Magnetic solid phase extraction sorbents using methyl-parathion and quinalphos dual-template imprinted polymers coupled with GC-MS for class-selective extraction of twelve organophosphorus pesticides.

A novel magnetic dual-template molecularly imprinted polymer (DMIP) was prepared with methyl-parathion and quinalphos as templates. For comparison, a series of single-template polymers with only methyl-parathion (MPMIP) or quinalphos (QPMIP) as template as well as a non-imprinted polymer (NIP) in the absence of the template, were synthesized using the same procedure of DMIP. The obtained MIPs were characterized by scanning electron microscopy(SEM), Fourier transform infrared (FT-IR) spectroscopy, vibrating sample magnetometer (VSM), and X-ray diffraction (XRD). The properties including kinetic effect, thermodynamic effect, selectivity, and reusability of MIPs were investigated . Only DMIP possessed high affinity and good recognition for all twelve OPPs including quinalphos, isazophos, chlorpyrifos-methyl, chlorpyrifos, methidathion, triazophos, profenofos, fenthion, fenitrothion, methyl-parathion, parathion, and paraoxon in comparison to MPMIP, QPMIP, or NIP. Moreover, DMIP was used as magnetic solid phase extraction (MSPE) sorbent for the pre-concentration of twelve OPPs in cabbage samples. The developed DMIP-MSPE-GC-MS method showed high sensitivity, low LODs (1.62-13.9 ng/g), fast adsorption equilibrium (10 min), and acceptable spiked recoveries (81.5-113.4%) with relative standard deviations (RSD) in the range 0.05-7.0% (n = 3). The calibration plots were linear in the range 10-800 ng/mL with coefficients of determination (R2) better 0.99 for all twelve compounds. These results suggest that the DMIP is applicable for rapid determination and high throughput analysis of multi-pesticide residues. Graphical abstract.

A robust electrochemical sensing platform using carbon paste electrode modified with molecularly imprinted microsphere and its application on methyl parathion detection.

A highly sensitive electrochemical sensor using a carbon paste electrode (CPE) modified with surface molecularly imprinted polymeric microspheres (SMIPMs) was developed for methyl parathion (MP) detection. Molecular imprinting technique based on distillation precipitation polymerization was applied to prepare SMIPMs and non-surface imprinted microspheres (MIPMs). The polymer properties including morphology, size distribution, BET specific surface area and adsorption performance were investigated and compared carefully. Both MIPMs and SMIPMs were adopted to prepare CPE sensors and their electrochemical behaviors were characterized via cyclic voltammetry and electrochemical impedance spectroscopy. Compared with MIPMs packed sensor, SMIPMs/CPE exhibits a higher sensing response towards MP with linear detection range of 1 × 10-12-8 × 10-9 mol L-1 and detection limit of 3.4 × 10-13 mol L-1 (S/N = 3). Moreover, SMIPMs/CPE exhibits good selectivity and stability in multiple-cycle usage and after long-time storage. Finally, the developed sensor was used to determine MP in real samples including soil and vegetables and only simple pretreatment is needed. The detection results were consistent with those obtained from liquid chromatography. Collectively, this newly developed sensor system shows significant potential for use in a variety of fields like food safety, drug residue determination and environmental monitoring.

Determination of pesticides in lettuce using solid-liquid extraction with low temperature partitioning.

This work describes the optimization and validation of a method employing solid-liquid extraction with low temperature partitioning (SLE/LTP) together with analysis by gas chromatography with electron capture detection (GC/ECD) for the determination of nine pesticides (chlorothalonil, methyl parathion, procymidone, endosulfan, iprodione, λ-cyhalothrin, permethrin, cypermethrin, and deltamethrin) in lettuce. The method was found to be selective, accurate, and precise, with means recovery values in the range of 72.3-103.2%, coefficients of variation ⩽ 12%, and detection limits in the range 0.4-37 µg kg(-1). The matrix components significantly influence the chromatographic response of the analytes (above 10%). The optimized and validated method was applied to determine the residual concentrations of the fungicides iprodione and procymidone that had been applied to field crops of lettuce. The maximum residual concentrations of the pesticides in the lettuce samples were 13.6 ± 0.4 mg kg(-1) (iprodione) and 1.00 ± 0.01 mg kg(-1) (procymidone), on the day after application of the products.

A simple and sensitive fluorescent sensor for methyl parathion based on L-tyrosine methyl ester functionalized carbon dots.

