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Toxicological Sciences : An Official... Apr 2024Organophosphorus pesticides (OPPs) having a phosphate ester moiety, such as malathion (MA) and methidathion (DMTP), are widely used and have been detected in many fatal...
Organophosphorus pesticides (OPPs) having a phosphate ester moiety, such as malathion (MA) and methidathion (DMTP), are widely used and have been detected in many fatal cases of accidental exposure or suicide in Japan. In forensic toxicology, the accurate determination of blood OPP concentration is mandatory to prove death by OPP poisoning. However, fatal pesticide concentration in blood at autopsy varies depending on the circumstances surrounding the dead body. In this study, we found that 16 OPPs were degraded by human serum albumin (HSA) in a temperature-dependent fashion. The mechanism underlying MA, DMTP, azinphos-methyl, etrimfos, fenthion (MPP), pirimiphos-methyl, (E)-dimethylvinphos, (Z)-dimethylvinphos, vamidothion, edifenphos (EDDP), fosthiazate, and pyraclofos degradation involves the formation of adducts with tyrosine residues in HSA. The mass spectra obtained by liquid chromatography quadrupole Orbitrap mass spectrometry revealed that phosphate ester amino acid adducts such as Y-adduct1, Y-adduct2, Y-adduct3, Y-adduct4, and Y-adduct5 were formed in HSA solution incubated with OPPs. These results indicate that the 16 OPPs are postmortem changed by HSA. The detection of phosphate ester amino acid adducts such as Y-adduct1, Y-adduct2, Y-adduct3, Y-adduct4, and Y-adduct5, instead of MA, DMTP, azinphos-methyl, etrimfos, MPP, pirimiphos-methyl, (E)-dimethylvinphos, (Z)-dimethylvinphos, vamidothion, EDDP, fosthiazate, and pyraclofos per se, may be used to determine death by these OPPs poisoning.
Topics: Humans; Organophosphorus Compounds; Tyrosine; Pesticides; Serum Albumin, Human; Postmortem Changes; Chromatography, Liquid; Mass Spectrometry; Forensic Toxicology
PubMed: 38366941
DOI: 10.1093/toxsci/kfae023 -
Journal of Economic Entomology Sep 2019Organisms live in complex multivariate environments. In agroecosystems, this complexity is often human-induced as pest individuals can be exposed to many xenobiotics...
Organisms live in complex multivariate environments. In agroecosystems, this complexity is often human-induced as pest individuals can be exposed to many xenobiotics simultaneously. Predicting the effects of multiple stressors can be problematic, as two or more stressors can have interactive effects. Our objective was to investigate whether indirect glyphosate-based herbicide (GBH) exposure of the host plant has interactive effects in combination with an insecticide (azinphos-methyl) on an invasive pest Colorado potato beetle (Leptinotarsa decemlineata Say). We tested the effects of GBH and insecticide on the survival, insecticide target genes expression (acetylcholinesterase genes) and oxidative status biomarkers (glutathione S-transferase [GST], glucose-6-phosphate dehydrogenase [G6PDH], glutathione reductase homolog [GR], glutathione peroxidase homolog [GPx], total glutathione [totGSH], glutathione reduced-oxidized [GSH: GSSG], catalase [CAT], superoxide dismutase [SOD], lipid hydroperoxides). We found that exposure to indirect GBH has no single or interactive effects in combination with the insecticide on larval survival. However, prior exposure to GBH inhibits Ldace1 gene expression by 0.55-fold, which is the target site for the organophosphate and carbamate insecticides. This difference disappears when individuals are exposed to both GBH and insecticide, suggesting an antagonistic effect. On the other hand, oxidative status biomarker scores (PCAs of GPx, GR, and CAT) were decreased when exposed to both stressors, indicating a synergistic effect. Overall, we found that indirect GBH exposure can have both antagonistic and synergistic effects in combination with an insecticide, which should be considered when aiming for an ecologically relevant risk assessment of multiple human-induced stressors.
Topics: Animals; Coleoptera; Colorado; Glutathione Transferase; Herbicides; Insecticides; Organophosphates; Solanum tuberosum
PubMed: 31081887
DOI: 10.1093/jee/toz115 -
Talanta Apr 2024Biodegradable molecularly imprinted polymer-coated paper (MIP@paper) was effectively produced by polymerization using azinphos-methyl as a template molecule,...
Biodegradable molecularly imprinted polymer-coated paper (MIP@paper) was effectively produced by polymerization using azinphos-methyl as a template molecule, terephthalic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, and aqueous ethanol as a green porogenic solvent. The material was subsequently composited onto cellulose paper, which served as the natural substrate, by dip coating with the aid of chitosan and citric acid natural adhesive. The properties, such as static and dynamic adsorption, selectivity, and reusability, were assessed. At rapid adsorption equilibrium (10 min), the MIP@paper had a high adsorption capacity in the range of 2.5-3.7 mg g and good recognition with imprinting factors up to 2.1. In addition, the proposed MIP@paper was utilized efficiently as a sorbent for dispersive solid phase extraction (d-SPE) of eight organophosphorus pesticides (OPPs) prior to high-performance liquid chromatography (HPLC) analysis. The d-SPE-HPLC method displayed low detection limits of 1.2-4.5 μg kg and significant enrichment factors (up to 320-fold). The proposed method was effectively applied for the determination of OPP residues in agricultural products, including fruits, vegetables, and cereal grains, with satisfactory spiked recoveries (80.1-119.1 %). Thus, the MIP@paper material provided a selective and environmentally favorable method for extracting and determining organophosphorus pesticides.
Topics: Pesticides; Vegetables; Molecularly Imprinted Polymers; Organophosphorus Compounds; Edible Grain; Fruit; Solid Phase Extraction; Molecular Imprinting; Adsorption; Chromatography, High Pressure Liquid
PubMed: 38101032
DOI: 10.1016/j.talanta.2023.125536 -
Ecotoxicology (London, England) Aug 2019The presence of pesticides has recently been reported in shrimp farms adjacent to agricultural areas on the east coast of the Gulf of California. This study assessed the...
The presence of pesticides has recently been reported in shrimp farms adjacent to agricultural areas on the east coast of the Gulf of California. This study assessed the possible effect of organophosphorus pesticides in the coastal environment of Sinaloa, México, using the white shrimp Litopenaeus vannamei as a bioindicator since their presence, abundance or behavior indicate some process or state of the system in which they live. Sublethal bioassays were performed on shrimps in intermolt state using commercial brands of organophosphorus pesticides, chlorpyrifos (0.0015 mg l), diazinon (0.0120 mg l), methamidophos (1.207 mg l), azinphos-methyl (0.0101 mg l), and methyl parathion (0.0075 mg l) were tested. Results showed reductions in glycogen, triglycerides, and total protein concentrations in shrimp muscle, except for the diazinon treatments, in which an increase in triglyceride level was detected. The observed alterations in the three cellular components were probably due to the metabolic compensation mechanism of the shrimp in reaction to the stress produced by organophosphorus pesticides, which act as endocrine disruptors. The establishment of continuous environmental monitoring programs of the coastal zone of Northwestern Mexico is strongly recommended.
Topics: Animals; Arthropod Proteins; Energy Metabolism; Glycogen; Insecticides; Mexico; Organophosphates; Penaeidae; Triglycerides; Water Pollutants, Chemical
PubMed: 31222580
DOI: 10.1007/s10646-019-02066-6