Bifenthrin Residues in Table Grapevine: Method Optimization, Dissipation and Removal of Residues in Grapes and Grape Leaves.

The QuEChERS method was adjusted to determine bifenthrin residues in grapes and grape leaves. Extraction and cleanup procedures were optimized to decrease co-extracted materials and enhance the detection of bifenthrin. The method was validated per the European Union (EU) Guidelines criteria. Accuracy ranged from 98.8% to 93.5% for grapes and grape leaves, respectively. Precision values were 5.5 and 6.4 (RSDr) and 7.4 and 6.7 (RSDR) for grapes and grape leaves, respectively. LOQs (the lowest spiking level) were 2 and 20 µg/kg for grapes and grape leaves, respectively. Linearity as determination coefficient (R2) values were 0.9997 and 0.9964 for grapes and grape leaves, respectively, in a matrix over 1-100 µg/L range of analyte concentration. This was very close to the value in the pure solvent (0.9999), showing the efficiency of the cleanup in removing the co-extracted and co-injected materials; the matrix effect was close to zero in both sample matrices. Dissipation of bifenthrin was studied in a supervised trial conducted in a grapevine field during the summer of 2023 at the recommended dose and double the dose. Dissipation factor k values were 0.1549 and 0.1672 (recommended dose) and 0.235 and 0.208 (double dose) for grapes and grape leaves, respectively. Pre-harvest interval (PHI) was calculated for the Maximum Residue Limit (MRL) values of the EU database. Residues of bifenthrin were removed effectively from grapes using simple washing with tap water in a laboratory study. Residues reached the MRL level of 0.3 mg/kg in both washing treatments, running or soaking in tap water treatments for 5 min. Removal from leaves did not decrease residue levels to the MRL in grape leaves.

Development of Green and Facile Sample Preparation Method for Determination of Seven Neonicotinoids in Fresh Vegetables, and Dissipation and Risk Assessment of Imidacloprid and Dinotefuran.

A facile procedure for extracting and determining seven neonicotinoids was developed. Water was the only extraction solvent without phase separation and cleanup steps. The method was validated according to European Union standards, and the values obtained were compared with the criteria. The accuracy values were between 99.8% (thiamethoxam) and 106.8% (clothianidin) at the spiking levels of 0.01, 0.1, and 1 mg/kg in the tested matrices. The precision as pooled RSD values was ≤6.1% (intra-day) and ≤6.9% (inter-day). The limit of quantification was set and tested at 0.01 mg/kg. The matrix effect was evaluated, and all matrices had a suppressive effect. The matrix of the cucumber was the most effective, with -20.9% for dinotefuran and an average of -9.8% for all compounds, while the tomato matrix had the slightest effect. Real marketed samples were analyzed using the developed and QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) methods; the results were not significantly different. A supervised field trial was conducted in the open field to study the dissipation patterns of imidacloprid and dinotefuran in tomatoes. The dissipation of both compounds followed first-order kinetics. The half-life (T½) values were 3.4 and 2.5 days, with dissipation rates k of 0.2013 and 0.2781 days, respectively. Following the EU-MRL database, the calculated pre-harvest interval (PHI) values were 7 and 14 days for imidacloprid and dinotefuran, respectively, and 3 days for both compounds following Codex Alimentarius regulations. The risk of imidacloprid and dinotefuran residues was estimated from chronic and acute perspectives. The risk factors of dinotefuran were lower than those of imidacloprid. Nonetheless, the highest expected residues of both compounds were below the tolerance limits.

Polychlorinated biphenyl congeners in water canals and their relationships with water quality parameters: Insights into their risk assessment.

