Hydrolysis Of Pesticides Research Articles

A new method to treat fumigant pesticides-spent granular activated carbon utilizing alkaline hydrolysis

Groundwater treatment of recalcitrant fumigant pesticides (1,2-dibromo-3-chloropropane (DBCP), 1,2-dibromoethane (EDB), 1,2-dichloropropane (DCP), and 1,2,3-trichloropropane (TCP)) often involves a pump and treat system with granular activated carbon (GAC). A novel and promising method of treating the pesticide-spent GAC is based on alkaline hydrolysis, a well-understood abiotic transformation mechanism, that offers a potentially greener approach to conventional thermal regeneration. Here, alkaline hydrolysis of these pesticide chemicals was evaluated under homogeneous (aqueous), and heterogeneous (pesticide spent-GAC) conditions involving bituminous- and coconut-based GAC. Aqueous treatment occurred at elevated pH (pH 12.0–12.4) and the pesticide rate of hydrolysis transformation was first-order (DBCP ≫ TCP ≫ EDB ≫ DCP). Significant pesticide loss (94.95–99.98%) was achieved in both types of GAC (pH 12.0–12.4; 30 d). GAC suspensions held (5 d) at pH 11.0, 12.0, and 12.6, resulted in the DBCP loss of 74%, 89%, and 99%, respectively. The pH dependency of DBCP hydrolysis underscores the correlation between alkaline conditions, aggressive hydrolysis treatment, and reaction time for engineered systems. The estimated time (4–8 min) for full OH- intraparticle diffusion into the GAC from bulk solution was much less than the pesticide hydrolysis half-lives indicating that alkaline hydrolysis treatment of pesticides in GAC was reaction rate limited. Rapid small scale column tests demonstrated that the post-treatment (i.e., base hydrolysis) impact on adsorptive characteristics of the GAC was limited.

Kinetics, mechanism, and tautomerism in ametryn acid hydrolysis: From molecular structure to environmental impacts

The excessive use of pesticides and the demand for environmentally friendly compounds have driven the focus to detailed studies of the environmental destination of these compounds. Degradation by hydrolysis of pesticides, when released into the soil, can result in the formation of metabolites with potentially adverse effects on the environment. Moving in this direction, we investigated the mechanism of acid hydrolysis of the herbicide ametryn (AMT) and predicted the toxicities of metabolites through experimental and theoretical approaches. The formation of ionized hydroxyatrazine (HA) occurs with the release of the SCH3- group and the addition of H3O+ to the triazine ring. The tautomerization reactions privileged the conversion of AMT into HA. Furthermore, the ionized HA is stabilized by an intramolecular reaction that provides the molecule in two tautomeric states. Experimentally, the hydrolysis of AMT was obtained under acidic conditions and at room temperature with HA as the main product. HA was isolated in a solid state through its crystallization as organic counterions. The mechanism of conversion of AMT to HA and the experimental investigation of the reaction kinetics allowed us to determine the dissociation of CH3SH as the rate-controlling step in the degradation process that culminates in a half-life between 7 and 24 months under typical acid soil conditions of the Brazilian Midwest – region with strong agricultural and livestock vocation. The keto and hydroxy metabolites showed substantial thermodynamic stability and a decrease in toxicity compared to AMT. We hope that this comprehensive study will support the understanding of the degradation of s-triazine-based pesticides.

Rapid detection of carbamate pesticide residues using microchip electrophoresis combining amperometric detection

The long-term consumption of food with pesticide residues has harmful effects on human health and the demand for pesticide detection technology tends to be miniaturized and instant. To this end, we demonstrated the first application of indirectly detecting two carbamate pesticides, metolcarb and carbaryl, by gold nanoparticle-modified indium tin oxide electrode in dual-channel microchip electrophoresis and amperometric detection (ME-AD) system. m-Cresol and α-naphthol were obtained after pesticide hydrolysis in alkaline solution, and then separated and detected by ME-AD. Parameters including the detection potential and running buffer concentration and pH were optimized to improve the detection sensitivity and separation efficiency. Under the optimal conditions, the two analytes were completely separated within 80s. m-Cresol and α-naphthol presented a wide linear range from 1 to 100μM, with limits of detection of 0.16μM and 0.34μM, respectively (S/N = 3). Moreover, the reliability of this system was demonstrated by analyzing metolcarb and carbaryl in spiked vegetable samples.

