Controlled release of carbofuran from an alginate-bentonite formulation: water release kinetics and soil mobility

The insecticide-nematicide carbofuran was incorporated in alginate-based granules to obtain controlled-release (CR) properties. The basic formulation [sodium alginate (1.61%)-carbofuran (0. 59%)-water] was modified by addition of sorbents. The effect on carbofuran release rate, caused by the incorporation of natural and acid-treated bentonite (0.5 and 1.0 M H(2)SO(4)) in alginate formulation, was studied by immersion of the granules in water under shaking. The time taken for 50% of the active ingredient to be released into water, t(50), was longer for those formulations containing natural bentonite (6.1 h) or acid-treated bentonite (9.0 and 11.7 h for 0.5 and 1.0 M H(2)SO(4) treatments, respectively) than for the preparation without bentonite (4.7 h). It appears from the results that the release of carbofuran from the various formulations is controlled by a diffusion mechanism according to the n values obtained, which were close to 0.5 in all cases. The mobility of carbofuran from alginate-based CR formulations was investigated by using soil columns packed with a clay soil (53% clay and 0.08% organic matter). Two alginate-based CR formulations containing natural bentonite or acid-treated bentonite (0.5 M H(2)SO(4)) were compared to technical grade carbofuran. The use of alginate-based CR formulations resulted in a reduction of the leached amount of carbofuran compared with the total amount of pesticide leached using the technical product (50 and 75% for CR granules containing natural and acid-treated bentonite, respectively). Alginate-bentonite CR formulations might be efficient systems for reducing carbofuran leaching in clay soils, which would reduce the risk of groundwater pollution.     

Volatilization of alachlor from polymeric formulations

Pesticides may be dispersed throughout the environment by several means, including groundwater contamination, surface water contamination, and volatilization with subsequent atmospheric transport and deposition. In earlier research primarily directed at reducing the potential for groundwater contamination, a number of herbicides were microencapsulated within several different polymers. These polymeric formulations were evaluated for efficacy in the greenhouse. In the studies described in this paper, three polymeric alachlor formulations that were the most effective in the greenhouse were evaluated in laboratory volatility studies using pure alachlor and a commercial formulation (Lasso 4EC) for comparison purposes. In a given experiment, technical alachlor, Lasso 4EC, and two polymeric formulations were applied to soil and evaluated in a contained system under 53% humidity with a fixed flow rate. Evolved alachlor was collected in ethylene glycol, recovered with C18 solid phase extraction cartridges, and analyzed by reverse-phase high-performance thin-layer chromatography with densitometry. Duration of the studies ranged from 32 to 39 days. In studies in which all formulations were uniformly incorporated in the soil, total alachlor volatilization from the polymeric microcapsules was consistently lower than that from the alachlor and Lasso 4EC formulations. In studies in which the polymeric formulations were sprinkled on the surface of the soil, microcapsules prepared with the polymer cellulose acetate butyrate released the smallest quantity of volatilized alachlor.     

Ethylcellulose formulations for controlled release of the herbicide alachlor in a sandy soil

The development of controlled-release formulations of alachlor to diminish its leaching in sandy soils, avoiding groundwater contamination and maintaining its efficacy, was studied. For this purpose, ethylcellulose (EC) microencapsulated formulations (MEFs) of alachlor were prepared under different conditions and applied to soil columns to study their mobility. The results show that in all cases the release into water of alachlor from MEFs was retarded when compared with commercial formulation. Total leaching losses in soil columns were reduced to 59% from 98%. The mobility of alachlor from EC microspheres into soil columns has been greatly diminished in comparison with its current commercial formulation (CF), above all with increasing EC/herbicide ratios. Distribution of alachlor applied as MEFs at different depths in the soil was higher in the soil surface (66.3-81.3% of herbicide applied at the first 12 cm). In contrast, the residues from CF along the complete soil column were only 20.4%. From the results of bioassays, MEFs showed a higher efficacy than CF at 30 days after the treatment. The use of ME formulations could provide an advantage in minimizing the risk of groundwater contamination by alachlor and reducing the application rates, as a result of maintaining the desired concentration of the herbicide in the top soil layer, obtaining longer periods of weed control.     

