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Environmental Analysis, Health and... Mar 2024For farmers around the world to protect crops from disturbing pests, it is common to use pesticides to ward off the growth of pests or even eliminate them. Even though...
For farmers around the world to protect crops from disturbing pests, it is common to use pesticides to ward off the growth of pests or even eliminate them. Even though pesticides are seen as a good thing for protecting crops, there is one thing that mustn't be forgotten the origin of the pesticide itself is a toxin compound that is dangerous if used irresponsibly. The main concern of this study is excessive use of pesticides may cause serious consequences to the ecosystem and environment through the accumulation of pesticide residue by irresponsible farmers. To minimize the effects of pesticide residues, the selection of the type of pesticide needs to be considered which type may not be harmful to the environment's health even though accumulation happens. Therefore, in this study, a fuzzy-based computational model assessor was built to measure the safety level of pesticides toward the environment. The fuzzy model was created with consideration of several parameters related to pesticide behaviors, its effects on beneficial organisms, and its persistence in the environment. The method used for this study includes literature reviewing, fuzzification, statistical approach, expert knowledge sharing, and quantitative analysis. The model created in this study can assist in a more accurate and realistic method of selecting better pesticide options that will be used by farmers. To ensure the validity of the model, verifying and validating the formula and pesticide result assessment were done with related literature articles. In this study, from 10 types of pesticides used as a sample, dodine, and iprodione pesticides are the best option for protecting crops with a safety level of 7.36, and abamectin, dimethoate, chorpyrifos, and methidathion are not safe options for farming use because of its potential of harming the environment.
PubMed: 38631395
DOI: 10.5620/eaht.2024003 -
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 -
Toxics Sep 2023New approach methods (NAMs) can reduce the need for chronic animal studies. Here, we apply benchmark dose (concentration) (BMD(C))-response modeling to transcriptomic...
New approach methods (NAMs) can reduce the need for chronic animal studies. Here, we apply benchmark dose (concentration) (BMD(C))-response modeling to transcriptomic changes in the liver of mice and in fathead minnow larvae after short-term exposures (7 days and 1 day, respectively) to several dose/concentrations of three organophosphate pesticides (OPPs): fenthion, methidathion, and parathion. The mouse liver transcriptional points of departure (TPODs) for fenthion, methidathion, and parathion were 0.009, 0.093, and 0.046 mg/Kg-bw/day, while the fathead minnow larva TPODs were 0.007, 0.115, and 0.046 mg/L, respectively. The TPODs were consistent across both species and reflected the relative potencies from traditional chronic toxicity studies with fenthion identified as the most potent. Moreover, the mouse liver TPODs were more sensitive than or within a 10-fold difference from the chronic apical points of departure (APODs) for mammals, while the fathead minnow larva TPODs were within an 18-fold difference from the chronic APODs for fish species. Short-term exposure to OPPs significantly impacted acetylcholinesterase mRNA abundance (FDR -value <0.05, |fold change| ≥2) and canonical pathways (IPA, -value <0.05) associated with organism death and neurological/immune dysfunctions, indicating the conservation of key events related to OPP toxicity. Together, these results build confidence in using short-term, molecular-based assays for the characterization of chemical toxicity and risk, thereby reducing reliance on chronic animal studies.
PubMed: 37888672
DOI: 10.3390/toxics11100820 -
Foods (Basel, Switzerland) Sep 2023Pesticide residues in kumquat fruits from China, and the quality and chronic/acute intake risks in Chinese consumers, were assessed using the QuEChERS procedure and...
