High-efficiency degradation of methomyl by the novel bacterial consortium MF0904: Performance, structural analysis, metabolic pathways, and environmental bioremediation.

Methomyl is a widely used carbamate pesticide, which has adverse biological effects and poses a serious threat to ecological environments and human health. Several bacterial isolates have been investigated for removing methomyl from environment. However, low degradation efficiency and poor environmental adaptability of pure cultures severely limits their potential for bioremediation of methomyl-contaminated environment. Here, a novel microbial consortium, MF0904, can degrade 100% of 25 mg/L methomyl within 96 h, an efficiency higher than that of any other consortia or pure microbes reported so far. The sequencing analysis revealed that Pandoraea, Stenotrophomonas and Paracoccus were the predominant members of MF0904 in the degradation process, suggesting that these genera might play pivotal roles in methomyl biodegradation. Moreover, five new metabolites including ethanamine, 1,2-dimethyldisulfane, 2-hydroxyacetonitrile, N-hydroxyacetamide, and acetaldehyde were identified using gas chromatography-mass spectrometry, indicating that methomyl could be degraded firstly by hydrolysis of its ester bond, followed by cleavage of the C-S ring and subsequent metabolism. Furthermore, MF0904 can successfully colonize and substantially enhance methomyl degradation in different soils, with complete degradation of 25 mg/L methomyl within 96 and 72 h in sterile and nonsterile soil, respectively. Together, the discovery of microbial consortium MF0904 fills a gap in the synergistic metabolism of methomyl at the community level and provides a potential candidate for bioremediation applications.

A microwave-induced plasma jet for efficient degradation of methomyl in aqueous solution.

As a typical carbamate pesticide, methomyl was once widely used in agriculture for its excellent broad-spectrum insecticidal effect. However, due to its high toxicity, long half-life, and difficult degradation properties, it poses a serious challenge to water environment pollution. In this study, an electrode-free discharge microwave-induced plasma technology was used to rapidly and efficiently degrade methomyl in aqueous solution. In this experiment, the statistical design of experiments (DOE) was adopted to optimize the plasma degradation parameters. Under the optimized parameters (P = 140 W, D = 0 mm, R = 0.5 L/min), 78.4% removal of 50 mg/L of methomyl was achieved after 8 min. The optical emission spectrometry and free radical detection experiments showed that the active substances generated by the collision reaction between plasma and water molecules occurring at the gas-liquid interface were the key factors to exert the degradation effect. The degradation rate of methomyl decreased by 73.2% after the addition of tert-butanol (OH burster), while it decreased by only about 12.0% after the addition of peroxidase. These implied that ∙OH was largely responsible for methomyl degradation. In addition, based on the detected intermediates, possible degradation mechanisms and pathways were analyzed.

Evaluation of Post-Mortem Interaction between Hemoglobin and Oxime-Type Carbamate Pesticides.

Oxime-type carbamate pesticides having an oxime moiety such as aldicarb, butocarboxim, methomyl, oxamyl, and thiofanox are widely used and have been detected in many fatal cases of accidental exposure or suicide. In forensic toxicology, the accurate determination of blood pesticide concentration is obligatory to prove death by oxime-type carbamate pesticide poisoning. However, the fatal pesticide concentration in blood at autopsy differs from that at the time of death. In this study, we found that oxime-type carbamate pesticides were decomposed by Hb in a temperature-dependent fashion. The mechanism underlying methomyl, aldicarb, oxamyl, and thiofanox decomposition involves the formation of adducts with the amino acids in Hb. With regard to butocarboxim, its decomposition involves the oxidation of the free form and the formation of adducts with the amino acids in Hb. The mass spectra obtained by liquid chromatography quadrupole time-of-flight mass spectrometry revealed that carbamylated amino acid adducts such as Wcar-adduct and Vcar-adduct were formed in Hb solution incubated with methomyl, aldicarb, oxamyl, and thiofanox, whereas alkylated amino acid adducts such as Walkyl-adduct were formed in Hb solution incubated with butocarboxim. These results indicate that aldicarb, butocarboxim, methomyl, oxamyl, and thiofanox are post-mortem changed by Hb.

Post-Mortem Changes of Methomyl in Blood with Hemoglobin.

