Journal of Environmental Science and Health Part B-pesticides Food Contaminants and Agricultural Wastes最新文献

This study addresses the refinement of non-dietary risk assessments for plant protection products (PPPs) by evaluating the use of total residue (TR) half-lives (DT50) from magnitude of residue (MOR) studies as surrogates for dislodgeable foliar residue (DFR) decline, which is critical for estimating worker, resident, and bystander dermal exposure. While DFR field studies are not routinely conducted for every PPP, supervised MOR field trials to determine TR are standard regulatory requirements worldwide. To assess the viability of using TR decline rates for DFR decline in risk assessment models, we analyzed a comprehensive dataset comprising 71 DFR and 275 MOR GLP-compliant paired trials across various crops. Statistical analysis revealed that DFR residues dissipate, on average, three times faster than total residues from MOR studies, with the 95th percentile indicating a 2- to 4-fold faster decline. These findings suggest that, in the absence of DFR field data, TR decline rates provide a conservative and protective surrogate for modeling DFR decline and refining non-dietary risk assessments. This approach could also inform the design and duration of future DFR studies, potentially reducing the need for extended GLP-complaint DFR field trials without compromising regulatory rigor or worker safety.

Fluopyram is a fungicide with nematicidal properties widely used in agriculture, found in commercial products for agricultural pest management. Despite its increasing agricultural use, limited information exists on its cytogenotoxic and plant-level impacts. This study evaluated the cytogenotoxic and ecotoxicological effects of a fluopyram-based formulation on non-target organisms, including Salmonella typhimurium (TA98 and TA100 strains), Artemia salina, and seeds of Lactuca sativa (lettuce), Allium cepa (onion), and Cucumis sativus (cucumber). Concentrations ranging from 0.017 to 5.00 mg mL^-1 were tested. The pesticide did not induce mutagenic responses in the Salmonella strains tested but demonstrated cytotoxicity at high concentrations (≥1.67 mg mL^-1). In A. salina, increasing mortality was observed from 0.210 mg mL^-1, with an estimated LC₅₀ of 1.021 mg mL^-1. Regarding germination, onion seeds were affected at the highest tested concentration, while root growth in plant species exhibited a hormetic response, with stimulation at low concentrations and inhibition at higher ones. These findings underscore the need for continued environmental monitoring and risk assessment of fluopyram-based formulations, particularly regarding aquatic and plant ecosystems.

Animal feed significantly influences the content and quality of animal products consumed by humans and plays a crucial role in the food chain. To simultaneously analyze 345 pesticide residues in poultry feed, a modified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method was developed, utilizing gas chromatography-tandem mass spectrometry (GC-MS/MS). Validation studies were conducted with spiked pesticide standards, and commercial poultry feed samples were analyzed. The linearity of the QuEChERS method was evaluated, showing high coefficients of determination (R² ≥0.995) for all analytes. The method demonstrated excellent linearity (R² ≥0.995), recovery rates (86.8-109.2%), and precision (RSD ≤14.8%), meeting SANTE criteria. Limits of detection (LOD) ranged from 0.5 to 5 ng/kg and limits of quantification (LOQ) from 1 to 10 ng/kg, enhancing the method's reliability. Analysis of the poultry feed revealed that 15 out of the 345 pesticide residues were detected in the samples, with concentrations ranging from 2.1 to 120 µg/kg. The detected pesticide categories included insecticides, fungicides, plant growth regulators, and herbicides, in that order. In conclusion, the QuEChERS method combined with the GC-MS/MS approach provides a reliable technique for the multi-residue analysis of pesticides in complex feed matrices.

Glyphosate is an ingredient widely used in various commercial formulations, including Roundup®. This study focused on tight junctions and the expression of inflammatory genes in the small intestine of chicks. On the sixth day of embryonic development, the eggs were randomly assigned to three groups: the control group (CON, n = 60), the glyphosate group (GLYP, n = 60), which received 10 mg of active glyphosate/kg egg mass, and the Roundup®-based glyphosate group also received 10 mg of glyphosate. The results indicated that the chicks exposed to glyphosate or Roundup® exhibited signs of oxidative stress. Additionally, histopathological alterations in the small intestine tissues included villi fusion, complete fusion of some intestinal villi, a reduced number of goblet cells, and necrosis of some submucosal epithelial cells in chicks. Genes related to the small intestine (ZO-1, ZO-2, Claudin-1, Claudin-3, JAM2, and Occludin), as well as the levels of pro-inflammatory cytokines (IFNγ, IL-1β, and IL-6), exhibited significant changes in the groups exposed to glyphosate or Roundup® compared to the control group. In conclusion, the toxicity of pure glyphosate or Roundup® likely disrupts the small intestine of chicks by modulating the expression of genes associated with tight junctions in the small intestine.

