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Journal of Agricultural and Food... Mar 2012Solid-phase extraction (SPE) and direct competitive chemiluminescence enzyme immunoassay (dcCL-EIA) were combined for the detection of organophosphorus pesticides (OPs)...
Solid-phase extraction (SPE) and direct competitive chemiluminescence enzyme immunoassay (dcCL-EIA) were combined for the detection of organophosphorus pesticides (OPs) in environmental water samples. dcCL-EIA based on horseradish peroxidase labeled with a broad-specificity monoclonal antibody against OPs was developed, and the effects of several physicochemical parameters on dcCL-EIA performance were studied. SPE was used for the pretreatment of water samples to remove interfering substances and to concentrate the OP analytes. The coupling of SPE and dcCL-EIA can detect seven OPs (parathion, coumaphos, phoxim, quinalphos, triazophos, dichlofenthion, and azinphos-ethyl) with the limit of quantitation below 0.1 ng/mL. The recoveries of OPs from spiked water samples ranged from 62.5% to 131.7% by SPE-dcCL-EIA and 69.5% to 112.3% by SPE-HPLC-MS/MS. The screening of OP residues in real-world environmental water samples by the developed SPE-dcCL-EIA and their confirmatory analysis using SPE-HPLC-MS/MS demonstrated that the assay is ideally suited as a monitoring method for OP residues prior to chromatographic analysis.
Topics: Animals; Antibodies, Monoclonal; Antibody Specificity; Chromatography, High Pressure Liquid; Female; Immunoenzyme Techniques; Luminescent Measurements; Mice; Mice, Inbred BALB C; Organophosphorus Compounds; Pesticides; Solid Phase Extraction; Tandem Mass Spectrometry; Water; Water Pollutants, Chemical
PubMed: 22329773
DOI: 10.1021/jf300225b -
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 -
Rapid Communications in Mass... Nov 2010A simple, rapid and sensitive method is described for the determination of omethoate, dimethoate, diazinon, chlorpyrifos, parathion-ethyl, chlorfenvinphos, quinalphos...
A simple, rapid and sensitive method is described for the determination of omethoate, dimethoate, diazinon, chlorpyrifos, parathion-ethyl, chlorfenvinphos, quinalphos and azinphos-ethyl in postmortem whole blood samples. The analytes and internal standard (ethion) were isolated from the matrix by solid-phase extraction, and were analysed by gas chromatography/mass spectrometry in the selected ion monitoring mode. The method has shown to be selective after analysis of postmortem samples of 40 different origins. Calibration curves were established between 0.05 (0.1 for omethoate) and 25 µg/mL, and the values obtained for intra- and interday precision and accuracy were within the criteria usually accepted for bioanalytical method validation. Lower limits of quantitation were 50 ng/mL for all compounds, except for omethoate (100 ng/mL); the limits of identification of the method were 25 ng/mL for all analytes, except for omethoate, for which 50 ng/mL was obtained. Absolute recovery was determined at three concentration levels, and ranged from 31 to 108%. The proposed method is simple and fast, and can be routinely applied in the determination of these compounds in postmortem whole blood samples within the scope of forensic toxicology. In addition, mass spectrometry has demonstrated to be a powerful and indispensable tool for the unequivocal identification of the analytes, since the acceptance criteria were accomplished even at very low levels, thus allowing obtaining forensically valid and sound results.
Topics: Autopsy; Gas Chromatography-Mass Spectrometry; Humans; Insecticides; Organothiophosphorus Compounds; Regression Analysis; Reproducibility of Results; Sensitivity and Specificity; Solid Phase Extraction
PubMed: 20941767
DOI: 10.1002/rcm.4765 -
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 -
Journal of Agricultural and Food... Jun 2012An immunoaffinity chromatographic (IAC) method for the selective extraction and concentration of 13 organophosphorus pesticides (OPs, including coumaphos, parathion,...
