Search Results (214)

The widespread use of pesticides in modern agriculture contributes to a range of environmental and food-safety concerns, including the persistence of chemical residues in food products, contamination of soil and water, and potential risks to human and ecosystem health. Among food and feed commodities, cereal-based products represent an important potential source of dietary exposure due to their extensive consumption and the possibility of residue transfer from wheat grains to processed flours. In this study, a direct acetone extraction combined with gas chromatography–ion-trap mass spectrometry (GC–MS) was explored as a simplified analytical approach for the determination of selected pesticide residues in wheat flour. Nine pesticides were initially screened, and six compounds (ethoprophos, dimethoate, terbufos, diazinon, chlorpyrifos, and methoxychlor) were retained for method development based on their extractability and chromatographic behavior. Chromatographic and ionization conditions were optimized in Full Scan, SIM, and MS/MS modes, and matrix-matched calibration was applied to compensate for matrix-induced signal variations. The method was evaluated in a composite wheat-flour matrix, demonstrating acceptable process efficiency, a characterized matrix effect, and satisfactory quantitative performance for four analytes over the experimentally evaluated range of 5–50 µg/kg. Two commercial flour samples contained estimated diazinon concentrations of 0.4 and 1.0 µg/kg, respectively, which were further assessed using the standard addition method. Overall, this study provides a proof of concept for the use of direct acetone extraction coupled with ion-trap GC–MS for the exploratory monitoring of selected pesticide residues in wheat flour. Full method validation in accordance with SANTE/11312/2021 v2026 was outside the scope of this work. Full article

The use of insect larvae for plastic waste biodegradation has attracted increasing attention as a potential strategy to mitigate environmental plastic pollution. However, the toxicological consequences of ingesting plastics recovered from the environment, particularly those acting as vectors for sorbed contaminants, remain poorly understood. In this study, we investigated the endocrine and neurotoxic effects of field-recovered (environmental) polystyrene (ePS) in the plastivorous insect Zophobas morio. Larvae were fed virgin PS (vPS) or PS collected from a marine coastal area known to be impacted by anthropogenic activities. Chemical analyses revealed that ePS was characterized by a mixture of organochlorine and organophosphorus pesticides, with a total complex residue concentration of 23.7 ± 5.5 µg g⁻¹, whereas only trace levels of hexachlorocyclopentadiene (HCCPD) were detected in vPS (2.55 ± 0.65 µg g⁻¹). All compounds detected in ePS were also detected in larvae from the ePS-fed group, indicating effective trophic transfer from plastic to the organism. Despite the absence of mortality, PS-fed larvae exhibited reduced growth compared to controls. At the molecular level, ingestion of ePS caused a significant downregulation of key genes involved in the ecdysteroid signaling pathway (ecdysone receptor, EcR; ultraspiracle, USP; and early response genes E74 and E75), coupled with an upregulation of juvenile hormone-responsive genes (methoprene-tolerant, Met; Krüppel homolog 1, Kr-h1), suggesting endocrine imbalance potentially affecting developmental progression. In parallel, acetylcholinesterase (AChE) enzymatic activity was significantly inhibited, particularly in larvae fed ePS, despite no changes in AChE or acetylcholine receptor transcript levels, indicating functional neurotoxicity. This study highlights the importance of considering plastic-associated contaminant toxicity when evaluating insect-based plastic biodegradation strategies. Full article

Organophosphorus pesticides (OPPs) are widely used and have recently been linked to metabolic syndrome (MS). This study aimed to investigate the probable association between chronic OPP exposure and MS among farm workers in Sharkia Governorate, Egypt, and to assess the potential role of peroxisome proliferator-activated receptor gamma (PPARγ). This comparative cross-sectional study included 140 participants, equally divided into OPP-exposed farm workers and non-exposed subjects. OPP exposure was confirmed by detecting plasma residues and cholinesterase activity. MS was diagnosed by assessing body mass index (BMI), waist circumference (WC), blood pressure, plasma glucose, serum insulin, and lipid parameters. Oxidative and inflammatory markers, including malondialdehyde (MDA), gamma-glutamyl transferase (GGT), ferritin, superoxide dismutase (SOD), tumor necrosis factor-alpha (TNF-α), and high-sensitivity C-reactive protein (hs-CRP), were measured. The mRNA expression of the PPARγ and paraoxonase 1 (PON1) genes was also investigated. In total, 60% of farm workers demonstrated MS, compared with 10% of non-exposed participants. Workers exhibited elevated oxidative and inflammatory indices and reduced PPARγ and PON1 expression. PPARγ positively correlated with high-density lipoprotein (HDL), SOD, and PON1, while negatively correlating with glucose, insulin resistance (IR), low-density lipoprotein (LDL), triglycerides (TGs), MDA, GGT, ferritin, TNF-α, and hs-CRP. The study concluded that chronic OPP exposure was associated with increased oxidative stress and inflammation, reduced PPARγ and PON1 expression, disturbed glucose and lipid metabolism, and increased IR. The observed associations between PPARγ downregulation, metabolic disturbances, and oxidative and inflammatory markers suggest that PPARγ dysregulation may represent a potential mechanistic link between chronic OPP exposure and MS. However, this proposed mechanism requires further validation. Full article

