J.E. López-Periago

Phosphorus effect on Zn adsorption-desorption kinetics in acid soils.

The adsorption-desorption kinetics of Zn in the absence and presence of P was studied by using the stirred flow chamber technique. The results thus obtained were compared with those previously obtained for Cu. As with copper, the simultaneous addition of P and Zn in a 1:1 mole ratio to soil was found to significantly increased Zn adsorption relative to the absence of P. Unlike Cu, however, Zn was only adsorbed at fast adsorption sites in the absence of P. In any case, the increased adsorption of Zn in the presence of P was largely due to slow adsorption sites, where Zn(2+) ion acted as a bridging element between P and organic matter. Following adsorption in both the presence and absence of P, Zn was desorbed to a much higher extent than was Cu. However, the proportion of Zn desorbed after adsorption in the presence of P was significantly lower than in the absence of P. This indicates that Zn binds more strongly to adsorbing surfaces in the presence of P than in its absence.

Behaviour of metalaxyl as copper oxychloride–metalaxyl commercial formulation vs. technical grade-metalaxyl in vineyards-devoted soils

The objective of this work is to asses the sorption of metalaxyl applied as a copper oxychloride (CO)-metalaxyl formulation, for a set of selected soils devoted to vineyards. The method involved batch incubation of soils suspended with a commercial copper oxychloride-metalaxyl-based fungicide in 0.01M CaCl(2). Afterwards, the metalaxyl concentration remaining in solution was determined by high-performance liquid chromatography (HPLC). The amount of dissolved metalaxyl in the fungicide suspension depends mainly on the soil pH, its potential acidity, and the cation exchange capacity. Of the approx. 20% metalaxyl retained by the solid colloids, the effect of organic matter colloids in soils (15-20 mg kg(-1)) had a poor contribution (six times lower) than the copper oxychloride colloids (40%, w/w) in the commercial fungicide formulation (100-130 mg kg(-1)). When comparing these retention data with the behaviour of metalaxyl used as a technical grade fungicide of about 100% purity (10-15 mg kg(-1) in solids), it is clear that the commercial formulation increases a 30% retention of metalaxyl by soil (15-20 mg kg(-1) in solids). The overall effect of the metalaxyl formulation plus soil show values of 10 times higher retention than technical grade-metalaxyl plus soil. Commercial formulation can decrease the mobility of soluble metalaxyl in agricultural soils with regard to the expected values obtained from batch studies using analytical grade-metalaxyl. Therefore, the effect of surfactants should be considered in the assessment of water contamination by the pesticides used in agriculture.

Sorption of penconazole applied as a commercial water-oil emulsion in soils devoted to vineyards.

The objective of this work was to assess the effect of surfactants and oils of a commercial formulation on the potential mobility of penconazole in agricultural soils that have been subjected to a high rate of application of agricultural chemicals. Soil-water partition tests on a commercial water-oil emulsion formulation of penconazole (WOEP) in 0.01 M CaCl(2) containing 35 mg L(-1) penconazole, incubated for 24 h, showed a maximum retention of approximately 250-300 mg penconazole kg(-1) soil. Approximately 70% of the total penconazole retained by the solid phase was sorbed on the soil (175-200 mg kg(-1)). The other 30% was retained by the adjuvants present in the commercial formulation. The formulation also influenced the water-soil partition, increasing the sorption in tests on batch studies using technical-grade penconazole (TGP). Soils with high total copper and organic matter had the greatest affinity for penconazole when added as WOEP. Additionally, adsorption of penconazole followed an S-type isotherm, whose behavior was consistent with the ability of the technical-grade penconazole to form aggregates. In the case of the WOEP, the S-type behavior could be attributed to the surfactant present in the formulation, which could be adsorbed onto soil as hemimicelles, which in turn may facilitate adsorption of penconazole.

Influence of phosphorus on Cu sorption kinetics: stirred flow chamber experiments.

A stirred flow reactor was used to study the influence of phosphorus on the adsorption and desorption kinetics of copper in two acid soils on granite and amphibolite. The presence of P was found to significantly increase Cu adsorption in both soils, albeit at different types of sites (mainly in slow adsorption sites in the soil on granite, and both in fast and slow adsorption sites in that on amphibolite). The increased Cu sorption at fast sites in the amphibolite soil was due to its high content in Fe oxyhydroxides, which bound P and released OH(-) as a result, thereby raising the pH and leading to a higher sorption capacity during fast reactions. On the other hand, the increased Cu sorption at slow adsorption sites was due to Cu(2+) acting as a bridging element between P and organic matter.

