Insight into the application of supercritical water oxidation for dichlorvos degradation: experimental and simulation aspects.

Dichlorvos or 2,2-dichlorovinyl dimethyl phosphate (DDVP) (C4H7Cl2O4P) is a chlorinated organophosphorus pesticide, which is frequently detected in agricultural wastewater. Herein, a batch reactor was used to carry out the supercritical water oxidation (SCWO) of a synthetic wastewater containing dichlorvos as a very hazardous agricultural pollutant. To do so, the impact of four operating parameters including dichlorvos concentration (100-500 ppm), oxidant coefficient (0.7-2), temperature (300-500°C) and time (0-100 s) on dichlorvos removal was optimized by the response surface method (RSM). According to the obtained results, at optimal conditions (i.e. initial concentration of dichlorvos 107.5 ppm, oxidation ratio 1.9234, temperature 419.9°C and time 79.94 s), as an index for dichlorvos removal, the chemical oxygen demand (COD) was found to be about 96.34%. Also, the results of high-performance liquid chromatography test showed that dichloroacetaldehyde (C2CL2H2O) and dichloroacetic acid (C2CL2H2O2) were created as intermediate substances during the dichlorvos degradation. Further, the molecular dynamics simulation was performed using ReaxFF force field to show the reaction path and products obtained in each step of the dichlorvos removal. Finally, as an indication, the simulation results indicated a good coordination with the experimental results.

Photocatalytic activity of graphene oxide-TiO2 nanocomposite on dichlorvos and malathion and assessment of toxicity changes due to photodegradation.

Heterogeneous photocatalysis was used for the removal of two widely used organophosphorus pesticides, dichlorvos, and malathion from water. Graphene oxide-TiO2 nanocomposite (GOT) was synthesized and used as a photocatalyst for the removal of these pesticides. Batch studies for optimizing photocatalytic degradation and mineralization of pesticides over 80 min were conducted by varying the pH (2-10), catalyst dose (20 mg/L-200 mg/L), and initial pesticide concentration (0.5 mg/L-20 mg/L), and the irradiation source (125 W UV and visible lamp). Degradation kinetics for the pesticides were evaluated. Ellman assay was used to estimate the toxic effect of pesticides and evaluate toxicity reduction due to treatment. The highest degradation and mineralization of dichlorvos and malathion was observed at pH 6 and the optimum catalyst dose was 60 mg/L. Under UV irradiation, 80% and 90% degradation were observed for dichlorvos and malathion, respectively for 0.5 mg/L initial pesticide concentration. The photocatalytic degradation reaction followed Langmuir-Hinshelwood kinetics. A high degree of mineralization was achieved for both the pesticides. Analysis of the results revealed that the residual toxic effect after photocatalysis was primarily due to the residual parent compound. A comparative study revealed that GOT yielded better pesticide degradation compared to commercially available TiO2 under both UV and visible irradiation.

Dichlorvos-induced formation of isopeptide crosslinks between proteins in SH-SY5Y cells.

Chlorpyrifos oxon catalyzes the crosslinking of proteins via an isopeptide bond between lysine and glutamic acid or aspartic acid in studies with purified proteins. Our goal was to determine the crosslinking activity of the organophosphorus pesticide, dichlorvos. We developed a protocol for examining crosslinks in a complex protein mixture consisting of human SH-SY5Y cells exposed to 10 µM dichlorvos. The steps in our protocol included immunopurification of crosslinked peptides by binding to anti-isopeptide antibody 81D1C2, stringent washing of the immobilized complex, release of bound peptides from Protein G agarose with 50% acetonitrile 1% formic acid, liquid chromatography tandem mass spectrometry on an Orbitrap Fusion Lumos mass spectrometer, Protein Prospector searches of mass spectrometry data, and manual evaluation of candidate crosslinked dipeptides. We report a low quantity of dichlorvos-induced KD and KE crosslinked proteins in human SH-SY5Y cells exposed to dichlorvos. Cells not treated with dichlorvos had no detectable KD and KE crosslinked proteins. Proteins in the crosslink were low abundance proteins. In conclusion, we provide a protocol for testing complex protein mixtures for the presence of crosslinked proteins. Our protocol could be useful for testing the association between neurodegenerative disease and exposure to organophosphorus pesticides.

