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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 -
Environmental Toxicology and... Apr 2024Endocrine disruptors chemicals (EDCs) pose significant health risks, including cancer, behavioral disorders, and infertility. In this study, we employed the...
Endocrine disruptors chemicals (EDCs) pose significant health risks, including cancer, behavioral disorders, and infertility. In this study, we employed the photoelectrocatalysis (PEC) technique with optimized tungsten oxide (WO) nanostructures as a photoanode to degrade three diverse EDCs: methiocarb, dimethyl phthalate, and 4-tert-butylphenol. PEC degradation tests were carried out for individual contaminants and a mixture of them, assessing efficiency across different EDC families. Ultra High-Performance Liquid Chromatography and Mass Spectrometry was used to control the course of the experiments. For individual solutions, 4-tert-butylphenol and methiocarb were 100% degraded at 1 hour of PEC degradation. Among the tested EDCs, dimethyl phthalate showed the highest resistance to degradation when treated individually. However, when assessed in a mixture with the other EDCs, the degradation efficiency of dimethyl phthalate increased compared to its individual treatment. Furthermore, four degradation intermediates were identified for each contaminant. Finally, toxicity tests revealed that the initial solution was more toxic than the samples treated for all the contaminants tested, except for the phthalate.
Topics: Humans; Endocrine Disruptors; Methiocarb; Tandem Mass Spectrometry; Phenols; Phthalic Acids
PubMed: 38499263
DOI: 10.1016/j.etap.2024.104420 -
Environmental Research May 2024This study investigates for the first time the contamination of water and sediment of the Venice Lagoon by twenty Contaminants of Emerging Concern (CECs): three...
This study investigates for the first time the contamination of water and sediment of the Venice Lagoon by twenty Contaminants of Emerging Concern (CECs): three hormones, six pharmaceutical compounds (diclofenac and five antibiotics, three of which are macrolides), nine pesticides (methiocarb, oxadiazon, metaflumizone, triallate, and five neonicotinoids), one antioxidant (BHT), and one UV filter (EHMC). Water and sediment samples were collected in seven sites in four seasons, with the aim of investigating the occurrence, distribution, and possible emission sources of the selected CECs in the studied transitional environment. The most frequently detected contaminants in water were neonicotinoid insecticides (with a frequency of quantification of single contaminants ranging from 73% to 92%), and EHMC (detected in the 77% of samples), followed by BHT (42%), diclofenac (39%), and clarithromycin (35%). In sediment the highest quantification frequencies were those of BHT (54%), estrogens (ranging from 35% to 65%), and azithromycin (46%). Although this baseline study does not highlight seasonal or spatial trends, results suggested that two of the major emission sources of CECs in the Venice Lagoon could be tributary rivers from its drainage basin and treated wastewater, due to the limited removal rates of some CECs in WWTPs. These preliminary results call for further investigations to better map priority emission sources and improve the understanding of CECs environmental behavior, with the final aim of drawing up a site-specific Watch List of CECs for the Venice Lagoon and support the design of more comprehensive monitoring plans in the future.
Topics: Geologic Sediments; Water Pollutants, Chemical; Italy; Environmental Monitoring; Pesticides; Pharmaceutical Preparations
PubMed: 38331156
DOI: 10.1016/j.envres.2024.118401 -
The Science of the Total Environment Mar 2024The presence of pesticides in aquatic ecosystems poses significant risks to non-target organisms, necessitating monitoring and environmental risk assessment. This study...