Controlled release of diuron from an alginate-bentonite formulation: water release kinetics and soil mobility study

The herbicide diuron was incorporated in alginate-based granules to obtain controlled release (CR) properties. The standard formulation (alginate-herbicide-water) was modified by the addition of different sorbents. The effect on diuron release rate caused by incorporation of natural and acid-treated bentonites in alginate formulation was studied by immersion of the granules in water under static conditions. The release of diuron was diffusion-controlled. The time taken for 50% release of active ingredient to be released into water, T(50), was calculated for the comparison of formulations. The addition of bentonite to the alginate-based formulation produced the higher T(50) values, indicating slower release of the diuron. The mobility of technical and formulated diuron was compared by using soil columns. The use of alginate-based CR formulations containing bentonite produced a less vertical distribution of the active ingredient as compared to the technical product and commercial formulation. Sorption capacities of the various soil constituents for diuron were also determined using batch experiments.     

Use of bentonite and activated carbon in controlled release formulations of carbofuran

Controlled release systems (CRS), unlike the conventional formulations, facilitate a gradual and controlled discharge of the pesticides, reducing the losses by evaporation and leaching and minimizing pesticide pollution. In this study, carbofuran-an insecticide-nematicide identified as a groundwater pollutant-was incorporated in alginate-based granules to obtain controlled release properties. The effect on carbofuran release rate caused by the incorporation of bentonite, activated carbon, and different mixtures of both sorbents in alginate basic formulation was studied by immersion of the granules in water. The water uptake, sorption capacity of the sorbent, permeability, and time taken for 50% of the active ingredient to be released into water, T(50), were calculated by the comparison of the preparations. T(50) values were higher for those formulations containing bentonite and/or activated carbon (T(50) values range from 14.76 h for the alginate formulation containing only bentonite as the sorbent to 29.5 weeks for the alginate formulation containing only activated carbon as the sorbent) than for the preparation without these sorbents (11.72 h). On the basis of a parameter of an empirical equation used to fit the insecticide-nematicide release data, it appears that the release of carbofuran from the various formulations into water is controlled by a diffusion mechanism. The sorption capacity of the sorbents for carbofuran was the most important factor modulating carbofuran release. In addition, it was observed that there is a linear correlation of the T(50) values and the content of activated carbon in dry granules.     

Controlled release of herbicide acetochlor from clay/carboxylmethylcellulose gel formulations

Controlled-release formulations of the herbicide acetochlor were prepared by using carboxylmethylcellulose (CMC) gel and different types of clay, which were obtained by acid activation, pillared with metal hydroxides, or saturated with organic cations. The effect of formulation parameters (amount and type of clay used, cross-linking time, and drying of the hydrogel formulations) on the acetochlor release rate from different formulations was evaluated by water-release studies. The time taken for 50% of acetochlor to be released, t 50, showed a wide variation (151-522 h) for dried gel formulations, the largest value corresponding to the formulation incorporating aluminum hydroxide pillared clay into CMC gels. The release rate of acetochlor from clay/CMC hydrogel formulations decreased with the increase of the hydrogels' cross-linking time (t50 values ranged from 2.18 to 14.0 h for cross-linking times ranging from 2.0 to 120 min). The performance of inorganic clays in dried gel formulations on slowing the release of acetochlor is related to their sorption capacities, but the addition of organic clay did not lead to the slowest release despite its highest sorption capacity. According to the parameters of an empirical equation used to fit herbicide-release data, the release of acetochlor from clay/CMC gel formulations is controlled by diffusion mechanism.     

