyl and cypermethrin were similar and within the range of 10–13 days. Imidacloprid and λ-cyhalothrin had similar PHI of 4.5 days. Spinosad was the fastest-degrading chemical with PHI of 2 days. The combined bioefficacy and residue dynamics information will support label-claim of these insecticides for the management of thrips in onion, help in scheduling their applications in pest management program as per relative PHIs and minimize the residue accumulations at harvest. The dietary exposure was less than the maximum permissible intake for most of the insecticides on all sampling days except for dimethoate and monocrotophos.     

Biodegradation of chlorpyrifos by either single or combined cultures of some soilborne plant pathogenic fungi

Abstract

Biodegradation of chlorpyrifos was studied in liquid culture media amended with either single or combined eight different plant pathogenic fungi isolated from the continuous cropping wheat fields. The average recovery of chlorpyrifos from the liquid media was found to be 86.1%. The detection limit of chlorpyrifos by the analytical method used was 19 ppb. Data showed that the growth of mixed fungi at concentrations up to 200 ppm of chlorpyrifos was higher than in the control treatment. Chlorpyrifos concentrations declined in the medium of combined fungi more than it did in the medium of any single fungus with increase in the incubation period. The amount of chlorpyrifos recovered was 79.8 ppm (39.9%) in the combined fungal cultures after 21 days. However, those recovered from the media of Fusarium graminearum, F. oxysporum, Rhizoctonia solani, Cladosporhim cladosporiodes, Cephalosporium sp., Trichoderma viridi, Alternaria alternata, and Cladorrhinum brunnescens, ranged from 48.0 to 74.8%. The half‐life value (T_1/2) for chlorpynfos was 15.8 day in the medium amended with mixed fungi. However, for the single cultures it ranged from 19.3 to 33.0 day.     

Adaptation and validation of QuEChERS method for the analysis of trifluralin in wind-eroded soil

This study was carried out to develop and validate a reliable analytical procedure for trifluralin analysis in wind-eroded sediments. Soil sediments trapped in BEST sediment traps were subjected to QuEChERS extraction method, incorporating a simple simultaneous cleanup step, followed by trifluralin analysis with GC-ECD. Results revealed that QuEChERS method offered a potential alternative technique for pesticide extraction from soil samples. The validity of analytical method was performed by the method-performance criteria such as, recovery, LOD, LOQ repeatability, precision, and all found to be within the required limits. It was also observed in this study that herbicide concentrations in the wind-eroded sediment did not vary with the time and trap height. Trifluralin concentrations of surface soil after four erosion events were higher (626.05 μg/kg) than wind-eroded soil (450.08 μg/kg).     

Biodegradation of imidacloprid in liquid media by an isolated wastewater fungus Aspergillus terreus YESM3

In the present study, a new fungal strain capable of imidacloprid degradation was isolated from agricultural wastewater drain. The fungal strain of YESM3 was identified as Aspergillus terreus based on ITS1-5.8S rDNA-ITS2 gene sequence by PCR amplification of a 500 bp sequence. Screening of A. terreus YESM3 to the insecticide imidacloprid tolerance was achieved by growing fungus in Czapek Dox agar for 6 days at 28°C. High values (1.13 and 0.94 cm cm^?1) of tolerance index (TI) were recorded at 25 and 50 mg L^?1 of imidacloprid, respectively in the presence and absence of sucrose. However, at 400 mg L^?1 the fungus did not grow. Effects of the imidacloprid concentration, pH, and inoculum size on the biodegradation percentage were tested using Box–Behnken statistical design and the biodegradation was monitored by HPLC analysis at different time intervals. Box–Behnken results indicated that optimal conditions for biodegradation were at pH 4 and two fungal discs (10 mm diameter) in the presence of 61.2 mg L^?1 of imidacloprid. A. terreus YESM3 strain was capable of degrading 85% of imidacloprid 25 mg L^?1 in Czapek Dox broth medium at pH 4 and 28°C for 6 days under static conditions. In addition, after 20 days of inoculation, biodegradation recorded 96.23% of 25 mg L^?1 imidacloprid. Degradation kinetics showed that the imidacloprid followed the first order kinetics with half-life (t₅₀) of 1.532 day. Intermediate product identified as 6-chloronicotinic acid (6CNA) as one of the major metabolites during degradation of imidacloprid by using HPLC. Thus, A. terreus YESM3 showed a potential to reduce pollution by pesticides and toxicity in the effected environment. However, further studies should be conducted to understand the biodegradation mechanism of this pesticide in liquid media.