The presence of pesticides in aquatic ecosystems poses significant risks to non-target organisms, necessitating monitoring and environmental risk assessment. This study aimed to evaluate the dynamics and environmental risk of pesticides in a hydro-agricultural area with intensive agricultural practices, in the Mediterranean region (South of Portugal). Seasonality and location influenced pesticide numbers and concentrations, with the highest levels observed during the dry season. Triazines, phenylureas, and organophosphates were the predominant pesticide classes, with terbuthylazine, bentazone, terbutryn, diazinon, and metolachlor exhibiting the highest detection frequencies (68 % to 72 %). Notably, 44 % of the quantified pesticides are no longer authorized in Portugal, with 33 % posing a high environmental risk. Some insecticides, including imidacloprid, methiocarb, and malathion, were occasionally detected at concentrations that posed high risks to the aquatic ecosystem (RQ ≥ 1). Irgarol, an algicide used in irrigation canals, presented a high risk in 91 % of the analysed samples. The study's distribution profile of pesticides revealed a significant transportation of these compounds from reservoirs to irrigation hydrants, establishing them as a secondary source of crop and environmental contamination. Additionally, the assessment of spatial distribution and environmental risk allowed for the identification of specific pollutants in different locations, prioritizing them based on their ecotoxicological risk to aquatic ecosystems. These findings reinforce the importance of implementing management measures at the level of hydro-agricultural areas, helping to stop the cycle of pesticide contamination. Only this type of strategy will make it possible to protect water quality, biodiversity and the health of citizens, contributing to the European Union's objectives of improving the condition of freshwater bodies and promoting the sustainable use of pesticides.
Topics: Pesticides; Ecosystem; Environmental Monitoring; Water Pollutants, Chemical; Agriculture; Water Supply
PubMed: 38278229
DOI: 10.1016/j.scitotenv.2024.170304 -
The Science of the Total Environment Nov 2023Sublethal effects are becoming more relevant in ecotoxicological test methods due to their higher sensitivity compared to lethal endpoints and their preventive nature....
Sublethal effects are becoming more relevant in ecotoxicological test methods due to their higher sensitivity compared to lethal endpoints and their preventive nature. Such a promising sublethal endpoint is the movement behavior of invertebrates which is associated with the direct maintenance of various ecosystem processes, hence being of special interest for ecotoxicology. Disturbed movement behavior is often related to neurotoxicity and can affect drift, mate-finding, predator avoidance, and therefore population dynamics. We show the practical implementation of the ToxmateLab, a new device that allows monitoring the movement behavior of up to 48 organisms simultaneously, for behavioral ecotoxicology. We quantified behavioral reactions of Gammarus pulex (Amphipoda, Crustacea) after exposure to two pesticides (dichlorvos and methiocarb) and two pharmaceuticals (diazepam and ibuprofen) at sublethal, environmentally relevant concentrations. We simulated a short-term pulse contamination event that lasted 90 min. Within this short test period, we successfully identified behavioral patterns that were most pronounced upon exposure to the two pesticides: Methiocarb initially triggered hyperactivity, after which baseline behavior was restored. On the other hand, dichlorvos induced hypoactivity starting at a moderate concentration of 5 μg/L - a pattern we also found at the highest concentration of ibuprofen (10 μg/L). An additional acetylcholine esterase inhibition assay revealed no significant impact of the enzyme activity that would explain the altered movement behavior. This suggests that in environmentally realistic scenarios chemicals can induce stress - apart from mode-of-action - that affects non-target organisms' behavior. Overall, our study proves the practical applicability of empirical behavioral ecotoxicological approaches and thus represents a next step towards routine practical use.
Topics: Animals; Ecosystem; Ibuprofen; Dichlorvos; Methiocarb; Ecotoxicology; Invertebrates; Pesticides; Water Pollutants, Chemical; Amphipoda
PubMed: 37433332
DOI: 10.1016/j.scitotenv.2023.165418 -
Spectrochimica Acta. Part A, Molecular... Oct 2023The increasing use of pesticides in the agriculture fields strengthen the crop production to meet the needs of increasing population. The residues in water and food...
