A tailored dual core-shell magnetic SERS substrate with precise shell-thickness control for trace organophosphorus pesticides residues detection.

For addressing the challenges of strong affinity SERS substrate to organophosphorus pesticides (OPs), herein, a rapid water-assisted layer-by-layer heteronuclear growth method was investigated to grow uniform UiO-66 shell with controllable thickness outside the magnetic core and provide abundant defect sites for OPs adsorption. By further assembling the tailored Au@Ag, a highly sensitive SERS substrate Fe3O4-COOH@UiO-66/Au@Ag (FCUAA) was synthesized with a SERS enhancement factor of 2.11 × 107. The substrate's suitability for the actual vegetable samples (cowpeas and peppers) was confirmed under both destructive and non-destructive detection conditions, showing a strong SERS response to fenthion and triazophos, with limits of detection of 1.21 × 10-5 and 2.96 × 10-3 mg/kg in the vegetables under destructive conditions, and 0.13 and 1.39 ng/cm2 for non-destructive detection, respectively. The FCUAA substrate had high SERS performance, effective adsorption capability for OPs, and demonstrated good applicability, thus exhibiting great potential for rapid detection of trace OPs residues in the food industry.

Effects of the pyriproxyfen and fenthion on the gonadal morphology of Nile tilapia (Oreochromis niloticus: Perciformes, Cichlidae).

Commercially available insecticides present acute toxicity to the health of fish and other aquatic organisms, which may impair the local aquaculture. This study evaluated the gonadal morphology of freshwater fish exposed to pyriproxyfen and fenthion. Forty-five juvenile male Nile tilapias (Oreochromis niloticus) were divided into control, pyriproxyfen-exposed (0.01 g/L), and fenthion-exposed (0.001 g/L) groups. They were evaluated in three moments (30, 60, and 90 days). The variables analyzed were the gonadosomatic index (GSI), weight to length ratio, seminiferous tubules morphometry (diameter and height), tissue damage, and immunohistochemical analysis for caspase-3, tumor necrosis factor alpha (TNF-α), and vascular endothelial growth factor (VEGF). Pyriproxyfen and fenthion injured the seminiferous tubule tissue, and the damage progressed according to the exposure time. In addition, the GSI gradually reduced over time in all groups compared with the first moment (30 days), while caspase-3, TNF-α, and VEGF values increased only in the fenthion-exposed group. Therefore, pyriproxyfen and fenthion changed the gonadal morphology of male Oreochromis niloticus, which may affect their reproduction in the wild or captivity.

Evaluation of insecticide resistance among Malaysian Aedes albopictus Skuse larvae based on revised diagnostic doses of larvicides.

The susceptibility levels of Malaysian Aedes albopictus larvae sampled from several agricultural, fogging-free residential and dengue prone residential areas against different larvicides were evaluated using revised diagnostic doses derived from the 2xLC99 values of the reference strain. Upon 24-hour recovery period of WHO larval bioassay, incipient resistance was observed among Ae. albopictus larvae from rubber estates against fenitrothion (96.67% mortality) and permethin (97.00% mortality) while Ae. albopictus larvae from rice cultivation areas were moderately resistant to fenthion (94.33% mortality). Aedes albopictus larvae from dengue prone residential areas developed moderate to high resistance against dichlorodiphenyltrichloroethane (DDT), fenitrothion, fenthion, propoxur and permethrin (79.67% - 97.33% mortality). Moderate to high resistance were also demonstrated among all populations of Ae. albopictus larvae against temephos and chlorpyrifos (63.00% - 97.67% mortality). Except for Ae. albopictus larvae from oil palm plantations, all Ae. albopictus larval populations were also highly resistant to bendiocarb (65.67% - 89.67% mortality). Cross resistance between larvicides from similar and different insecticide classes were also revealed in this study. The use of revised diagnostic doses established from the local reference strain could reduce the possibility of underestimation or overestimation of the insecticide susceptibility status of field strain populations.

Simultaneous determination of fenthion and its metabolites in a case of fenthion self-poisoning.

