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Journal of Chromatography. A Jun 2024In the past few decades, the employment of green analytical approaches in chromatographic method development has attracted the analytical separation community. The...
In the past few decades, the employment of green analytical approaches in chromatographic method development has attracted the analytical separation community. The greenness of the developed method depends upon the toxicity of solvents and the amount of generated post-analysis waste generated. In this concern, micellar liquid chromatography (MLC) is a simple and rapid technique that generates very low toxic waste compared to traditional chromatographic pesticide detection methods. Here, MLC method has been validated and applied for the determination of monocrotofos (MCF), imidacloprid (ICP), dimethoate (DM) and profenofos (PFF) in spinach and chickpea leaves. The optimized mobile phase was 0.065 M SDS-2 % 1-propanol, 0.01 M NaHPO buffered to pH 7. A C column was used for separation with a flow rate of 1 mL/min. The developed method has been validated following the guidelines of SANTE/11,312/2021 and ICH guidelines for; limit of quantification (0.05-0.20 mg/kg), linearity (r> 0.997-0.999), precision (<6.3 %), accuracy (96.3 %-99.8 %) and robustness (<6) in real samples. ICP and MCF, apart from DM and PFF, were detected in the present work. After detecting insecticides in spinach and chickpea leaves both were washed with different household chemicals i.e. normal, lukewarm, common salt, lemon juice water and commercial ozonizer. Based on five washing techniques with insecticide concentration time intervals reduction rates were calculated for each washing treatment. The results show that lemon juice, common salt water, and ozonizer can be used as washing techniques for the reduction of superficial and systematic residues of ICP and MCF. Common salt and lemon juice water were better for washing over vinegar and potassium permanganate (KMnO) as they enhance the colour of the green leafy vegetables and are available in every Indian kitchen. They can be easily used by lower socioeconomic classes who cannot afford KMnO and vinegar.
PubMed: 38908066
DOI: 10.1016/j.chroma.2024.465043 -
Chemosphere Jun 2024In the last years, issues related to intensive agriculture have been found in protected areas potentially harming wildlife. This study aimed to analyze a wide range of...
In the last years, issues related to intensive agriculture have been found in protected areas potentially harming wildlife. This study aimed to analyze a wide range of pesticides in water and sediments of two protected areas namely Doñana Natural Park (DNP) and Tablas de Daimiel National Park (TDNP) performing an environmental risk assessment in order to highlight potential risks to living organisms derived from pesticide burden. Higher pesticide load was found in DNP than TDNP with similar distribution profiles, with pyrethroid insecticides (PYRs) the main detected class. Particularly problematic are two PYRs, cyhalothrin and fenvalerate, which were detected at high concentrations that can pose a high risk to aquatic organisms. In addition, despite being detected at lower concentrations, the presence of chlorpyrifos, cypermethrin, and permethrin in water, and of chlorpyrifos, dicofol, and diflufenican in sediments, must be taken into account due to their potential risks for aquatic organisms. Moreover, some banned pesticides such as dimethoate, terbutryn, diazinon, and tricyclazol were detected in water at levels which deserve further investigation to assess their potential sources, including potential illegal practices.
PubMed: 38885764
DOI: 10.1016/j.chemosphere.2024.142628 -
Pesticide Biochemistry and Physiology Jun 2024Sitobion miscanthi is a destructive wheat pest responsible for significant wheat yield losses. Pirimicarb, one of the most important representatives of N,...
Sitobion miscanthi is a destructive wheat pest responsible for significant wheat yield losses. Pirimicarb, one of the most important representatives of N, N-dimethylcarbamate insecticides, is widely used to control wheat aphids. In present work, heterozygous S431F mutation of acetylcholinesterase 1 (AChE1) was identified and verified in three pirimicarb-resistant S. miscanthi populations (two field populations (HA and HS, >955.8-fold) and one lab-selected population (PirR, 486.1-fold)), which has not been reported in S. miscanthi yet. The molecular docking results revealed that AChE1 containing the S431F mutation of S. miscanthi (SmAChE1) showed higher free binding energy to three insecticides (pirimicarb, omethoate, and methomyl) than wild-type AChE1 of S. miscanthi (SmAChE1). Enzyme kinetic and inhibition experiments showed that the recombinant SmAChE1 was more insensitive to pirimicarb and omethoate than the recombinant SmAChE1. Furthermore, two overexpression P450 genes (CYP6K1 and CYP6A14) associated with pirimicarb resistance of S. miscanthi were verified by RNAi. These results suggested both target alteration and enhanced metabolism contributed to high pirimicarb resistance of S. miscanthi in the field and laboratory. These findings lay a foundation for further elucidating the mechanism of pirimicarb resistance in S. miscanthi, and have important implications for the resistance management of S. miscanthi control.
