title: Influence of soil copper content on the kinetics of thiram adsorption and on thiram leachability from soils.
abstract: This work aimed to assess the influence of soil copper content on the sorption processes of thiram, a fungicide widely used in agriculture, most of the times together with copper. Two different types of studies were performed: (1) desorption studies of thiram with acetonitrile after batch adsorption equilibration, and ageing of the wet soil for a variable period of time; (2) kinetic studies of thiram adsorption performed using the soil in its original form and after fortification with copper ions. In the desorption studies, with the increase of the ageing time, a decrease of the thiram peak and a simultaneous increase of a new peak, assigned to a copper complex, were observed in the chromatograms. This new peak increases sharply until an ageing period of about 4d and then this area is maintained approximately constant until 18 d, the maximum ageing period studied. These results indicate that thiram reacts with copper ions along time giving rise to the formation of relatively persistent copper complexes in soil. Desorption studies with CaCl(2) 0.01 M solution showed that this complex is not extracted. Thus, it is not easily leached to ground and surface waters and copper may contribute to thiram immobilization in soil. The kinetic studies of thiram adsorption were performed in both soils and for two initial thiram concentrations (~7 and 20 mg L(-1)). For the soil fortified with copper the percentage of adsorbed thiram is higher than observed for the original soil at the same initial concentrations and equilibration times and 100% of adsorption is attained in 15 h or 48 h, depending on the thiram initial concentration. Four kinetic equations, the pseudo first- and second-order equations, the Elovich and the intraparticle diffusion equations were selected to fit the kinetic data of the adsorption process of thiram onto both original and fortified soil. The best model to describe the kinetics of thiram adsorption onto the original soil is the intraparticle diffusion model. For the soil fortified with copper ions we verified that for the highest initial thiram concentration, the best model is also the intraparticle diffusion model, however, for the lower initial thiram concentration the best model is the pseudo second-order kinetic equation, suggesting that, for a high Cu:Thi ratio, a chemical reaction of thiram with copper ions on the soil surface can occur, and it may be the rate controlling step. Since the kinetics of adsorption depends on both soil copper content and the initial thiram concentration in solution, i.e. depends on Cu:Thi ratio, it is difficult to choose a fixed batch equilibration time for adsorption studies of thiram.
authors.affiliation: CERNAS (Center of Natural Resources, Environmental and Society Studies), Department of Pure Sciences, ESAC, Bencanta, 3040-316 Coimbra, Portugal.
authors.forename: Olga M S
authors.initials: OM
authors.lastname: Filipe
authors.forename: Carina A E
authors.initials: CA
authors.lastname: Costa
authors.forename: Maria M
authors.initials: MM
authors.lastname: Vidal
authors.forename: Eduarda B H
authors.initials: EB
authors.lastname: Santos
mesh_terms: D000327:Adsorption; D000383:Agriculture / Q000706:statistics & numerical data; D003300:Copper / Q000032:analysis / Q000737:chemistry*; D004784:Environmental Monitoring; D005659:Fungicides, Industrial / Q000032:analysis / Q000737:chemistry*; D007700:Kinetics; D011174:Portugal; D012987:Soil / Q000737:chemistry; D012989:Soil Pollutants / Q000032:analysis / Q000737:chemistry*; D013893:Thiram / Q000032:analysis / Q000737:chemistry*
chemical_list: D005659:Fungicides, Industrial; D012987:Soil; D012989:Soil Pollutants; D013893:Thiram; D003300:Copper