Critical review on the environmental fate of quaternary ammonium herbicides in soils devoted to vineyards.

Quaternary Ammonium Herbicides (QUATs) are nonselective contact herbicides, widely used at weed emergence to protect a wide range of crops. The benefits achieved by the use of these herbicides are indisputable. In soils devoted to vineyards, their uses increase the yield and the quality of the grapes for winemaking. However, several environmental dangers have emerged from the overuse of these compounds. Therefore, there has been a great interest in the presence of these compounds in soils, water, and food. Once in the soil, the mobility of these agrochemicals plays an important role in their fate and transport in the environment. This is why we mainly focused our review on (a) their physical and chemical properties and their activity, (b) the factors affecting their mobility in soils, (c) the quality of surrounding waters, and (d) the measures to reduce their contamination, especially in the case of agricultural soils devoted to vineyards.

Zinc distribution and acid-base mobilisation in vineyard soils and sediments.

Nineteen vineyard stands located in steep-slope areas of three wine-growing regions in northwest Spain were selected for this study. In each stand, a representative soil sample (19) and one or two sediment samples (24) were collected. In these samples, the Zn distribution in the solid phase was assessed. Moreover, the effect of pH on the release of zinc was determined using a batch-type experiment. The mean zinc concentration (109 mg kg(-1)) of the samples was lower than the maximum concentrations allowed by the European Union. Moreover, most of the zinc that appeared in vineyard soils was residual zinc, suggesting a tendency for zinc in these soils to be irreversibly bound to soil components, reducing its potential environmental impact. In sediments, the mean total Zn concentration (126 mg kg(-1)) was higher than those in the original soils and in the mobile fractions, which could mean a higher risk of liberation. Zinc release was higher under acidic conditions, in which release depends mainly on labile fractions. Under basic conditions, the release of Zn was lower and depended on Zn bound to crystalline oxyhydroxides.

Effect of organic matter and iron oxides on quaternary herbicide sorption-desorption in vineyard-devoted soils.

Herbicide soil/solution distribution coefficients (K(d)) are used in mathematical models to predict the movement of herbicides in soil and groundwater. Herbicides bind to various soil constituents to differing degrees. The universal soil colloid that binds most herbicides is organic matter; however metallic hydrous oxides might also have some influence. The adsorption-desorption of three quaternary ammonium herbicides on soils with different chemical-physical characteristics was determined using a batch equilibration method before and after the following sequential selective dissolution procedures: removal of organic matter, and removal of organic matter plus free iron oxides. The experimentation involved paraquat (PQ), diquat (DQ) and difenzoquat (DFQ) herbicides. The distribution coefficients (K(d)) of the molecules and their correlation to the soil components were determined and a significant negative correlation with organic carbon was highlighted (r<-0.610, p<0.035, n=12). All quats cations experiment high adsorption in the control soils with a Zeta potential at about -21 mV. The order of adsorption on soils (based on K(d)) was the following: PQ>DQ>>DFQ. The adsorption isotherms of these three herbicides on the natural and processed soils were satisfactorily fitted with the Freundlich equation, and a significant correlation with organic carbon was highlighted for quats K(F) (r<-0.696, p<0.012, n=12). The removal of organic matter from soils seems to leave free new adsorption sites for quats on the clay surface, which is no longer occluded by organic matter. This work shows that the amount and nature of the surface that remains available after the removal of single soil constituents is a critical parameter in determining the sorptive behavior of cationic contaminants.

Occurrence and downslope mobilization of quaternary herbicide residues in vineyard-devoted soils.

The aim of this study was to examine the fate of quaternary herbicides in soil deposits derived from erosion of vineyard-devoted soils. Herbicide occurrence in the crop soils was due to the farmer application inputs. Special attention should be paid to the presence of paraquat (PQ) in the studied vineyard-devoted soils. The major factor governing the sorption of PQ was the solid state organic fraction with the clay mineral content also making a significant contribution. The mobilization and transport of quats-enriched soil particles may generate downslope and downstream environmental problems that mainly affect detritivore ecology.