Environmentally friendly slow-release nitrogen fertilizer

To sustain the further world population, more fertilizers are required, which may become an environmental hazard, unless adequate technical and socioeconomic impacts are addressed. In the current study, slow-release formulations of nitrogen fertilizer were developed on the basis of natural attapulgite (APT) clay, ethylcellulose (EC) film, and sodium carboxymethylcellulose/hydroxyethylcellulose (CMC/HEC) hydrogel. The structural and chemical characteristics of the product were examined. The release profiles of urea, ammonium sulfate, and ammonium chloride as nitrogen fertilizer substrates were determined in soil. To further compare the release profiles of nitrogen from different fertilizer substrates, a mathematical model for nutrient release from the coated fertilizer was applied to calculate the diffusion coefficient D. The influence of the product on water-holding and water-retention capacities of soil was determined. The experimental data indicated that the product can effectively reduce nutrient loss, improve use efficiency of water, and prolong irrigation cycles in drought-prone environments.     

Use of activated bentonites in controlled-release formulations of atrazine

The herbicide atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) was incorporated in alginate-based granules to obtain controlled-release (CR) properties. The basic formulation [sodium alginate (1.40%)-atrazine (0.60%)-water] was modified by the addition of sorbents. The effect on atrazine release rate caused by the incorporation of acid-treated bentonite (0.5 and 2.5 M H2SO4) in alginate formulation was studied by immersion of the granules in water under static conditions. The water uptake, sorption capacity of the sorbent, permeability, and time taken for 50% of the active ingredient to be released into water, t50, were calculated for the comparison of the preparations. t50 values were longer for those formulations containing acid-treated bentonite (36.78 and 29.01 days for 0.5 and 2.5 M H2SO4 treatments, respectively) than for the preparation without bentonite (9.69 days). On the basis of a parameter of an empirical equation used to fit the herbicide release data, it appears that the release of atrazine from the various formulations into water is controlled by diffusion mechanism. The sorption capacity of the sorbents and the permeability of the formulations (ranging from 4.99 to 20.83 mg day(-1) mm(-1)) were the most important factors affecting herbicide release.     

Norflurazon mobility, dissipation, activity, and persistence in a sandy soil as influenced by formulation

Five ethylcellulose (EC) microencapsulated formulations (MEFs) of norflurazon were prepared and applied in soil to study their mobility, dissipation, activity, and persistence. The results show that the release into water of norflurazon from EC microspheres was retarded when compared with that of commercial herbicide. The mobility of norflurazon from MEFs into soil columns has been greatly diminished in comparison with that of its current commercial formulation (CF). Norflurazon distribution at different depths in the soil was higher in the upper ring (up to 50% of the initial application). In contrast, the residues from commercial norflurazon along the complete soil column were only about 2%. Degradation and bioassay experiments showed that the MEFs had greater persistence (t1/2 values were 7.72 and 30.83 weeks for CF and MEFs, respectively) and herbicidal activity than the commercial formulation. The use of these formulations can be advantageous, because they can minimize the risk of groundwater contamination and permit herbicide use at reduced rates, maintaining the desired concentrations of herbicide in the topsoil layer for longer periods of weed control.     

Slow-release formulations of sulfometuron incorporated in micelles adsorbed on montmorillonite

The design and tests of slow-release formulations of sulfometuron (SFM), an anionic sulfonylurea herbicide, are described. The formulations are based on incorporation of the herbicide in octadecyltrimethylammonium (ODTMA) micelles, which adsorb on a clay mineral, montmorillonite. An optimization of herbicide/micelle clay ratios yielded high adsorption of SFM (95%), and at a 1% (w/w) water suspension only 0.5% of the adsorbed SFM was released at times varying from hours to 9 days. An analytical test in Seville soil showed that under excessive irrigation (400 mm) 100% of the commercial formulation leached, whereas the micelle-clay formulations showed only 50-65% elution. A plant bioassay in Rehovot soil showed that the commercial dispersible granule formulation (Oust, 75% ai sulfometuron methyl) yielded only 23% root elongation inhibition at the top 5 cm of the soil, whereas complete inhibition was achieved with the micelle-clay formulation. The detected concentration of SFM for the micelle-clay formulation at a depth of 15-20 cm was half of that detected for the commercial one, indicating a reduction in leaching when applying the micelle-clay formulation. A 10-fold reduction in the applied dose of SFM in the micelle-clay formulations resulted in good herbicidal activity of 60-87% inhibition. These characteristics make the new formulation promising from the environmental and economic points of view.     