The increasing use of pesticides in the agriculture fields strengthen the crop production to meet the needs of increasing population. The residues in water and food materials cause several health hazards. Herein, nitrogen-doped carbon quantum dot (N-CQDs) is designed for determination of methiocarb pesticide in vegetables by fluorescent paper sensor and compared the results with fluorimetry. The fluorescent paper-based detection is performed by recording the change in fluorescence of N-CQDs with introduction of methiocarb using smartphone and ImageJ software. Good linear range was acquired for analysis of methiocarb from 10 to 1000 μgL with a low detection limit (LOD) of 3.5 μgL in fluorimetry; and 700-10,000 μgL with a LOD of 500 μgL in fluorescent paper sensor. A better recovery from 92.0 to 95.4% illustrating the selectivity of both methods for analysis of methiocarb in vegetables. Thus, the advantage of using N-CQDs as a fluorescent sensor for analysis of methiocarb in vegetables is instrument free, portable and user-friendly.
Topics: Fluorescent Dyes; Methiocarb; Vegetables; Quantum Dots; Pesticides; Nitrogen; Carbon; Smartphone; Fluorometry; Spectrometry, Fluorescence
PubMed: 37192578
DOI: 10.1016/j.saa.2023.122824 -
ACS Environmental Au Nov 2022Cell-based assays covering environmentally relevant modes of action are widely used for water quality monitoring. However, no high-throughput assays are available for...
Cell-based assays covering environmentally relevant modes of action are widely used for water quality monitoring. However, no high-throughput assays are available for testing developmental neurotoxicity of water samples. We implemented an assay that quantifies neurite outgrowth, which is one of the neurodevelopmental key events, and cell viability in human neuroblastoma SH-SY5Y cells using imaging techniques. We used this assay for testing of extracts of surface water collected in agricultural areas during rain events and effluents from wastewater treatment plants (WWTPs), where more than 200 chemicals had been quantified. Forty-one chemicals were tested individually that were suspected to contribute to the mixture effects among the detected chemicals in environmental samples. Sample sensitivity distributions indicated higher neurotoxicity for surface water samples than for effluents, and the endpoint of neurite outgrowth inhibition was six times more sensitive than cytotoxicity in the surface water samples and only three times more sensitive in the effluent samples. Eight environmental pollutants showed high specificity, and those ranged from pharmaceuticals (mebendazole and verapamil) to pesticides (methiocarb and clomazone), biocides (1,2-benzisothiazolin-3-one), and industrial chemicals (-methyl-2-pyrrolidone, 7-diethylamino-4-methylcoumarin, and 2-(4-morpholinyl)benzothiazole). Although neurotoxic effects were newly detected for some of our test chemicals, less than 1% of the measured effects were explained by the detected and toxicologically characterized chemicals. The neurotoxicity assay was benchmarked against other bioassays: activations of the aryl hydrocarbon receptor and the peroxisome proliferator-activated receptor were similar in sensitivity, highly sensitive and did not differ much between the two water types, with surface water having slightly higher effects than the WWTP effluent. Oxidative stress response mirrored neurotoxicity quite well but was caused by different chemicals in the two water types. Overall, the new cell-based neurotoxicity assay is a valuable complement to the existing battery of effect-based monitoring tools.
PubMed: 37101724
DOI: 10.1021/acsenvironau.2c00026 -
Bioelectrochemistry (Amsterdam,... Apr 2023It is highly advantageous to devise an in vitro platform that can predict the complexity of an in vivo system. The first step of this process is the identification of a...
It is highly advantageous to devise an in vitro platform that can predict the complexity of an in vivo system. The first step of this process is the identification of a xenobiotic whose monooxygenation is carried out by two sequential enzymatic reactions. Pesticides are a good model for this type of tandem reactions since in specific cases they are initially metabolised by human flavin-containing monooxygenase 1 (hFMO1), followed by cytochrome P450 (CYP). To assess the feasibility of such an in vitro platform, hFMO1 is immobilised on glassy carbon electrodes modified with graphene oxide (GO) and cationic surfactant didecyldimethylammonium bromide (DDAB). UV-vis, contact angle and AFM measurements support the effective decoration of the GO sheets by DDAB which appear as 3 nm thick structures. hFMO1 activity on the bioelectrode versus three pesticides; fenthion, methiocarb and phorate, lead to the expected sulfoxide products with K values of 29.5 ± 5.1, 38.4 ± 7.5, 29.6 ± 4.1 µM, respectively. Moreover, phorate is subsequently tested in a tandem system with hFMO1 and CYP3A4 resulting in both phorate sulfoxide as well as phoratoxon sulfoxide. The data demonstrate the feasibility of using bioelectrochemical platforms to mimic the complex metabolic reactions of xenobiotics within the human body.
