alpha(-(cyclopropylcarbonyl)-2-(methyvlsulfonyl)-beta-oxo-4-(trifluromethyl)benzenepropanenitrile) and isoxaflutole

The herbicide isoxaflutole has the potential to contaminate drinking water directly, as well as upon hydrolyzing to its active form diketonitrile. Diketonitrile also may impact water quality by acting as a precursor for dichloroacetonitrile (DCAN), which is an unregulated but highly toxic disinfection byproduct (DBP). In this study, we investigated the reaction of diketonitrile with free chlorine and chloramine to form DCAN. We found that diketonitrile reacts with free chlorine within seconds but reacts with chloramine on the time scale of hours to days. In the presence of both oxidants, DCAN was generated at yields up to 100%. Diketonitrile reacted fastest with chlorine at circumneutral pH, which was consistent with base-catalyzed halogenation involving the enolate form of diketonitrile present at alkaline pH and electrophilic hypochlorous acid, which decreases in abundance above its p

Topics: Chloramines; Chlorine; Disinfectants; Disinfection; Drinking Water; Halogenation; Water Pollutants, Chemical; Water Purification

Sorption largely controls pesticide fate in soils because it influences its availability for biodegradation or transport in the soil water. In this study, variability of sorption and desorption of isoxaflutole (IFT) and its active metabolite diketonitrile (DKN) was investigated under conventional and conservation tillage.. According to soil samples, IFT K(D) values ranged from 1.4 to 3.2 L kg(-1) and DKN K(D) values ranged from 0.02 to 0.17 L kg(-1) . Positive correlations were found between organic carbon content and IFT and DKN sorption. IFT and DKN sorption was higher under conservation than under conventional tillage owing to higher organic carbon content. Under conservation tillage, measurements on maize and oat residues collected from the soil surface showed a greater sorption of IFT on plant residues than on soil samples, with the highest sorbed quantities measured on maize residues (K(D) ≈ 45 L kg(-1) ). Desorption of IFT was hysteretic, and, after five consecutive desorptions, between 72 and 89% of the sorbed IFT was desorbed from soil samples. For maize residues, desorption was weak (<50% of the sorbed IFT), but, after two complementary desorptions allowing for IFT hydrolysis, DKN was released from maize residues.. Owing to an increase in organic carbon in topsoil layers, sorption of IFT and DKN was enhanced under conservation tillage. Greater sorption capacities under conservation tillage could help in decreasing DKN leaching to groundwater.

Topics: Adsorption; Agriculture; Avena; Biodegradation, Environmental; Herbicides; Isoxazoles; Nitriles; Soil; Sulfones; Zea mays

The fate of isoxaflutole (IFT) in soil is closely related to soil sorption. Sorption and transformation of IFT were investigated in laboratory incubations with four soils, and these results were used to interpret greenhouse studies using IFT to control several weed species.. Degradation proceeded by previously observed pathways to form diketonitrile (DKN) and benzoic acid (BA) derivatives, as well as traces of unidentified products. Over the course of the incubation, DKN was the dominant active form of the herbicide present in the experimental system, and was thus critical to the soil activity of the herbicide for weed control.. Control of most weed species appeared to be a function of both sorption and biodegradation of DKN, with greatest weed control being observed in soils in which a significant portion of the DKN that was formed persisted and remained bioavailable over the course of the incubation.

Topics: Adsorption; Benzoic Acid; Herbicides; Isoxazoles; Nitriles; Soil; Soil Pollutants; Sulfones

Laboratory studies were conducted to evaluate the effects of temperature and water pressure head on the degradation of the diketonitrile metabolite (DKN) of isoxaflutole during 84d in samples collected in a loamy soil under conventional (CT) and conservation (MT) tillage systems. Soil temperature was the major factor controlling DKN degradation in the two tillage systems. The shortest half-lives (T(1/2)) were measured in the seedbed samples under MT at 25 degrees C and -33cm water pressure head. We found that mouldboard ploughing under CT was responsible for the spatial variability of herbicide degradation properties, whereas under MT herbicide degradation was associated to the vertical distribution of organic matter.

Topics: Adsorption; Agriculture; Biodegradation, Environmental; Ecology; Herbicides; Humic Substances; Hydrostatic Pressure; Isoxazoles; Nitriles; Poaceae; Soil; Soil Pollutants; Sulfones; Temperature

Two-year field dissipation studies were conducted in three soil types in Minnesota to examine the processes affecting the dissipation of the herbicide isoxaflutole and its phytotoxic diketonitrile metabolite (DKN) under relatively cool, wet soil conditions. Plots of cuphea were treated with isoxaflutole and potassium bromide, a nonsorbed, nondegraded tracer. Replicate soil cores were collected six times during the growing season to a depth of 1 m, and the bromide or herbicide concentration was measured in each of five depth increments. The dissipation half-life (DT50) of isoxaflutole + DKN was 8-18 days in each soil. Bromide and herbicide concentrations were low at depths >40 cm throughout the study, and herbicide concentrations in soil 100 days after application were usually undetectable. Simulation modeling using Hydrus-1D for the loam soil suggested that plant uptake was an important mechanism of dissipation.