Controlled release of isoproturon, imidacloprid, and cyromazine from alginate-bentonite-activated carbon formulations

Different alginate-based systems of isoproturon, imidacloprid, and cyromazine have been investigated in order to obtain controlled release (CR) properties. The basic formulation [sodium alginate (1.50%), pesticide (0.30%), and water] was modified using different amounts of bentonite and activated carbon. The higher values of encapsulation efficiency corresponded to those formulations prepared with higher percentages of activated carbon, showing higher encapsulation efficiency values for isoproturon and imidacloprid than for cyromazine, which has a higher water solubility. The kinetic experiments of imidacloprid/isoproturon release in water have shown us that the release rate is higher in imidacloprid systems than in those prepared with isoproturon. Moreover, it can be deduced that the use of bentonite and/or activated carbon sorbents reduces the release rate of the isoproturon and imidacloprid in comparison with the technical product and with alginate formulation without modifying agents. The highest decrease in release rate corresponds to the formulations prepared with the highest percentage of activated carbon. The water uptake, permeability, and time taken for 50% of the active ingredient to be released into water, T50, were calculated to compare the formulations. On the basis of a parameter of an empirical equation used to fit the pesticide release data, the release of isoproturon and imidacloprid from the various formulations into water is controlled by a diffusion mechanism. The sorption capacity of the sorbents and the permeability of the formulations were the most important factors modulating pesticide release. Finally, a linear correlation of the T50 values and the content of activated carbon in formulations were obtained.     

Sulfosulfuron incorporated in micelles adsorbed on montmorillonite for slow release formulations

Slow release formulations of the anionic herbicide sulfosulfuron (SFS) were prepared by incorporating it in micelles of an organic cation octadecyltrimethylammonium, which adsorb on the clay-mineral montmorillonite. The fraction of SFS adsorbed on the micelle-clay complex reached 98%, whereas for monomer-clay complexes, its adsorption was insignificant. Fluorescence studies showed surface contact between the micelles and the clay surface. The rate of SFS release from the micelle-clay formulations in aqueous suspensions was slow (<1%, 72 h). Spraying SFS formulations on a thin soil layer in a funnel, followed by irrigations (50 mm), resulted in complete elution of SFS from the commercial formulation (dispersible granular) versus 4% from the micelle-clay formulation. A plant bioassay in Rehovot soil showed that these respective formulations yielded 23 and 65% of shoot growth inhibition of foxtail. Consequently, the slow release micelle-clay formulations of SFS yield significantly reduced leaching and enhanced biological activity, thus providing environmental and agricultural advantages.     

Organo-clay formulation of acetochlor for reduced movement in soil.

This study aimed to design ecologically acceptable formulations of acetochlor by adsorbing it on montmorillonite exchanged by a small organic cation, phenyltrimethylammonium (PTMA). Adsorption of acetochlor on the clay mineral exchanged with different organic cations and its release from these complexes were determined by GC and modeled by Langmuir equation. Interactions between acetochlor molecules and the exchanged organic cation on the clay surface were studied by Fourier transform infrared spectroscopy. Leaching of acetochlor in soil was determined by a bioassay using a column technique and Setaria viridis as a test plant. The adsorbed amounts of acetochlor on montmorillonite exchanged by PTMA at a loading of 0.5 mmol/g of clay were higher than at a loading up to the cation-exchange capacity, i.e., 0.8 mmol/g, and were higher than obtained by using a clay mineral exchanged by other organic cations. Preloading montmorillonite by PTMA at 0.5 mmol/g yielded maximal shifts of the infrared peaks of the herbicide. The above formulation of acetochlor yielded slow release in water and showed improved weed control in field and greenhouse experiments in comparison with the commercial formulation. The PTMA-clay formulation of acetochlor maintained herbicidal activity in the topsoil and yielded the most significant reduction in herbicide leaching and persistence under field conditions. The application of this formulation can minimize the risk to groundwater and can reduce the applied rates.     