Methomyl, (E,Z)-methyl N-{[(methylamino)carbonyl]oxy}ethanimidothioate, is a widely used pesticide that has been detected in many fatal cases of accidental exposure or suicide. Forensic toxicologists have been baffled that the blood methomyl concentration in persons who have died of methomyl poisoning is much lower than the expected concentration in blood. In this study, we speculated two mechanisms underlying the insufficient recovery of methomyl in blood. First, methomyl is decomposed by serum albumin as esterase. Second, methomyl is bound to a specific blood protein, resulting in insufficient recovery in the free form. However, human serum albumin does not show esterase activity for the decomposition of methomyl. On the contrary, specific methomyl hemoglobin adducts have been detected by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-Q/TOF-MS). The mass spectra indicated that methomyl was specifically bound to tryptophan (W), tyrosine (Y), and valine (V) residues in hemoglobin. The amounts of W- and V-adducts dose-dependently increased in vitro when the methomyl concentration was lower than the lethal concentration. In addition, the W-adduct was detected in blood sampled from an autopsied subject who died of intentional methomyl ingestion, suggesting that the W-adduct could be used as a biomarker of methomyl poisoning. We were able to estimate the amount of methomyl ingested on the basis of the amount of the W-adduct.

Investigation of pesticides on honey bee carbonic anhydrase inhibition.

Carbonic anhydrase (CA, EC 4.2.1.1) plays crucial physiological roles in many different organisms, such as in pH regulation, ion transport, and metabolic processes. CA was isolated from the European bee Apis mellifera (AmCA) spermatheca and inhibitory effects of pesticides belonging to various classes, such as carbamates, thiophosphates, and pyrethroids, were investigated herein. The inhibitory effects of methomyl, oxamyl, deltamethrin, cypermethrin, dichlorodiphenyltrichloroethane (DDT) and diazinon on AmCA were analysed. These pesticides showed effective in vitro inhibition of the enzyme, at sub-micromolar levels. The IC50 values for these pesticides ranged between of 0.0023 and 0.0385 µM. The CA inhibition mechanism with these compounds is unknown at the moment, but most of them contain ester functionalities which may be hydrolysed by the enzyme with the formation of intermediates that can either react with amino acid residues or bid to the zinc ion from the active site.

Photoformation of reactive oxygen species and their potential to degrade highly toxic carbaryl and methomyl in river water.

Reactive oxygen species (ROS) including singlet oxygen (1O2) and hydroxylradicals (OH) photogenerated in natural waters play important roles in indirect photolysis of man-made pollutants. This study was conducted to investigate how the generation of these two ROS influences the degradation of two highly toxic insecticides (methomyl and carbaryl) in river water. To accomplish this, the reaction rate constants of 1O2 and OH with carbaryl and methomyl were determined; the degradation rate constants of the tested insecticides in ultrapure water (direct photolysis) and in river water in the presence and absence of 1O2 and OH scavengers were also measured. The rate constants for the reaction of OH with carbaryl and methomyl were found to be (14.8 ±â€¯0.64) × 109 and (4.68 ±â€¯0.52) × 109 M-1 s-1, respectively. The reaction rate constant of 1O2 with carbaryl (2.98 ±â€¯0.10) × 105 M-1 s-1, was much higher than that of methomyl (<104 M-1 s-1). Indirect photolysis by OH accounted for 63% and 62%, while 1O2 accounted for 26% and 30% and direct photolysis accounted for 1.4% and 7% of methomyl and carbaryl degradation, respectively. The high degradation rate in river water demonstrated by both insecticides suggests that indirect photolysis mediated by OH is an important means of their degradation in river water. In addition, kinetic calculations of OH-mediated degradation rate constants of the compounds agrees with their experimentally-determined values thereby confirming the importance of OH towards their degradation.

Soluble esterases as biomarkers of neurotoxic compounds in the widespread serpulid Ficopomatus enigmaticus (Fauvel, 1923).

The characterization of soluble cholinesterases (ChEs) together with carboxylesterases (CEs) in Ficopomatus enigmaticus as suitable biomarkers of neurotoxicity was the main aim of this study. ChEs of F. enigmaticus were characterized considering enzymatic activity, substrate affinity (acetyl-, butyryl-, propionylthiocholine), kinetic parameters (Km and Vmax) and in vitro response to model inhibitors (eserine hemisulfate, iso-OMPA, BW284C51), and carbamates (carbofuran, methomyl, aldicarb, and carbaryl). CEs were characterized based on enzymatic activity, kinetic parameters and in vitro response to carbamates (carbofuran, methomyl, aldicarb, and carbaryl). Results showed that cholinesterases from F. enigmaticus showed a substrate preference for acetylthiocholine followed by propionylthiocholine; butyrylthioline was not hydrolyzed differently from other Annelida species. CE activity was in the same range of cholinesterase activity with acetylthiocholine as substrate; the enzyme activity showed high affinity for the substrate p-nytrophenyl butyrate. Carbamates inhibited ChE activity with propionylthiocholine as substrate to a higher extent than with acetylthiocoline. Also CE activity was inhibited by all tested carbamates except carbaryl. In vitro data highlighted the presence of active forms of ChEs and CEs in F. enigmaticus that could potentially be inhibited by pesticides at environmentally relevant concentration.