Fenthion (MPP) is a popular organophosphorus pesticide that acts via inhibition of the enzyme cholinesterase. It is well known that fenthion is metabolized by plants, animals and soil microorganisms to sulfone and sulfoxide by oxidation of thioether and is further metabolized by conversion of P = S to P = O (oxon). Although human fenthion poisonings sometimes occur, details of the distribution of fenthion and its metabolites within the bodies of victims are unclear. In this study, we developed and validated an approach that uses liquid chromatography coupled with electrospray ionization-tandem mass spectrometry to quantify the concentrations of fenthion and its five metabolites (MPP-sulfoxide, MPP-sulfone, MPP-oxon, MPP-oxon sulfoxide and MPP-oxon sulfone) in the fluids [blood, cerebral spinal fluid (CSF) and urine] of a human cadaver. The calibration curves were linear in the concentration range 5-200 ng/mL. Our method allowed for repeatable and accurate quantification with intra- and inter-assay coefficients of variation smaller than 8.6% and 11.0%, respectively, for each target compound. We used the developed method to measure the fenthion concentration in the blood of a dead victim of fenthion poisoning and found the concentration to be in the comatose-fatal range. In addition, we detected for the first time fenthion and all five fenthion metabolites in the cadaveric blood and CSF. The concentrations of the oxidized forms of fenthion, including MPP-sulfone and MPP-sulfoxide, were higher in CSF than in the blood.

Heterogeneous kinetics of the OH-initiated degradation of fenthion and parathion.

Fenthion and parathion are two representative kinds of organophosphorus pesticides and widely used in agriculture. They are directly or indirectly released into the atmosphere by spraying or volatilization processes. However, their heterogeneous reactivity toward OH radicals has not yet been well understood. Therefore, this work investigated the heterogeneous kinetics of the OH-initiated degradation of surface-bound fenthion and parathion using a flow reactor. The results showed that OH radicals played an important role in the atmospheric degradation of fenthion and parathion. Their average rate constants were (7.20 ± 0.77) × 10-12 and (10.40 ± 0.60) × 10-12 cm3/(mol· sec) at a relative humidity (RH) and temperature of 35% and 20 °C, respectively, suggesting that they have relatively short lifetimes in the atmosphere. In addition, a negative RH dependence and a positive temperature dependence of the rate constants were observed. The Arrhenius expressions of fenthion and parathion were k2 = (1.34 ± 0.48) × 10-9exp[-(1432.59 ± 105.29)/T] and k2 = (1.96 ± 1.38) × 10-9exp[-(1619.98 ± 222.02)/T], respectively, and their overall activation energy was estimated to be (11.88 ± 0.87) and (13.48 ± 1.83) kJ/mol. The experimental results will update the kinetic data of fenthion and parathion in the atmosphere and be helpful to further understand their atmospheric transportation processes.

Effects of acaricides on the activities of monooxygenases in bovine liver microsomes.

Organophosphates (OPs), pyrethrins and fipronil, are acaricides commonly used in cattle, mainly as pour on formulations. Scant information is available on their potential interactions with hepatic xenobiotic metabolizing enzymes. This work aimed to evaluate in vitro the potential inhibitory effects of widely employed acaricides on catalytic activities mediated by hepatic cytochrome P450 (CYP) and flavin-monooxygenase (FMO) enzymes in cattle. Bovine (n = 4) liver microsomes were incubated in the absence (control assays) and in presence of different OPs (fenthion, chlorpyrifos, ethion, diazinon and dichlorvos), fipronil and cypermethrin at 0.1-100 µm. Five oxidative enzyme activities were assayed by spectrofluorimetric or HPLC methods: 7-ethoxyresorufin O-deethylase (for CYP1A1), methoxyresorufin O-demethylase (for CYP1A2), benzyloxyresorufin O-debenzylase (for CYP2B), testosterone 6-beta hydroxylase (for CYP3A) and benzydamine N-oxidase (for FMO). All acaricides, particularly phosphorothionate-containing OPs, inhibited to some extent more than one enzyme activity. The most frequent inhibitor was fenthion, which inhibited (p < .05) all enzyme activities tested (from 22% at 1 µm to 72% at 100 µm). However, low inhibitory potencies (IC50s higher than 7 µm) of all acaricides studied were observed against the catalytic activities assayed. Therefore, the risk of in vivo metabolic interactions due to inhibition of monooxygenases would be low under common husbandry conditions.