Effect of storage states on stability of three organophosphorus insecticide residues on cowpea samples.

BACKGROUND: The stability of pesticide residues in stored samples is very important to ensure the quality of data about the residues. The evaluation of pesticide residues in food and environment samples is an important means to ensure food quality and protect consumers against potential dietary risks. Improper storage of pesticide residue samples may result in loss of pesticide and unreliable data, which could affect safety assessments. RESULTS: The influences of storage conditions, including temperature (-20 °C, 4 °C, and ambient temperature) and sample state (homogenized state and coarsely chopped state) on the storage stability of dichlorvos, malathion, and diazinon on cowpea were studied. Dichlorvos and malathion were more stable in an homogenized state than in a coarsely chopped state. At 4 °C, the residual dichlorvos in the coarsely chopped state and the homogenized state, respectively, was 12% and 69%; the residual malathion was 26% and 92%, respectively. Dichlorvos suffered a large loss of 89% and 59% for coarsely chopped and homogenized cowpea, even at -20 °C. It was obvious that the stability of dichlorvos and malathion were more affected by storage state than diazinon. The stability of diazinon was significantly affected by temperature. The effect of storage state and temperature on stability is likely to be correlated with enzymes in the matrix, such as superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD). CONCLUSION: The optimal stable storage conditions for three organophosphorus insecticides residues on cowpea were in the homogenized state and under a lower temperature. © 2021 Society of Chemical Industry.

The stability of four organophosphorus insecticides in stored cucumber samples is affected by additives.

The influence of some additives, including metal ions, antioxidants, enzyme inhibitors and organic solvents, on the storage stability of four organophosphorus pesticides in cucumber samples were investigated. It was found that metal ions, including Al3+, Fe3+, and Co2+, increased the stability of dichlorvos, malathion, and chlorpyrifos. Conversely, Al3+, Fe3+, Fe2+, and Co2+ caused catalytic degradation of diazinon. With the addition of organic solvents (CH2Cl2, CHCl3, CCl4, CH3OH and CH3COCH3), remaining of diazinon residues was higher (16-54%) after storage for seven days. CCl4 was associated with the highest retention of malathion, diazinon, and chlorpyrifos (33%, 48% and 44%, respectively) in samples. SDS also stabilized the pesticides since residues were, again, higher (13-38%) after seven days storage. Furthermore, addition of Al3+ and Fe3+ decreased peroxidase (POD) activity and inhibited degradation of dichlorvos and malathion. After 14 days, lyophilization increased the pesticide residues remaining by 36%, 29%, and 58% for diazinon, malathion and chlorpyrifos, respectively. Overall, the stability of these pesticides during storage is impacted by water content and addition of exogenous substances. This could ensure higher quality of pesticide residue data in samples.

Similarities and differences in adsorption mechanism of dichlorvos and pymetrozine insecticides with coconut fiber biowaste sorbent.

In this study, the similarities and differences of the adsorption mechanisms between dichlorvos and pymetrozine and coconut fiber biowaste sorbent (CF-BWS) were investigated. CF-BWS was produced using the slow pyrolysis process at 600 °C for 4 h. HCl acid modification was used to improve the specific surface area. The properties of CF-BWS were analyzed by SEM, FT-IR, BET, and pHpzc. The adsorption kinetics of dichlorvos and pymetrozine on the CF-BWS were well explained by the pseudo-second-order model. The adsorption isotherms for both insecticides were followed the Langmuir isotherm. The difference in molecular structures and surface chemistry caused the difference in adsorption mechanisms of both insecticides. The pore-filling and the hydrophobic interactions were the key mechanisms for both insecticide adsorptions. However, the π-π electron donor-acceptor interaction played the major role in the pymetrozine adsorption but hardly impacted on the adsorption of dichlorvos. The hydrogen bonding mechanism was pronounced in the pymetrozine adsorption, but it had little influence on the dichlorvos adsorption. The CF-BWS is exhibited as an excellent material for the removal of both pollutants and has high potential to be used further as the adsorbent in water treatment process.

Adsorption mechanism of dichlorvos onto coconut fibre biochar: the significant dependence of H-bonding and the pore-filling mechanism.

