Fluorescent hydrogel test kit coordination with smartphone: Robust performance for on-site dimethoate analysis.

Precise monitoring of pesticide with portable device was challenging because it required high sensitivity, short response time, strong stability and excellent selectivity. Herein, we newly constructed a stimuli-responsive hydrogel (SRHg)-based portable kit by embedding copper nanoparticles (CuNPs) in agarose hydrogel. In this work, dimethoate as inhibitor of urease restrained the generation of ammonia, which reduced in-situ etching of CuNPs, resulting in the fluorescence color response of test kit under ultraviolet illumination. Interestingly, by means of smartphone-based nanocolorimetry, the photo image of portable kit could be translated into digital information using ImageJ software, achieving a direct quantitative tool for dimethoate identification. The simplicity of SRHg-based portable kit combined with smartphone-based color recognition not only improved the analysis sensitivity (detection limit of 1.0 µg L-1), accuracy and stability, but also simplified operation process and shortened sample-to-answer analysis time (55 min), demonstrating that the methodology met the needs of daily testing and provided a new sight for on-site monitoring of food safety and human health.

NIR Hyperspectral Imaging Technology Combined with Multivariate Methods to Study the Residues of Different Concentrations of Omethoate on Wheat Grain Surface.

In this study, a hyperspectral imaging system of 866.4-1701.0 nm was selected and combined with multivariate methods to identify wheat kernels with different concentrations of omethoate on the surface. In order to obtain the optimal model combination, three preprocessing methods (standard normal variate (SNV), Savitzky-Golay first derivative (SG1), and multivariate scatter correction (MSC)), three feature extraction algorithms (successive projections algorithm (SPA), random frog (RF), and neighborhood component analysis (NCA)), and three classifier models (decision tree (DT), k-nearest neighbor (KNN), and support vector machine (SVM)) were applied to make a comparison. Firstly, based on the full wavelengths modeling analysis, it was found that the spectral data after MSC processing performed best in the three classifier models. Secondly, three feature extraction algorithms were used to extract the feature wavelength of MSC processed data and based on feature wavelengths modeling analysis. As a result, the MSC-NCA-SVM model performed best and was selected as the best model. Finally, in order to verify the reliability of the selected model, the hyperspectral image was substituted into the MSC-NCA-SVM model and the object-wise method was used to visualize the image classification. The overall classification accuracy of the four types of wheat kernels reached 98.75%, which indicates that the selected model is reliable.

KOH modified Thevetia peruviana shell activated carbon for sorption of dimethoate from aqueous solution.

Modified Thevetia peruviana shell activated carbon for sorption of dimethoate from aqueous solution derived with potassium hydroxide (KOH) was studied at different concentrations for its potential application in water treatment. The batch sorption was investigated using dimethoate solution of 10-100 mg/L concentrations. Proximate analysis was determined and changes on the surfaces and structure of the TPS were characterized after chemical activation with KOH using XRD, FTIR, SEM-EDAX, pHpzc, BET. The quantum chemical calculation for dimethoate yielded molecule associated energies of -9.8421 (HOMO) and -2.3879 (LUMO) and a total energy of -53,376.2. The kinetic of the sorption was modeled which indicated the sorption equilibrium time as 90 min and pseudo-first order kinetics model showing R2 = 0.994 provided a better description of the process. Analysis of sorption equilibrium revealed that the data fitted well to Freundlich sorption isotherm model (R2 = 0.966), indicating multi-layer sorption of dimethoate on the surface of sorbent. The sorption of dimethoate onto KOHTPS shows 92.60% removal efficiency.

A photoswitchable "host-guest" approach for the selective enrichment of dimethoate from olive oil.

This work describes the development of a new selective photocontrollable molecularly imprinted-based sorbent for the selective enrichment/pre-concentration of dimethoate from spiked olive oil samples. To achieve this goal an improved molecularly imprinted strategy relying on the embedding of a functional monomer containing an azobenzene chromophore as light-responsive element, on the crosslinked tridimensional molecular imprinted network, has been assessed. To address the mechanisms underlying template recognition and uptake/release of the analyte from the functional imprinted material, computational studies using a quantum chemical approach, have been explored. This new functional sorbent provides a straightforward controllable uptake/release of the target template using light as the stimuli tool, which is highly advantageous due to light manipulation characteristics, such as superior clean, precision and remote controllable properties. In general, this work will contribute to the implementation of a photoswitchable analytical methodology that proves to be suitable for the selective isolation and further quantification of dimethoate from olive oil matrices at levels similar to the maximum residues limits imposed by the legislation. The limits of detection, calculated based on 3σ, was 1.6 mgL-1 and the limit of quantification, based on 10σ, was 5.2 mgL-1. The implemented sample preparation shows high reproducibility and recoveries (93.3 ±â€¯0.4%).