Co-exposure of organophosphorus pesticides is associated with increased risk of type 2 diabetes mellitus in a Chinese population.

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 ß 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.

Lanthanum ions assisted non-enzymatic ratiometric fluorescence probe for monitoring fenthion residues in agro-product samples.

In this work, a La3+ assisted glutathione-capped gold nanoclusters and carbon dots (GSH-Au NCs/CDs) nanoplatform for sensitive detection of fenthion (FEN) is fabricated. The fluorescence response of GSH-Au NCs significantly increases due to aggregation-induced emission enhancement (AIEE) effect induced by La3+, which is further enhanced with adding FEN due to the coordination between La3+ and FEN. Taking the fluorescence intensity of CDs as the signal background, the ratiometric fluorescence of GSH-Au NCs and CDs has a good linear relationship with the FEN concentration from 0.01 to 1.10 µg mL-1, and detecting FEN exhibits a good sensitivity at a low detection limit of 6.74 ng g-1. The La3+ assisted GSH-Au NCs/CDs nanoplatform demonstrates desirable selectivity and applicability for monitoring trace level of FEN in fruit and vegetable samples. The non-enzymatic strategy by taking advantage of successive AIEE of GSH-Au NCs has a great potential for facile screening organophosphate pesticides in agro-products.

Exposure to organophosphorus compounds of Japanese children and the indoor air quality in their residences.

Several organophosphorus compounds such as organophosphate pesticides (OPPs) and trialkylphosphates (TAPs) are suspected to inhibit cholinesterase activities, to affect endocrine systems or to possibly be carcinogenic. To evaluate their adverse effects on health with chronic exposure in the general population, especially in children, we measured the household exposure to OPPs and TAPs by Japanese children via all exposure pathways and the contribution of indoor air quality. First-morning void urine was collected from subjects aged 6 to 15 years (n = 132), and airborne organophosphorus compounds were sampled in the subject's bedroom for 24 h. Airborne levels of nine OPPs and three TAPs and their urinary metabolites were determined. No significant correlations were detected for any compounds between their airborne concentrations and the urinary excretion amounts of their corresponding metabolites. The estimated daily intakes were as follows (median, µg/kg b.w./d): chlorpyrifos, 0.042; diazinon, 0.067; tri-n-butylphosphate, 0.094. The 95th percentiles of the intakes for fenthion, fenitrothion and the above three compounds did not exceed their reference limit values, although one subject had a daily intake of tri-n-butylphosphate that was about twice its reference limit value. The concentration levels of the urinary metabolite of tri-n-butylphosphate in our subjects tended to be higher than those for children in many other countries. The fractions of the amounts absorbed by inhalation to the amounts absorbed via all of the exposure pathways was only 2.3 % (median) for tri-n-butylphosphate. Inhalation did not seem to contribute very much as an absorption pathway of the organophosphorus compounds in these Japanese children while they were at home. The exposure amounts of OPPs were not suggested to be high enough to adversely affect the health of these children at present on the basis of their daily intakes compared to their reference limit values.

Pesticide Residues in Commonly Consumed Vegetables in Henan Province of China in 2020.