Herbicide solubilization in micelle-clay composites as a basis for controlled release sulfentrazone and metolachlor formulations

Sulfentrazone and metolachlor have been detected in groundwater due to extensive leaching. To reduce herbicide leaching and increase weed control, we have developed, designed, and tested controlled release formulations (CRFs) for both herbicides based on their solubilizion in cationic micelles and adsorption of the mixed micelles (surfactant and herbicide) on a clay mineral, montmorillonite. A better understanding of solubilizing anionic (sulfentrazone) and nonionic (metolachlor) organic molecules in cationic micelles was reached. The percent of active ingredient in the formulations was much higher than previously designed CRFs due to the enhanced solubilization of the herbicides in the micelles and due to their adsorption on the clay. Both CRFs demonstrated controlled release (compared to the commercial formulations) when applied to a thin soil layer. A bioassay in soil columns determined that the new sulfentrazone and metolachlor CRFs significantly improve weed control and reduce leaching (for the latter) in comparison with the commercial formulations.     

Effect of soil wetting and drying cycles on metolachlor fate in soil applied as a commercial or controlled-release formulation

A controlled-release formulation (CRF) has been developed for metolachlor, which reduced its leaching in a sandy soil and improved weed control in comparison with the commercial formulation. The current study tested the effect of soil wetting and drying cycles (WDCs) on metolachlor fate (desorption, leaching, and weed control) applied as the CRF and as the commercial formulation. Metolachlor adsorption to a heavy soil (Terra-Rosa) was predominately to the clay minerals and oxides. Metolachlor release from a heavy soil subjected to WDCs was higher than its release from the soil not subjected to WDCs. Consequently, a bioassay in soil columns treated with the commercial formulation indicated enhanced metolachlor leaching in heavy soils under WDCs. In contrast, when metolachlor was applied as the CRF, leaching was suppressed and not affected by WDCs. These results emphasize the advantages of the CRF also in heavy soils subjected to WDCs.     

CONTROLLED RELEASE OF FERTILIZER MICROCAPSULES USING ETHYLENE VINYL ACETATE POLYMER TO ENHANCE MICRONUTRIENT AND WATER USE EFFICIENCY

There have as yet been no detailed studies of micronutrient release from polymer coated fertilizers (PCFs). In this research, slow release microcapsules containing iron fertilizer was made and its release pattern evaluated. Three polymers ethyl cellulose (EC), glycerol mono stearate (GMS) and Compritol 888 ATO, were mixed with avicel and lactose and the microcaopsules were made by extrusion/spheronization method. The dissolution test carried out to determine the Fe release rate versus time. The results showed that, microcaopsules containing Compritol 888 ATO, released iron ions slower than that of EC and GMS. The release rate reached 85% after 7 days. In order to reduce the release rate, these microcaopsules were coated with ethylene vinyl acetate (EVA) polymer by dip coating method. It is concluded that the combination of matrix type formulation and the coating with EVA polymer caused a significant decrease in the release rate of iron.     

Inorganic and organic clays as carriers for controlled release of the herbicide hexazinone

The risk of ground water contamination resulting from rapid leaching of highly soluble pesticides can be minimized through the application of the pesticide adsorbed on a matrix or carrier, which limits the amount of pesticide immediately available for undesirable losses. The use of natural materials for this purpose is of special interest in terms of economy and sustainability. In this work the adsorption of the herbicide hexazinone by two montmorillonites saturated with various inorganic and organic cations was determined and the ability of the two clays displaying the highest adsorption capacities [Fe(3+)-saturated Wyoming montmorillonite, (Fe-SW) and hexadecyltrimethylammonium-saturated Arizona montmorillonite (HDTMA-SA)] to act as carriers for slow release of hexazinone and to reduce herbicide leaching losses was evaluated. Hexazinone formulations based on Fe-SW and HDTMA-SA displayed slow release properties in water and soil/water suspensions, reduced herbicide leaching in soil columns, and maintained herbicidal activity, as compared with the currently available commercial hexazinone formulation (wettable powder). Loosely bound hexazinone-HDTMASA formulations, which led to the slowest breakthrough of hexazinone in soil columns along with the greatest amounts of herbicide released from the clay particles, displayed the most interesting characteristics for their use as slow release formulations and to prevent ground water contamination.     