In this paper, a simple and sensitive fluorescent sensor for methyl parathion is developed based on L-tyrosine methyl ester functionalized carbon dots (Tyr-CDs) and tyrosinase system. The carbon dots are obtained by simple hydrothermal reaction using citric acid as carbon resource and L-tyrosine methyl ester as modification reagent. The carbon dots are characterized by transmission electron microscope, high resolution transmission electron microscopy, X-ray diffraction spectrum, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The carbon dots show strong and stable photoluminescence with a quantum yield of 3.8%. Tyrosinase can catalyze the oxidation of tyrosine methyl ester on the surface of carbon dots to corresponding quinone products, which can quench the fluorescence of carbon dots. When organophosphorus pesticides (OPs) are introduced in system, they can decrease the enzyme activity, thus decrease the fluorescence quenching rate. Methyl parathion, as a model of OPs, was detected. Experimental results show that the enzyme inhibition rate is proportional to the logarithm of the methyl parathion concentration in the range 1.0×10(-10)-1.0×10(-4) M with the detection limit (S/N=3) of 4.8×10(-11) M. This determination method shows a low detection limit, wide linear range, good selectivity and high reproducibility. This sensing system has been successfully used for the analysis of cabbage, milk and fruit juice samples.

Vortex-assisted low density solvent liquid-liquid microextraction and salt-induced demulsification coupled to high performance liquid chromatography for the determination of five organophosphorus pesticide residues in fruits.

A simple and rapid microextraction method, vortex-assisted low density solvent liquid-liquid microextraction and salt-induced demulsification (VLLME-SID) coupled to high performance liquid chromatography (HPLC) was developed for the determination of organophosphorus pesticide (OPP) residues in fruits. The studied OPPs were azinphos-methyl, parathion-methyl, fenitrothion, diazinon and chlorpyrifos. For VLLME-SID, a mixture of low density solvents (1-dodecanol and hexane) was used as the extraction solvent under vortex agitation for enhancing dispersion. After complete dispersion, the emulsion was formed and the OPPs were extracted into extraction solvent droplets. Then, the emulsion was quickly broken up into two clear phases after the addition of AlCl3 as a demulsifier. Centrifugation was not required in this procedure. Under the optimal conditions, high enrichment factors (180-282), low limit of detections (LODs) (0.05-1 ng mL(-1)) and good precision (RSD≤7% for retention time and peak area) were obtained. The proposed method was successfully applied to the analysis of OPP residues in fruit samples (watermelon, grape, and cantaloupe). The LODs for samples were in the range 0.0006-0.0015 mg kg(-1) which are below the established EU-MRLs (0.01-0.3 mg kg(-1)). Good recoveries were also obtained (80-104%).

Development of surface imprinted core-shell nanoparticles and their application in a solid-phase dispersion extraction matrix for methyl parathion.

Applying molecular imprinting techniques to the surface of functionalized SiO2 allows the preparation of molecularly imprinted polymers (MIPs) with accessible, high affinity and surface exposed binding sites. This paper demonstrates a new strategy for producing such hybrid organic-inorganic surface imprinted silica nanoparticles for specific recognition of methyl parathion. The technique provides surface grafting imprinting in chloroform using amino modified silica nanoparticles as supports, acrylamide as the functional monomer, γ-methacryloxypropyl trimethoxy silane as the grafting agent, and methyl parathion as a template. The amino propyl functional monomer layer directs the selective occurrence of imprinting polymerization at the silica surface through copolymerization of grafting agents with functional monomers, but also acts as an assistive monomer to drive the template into the formed polymer shells to create effective recognition sites. The resulting MIPs-SiO2 nanoparticles display three-dimensional core-shell architectures and large surface areas. The molecularly imprinted shell provides recognition sites for methyl parathion, with the materials exhibiting excellent performance for selecting the template. Using MIPs-SiO2 nanoparticles as a matrix of solid-phase dispersion extraction sorbents, trace amounts of methyl parathion are selectivity extracted from pear and green vegetable samples while simultaneously eliminating matrix interferences, attaining recoveries of 84.7-94.4% for the samples.

Covalent fabrication of methyl parathion hydrolase on gold nanoparticles modified carbon substrates for designing a methyl parathion biosensor.