The adsorption mechanism of dichlorvos onto coconut fibre biochar (CFB) was investigated by the batch adsorption technique. Coconut fibre waste material was synthesised at 600 °C for 4 h under oxygen-limited conditions. The biochar was modified by HCl acid to enhance the specific surface area and porosity. The characteristics of the biochar were analysed by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) specific surface area, and Fourier transform-infrared (FT-IR). The results showed that the BET specific surface area of biochar was 402.4 m2/g. Experimental data presented a good fit to Langmuir isotherm and the pseudo-second-order model. Langmuir isotherm illustrated that monolayer adsorption of dichlorvos occurred on the surface of CFB, with a maximum adsorption capacity of 90.9 mg/g. The diffusion model confirmed that the liquid film diffusion was the rate-limiting step, and the major diffusion mechanism of dichlorvos onto biochar. The BET result after dichlorvos adsorption demonstrated that pore-filling occurred and occupied 58.27%. The pore-filling and chemical interactions, performed important roles in the adsorption of dichlorvos onto CFB. Chemical adsorption is comprised of two interactions, which are hydrophobic and H-bonding, but the prime is H-bonding. CFB is a very potential material for the removal of dichlorvos and environmental pollutants.

Degradation of 2, 2-Dichlorovinyl dimethyl phosphate (dichlorvos) through the rhizosphere interaction between Panicum maximum Jacq and some selected fungi.

Many fungi have been reported to enhance the plant responses and degradation of several persistent pollutants in soils. In this study, five dominant fungi strains were identified from a pesticides polluted soil in Nigeria and screened for the expression of phosphoesterase (opd and mpd) and catechol 1, 2-dioxygenase (afk2 and afk4) genes using Reverse Transcriptase-PCR technique. Their rhizosphere interaction with plant (Panicum maximum) was further studied for the degradation of 2, 2 Dichlorovinyl dimethyl phosphate (dichlorvos). Fungal strains were mixed with Spent Mushroom Compost (SMC) of Pleurotus ostreatus in 1:100 w/w and then applied to a sterilized pesticide polluted soil (5 kg) at increasing concentrations of 10, 20, 30 and 40% with two controls (plant only and fungi-SMC mixture only). Degradation efficiency (DE), degradation rate (K1) and half-life (t1/2) of dichlorvos was calculated in each treatment after 90-day of planting. All the strains were registered at NCBI gene-bank with accession numbers KY693969, KY488464, KY488465, KY693971 and KY693972: they all possess the tested genes although mpd and opd were over-expressed in all the strains while afk2 and afk4 were moderately expressed. The plant-fungi-SMC interaction synergistically sped-up dichlorvos degradation rate in less time period, appreciable loss of dichlorvos at 72.23 and 82.70% DE were observed in 30 and 40% treatments respectively as compared to controls 1 and 2 having 62.20 ±â€¯3.07 and 62.33 ±â€¯4.69% DE respectively. In the same way, the 40% treatment gave the best k1 and t1/2 of 1.755 and 0.40 ±â€¯0.02/day respectively.

Dose-response modeling of reactivating potency of oximes K027 and K203 against a direct acetylcholinesterase inhibitor in rat erythrocytes.

Inhibition of acethylcholinesterase (AChE) as a key molecular event induced by organophosphate (OP) pesticides and nerve agents presents a human health concern. In efficacy testing of experimental oximes, potential antidotes in OP poisoning, reactivation of OP-inhibited AChE is used as specific endpoint. However, according to our best knowledge, so far oximes have not been quantitatively evaluated by comprehensive benchmark dose (BMD) approach, that would improve both identification and quantification of the effect and allow more rigorous comparison of efficacies. Thus, we have examined in vivo dose-response relationship for two promising experimental oximes, K203 and K027, concerning reactivation of erythrocyte AChE inhibited by dichlorvos (DDVP). Groups of Wistar rats were treated with six different doses of oximes (i.m) immediately after DDVP challenge (s.c) and AChE was measured 60 min later. Dose-response modeling was done by PROAST software 65.5 (RIVM, The Nederlands). BMD-covariate method resulted in four-parameter model from both exponential and Hill model families as the best estimate of relationship between AChE activity and oxime dose, with potency parameter being oxime-dependent. Oxime K027 was shown to be 1.929-fold more potent considering that 58% increase in AChE activity was achived with the dose BMD58-K027 = 52 µmol/kg in contrast to BMD58-K203 = 100 µmol/kg.