Background: Pesticides are widely used in agricultural production to control insect pests and regulate plant growth in China, which may result in the presence of some pesticide residues in the vegetables. However, few studies of monitoring pesticides have been conducted in Henan Province. The aim of this study was to evaluate the level of pesticide residues in commonly consumed vegetables in the regions of Henan Province. Methods: In this study, we collected 5,576 samples of 15 different vegetables in 17 areas from Henan Province during 2020. Eight kinds of pesticides were analyzed by gas chromatography-mass spectrometry (GC-MS), including procymidone, lambda-cyhalothrin, cypermethrin, pendimethalin, isocarbophos, isazophos, fenthion and deltamethrin. The chi-square test was used to compare the detection rates of pesticide residues in different regions. Results: Of all the pesticides above, procymidone, lambda-cyhalothrin, cypermethrin, pendimethalin and isocarbophos were detected in vegetables, the detection rates were 27.0%, 16.2%, 11.4%, 3.5%, and 1.9%, respectively. However, isazophos, fenthion, and deltamethrin were not detected. In addition, procymidone, lambda-cyhalothrin, and cypermethrin were detected in urban areas, while pendimethalin was detected in rural areas. The detection rates of cypermethrin and pendimethalin in rural were 19.8% and 5.4%, respectively, which in urban were at relatively lower levels (13.7% and 1.9%, respectively) (P < 0.05). Compared the differences of pesticide detection rates among five areas of Henan province, we found that there were statistical differences in the detection rates of procymidone, cypermethrin and lambda-cyhalothrin in different regions (all P < 0.05). Conclusion: The results have revealed that the pesticide residues are present. Higher detection rates and more types of pesticides were found in rural areas than urban areas. In addition, there were higher detection rates in Eastern Henan. The findings provided valuable information on the current pesticide residues status, which can be a reference of pesticide supervision and management.

[Determination of organophosphorus pesticide residues in milk of cows and sheep by ultra-high-performance liquid chromatography- tandem mass spectrometry combined with passing type purification method].

OBJECTIVE: A method for the rapid determination of dichlorvos, trichlorfon, fenthion, fenthion-sulfone, fenthion-sulfoxide, fenthion-oxon, fenthion-oxon-sulfone, fenthion-oxon-sulfoxide, phoxim, propetamphos, malathion, diazinon and coumaphos 13 common organophosphorus pesticides and their metabolites poison residues in milk of cows and sheep by ultra-high-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) with passing type solid phase extraction(SPE) purification was developed. METHODS: After centrifugation at 4 ℃, the milk was purified by passing type SPE with acetonitrile precipitating protein and determined by UPLC-MS/MS in electrospray positive ion mode(ESI+) and multi-reaction monitoring scanning(MRM), external standard method for quantitative analysis with matrix matching standard curve. RESULTS: The recoveries of 13 target compounds were between 81.5% and 107.5% and relative standard deviation was between 1.24% and 6.23% at three spiked levels of 5, 10, 20 µg/L. The detection limits of 13 target compounds were between 0.015 and 0.15 µg/L, and the quantitative limits were between 0.05 and 0.50 µg/L. No organophosphorus pesticide residues were detected in 20 samples of cows and sheep milk. CONCLUSION: The method has the advantages of good linear independence, low detection limit, high precision and accuracy, and can be used for daily monitoring of milk and related products.

Facile synthesis disposable MOF membrane filter: Growth of NH2-MIL-125 (Ti) on filter paper for fast removal of organophosphorus pesticides in aqueous solution and vegetables.

Metal-organic frameworks (MOFs) have great potential to remove pesticide residues. However, the lack of affinity between the materials and target and the process of trivial sample preparation resulted in limited removal efficiency. Here, we report a one-pot method for the fast preparation of NH2-MIL-125 (Ti)-based filter paper to synthesise NH2-MIL-125 (Ti)-based filter paper membranes. The NH2-MIL-125 (Ti)-based filter paper membrane takes advantage of π-π interactions between the organophosphorus pesticides (OPPs) and the benzene ring of MOFs. The affinity of amino groups and metal Ti for phosphorus atoms in the OPPs exhibits rapid removal efficiency for three OPPs, imidan, fenthion, and fenitrothion. The isothermal adsorption results for imidan, fenthion, and fenitrothion were consistent with the Langmuir, Freundlich, and Langmuir models, respectively. The kinetic results for imidan, fenthion, and fenitrothion agreed with the pseudo-second-order kinetic model, and the removal efficiency reached equilibrium within 1 min. There was no significant change in the adsorption capacity of OPPs in different pH solutions (pH = 2-10). Compared with that of MOFs, the NH2-MIL-125 (Ti)-based filter paper membrane removal efficiency of OPPs is the same, and it also has better removal efficiency in actual spinach samples. As a result, the sample pretreatment procedure was simplified using a low-cost and simple-to-synthesize disposable NH2-MIL-125 (Ti)-based filter paper membrane, samples' quick separation and the simultaneous fast removal of OPPs.

