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We report on the rates of decomposition of a group of N-methylcarbamate (NMC) pesticides (carbaryl, carbofuran and propoxur) under pre-determined tropical field conditions. Rates of decomposition for three NMCs were determined at pH 7.08 and T = 20 °C and pH 7.70 and T = 33 °C respectively, as follows: carbaryl (78 days and 69 days); carbofuran (143 days and 83 days) and propoxur (116 days and 79 days). Investigation on methods for removal of NMCs and their phenolic decomposition products shows that activated charcoal outperforms zeolite, alumina, diatomaceous earth, cellulose and montmorillonite clay in the removal of both NMCs and phenols from aqueous solution. Furthermore, metal complexation studies on the NMCs and phenols showed that Fe (III) forms a complex with isopropoxyphenol (IPP) within which the Fe:IPP ratio is 1:3, indicative of the formation of a metal chelate complex with the formula Fe(IPP) 3 .

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 ( K m and V max ) 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.

Water quality assessment was conducted on the Ruiru River, a tributary of an important tropical river system in Kenya, to determine baseline river conditions for studies on the aquatic fate of N-methyl carbamate (NMC) pesticides. Measurements were taken at the end of the long rainy season in early June 2013. Concentrations of copper (0.21-1.51 ppm), nitrates (2.28-4.89 ppm) and phosphates (0.01-0.50 ppm) were detected at higher values than in uncontaminated waters, and attributed to surface runoff from agricultural activity in the surrounding area. Concentrations of dissolved oxygen (8-10 ppm), ammonia (0.02-0.22 ppm) and phenols (0.19-0.83 ppm) were found to lie within normal ranges. The Ruiru River was found to be slightly basic (pH 7.08-7.70) with a temperature of 17.8-21.2°C. The half-life values for hydrolysis of three NMC pesticides (carbofuran, carbaryl and propoxur) used in the area were measured under laboratory conditions, revealing that rates of decay were influenced by the electronic nature of the NMCs. The hydrolysis half-lives at pH 9 and 18°C decreased in the order carbofuran (57.8 h) > propoxur (38.5 h) > carbaryl (19.3 h). In general, a decrease in the electron density of the NMC aromatic ring increases the acidity of the N-bound proton removed in the rate-limiting step of the hydrolysis mechanism. Our results are consistent with this prediction, and the most electron-poor NMC (carbaryl) hydrolyzed fastest, while the most electron-rich NMC (carbofuran) hydrolyzed slowest. Results from this study should provide baseline data for future studies on NMC pesticide chemical fate in the Ruiru River and similar tropical water systems.

Chlorpyrifos (O, O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) and carbaryl (1-naphthyl methylcarbamate) are often applied concurrently as insecticides in food production. The aim of this study was to research their migration behavior in a real environment. We researched the leaching of both pesticides by setting up field lysimeters on a farm with the typical soil used in fruit production today. In order to analyze the variables involved in this process, we performed complementary adsorption studies, we performed complementary adsorption studies using batches and undisturbed soil laboratory columns for both compounds. The results for pesticide transport through the lysimeters showed that less than 1% of chlorpyrifos was recovered in the leachates, while almost 17% was recovered for carbaryl. Having completed the experiment in undisturbed laboratory columns, soil analysis showed that chlorpyrifos mainly remained in the first 5 cm, while carbaryl moved down to the lower sections. These results can be explained in view of the sorption coefficient values (K D ) obtained in horizons A and B for chlorpyrifos (393 and 184 L kg -1 ) and carbaryl (3.1 and 4.2 L kg -1 ), respectively. By integrating the results obtained in the different approaches, we were able to characterize the percolation modes of these pesticides in the soil matrix, thus contributing to the sustainable use of resources.

This study was undertaken to investigate the adsorption capacity of carbaryl on four Indian soils with different physiochemical properties. A batch adsorption study was carried out in order to evaluate the maximum adsorption capacity of carbaryl using a Response Surface Methodology (RSM). The effects of operating parameter such as initial carbaryl concentration (1-20 mgL⁻¹), adsorbent dosage (0.5-6 g) and contact time (10-180 min) were examined. The proposed quadratic model for Box-Behnken design fits very well to the experimental data because it may be used to navigate design space according to ANOVA results. The regression co-efficient (R²) of the models developed and the results of validation experiments conducted at optimal conditions strongly suggests that the predicted values are in good agreement with experimental results. Contour and response surface plots are used to determine the interactions effects of main factors and optimal conditions of the process. The experiment can be utilized as a guideline for better understanding of carbaryl adsorption onto soil under different operating conditions. The results show that the forest soil is most efficient in binding carbaryl (Sevin) than the other types of soil tested.