Chlorpyrifos (CPF) is the most commonly used organophosphorus insecticide in agriculture globally. This has raised concerns due to its persistence, bioaccumulation, neurotoxicity, and environmental and human health effects. Until 2020, CPF was the most commonly used pesticide in European Union (EU) food production. CPF is also used in other parts of the world, though it has been discontinued in the EU, as national pesticide surveillance programs indicate it is found in soil, water, and food. This type of persistence is potentially harmful to farmers, consumers, and animals because CPF is toxic. Markedly, CPF has the potential to change the microbiota composition of soils, i.e., fungal, bacterial, and actinomycete communities, and inhibit the mineralization of nitrogen. The key CPF activity is associated with the inhibition of acetylcholinesterase (AChE), leading to reproductive, neurotoxic, and genotoxic effects. Microbial degradation, especially when applied by means of bacteria, has become one of the promising alternatives to the traditional physicochemical means since it is inexpensive, does not harm the environment and may possibly be fully detoxified. This review summarizes the latest developments in the study of CPF-degrading bacteria, enzyme pathways, microbial diversity, and the evaluation of the environmental impact of microbial remediation. Recent research findings, genomic research developments, and potential applications of CPF-degrading bacteria are addressed. In addition, this study reveals the current knowledge gaps, presents biotechnological challenges, and suggests future directions in the application of field-scale studies, focusing on the application of microbial solutions in sustainable agriculture. Full article

Organophosphorus pesticides (OPs) are persistent environmental contaminants requiring monitoring in aquatic ecosystems. In this study, four novel mineral–carbon composites (K-HNT, K-C-HNT, D-HNT, and D-C-HNT) were synthesized via thermal treatment at 800 °C from halloysite nanotubes, casein, dextrin, and pyrolyzed sawdust. Moreover, these materials were characterized (BET, FT-IR, Raman, SEM/EDS), revealing high specific surface areas (up to 218.3 m²/g for the D-C-HNT composite), and evaluated as solid-phase extraction (SPE) sorbents for the determination of six OPs from water. The eluates were analyzed using GC-MS/MS in MRM mode. This study examined the effect of eluent, sorbent mass, and multiple extractions on SPE efficiency. Ethyl acetate-n-hexane (1:1, v/v) was confirmed to be the most effective eluent, achieving high pesticide recoveries (>80%) at optimal sorbent masses of 50 and 75 mg. The method demonstrated satisfactory sensitivity, with limits of detection (LODs) ranging from 1.6 to 3.3 μgL⁻¹. Notably, the synthesized composites outperformed pure precursors and demonstrated extraction efficiency comparable to commercial sorbents (C-18, Florisil, active carbon). Furthermore, reusability tests confirmed that second and third extraction repetitions reduced the efficiency of the SPE process only slightly, indicating that these waste-derived composites can be reused multiple times without cartridge replacement. Full article