Carbon and nitrogen stable isotope fractionation during abiotic hydrolysis of pesticides

Compound-specific Stable Isotope Analysis (CSIA) has been recently established as a tool to study pesticide degradation in the environment. Among degradative processes, hydrolysis is environmentally relevant as it can be chemically or enzymatically mediated. Here, CSIA was used to examine stable carbon and nitrogen isotope fractionation during abiotic hydrolysis of legacy or currently used pesticides (chloroacetanilide herbicides: Acetochlor, Alachlor, S-Metolachlor and Butachlor, acylalanine fungicide: Metalaxyl, and triazine herbicide: Atrazine). Degradation products analysis and CN dual-CSIA allowed to infer hydrolytic degradation pathways from carbon and nitrogen isotopic fractionation. Carbon isotopic fractionation for alkaline hydrolysis revealed similar apparent kinetic isotope effects (AKIEC = 1.03–1.07) for the 6 pesticides, which were consistent with SN2 type nucleophilic substitutions. Neither enantio-selectivity (EF ≈ 0.5) nor enantio-specific isotope fractionation occurred during hydrolysis of R (AKIEC = 1.04 ± 0.01) and S (AKIEC = 1.04 ± 0.02) enantiomers of a racemic mixture of Metalaxyl. Dual element isotope plots enabled to tease apart CCl bond breaking of alkane (Λ ≈ εN/εC ≈ 0, Acetochlor, Butachlor) and aromatic π-system (Λ ≈ 0.2, Atrazine) from CO bond breaking by dealkylation (Λ ≈ 0.9, Metalaxyl). Reference values for abiotic versus biotic SN2 reactions derived from carbon and nitrogen CSIA may be used to untangle pesticide degradation pathways and evaluate in situ degradation during natural and engineered remediation.

Simultaneous hydrolysis of carbaryl and chlorpyrifos by Stenotrophomonas sp. strain YC-1 with surface-displayed carbaryl hydrolase

Many sites are often co-contaminated with multiple pesticides. To date, there are no reports on simultaneous degradation of different classes of pesticides by a natural microorganism. In this work, we aim at constructing a live biocatalyst able to simultaneously hydrolyze carbaryl and chlorpyrifos. For this purpose, carbaryl hydrolase (CH) was displayed on the cell surface of a chlorpyrifos-degrading bacterium Stenotrophomonas sp. strain YC-1 using N- and C-terminal domain of ice nucleation protein (INPNC) from Pseudomonas syringae INA5 as an anchoring motif. The localization of INPNC-CH fusion protein in the outer membrane fraction was demonstrated by cell fractionation followed by Western blot analysis. Surface display of INPNC-CH was further confirmed by proteinase accessibility experiment and immunofluorescence microscope. CH was present in an active form on cell surface without causing any growth inhibition, suggesting that the INP-based display system is a useful tool for surface expression of macromolecular heterologous proteins on the bacterial cell surface. Because surface-displayed CH has free access to pesticides, this bacterium can be used as a whole-cell biocatalyst for efficient hydrolysis of pesticides.

Kinetic Study and Mechanism Hydrolysis of 4‐Bromo‐3,5 dimethylphenyl N‐methylcarbamate in Aqueous Media

ABSTRACTDegradation via hydrolysis is among the main transformation pathways and particularly for N‐methylcarbamates. Carbamate pesticide hydrolysis is known to proceed through alkaline catalysis, with reaction of the hydroxide ion with the carbonyl function or with abstraction of hydrogen in the α position with respect to the carbonyl. This reaction leads to the formation of methylamine and corresponding phenol. In this respect, the reaction kinetics of 4‐bromo‐3,5‐dimethylphenyl N‐methylcarbamate (BDMC) hydrolysis have been investigated in alkaline solution using a spectrophotometric technique and reversed phase liquid chromatography. The kinetic constants were determined following a proposed pseudo–first‐order kinetic model. The positive activation entropy ΔS≠ = +35.73 J mol−1 K−1 and the absence of general base catalysis indicated an unimolecular elimination conjugate base (E1cB) hydrolytic mechanism involving the formation of methyl isocyanate. This result was confirmed by the fact that BDMC fits well into brönsted and Hammett lines, obtained for a series of substituted N‐methylcarbamate whose decomposition in aqueous media was established to follow an E1cB mechanism.

