Effects of dissolved carbonates and carboxylates on the sorption of thiuram disulfide pesticides on humic acids and model surfaces

The sorption of a hydrophobic pesticide, thiram, on humic acid (HA) occurs via a specific pH-dependent binding of thiram at the deprotonated carboxylates of humic acid, forming a species thiram-[HACOO-] with K = 0.69. Similarly, thiram was sorbed by two model polycarboxylate-{SiO2COOH} Materials via the formation of a surface species thiram-{SiO2COO-} with K = 0.45 between thiram and the eprotonated carboxylates grafted on SiO2 particles. In all cases, allowance of presence of bicarbonate at natural concentration caused severe inhibition of thiram's sorption. Oxalate and formate mimic the inhibitive effect of bicarbonate. Theoretical fit of the data showed that the inhibitive effect of HCO3- is due to the formation of the anionic species [thiram-HCO3](-1) (with K = 0.90) which is water soluble and competes with the bound species thiram-{HACOO-}. The same phenomena were observed for the sorption of disulfiram. The specific interaction phenomena reported here bear relevance to the sorption properties of thiram and disulfiram on real soils and, therefore, may determine their environmental fate.