Soil pesticide-residue screening is important for ecological protection, food safety, and public health. However, conventional chromatographic and spectroscopic methods often require complex sample pretreatment, expensive instruments, trained operators, and long analysis times, which limits their use for rapid and large-scale screening. In this study, an electronic-nose system was developed for volatile-fingerprint classification of pesticide-treated loess soil. Six commercial pesticide formulations from three chemical categories were evaluated: deltamethrin and cyfluthrin as pyrethroids, glyphosate and chlorpyrifos as organophosphorus pesticides, and zineb and mancozeb as organosulfur pesticides. These compounds were selected to represent commonly used pesticides with different chemical structures and volatile profiles. A mirror-symmetric gas-sensing chamber was designed for a 26-sensor metal oxide semiconductor (MOS) array to improve gas-flow uniformity and response repeatability. A total of 960 pesticide-treated electronic-nose response curves were collected from four soil depths. Eight feature extraction methods and four classifiers were compared. The Synthetic Minority Over-sampling Technique (SMOTE) and Geometric SMOTE (G-SMOTE) were then evaluated using training-fold-only oversampling to reduce data-leakage risk in imbalanced classification. The results showed that k-nearest neighbors (KNN) combined with direct or transform-based features provided strong classification performance under controlled laboratory conditions. For minority-class recognition, SMOTE showed more consistent improvement than G-SMOTE in the tested pesticide–depth–feature combinations, although the effect depended on feature representation and pesticide class. These findings indicate that the proposed chamber/sensor-array/SMOTE framework is feasible for rapid volatile-fingerprint classification of pesticide-treated soil, but larger independent field datasets and quantitative chemical validation are still required before general deployment. Full article

In this work, we developed a novel, ultrasensitive fluorescence sensing platform for determination of organophosphorus pesticides (OPs), using chlorpyrifos as a representative model analyte. The sensing strategy was constructed upon the key inner filter effect (IFE) between graphitic carbon nitride (g-C₃N₄) nanosheets and silver-coated gold core–shell nanoparticles (Au@Ag NPs). Initially, gold nanoparticles (Au NPs), silver nanoparticles (Ag NPs), and Au@Ag NPs were successfully synthesized, and their fluorescence quenching efficiencies toward g-C₃N₄ were systematically evaluated. Owing to the superior spectral overlap with the fluorescence emission of g-C₃N₄, Au@Ag NPs exhibited the most obvious quenching effect and were thereby selected as the optimal quencher for sensor fabrication. Then, acetylcholinesterase (AChE) catalyzed the hydrolysis of acetylthiocholine (ATCH) into thiocholine. The generated thiocholine then induced aggregation of Au@Ag NPs via electrostatic and Ag-S interactions, which reduced the IFE efficiency and ultimately restored the fluorescence of g-C₃N₄. In contrast, the presence of chlorpyrifos effectively inhibits AChE activity, thereby suppressing ATCH hydrolysis and the subsequent aggregation of Au@Ag NPs. The fluorescence intensity of g-C₃N₄ was quenched by Au@Ag NPs and the signal was low. Under optimal experimental conditions, the response signal was found to be proportional to chlorpyrifos (CPF). This work presents a rapid, cost-effective, and highly sensitive approach for CPF residue analysis, holding great potential for applications in food safety monitoring and environmental surveillance. Full article

Both domestic and wild animals are frequently affected by accidental, intentional, or illegal poisoning globally, but data from some regions, including Italy, remain scarce. This study aimed to characterize animal poisoning events in a central Italian region over the period 2011–2020. A total of 2722 suspected cases were analyzed, of which 51.3% were confirmed positive for at least one poison. Among the 1397 confirmed cases, 863 animal carcasses and 534 poisoned baits were recorded, corresponding to 762 distinct poisoning events. The most frequently involved toxicants were metaldehyde, carbamates, and organophosphorus pesticides, followed by anticoagulant rodenticides and other compounds. Spatial analysis revealed distinct patterns in the use of toxicants. Sub-regional areas encompassing national and regional parks were primarily associated with agricultural pesticides, whereas urban areas were dominated by metaldehyde and anticoagulant rodenticides. These differences suggest that, in addition to their illegal nature, poisoning events may reflect underlying socio-environmental conflicts between humans and animals. The results highlight the value of an interdisciplinary approach to mitigate poisoning, involving coordinated efforts among scientific, veterinary, enforcement, and public stakeholders. Such strategies could reduce both the frequency and ecological impact of this illegal practice. Full article