Herbicide residue levels were analyzed in agricultural soils of Batak plain and health risk assessments were made for relevant pesticides. Herbicide contamination levels were analyzed with the use of Quick-Easy-Cheap-Efficient-Rugged-Safe (QuEChERS)-liquid chromatography/tandem mass spectrometry (LC-MS/MS) procedure. Herbicide-free soil samples were spiked at two different levels. Overall recovery of the method was 87.32%. Present findings were parallel to SANTE recovery limits. About 50% of collected samples from the study sites contained herbicides at different concentrations. Totally, eight herbicides were detected, and herbicide concentrations ranged between 1.085 and 1724.23 μg kg^-1. Metolachlor had the highest concentration (1724.23 μg kg^-1) in a sample taken close to the pesticide waste disposal area. Six herbicides were detected at different concentrations in the same sample. Persistent herbicides (terbuthylazine and pendimethalin) were detected in 35 samples. Risk assessments revealed that hazard index (HI) and hazard quotient (HQ) were less than 1. The greatest HQ values were identified for terbuthylazine as 2772.48 × 10^-7 and 20793.61 × 10^-7 for adults and children, respectively. The HI for all herbicides were 3916.05 × 10^-7 for adult and 29370.39 × 10^-7 for children.

Acrylamide, a probable human carcinogen present in heat-processed foods and environmental contaminants, requires sample extraction and preconcentration before chromatographic analysis. The method developed in this study employed derivatization with xanthydrol and dispersive liquid-liquid microextraction utilizing low-density anisole. Durian or potato chips were combined with deionized water, defatted with hexane, and subjected to precipitation of soluble carbohydrates and proteins using clarification reagents. Water samples were filtered through a membrane filter. Acrylamide was derivatized by introducing an acidic methanolic solution of xanthydrol at 50 °C. The derivatized acrylamide was extracted with 70 µL of anisole and vortexed, with the methanol from the xanthydrol solution serving as the disperser solvent. The anisole layer was analyzed using gas chromatography with both flame ionization and mass spectrometric detection. Linear calibration plots exhibited coefficients of determination >0.9997. The precision was measured at <10% RSD, and recoveries ranged from 84% to 107%. The quantitation limit varied from 2 to 10 µg kg^-1 for processed chips and from 0.05 to 0.10 µg L^-1 for water samples. Acrylamide was detected in all processed chip samples, with some concentrations exceeding the benchmark value of 750 μg kg^-1. However, no acrylamide was identified in any of the water samples.

Free enzymes cause difficulties in many applications due to their insufficient stability, loss of activity in a short time, and most importantly, although they are costly, they are used only once in reactions, lose their effect and cannot be recovered from the environment. Magnetic nanoparticles coated with biocompatible polymeric material are potential candidates for promising enzyme carriers due to their multifunctional pore surfaces, easy removal from the environment provided by the magnetization, ability to main stability under various harsh conditions. This study prepared a biosensor candidate based on the inhibiting acetylcholinesterase enzyme by organophosphate pesticides from chitosan-coated magnetic nanoparticles doped with gold. Transmission electron microscopy, scanning electron microscopy, X-ray diffraction diffractometry, and Fourier transform infrared spectroscopy analysis confirmed the structure of synthesized nanocomposites. Magnetic characteristics of the nanocomposites were assessed using VSM. Bio-nanocomposite (Fe₃O₄@Cht/Au/AChE) was used to determine environmental pollutants qualitatively. Remediation of organophosphate-containing wastewater is an essential issue for environmental sustainability. In this work, Dichlorvos and Chlorpyrifos were selected as organic pollutants to assess the enzymatic activity of immobilized Fe₃O₄@Cht/Au/AChE. Optimum conditions for AChE enzyme were immobilized nanostructures (Fe₃O₄@Cht/Au/AChE) were determined. The optimum pH for the immobilized enzyme was found to be 8, and the optimum temperature was found to be 60 °C. Retained immobilized enzyme activity is found to be around 50% for the 20th reuse. In the presence of 150 µL pesticide, retained immobilized enzyme activity is found to be around 25%. Method validation was performed for pesticides. When using immobilized AChE, the LOD (limit of detection)-LOQ (limit of quantitation) values for Dichlorovos and Chlorpyrifos was obtained in the range of 0.0087-0.029 nM and 0.0014-0.0046 nM, respectively. The relative standard deviation (RSD%) values, which are indicators of precision, were found to be below 2%.