A biosensor based on AuNP modified GC electrodes has been developed for direct detection of methyl parathion. AuNP can be introduced to mixed monolayers of aryldiazonium salt modified GC electrodes by Au-C bonding through aryldiazonium salt chemistry, which provides a stable interface showing efficient electron transfer between biomolecules and electrodes. PEG molecules were introduced to the interface to resist non-specific protein adsorption. AuNP surfaces were further modified with 4-carboxyphenyl followed by covalent immobilization of methyl parathion hydrolase (MPH), a specific biocatalytic enzyme to methyl parathion. Exposure of this interface to methyl parathion resulted in a change in amperometric signal due to the MPH catalytic hydrolysis of methyl parathion producing electroactive compound 4-nitrophenol. This biosensor shows high selectivity, specificity, reproducibility and stability, and is functional for the detection of methyl parathion in real samples. The linear range for detection of methyl parathion is 0.2-100 ppb with a detection limit of 0.07 ppb in 0.1M phosphate buffer at pH 7.0.

Methyl parathion imprinted polymer nanoshell coated on the magnetic nanocore for selective recognition and fast adsorption and separation in soils.

Core-shell magnetic methyl parathion (MP) imprinted polymers (Fe3O4@MPIPs) were fabricated by a layer-by-layer self-assembly process. In order to take full advantage of the synergistic effect of hydrogen-binding interactions and π-π accumulation between host and guest for molecular recognition, methacrylic acid and 4-vinyl pyridine were chosen as co-functional monomers and their optimal proportion were investigated. The core-shell and crystalline structure, morphology and magnetic properties of Fe3O4@MPIPs were characterized. The MP-imprinted nanoshell was almost uniform and about 100nm thick. Binding experiments demonstrated that Fe3O4@MPIPs possessed excellent binding properties, including high adsorption capacity and specific recognition, as well as fast adsorption kinetics and a fast phase separation rate. The equilibration adsorption capacity reached up to 9.1mg/g, which was 12 times higher than that of magnetic non-imprinted polymers, while adsorption reached equilibrium within 5min at a concentration of 0.2mmol/L. Furthermore, Fe3O4@MPIPs successfully provided selective separation and removal of MP in soils with a recovery and detection limit of 81.1-87.0% and 5.2ng/g, respectively.

Genetic surface-display of methyl parathion hydrolase on Yarrowia lipolytica for removal of methyl parathion in water.

In this study, the mph gene encoding methyl parathion hydrolase from Pseudomonas sp. WBC-3 was expressed in Yarrowia lipolytica and the expressed methyl parathion hydrolase was displayed on cell surface of Y. lipolytica. The activity of methyl parathion hydrolase displayed on the yeast cells of the transformant Z51 was 59.5 U mg⁻¹ of cell dry cells (450.6 U per mL of the culture) in the presence of 5.0 mM of Co²âº. The displayed methyl parathion hydrolase had the optimal pH of 9.5 and the optimal temperature of 40 °C, respectively and was stable in the pH range of 4.5-11 and up to 40 °C. The displayed methyl parathion hydrolase was also stimulated by Co²âº, Cu²âº, Ni²âº and Mn²âº, and was not affected by Fe²âº, Fe³âº, Na⁺, K⁺, Ca²âº and Zn²âº, but was inhibited by other cations tested. Under the optimal conditions (OD(600 nm) = 2.6, the substrate concentration = 100 mg L⁻¹ and 40 °C), 90.8 % of methyl parathion was hydrolyzed within 30 min. Under the similar conditions, 98.7, 97.0, 96.5 and 94.4 % of methyl parathion in tap water (pH 9.5), tap water (pH 6.8), seawater (pH 9.5) and natural seawater (pH 8.2) were hydrolyzed, respectively, suggesting that the methyl parathion hydrolase displayed on the yeast cells can effectively remove methyl parathion in water.

Evaluation of vermicompost as a raw natural adsorbent for adsorption of pesticide methylparathion.