An immunoaffinity chromatographic (IAC) method for the selective extraction and concentration of 13 organophosphorus pesticides (OPs, including coumaphos, parathion, phoxim, quinalphos, dichlofenthion, triazophos, azinphos-ethyl, phosalone, isochlorthion, parathion-methyl, cyanophos, disulfoton, and phorate) prior to analysis by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed. The IAC column was prepared by covalently immobilizing a monoclonal antibody with broad specificity for OPs on CNBr-activated Sephrose 4B. The column capacity ranged from 884 to 2641 ng/mL of gel. The optimum elution solvent was 0.01 M phosphate-buffered saline containing 80% methanol. The breakthrough volume of the IAC column was found to be 400 mL. Recoveries of OPs from spiked environmental samples by IAC cleanup and HPLC-MS/MS analysis ranged from 60.2 to 107.1%, with a relative standard deviation below 11.1%. The limit of quantitation for 13 OPs ranged from 0.01 to 0.13 ng/mL (ng/g). The application of IAC cleanup coupled to HPLC-MS/MS in real environmental samples demonstrated the potential of this method for the determination of OP residues in environmental samples at trace levels.
Topics: Antibodies, Monoclonal; Chromatography, Affinity; Chromatography, High Pressure Liquid; Environmental Monitoring; Organophosphorus Compounds; Pesticides; Sensitivity and Specificity; Tandem Mass Spectrometry; Water Pollutants, Chemical
PubMed: 22612520
DOI: 10.1021/jf300896z -
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 -
Analytical and Bioanalytical Chemistry Feb 2006Several triazine pesticides, such as atrazine, are much more soluble in several organic solvents, such as chloroform, than in water. Our recent research was aimed at...
Several triazine pesticides, such as atrazine, are much more soluble in several organic solvents, such as chloroform, than in water. Our recent research was aimed at analyzing this class of pesticides using tyrosinase OPEE (organic phase enzyme electrodes), exploiting their inhibiting action on the tyrosinase enzyme when operating in water-saturated chloroform medium. In this work we studied the response of a tyrosinase inhibition enzyme sensor to several triazinic (simazine, propazine, terbuthylazine) and benzotriazinic (azinphos-ethyl and azinphos-methyl) pesticides (LOD=0.5x10(-9) mol l(-1)). Recovery trials were also performed in vegetal matrixes (corn, barley, lentils). Lastly, the effect of the solvent (chloroform or water) on the inhibition process was investigated via Hill's equation and the diffusion of analyte from the solvent to the enzyme membrane.
Topics: Biosensing Techniques; Monophenol Monooxygenase; Pesticides; Triazines
PubMed: 16328240
DOI: 10.1007/s00216-005-0175-6 -
Talanta Nov 2007A statistical approach for the analysis of complex samples by immunoassay is proposed in this article. Two enzyme-linked immunosorbent assays (ELISAs), one of them in...
A statistical approach for the analysis of complex samples by immunoassay is proposed in this article. Two enzyme-linked immunosorbent assays (ELISAs), one of them in the conjugate-coated format and the other in the antibody-coated format, were evaluated for their suitability to the analysis of mixtures of three organodithiophosphorus pesticides: azinphos-methyl, azinphos-ethyl and phosmet. It was found that the apparent affinity of the antibody to each analyte changed in the presence of a cross-reacting compound in the antibody-coated ELISA format, but not when the conjugate-coated ELISA format was used. The assays were thereafter applied to the analysis of mixtures of the three recognized pesticides. With the conjugate-coated ELISA format, accurate and precise determinations of mixtures could be performed if an azinphos-methyl standard curve was employed, with recoveries between 71% and 130% and with coefficients of variation lower than 12.7%. Neither accurate nor precise measurements could be accomplished with the enzyme immunoassay using the antibody-coated ELISA format, independently of the standard curve used. It is thought that the study presented here will have applicability in a variety of cases where the analytical goal is semiquantitative screening based on the total quantity of an unknown mixture of related compounds.
Topics: Antibodies, Monoclonal; Azinphosmethyl; Cross Reactions; Enzyme-Linked Immunosorbent Assay; Insecticides; Phosmet
PubMed: 18371612
DOI: 10.1016/j.talanta.2007.05.025