Topics: Acetylcholinesterase; Animals; Insecticide Resistance; Aphids; Insecticides; Carbamates; Cytochrome P-450 Enzyme System; Mutation; Pyrimidines; Molecular Docking Simulation; Triticum; Dimethoate
PubMed: 38879339
DOI: 10.1016/j.pestbp.2024.105957 -
The Science of the Total Environment Sep 2024Spatiotemporal monitoring of pesticide residues in river water is urgently needed due to its negative environmental and human health consequences. The present study is...
Spatiotemporal distribution, ecological risk assessment, and human health implications of currently used pesticide (CUP) residues in the surface water of Feni River, Bangladesh.
Spatiotemporal monitoring of pesticide residues in river water is urgently needed due to its negative environmental and human health consequences. The present study is to investigate the occurrence of multiclass pesticide residue in the surface water of the Feni River, Bangladesh, using an optimized salting-out assisted liquid-liquid microextraction (SALLME) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS). The optimized SALLME method was developed and validated following the SANTE/11312/2021 guidelines. A total of 42 water samples were collected and analyzed to understand the spatiotemporal distribution of azoxystrobin (AZ), buprofezin (BUP), carbofuran (CAR), pymetrozine (PYM), dimethoate (DMT), chlorantraniliprole (CLP), and difenoconazole (DFN). At four spike levels (n = 5) of 20, 40, 200, and 400 μg/L, the recovery percentages were satisfactory, ranging between 71.1 % and 107.0 % (RSD ≤13.8 %). The residues ranged from below the detection level (BDL) to 14.5 μg/L. The most frequently detected pesticide was DMT (100 %), followed by CLP (52.3809-57.1429), CAR (4.7619-14.2867), and PYM (4.7619-9.5238). However, AZ and BUP were below the detection limit in the analyzed samples of both seasons. Most pesticides and the highest concentrations were detected in March 2023, while the lowest concentrations were present in August 2023.Furthermore, ecological risk assessment based on the general-case scenario (RQ) and worst-case scenario (RQ) indicated a high (RQ > 1) risk to aquatic organisms, from the presence of PYM and CLP residue in river water. Human health risk via dietary exposure was estimated using the hazard quotient (HQ). Based on the detected residues, the HQ (<1) value indicated no significant health risk. This report provides the first record of pesticide residue occurrences scenario and their impact on the river environment of Bangladesh.
Topics: Bangladesh; Water Pollutants, Chemical; Rivers; Pesticide Residues; Risk Assessment; Environmental Monitoring; Humans; Tandem Mass Spectrometry; Chromatography, Liquid; Spatio-Temporal Analysis; Liquid Phase Microextraction
PubMed: 38871333
DOI: 10.1016/j.scitotenv.2024.173857 -
Experimental & Applied Acarology Jun 2024Phytoseiulus longipes is a predatory mite of Tetranychus evansi, which is an invasive pest in Africa and elsewhere. The introduction of this predator in Africa has...
Phytoseiulus longipes is a predatory mite of Tetranychus evansi, which is an invasive pest in Africa and elsewhere. The introduction of this predator in Africa has considerable potential, but little is known about the compatibility of P. longipes with commonly used pesticides. Here, we examined lethal and sublethal effects of two pyrethroids (cypermethrin and deltamethrin), two organophosphates (dimethoate and chlorpyrifos), one nicotinoid (imidacloprid), two acaricides (propargite and abamectin), two naturally derived pesticides (oxymatrine and azadirachtin), and one entomopathogenic fungal-based formulation (Hirsutella thompsonii) on P. longipes eggs and adults. The pesticides were sprayed at their maximum recommended concentrations. Topical exposures to azadirachtin, imidacloprid, propargite, abamectin, oxymatrine, and H. thompsonii significantly reduced the net reproductive rate (R), intrinsic rate of increase (r) and finite rate of increase (λ)of P. longipes. Pesticide lethal and sublethal effects on the predator were summarized in a reduction coefficient (E) for the classification based on IOBC toxicity categories. Results revealed that Azadirachtin and H. thompsonii were slightly harmful effects to adults. Imidacloprid, propargite, abamectin, and oxymatrine were moderately harmful to both eggs and adults. Residual persistence bioassays revealed that 4-day-old residue of azadirachtin had no harmful effect on the predator. Abamectin, oxymatrine, and H. thompsonii became harmless to it 10 days post-spraying, and propargite and imidacloprid were considered harmless after 20 days. Cypermethrin, deltamethrin, dimethoate, and chlorpyrifos were highly harmful to both eggs and adults, persistence remaining high even after 31 days of application. These findings provide valuable insights into decision-making when considering P. longipes for use in IPM programs.