The assessment of vermicompost (VC) as a low-cost and alternative adsorbent for the removal of the pesticide methylparathion (MP) from an aqueous medium has been investigated by batch and column experiments. Parameters related to MP adsorption, i.e. equilibrium time (61.5 min) and adsorption pH (6.8) were optimized by using Doehlert design. The initial and final MP concentrations after adsorption assays were determined by square-wave adsorptive cathodic stripping voltammetry using an electrode composed of a multiwalled carbon nanotube dispersed in mineral oil. Batch adsorption experimental data were fitted to the Langmuir and Freundlich isotherm adsorptions, and a very good fit to the Langmuir linear model, giving a maximum adsorption capacity (MAC) of 0.17 mg g(-1). This result was very similar to that obtained with the column experiments. In order to evaluate the MP desorption from column packed VC, 100.0 ml of nitric acid solution (pH 3.0) has been percolated through material. No leaching of MP was observed, thus confirming the strong interaction between MP and VC. The satisfactory MAC obtained and low cost makes the VC a reliable natural material for the removal of MP from aqueous effluents.

Application of graphene for preconcentration and highly sensitive stripping voltammetric analysis of organophosphate pesticide.

Electrochemical reduced ß-cyclodextrin dispersed graphene (ß-CD-graphene) was developed as a sorbent for the preconcentration and electrochemical sensing of methyl parathion (MP), a representative nitroaromatic organophosphate pesticide with good redox activity. Benefited from the ultra-large surface area, large delocalized π-electron system and the superconductivity of ß-CD-graphene, large amount of MP could be extracted on ß-CD-graphene modified electrode via strong π-π interaction and exhibited fast accumulation and electron transfer rate. Combined with differential pulse voltammetric analysis, the sensor shows ultra-high sensitivity, good selectivity and fast response. The limit of detection of 0.05 ppb is more than 10 times lower than those obtained from other sorbent based sensors. The method may open up a new possibility for the widespread use of electrochemical sensors for monitoring of ultra-trace OPs.

[Effect of physico-chemical characteristics of activated carbon on the adsorption of organic pollutants in natural water].

In this paper, the adsorption characteristics of two synthetic organic compounds (SOCs), i. e., methyl parathion(MP) and trichloroethylene (TCE), and natural organic matter (NOM) on powdered activated carbons (PAC) in natural water were studied. On the basis of fully characterizing the physical and chemical characteristics of PAC, the effect of physical and chemical properties of PAC on the adsorption of low molecular weight SOCs in natural water was studied by correlation analysis. The effect of molecular weight fractionation on the adsorption of NOM on PAC was investigated using high performance size exclusion chromatography (HPSEC). It was found that, compared to the surface chemistry, the physical property (pore properties) of PAC was the critical factor to determine its adsorption capacity of MP and TCE in natural water. The adsorption of the low molecular weight SOC and NOM with apparent molecular weight (AMW) < 500 on PAC was primarily impacted by the micropore surface area, and that of NOM with 500 < AMW < 3 000 was affected by the mesopore surface area combined with the mesopore size distribution.

Photocatalytic degradation of commercial methyl parathion in aqueous suspension containing La-doped TiO2 nanoparticles.

The photocatalytic degradation of a commercial methyl parathion (MP) under UV irradiation was investigated in aqueous suspension containing lanthanum-doped mesoporous TiO2 nanoparticles (La/m-TiO2) as photocatalyst. The rate of photodecomposition of MP was measured using UV-Vis spectrophotometry, and its mineralization was followed using ion chromatography (IC). The identification of possible intermediate products was carried out using several powerful analytical techniques such as gas chromatography-pulsed flame photometric detector (GC-PFPD) and high performance liquid chromatography-mass spectroscopy (HPLC-MS). Under our conditions, complete disappearance of 20 mg/L of MP occurred within 2 h of illumination, whereas complete mineralization of MP was not achieved through IC analysis. There was a single intermediate product found in the research, which was identified to be methyl paraoxon, owing to the substitution of S by the O atom in the MP molecule. Based on the experimental facts, it is concluded that MP was mainly attacked not by OH radicals but photo-generated holes (h+), resulting from the good adsorption of MP on the catalyst surfaces due to the enhanced adsorption by La doping.

A matrix solid-phase dispersion method for the extraction of seven pesticides from mango and papaya.