Topics: Humans; Phorate; Cytochrome P-450 CYP3A; Pesticides; Sulfoxides
PubMed: 36446195
DOI: 10.1016/j.bioelechem.2022.108327 -
Analytical Methods : Advancing Methods... Aug 2022High-temperature comprehensive two-dimensional gas chromatography (HTGC × GC) using a longitudinally modulated cryogenic system (LMCS) was developed for the analysis of...
High-temperature comprehensive two-dimensional gas chromatography (HTGC × GC) using a longitudinally modulated cryogenic system (LMCS) was developed for the analysis of low-volatility pesticides in cabbage. The method applied DB-17HT and DB-5HT as the first and second dimensional (D and D) columns, respectively. Twelve pesticides, namely 6 organochlorines (4,4'-DDT, β-endosulfan, endosulfan sulfate, endrin, heptachlor, and dicofol), 4 carbamates (metolcarb, isoprocarb, methiocarb, and carbofuran), 1 organophosphate (chlorpyrifos), and 1 pyrethroid (permethrin), were spiked into cabbage samples and prepared using QuEChERS. The applied oven temperature was up to 340 °C, enabling the elution of all the target pesticides and the matrix. The effects of initial oven temperature program, temperature ramp rate, LMCS trap temperature, and modulation period () on the separation results were investigated, leading to the suitable conditions of 80 °C, 15 °C min, 10 °C, and 12 s, respectively. The method detection limits, signal-to-noise ratio, and recoveries of the compounds were within the ranges of 0.01-0.09 mg kg, 4.26-32.7, and 78-104%, respectively. Good linearity ranges within the concentration range of 0.1-1 ppm with > 0.9134 were also obtained with the intra and interday precisions of the peak areas of 0.4-9.8% and 1.0-10.2%, respectively.
Topics: Brassica; Chromatography, Gas; Hydrocarbons, Chlorinated; Pesticides; Temperature
PubMed: 35929731
DOI: 10.1039/d2ay00998f -
International Journal of Environmental... Feb 2022Pesticides are widely applied all over the world, and pesticide exposure can induce different biological effects posing a possible threat to human health. Due to their...
Pesticides are widely applied all over the world, and pesticide exposure can induce different biological effects posing a possible threat to human health. Due to their effects on the endocrine system, some pesticides are classified as endocrine disruptors. The aim of the study is to assess the interference of five pesticides on estrogen biosynthesis and estrogen signaling. Three neonicotinoid insecticides (Acetamiprid, Clothianidin, and Thiamethoxam), a carbamate insecticide (Methiocarb) and a herbicide (Oxadiazon) were tested. The effect of pesticides on estrogen biosynthesis was studied through an ELISA assay using a recombinant form of human aromatase, the enzyme that catalyzes the transformation of androgens to estrogens. Moreover, the effect of pesticides on estrogen signaling was assessed using a gene reporter assay on MELN cells, which measures estrogen receptor-mediated estrogenic activity. The results of the ELISA assay showed that the pesticides did not alter aromatase activity (no interference with estrogen biosynthesis), while the results of the gene reporter assay showed that only Methiocarb was able to alter estrogen signaling at high doses. The estrogenic activity of Methiocarb, expressed as 17β-estradiol equivalency factor (EEF), was equal to 8.0 × 10. In conclusion, this study suggested that Methiocarb should be considered a potential endocrine disruptor.
Topics: Aromatase; Endocrine Disruptors; Estrogens; Humans; Pesticides; Receptors, Estrogen
PubMed: 35206146
DOI: 10.3390/ijerph19041959