PubMed: 38869728
DOI: 10.1007/s10493-024-00926-3 -
Environmental Science and Pollution... Jun 2024Bacillus genera, especially among rhizobacteria, are known for their ability to promote plant growth and their effectiveness in alleviating several stress conditions....
Microbial detoxification of chlorpyrifos, profenofos, monocrotophos, and dimethoate by a multifaceted rhizospheric Bacillus cereus strain PM38 and its potential for the growth promotion in cotton.
Bacillus genera, especially among rhizobacteria, are known for their ability to promote plant growth and their effectiveness in alleviating several stress conditions. This study aimed to utilize indigenous Bacillus cereus PM38 to degrade four organophosphate pesticides (OPs) such as chlorpyrifos (CP), profenofos (PF), monocrotophos (MCP), and dimethoate (DMT) to mitigate the adverse effects of these pesticides on cotton crop growth. Strain PM38 exhibited distinct characteristics that set it apart from other Bacillus species. These include the production of extracellular enzymes, hydrogen cyanide, exopolysaccharides, Indol-3-acetic acid (166.8 μg/mL), siderophores (47.3 μg/mL), 1-aminocyclopropane-1-carboxylate deaminase activity (32.4 μg/mL), and phosphorus solubilization (162.9 μg/mL), all observed at higher concentrations. This strain has also shown tolerance to salinity (1200 mM), drought (20% PEG-6000), and copper and cadmium (1200 mg/L). The amplification of multi-stress-responsive genes, such as acdS, ituC, czcD, nifH, sfp, and pqqE, further confirmed the plant growth regulation and abiotic stress tolerance capability in strain PM38. Following the high-performance liquid chromatography (HPLC) analysis, the results showed striking compatibility with the first kinetic model. Strain PM38 efficiently degraded CP (98.4%), PF (99.7%), MCP (100%), and DMT (95.5%) at a concentration of 300 ppm over 48 h at 35 °C under optimum pH conditions, showing high coefficients of determination (R) of 0.974, 0.967, 0.992, and 0.972, respectively. The Fourier transform infrared spectroscopy (FTIR) analysis and the presence of opd, mpd, and opdA genes in the strain PM38 further supported the potential to degrade OPs. In addition, inoculating cotton seedlings with PM38 improved root length under stressful conditions. Inoculation of strain PM38 reduces stress by minimizing proline, thiobarbituric acid-reactive compounds, and electrolyte leakage. The strain PM38 has the potential to be a good multi-stress-tolerant option for a biological pest control agent capable of improving global food security and managing contaminated sites.
Topics: Chlorpyrifos; Bacillus cereus; Monocrotophos; Dimethoate; Gossypium; Biodegradation, Environmental; Organothiophosphates; Rhizosphere; Phosphoramides
PubMed: 38831144
DOI: 10.1007/s11356-024-33804-x -
Food Chemistry Sep 2024Pesticide residues in agricultural products pose a significant threat to human health. Herein, a sensitive fluorescence method employing upconversion nanoparticles was...
Pesticide residues in agricultural products pose a significant threat to human health. Herein, a sensitive fluorescence method employing upconversion nanoparticles was developed for detecting organophosphorus pesticides (OPs) based on the principle of enzyme inhibition and copper-triggered o-phenylenediamine (OPD) oxidation. Copper ions (Cu) oxidized the colorless OPD to a yellow 2,3-diaminophenazine (oxOPD). The yellow solution oxOPD quenched the fluorescence of upconversion nanoparticles due to the fluorescence resonance energy transfer. The high affinity of Cu for thiocholine reduced the level of oxOPD, resulting in almost no fluorescence quenching. The addition of dimethoate led to the inhibition of acetylcholinesterase activity and thus prevented the formation of thiocholine. Subsequently, Cu oxidized OPD to form oxOPD, which attenuated the fluorescence signal of the system. The detection system has a good linear range of 0.01 ng/mL to 50 ng/mL with a detection limit of 0.008 ng/mL, providing promising applications for rapid detection of dimethoate.