A simple and effective extraction method based on matrix solid-phase dispersion was developed to determine trichlorfon, pyrimethanil, methyl parathion, tetraconazole, thiabendazole, imazalil, and tebuconazole in papaya and mango using gas chromatography-mass spectrometry with selected ion monitoring. Different parameters of the method were evaluated, such as type of solid-phase (silica-gel, neutral alumina, and Florisil), the amount of solid-phase, and eluent [dichloromethane, ethyl acetate-dichloromethane (4:1, 1:4, 1:1, 2:3, v/v)]. The best results were obtained using 2.0 g of mango or papaya, 3.0 g of silica as dispersant sorbent, and ethyl acetate-dichloromethane (1:1, v/v) as eluting solvent. The method was validated using mango and papaya samples fortified with pesticides at different concentration levels (0.05, 0.10, and 1.0 mg/kg). Average recoveries (4 replicates) ranged from 80% to 146%, with relative standard deviations between 1.0% and 28%. Detection and quantification limits for mango and papaya ranged from 0.01 to 0.03 mg/kg and 0.05 to 0.10 mg/kg, respectively. The proposed method was applied to the analysis of these compounds in commercial fruit samples from a local market (Aracaju/SE, Brazil), and residues of the pesticides were not detected on the samples.

Sorption of organophosphorous pesticides onto chickpea husk from aqueous solutions.

The sorption efficiency of chickpea husk of black gram variety (BGH), for the removal of organophosphorous pesticides (OPPs), i.e. triazophos (TAP) and methyl parathion (MP) from aqueous media has been investigated. Optimization of operating sorption parameters, i.e. particle size, sorbent dose, agitation time, pH, initial concentration of sorbates, and temperature has been studied. The sorption data fitted well to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) sorption isotherms. The maximum sorption capacities of BGH for TAP and MP were calculated to be 3.5+/-0.45 and 10.6+/-0.83 mmol g(-1) by Freundlich, 0.0077+/-0.021 and 0.025+/-0.0094 mmol g(-1) by Langmuir and 0.48+/-0.037 and 0.15+/-0.077 mmol g(-1) by D-R isotherms respectively, employing 0.2g of sorbent, at pH 6, 90 min agitation time and at 303 K. Application of first order Lagergren and Morris-Weber equations to the kinetic data yielded correlation coefficients, close to unity and showed partial intra-particle diffusion. The negative values of thermodynamic parameters, i.e. DeltaH (kJ mol(-1)), DeltaS (J mol(-1) K(-1)) and DeltaG (kJ mol(-1)) indicate the exothermic and spontaneous nature of the sorption process. The sorbed pesticides were recovered by sonication with methanol, making the regeneration and reutilization of the sorbents promising. The investigated sorbent exhibited potential applications in water decontamination, treatments of industrial and agricultural waste waters and thus productively demonstrated viable use of agricultural waste material.

The removal efficiency of chestnut shells for selected pesticides from aqueous solutions.

The removal of selected pesticides such as carbofuran (CF) and methyl parathion (MP) using low-cost abundant sorbent chestnut shells from aqueous solutions has been investigated in the present study. The sorption parameters, i.e., contact time, pH, initial pesticide solution concentration and temperature have been studied. Maximum percent sorption (99+/-1%) was achieved for (0.38-3.80) x10(-4) and (0.45-4.5) x10(-4) mol dm(-3) of MP and CF pesticide solutions respectively, using 0.4 g of sorbent in 100 ml of solution for 30 min agitation time at pH 6. The Freundlich, Langmuir and Dubinin-Radushkevich (D-R) models have been applied, and their constants for methyl parathion and carbofuran, sorption intensity 1/n (0.55+/-0.02 and 0.54+/-0.04), multilayer sorption capacity C(m) (28.3+/-0.5 and 16.4+/-0.7) x10(-3) mol l(1-1/n)dm(3/n)g(-1), monolayer sorption capacity Q (22.5+/-0.5 and 10.8+/-0.3) x10(-6) mo lg(-1), binding energy, b (2.9+/-0.2 and 5.2+/-0.5) x10(4) dm(3)mol(-1), and sorption energy E (11.2+/-0.1 and 11.5+/-0.2 kJ mol(-1)) have been evaluated respectively. Lagergren, Morris-Weber and Reichenberg equations were employed to study kinetics of sorption process. Thermodynamic parameters DeltaH (-5.09+/-0.1 and 22.8+/-0.4 kJ mol(-1)), DeltaS (-4.33+/-0.0003 and 0.09+/-0.001 kJ mol(-1)K(-1)) and DeltaG((303K)) (-2.9 and -3.8 kJ mol(-1)) have been calculated for methyl parathion and carbofuran, respectively. The developed sorption procedure has been employed to environmental samples.

Low cost sorbents for the removal of methyl parathion pesticide from aqueous solutions.

