Little information is available on the adverse effects of expired pesticides on the environment, so it is essential to characterize the risk of these chemicals to non-target organisms. Therefore, this work aims to estimate and compare the acute toxicity (LD50) of unexpired and expired formulations of malathion, chlorpyrifos, and lambda-cyhalothrin in rats and to determine their residues in the liver and kidneys of treated rats. This is the first study to investigate the toxic effects of expired pesticides on rats. The acute toxicity of expired lambda-cyhalothrin was higher than that of non-expired rats, while the opposite was observed in rats treated with malathion and chlorpyrifos. All formulations tested caused clinical signs of toxicity in the treated rats. The data showed that some expired formulations significantly affected body weight and estimated vital signs compared to non-expired pesticides. The data showed that the highest residues were found in the liver and kidneys of rats treated with both malathion formulations, followed by chlorpyrifos; however, the lowest residues were found in rats treated with lambda-cyhalothrin, which can be referred to as LD50 values of the insecticides tested. The residues detected after the 10th dose gradually decreased at the end of the recovery period, and their losses ranged from 80.0 to 95.4% in the liver and from 92.3 to 99.99% (undetectable). The results show that the toxic effects of expired and non-expired formulations are different. This underlines the need to dispose of expired compounds carefully to prevent their discharge into the ecosystem.

Spinetoram is one of the most extensively used insecticides globally and is a new spinosyn-based insecticide registered for direct treatment of Egyptian grapes. This work established and validated a developed method for determining spinetoram in grape berries and leaves using the QuEChERS coupled LC-MS/MS technique. The average recoveries ranged between 98.52-101.19% and 100.53-104.93%, with RSDs of 2.74-6.21% and 2.79-7.26% for grape berries and leaves, respectively. Spinetoram residues degraded in grape berries and leaves through a first-order kinetic, with an estimated half-life (t1/2) of 4.3 and 2.8 days in grape berries and leaves, respectively, and significant degradation (91.4-97.5%, respectively) after 14 days. Besides, the terminal residues of spinetoram detected in grape berries and leaves samples ranged between 0.017-0.077 mg‧kg-1 and 0.79-0.023 mg·kg-1, respectively, when applied two to three times at a single recommended rate, while it was varied between 0.026-0.44mg‧kg-1 and 0.79-0.023mg‧kg-1 when applied two to three times at a double recommended rate, respectively. A dietary risk assessment was conducted using scientific data from field trials, acceptable daily intake (ADI), and food consumption. It was determined that no noteworthy health hazards were connected to eating grape berries and leaves that had been treated with spinetoram since the risk quotients (RQs) were ≤ 0.4.

Drug residues that contaminate food and water represent a serious concern for human health. The major concerns regard the possible irrational use of these contaminants, since this might increase the amplitude of exposure. Multiple sources contribute to the overall exposure to contaminants, including agriculture, domestic use, personal, public and veterinary healthcare, increasing the possible origin of contamination. In this review, we focus on crop pesticides and veterinary drug residues because of their extensive use in modern agriculture and farming, which ensures food production and security for the ever-growing population around the world. We discuss crop pesticides and veterinary drug residues with respect to their worldwide distribution and impacts, with special attention on their harmful effects on human reproduction and embryo development, as well as their link to epigenetic alterations, leading to intergenerational and transgenerational diseases. Among the contaminants, the most commonly implicated in causing such disorders are organophosphates, glyphosate and antibiotics, with tetracyclines being the most frequently reported. This review highlights the importance of finding new management strategies for pesticides and veterinary drugs. Moreover, due to the still limited knowledge on inter- and transgenerational effects of these contaminants, we underlie the need to strengthen research in this field, so as to better clarify the specific effects of each contaminant and their long-term impact.