Pesticide residues in kumquat fruits from China, and the quality and chronic/acute intake risks in Chinese consumers, were assessed using the QuEChERS procedure and UHPLC-MS/MS and GC-MS/MS methods. Our 5-year monitoring and survey showed 90% of the 573 samples of kumquat fruits collected from two main production areas contained one or multiple residual pesticides. Overall, 30 pesticides were detected, including 16 insecticides, 7 fungicides, 5 acaricides, and 2 plant growth modulators, of which 2 pesticides were already banned. Two or more residual pesticides were discovered in 81% of the samples, and pesticide residues in 9.4% of the samples surpassed the , such as profenofos, bifenthrin, triazophos, avermectin, spirodiclofen, difenoconazole, and methidathion. The major risk factors on the safety of kumquat fruits before 2019 were profenofos, bifenthrin, and triazophos, but their over-standard frequencies significantly declined after 2019, which was credited to the stricter supervision and management policies by local governments. Despite the high detection rates and multi-residue occurrence of pesticides in kumquat fruits, about 81% of the samples were assessed as qualified. Moreover, the accumulative chronic diet risk determined from is very low. To better protect the health of customers, we shall formulate stricter organic phosphorus pesticide control measures and stricter use guidelines, especially for methidathion, triazophos, chlorpyrifos, and profenofos. This study provides potential data for the design of kumquat fruit quality and safety control guidelines and for the reduction in health risks to humans.
PubMed: 37761133
DOI: 10.3390/foods12183423 -
Pesticide Biochemistry and Physiology Aug 2023Methidathion is a highly effective organophosphorus pesticide and is extensively utilized for the control of insects in agricultural production. However, there is little...
Methidathion is a highly effective organophosphorus pesticide and is extensively utilized for the control of insects in agricultural production. However, there is little information on the adverse effects and underlying mechanisms of methidathion on aquatic organisms. In this work, embryonic zebrafish were exposed to methidathion at concentrations of 4, 10, and 25 mg/L for 96 h, and morphological changes and activities of antioxidant indicators alterations were detected. In addition, the locomotor behavioral abilities of zebrafish exposed to methidathion were also measured. To further explore the mechanism of the toxic effects of methidathion, gene expression levels associated with cardiac development, cell apoptosis, and the immune system were tested through qPCR assays. The findings revealed that methidathion exposure could induce a decrease in survival rate, hatchability, length of body, and increase in abnormality of zebrafish, as well as cardiac developmental toxicity. The LC value of methidathion in zebrafish embryos was determined to be about 30.72 mg/L at 96 hpf. Additionally, methidathion exposure triggered oxidative stress in zebrafish by increasing SOD activity, ROS, and MDA content. Acridine orange (AO) staining indicated that methidathion exposure led to apoptosis, which was mainly distributed in the pericardial region. Furthermore, significant impairments of locomotor activity in zebrafish larvae were induced by methidathion exposure. Lastly, the expression of pro-inflammatory factors including IFN-γ, IL-6, IL-8, CXCL-clc, TLR4, and MYD88 significantly up-regulated in exposed zebrafish. Taken together, the results in this work illustrated that methidathion caused developmental toxicity, cardiotoxicity, and immunotoxicity in embryogenetic zebrafish.
Topics: Animals; Zebrafish; Cardiotoxicity; Organophosphorus Compounds; Pesticides; Oxidative Stress; Embryo, Nonmammalian; Water Pollutants, Chemical
PubMed: 37532338
DOI: 10.1016/j.pestbp.2023.105526 -
Talanta Jan 2024Most of covalent organic frameworks (COFs) are non or weakly emissive due to either the molecular thermal motion-mediated energy dissipation or the aggregation-caused...
Most of covalent organic frameworks (COFs) are non or weakly emissive due to either the molecular thermal motion-mediated energy dissipation or the aggregation-caused quenching (ACQ) effect. Herein, we synthesize an imine-linked COF (TFPPy-TPh-COF) with high electrochemiluminescence (ECL) emission and the capability of eliminating the ACQ effect and further construct an ECL sensor for malathion detection. The imine-linked COF is obtained by the condensation reaction of (1,1':3',1″-terphenyl)-4,4″-diamine (TPh) and 1,3,6,8-tetrakis(p-formylphenyl)pyrene (TFPPy), and it has higher ECL efficiency than TFPPy aggregates due to the separation of ACQ luminophores (i.e., TFPPy) from each other by TPh and the restriction of intramolecular motions of TFPPy and TPh to reduce the nonradiative decay. The efficient quenching of ECL is achieved by electrochemiluminescence resonance energy transfer (ERET) from the excited state of the TFPPy-TPh-COF to zeolite imidazolate framework-8 (ZIF-8) and the steric hindrance of ZIF-8. Acetylcholinesterase (AChE) can enzymatically hydrolyze acetylcholine (ACh) to generate acetic acid. The resultant acetic acid can trigger the dissolution of ZIF-8 to produce an enhanced ECL signal. Malathion as an organophosphorus pesticide serves as an AChE inhibitor to prevent the production of acetic acid, inducing the decrease of ECL signal. This sensor displays a limit of detection (LOD) of 2.44 pg/mL and a wide dynamic detection range of 0.01-1000 ng/mL. Furthermore, it can be used to detect other organophosphates pesticides (e.g., methidathion, chlorpyrifos, and paraoxon) and measure malathion in real samples (i.e., pakchoi, lettuce, and apples).