A magnetic controllable tool for the selective enrichment of dimethoate from olive oil samples: A responsive molecular imprinting-based approach.

Aiming to develop a straightforward magnetic-based sample preparation methodology for the selective extraction of dimethoate from olive oil, the synthesis of dimethoate-imprinted polymer on the surface of modified magnetic nanoparticles has been attempted. Molecular recognition assays have proven their suitability for the selective pre-concentration of dimethoate. Mechanistic basis for template selective recognition has been explored using a quantum chemical approach, providing new insights about the mechanisms underlying template recognition. Thus, a magnetic molecularly imprinted solid-phase extraction method was developed allowing the extraction of dimethoate from spiked olive oil samples, at levels similar to the maximum residue limits imposed by legislation, followed by the quantification of their levels by high-performance liquid chromatography with diode-array detection. Recoveries of 94.55% were obtained, with relative standard deviations lower than 0.53% (n = 3). The developed sample preparation technique enables a selective pre-concentration/enrichment of dimethoate from olive oil matrix with minimum handling and less solvent consumption.

MIP-MEPS based sensing strategy for the selective assay of dimethoate. Application to wheat flour samples.

The aim of this work was to demonstrate the potentialities of the use of a molecularly imprinted (MIP) sensor coupled to a microextraction by packed sorbent (MEPS) strategy for the selective and sensitive detection of dimethoate in real samples. A dimethoate-polypyrrole MIP film was realised by cyclic voltammetry (CV) on the surface of a glassy carbon electrode (GCE). Being dimethoate electro-inactive, K3[Fe(CN)6] was used as probe for the indirect quantification of the analyte via the decrease of redox peaks observed upon binding of the target analyte. Detection of dimethoate at low nanomolar range was achieved with linearity in the 0.1-1nM range. Relative standard deviation calculated for different electrodes at 0.5nM of dimethoate was < 3% and selectivity was very satisfactory being the response for omethoate only 23% of dimethoate. A MEPS strategy for the extraction of dimethoate from a challenging matrix as wheat flour was then used in conjunction with the MIP electrochemical sensor. The procedure applied to flour samples spiked with dimethoate at 0.5 MRL, MRL, and 1.5 MRL gave very favourable comparison with a validated UHPLC-MS/MS method with deviations in the -21% /+17% range, demonstrating the feasibility of the approach as screening assay. This work clearly shows that the sequential use of a microextraction based procedure and electrochemical sensing system is low cost, easy to realise and use and can open new perspectives for the development of selective sensing system to be used in field or decentralised lab testing for the selective screening of target analytes.

Computational and experimental investigation of molecular imprinted polymers for selective extraction of dimethoate and its metabolite omethoate from olive oil.

This work presents the development of molecularly imprinted polymers (MIPs) for the selective extraction of dimethoate from olive oil. Computational simulations allowed selecting itaconic acid as the monomer showing the highest affinity towards dimethoate. Experimental validation confirmed modelling predictions and showed that the polymer based on IA as functional monomer and omethoate as template molecule displays the highest selectivity for the structurally similar pesticides dimethoate, omethoate and monocrotophos. Molecularly imprinted solid phase extraction (MISPE) method was developed and applied to the clean-up of olive oil extracts. It was found that the most suitable solvents for loading, washing and elution step were respectively hexane, hexane-dichloromethane (85:15%) and methanol. The developed MIPSE was successfully applied to extraction of dimethoate from olive oil, with recovery rates up to 94%. The limits of detection and quantification of the described method were respectively 0.012 and 0.05 µg g(-1).

Desorption of two organophosphorous pesticides from soil with wastewater and surfactant solutions.