Topics: Copper; Oxidation-Reduction; Phenylenediamines; Dimethoate; Acetylcholinesterase; Pesticides; Nanoparticles; Limit of Detection; Biosensing Techniques; Fluorescence; Cholinesterase Inhibitors
PubMed: 38759443
DOI: 10.1016/j.foodchem.2024.139666 -
Mikrochimica Acta May 2024The high-residual and bioaccumulation property of organophosphorus pesticides (OPs) creates enormous risks towards the ecological environment and human health, promoting...
The high-residual and bioaccumulation property of organophosphorus pesticides (OPs) creates enormous risks towards the ecological environment and human health, promoting the research for smart adsorbents and detection methods. Herein, 2D hemin-bridged MOF nanozyme (2D-ZHM) was fabricated and applied to the efficient removal and ultrasensitive dual-mode aptasensing of OPs. On the one hand, the prepared 2D-ZHM contained Zr-OH groups with high affinity for phosphate groups, endowing it with selective recognition and high adsorption capacity for OPs (285.7 mg g for glyphosate). On the other hand, the enhanced peroxidase-mimicking biocatalytic property of 2D-ZHM allowed rapid HO-directed transformation of 3,3',5,5'-tetramethylbenzidine to oxidic product, producing detectable colorimetric or photothermal signals. Using aptamers of specific recognition capacity, the rapid quantification of two typical OPs, glyphosate and omethoate, was realized with remarkable sensitivity and selectivity. The limit of detections (LODs) of glyphosate were 0.004 nM and 0.02 nM for colorimetric and photothermal methods, respectively, and the LODs of omethoate were 0.005 nM and 0.04 nM for colorimetric and photothermal methods, respectively. The constructed dual-mode aptasensing platform exhibited outstanding performance for monitoring OPs in water and fruit samples. This work provides a novel pathway to develop MOF-based artificial peroxidase and integrated platform for pollutant removal and multi-mode aptasensing.
Topics: Pesticides; Metal-Organic Frameworks; Hemin; Limit of Detection; Glycine; Glyphosate; Colorimetry; Benzidines; Adsorption; Water Pollutants, Chemical; Hydrogen Peroxide; Dimethoate; Aptamers, Nucleotide; Organophosphorus Compounds
PubMed: 38727763
DOI: 10.1007/s00604-024-06398-x -
Chemosphere Jul 2024In the conventional drinking water treatment process (CDWTP), powdered activated carbon (PAC) is commonly used for removing organic pesticides, or other organic...
In the conventional drinking water treatment process (CDWTP), powdered activated carbon (PAC) is commonly used for removing organic pesticides, or other organic contaminants. However, the hydraulic retention time (HRT) in CDWTP is insufficient for fulfilling PAC adsorption equilibrium to realize its full capacity. This study examined the adsorption kinetics, adsorption thermal dynamics, and removal efficiency for six organic pesticides using the ball-milled PAC (BPAC) with varying particle sizes in CDWTP. Based on the experiments with the pesticides of atrazine, diazinon, dimethoate, fenitrothion, isoproturon and thiometon, the results indicated that as the particle size reduced from around 38 μm for the commercial PAC to 1 μm for the BPAC, the adsorption rates for hydrophobic pesticides increased up to twentyfold. Diffusional adsorption from the bulk solution to the external PAC surface is the most likely predominant mechanism. This could allow a sufficient pesticides' adsorption within the limited HRT and to achieve a great depth removal of these toxic compounds. However, the addition of BPAC with a diameter of 1 μm was observed to significantly increase residual particles in treated water after the conventional treatment process. With a further systematic evaluation of both adsorption rate and particle penetration, a particle size of around 6 μm BPAC was considered a practical compromise between the adsorption rate and particle penetration for real application. Results from five surface waters of different water quality indicated that, compared to commercial PAC, application of 6 μm BPAC could achieve up to a 75% reduction in adsorbent dosage while maintaining around the same pesticide removal efficiencies. Additionally, thermodynamic analyses suggest that adsorption of these pesticides could be enthalpically or entropically driven depending on the degree of pesticide hydrophobicity.
Topics: Pesticides; Water Pollutants, Chemical; Adsorption; Water Purification; Charcoal; Drinking Water; Kinetics; Atrazine; Carbon
PubMed: 38723688
DOI: 10.1016/j.chemosphere.2024.142229 -
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