Degradation of methomyl by the combination of Aminobacter sp. MDW-2 and Afipia sp. MDW-3.

Methomyl (S-methyl N-(methylcarbamoyloxy) thioacetimidate) is a kind of oxime carbamate insecticide. It is considered to be extremely toxic to nontarget organism. To date, no pure culture or consortium has been reported to have the ability to degrade methomyl completely. In this study, a methomyl-degrading enrichment E1 was obtained by using the sludge from the wastewater-treating system of a pesticide manufacturer as the original inoculant. Two bacterial strains named MDW-2 and MDW-3 were isolated from this enrichment, and they were preliminarily identified as Aminobacter sp. and Afipia sp. respectively. Strains MDW-2 and MDW-3 could coexist and degrade 50 mg l-1 methomyl completely within 3 days by the cooperative metabolism. Methomyl was first converted to methomyl oxime and methylcarbamic acid by strain MDW-2, and the latter could be used as the carbon source for the growth of strain MDW-2. But methomyl oxime could not be sequentially degraded by strain MDW-2. However, it could be degraded and used as the carbon source by strain MDW-3. SIGNIFICANCE AND IMPACT OF THE STUDY: This study presents a bacterial combination of Aminobacter sp. MDW-2 and Afipia sp. MDW-3, which could degrade methomyl completely by biochemical cooperation. This study also proposes the biodegradation pathway of methomyl for the first time and highlights the application potential of a bacterial combination in the remediation of methomyl-contaminated environments.

Intensification of degradation of methomyl (carbamate group pesticide) by using the combination of ultrasonic cavitation and process intensifying additives.

In the present work, the degradation of methomyl has been carried out by using the ultrasound cavitation (US) and its combination with H2O2, Fenton and photo-Fenton process. The study of effect of operating pH and ultrasound power density has indicated that maximum extent of degradation of 28.57% could be obtained at the optimal pH of 2.5 and power density of 0.155 W/mL. Application of US in combination with H2O2, Fenton and photo-Fenton process has further accelerated the rate of degradation of methomyl with complete degradation of methomyl in 27 min, 18 min and 9 min respectively. Mineralization study has proved that a combination of US and photo-Fenton process is the most effective process with maximum extent of mineralization of 78.8%. Comparison of energy efficiency and cost effectiveness of various processes has indicated that the electrical cost of 79892.34Rs./m(3) for ultrasonic degradation of methomyl has drastically reduced to 2277.00Rs./m(3), 1518.00Rs./m(3) and 807.58Rs./m(3) by using US in combination with H2O2, Fenton and photo-Fenton process respectively. The cost analysis has also indicated that the combination of US and photo-Fenton process is the most energy efficient and cost effective process.

Encapsulation and controlled release of hydrophilic pesticide in shell cross-linked nanocapsules containing aqueous core.

In this study, amphiphilic biocopolymers, synthesized by mixing azidobenzaldehyde (Az) and an aqueous solution of carboxymethyl chitosan (CMCS), which self-assemble into nanocapsules with a aqueous core (ACN) in aqueous media followed by photo-cross-linking to obtain shell cross-linked nanocapsules, were used to develop a controlled release pesticide system. The system was characterized by TEM and DLS. Its encapsulation efficiency was determined. The obtained result showed that it is efficient to encapsulate methomyl reaching encapsulation efficiency as high as 90% in an aqueous medium at pH 4.0, which is mainly attributed to the hydrogen bonding adsorption between methomyl molecules and the inner surface of nanocapsules. Release profiles of methomyl from methomyl-loaded nanocapsules in an aqueous solution at pH 6.0 were shown to be diffusion controlled with a half-release time (t(½)) of 36.3-69.5h from different samples. The shell cross-linking and its degree of cross-linking are assumed to be responsible for this diffusion behavior. The insecticidal activity test in laboratory showed that the control efficacy of methomyl-loaded nanocapsules against the armyworm larvae was significantly superior to the original. The relative control efficacy still maintained 100% over 7 days.