A hazardous waste stream, generated during the manufacture of carbaryl (1-naphthyl-n-methylcarbamate), an insecticide, was explored for assessing its suitability for incineration. The physico-chemical characteristics such as proximate analysis (moisture, volatile matter, fixed carbon and ash), ultimate analysis (carbon, hydrogen, nitrogen, sulphur and oxygen), calorific value and the heavy metal content of the waste indicated that carbaryl waste was suitable for incineration. The incineration experiments were conducted in a bench-scale (25 mm ID, 450 mm long) quartz reactor at various operating temperatures (800 to 1200 degrees C) at a fixed gas-phase residence time of two seconds. Results of the experiments showed that carbaryl waste could be effectively incinerated at a temperature of 1200 degrees C with a gas-phase residence time of two seconds. The destruction and removal efficiency (DE) at these operating conditions was > 99.99% for carbaryl, which was monitored as a principal organic hazardous compound (POHC). The ash generated at these operating conditions was subjected to the Toxicity Characteristic Leaching Procedure (TCLP) and was found to be non-toxic in nature.

The sorption of carbaryl (1-naphthyl methyl carbamate) and ethion [O,O,O',O'-tetraethyl S,S'-methylene bis(phosphorodithioate)] was studied in whole soils as well as after treatment of soil with 2% hydrofluoric acid (HF) to remove paramagnetic materials and to oxidize most forms of labile carbon by photo-oxidation with high energy (UV) on < 53 microm fractions. The sorption coefficient (K(d)) values for carbaryl and ethion in soils did not follow the order of their organic carbon (OC) content, and specially their char content However, the K(oc) values in < 53 microm fractions after hydrofluoric acid/photo-oxidation with high energy (hydrofluoric acid/ultraviolet; HF/UV) treatment were found to be much higher than those in bulk untreated soils. The effect of organic matter chemistry was determined by correlating K(oc) values of contaminants in bulk soils or 53 microm fractions against sample aromaticity. A poor correlation of K(oc) in bulk soil and aromatic C values of both carbaryl and ethion was observed. However, the correlation between the K(oc) and the aromatic fraction of C after the HF/UV treatment improved significantly, reflecting the contribution of char fraction of carbon in soils towards sorption of pesticides. The increase in sorption after HF/UV treatment suggested that the sorption potential of biochars, which are expected to contribute significantly to contaminant sorption due to their high surface area, can remain masked by the organo-mineral interactions of char in whole soils. This has implications for the modification of surfaces of the freshly applied biochars in soils due to organo-mineral interactions.

The dissipation of (O-methyl-14C) monocrotophos and U-ring labelled 14C-carbaryl was monitored for over two years in absence and presence of other insecticides using in situ soil columns. The dissipation of 14C-monocrotophos from soil treated with methomyl and carbaryl showed a faster rate of downward movement than in a control column tagged with the labelled insecticide alone. The same trend was observed in experiments with 14C-carbaryl that dissipated more readily in soil treated with non-labelled monocrotophos and methomyl. In the presence of other insecticides the percentage of bound residues was generally lower than in control experiments. The bound residues at the top of the column are released at a low rate under conditions prevailing in the field. The overall time required for dissipation of 50% of monocrotophos and carbaryl (t50) as estimated from control experiment was approximately 20 and 24 weeks, respectively. The data indicate that repeated applications of pesticides might enhance the release of 14C-bound residues.

Carbofuran (2,3-dihydro-2,2-dimethyl-7-benzofuranol-N-methylcarbamate) and carbaryl (1-naphthyl-N-methylcarbamate) are insecticides widely used in tea plantations. The objective of the present study was to evaluate the dissipation of carbofuran and carbaryl during the growth periods of Oolong tea, processing and roasting. Analysis of the residual insecticides was carried out using high-pressure liquid chromatography with a post-column fluorescence detector. Results showed that in the tea field carbofuran dissipated faster then carbaryl. Manufacturing processes of Oolong tea further reduced the carbofuran and carbaryl contents. The persistence of carbofuran and carbaryl was decreased with increasing roasting temperature. From the results, we conclude that the presence of carbofuran and carbaryl in tea can be reduced by proper field management, manufacturing and roasting processes.

The potential of five nonionic surfactants, Triton X-100, Brij35, Ethylan GE08, Ethylan CD127, and Ethylan CPG660 for enhancing release of carbaryl and ethion from two long-term contaminated soils was evaluated using the batch method. Incorporation of the surfactants into soils enhanced the release of both pesticides to various extents, which could be related to the type of pesticides and type and the amount of surfactants added. Release of ethion was dramatically enhanced by aqueous concentrations of surfactants above their critical micelle concentration values. This was attributed to solubility enhancement through incorporation of the highly hydrophobic compound within surfactant micelles. A concentration of 10 g L(-1) of various surfactants released >70% of the total ethion from the soil irrespective of the surfactant. For carbaryl, the surfactants were effective at low concentrations and dependence on concentration was lower than in the case of ethion. The ethylan surfactants (GE08, CD127, and CPG660) had a higher potential than Triton X-100 and Brij35 for releasing the pesticides. However, there was still a significant portion of carbaryl (11% of the total) and ethion (17% of the total) left in the soil. Our study also showed that there must be an optimal concentration of each surfactant to maximize the mass transfer of pesticides. At some threshold concentration level, additional surfactant started to inhibit the mass transfer of solute from the soil into the water. The results suggested that surfactants could help remediation of soils polluted by pesticides. The choice of surfactant should be made based on the properties of pesticides.