Assessment of pesticide availability in soil fractions after the incorporation of winery-distillery vermicomposts.

The influence of two vermicomposts from winery and distillery wastes on the distribution of diuron in agricultural soil was studied. Physical soil fractionations at 0, 9, 27, 49 and 77 days, allowed the quantification of pesticide residues in different particle-size fractions, coarse waste (WF), sand-sized (SF), silt-sized (SiF), clay-sized (CF) and dissolved organic matter-sized fraction (DOM). The SiF made a greater contribution to the formation of non-extractable residues in unamended soil, but when vermicomposts were added, new sorption sites in WF appeared, being higher for the more humified vermicompost V2. The dissolved organic carbon (DOC) increased with the addition of vermicompost, but the concentration of the desorbed 14C-radiochemical did not increase. Non-significant increment was observed with time for the non-extractable fraction with amendments. Diuron was transformed in all samples, although less than 0.5% was mineralized. The main effect caused by vermicomposts was a reduction in the availability of diuron in soil.

Equilibrium partitioning of (14)C-benzo(a)pyrene and (14)C-benazolin between fractionated phases from an arable topsoil.

Equilibrium partitioning of hydrophobic (14)C-benzo(a)pyrene and hydrophilic (14)C-benazolin between fractionated phases from an arable topsoil of Merzenhausen (Germany) was investigated. Topsoil samples were collected from lysimeters which were incubated with different residual crops. A physical soil fractionation based on sedimentation and centrifugation steps was performed after water extraction. Four soil phases were obtained designated sediment (SED) phase (>20 microm), microaggregate (MA) phase (2 microm-20 microm), colloid (COL) phase (<2 microm) and electrolyte (EL) phase. The distribution of (14)C-benzo(a)pyrene, (14)C-benazolin and organic carbon between the soil phases was established. Enrichment factors for the two chemicals and organic carbon are higher in the COL and MA phases than in the SED phase. The distribution constant K(d) of chemicals for Merzenhausen topsoil was calculated according to two-phase or three-phase partitioning models. The three-phase partitioning model presumes the contribution of the organic carbon for the binding of chemicals. A log K(oc) of 5.55 can be calculated in the case of (14)C-benzo(a)pyrene, which is typical of the hydrophobic association with the soil organic carbon. In the case of (14)C-benazolin, much higher K(d) and K(oc) values were calculated than found with parent molecules after short-time experiments. Long-term aging processes must be considered. Specific effects on the chemical distribution due to the different crop residues were not detected.

Formation and long-term fate of non-extractable residues in outdoor lysimeter studies.

Long-term outdoor lysimeter studies using (14)C-labelled compounds allow the quantification of the 'non-extractable residue fraction'. More than 20 lysimeter studies under realistic environmental conditions showed that more than 80% of residual carbon of the molecule is retained in the topsoil layer even after several years. Generally, 50-90% of this residual radiocarbon is regarded as 'soil bound residue'. Microbial biomass is present in large quantities in topsoil and continuously influences chemical and biochemical alteration of pesticide molecules that may interact directly with the total soil organic matter. Labelling techniques using radioactive isotopes like (14)C have been used to characterize these residues in the humus matrix. Our studies have been directed to the investigation of extractability and/or bioavailability of these residues in long-term investigations.

Characterisation of soil-bound residue fractions of the fungicide dithianon by gel permeation chromatography and polyacrylamide gel electrophoresis.

The degradation of the (14)C-labelled fungicide dithianon in an orthic luvisol was investigated under standardized conditions in comparison to stimulated microbial activity by an amendment of maize straw. The compound is characterized by mineralization losses of approximately 33% and the formation of non-extractable bound residues of approximately 63% in 64 days. Despite the major role of microorganisms in mineralizing this compound, the formation of bound residues is not biotically induced. Gel permeation chromatography and polyacrylamide gel electrophoresis, as different size separation techniques of the humic acids fractions, showed differences in the distribution patterns of non-extractable residues depending on the addition of straw material. The results presented support the existence of humic substances in soil as a micellar system rather than as a biopolymer.

Microbial release and degradation of nonextractable anilazine residues.

Humic substance fractions obtained from a degraded loess soil taken from a long-term lysimeter experiment with the fungicide anilazine were incubated in aerated liquid cultures together with native soil microorganisms. Biomineralization, remobilization of [U-phenyl-(14)C]anilazine, respectively, its metabolites, and changes of the humic matrix were observed under variable nutrient conditions. Stimulated microbial activity favored the degradation of nonextractable (14)C-anilazine residues. However, nitrogen deficiency enhanced structural changes in the humic substances, which seemed to be used then as a nitrogen source. Along with the microbial degradation of the humic substances, parts of the bound anilazine residues became remobilized. Furthermore with the use of AMD-TLC, dihydroxy anilazine was detected within the nonextractable residues. The portion of rather weak bondings between the soil organic acids and the anilazine residues turned out to be considerably lower in the humic acids fractions than in the fulvic acids fraction.