Topics: Metal-Organic Frameworks; Pesticides; Organophosphorus Compounds; Malathion; Acetylcholinesterase; Luminescent Measurements; Biosensing Techniques; Electrochemical Techniques
PubMed: 37481885
DOI: 10.1016/j.talanta.2023.124964 -
RSC Advances Jun 2023Water contamination by pesticides is a critical environmental issue, necessitating the development of sustainable and efficient degradation methods. This study focuses...
Water contamination by pesticides is a critical environmental issue, necessitating the development of sustainable and efficient degradation methods. This study focuses on synthesizing and evaluating a novel heterogeneous sonocatalyst for degrading pesticide methidathion. The catalyst consists of graphene oxide (GO) decorated CuFeO@SiO nanocomposites. Comprehensive characterization using various techniques confirmed the superior sonocatalytic activity of the CuFeO@SiO-GOCOOH nanocomposite compared to CuFeO@SiO alone. The enhanced performance is attributed to the combined effects of GO and CuFeO@SiO, including increased surface area, enhanced adsorption capabilities, and efficient electron transfer pathways. Reaction parameters such as time, temperature, concentration, and pH significantly influenced the degradation efficiency of methidathion. Longer reaction times, higher temperatures, and lower initial pesticide concentrations favored faster degradation and higher efficiency. Optimal pH conditions were identified to ensure effective degradation. Remarkably, the catalyst demonstrated excellent recyclability, indicating its potential for practical implementation in pesticide-contaminated wastewater treatment. This research contributes to the development of sustainable methods for environmental remediation, highlighting the promising potential of the graphene oxide decorated CuFeO@SiO nanocomposite as an effective heterogeneous sonocatalyst for pesticide degradation.
PubMed: 37388148
DOI: 10.1039/d3ra02773b -
Journal of Mass Spectrometry : JMS Jun 2023Gas chromatography-mass spectrometry (GC-MS) with Cold EI is based on interfacing GC and MS with supersonic molecular beams (SMBs) along with electron ionization of...
Gas chromatography-mass spectrometry (GC-MS) with Cold EI is based on interfacing GC and MS with supersonic molecular beams (SMBs) along with electron ionization of vibrationally cold sample compounds in SMB in a fly-through ion source (hence the name Cold EI). Cold EI improves all the central performance aspects of GC-MS, and in this paper, we focus on its improvement of signal-to-noise ratio (S/N) and limits of detection (LODs). We found that the harder the compound for analysis with standard EI, the greater the Cold EI gain in S/N and LOD. The lower LOD and higher S/N of Cold EI emerge from a few reasons: (a) similar ionization yield as standard EI, (b) enhanced abundance of molecular ions, (c) elimination of vacuum background noise, (d) elimination of ion source-related peak tailing and degradation, (e) ability to lower the elution temperatures via the use of high column flow rates, and (f) greater range of thermally labile and low-volatility compounds that can be analyzed. We demonstrate the superior S/N and lower LOD of Cold EI versus standard EI in a range of compounds, from the simple-to-analyze octafluoronaphthalene all the way to reserpine and an organo-metallic compound that cannot be analyzed by standard EI. These compounds include methyl stearate, cholesterol, n-C H , large polycyclic aromatic hydrocarbons, dioctyl phthalates, diundecyl phthalate, pentachlorophenol, benzidine, lambda-cyhalothrin, and methidathion. The significantly lower Cold EI LODs that can be over 1000 times better than in standard EI further result in far superior response linearity and greater measurement dynamic range.
PubMed: 37271583
DOI: 10.1002/jms.4950 -
Chemosphere Aug 2023The epidemiological evidence of human exposure to organophosphorus pesticides (OPPs) with type 2 diabetes mellitus (T2DM) and prediabetes (PDM) is scarce. We aimed to...