Topics: Bromides; Climate; Half-Life; Herbicides; Isoxazoles; Nitriles; Soil; Sulfones

Isoxaflutole (IXF; Balance) belongs to a new class of isoxazole herbicides. Isoxaflutole has a very short half-life in soil and rapidly degrades to a stable and phytotoxic degradate, diketonitrile (DKN). DKN was previously discovered to rapidly react with hypochlorite (OCl-) in tap water, yielding the benzoic acid (BA) degradate as a major product, but the complete reaction pathway and mechanism have not been elucidated. Thus, the objectives of this work were to (1) determine the stoichiometry of the reaction between DKN and OCl-; (2) identify products in addition to BA; and (3) propose a complete pathway and reaction mechanism for oxidation of DKN by OCl-. Stoichiometry of the reaction showed a molar ratio of OCl-/DKN of 2. In addition, two previously uncharacterized chlorinated intermediates were identified under conditions in which OCl- was the limiting reactant. The proposed chemical structure of a chlorinated benzoyl intermediate was inferred from a series of HPLC/MS and HPLC/MS/MS experiments and the use of mass spectral simulation software. A chlorinated ketone intermediate was also identified using ion trap GC/MS. Two additional end products were also identified: cyclopropanecarboxylic acid (CPCA) and dichloroacetonitrile (DCAN). On the basis of the reaction stoichiometry, the structure of the chlorinated intermediates, and the identification of the products, two reaction pathways are proposed. Both pathways involve a two-step nucleophilic attack and oxidation of the diketone structure of DKN, leading to formation of BA, DCAN, and CPCA.

Topics: Gas Chromatography-Mass Spectrometry; Herbicides; Hypochlorous Acid; Isoxazoles; Nitriles; Oxidation-Reduction; Sulfones; Water; Water Pollution

When analyzing the sorption characteristics of weakly sorbing or labile pesticides, batch methods tend to yield a high margin of error attributable to errors in concentration measurement and to degradation, respectively. This study employs a recently developed unsaturated transient flow method to determine the sorption of isoxaflutole's herbicidally active diketonitrile degradate (DKN) and dicamba. A 20-cm acrylic column was packed with soils with varied texture that had been uniformly treated with 14C-labeled chemical. The antecedent solution herbicide in equilibrium with sorbed phase herbicide was displaced by herbicide-free water, which was infiltrated into the column. Sorption coefficients, Kd, were obtained from a plot of total herbicide concentration in the soil versus water content in the region where the antecedent solution accumulated. DKN Kd values were approximately 2-3 times (average Kd = 0.71 L kg-1) greater using the unsaturated transient flow method as compared to the batch equilibration method in clay loam (Kd = 0.33 L kg-1), but similar for the two methods in sand (0.12 vs 0.09 L kg-1) soils. Dicamba Kd values were 3 times greater using the unsaturated transient flow method as compared to the batch equilibration method in the clay loam soil (0.38 vs 0.13 L kg-1), however, the Kd values were the same for the two methods in the sand (approximately 0.06 L kg-1). This demonstrates that to determine sorption coefficients for labile hydrophilic pesticides, an unsaturated transient flow method may be a suitable alternative to the batch method. In fact, it may be better in cases where transport models have overpredicted herbicide leaching when batch sorption coefficients have been used.

Topics: Adsorption; Carbon Radioisotopes; Dicamba; Environmental Monitoring; Herbicides; Isoxazoles; Nitriles; Reproducibility of Results; Soil Pollutants; Sulfones

The transformation of isoxaflutole (ISOX) to its herbicidally active diketonitrile degradate (DKN) was significantly enhanced in the presence of soil and occurred more rapidly in systems containing soil with a greater soil pH. Sorption-desorption of ISOX and DKN in five soils collected within a field revealed both ISOX and DKN were more readily sorbed to soils with greater organic matter, clay content, and lower soil pH. Sorption of ISOX residues occurred within 2 h, and extracts contained similar concentrations of ISOX and DKN at 24 h, suggesting the 24-h sorption coefficients for ISOX-treated systems were actually for mixed ISOX residues. Freundlich sorption coefficients were 3 and 4 times greater for ISOX than for DKN. On the basis of the Freundlich organic carbon sorption constants, ISOX and DKN can be categorized in the very high and high mobility classes, suggesting their potential to leach in the soils needs to be evaluated.

Topics: Adsorption; Herbicides; Hydrogen-Ion Concentration; Hydrolysis; Isoxazoles; Nitriles; Soil; Sulfones