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Journal of Pharmaceutical and... Aug 2024Pesticides play an important role in forensic toxicology and are usually classified as a single class of chemicals. Despite their commonly perceived unity, pesticides...
Development and validation of a multi-substance method for routine analysis of pesticides in post-mortem samples by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry.
Pesticides play an important role in forensic toxicology and are usually classified as a single class of chemicals. Despite their commonly perceived unity, pesticides encompass a spectrum of compounds, including organophosphates, carbamates, pyrethroids or organochlorines, among others, each with varying degrees of toxicity. Pesticide analysis in post-mortem samples can be difficult due to the complexity of the samples and to the high toxicity of these compounds. The aim of this study was to develop and validate an easy to use, sensitive, and robust method, using ultra-performance liquid chromatography-tandem mass spectrometry to be incorporated in the routine flow for pesticide analysis in post-mortem blood samples. Described herein is a streamlined, expeditious, yet highly efficient method facilitating the screening, qualitative assessment, and quantitative confirmation of 15 pesticides, including acetamiprid, azinphos-ethyl, bendiocarb, carbofuran, chlorfenvinphos, dimethoate, imidaclopride, malathion, methiocarb, methomyl, parathion, pirimicarb, strychnine, tetrachlorvinphos, and thiacloprid in post-mortem blood, recognizing the pivotal role blood plays in forensic investigations. The developed method was linear from 10 to 200 ng/mL; limits of detection were between 1 and 10 ng/mL, depending on the compound; it was successfully evaluated a dilution ratio of 1-2, 5 and 10; and 8 substances showed maximum stability for the time interval studied. This UHPLC-MS/MS method is useful and a powerful tool in a toxicology lab because it is fast, simple, effective, and trustworthy. The results of this validation highlight the robustness of the analytical method, providing a valuable tool for the accurate and sensitive detection of pesticides in post-mortem blood. Poised for routine implementation, this method has already found success in suspected intoxication cases, promising to elevate the standards of forensic pesticide analysis.
Topics: Tandem Mass Spectrometry; Chromatography, High Pressure Liquid; Humans; Pesticides; Forensic Toxicology; Reproducibility of Results; Autopsy; Limit of Detection
PubMed: 38701535
DOI: 10.1016/j.jpba.2024.116176 -
Nature Chemical Biology Jan 2024Plants sense abscisic acid (ABA) using chemical-induced dimerization (CID) modules, including the receptor PYR1 and HAB1, a phosphatase inhibited by ligand-activated...
Plants sense abscisic acid (ABA) using chemical-induced dimerization (CID) modules, including the receptor PYR1 and HAB1, a phosphatase inhibited by ligand-activated PYR1. This system is unique because of the relative ease with which ligand recognition can be reprogrammed. To expand the PYR1 system, we designed an orthogonal '*' module, which harbors a dimer interface salt bridge; X-ray crystallographic, biochemical and in vivo analyses confirm its orthogonality. We used this module to create PYR1*/HAB1* and PYR1*/HAB1*, which possess nanomolar sensitivities to their activating ligands mandipropamid and azinphos-ethyl. Experiments in Arabidopsis thaliana and Saccharomyces cerevisiae demonstrate the sensitive detection of banned organophosphate contaminants using living biosensors and the construction of multi-input/output genetic circuits. Our new modules enable ligand-programmable multi-channel CID systems for plant and eukaryotic synthetic biology that can empower new plant-based and microbe-based sensing modalities.
Topics: Abscisic Acid; Arabidopsis; Arabidopsis Proteins; Dimerization; Ligands; Membrane Transport Proteins
PubMed: 37872402
DOI: 10.1038/s41589-023-01447-7 -
The Science of the Total Environment Nov 2021The study aimed to assess the occurrence and the environmental risk of a group of 51 selected pesticides in the Guadiana Basin (a biodiversity hotspot, in the...
The study aimed to assess the occurrence and the environmental risk of a group of 51 selected pesticides in the Guadiana Basin (a biodiversity hotspot, in the Mediterranean). The most abundant pesticides were bentazone and 2,4-D, while terbuthylazine together with terbutryn constituted the most ubiquitous pesticides. Eighteen out of the 38 pesticides detected are no longer approved in Europe, and 5 of them are included in the list of priority substances. The risk assessment showed that azinphos ethyl, diflufenican, irganol, imidacloprid, and oxadiazon occurred occasionally, but always in concentrations above their respective ecotoxicological threshold value. Contrary, bentazone, terbuthylazine, and terbutryn presented a high risk in most of the sampled locations and periods. The site-specific risk assessment showed a spatial and temporal pattern, with a higher risk occurring mainly in intermittent streams, in the drought period. The presence of pesticides banned from the EU market since 2009 showed the importance of improving the monitoring process, to identify the main sources of pollution and the fate of these emerging compounds. The results showed the need of implementing actions to improve the sustainable use of pesticides in agricultural areas, working with farmers and management entities to reduce the contamination of aquatic ecosystems. Transboundary water governance is also required to solve potential transboundary contamination problems.