Storage stability of three organophosphorus pesticides on cucumber samples for analysis.

The residue sample storage stability of three organophosphorus pesticides, dichlorvos, diazinon, and malathion, under different conditions was investigated. The storage conditions studied included storage time, temperature, and sample form. The addition of extra enzyme to the samples was also studied to investigate its effect on stability. It was found that malathion was more unstable than dichlorvos and diazinon, there was an over 70% loss in 90 days even at -20 °C in coarsely chopped form. The pesticide residues were more stable when the cucumber was in homogenate form than coarsely chopped. Furthermore, the addition of catalase increased the degradation of malathion, where there was more decomposition with increasing levels of catalase. However, there was no obvious relationship between degradation of dichlorvos and diazinon and catalase concentration. Overall, this study revealed factors that can be optimized to increase the storage stability of organophosphorus pesticides, where enzyme was one of the main influencing factors.

Organophosphorus pesticide exposure in agriculture: effects of temperature, ultraviolet light and abrasion on PVC gloves.

Elbow length PVC gloves are often recommended for protection against organophosphorus pesticide (OP) exposure in agriculture. However, performance may be reduced due to high temperature, UV exposure and abrasion. We sought to assess these impacts for two OPs under normal use and reasonable worst-case scenarios. Glove permeation tests were conducted using ASTM cells with two PVC glove brands at 23°C and 45°C for up to 8 h. Technical grade dichlorvos and formulated diazinon were used undiluted and at application strength. Breakthough of undiluted dichlorvos occurred at both 23°C and 45°C, but only at 45°C for application strength. Breakthrough of diazinon was not achieved, except when undiluted at 45°C. UV-exposed and abraded gloves showed reduced performance, with the effect being approximately two-fold for dichlorvos. Only small differences were noted between glove brands. Extra precautions should be taken when handling concentrated OPs at high temperature, or when using abraded or sunlight-exposed gloves.

Investigation of the Nucleophilic Attack of Dichlorvos by Reduced Sulfur Species Using 1H NMR.

The mechanism of the reaction of dichlorvos through hydrolysis reactions and through the reaction with polysulfide (Sn2-) and thiophenolate (PhS-) was investigated by proton nuclear magnetic resonance (1H NMR). The study confirmed product identities of an organophosphorus insecticide reacting with reduced sulfur species using 1H NMR in oxygen sensitive solutions. The experiments of dichlorvos with polysulfide led to the detection of a previously undetected product. The thiophenolate experiments were further advanced to investigate second-order rate kinetics using an internal standard. The experiments provide new evidence for a nucleophilic attack by the reduced sulfur species at the methoxy carbon of dichlorvos. In addition, the observation of in situ reaction dynamics illustrates the applicability of 1H NMR spectroscopy toward kinetic investigations in environmental science.

Chemical Degradation of TMR Multilure Dispensers for Fruit Fly Detection Weathered Under California Climatic Conditions.

Degradation models for multilure fruit fly trap dispensers were analyzed to determine their potential for use in large California detection programs. Solid three-component male lure TMR (trimedlure [TML], methyl eugenol [ME], raspberry ketone [RK]) dispensers impregnated with DDVP (2, 2-dichlorovinyl dimethyl phosphate) insecticide placed inside Jackson traps were weathered during summer (8 wk) and winter (12 wk) in five citrus-growing areas. Additionally, TMR wafers without DDVP, but with an insecticidal strip, were compared to TMR dispensers with DDVP. Weathered dispensers were sampled weekly and chemically analyzed. Percent loss of TML, the male lure for Ceratitis capitata (Wiedemann) Mediterranean fruit fly; ME, the male lure for Bactrocera dorsalis (Hendel), oriental fruit fly; RK, the male lure for Bactrocera cucurbitae (Coquillett), melon fly; and DDVP was measured. Based on regression analyses for the male lures, TML degraded the fastest followed by ME. Degradation of the more chemically stable RK was discontinuous, did not fit a regression model, but followed similar seasonal patterns. There were few location differences for all three male lures and DDVP. Dispensers degraded faster during summer than winter. An asymptotic regression model provided a good fit for % loss (ME, TML, and DDVP) for summer data. Degradation of DDVP in TMR dispensers was similar to degradation of DDVP in insecticidal strips. Based on these chemical analyses and prior bioassay results with wild flies, TMR dispensers could potentially be used in place of three individual male lure traps, reducing costs of fruit fly survey programs. Use of an insecticidal tape would not require TMR dispensers without DDVP to be registered with US-EPA.

