posted on 2006-01-01, 00:00authored byPanagiota Stathi, Konstantinos C. Christoforidis, Athanasios Tsipis, Dimitra G. Hela, Yiannis Deligiannakis
The adsorption of thiram and disulfiram onto α-Al2O3 and
montmorillonite clay has been studied in the presence
of small carboxylate anions, bicarbonate, formate, and
oxalate. At natural concentrations, HCO3- enhances
dramatically the adsorption of both pesticides on α-Al2O3
and clay. An analogous significant enhancement of
pesticide adsorption is also observed in the presence of
formate and oxalate. Density functional theory calculations
demonstrate that in solution a stable molecular complex
between one molecule of thiram and one molecule of HCO3-
is formed with interaction energy −35.6 kcal/mol. In
addition, two H2O molecules further stabilize it by an
interaction energy of −3.6 kcal/mol. This clustering [thiram−HCO3-−2H2O] leads to a change of the electronic structure
and the ultraviolet−visible spectrum of thiram that is
observed experimentally. Surface complexation modeling
shows that the molecular cluster [thiram−HCO3-−2H2O], which bears a total net charge of −1, is responsible
for the observed enhanced adsorption on the charged
surface of alumina and clay at pH below their points of
zero surface charge. The results reveal a novel pervasive
role of carboxylate anions and particularly HCO3- on
the adsorption of dithiocarbamate pesticides in natural
waters.