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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 ( K  soil-air,AI ), as part of commercial formulations ( K  soil-air,formulation ), and as formulation mixtures with an additional spray adjuvant added ( K  soil-air,formulation+spray adjuvan ). Chlorpyrifos K  soil-air,formulation values were also measured over 15-30 °C, allowing for the change in internal energy of the phase transfer reaction (Δ soil-air  U ) to be calculated and compared to the Δ soil-air  U for K  soil-air,AI from the literature. Measured K  soil-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 Δ soil-air  U 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.

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