Genomic comparisons between hepatocarcinogenic and non-hepatocarcinogenic organophosphate insecticides in the mouse liver.

Short-term biomarkers of toxicity have an increasingly important role in the screening and prioritization of new chemicals. In this study, we examined early indicators of liver toxicity for three reference organophosphate (OP) chemicals, which are among the most widely used insecticides in the world. The OP methidathion was previously shown to increase the incidence of liver toxicity, including hepatocellular tumors, in male mice. To provide insights into the adverse outcome pathway (AOP) that underlies these tumors, effects of methidathion in the male mouse liver were examined after 7 and 28 day exposures and compared to those of two other OPs that either do not increase (fenthion) or possibly suppress liver cancer (parathion) in mice. None of the chemicals caused increases in liver weight/body weight or histopathological changes in the liver. Parathion decreased liver cell proliferation after 7 and 28 days while the other chemicals had no effects. There was no evidence for hepatotoxicity in any of the treatment groups. Full-genome microarray analysis of the livers from the 7 and 28 day treatments demonstrated that methidathion and fenthion regulated a large number of overlapping genes, while parathion regulated a unique set of genes. Examination of cytochrome P450 enzyme activities and use of predictive gene expression biomarkers found no consistent evidence for activation of AhR, CAR, PXR, or PPARα. Parathion suppressed the male-specific gene expression pattern through STAT5b, similar to genetic and dietary conditions that decrease liver tumor incidence in mice. Overall, these findings indicate that methidathion causes liver cancer by a mechanism that does not involve common mechanisms of liver cancer induction.

Human flavin-containing monooxygenase 1 and its long-sought hydroperoxyflavin intermediate.

Out of the five isoforms of human flavin-containing monooxygenase (hFMO), FMO1 and FMO3 are the most relevant to Phase I drug metabolism. They are involved in the oxygenation of xenobiotics including drugs and pesticides using NADPH and FAD as cofactors. Majority of the characterization of these enzymes has involved hFMO3, where intermediates of its catalytic cycle have been described. On the other hand, research efforts have so far failed in capturing the same key intermediate that is responsible for the monooxygenation activity of hFMO1. In this work we demonstrate spectrophotometrically the formation of a highly stable C4a-hydroperoxyflavin intermediate of hFMO1 upon reduction by NADPH and in the presence of O2. The measured half-life of this flavin intermediate revealed it to be stable and not fully re-oxidized even after 30 min at 15 °C in the absence of substrate, the highest stability ever observed for a human FMO. In addition, the uncoupling reactions of hFMO1 show that this enzyme is <1% uncoupled in the presence of substrate, forming small amounts of H2O2 with no observable superoxide as confirmed by EPR spin trapping experiments. This behaviour is different from hFMO3, that is shown to form both H2O2 and superoxide anion radical as a result of ∼50% uncoupling. These data are consistent with the higher stability of the hFMO1 intermediate in comparison to hFMO3. Taken together, these data demonstrate the different behaviours of these two closely related enzymes with consequences for drug metabolism as well as possible toxicity due to reactive oxygen species.

In situ growth of copper-based metal-organic framework on a helical shape copper wire as a sorbent in stir-bar sorptive extraction of fenthion followed by corona discharge ion mobility spectrometry.