Sulfonamide antibiotics (SAs) are widely used antimicrobial agents in livestock and aquaculture, and most of them entering the animal's body will be released into the environment as prodrugs or metabolites, which ultimately affect human health through the food chain. Both acid deposition and salinization of soil may have an impact on the migration and degradation of antibiotics. Sulfamethazine (SM2), a frequently detected compound in agricultural soils, has a migration and transformation process in the environment that is closely dependent on environmental pH. Nevertheless, scarcely any studies have been conducted on the effect of soil pH changes on the environmental behavior of sulfamethazine. We analyzed the migration and degradation mechanisms of SM2 using simulation experiments and ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-Q-TOF-MS) techniques. The results showed that acidic conditions limited the vertical migration of sulfadimidine, and SM2 underwent different reaction processes under different pH conditions, including S-C bond breaking, S-N bond hydrolysis, demethylation, six-membered heterocyclic addition, methyl hydroxylation and ring opening. The study of the migration pattern and degradation mechanism of SM2 under different pH conditions can provide a solid theoretical basis for assessing the pollution risk of sulfamethazine degradation products under acid rain and saline conditions, and provide a guideline for remediation of antibiotic contamination, so as to better prevent, control and protect groundwater resources.

Two years of monthly sampling and hydrological monitoring were performed at the outlet of a Mediterranean watershed in northern Tunisia to determine the contents of 469 pesticide active ingredients and metabolites in water and evaluate their behavior. Wadi Guenniche is a tributary of the Bizerte coastal lagoon, with a watershed area of 86 km², which exhibits pluvial cereal, legume, and orchid cultivation and irrigated market gardening. Twenty-nine pesticide active ingredients and 2 metabolites were detected in water. Twenty-four pesticide active ingredients were authorized for use in Tunisia. Among them, 14 had never been mentioned in previous farmer surveys. Five herbicides and their metabolites were the most frequently detected: aminomethylphosphonic acid (AMPA) (100%), glyphosate (94%), simazine (94%), 2,4-D (70%), and deisopropylatrazine (DIA) (47%). The detection frequency and concentration range suggested that the phytosanitary pressure and resulting water contamination are close to those on the northern Mediterranean shore. These results, in addition to characterizing the pollution state, emphasized the need for additional studies on the use and fate of pesticides on the southern shore of the Mediterranean Sea, particularly in Tunisia.

Further studies are necessary to evaluate not only the effectiveness of preemergent herbicides for weed control and selectivity in soybeans but also the potential carryover damage to crops planted in succession, such as sorghum and maize. This study aimed to assess the efficacy of preemergent herbicides in controlling Euphorbia heterophylla L. and Digitaria insularis L., as well as their selectivity in soybeans (Glycine max L.) and the residual effects on crops sown in succession, including maize (Zea mays L.) and sorghum (Sorghum bicolor (L.) Moench). Two field experiments were conducted with soybean, both in a randomized block design, consisting of the following treatments: sulfentrazone + diuron, flumioxazin + imazethapyr, diclosulam, sulfentrazone, s-metolachlor and flumioxazin, in addition to weeded controls and without weeding, with four replicates. Subsequently, the sowing of maize and sorghum was performed. Visual evaluations of weed control were performed at 14, 21, 28, 35 and 42 days after application of the treatments (DAA) and of phytotoxicity in soybean, sorghum and maize at 14, 21, 28, 35 and 42 days after planting emergence (DAE), and at the end, yield estimate. It was found that the sulfentrazone, sulfentrazone + diuron and imazethapyr + flumioxazin treatments were effective in controlling D. insularis and E. heterophylla up to 42 DAA. For sorghum and maize, no significant injury levels were observed for any treatment, with the exception of sulfentrazone alone, which provided significant reductions in productivity.