Predicting release and transport of pesticides from a granular formulation during unsaturated diffusion in porous media.

The release and transport of active ingredients (AIs) from controlled-release formulations (CRFs) have potential to reduce groundwater pesticide pollution. These formulations have a major effect on the release rate and subsequent transport to groundwater. Therefore the influence of CRFs should be included in modeling non-point source pollution by pesticides. We propose a simplified approach that uses a phase transition equation coupled to the diffusion equation that describes the release rate of AIs from commercial CRFs in porous media; the parameters are as follows: a release coefficient, the solubility of the AI, and diffusion transport with decay. The model gives acceptable predictions of the pesticides release from commercial CRFs in diffusion cells filled with quartz sand. This approach can be used to study the dynamics of the CRF-porous media interaction. It also could be implemented in fate of agricultural chemical models to include the effect of CRFs.

Influence of pore water velocity on the release of carbofuran and fenamiphos from commercial granulates embedded in a porous matrix.

Pore water flow velocity can influence the processes involved in the contaminant transport between relative stagnant zones of porous media and their adjacent mobile zones. A particular case of special interest is the occurrence of high flow rates around the controlled release granules containing pesticides buried in soil. The release of the pesticides carbofuran and fenamiphos from commercial controlled release formulations (CRFs) was studied, comparing release tests in a finite volume of water with water flow release tests in saturated packed sand at different seepage velocities. For water release kinetics, the time taken for 50% of the pesticide to be released (T(50)) was 0.64 hours for carbofuran and 1.97 hours for fenamiphos. In general, the release rate was lower in the porous matrix than in the free water tests. The faster release rate for carbofuran was attributed to its higher water diffusivity. The seepage velocity has a strong influence on the pesticide release rate. The dominant release mechanism varies with the progress of release. The evolution of the mechanism is discussed on the basis of the successive steps that involve the moving boundary of the dissolution front of the pesticide inside the granule, the concentration gradient inside the granule and the flow boundary layer resistance to solute diffusion around the granule. The pore water velocity influences the overall release dynamics. Therefore, seepage velocity should be considered in pesticide release to evaluate the risk of pesticide leaching, especially in scenarios with fast infiltration.

Influence of soluble copper on the electrokinetic properties and transport of copper oxychloride-based fungicide particles.

This article describes the influence of dissolved copper on the electrokinetic properties and transport of a copper oxychloride-based fungicide (COF) in porous media. The Zeta potential (ζ) of COF particles increases (viz. becomes less negative) with increasing concentration of Cu(2+) in the bulk solution. ζ decreases for COF when the electrolyte (NaNO(3)) concentration is raised from 1 to 10mM. This can be ascribed to ion correlation of Cu(2+) in the electrical double layer (EDL). COF transport tests in quartz sand columns showed the addition of Cu(2+) to the bulk solution to result in increased retention of the metal. Modelling particle deposition dynamics provided results consistent with kinetic attachment. Based on the effect of soluble Cu on colloid mobility, the transport of particulate and soluble forms of copper is coupled via the chemistry of pore water and colloid interactions. Mutual effects between cations and colloids should thus be considered when determining the environmental fate of particulate and soluble forms of copper in soil and groundwater (especially at copper-contaminated sites).

Effect of particle size on copper oxychloride transport through saturated sand columns.

Understanding the mechanisms behind the transport of particulate contaminants in porous media is crucial with a view to evaluating their potential impact on the environment. Much of the copper used in agriculture is sprayed as colloidal copper oxychloride, and despite its potential environmentally adverse consequences, colloidal transport of particulate formulations of copper remains poorly understood. In this work, transport of copper colloids from a commercial copper oxychloride based fungicide formulation was studied by measuring its breakthrough in saturated quartz sand columns. The influence of ionic strength and flow rate on the test results suggests that retention of copper oxychloride based colloids is governed by weak forces. The particle deposition dynamics of the studied copper formulation was consistent with a two-site kinetic attachment model. The proposed colloid retention mechanisms are highly sensitive to the fungicide particle size. A comparison of our test results with reported data for other copper oxychloride wettable powder fungicide formulations revealed that transport of copper oxychloride is strongly influenced by its particle size. This is consistent with the theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO), but only if binding occurs at the secondary minimum in the potential, where attachment is less favorable with small particles. The influence of particle size is also consistent with the results of previous studies where deposition was ascribed to retention at a secondary minimum. The mobility of colloidal formulations of these copper-based fungicides in saturated porous media increases with increasing particle size.