BACKGROUND: Although pesticides play an integral role in food security and preventing public health from vector-borne diseases, inappropriate handling and continual use of restricted organochlorine pesticides pose short- and long-term adverse effects and become public health concerns in the African region. This study aimed to determine the combined level of protective equipment use, management of empty pesticide containers, and leftover pesticide residues in the African region.
METHODS: The preferred reporting items for systematic reviews and the meta-analysis protocol were used to carry out this study. The Scopus, PubMed, Web of Science, Google Scholar, DOAJ, and National Repository databases were searched for articles published between November 12, 2023, and January 2, 2024. The meta-analysis data were visualized using a forest plot. A random-effects model was applied when heterogeneity existed in pooled studies. Subgroup analysis of the data was performed based on the location where the study was conducted and the publication year. Meta-regression and sensitivity analysis were performed to evaluate the robustness of the pooled prevalence of studies. Publication bias was assessed using a funnel plot. The authors used the Joanna Briggs Institute Critical Assessment tool to determine the quality of the studies.
RESULTS: In this review, 2174 articles were identified from the included electronic databases, 24 of which were included in the present study. The study revealed that the combined mean prevalence of wearing a mask, glove, boot/safety shoes, overall wear, and head cover accounted for 18% (95% CI: 11.9 to 26.1%, p < 0.001), 18% (95% CI: 11.7 to 26.9%, p < 0.001), 23% (95% CI: 15.7 to 33.3%, p < 0.001), 26% (95% CI: 16.2 to 38.7%, p < 0.001), and 14% (95% CI: 8.90 to 22.0%, p < 0.001), respectively. The prevalence of pesticides stored in the living room and pesticide containers used for different purposes was 51% and 26%, respectively.
CONCLUSIONS: Poor pesticide safety practices were identified. A substantial proportion of the respondents reported storing pesticide residues in their living rooms, and the reuse of pesticide empty containers. Regional institutions should lead the designing of safety strategies to reduce the public health risks of pesticide exposure.

Among bee species, the western honey bee (Apis mellifera) is preferred in monitoring studies performed in the agricultural landscape, while bee matrices, pollen, and honey are mostly a subject of these studies due to their unique composition. A justified question about the relevance of other bee matrices, like larvae, foragers, beebread, and/or wax, has been raised. The ability of different bee matrices (wax, pollen grains, bee bread, foragers, larvae, nectar, and honey) to absorb pesticide residues is subjected in this study. All samples were collected during a crop flowering season (oilseed rape) on intensively managed agricultural land in Slovakia and Germany. The observed high variability in residue levels, profile, and number of detections among studied matrices from Germany, west, and east Slovakia gave us an assumption of the use of different agricultural practices between these two countries. Fungicides clearly dominated across all samples in all sampling regions. The increased pesticide profile positively correlated with the oilseed rape pollen grains in pollen pellets and/or bee bread. Bee wax, pollen, and bee bread showed a high number of detected active substances and total residue concentrations among matrices, indicating their high ability to absorb pesticide residues in the surrounding hive environment.

Food safety is an important issue to protect humane health and improve the life quality. Hence, analysis of the possible contaminants in food samples is essential. A rapid and efficient vortexed-assisted dispersive µ-solid-phase extraction coupled with gas chromatography-mass spectrometry was proposed for simultaneous separation/preconcentration and determination of five commonly used organophosphorus pesticides. Reduced graphene oxide decorated NiCo2(OH)6 nanoflowers as a novel nanostructure was synthetized and introduced for separation of the target pesticides from the wheat flour, rice flour, and baby food cereal samples. The characterization of the nanoflowers was accomplished by SEM-EDX, XRD, and FT-IR techniques. The main factors including pH, the amount of nanoflower, the volume of sample solution, salt concentration (ionic strength), desorption conditions (i.e. desorption solvent type and volume, and desorption time) on the pesticides extraction efficiencies were inquired using matrixed match method. Applying the optimum conditions, the linearity of 0.100-500.000 µg kg-1, LODs and LOQs in the range of 0.03-0.04 µg kg-1 and 0.1 µg kg-1 for the studied food samples were obtained. The repeatability (intra-day precision (n = 5)) of ≤ 2.0 % and reproducibility (inter-day precision, days = 5, n = 3) of ≤3.1 % and were appraise at three concentration levels (10, 50 and 100 μg kg-1 of each analyte). High relative recoveries of 90.0-99.3 % ascertained high potential of the presented method for complex matrix analysis.