In this paper, a helical copper wire, coated with copper-benzene-1,4-dicarboxylic acid metal-organic framework (Cu-BDC) was used as a sorbent for stir-bar sorptive extraction of fenthion from water and fruit samples. The homogenous coating was fabricated through two simple and fast steps. The chemical conversion of copper substrate to copper hydroxide nanotubes (Cu(OH)2 NTs) was performed in an alkaline solution and then Cu-BDC was formed through a neutralization reaction. Corona discharge ion mobility spectrometry in positive mode was applied for the detection of fenthion. To improve the sensitivity of the method, some synthesis and extraction parameters affecting the extraction efficiency such as benzene-1,4-dicarboxylic acid concentration, ionic strength, sample pH, stirring rate, extraction temperature, and extraction time were investigated. The linear dynamic range between 0.5 and 80 µg L-1 and detection limit of 0.1 µg L-1 were obtained under optimal conditions. The intra- and inter-day relative standard deviations were less than 6.4 and 8.6%, respectively. The applicability of the method was examined for the analysis of different samples (i.e., well water, agricultural wastewater, and orange). The recovery for the determination of fenthion in spiked samples varied from 88 to 111%.

Magnetic Fe3O4@SiO2@ß-cyclodextrin for solid phase extraction of methyl parathion and fenthion in lettuce samples.

In this study, magnetic Fe3O4@SiO2@ß-cyclodextrin copolymerized microparticles were synthesized and applied for the extraction of methyl parathion and fenthion in lettuce samples followed by HPLC-UV detection. The magnetic ß-cyclodextrin copolymerized microparticles were prepared by dispersion polymerization with acryloyl ß-cyclodextrin as the functional monomer and ethylene glycol dimethyacrylate as the crosslinker. The composite magnetic microparticles were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, magnetic measurement, and thermogravimetric analysis, and used as the adsorbent of magnetic solid-phase extraction (MSPE) for methyl parathion and fenthion. The extraction conditions including sample pH and ionic strength, desorption solvent type and volume, and adsorption and desorption times were optimized. Under the optimal extraction conditions, an MSPE-HPLC-UV method was developed for the detection of methyl parathion and fenthion in lettuce. Wide linear ranges of 1.0-200 µg kg-1 (R2 = 0.9998) for methyl parathion and 1.5-200 µg kg-1 (R2 = 0.9978) for fenthion were obtained and the limits of detection were 0.3 µg kg-1 for methyl parathion and 0.5 µg kg-1 for fenthion in lettuce, respectively. The proposed method was applied for the determination of methyl parathion and fenthion in lettuce with satisfactory recoveries between 89.2-101.2%, and relative standard deviations were less than 9.1%. Thus, the MSPE-HPLC-UV method has high accuracy and sensitivity for the analysis of methyl parathion and fenthion in lettuce samples.

The cytotoxicity and genotoxicity of single and combined fenthion and terbufos treatments in human liver cells and zebrafish embryos.

The mechanism of genotoxicity of the individual and combined pesticides of terbufos and fenthion were evaluated using HepG2 cells and zebrafish embryos. We determined genotoxicity by neutral comet assay and phosphorylation of H2AX (γH2AX), which indicated that cells treated with terbufos and/or fenthion caused DNA double-strand breaks (DSBs). The combination of these pesticides at the equimolar concentration (40 µM) exhibited less toxicity, genotoxicity, and did not impact DNA homologous recombination (HR) repair activity compare to terbufos or fenthion alone treatment. In HepG2 cells, terbufos, fenthion and their combination decreased only Xrcc2 expression (one of DNA HR repair genes). Moreover, the combined pesticides decreased Xrcc6 expression (one of DNA non-homologous end joining (NHEJ) repair genes). In addition, only terbufos or fenthion decreased XRCC2 protein expression, while Ku70 was impacted in all of the treated cells irrespective of up or down regulation. In zebrafish embryos, only fenthion impaired HR genes (Rad51 and Rad18) expression at 24 h. After 48 h exposure to pesticides, the combined pesticides elevated HR genes (Rad51 and Xrcc2) expression while terbufos or fenthion inhibited the expression of these four genes (Rad51, Rad18, Xrcc2, Xrcc6). In addition, the hatching rate of zebrafish embryos with fenthion or the combined pesticide at 72 hpf was significantly impaired. Collectively, terbufos and/or fenthion in combining caused DSBs in HepG2 cells and zebrafish embryos. Moreover, the specific mechanism of combined pesticide both HepG2 and zebrafish embryos revealed antagonism interaction.