Micro-mechanism and rate constants for OH-initiated degradation of methomyl in atmosphere.

The atmospheric degradation reactions of the two isomers of methomyl (MTL) initiated by OH radical in the presence of O2, NO and H2O have been investigated by density functional theory (DFT). The calculations were all carried out at MPWB1K level. The geometrical parameters and vibrational frequencies of stationary points were calculated with 6-31+G (d, p) basis sets. Single-point energy calculations were performed with 6-311+G (3df, 2p) basis sets. Profiles of the potential energy surface were constructed and all possible channels involved in the reactions were discussed. The rate constants of main elementary reactions were calculated over a temperature range of 200-400 K and mostly fitted to Arrhenius formulas. The atmospheric lifetimes of reaction species were discussed for the first time, which can be applied to the study on model simulation and management of hazardous materials.

Effective photodegradation of methomyl pesticide in concentrated solutions by novel enhancement of the photocatalytic activity of TiO2 using CdSO4 nanoparticles.

Annihilation of electrons-holes recombination process is the main remedy to enhance the photocatalytic activity of the semiconductors photocatalysts. Doping of this class of photocatalysts by foreign nanoparticles is usually utilized to create high Schottky barrier that facilitates electron capture. In the literature, because nonpolar nanoparticles (usually pristine metals, e.g., Ag, Pt, Au, etc.) were utilized in the doping process, the corresponding improvement was relatively low. In this study, CdSO4-doped TiO2 nanoparticles are introduced as a powerful and reusable photocatalyst for the photocatalytic degradation of methomyl pesticide in concentrated aqueous solutions. The utilized CdSO4 nanoparticles form polar grains in the TiO2 matrix due to the electrons leaving characteristic of the sulfate anion. The introduced nanoparticles could successfully eliminate the harmful pesticide under the sunlight radiation within a very short time (less than 1 h), with a removal capacity reaching 1,000 mg pesticide per gram of the introduced photocatalyst. Moreover, increase in the initial concentration of the methomyl did not affect the photocatalytic performance; typically 300, 500, 1,000, and 2,000 mg/l solutions were completely treated within 30, 30, 40, and 60 min, respectively, using 100 mg catalyst. Interestingly, the photocatalytic efficiency was not affected upon multiple use of the photocatalyst. Moreover, negative activation energy was obtained which reveals super activity of the introduced photocatalyst. The distinct photocatalytic activity indicates the complete annihilation of the electrons-holes recombination process and abundant existence of electrons on the catalyst surfaces due to strong electrons capturing the operation of the utilized polar CdSO4 nanoparticles. The introduced photocatalyst has been prepared using the sol-gel technique. Overall, the simplicity of the synthesizing procedure and the obtained featured photocatalytic activity strongly recommend the introduced nanoparticles to treat the methomyl-containing polluted water.

Structural characterization of natural organic matter and its impact on methomyl removal efficiency in Fenton process.

This study aimed to characterize the NOM structural variation during Fenton process, in which the methomyl and humic acid were selected as the investigated compounds. The preliminary degradation experiments were conducted at various H2O2 and Fe(2+) concentrations without the presence of NOM to determine the applied Fenton reagent dosages for subsequent NOM impact on Fenton degradation. The methomyl removal at 80% was observed at the Fenton reagent ratio ([H2O2]/[Fe(2+)]) of 1 while Fe(2+) concentration was no less than 2mM. In the presence of NOM, the methomyl removal by Fenton process was further enhanced apparently. The NOM used in this study was found to be a macromolecule with tryptophan-like and tyrosine-like functional groups through fluorescence spectrometry analysis. The addition of ferrous ions in the NOM solution initiated the reactions between Fe(2+)/Fe(3+) redox couples and NOM molecules, breaking the NOM into smaller organic fractions. These organic fractions were further oxidized into even smaller molecules by hydroxyl radicals after H2O2 addition. The NOM might compete with methomyl for hydroxyl radicals, and enhance the catalytical generation of hydroxyl radicals by reducing Fe(3+) to Fe(2+) at the same time. Apparently, the increase in OH generation was more than the OH consumption by NOM presence, resulting in the observed enhancement of methomyl removal.

Effect of methomyl formulation, a carbamate pesticide on ovarian follicular development and fertility in albino mice.