Microplastics (MPs), a type of emerging persistent pollutant, are attracting increasing attention from both scholars and governments. Agricultural soil is considered an important sink for MPs due to the use of plastic mulches and the application of sewage sludge to fields. Widely used pesticides often coexist with MPs in soils, potentially causing co-contamination that threatens the ecosystem. The interaction between pesticides and soil organic matter (SOM) influences the behavior and toxicity of pesticides in the soil environment, and MPs may participate in this interaction. Preliminary theoretical studies using a combination of molecular mechanics (MM), molecular dynamics (MD), and quantum mechanics (QM) simulations revealed that model MPs and fragments of humic substances (HS) exhibited different adsorption affinities for chlorpyrifos (CPF), a model organophosphorus pesticide, in both vacuum and water. Polypropylene (PP) MPs showed significantly higher adsorption capacity than HS in vacuum, while HS outperformed polyethylene (PE) MPs in water significantly. Furthermore, PP consistently exhibited a significantly higher adsorption capacity than PE regardless of the medium. The adsorption between HS and CPF, as well as between MPs and CPF, was attributed to physical interaction. Furthermore, van der Waals interactions contributed to the mechanism underlying the interactions of MPs/HS with CPF. These findings theoretically demonstrate that MPs can serve as important vectors for the migration of pesticides through the soil system. This work offers a new perspective on the role of MPs in the environmental behavior and toxic effects of pesticides under field-relevant conditions. Full article

The development of low-cost and highly sensitive electrochemical sensing platforms for pesticide monitoring has attracted significant attention in recent years. In this study, coke-derived carbon (CDC) was successfully synthesized from petroleum coke through high-temperature carbonization under a nitrogen atmosphere. Subsequently, a CDC@CuO-NP nanocomposite was fabricated by depositing copper oxide nanoparticles onto the CDC matrix. The morphology, structure, and elemental composition of the synthesized materials were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and elemental mapping analyses, confirming the successful formation of the composite and the uniform distribution of CuO nanostructures on the carbon surface. Electrochemical characterization demonstrated that the incorporation of CuO significantly enhanced the electrochemical performance of CDC by increasing the electroactive surface area and facilitating electron transfer. The CDC@CuO-NP-modified glassy carbon electrode was applied for the electrochemical detection of dichlorvos (DDVP) using electrochemical impedance spectroscopy (EIS). The sensor exhibited a concentration-dependent increase in charge-transfer resistance and showed a linear response in the concentration range of 247–3770 nM, with the regression equation y = 47.1458C + 111.8162 and a correlation coefficient of R² = 0.9832. The developed sensor achieved a low limit of detection (LOD) of 2.3 nM, demonstrating high sensitivity toward DDVP. These results indicate that the CDC@CuO-NP nanocomposite is a promising, low-cost, and efficient electrode material for the sensitive determination of organophosphorus pesticides and has considerable potential for environmental monitoring and food safety applications. Full article

This study compares the performance of novel fluorescent nanobiosensors and liquid chromatography–mass spectrometry (LC-MS) for detecting organophosphorus pesticide residues in Angelica sinensis. Key parameters such as recovery rate and relative standard deviation (RSD) were evaluated to identify a preferable detection method. The results show that the fluorescent nanobiosensor offers superior sensitivity, whereas LC-MS excels in accuracy and quantitative analysis. For phoxim, the GQDs@GSH sensor achieved an LOD of 0.075 μmol·L⁻¹, with recoveries of 97.65–100.62% (RSD < 3.35%). For glyphosate, the PDOA/Cu²⁺ sensor achieved an LOD of 1.8 nmol·L⁻¹, and the AgNCs sensor achieved an LOD of 21 nmol·L⁻¹, with recoveries of 91.30–105.34% (RSD < 3.35%). The originality of this work is threefold and does not claim de novo synthesis of unknown materials: (i) it is the first validation of three existing fluorescent nanosensors (GQDs@GSH, PDOA/Cu²⁺, and AgNCs) specifically for organophosphorus pesticide detection in the complex medicinal plant matrix Angelica sinensis; (ii) it provides the first systematic comparison of these nanosensors against the pharmacopeia-standard LC-MS method in this matrix, delineating their complementary advantages; (iii) it is the first assessment of their phytotoxicity in Angelica sinensis seedlings, demonstrating biocompatibility and potential for in planta imaging. Full article

Chlorpyrifos (CP) remains one of the most globally pervasive organophosphorus pesticides, and its toxicological profile continues to raise substantial public health and environmental concerns. While traditionally characterized by its potent acetylcholinesterase-inhibitory properties, accumulating evidence now shows that chlorpyrifos and its bioactive metabolite, chlorpyrifos-oxon (CPO), exert far broader toxic effects, including the induction of oxidative stress, enhancement of neuroinflammatory processes, and the triggering of persistent epigenetic alterations. In this review, we synthesize current findings to highlight the expanding spectrum of CP-induced toxicity, while also providing a multidisciplinary overview of chlorpyrifos characteristics, including its environmental fate, metabolism, and transformation pathways. The analysis encompasses not only classical neurotoxicity but also disruptions in neurodevelopment, endocrine signaling, gut microbiota composition, hepatic function, musculoskeletal integrity and carcinogenic pathways. By synthesizing results across human, animal, and environmental studies, this review offers a comprehensive overview of CP’s multidimensional toxicity and highlights the urgent need for improved biomonitoring, regulatory harmonization, and global strategies to reduce exposure. Full article