Catalytic Degradation of Dichlorvos Using Biosynthesized Zero Valent Iron Nanoparticles.

The removal of dichlorvos contamination from water is a challenging task because of the presence of direct carbon to phosphorous covalent bond, which makes them resistant to chemical and thermal degradation. Although there have been reports in the literature for degradation of dichlorvos using nanomaterials, those are based on photocatalysis. In this paper, we report a simple and rapid method for catalytic degradation of dichlorvos using protein-capped zero valent iron nanoparticles (FeNPs). We have developed an unprecedented reliable, clean, nontoxic, eco-friendly, and cost-effective biological method for the synthesis of uniformly distributed FeNPs. Yeast extract was used as reducing and capping agent in the synthesis of FeNPs, and synthesized particles were characterized by the UV-visible spectroscopy, X -ray diffraction, Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM). TEM micrographs reveal that the nanoparticles size is distributed in the range of 2-10 nm. Selected area electron diffraction pattern shows the polycrystalline rings of FeNPs. The mean size was found to be 5.006 nm from ImageJ. FTIR spectra depicted the presence of biomolecules, which participated in the synthesis and stabilization of nanoparticles. As synthesized, FeNPs were used for the catalytic degradation of dichlorvos in aqueous medium. The degradation activity of the FeNPs has been investigated by the means of incubation time effect, oxidant effect, and nanoparticle concentration effect. The ammonium molybdate test was used to confirm the release of phosphate ions during the interaction of dichlorvos with FeNPs.

Investigation of Lysine-Functionalized Dendrimers as Dichlorvos Detoxification Agents.

Lysine-containing polymers have seen broad application due to their amines' inherent ability to bind to a range of biologically relevant molecules. The synthesis of multiple generations of polyester dendrimers bearing lysine groups on their periphery is described in this report. Their hydrolytic stabilities with respect to pH and time, their toxicity to a range of cell lines, and their possible application as nano-detoxification agents of organophosphate compounds are all investigated. These zeroth-, first-, and second-generation water-soluble dendrimers have been designed to bear exactly 4, 8, and 16 lysine groups, respectively, on their dendritic periphery. Such monodisperse bioactive polymers show potential for a range of applications including drug delivery, gene delivery, heavy metal binding, and the sequestration of organic toxins. These monodisperse bioactive dendrimers were synthesized using an aliphatic ester dendritic core (prepared from pentaerythritol) and protected amino acid moieties. This library of lysine-conjugated dendrimers showed the ability to efficiently capture the pesticide dichlorvos, confirming the potential of dendrimer-based antidotes to maintain acetylcholinesterase activity in response to poisoning events.

Molecular dynamics simulations of acylpeptide hydrolase bound to chlorpyrifosmethyl oxon and dichlorvos.

Acylpeptide hydrolases (APHs) catalyze the removal of N-acylated amino acids from blocked peptides. Like other prolyloligopeptidase (POP) family members, APHs are believed to be important targets for drug design. To date, the binding pose of organophosphorus (OP) compounds of APH, as well as the different OP compounds binding and inducing conformational changes in two domains, namely, α/ß hydrolase and ß-propeller, remain poorly understood. We report a computational study of APH bound to chlorpyrifosmethyl oxon and dichlorvos. In our docking study, Val471 and Gly368 are important residues for chlorpyrifosmethyl oxon and dichlorvos binding. Molecular dynamics simulations were also performed to explore the conformational changes between the chlorpyrifosmethyl oxon and dichlorvos bound to APH, which indicated that the structural feature of chlorpyrifosmethyl oxon binding in APH permitted partial opening of the ß-propeller fold and allowed the chlorpyrifosmethyl oxon to easily enter the catalytic site. These results may facilitate the design of APH-targeting drugs with improved efficacy.