Administration of 5 mg methomyl (40%) kg(-1) b.wt. mouse(-1) (equal to 50% of LD50 dose), every day for 90 days to adult female mice resulted in a significant decrease in body weight, relative weight of the ovary, uterus and fallopian tube; mean number of small, preantral, antral and pre-ovulatory follicles and fertility compared to controls. On the other hand, total duration of the estrous cycle was significantly increased compared to controls. One month after the cessation of the treatment (a commercial methomyl preparation-lannate) the effect on estrous cycle and organ weight was not restored. Treatment of 2.5 mg or 1 mg lannate kg(-1) b. wt., although did not alter duration of the estrous cycle; relative weight of the ovary, uterus, and fallopian tube and fertility, caused a significant decrease in mean number of small follicles compared to controls. All the groups of mice treated with lannate showed loss in body weight (15.15% in 1 mg, 6.61% in 2 mg and 12.16% in 5 mg treated groups) whereas controls showed a gain in body weight (20.02%) during the period of experimentation. The results indicate that 5 mg lannate kg(-1) b. wt causes loss of follicles and infertility, whereas lower dosages (2.5 and 1 mg) reduce the number of small follicles which might shorten reproductive life span of mice.

A novel luminescent terbium-3-carboxycoumarin probe for time-resolved fluorescence sensing of pesticides methomyl, aldicarb and prometryne.

The luminescence arising from lanthanide cations offers several advantages over organic fluorescent molecules: sharp, distinctive emission bands allow for easy resolution between multiple lanthanide signals; long emission lifetimes (µs-ms) make them excellent candidates for time-resolved measurements; and high resistance to photo bleaching allow for long or repeated experiments. A time-resolved (gated) luminescence-based method for determination of pesticides methomyl, aldicarb and prometryne in microtiterplate format using the long-lived terbium-3-carboxycoumarin in 1:3 metal:ligand ratio has been developed. The limit of detection is 1.20×10(6), 5.19×10(5) and 2.74×10(6)ng L(-1) for methomyl, prometryne and aldicarb, respectively. The quantum yield (QY=0.08) of Tb(III)-3-carboxycoumarin was determined using 3-(2-benzothiazolyl)-7-diethylamino-coumarin (coumarin 6). Stern-volmer studies at different temperatures indicate that collisional quenching dominates for methomyl, aldicarb and prometryne. Binding constants were determined at 303, 308 and 313 K by using Lineweaver-Burk equation. A thermodynamic analysis showed that the reaction is spontaneous with negative ΔG. Effect of some relevant interferents on the detection of pesticides has been investigated.

Adsorption behavior of pesticide methomyl on activated carbon in a high gravity rotating packed bed reactor.

High gravity rotating packed bed (HGRPB) reactor possesses the property of high mass transfer rate, which is expected to promote the adsorption rate for the process. In this study, HGRPB has been applied on adsorption removal of methomyl from solution, adopting the adsorbent of activated carbon F400. The influence of operating parameters of HGRPB on mass transfer such as the rotating speed (N(R)), the flow rate of solution (F(L)) and initial concentration of methomyl (C(b0)) were examined. The traditionally internal mass transfer models combined with Freundlich isotherm were used to predict the surface and effective diffusion coefficients. In addition, the results have also been compared with those obtained from the traditional basket stirred batch reactor (BBR). The results showed that the larger values of N(R) and F(L) enhanced the effective intraparticle diffusion and provided more accessible adsorption sites so as to result in lower equilibrium concentration in HGRPB system when compared to SBR system. The results of adsorption kinetics demonstrated that surface and effective diffusions were both significantly greater in HGRPB system instead of BBR system. Furthermore, the values of Bi(S) also manifested less internal mass transfer resistance in HGRPB system. The contribution ratio (R(F)) of the surface to pore diffusion mass transport showed that the larger contribution resulted from the surface diffusion in HGRPB system. Therefore, the results reasonably led to the conclusion that when the HGRPB system applied on the adsorption of methomyl on F400, the lower equilibrium concentration and faster internal mass transfer can be obtained so as to highly possess great potential to match the gradually stricter environmental standard.

Fluorescence and electrochemical sensing of pesticides methomyl, aldicarb and prometryne by the luminescent europium-3-carboxycoumarin probe.