Sorptive potential of selected agricultural waste materials i.e. rice (Oryza sativa) bran (RB), bagasse fly ash (BFA) of sugarcane (Saccharum officinarum), Moringa oleifera pods (MOP) and rice husk (RH) for the removal of methyl parathion pesticide (MP) from surface and ground waters has been investigated. Optimization of operating parameters of sorption process, i.e. sorbent dose, agitation time, pH, initial concentration of sorbate, and temperature have been studied. The sorption data fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) sorption isotherms. The maximum capacities of RB, BFA, MOP and RH for MP were calculated to be 3.6+/-0.8, 5.3+/-1.4, 5.2+/-1.5 and 4.7+/-1.0 mmolg(-1) by Freundlich, 0.39+/-0.009, 0.39+/-0.005, 0.36+/-0.004 and 0.35+/-0.008 mmolg(-1) by Langmuir and 0.9+/-0.08, 1.0+/-0.10, 1.0+/-0.10 and 0.9+/-0.07 mmolg(-1) by D-R isotherms respectively, employing 0.1g of each sorbent, at pH 6, 90 min agitation time and at 303 K. Application of first order Lagergren and Morris-Weber equations to the kinetic data yielded correlation coefficients, close to unity. Thermodynamic parameters of sorption process, i.e. DeltaH, DeltaS and DeltaG were computed and their negative values indicated the exothermic and spontaneous nature of sorption process. The pesticide may be stripped by sonication with methanol, making the regeneration and reutilization of sorbents promising. The sorbents investigated exhibited their potential applications in water decontamination, treatment of industrial and agricultural waste waters.

Sorption and detoxification of toxic compounds by a bifunctional organoclay.

Organoclays are excellent sorbents for nonionic contaminants and therefore may have many environmental applications. A major limitation on the use of organoclays is that the contaminant merely changes its location from one environmental compartment to another while still remaining intact. In this study, a new type of organoclay, termed a bifunctional organoclay, has been prepared. It is able not only to sorb organophosphate pesticides, but also to catalyze their hydrolysis, and thereby detoxify them. The bifunctional organoclay prepared in this study is based on sodium montmorillonite, in which the inorganic counter ions are replaced by N-decyl-N,N-dimethyl-N-(2-aminoethyl) ammonium (DDMAEA). The detoxifying capacity of this organoclay for two organophosphate pesticides, methyl parathion [O,O-dimethyl O-(p-nitrophenyl) thionophosphate] and tetrachlorvinphos [2-chloro-1-(2,4,5-trichlorophenyl)ethenyl dimethyl phosphate], was demonstrated. It was shown that although the sorption of these pesticides on the bifunctional organoclay is very similar to that on N-decyl-N,N,N-trimethyl ammonium (DTMA) organoclay (the corresponding nonbifunctional organoclay), the hydrolysis of these pesticides is substantially enhanced only by the bifunctional organoclay. The half-life for the hydrolysis of the investigated pesticides in the presence of the bifunctional organoclay is about 12 times less than for their spontaneous hydrolysis, and the enhancement is even more pronounced relative to the hydrolysis of these pesticides in the presence of the DTMA organoclay (which actually inhibits their hydrolysis). Based on kinetic measurements, the pK(a) of the ethylamino group of the bifunctional organoclay was estimated to be around 9.0. It is postulated that the catalytic effect of the bifunctional organoclay can be attributed to a nucleophilic attack of the unprotonated ethylamino group of the organoclay on the organophosphate ester.

[Use of methyl parathion (MP)-degrading strain DLL-E4 (Pseudomonas sp.) to remove MP residue on the surface of agricultural products].

In this paper, derivations from DLL-E4, including fermented liquid, its centrifuged (3000 x g, 10 min) supernatant, pellet extract with supersonic, crude enzyme(supernatant and pellet extract), detergent, and mixture of detergent and pellet extract, were used to degrade the MP residue on the surface of Chinese cabbage, tea and cucumber. The results showed that all of them were effective, with the best effect of 100%. Some constituents in the supernatant of fermented liquid could stimulate the enzymatic activity. For tea, the mixture of detergent and enzyme was more effective, but the opposite was found for the other two crops. In all treatments, crude enzyme and pellet extract had the best effect, and the rational added amount of enzyme was 2%, 5% and 10% for cucumber, Chinese cabbage and tea, respectively. Crude enzyme also could degrade methamidophos phoxim and chlorpyrifos.

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.