Efficacy of biochar in removal of organic pesticide, Bentazone from watershed systems.

Bentazone is one of the toxic insecticides used to control forest tent caterpillar moths, boll weevils, gypsy moths, and other types of moths in various field crops. We report the efficacy of biochar prepared from the Azardirachta Indica waste biomass as adsorbent for removal of Bentazone. Biochar material was prepared by pyrolysis process under limited oxygen conditions. Biochar material was characterized by proximate and ultimate analysis, SEM analysis, FTIR analysis and TG/DTA analyses. The Bentazone adsorption capacity by biochar from aqueous solutions was assessed. Effect of time, adsorbent dosage, insecticide concentration and pH on the adsorption characteristics of the biochar were evaluated. Adsorption parameters were obtained at equilibrium contact time of 150 min, with biochar dosage of 0.5 g at pH 8. From the optimization studies, desirability of 0.952 was obtained with response (adsorption uptake) of 79.40 mg/g, for initial concentration of insecticide (50 mg/L), adsorbent dosage (0.448 g), time 30.0 min and pH 2. The adsorption isotherm data for the removal of Bentazone fitted well with the Freundlich isotherm. This study indicates that the biochar produced from the bark of Azardirachta Indica biomass could be employed as a potential adsorbent for removal of synthetic organic pollutants from the water streams.

Photocatalytic degradation of herbicide bentazone in aqueous suspension of TiO2: mineralization, identification of intermediates and reaction pathways.

Semiconductor-mediated hydrogen peroxide-assisted photocatalytic degradation of a selected herbicide, Bentazone (1) has been investigated in aqueous suspensions of TiO2 under a variety of conditions. The degradation was studied by monitoring the depletion in total organic carbon content as a function of irradiation time. The degradation kinetics was investigated under different conditions such as type of TiO2 (Anatase/Anatase-Rutile mixture), reaction pH, catalyst dosage and hydrogen peroxide (H202) concentration. The degradation rates were found to be strongly influenced by all the above parameters. Titanium dioxide Degussa P25 was found to be more efficient as compared with other two commercially available TiO2 powders like Hombikat UV100 and PC500 from Millennium Inorganic Chemicals. Gas Chromatography-Mass Spectrometry (GC-MS) analysis of the irradiated mixture of Bentazone (1) indicates the formation of several intermediate products which have been characterized on the basis of molecular ion/mass fragmentation pattern and also on comparison with the National Institute of Standards and Technology (NIST) library. Plausible mechanism for the formation of different products during photocatalytic treatment of Bentazone in the presence of TiO2 has been proposed. The use of H202 substantially increased the efficiency of TiO2 photocatalytic degradation.

Nylon membrane as a fluorimetric probe for the herbicide bentazone.

The fluorimetric signal produced by bentazone retained in selected solid surfaces was investigated. Among the different tested supports, only a microporous nylon membrane produced the desired signal. The quantitative study was carried out by second-order calibration using parallel factor analysis, allowing the determination in a highly interfering medium. A detection limit of 0.4 ng mL(-1), a prediction relative error of 8%, and a sample frequency of ten samples per hour were obtained in spiked natural waters using green analytical chemistry principles.

Evaluation of stereo and chemical stability of chiral compounds.

A stopped-flow bidimensional recycle HPLC (sf-BD-rHPLC) configuration has been used to investigate simultaneously the stereo and chemical stability of labile chiral compounds. The single enantiomers of a racemate can be separated on chiral column (first dimension) and each one can be trapped in the achiral column (second dimension) that works as reactor.By filling the achiral column with the appropriate aqueous buffers it is possible to evaluate the stability of the trapped enantiomer toward aqueous buffer itself. It was possible to recycle the reaction products formed in the chiral column (first dimension) where they are separated by a second six valve port. The reaction rate constants were calculated for the different processes occurred in the achiral column by means of corresponding peak areas. The method was applied to a pharmacological active compound: (±)7-chloro-5-ethyl-3-methyl-3,4-dihydro-2H-benzo[1,2,4]thiadiazine 1,1-dioxide ((±)-1) to evaluate enantiostability and hydrolysis in conditions similar to those of biological fluid. A classical batchwise kinetic method was used to calculate rate constants of hydrolysis and enantiomerization at the same temperature and in the same solvents used in sf-BD-rHPLC. The good agreement of the results obtained validate the novel procedure developed. Furthermore, the results generated off-line were used to determine the influence of solvents on the racemization of (±)-1.