A comprehensive ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed for the simultaneous quantification of 50 pesticide biomarkers across nine current-use chemical classes in human urine. These classes include organophosphorus insecticides (which encompass dialkyl phosphates and specific metabolites), pyrethroid insecticides, fungicides, neonicotinoid insecticides, herbicides, insect repellents, organochlorine pesticide metabolites, and plant growth regulators. The method employs solid-phase extraction (SPE) for sample preparation, requiring only 0.2 mL of urine. Chromatographic separation was optimized using a Hypersil Gold AQ column, achieving a total run time of 18 min. Mass spectrometric detection utilized polarity switching in electrospray ionization mode with multiple reaction monitoring. Method validation demonstrated satisfactory linearity (R² > 0.99), high sensitivity with limits of detection ranging from 0.01 to 0.88 ng/mL, and extraction efficiencies between 85% and 113%. Precision and accuracy were within acceptable ranges, with relative standard deviations generally below 15%. The method’s robustness was confirmed through participation in external quality assessment schemes. Application to real samples revealed significant inter-individual variability in pesticide biomarker concentrations, with total measured biomarker levels ranging from 89 to 1242 ng/mL across the 10 individuals analyzed. This method offers comprehensive coverage of current-use pesticide chemical classes, including 30 biomarkers from the U.S. National Health and Nutrition Examination Survey (NHANES) biomonitoring program, and demonstrates improved sensitivity and broader analyte coverage compared to existing methods. The developed assay provides a valuable tool for large-scale biomonitoring studies and environmental health research. Full article

The rapid detection of organophosphorus (OP) compounds is crucial for safeguarding human health and ensuring food safety. This study presents a novel wearable electrochemical biosensor that integrates miniaturized screen-printed electrodes with wearable devices to achieve real-time, on-site OP detection. The biosensor was fabricated by constructing a screen-printed carbon electrode (SPCE) on a thermoplastic polyurethane (TPU) substrate, sequentially modified with graphene (GR), gold nanoparticles (AuNPs), and organophosphorus hydrolase (OPH), and finally encapsulated with Nafion. This SPCE/GR/AuNPs/OPH/Nafion configuration yields a highly flexible and portable device. The detection principle relies on the enzymatic hydrolysis of methyl paraoxon (MPOX) by OPH, generating p-nitrophenol (PNP), which is quantitatively measured via square wave voltammetry (SWV). The sensor exhibits a broad linear detection range (30–400 μM) with a strong linear correlation (R² = 0.995) and a low detection limit (0.321 μM). It demonstrates excellent selectivity against common interfering substances, including urea, sucrose, and various metal ions. Application to real-world samples such as cabbage and tap water yielded high recoveries (107.2% for cabbage and 101.2% for tap water), with relative standard deviations (RSDs) below 8%. Furthermore, the biosensor maintains robust flexibility and mechanical resilience, with less than 5% signal loss after 100 bending cycles, confirming its suitability for wearable applications and reliable operation under mechanical stress. This innovative, flexible electrochemical biosensor provides a powerful and reliable platform for rapid OP detection, particularly in complex testing environments. Full article

Organophosphorus pesticide residues (OPPs) pose significant threats to ecological systems and human health, and conventional detection techniques are cumbersome, time-consuming, and costly. Herein, a facile electrochemical biosensor has been constructed based on a methyl green/chitosan (MG/Chi) composite membrane-modified electrode for the selective detection of OPPs, using isazofos (Isa) as the model analyte. Experimental results demonstrated that Isa significantly decreases the redox peak current of the modified electrode in buffer solution, and a good linear relationship was observed between the change in peak current and Isa concentration within a specific range. This biosensor exhibits excellent anti-interference capability and high sensitivity, with a limit of detection (LOD) as low as 0.60 μM. Furthermore, it was successfully applied for the quantitative determination of OPPs in real food and environmental samples, which confirms its reliable practical applicability and potential for on-site monitoring. Full article