Influence of Adjuvants on Pesticide Soil–Air Partition Coefficients: Laboratory Measurements and Predicted Effects on Volatilization

Abstract

A solid-phase fugacity meter was used to measure the soil-air partition coefficients of three semivolatile pesticides (chlorpyrifos, pyrimethanil, and trifluralin) in the absence of additional adjuvants (Ksoil-air,AI), as part of commercial formulations (Ksoil-air,formulation), and as formulation mixtures with an additional spray adjuvant added (Ksoil-air,formulation+sprayadjuvant). Chlorpyrifos Ksoil-air,formulation values were also measured over 15-30 °C, allowing for the change in internal energy of the phase transfer reaction (Δsoil-airU) to be calculated and compared to the Δsoil-airU for Ksoil-air,AI from the literature. Measured Ksoil-air values were then used as input parameters in a pesticide volatilization model to understand how their variability affects pesticide volatilization rates under different conditions. Initial experiments conducted at ∼24 °C indicated that all pesticides volatilized more readily in the presence of adjuvants than in their absence and that the additional spray adjuvant had minimal impact. The Δsoil-airU values were 328 and 90 kJ/mol for chlorpyrifos in the absence and presence of formulation adjuvants, respectively, suggesting that adjuvants may weaken or disrupt intermolecular attractions between pesticide molecules and soil. At temperatures below 24.5 °C, modeled chlorpyrifos volatilization rates were higher in the presence of adjuvants than in their absence; however, the opposite occurred at temperatures above 24.5 °C.