Transport of copper oxychloride-based fungicide particles in saturated quartz sand.

Intensive use of copper-based fungicides in agriculture causes contamination of subsurface environment. While the transport of dissolved copper in porous media has been widely studied, transport mechanisms of particles of copper-based fungicides are poorly understood. This paper reports the results of tests involving the transport of colloid-size particles of a copper oxychloride-based fungicide (COF) in water-saturated quartz sand columns under varying electrochemical and hydrodynamic conditions. The effect of the ionic strength on colloid attachment and exclusion suggests that interactions of COF in water depend on the characteristics of the diffuse layer. Hydrodynamic shear influences the deposition of fungicide particles, indicating that attachment forces are weak. Particle deposition dynamics was well-fitted with the two-site kinetic attachment model, which reflects the heterogeneity of the quartz surface. Retention also occurs for unfavorable electrochemical conditions, which was attributed to stagnation zones arising from the physical and chemical heterogeneity of the quartz surface.

Influence of soil characteristics on copper sorption from a copper oxychloride fungicide.

The objective of this work was to assess the sorption of copper (Cu) applied as a Cu-oxychloride metalaxyl formulation by soils characterized by anthropogenic accumulation of Cu due to agricultural activity. The methods involved batch incubation of soils with a Cu-oxychloride metalaxy-based fungicide suspended in 0.01 M CaCl(2), phase separation, and determination of the concentration of Cu (Cu) in solution. Results showed that specific soil properties influenced solubilization of the Cu from the fungicide. The amount of dissolved Cu depended on the soil pH, its potential acidity, and its cation exchange capacity. The amount of anthropogenic Cu in the soil had a minor influence on soluble Cu after the addition of the fungicide. Thus, Cu-based antifungal treatment can increase the local concentration of soluble Cu in acid soils but is not likely to affect the [Cu] in moderately acidic or neutral soils.

Simulating washoff of Cu-based fungicide sprays by using a rotating shear device.

Foliar washoff causes a loss of copper-based pesticides sprayed on crops, leading to an increase in the number of applications and contamination of the soil with Cu. In field studies, the variables that determine the amount of Cu loss are difficult to control. An experimental setup based on a rotating shear device (RSD) was used to estimate the influence of physical factors in the loss of Cu due to washoff of three copper-based fungicides: copper oxychlorhide (CO), Bordeaux mixture (BM), and a mixture of copper oxychlorhide and propylene glycol (CO-PG). Full factorial designs were used to model the loss of Cu from fungicides sprayed on the polypropylene surface of the RSD. Variables in the experiments were rotation speed, wash water volume, and fungicide dose. Good reproducibility was obtained for Cu loss, with a coefficient of variation less than 8%. Mean Cu losses were 27.0, 33.0, and 13.5% of the copper applied in fungicide for the BM, CO, and CO-PG, respectively. Empirical equations were obtained to calculate Cu losses from the rotation speed, wash water volume, and dose, as well as their interactions. CO losses were consistent with a model of particle detachment in which such losses depended on a threshold boundary shear stress required to initiate particle motion. Also, percent CO losses were found to be significantly correlated with the linear momentum at the surface boundary. The momentum values obtained in the RSD tests were similar to those estimated for a rainfall event of 20 mm h(-1) lasting 10 min. The most important mechanism in the loss of CO was the erosion of Cu-bearing particles.