Cloning of a Novel Arylamidase Gene from Paracoccus sp. Strain FLN-7 That Hydrolyzes Amide Pesticides

The bacterial isolate Paracoccus sp. strain FLN-7 hydrolyzes amide pesticides such as diflubenzuron, propanil, chlorpropham, and dimethoate through amide bond cleavage. A gene, ampA, encoding a novel arylamidase that catalyzes the amide bond cleavage in the amide pesticides was cloned from the strain. ampA contains a 1,395-bp open reading frame that encodes a 465-amino-acid protein. AmpA was expressed in Escherichia coli BL21 and homogenously purified using Ni-nitrilotriacetic acid affinity chromatography. AmpA is a homodimer with an isoelectric point of 5.4. AmpA displays maximum enzymatic activity at 40°C and a pH of between 7.5 and 8.0, and it is very stable at pHs ranging from 5.5 to 10.0 and at temperatures up to 50°C. AmpA efficiently hydrolyzes a variety of secondary amine compounds such as propanil, 4-acetaminophenol, propham, chlorpropham, dimethoate, and omethoate. The most suitable substrate is propanil, with K(m) and k(cat) values of 29.5 μM and 49.2 s(-1), respectively. The benzoylurea insecticides (diflubenzuron and hexaflumuron) are also hydrolyzed but at low efficiencies. No cofactor is needed for the hydrolysis activity. AmpA shares low identities with reported arylamidases (less than 23%), forms a distinct lineage from closely related arylamidases in the phylogenetic tree, and has different biochemical characteristics and catalytic kinetics with related arylamidases. The results in the present study suggest that AmpA is a good candidate for the study of the mechanism for amide pesticide hydrolysis, genetic engineering of amide herbicide-resistant crops, and bioremediation of amide pesticide-contaminated environments.

Probing the simulant behavior of PNPDPP toward parathion and paraoxon: A computational study

The extreme toxicity of organophosphorus nerve agents and pesticides mandates to employ models or simulants in place of the actual compounds in the laboratory. The importance of simulants is known, however, their efficacy for direct comparison with the toxic organophosphorus compounds is not well documented. We have examined the potential energy surfaces (PES) for the alkaline hydrolysis of pesticides like paraoxon (diethyl 4-nitrophenyl phosphate), parathion (O,O-diethyl O-4-nitrophenyl phosphorothioate) and PNPDPP (4-nitrophenyl diphenyl phosphate), a simulant with MP2/6-311+G*//B3LYP/6-311+G*+ΔGsolv (HF/6-31+G*) level of theory. The effect of aqueous solvation was considered with the Integral Equation Formalism Polarizable Continuum Model (IEF-PCM). The alkaline hydrolysis of these organophosphorus compounds reveals that the reaction proceeds through the attack of hydroxide ion at the phosphorus center to form a pentacoordinate intermediate. The calculated free energies of activation for the alkaline hydrolysis of paraoxon and parathion are in good agreement with the available experimental activation free energies. The computed results show that the reaction profiles for the alkaline hydrolysis of paraoxon, parathion and PNPDPP are largely similar; however, the rate of hydrolysis of parathion may be higher than that of paraxon and PNPDPP. Such difference arises due to the less electrophilic nature of the phosphorus atom of parathion molecule as observed in the charge analysis study. The conceptual DFT analysis also showed the similar trend for the alkaline hydrolysis of paraoxon, parathion and PNPDPP with hydroxide anion. This computational study provides a quantitative support toward the use of PNPDPP as a simulant for organophosphorus compounds, which cannot be used directly for the laboratory purposes.