Topics: Ecosystem; Environmental Monitoring; Pesticides; Portugal; Risk Assessment; Rivers; Water Pollutants, Chemical
PubMed: 34214808
DOI: 10.1016/j.scitotenv.2021.148703 -
The Science of the Total Environment Nov 2020Water is an essential resource for all living organisms. The continuous and increasing use of pesticides in agricultural and urban activities results in the pollution of...
Improved fully automated method for the determination of medium to highly polar pesticides in surface and groundwater and application in two distinct agriculture-impacted areas.
Water is an essential resource for all living organisms. The continuous and increasing use of pesticides in agricultural and urban activities results in the pollution of water resources and represents an environmental risk. To control and reduce pesticide pollution, reliable multi-residue methods for the detection of these compounds in water are needed. In this context, the present work aimed at providing an analytical method for the simultaneous determination of trace levels of 51 target pesticides in water and applying it to the investigation of the target pesticides in two agriculture-impacted areas of interest. The method developed, based on an isotopic dilution approach and on-line solid-phase extraction-liquid chromatography-tandem mass spectrometry, is fast, simple, and to a large extent automated, and allows the analysis of most of the target compounds in compliance with European regulations. Application of the method to the analysis of selected water samples collected at the lowest stretches of the two largest river basins of Catalonia (NE Spain), Llobregat and Ter, revealed the presence of a wide suite of pesticides in the Llobregat basin, some of them at concentrations above the water quality standards (irgarol and dichlorvos) or the acceptable method detection limits (methiocarb, imidacloprid, and thiacloprid), and much cleaner waters in the Ter River basin. Risk assessment of the pesticide concentrations measured in the Llobregat River indicated high risk due to the presence of irgarol, dichlorvos, methiocarb, azinphos ethyl, imidacloprid, and diflufenican (hazard quotient (HQ) values>10), and moderate potential risk in the Ter River, associated to the occurrence of bentazone and irgarol (HQ > 1).
PubMed: 32736100
DOI: 10.1016/j.scitotenv.2020.140650 -
Journal of the Science of Food and... Apr 2020Pesticides are extensively used worldwide to control plant pathogens and prevent agricultural product damage. However, they can pollute the environment and endanger...
Hyphenated dispersive solid- and liquid-phase microextraction technique based on a hydrophobic deep eutectic solvent: application for trace analysis of pesticides in fruit juices.
BACKGROUND
Pesticides are extensively used worldwide to control plant pathogens and prevent agricultural product damage. However, they can pollute the environment and endanger human health. So far, a variety of sample preparation methods have been developed for the analysis of pesticide residues.
RESULTS
A hyphenated solid-liquid microextraction method based on a new adsorbent of magnetic graphene oxide functionalized by (3-glycidyloxypropyl)trimethoxysilane and a deep eutectic solvent (choline chloride/4-chlorophenol (1:2)) was developed for extraction/preconcentration of trace levels of pesticides. The sorbent was characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, and vibrating sample magnetometry. In-syringe magnetic dispersive solid-phase extraction in tandem with dispersive liquid-liquid microextraction followed by gas chromatography was applied for the analysis of the selected pesticides. The main parameters governing sample preparation efficiency, including adsorbent dosage, desorption conditions, pH, extraction time, deep eutectic solvent volume, and salt concentration, were investigated. The linear ranges were 0.024-500 μg L with 0.9971-0.9999 linearity factor (R ). The limits of detection and quantification were 0.006-0.038 and 0.024-0.126 μg L , respectively. The relative standard deviations were 0.5-4.2% for intra-day analysis and 2.7-4.6% for inter-day analysis. Enrichment factors were in the range 210-540.
CONCLUSIONS
The method was successfully applied for the determination of malathion, heptachlor epoxide, endrin, dichlorodiphenyltrichloroethane, azinphos ethyl, cypermethrin, and deltamethrin in fruit juice samples (apple, pineapple, cherry, peach, and red and green grape juices) and the recoveries were within the range 71-115%. © 2020 Society of Chemical Industry.