Evaluation of pheromone release from commercial mating disruption dispensers

Pome fruit growers and crop consultants have expressed concerns about the seasonal release performance of commercial codling moth mating disruption dispenser products. Because of these concerns, we developed a laboratory flow-through volatile collection system (VCS) for measuring the volatile release of the codling moth sex pheromone, codlemone, from commercially available hand-applied dispensers. Under controlled air-flow and temperature conditions, the released vapor was trapped onto a polyurethane foam adsorbent followed by solvent extraction, solvent reduction, and GC/MS determination. Method recovery and breakthrough validations were performed to demonstrate system reliability before determining codlemone release from commercial dispensers field-aged over 140 days. The volatile collection was carried out in a consistent manner among five dispenser types most commonly used by growers, so that direct comparison of performance could be made. The comparison showed differences in the amount of pheromone released and in the patterns of release throughout the season between dispenser types. The variation in release performance demonstrates the need for routine evaluation of commercially marketed mating disruption dispensers. We believe that the simple and cost-effective volatile collection system can assist pheromone dispenser manufacturers in determining seasonal dispenser performance before new products are introduced into the commercial market and in rapidly verifying dispenser release when field-aged dispenser efficacy is in question.     

Polymeric microcapsules of alachlor and metolachlor: preparation and evaluation of controlled-release properties.

The microencapsulation of alachlor and metolachlor in the polymers cellulose acetate butyrate, ethyl cellulose, poly(methyl methacrylate), and poly(alpha-methylstyrene) with different emulsifiers is described. The controlled-release properties of these formulations were measured under greenhouse conditions on barnyardgrass, crowfootgrass, smallflower morningglory, and Palmer amaranth. The emulsifiers had little effect on the activity of the herbicides. The herbicidal activities of the poly(methyl methacrylate) and poly(alpha-methylstyrene) formulations were consistently lower on all weed species when compared to the activities of the cellulose acetate butyrate, ethyl cellulose, and commercial formulations. The ethyl cellulose formulation of alachlor exhibited controlled-release properties. The results with metolachlor were similar to those with alachlor except that none of the metolachlor formulations exhibited efficacy superior to that of the commercial formulation or controlled release properties.     

Organo-clay formulations of the hydrophobic herbicide norflurazon yield reduced leaching

The study aimed to reduce leaching of the hydrophobic herbicide norflurazon (4-chloro-5-methylamino-2-(alpha,alpha, alpha)-trifluoro-m-tolylpyridazin-3-(2H)-one) by adsorbing it on clays or organo-clays. The surface of the clay mineral montmorillonite was modified from hydrophilic to hydrophobic by preadsorbing it with organic cations, of which thioflavin-T (TFT) at a loading corresponding to (5)/(8) of the cation-exchange capacity of the clay mineral yielded the highest affinity of adsorption of norflurazon. Pillared clay (PC) used without organic cations exhibited enhanced affinity for norflurazon adsorption, much higher than that of montmorillonite or sepiolite. Fourier transform infrared (FTIR) results showed interactions between aromatic moieties of preadsorbed TFT and the herbicide. Stronger interaction of the herbicide with a clay mineral or organo-clay corresponded to its slower release. Formulations prepared on the basis of montmorillonite-TFT and PC were more effective in reducing herbicide leaching in soil columns in comparison to the commercial formulation, whereas the herbicidal efficiencies were comparable.