Water pollution with pesticides is one of the most important environmental problems. Polychlorinated biphenyls (PCBs) reach water bodies via agricultural discharge. The aim of this study was to determine the contamination of different water bodies with PCB congeners, and detect the correlation between water quality parameters and seasonal distribution of these PCBs. The results indicated that water canals of AlGharbiah showed the highest ranges of temperature, total dissolved solids (TDS) in spring, and dissolved oxygen (DO) in autumn, while AlQaliobiah water bodies witnessed the highest pH and electrical conductivity (EC) ranges in summer. The highest range of a PCB congener was that of PCB44 (7.96-118.29 µg/g) in sediment samples of Giza, followed by its range (18.01-85.44 µgL-1) in surface water of AlQaliobiah. We found a potential cancer risk from dermal contact with all the investigated PCBs. Principal component analysis (PCA) showed positive correlations between most PCBs and each of EC and TDS, and a negative correlation with DO. While the correlation between PCBs and each of temperature and pH varied according to the geographic location of the governorate. In conclusion, the investigated water canals were contaminated with PCBs, which posed a potential cancer risk and deteriorated water quality.

Residues of pyrethroids and triazoles pesticides in water and sediment of certain Egyptian watercourses: assessing their influence on fungal diversity.

Contamination of water and sediment with pyrethroids and triazoles residues can affect fungal diversity, and hence the aquatic system functioning. The aim of the present study is to investigate the effect of water and sediment contamination with pyrethroids and triazoles on fungal diversity. Water and sediment samples were seasonally collected along 2019 from water bodies representing Gharbeya and Qualubeya governorates. Concentrations of pyrethroids and triazoles were determined, and fungal species in water and sediment samples were molecularly identified. The results indicated that temperature and pH varied according to the season. Permethrin, deltamethrin, lambda-cyhalothrin and esfenvalerate showed the highest pyrethroids concentrations, whereas tetraconazole, tebuconazole and difenconazole were of the highest triazoles concentrations. Aspergillus niger was one of the most frequent species, in addition to Trichoderma capillare, Fusarium oxysporum, Penicillium commune and Penicillium polonicum. Principal component analysis indicated a positive correlation between temperature and different Aspergillus spp., and between pH and each of pyrethroids and triazoles. Moreover, a negative correlation was observed between triazoles and Trichoderma asperellum, Penicillium griseofulvum and Aspergillus fumigatus. In conclusion, contamination of water with pesticides affected fungal diversity. This disturbance in fungal assemblages might result in a reduction of some key organisms, or an increase and emergence of new pathogens.

Terminal Residues and Risk Assessment of Spiromesifen and Spirodiclofen in Tomato Fruits.

Insecticides are important to increase crop yields, but their overuse has damaged the environment and endangered human health. In this study, residues of spiromesifen and spirodiclofen were determined in tomato fruit using a simple and efficient analytical procedure based on acetonitrile extraction, extract dilution, and UPLC-MS/MS. The linearity range was 1-100 µg/kg and 0.5-100 µg/kg, and the correlation coefficient (R2) and residuals were ≥0.9991 and ≤16.4%, respectively. The limit of determination (LOD) was 0.26 and 0.08 µg/kg, while the limit of quantification (LOQ) was verified at 5 µg/kg. The relative standard deviation of spiked replicates at 5 µg/kg analyzed in one day (RSDr, n = 6) was ≤8.35%, and within three different days (RSDR, n = 18) it was ≤15.85%, with recoveries exceeding 91.34%. The method recovery test showed a satisfactory value of 89.23-97.22% with an RSD of less than 12.88%. The matrix effect was determined after a 4-fold dilution of the raw extract and was -9.8% and -7.2%, respectively. The validated method was used to study the dissipation behavior of the tested analytes in tomato fruit under field conditions. First-order kinetics best described the dissipation rates. The calculated half-lives were 1.49-1.83 and 1.91-2.38 days for spiromesifen and spirodiclofen, respectively, after application of the authorized and doubled authorized doses, indicating that spiromesifen dissipated more rapidly than spirodiclofen. The final residue concentrations of spiromesifen and spirodiclofen were 0.307-0.751 mg/kg and 0.101-0.398 mg/kg, respectively, after two or three applications, and were below the European Union (EU) maximum residue limits. The chronic risk assessment indicates that both insecticides are safe for adult consumers.