Effects of Past Copper Contamination and Soil Structure on Copper Leaching from Soil

Copper contamination affects biological, chemical, and physical soil properties and associated ecological functions. Changes in soil pore organization as a result of Cu contamination can dramatically affect flow and contaminant transport in polluted soils. This study assessed the influence of soil structure on the movement of water and Cu in a long-term polluted soil. Undisturbed soil cores collected along a Cu gradient (from about 20 to about 3800 mg Cu kg soil) were scanned using X-ray computed tomography (CT). Leaching experiments were performed to analyze tracer transport, colloid leaching, and dissolved organic carbon (DOC) and Cu losses. The 5% arrival time () and apparent dispersivity (λ) for tracer breakthrough were calculated by fitting the experimental data to a nonparametric, double-lognormal probability density function. Soil bulk density, which did not follow the Cu gradient, was the main driver of preferential flow, while macroporosity determined by X-ray CT (for pores >180 μm) proved the best predictor of solute transport. Higher preferential flow due to the presence of well-aligned pores and small cracks controlled water movement in compacted soil. Transport of Cu was rapid during the first flush (≈1 pore volume) in association with the movement of colloid particles, followed by slower transport in association with the movement of DOC in the soil solution. The relative amount of Cu released was strongly correlated with macroporosity as determined by X-ray CT, indicating the promising potential of this visualization technique for predicting contaminant transport through soil.

Modeling the influence of raindrop size on the wash-off losses of copper-based fungicides sprayed on potato (Solanum tuberosum L.) leaves

Modeling the pesticide wash-off by raindrops is important for predicting pesticide losses and the subsequent transport of pesticides to soil and in soil run-off. Three foliar-applied copper-based fungicide formulations, specifically the Bordeaux mixture (BM), copper oxychloride (CO), and a mixture of copper oxychloride and propylene glycol (CO-PG), were tested on potato (Solanum tuberosum L.) leaves using a laboratory raindrop simulator. The losses in the wash-off were quantified as both copper in-solution loss and copper as particles detached by the raindrops. The efficiency of the raindrop impact on the wash-off was modeled using a stochastic model based on the pesticide release by raindrops. In addition, the influence of the raindrop size, drop falling height, and fungicide dose was analyzed using a full factorial experimental design. The average losses per dose after 14 mm of dripped water for a crop with a leaf area index equal to 1 were 0.08 kg Cu ha−1 (BM), 0.3 kg Cu ha−1 (CO) and 0.47 kg Cu ha−1 (CO-PG). The stochastic model was able to simulate the time course of the wash-off losses and to estimate the losses of both Cu in solution and as particles by the raindrop impacts. For the Cu-oxychloride fungicides, the majority of the Cu was lost as particles that detached from the potato leaves. The percentage of Cu lost increased with the decreasing raindrop size in the three fungicides for the same amount of dripped water. This result suggested that the impact energy is not a limiting factor in the particle detachment rate of high doses. The dosage of the fungicide was the most influential factor in the losses of Cu for the three formulations studied. The results allowed us to quantify the factors that should be considered when estimating the losses by the wash-off of copper-based fungicides and the inputs of copper to the soil by raindrop wash-off.

Rainfall-induced removal of copper-based spray residues from vines.

The continuous use of copper against fungal diseases and off-target effects causes major environmental and agronomic problems. However, the rain-induced removal of Cu-based residues is known only for a limited number of crops. We present the results of rain-induced removal of fungicides from two monitored vineyard plots which were sprayed with two widely used Cu-based formulations: copper-oxychloride (CO) and Bordeaux mixture (BM), respectively. Cu removal per growing season was 0.60±0.12kgha(-1) (30% of the applied fungicide) for CO and 0.80±0.10kgha(-1) for BM (70% of the applied fungicide). Fractioning the Cu in soluble (CuS) and particulate fractions (CuP) showed that most of the Cu was removed as CuP, but CuS concentrations found in throughfall collectors exceeded the regulatory threshold for toxicity in surface waters. The first few millimeters of rain caused most of the Cu removal. Our findings agreed with the data reported in the scientific literature, in which a significant fraction of the Cu-based formulation is loosely attached to the plant surfaces. In addition, we found that rainfall energy had a minor influence on the removal.

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.

Concentration levels of new-generation fungicides in throughfall released by foliar wash-off from vineyards

The presence of agricultural pesticides in the environment and their effects on ecosystems are major concerns addressed in a significant number of articles. However, limited information is available on the pesticide concentrations released from crops. This study reports losses of new-generation fungicides by foliar wash-off from vineyards and their potential impact on the concentrations of their main active substances (AS) in surface waters. Two experimental plots devoted to vineyards were treated with various combinations of commercial new-generation fungicide formulations. Then, up to sixteen throughfall collectors were installed under the canopy. Concentrations of sixteen different AS in throughfall were determined along nine rainfall episodes. Concentrations in throughfall far exceeded the maximum permissible levels for drinking water established by the European Union regulations. Dynamics of fungicide release indicated a first-flush effect in the wash-off founding the highest concentrations of AS in the first rain episodes after application of the fungicides. This article shows that foliar spray application of commercial formulations of new-generation fungicides does not prevent the release of their AS to soil or the runoff. Concentration data obtained in this research can be valuable in supporting the assessment of environmental effects of new-generation fungicides and modeling their environmental fate.