Hydrolysis and Hydrolysis Pathways of Composite of Copper (II) and Cypermethrin

The composite of copper ion and cypermethrin (CPM) may affect the hydrolysis of CPM. The experiments considered different factors which may affect the hydrolysis of pesticides, using buffer solutions with different pH to study the hydrolysis of CPM. The results showed that the existence of Cu2+ significantly promoted the hydrolysis of CPM, which might be related to the complexes that Cu2+ and CPM had produced. The hydrolysis kinetics of CPM followed the first-order kinetics. We used GC/MS to detect the hydrolysis of CPM intermediates and proposed the possible hydrolysis pathways.

Hydrolysis of Pesticides in Wastewater Catalyzed by Cu(II) Complexes of Silyl Based Cationic Micelles

The effect of cationic surfactant micelles, namely hexadecyl trimethyl silane ammonium chloride (A), dodecyl trimethyl silane ammonium chloride, (B) and their copper (II) ion complexes on the hydrolysis of the pesticides: diazinon, cypermethrin, and carbaryl was studied. The rate of the pesticides decay in water was significantly accelerated in presence of these cationic micellar solutions. Furthermore, the copper (II) ion complexes of these micellar were found to be much more effective in hydrolysis of these pesticides. The results indicate that the complexes with a 1:1 ratio of both ligands to the metal ions are the active species in catalytic hydrolysis of carbaryl pesticide. Kinetic study is explained.

Overexpression of methyl parathion hydrolase and its application in detoxification of organophosphates

The coding region of mpd gene corresponding to mature methyl parathion hydrolase (MPH) was heterologously overexpressed in Escherichia coli BL21 (DE3) by using pET expression system. The lactose-induced expression yield of MPH is increased 2-fold compared with IPTG as inducer. Furthermore, it was found that specific activity of MPH increased 48% by reducing the induction temperature to 22 degrees C. The addition of 25 mM lactose at 22 degrees C, the MPH activity of fermentation broth had a specific activity of 1.4 x 10(4) U/mg protein. Plasmid was no significant decrease in the modified medium. The optimal pH and temperature of MPH were 8.0 and 30 degrees C, respectively. Over a period of 5 months, the dried cells showed no significant decrease in the activity of the detoxifying enzymes. The crude enzymes in 50 mM citrate-phosphate buffer (pH 8.0) were able to degrade about 98% of the organophosphate pesticides sprayed on cabbage. The detoxification efficiency was superior to that of the treatments of water, detergent, and a commercially available enzyme product. Additionally, the products of pesticide hydrolysis generated by treatment with the enzyme extract were determined to be virtually nontoxic.

Decontamination of vegetables sprayed with organophosphate pesticides by organophosphorus hydrolase and carboxylesterase (B1)

A genetically engineered Escherichia coli cell expressing both organophosphorus hydrolase (OPH) and carboxyl esterase (CaE) B1 intracellularly was constructed and cultivated. The harvested wet cells were vacuum dried, and the storage stability of the dried cell powder was determined in terms of OPH activity. Over a period of 5 mo, the dried cells showed no significant decrease in the activities of the detoxifying enzymes. The crude enzymes in 50 mM citrate-phosphate buffer (pH 8.0) were able to degrade approx 97% of the organophosphate pesticides sprayed on cabbage. The detoxification efficiency was superior to that of the treatments of water, detergent, and a commercially available enzyme product. Additionally, the products of pesticide hydrolysis generated by treatment with the enzyme extract were determined to be virtually nontoxic.

