Stabilizing mixed fatty acid and phthalate ester monolayer on artificial seawater

Phthalate esters which are widely used as industrial chemicals have become widespread contaminants in the marine environment. However, little information is available on the interfacial behavior of phthalate esters in the seawater, where contaminants generally occur at elevated concentrations and have the potential to transfer into the atmosphere through wave breaking on sea surface. We used artificial seawater coated with fatty acids to simulate sea surface microlayer in a Langmuir trough. The interactions of saturated fatty acids (stearic acid (SA) and palmitic acid (PA)) with one of the most abundant phthalate esters (di-(2-ethylhexyl) phthalate (DEHP)), were investigated under artificial seawater and pure water conditions. Pure DEHP monolayer was not stable, while more stable mixed monolayers were formed by SA and DEHP on the artificial seawater at relatively low surface pressure. Sea salts in the subphase can lower the excess Gibbs free energy to form more stable mixed monolayer. Among the ten components in the sea salts, Ca²⁺ ions played the major role in condensation of mixed monolayer. The condensed characteristic of the mixed SA (or PA)/DEHP monolayers suggested that the hydrocarbon chains were ordered on artificial seawater. By means of infrared reflection-absorption spectroscopy (IRRAS), we found that multiple sea salt mixtures induced deprotonated forms of fatty acids at the air-water interface. Sea salts can improve the stability and lifetime of mixed fatty acid and phthalate ester monolayer on aqueous droplets in the atmosphere. Interfacial properties of mixed fatty acid and phthalate ester monolayers at the air-ocean interface are important to help understand their behavior and fate in the marine environment.