A batch test was used to evaluate the extent of desorption of diazinon and dimethoate, preadsorbed on a calcareous agricultural soil, representative of the Mediterranean area. Urban wastewater from a secondary treatment and seven surfactant solutions, at concentrations ranging from 0.75 mg L(-1) to 10 gL(-1), were used. The surfactants assayed were cationic (hexadecyl trimethyl ammonium bromide (HD)), anionic (sodium dodecyl sulfate (SDS), Aerosol 22 (A22) and Biopower (BP)), and nonionic (Tween 80 (TW), Triton X 100 (TX) and Glucopon 600 (G600)). Desorption of dimethoate was either not affected or only slightly by the nonionic and anionic surfactants tested, while desorption of diazinon from the soil was only enhanced by A22, BP and TW. This desorption increase correlated significantly with the surfactant concentration of the solution used for desorption and with the concurrent increase in the supernatant of the dissolved organic carbon, in particular that originating from the surfactant. This parameter did not vary with the use of SDS, G600 and TX. The cationic surfactant HD was retained on the soil surface, as confirmed by an increase in soil organic carbon, resulting in a fall in desorption rate for both pesticides. Comparing treatment by wastewater with control water, there was no difference in desorption rate for either pesticide. Mixed TW/anionic surfactant solutions either did not modify or slightly increased desorption of both pesticides in comparison with individual surfactant solutions.

Identification of dimethoate-containing water using partitioned dispersive liquid-liquid microextraction coupled with near-infrared spectroscopy.

A simple, rapid and efficient extraction procedure, partitioned dispersive liquid-liquid microextraction, has been developed in combination with near-infrared spectroscopy for the extraction and discrimination of dimethoate from aqueous samples. For this technique, the appropriate mixture of extraction solvent (CCl(4)) and disperser solvent (THF) was utilized. Partial least squares discriminant analysis was applied to build the model with several pre-process methods over the wavenumber regions between 7100 cm(-1) to 7300 cm(-1). The best model gave satisfactory classification accuracy, 98.6% for calibration set (n=74) and 97.6% for prediction set (n=42), using preprocessing of standard normal variate followed by Savitzky-Golay first derivative. The method was successfully applied to bottled water, tap water, lake water and farm water samples. The results demonstrated the possibility of near-infrared spectroscopy after partitioned dispersive liquid-liquid microextraction for the identification of water contaminated by dimethoate.

Determination of pesticides in surface and ground waters by liquid chromatography-electrospray-tandem mass spectrometry.

The sensitive multiresidual analytical method for simultaneous analysis of 14 most commonly used agricultural pesticides in Serbia was developed and optimized. The selected insecticides, fungicides and herbicides belong to seven chemical classes (organophosphates, neonicotinoids, carbamates, diacylhydrazines, benzimidazoles, triazines and phenylureas). The method was based on solid-phase extraction followed by liquid chromatography-tandem mass spectrometry. The following parameters that may affect the SPE procedure efficiency were optimized: the sorbent type in combination with different elution solvents, the sample pH and the sample volume. For each pesticide, MS(n) analysis was performed and distinctive ions and transitions were selected for identification and quantification, as well as for confirmation purposes. External matrix-matched calibration method was used to eliminate variable matrix effect and ensure precise quantification. Good recoveries (72-129%), and low limits of detection (0.4-5.5 ng L(-1)) and quantification (1.1-18.2 ng L(-1)) were achieved for all selected pesticides. The developed and optimized method was successfully applied in the analysis of several river waters, as well as ground waters in Serbia, influenced by agriculture. The most frequently detected pesticide was carbendazim. Dimethoate, carbofuran and propazine were also found in the investigated samples.

[Rapid elimination of surface organophosphorous pollutants using hydroxyl radical].

According to the frequency of contamination accident for organic compounds in recent years, two kinds of organophosphorus pesticides dichlorvos and omethoate, as the simulated organic pollutants, were rapidly eliminated using spraying hydroxyl radical produced by strong electric-field ionization discharge method on an aluminium flat plate about 160 cm2. The high concentration aqueous *OH solution was produced from H2O(gas) and O2 with plasma reaction. In a condition, where pH is 6 and the initial densities of dichlorvos and omethoate on the simulation plane are both 60 microg x cm(-2), when the spray density of *OH reaches 3.9 microg x cm-2, removal efficiencies of dichlorvos and omethoate are 90%, and mineralization rates are 64% and 72%, respectively. The effect of pH for removal efficiency was also investigated. The results found that the removal efficiency of organophosphorus pollutants first decreased slowly and then increased fast with the increase of pH from 2 to 12 and the lowest removal rate appeared when pH close to neutral. The degradation rates of dichlorvos and omethoate both ascend by 21% and 26% respectively with pH 12 than that of pH 6. Four factors and three levels orthogonal test indicated that the degradation by *OH played a major role at the surface oxidation removal rapid of organophosphorus pollutants in a short period of time.