Nitrated phenols in the atmosphere: a review

This paper reviews the data concerning the atmospheric occurrence of nitrophenols, both in the gas and in the condensed phase (rainwater, cloud, fog and snow). Data obtained from field campaigns are reported, together with a description of the analytical techniques employed for the identification and quantification of nitrophenols. Analysis is usually performed using techniques such as High Performance Liquid Chromatography (HPLC) or Gas Chromatography-Mass Spectrometry (GC-MS), with the sampling method largely determined according to the matrix under investigation. The sources of atmospheric nitrophenols include direct emissions resulting from combustion processes, hydrolysis of pesticides (e.g. parathion) and the secondary formation of nitrophenols in the atmosphere. Atmospheric nitration of phenol can take place both in the gas and liquid phases, but the relative importance of these processes is still under discussion. The gas-phase nitration involves reaction between phenol and OH+NO2 during the day or NO3+NO2 during the night. Gas-phase nitration during the day yields only 2-nitrophenol (2-NP); while during the night it is thought that both 2-NP and 4-nitrophenol (4-NP) may be formed. Because of many gaps in the experimental evidence it is apparent that more research is required to indicate whether the 4-NP present in the environment can be accounted for by this nighttime process. Nitration in the condensed phase can be initiated by electrophilic nitration agents such as N2O5 and ClNO2. Other liquid-phase processes can also take place, in the presence of NO3, nitrate and nitrite, in the dark and under irradiation. Condensed-phase processes have been shown to yield 2- and 4-NP in similar amounts. It is also important to consider the atmospheric sinks of nitrophenols. The rate constant for the reaction between 2-NP and OH in the gas phase is rather low (9.0×10−13 cm3 molecule−1 s−1), while incomplete data are available for the reaction with NO3. In addition, condensed-phase processes might also represent an important nitrophenol sink. Potential loss routes include the reaction with radicals such as OH and NO3 in aqueous solution as well as the nitration to form the dinitrophenols.

Monitoring some phenoxyl-type N-methylcarbamate pesticide residues in fruit juices using high-performance liquid chromatography with peroxyoxalate-chemiluminescence detection

A systematic investigation of optimal conditions for determining three of the most common phenoxyl-type N-methylcarbamate pesticides (carbaryl, carbofuran and propoxur) in fruit juices by HPLC with peroxyoxalate-chemiluminescence detection is described. The required pre-column hydrolysis of pesticides and derivatization of their hydrolytic metabolites with dansyl chloride was simultaneously carried out in a short time thanks to the micellar catalytic effect provided by cetyltrimethyl ammonium bromide micelles on the hydrolysis step. The liquid chromatographic separation of the dansylated phenols was performed on a reversed-phase C 18 column with isocratic elution. The analytes were detected by using an integrated derivatization chemiluminescence detection unit based on the bis(2,4,6-trichlorophenyl)oxalate–hydrogen peroxide system. Fruit juice samples containing 4.0–1500 μg/l pesticides were analysed with a precision of ca. 6.5%. After contamination of the fruit juice samples, average recovery >93% at fortification levels of 10–100 μg/l was obtained.

Investigation of new indirect spectrophotometric method for the determination of carbofuran in carbamate pesticides

A new spectrophotometric method has been investigated for the determination of Carbofuran pesticide. The method was based on the hydrolysis of the pesticides. The hydrolyzed products, methylamine on reaction with sodium nitroprusside solution in acetone medium gives a purple colored solution. The absorbance of the resulting solution was measured at 530 nm. Conditions for the complete hydrolysis of pesticides and quantitative determination of methylamine were optimized. From the standard calibration plot of methylamine, the amount of pesticides was calculated. The amount of active ingredients in commercial products was determined from the amount of methylamine found. It was observed that lower concentration of the active ingredients were present in the commercial products. The limit of detection and quantification was calculated and found to be 0.804 and 2.68 ppm respectively.

Structural study on inclusion complexes of cyclodextrins with organophosphorus pesticides by use of rotational strength analysis method

For inclusion complexes of cyclodextrins with parathinons and paraoxon, inclusion depths were estimated with the rotational strength analysis method. The inclusion depths of pesticides were sensitive to the difference in the hydrophobic properties of the phosphate and monothiophosphate groups and were in close correlations with the substrate-specificity for the cyclodextrin-catalyzed hydrolysis of pesticides. The inclusion depths were also characteristically affected by surfactant material having high solubilization functions to aquatic environmental chemicals.

Paraoxon and parathion hydrolysis by aqueous molybdenocene dichloride (Cp2MoCl2): first reported pesticide hydrolysis by an organometallic complex.