Combined in silico and in vivo studies shed insights into the acute acetylcholinesterase response in rat and human brain.

Combined in vivo and in silico studies were undertaken to gain insights into the change in mammalian brain acetylcholinesterase (AChE) activity under acute toxicity conditions in response to two representatives of organophosphates (OPs)--dichlorvos (DCV) and dimethoate (DM). In vivo experiments elucidated that DCV, at multiple sublethal doses for acute time periods, markedly reduced (10-25%) AChE activity, whereas with DM intoxication, a decrease in enzyme activity appeared to be lower, that is, (2-15%), in contrast to respective normal control (100%). Furthermore, a significant inhibition (P < 0.01) in the brain esterase activity was recorded for positive control animals treated with an alkylating agent-cyclophosphamide, with spontaneous reactivation at later time periods. In vivo results were further substantiated with in silico molecular docking analysis using "Autodock 4.2." The lowest binding energy obtained through the computational study strongly augment that DCV binds to brain AChE with greater affinity compared with DM with reference to ∆G and Ki values. Thus, the animal biochemical assay and computational assessment suggest that DM is better to be used over DCV. The precautionary antidote for exposed humans can be developed prior to dealing with OPs. The study will aid in efficacious and safe clinical use of the above-mentioned compounds.

[Fe4L6](8+) cages: encapsulation and catalytic degradation of an insecticide.

Chiral bis(diimine) ligands (derived from chiral enantiopure diamines and 2-formylpyridine) enantioselectively self-assemble with an iron (II) salt to either the tetrahedral cage molecule ΔΔΔΔ-[Fe4L6](8+) or its enantiomer, ΛΛΛΛ-[Fe4L6](8+). These versatile water-soluble capsules are capable of binding a wide range of organic guests in their large hydrophobic cavities. Among these guests is the neurotoxic insecticide dichlorvos, for which the ΔΔΔΔ-[Fe4L6](8+) coordination capsule serves as a competent supramolecular catalyst for its hydrolysis.

Degradation of selected organophosphate pesticides in wastewater by dielectric barrier discharge plasma.

In this paper, degradation of selected organophosphate pesticides (dichlorvos and dimethoate) in wastewater by dielectric barrier discharge plasma (DBD) was studied. DBD parameters, i.e. discharge powers and air-gap distances, differently affect their degradation efficiency. The results show that better degradation efficiency is obtained with a higher discharge power and a shorter air-gap distance. The effect of radical intervention degradation was also investigated by adding radical scavenger (tert-butyl alcohol) to the pesticide solution during the experiments. The result shows that the degradation efficiency is restrained in the presence of radical scavenger. It clearly demonstrates that hydroxyl radicals are most likely the main driver for degradation process. Moreover, the kinetics indicate that the disappearance rate of pesticides follows the first-order rate law when the initial concentration of the solution is low, but shifts to zero-order at a higher initial concentration.

Preparation and characterization of TiO2/HZSM-11 zeolite for photodegradation of dichlorvos in aqueous solution.

The TiO2/HZSM-11 materials were synthesized using titanium isopropoxide as a TiO2 precursor and HZSM-11 a medium pore size zeolite with high thermal and chemical resistance as support. The amount of titanium isopropoxide was varied in order to obtain TiO2 concentrations of 3, 10, 20, 30 and 50 wt% in the final material. They were characterized by a series of complementary techniques: X-ray diffraction (XRD), ultraviolet-visible diffuse reflectance spectroscopy (DRS), transmittance Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The surface area of the TiO2/HZSM-11 samples decreased with the increment of TiO2 loading. As result of the increment of the calcination temperature from 450 to 800°C an increase in the size of the anatase crystals was observed. However, the X-ray diffraction patterns of the solids only presented the characteristic peaks of the anatase phase. The catalytic activity of the materials in the photodegradation of Dichlorvos (DDVP) depended on the TiO2 amount the thermal treatment temperature. The sample containing 30% TiO2 calcined at 450°C showed the best catalytic performance and it can be reused without noticeable activity loss during at least four cycles. The catalytic performance was similar to that of the P25 Degussa used as a reference but its separation, recovery and reuse was easier.