This work describes the application of time resolved fluorescence in microtiterplates and electrochemical methods on glassy carbon electrode for investigating the interactions of europium-3-carboxycoumarin with pesticides aldicarb, methomyl and prometryne. Stern-volmer studies at different temperatures indicate that static quenching dominates for methomyl, aldicarb and prometryne. By using Lineweaver-Burk equation binding constants were determined at 303 K, 308 K and 313 K. A thermodynamic analysis showed that the reaction is spontaneous with ΔG being negative. The enthalpy ΔH and the entropy ΔS of reactions were all determined. A time-resolved (gated) luminescence-based method for determination of pesticides in microtiterplate format using the long-lived europium-3-carboxycoumarin has been developed. The limit of detection is 4.80, 5.06 and 8.01 µmol L(-1) for methomyl, prometryne and aldicarb, respectively. This is the lowest limit of detection achieved so far for luminescent lanthanide-based probes for pesticides. The interaction of the probe with the pesticides has been investigated using cyclic voltammetry (CV), differential pulse polarography (DPP), square wave voltammetry (SWV) and linear sweep voltammetry (LSV) on a glassy carbon electrode in I = 0.1 mol L(-1) p-toluenesulfonate at 25 °C. The diffusion coefficients of the reduced species are calculated. The main properties of the electrode reaction occurring in a finite diffusion space are the quasireversible maximum and the splitting of the net SWV peak for Eu(III) ions in the ternary complex formed . It was observed that the increase of the cathodic peak currents using LSV is linear with the increase of pesticides concentration in the range 5 × 10(-7) to 1 × 10(-5) mol L(-1). The detection limit (DL) were about 1.01, 2.23 and 1.89 µmol L(-1) for aldicarb, methomyl and prometryne, respectively. In order to assess the analytical applicability of the method, the influence of various potentially interfering species was examined. Influence of interfering species on the recovery of 10 µmol L(-1) pesticides has been investigated.

Interaction of organic contaminants with natural clay type geosorbents: potential use as geologic barrier in urban landfill.

The aim of this work is to characterize the capability of several clay materials as preservative of organic pollution for use as landfill barrier. Interaction of representative organic pollutants with different polarity and water solubility (atrazine, benzamide, methomyl, paraquat and toluene) with several clay materials coming from several locations of Spain were studied. Batch suspension method was used to study the pesticide adsorption onto the clay sorbents in solution conditions that simulate the composition of a young leachate in its aerobic acetogenic stage (pH=5 and I=0.15) The obtained data of the analytes sorption were modelized by several sorption isotherm models, and the best fitted data were got with a generalized Langmuir adsorption isotherm. The higher maxima adsorptions were observed for paraquat (50-62 mmol kg(-1)) and toluene (19-34 mmol kg(-1)) whereas more hydrophobic compounds present lower adsorption (0.7-2.5 mmol kg(-1)). Paraquat is the compound that presents the higher bonding coefficients. Therefore these clays could be used as components of the multibarriers in controlled urban landfill.

Experimental design applied to photo-Fenton treatment of highly methomyl-concentrated water.

This work is focused on the study of the suitability of the photo-Fenton process as a pretreatment for water highly contaminated with a methomyl commercial formulation in Advanced Greenhouses devices. Initial concentrations of reagents and pesticide were evaluated according to a central composite experimental design, with methomyl depletion and biocompatibility of the final effluent as response functions. A triad of optimal operation conditions could be determined, [Met.](0)=50 mg L(-1), [H(2)O(2)](0)=254 mg L(-1) and [Fe(2+)](0)=77 mg L(-1) for the best elimination yield and an acceptable BOD(5)/COD value, and initial concentration of methomyl can be established as the most important parameter for the performance of the treatment due to the limitations that impose on the hydrogen peroxide doses in the presence of the excipients of the commercial formulation.

A novel inhibitory kinetic fluorimetric method for the determination of trace methomyl in environmental samples.

A novel inhibitory kinetic fluorimetric method for the determination of trace methomyl was proposed. It was shown that the Fenton reagent oxidized rhodamine B in acid medium which enabled the fluorescence quenching of the latter. The presence of trace methomyl clearly inhibited the reaction. Upon addition of EDTA, a good linear relationship between the inhibitory effect and the concentration of methomyl was observed, together with improved stabilization and sensitivity. Factors affecting the determination of trace methomyl were investigated systematically. Under the optimum conditions, the linear range for the determination of methomyl was 0.04-2.2 microg/mL; the detection limit and the quantification limit for methomyl were 0.011 and 0.037 microg/mL, respectively. The proposed method was applied to the determination of methomyl in four environmental soil samples, six environmental water samples and one synthetic sample; the results were compared with those determined by the HPLC method. The recoveries and the relative errors were 83.5-101.2 and 0.47-2.02%, respectively. The possible reaction mechanism has also been discussed.