OBJECTIVE
The epidemiological evidence of human exposure to organophosphorus pesticides (OPPs) with type 2 diabetes mellitus (T2DM) and prediabetes (PDM) is scarce. We aimed to examine the association of T2DM/PDM risk with single OPP exposure and multi-OPP co-exposure.
METHODS
Plasma levels of ten OPPs were measured using the gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) among 2734 subjects from the Henan Rural Cohort Study. We used generalized linear regression to estimate odds ratios (ORs) or β with 95% confidence intervals (CIs), and constructed quantile g-computation and Bayesian kernel machine regression (BKMR) models to investigate the association of OPPs mixture with the risk of T2DM and PDM.
RESULTS
High detection rates ranged from 76.35% (isazophos) to 99.17% (malathion and methidathion) for all OPPs. Several plasma OPPs concentrations were in positive correlation with T2DM and PDM. Additionally, positive associations of several OPPs with fasting plasma glucose (FPG) values and glycosylated hemoglobin (HbA1c) levels were observed. In the quantile g-computation, we identified significantly positive associations between OPPs mixtures and T2DM as well as PDM, and fenthion had the greatest contribution for T2DM, followed by fenitrothion and cadusafos. As for PDM, the increased risk was largely explained by cadusafos, fenthion, and malathion. Furthermore, BKMR models suggested that co-exposure to OPPs was linked to an increased risk of T2DM and PDM.
CONCLUSION
Our findings suggested that the individual and mixture of OPPs exposure were associated with an increased risk of T2DM and PDM, implying that OPPs might act an important role in the development of T2DM.
Topics: Humans; Bayes Theorem; Cohort Studies; Diabetes Mellitus, Type 2; East Asian People; Fenthion; Gas Chromatography-Mass Spectrometry; Malathion; Organophosphorus Compounds; Pesticides; Tandem Mass Spectrometry
PubMed: 37156283
DOI: 10.1016/j.chemosphere.2023.138865 -
Journal of Chromatography. A May 2023The determination of organophosphorus pesticides in urine is useful for evaluating human exposure. In this study, a simple micro-solid-phase extraction method based on a...
Rapid and simple determination of organophosphorus pesticides in urine using polydopamine-modified monolithic spin column extraction combined with liquid chromatography-mass spectrometry.
The determination of organophosphorus pesticides in urine is useful for evaluating human exposure. In this study, a simple micro-solid-phase extraction method based on a polydopamine-modified monolithic spin column combined with liquid chromatography-mass spectrometry (LC-MS) was developed for the determination of six organophosphorus pesticides (dimethoate, dichlorvos, carbofuran, methidathion, phosalone, and chlorpyrifos) in urine samples. A methacrylate polymer monolithic support was prepared in situ in the spin column, and dopamine solution was repeatedly passed through the monolith matrix via centrifugation to generate a polydopamine layer in the polymeric network. All extraction steps were performed via centrifugation. The monolith exhibited good permeability, which enabled high-flow-rate sample loading and significantly reduced the sample pre-treatment time. The addition of polydopamine significantly improved the extraction efficiency of the monolithic spin column owing to the catechol and amine groups in dopamine, which can enhance hydrogen bonding and π-π stacking. Factors affecting the extraction, including the solution pH, centrifugation speed, and desorption solvent, were investigated to determine the optimal extraction conditions. Under the optimal conditions, the OPP detection limits were 0.02-1.32 µg/L. The relative standard deviations of the single column (n = 5) and column-to-column (n = 3) precision for the extraction method were <11%. The monolithic spin column exhibited high stability and could be used for more than 40 extraction cycles. The recoveries for spiked urine samples were 72.1-109.3% (RSDs: 1.6-7.9%). The developed method was successfully applied to the simple and rapid analysis of organophosphorus pesticides in urine samples.
Topics: Humans; Organophosphorus Compounds; Chromatography, High Pressure Liquid; Pesticides; Dopamine; Chromatography, Liquid; Polymers; Mass Spectrometry; Solid Phase Extraction
PubMed: 37028207
DOI: 10.1016/j.chroma.2023.463959