We report the first case of an organometallic complex that effectively hydrolyzes the organophosphate pesticides parathion and paraoxon. The complex is the water-soluble compound bis(eta 5-cyclopentadienyl)molybdenum(IV) dichloride (1), which hydrolyzes parathion to produce ethanol and deethyl parathion in a biphasic reaction in D2O. Rate accelerations were 130 and 10(5) at pH 7 and 3, respectively. Paraoxon is readily hydrolyzed by 1 to yield p-nitrophenol and diethyl phosphate with rate accelerations of 2300 and 27 at pH 7 and 3, respectively. Kinetic data for paraoxon hydrolysis by 1 are consistent with a process that involves intermolecular (delta S++ = -49 +/- 10 eu) hydroxide attack on the phosphate triester in which the aquated 1 serves as a coordinated Lewis acid that activates the organophosphate. Interestingly parathion hydrolysis by 1 occurs via nucleophilic attack at the alpha-carbon of the phosphorothioate pesticide that involves C-O bond cleavage. These parathion results represent one of the few cases of this type of unusual hydrolytic chemistry and the first case of an organometallic complex that accelerates organophosphate pesticide hydrolysis.

Inhibition by Insecticides of Partially Purified Carboxylesterase from Aphis gossypii (Homoptera: Aphididae

Inhibition of partially purified carboxylesterase from a dichlorvos selected (ED-R) strain of cotton aphid, Aphis gossypii (Glover), by selected insecticides was demonstrated in vitro. Regeneration of active enzymes was not observed up to 5 h after removal of excess inhibitor. This result indicates that pesticide hydrolysis is not a likely resistance mechanism in A. gossypii Carboxylesterases from this aphid seem likely to bind permanently to inhibitors, rendering them ineffective and thus protecting the active sites of pesticide inhibition. Of 2 oregano phosphate and 2 carbamate insecticides tested, dichlorvos was most inhibitory. The order of toxicity ranked dichlorvos > naled > carbaryl > m-tolyl methylcarbamate.

Polarographic study of simazine in micellar and emulsified media

A polarographic study of the reduction of the herbicide simazine in micellar solutions and oil-water emulsions is reported. The anionic surfactant sodium pentanesulphonate was chosen as the most suitable agent for micellar solutions and emulsions. In micellar solutions two reduction peaks were observed in differential-pulse polarography (DPP) below pH 2.0, whereas only one peak was obtained above pH 2.0. Ethyl acetate was chosen as the organic solvent to form simazine emulsions. Unlike in micellar solutions, DP polarograms of simazine in oil-water emulsions showed only one peak even at pH values lower than 2.0, suggesting that pesticide hydrolysis is hindered in the emulsified medium. The limiting current is diffusion-controlled and the electrode process is irreversible. The diffusion coefficient of simazine in emulsified medium was 8.85 × 10−6 cm2 s−1, and the αna and K°f values were 0.82 and 8.03 × 10−14 cm s−1 respectively. Using DPP, simazine can be determined over the concentration ranges 8.0 × 10−7−4.0 × 10−5 mol l−1. The limit of detection was 2.2 × 10−7 mol l−1. The effect of the presence of other herbicides belonging to the s-triazine family on the simazine reduction peak was studied. The method was applied to the determination of simazine in spiked irrigation water with good recoveries.

Degradation of pesticides in soil as influenced by the presence of hydrolysis metabolites

Abstract The degradation of 8 pesticides was evaluated in a soil pretreated with their respective hydrolysis metabolites. 2,4‐Dichlorophenol, p‐nitrophenol, and salicylic acid conditioned the soil for enhanced degradation of 2,4‐dichlorophenoxyacetic acid (2,4‐D), parathion, and isofenphos, respectively. Repeated application of carbofuran phenol, 2‐isopropyl‐4‐methyl‐6‐hydroxypyrimidine, methyl phenyl sulfone, thiophenol, isopropyl salicylate, and 2,4,5‐trichlorophenol had no effect on the rate of degradation of their parent pesticides. Prior exposure of soil to 3,5,6‐trichloro‐2‐pyridinol resulted in increased persistence of its parent compound, chlorpyrifos. Results indicate that pesticide hydrolysis metabolites can effect the induction or inhibition of enhanced microbial degradation of some soil‐applied pesticides.