Influence of agricultural extension activities on tick control among cattle on family dairy farms in the southeast Brazil

The aim of the present study was to evaluate the resistance of tick populations on 16 family farms that were members of the agricultural producers' cooperative of the São Pedro region of the state of São Paulo (COOPAMSP). Bioassays were conducted on nine commercial products in 2018 and 2019. Their active agents were as follows: deltamethrin, amitraz, cypermethrin + chlorpyrifos + citronella, cypermethrin + chlorpyrifos + fenthion, cypermethrin + chlorpyrifos + piperonyl butoxide, dichlorvos + chlorpyrifos, cypermethrin, chlorfenvinphos + dichlorvos, and ivermectin. On some farms, a larval packet test (LPT) was also performed. Overall, four acaricides presented mean efficacy greater than 89%, among which two were associations of pyrethroids + organophosphates and two were associations of organophosphates + organophosphates. Deltamethrin, cypermethrin and ivermectin presented mean efficacy lower than 50%. In the bioassays using the LPT, all five farms showed resistance to diazinon, while only one farm presented resistance to cypermethrin. The results were handed over to each farmer with appropriate guidance for treatments. This study demonstrated that the important points to be implemented related directly to use control strategies, based on direct assistance for farmers and diagnosis of tick population sensitivities.

Sensitive Determination of Acetochlor, Alachlor, Metolachlor and Fenthion Utilizing Mechanical Shaking Assisted Dispersive Liquid-Liquid Microextraction Prior to Gas Chromatography-Mass Spectrometry.

A green, sensitive and accurate dispersive liquid-liquid microextraction (DLLME) method was used to preconcentrate four selected pesticides in dam lake water samples for determination by gas chromatography-mass spectrometry (GC-MS). Conditions of the DLLME method were comprehensively investigated and optimized according to type/volume of extraction solvent, type/volume of dispersive solvent, and type/period of mixing. The developed method was validated according to the limits of detection and quantitation, accuracy, precision and linearity. Under the optimum conditions, limit of detection values calculated for alachlor, acetochlor, metolachlor and fenthion were 1.7, 1.7, 0.2 and 7.8 µg/kg (mass based), respectively. The method recorded 202, 104, 275 and 165 folds improvement in detection power values for acetochlor, alachlor, metolachlor and fenthion, respectively, when compared with direct GC-MS measurements. In order to evaluate the accuracy of the developed method, real sample application with spiking experiments was performed on dam lake water samples, and satisfactory percent recovery results in the range of 81%-120% were obtained.

In vivo monitoring and exposure potency assessment of phase I metabolism of fenthion in vegetables.

In this study, the phase I metabolism of fenthion was monitored in three common vegetables in different chamber situations via an in vivo solid-phase microextraction method. The phase I metabolic pathways of fenthion were evaluated based on the in vivo monitoring results and their comparisons among the chamber situations. Enzyme catalysis was found to play a basic and dominant role, whereas light catalysis could promote subsequent transformations that were difficult for enzyme catalysis. Moreover, according to the concentrations of the metabolites and their toxicity, the total concentrations and total toxicity weighted concentrations were calculated to reveal actual residual levels. The relative total and weighted exposure potency values were calculated to account for the fact that only the parent pesticide was considered in the diet exposure risk assessment. In result, both total and weighted approaches indicated a much higher exposure risk. Present study uncovered the potential pesticide exposure risk associated with phase I metabolism and highlighted the toxicity weighted approach, both of which more realistically reflect the exposure risk than the parent compound concentration does. In general, this study may facilitate further illustrating the phase I metabolism of ubiquitous agricultural pesticides, and provide a more realistically understanding of their exposure risk.