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.
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.
Different ammonium nitrate controlled-release (CR) systems based on ethylcellulose have been investigated to reduce environmental pollution derived from nitrogen-fertilizer use. Coated ammonium nitrate granules were produced in Wurster-type fluidized-bed equipment using two different amounts of ethylcellulose. The highest one was modified by the addition of two plasticizers, dibutyl sebacate, and dibutyl phthalate. Having researched the encapsulation efficiency and the homogeneity of the coated granules, we carried out the kinetic-release experiments in water and soil. The release rate of the active ingredient was related to the thickness of the coating film, granule size, and type of plasticizer used. Using an empirical equation, the time taken for 50% of the active ingredient to be released into water and soil (T 50) was calculated. From the analysis of the T 50 values, we can deduce that the release rate of ammonium nitrate can be controlled, mainly changing the thickness of the coating film and using plasticizer as well. In water experiments, T 50 values for granules prepared without plasticizers ranged between 7.47 h for 1 mm < d < 2 mm granules coated with 10% of ethylcellulose and 24.06 h for 2 mm < d < 3 mm granules coated with 20% of ethylcellulose. For those prepared with plasticizers, T 50 ranged between 22.80 h for 1 mm < d < 2 mm granules containing dibutyl sebacate and 35.74 h for 1 mm < d < 2 mm granules containing dibutyl phthalate. However, in soil experiments T 50 values ranged between 10.24 h for 1 mm < d < 2 mm granules coated with 10% of ethylcellulose and 38.80 h for 1 mm < d < 2 mm granules containing dibutyl sebacate. Finally, a linear regression of the T 50 values was obtained by the results of the study carried out in water and soil. This allows us to predict the behavior of the formulations in soil. This could be useful in the design of systems which control the nitrogen release.
To evaluate the effects of dissolved organic carbon (DOC) on phosphate retention (including both sorption and/or precipitation reactions) on soils, experiments were performed by using two typical calcareous soils from southeastern Spain (Calcic Regosol and Luvic Xerosol) and two different types of DOC: (1) extracts from a commercial peat (DOC-PE) and (2) high-purity tannic acid (DOC-TA). The experiments were carried out from a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results obtained show that the presence of both DOC-PE and DOC-TA, over a concentration range of 15 (DOC-15) to 100 (DOC-100) mg L(-1), produces in all cases a decreasing amount of phosphate retained in the soils studied, the decrease observed being higher when DOC-PE is used as source of DOC. The values of the decrease observed when DOC-PE was added ranged between 19.9% (DOC-15) and 15.6% (DOC-100) for the Calcic Regosol and between 17.3% (DOC-70, DOC-100) and 14.6% (DOC-15) for the Luvic Xerosol. The variation observed when DOC-TA was added ranged between 8.5% (DOC-100) and 0.5% (DOC-35) for the Calcic Regosol and between 7.0% (DOC-100) and 1.0% (DOC-15) for the Luvic Xerosol.
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