Dimethoate and atrazine retention from aqueous solution by nanofiltration membranes.

In order to produce sufficient food supply for the ever-increasing human population, pesticides usage is indispensable in the agriculture sector to control crop losses. However, the effect of pesticides on the environment is very complex as undesirable transfers occur continually among different environmental sections. This eventually leads to contamination of drinking water source especially for rivers located near active agriculture practices. This paper studied the application of nanofiltration membrane in the removal of dimethoate and atrazine in aqueous solution. Dimethoate was selected as the subject of study since it is being listed as one of the pesticides in guidelines for drinking water by World Health Organization. Nevertheless, data on effectiveness of dimethoate rejection using membranes has not been found so far. Meanwhile, atrazine is classified as one of the most commonly used pesticides in Malaysia. Separation was done using a small batch-type membrane separation cell with integrated magnetic stirrer while concentration of dimethoate and atrazine in aqueous solution was analyzed using high performance liquid chromatography (HPLC). Four nanofiltration membranes NF90, NF200, NF270 and DK were tested for their respective performance to separate dimethoate and atrazine. Of all four membranes, NF90 showed the best performance in retention of dimethoate and atrazine in water.

Study on characteristics of biocometabolic removal of omethoate by the Aspergillus spp.

A strain Aspergillus spp. F1 which could effectively metabolized omethoate was screened out in this study. F1 tended to form granula with diameter 4-5mm after 5 days culture in shaker. The pH range from 4.5 to 6.5 was the suitable pH range for growth and metabolism of Aspergillus spp. F1. The maximum omethoate removal rate was about 3.0mg/(hL), and the removal fraction of omethoate reached 90% after 8 days culture when initial concentrations of omethoate were not more than 2000mg/L in medium. There was no obvious relativity between cell growth and cometabolism of omethoate. Starch was the best carbon source for omethoate removal and the result after 3 days reached 56.6% removal. F1 could use omethoate to metabolize as single nitrogen or phosphate source. The residual fragments in medium after treatment with the Aspergillus spp. F1 were determined by gas chromatography-mass spectrometry. The analysis results showed that only fragment o,o,s,-trimethyl phosphorothioate (TEP) containing phosphorus was available and the fragment containing nitrogen was consumed by F1 thoroughly in culture process. But no accumulations of TEP were observed in the omethoate bioremediation process. F1 could effectively remove omethoate in complex nutritional environment safely.

Study of the mechanism of Flavobacterium sp. for hydrolyzing organophosphate pesticides.

The biotransformation by Flavobacterium sp. of the following organophosphate pesticides was experimentally and theoretically studied: phorate, tetrachlorvinphos, methyl-parathion, terbufos, trichloronate, ethoprophos, phosphamidon, fenitrothion, dimethoate and DEF. The Flavobacterium sp. ATCC 27551 strain bearing the organophosphate-degradation gene was used. Bacteria were incubated in the presence of each pesticide for a duration of 7 days. Parent pesticides were identified and quantified by means of a gas-chromatography mass spectrum system. Activity was considered as the amount (micromol) of each pesticide degraded by Flavobacterium sp. Also, structural parameters obtained by means of the CAChe program package for biomolecules, the reactivity index of phosphorus, of oxygen at the P = O function and of sulfur at the P = S function, and lipophilicity (log Poct) (ALOGPS v. 2.0) were obtained for each pesticide. Pesticides were hydrolyzed at the bond between phosphorous and the heteroatom, producing phosphoric acid and three metabolites. Enzymatic activity was significantly explained by the following multiple linear relationship: Enzymatic activity = 162.2 - 9.5(dihedral angle energy) - 25.0(Total energy) - 0.51(Molecular weight). Finally, a mechanism of Flavobacterium sp. to hydrolyze pesticides was proposed.