Topics: Adsorption; Chromatography, Gas; Fruit and Vegetable Juices; Graphite; Liquid Phase Microextraction; Magnetic Phenomena; Pesticide Residues; Solid Phase Extraction; Solvents
PubMed: 31975389
DOI: 10.1002/jsfa.10279 -
The Science of the Total Environment Feb 2019Estuarine environments are being constantly stressed by new sources of pollution (e.g. pesticides) derived from activities of industry and intensive agriculture. The...
Estuarine environments are being constantly stressed by new sources of pollution (e.g. pesticides) derived from activities of industry and intensive agriculture. The present study aims at quantify pesticides of three different categories (fungicides, herbicides and insecticides) in the Louros River (Epirus region, North-Western Greece). A monitoring study of 34 compounds was carried out in surface river waters from June 2011 until May 2012. Seven water sampling stations were established and 35 water samples were collected. A solid-phase extraction (SPE) method coupled with gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS), depending on the compound, was developed and validated. During the monitoring study 25 pesticides were detected (13 herbicides, 9 insecticides, 3 fungicides). The most commonly encountered pesticides were quizalofop-ethyl, trifluralin and pendimethaline. Tebufenpyrad was found in all sampling stations and seasons, with the highest concentrations of 0.330 μg/L at Tsopeli Lagoon exceeding the rather low concentrations reported nationwide. Regarding the environmental risk due to the presence of target compounds in surface waters, this was estimated by calculating risk quotients (RQs) for different aquatic organisms (algae, zooplankton and fish). The results denoted a possible threat for the aquatic environment, rendering in this way the RQ method as a useful screening tool. In any case, further extensive study is needed for acetochlor, pirimiphos-methyl, endosulfan-a and azinphos-ethyl in order to better correlate their occurrence and potential toxic effects in aquatic life and humans.
Topics: Animals; Chromatography, Liquid; Environmental Monitoring; Fishes; Fungicides, Industrial; Gas Chromatography-Mass Spectrometry; Greece; Herbicides; Insecticides; Mass Spectrometry; Microalgae; Pesticide Residues; Risk Assessment; Rivers; Seaweed; Solid Phase Extraction; Water Pollutants, Chemical; Zooplankton
PubMed: 30292989
DOI: 10.1016/j.scitotenv.2018.09.185 -
Ecotoxicology and Environmental Safety Dec 2018A sensitive and fast ultrasound-assisted dispersive liquid-liquid microextraction procedure combined with ion mobility spectrometry has been developed for the...
Ultrasound-assisted dispersive liquid-liquid microextraction followed by ion mobility spectrometry for the simultaneous determination of bendiocarb and azinphos-ethyl in water, soil, food and beverage samples.
A sensitive and fast ultrasound-assisted dispersive liquid-liquid microextraction procedure combined with ion mobility spectrometry has been developed for the simultaneous extraction and determination of bendiocarb and azinphos-ethyl. Experimental parameters affecting the analytical performance of the method were optimized: type and volume of extraction solvent (chloroform, 150 µL), pH (9.0), type and volume of buffer (ammonium buffer pH = 9.0, 4.5 mL) and extraction time (3.0 min). Under optimum conditions, the linearity was found to be in the range of 2-40 and 6-100 ng/mL and the limits of detection (LOD) were 1.04 and 1.31 ng/mL for bendiocarb and azinphos-ethyl, respectively. The method was successfully validated for the analysis of bendiocarb and azinphos-ethyl in different samples such as waters, soil, food and beverage samples.
Topics: Azinphosmethyl; Beverages; Environmental Monitoring; Environmental Pollutants; Food; Food Analysis; Ion Mobility Spectrometry; Limit of Detection; Liquid Phase Microextraction; Phenylcarbamates; Soil; Solvents; Ultrasonics; Water
PubMed: 30218969
DOI: 10.1016/j.ecoenv.2018.09.021 -
Food Additives & Contaminants. Part A,... Jun 2016A method developed for the simultaneous analysis of aflatoxin M1, abamectin, doramectin, eprinomectin, ivermectin, moxidectin, acephate, azinphos-ethyl, azinphos-methyl,...
Multiresidue method for simultaneous analysis of aflatoxin M1, avermectins, organophosphate pesticides and milbemycin in milk by ultra-performance liquid chromatography coupled to tandem mass spectrometry.