Determination of kinetic parameters of enantiomerization of benzothiadiazines by DCXplorer.

Benzothiadiazines differently substituted at the sulfonamidic nitrogen atom, at the stereogenic carbon atom and at the anilinic nitrogen atom have been synthesized and fully characterized. Enantioseparation of these compounds has revealed rapid on-column enantiomerization. The recently developed software DCXplorer has been successfully applied to calculate enantiomerization kinetic parameters. Enantiomerization barriers of 3-phenyl substituted benzothiadiazines, calculated in this work, have indicated a higher enantiomerization rate suggesting that the aromatic substituent exerts a strong effect on the enantiomerization process. Methyl substitution on N(2) position led to higher free energy barriers of enantiomerization, suggesting negative influence of methyl in the N(2) position on enantiomerization kinetics. However, methylation on N(4) position increases the enantiomerization rates significantly. The results obtained have been employed to postulate an enantiomerization mechanism for chiral benzothiadiazine type compounds.

Measurement and modeling of bentazone in the river Main (Germany) originating from point and non-point sources.

A Water Framework Directive pilot project combines measured data and model approaches to calculate fluxes and mass balance of the pesticide bentazone in an 81 km section of the river Main (Germany). During the study period (six weeks in spring 2004) the observed bentazone inflow and outflow in the river section amounted to 52.8 and 53.1 kg, respectively; the maximum concentrations reached 220 and 290 ng l(-1). Based on sampling of seven sewage treatment plants a specific loss of 0.87 g bentazone per farm was calculated. Extrapolation to the entire sub-basin results in 2.6 kg bentazone in total as point source contribution from farms. Diffuse input into the surface water network occurred after an intensive rainfall event on May 7th. Total bentazone load was simulated with the pesticide emission model DRIPS to be 23.2 kg. One third of this load was estimated to be degraded by photolysis before reaching the main waterway, the river Main. The ATV water quality model was applied to predict the concentration profile of bentazone in river Main between Schweinfurt and Würzburg with reasonable results. The difference between total measured and modeled fluxes amounted to 1.5 kg corresponding to 2% of the overall input. The combined approach of monitoring and modeling appears to be a valuable strategy to quantify the relevance of point and non-point sources and to focus effective mitigation measures to the most relevant origins within a river basin.

Simultaneous determination of enantiomerization and hydrolysis kinetic parameters of chiral N-alkylbenzothiadiazine derivatives.

On-column stopped flow multidimensional HPLC (sfMDHPLC) and dynamic high-performance liquid chromatography were applied to investigate the influence of alkyl substituents at the sulfonamidic and amino moieties of benzothiadiazine 1,1-dioxide derivatives on hydrolysis and enantiomerization rate constants. The data obtained indicate the presence of pyrrolo substituent at the 3,4 positions on benzothiadiazine rings inhibits the hydrolysis, whereas the enantiomerization occurs in acidic medium. Hydrolysis rates are quite similar for the two benzothiadiazines methyl substituted to nitrogen at 2- and 4-positions. Conversely, enantiomerization rate of 4-N-methyl substituted is significantly higher than 2-N-methyl substituted.

Determination of bentazone, dichlorprop, and MCPA in different soils by sodium hydroxide extraction in combination with solid-phase preconcentration.

A method for the extraction of bentazone, dichlorprop, and MCPA in three selected Norwegian soils of different textures is described. Initially three different extraction methods were tested on one soil type. All methods gave recoveries >80% for the pesticide mixture, but extraction with sodium hydroxide in combination with solid-phase preconcentration was used for further recovery tests with soils of different properties spiked at four herbicide concentration levels (0.001-10 microg/g of wet soil). The method was rapid and easy and required a minimum of organic solvents. The recoveries were in the range of 82-109, 80-123, and 45-91% for the soils containing 1.4 (Hole), 2.5 (Kroer), and 37.8% (Froland) organic carbon, respectively. Limits of quantification using GC-MS were 0.0003 microg/g of wet soil for bentazone and 0.0001 microg/g of wet soil for both dichlorprop and MCPA.