Herein, the determination of chlordimeform and its metabolite 4-chloro-2-methylaniline residue in milk was performed for the first time using gas chromatography-tandem mass spectrometry (GC-MS/MS). Samples were extracted using acetonitrile, and cleaned using a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. Separation was performed using the DB-17 MS column. It was detected in a selected reaction monitoring (SRM) mode and quantified using a matrix-matched isotope internal standard method. Under optimal conditions, a good linear relationship was observed in the concentration range of 10-200 µg/kg. The limit of quantitation was 10.0 µg/kg. The spiked recoveries for the target substance ranged from 84.5 % to 107.3 %, with relative standard deviations (RSD) of <7.2 %. The spiked samples were further confirmed by gas chromatography-quadrupole-Orbitrap high-resolution mass spectrometry (GC-Orbitrap HRMS). The combined method resulted in high accuracy and sensitivity and was suitable for the determination of chlordimeform and its metabolite 4-chloro-2-methylaniline residue in milk.

Studies on nitenpyram determination and behavior within tea remain limited despite its widespread use as a neonicotinoid. An organic-saving analytical approach tailored for the detection of nitenpyram in tea was established. Nitenpyram was extracted by boiling water and cleaned up by Cleanert PCX solid-phase. The average recoveries were 75.1-94.5 %, with relative standard deviations (RSDs) of 0.7-8.6 % for saving 34.5-88.6 % organic solvent. The limits of quantification (LOQs) were 0.002 mg·kg-1 in fresh tea shoots, 0.005 mg·kg-1 in made tea, and 0.001 mg·L-1 in tea brew, satisfying the current minimum Maximum Residue Limit (MRL). Nitenpyram dissipated rapidly with half-lives of 1.2-1.4 days at the recommended dosage (27 g a.i. ha-1) in two locations. Remarkably, 20-110 % of nitenpyram was leached out from made tea in different brewing modes. This work provides insights into nitenpyram\'s rational application in tea cultivation and offers considerations to institutions tasked with unestablished MRLs in tea.

A modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) -LC-MS/MS method was developed for the determination of hexachlorophene in fruits and vegetables. Samples were extracted by acetonitrile and then salted with an acetate buffer system. Extractants neutral alumina (Al-N), strong cation exchange silica gel bonded adsorbent (SCX) and graphitized carbon black (GCB) were used for sample purification. The method demonstrates excellent accuracy and reproducibility. Under optimized conditions, the correlation coefficients of hexachlorophene were higher than 0.995 in the range of 0.5-20 ng/mL. The limit of quantification (LOQ) was 2.0 μg/kg. The average recoveries, assessed at three spiked levels (2.0, 4.0, and 20.0μg/kg) across various matrices including cabbage, celery, tomato, eggplant, potato, radish, cowpea, chives, apple, peach, grape, citrus, bitter melon, banana and hami melon ranged from 72.0 to 100.5% with relative standard deviations from 3.2 to 9.8% (n = 6).

In this paper, we present analytical methodologies for the determination of the thiazolidine fungicide flutianil (trade name GATTEN) and its primary metabolite OC56635 in hemp cannabis matrices. A total of nine crop matrices were tested: whole seed, fiber, flower buds, hemp hearts, hemp seed oil, hemp meal, hemp flour, ethanol extracted CBD resin (CBD-E), and supercritical CO2 extracted CBD resin (CBD-C). Processing of the CBD-E and CBD-C crop fractions was carried out in-house using methods detailed herein. Field sample analysis utilized sequential extractions, stacked solid phase extraction (SPE) column cleanups, and evaporation to prepare the samples for LC-MS/MS quantitation. Method validations for each fraction were carried out using untreated hemp matrices over a minimum of three levels, with lowest levels of method validation (LLMV) of 0.010 μg/g for all fractions except the CBD resins, for which LLMV was 0.020 μg/g. Flutianil-treated samples from nine field sites were collected from several crop production regions and analyzed to determine the distribution of incurred flutianil and OC56635 residues within the different hemp matrices. This data was generated in support of nationwide registration with the United States Environmental Protection Agency (USEPA).