A method developed for the simultaneous analysis of aflatoxin M1, abamectin, doramectin, eprinomectin, ivermectin, moxidectin, acephate, azinphos-ethyl, azinphos-methyl, diazinon, methamidophos, methidathion, mevinphos, pirimiphos-ethyl and pirimiphos-methyl in whole raw milk, based on the QuEChERS method for extraction and clean-up, with detection and quantification by ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) is described. The method was validated according to parameters of the Analytical Quality Assurance Manual from the Brazilian Ministry of Agriculture and Commission Decision 2002/657/EC, and proved suitable for analysis of these analytes within the proposed working range, with recovery values between 77% and 110%, a standard deviation lower than 20%, limits of detection between 0.05 and 0.99 µg l(-)(1), and limits of quantification between 0.15 and 1.98 µg l(-1). Samples from animals treated with abamectin, doramectin, ivermectin and diazinon were analysed by the validated method. Residues of aflatoxin M1 were also found in field samples at levels below the established maximum residue limit.
Topics: Aflatoxin M1; Animals; Brazil; Chromatography, High Pressure Liquid; Food Contamination; Ivermectin; Macrolides; Milk; Organophosphates; Pesticide Residues; Reproducibility of Results; Tandem Mass Spectrometry
PubMed: 27144891
DOI: 10.1080/19440049.2016.1175227 -
Journal of Agricultural and Food... Feb 2016A simple, rapid, and sensitive method using ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) combined with sweeping micellar electrokinetic...
Sensitive Detection of Organophosphorus Pesticides in Medicinal Plants Using Ultrasound-Assisted Dispersive Liquid-Liquid Microextraction Combined with Sweeping Micellar Electrokinetic Chromatography.
A simple, rapid, and sensitive method using ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) combined with sweeping micellar electrokinetic chromatography (sweeping-MEKC) has been developed for the determination of nine organophosphorus pesticides (chlorfenvinphos, parathion, quinalphos, fenitrothion, azinphos-ethyl, parathion-methyl, fensulfothion, methidathion, and paraoxon). The important parameters that affect the UA-DLLME and sweeping efficiency were investigated. Under the optimized conditions, the proposed method provided 779.0-6203.5-fold enrichment of the nine pesticides compared to the normal MEKC method. The limits of detection ranged from 0.002 to 0.008 mg kg(-1). The relative standard deviations of the peak area ranged from 1.2 to 6.5%, indicating the good repeatability of the method. Finally, the developed UA-DLLME-sweeping-MEKC method has been successfully applied to the analysis of the investigated pesticides in several medicinal plants, including Lycium chinense, Dioscorea opposite, Codonopsis pilosula, and Panax ginseng, indicating that this method is suitable for the determination of trace pesticide residues in real samples with complex matrices.
Topics: Chromatography, Micellar Electrokinetic Capillary; Limit of Detection; Liquid Phase Microextraction; Organophosphorus Compounds; Pesticide Residues; Plants, Medicinal; Ultrasonics
PubMed: 26758524
DOI: 10.1021/acs.jafc.5b05369 -
Journal of Hazardous Materials Jan 2014The Júcar River, in a typical Mediterranean Basin, is expected to suffer a decline in water quality and quantity as a consequence of the climate change. This study is...
The Júcar River, in a typical Mediterranean Basin, is expected to suffer a decline in water quality and quantity as a consequence of the climate change. This study is focused on the presence and distribution of pesticides in water and fish, using the first extensive optimization and application of the QuEChERS method to determine pesticides in freshwater fish. Majority pesticides in water - in terms of presence and concentration - were dichlofenthion, chlorfenvinphos, imazalil, pyriproxyfen and prochloraz (associated with a frequent use in farming activities), as well as buprofezin, chlorpyriphos and hexythiazox. In fish, the main compounds were azinphos-ethyl, chlorpyriphos, diazinon, dimethoate and ethion. The analysis of bio-concentration in fish indicated differences by species. The maximum average concentration was detected in European eel (a critically endangered fish species). The wide presence of pesticides in water and fish suggests potential severe effects on fish populations and other biota in future scenarios of climate change, in a river basin with several endemic and endangered fish species. The potential effects of pesticides in combination with multiple stressors require further research to prioritize the management of specific chemicals and suggest effective restoration actions at the basin scale.
Topics: Animals; Chromatography, Liquid; Environmental Monitoring; Fishes; Pesticides; Rivers; Spain; Tandem Mass Spectrometry; Water Pollutants, Chemical
PubMed: 24315814
DOI: 10.1016/j.jhazmat.2013.11.016