Relative solubilities of bifenox and 1-naphthylacetic acid (NAA) in plant cuticles and in selected pure or aqueous glycol additives

The driving force for foliar penetration is the product of the partition coefficient (K) between the cuticle and the formulation residue, and the concentration of the active ingredient in the spray residue. Ethylene glycols and polyethylene glycols (PEGs) are often contained in commercial formulations, because they are good solvents and not toxic. Since they are humectants, the water content of the formulation residue varies with humidity of the air. At 25 degrees C and 65% relative humidity PEG 400 contains about 50% water. The partition coefficients for the lipophilic herbicide, bifenox, increased with increasing water content of the ethylene glycols and PEGs, such that log K was a linear function of the mass fraction of water or PEG. The K value was about 0.5 for the system cuticle/pure PEG and 27500 for the system cuticle/water. When PEG contained 50% water, K was only 110. Partition coefficients of bifenox between cuticle and 'Tween' 80 depended also on humidity, having values of 0.75 in cuticle/pure 'Tween' 80 and 29.1 when 'Tween' 80 contained 50% water. With 1-naphthylacetic acid (NAA), which is a weak acid, partition coefficients also depended on water content of PEG 400, but a maximum curve was obtained. The maximum partition coefficient (211) was observed with a mixture of 30% PEG 400 and 70% water, which corresponded to a humidity of 88%. We suggest that this is due to an effect of PEG 400 on the ionisation of NAA. Our data demonstrate that partition coefficients are affected by humidity, because solubilities of lipophilic compounds and weak acids in PEG/water mixtures vary greatly with the water content. This in turn affects driving forces, mainly by the effect of humidity on partition coefficient. With non-ionisable lipophilic compounds, partition coefficients, driving forces and rates of foliar uptake therefore increase with increasing humidity.