Evaluating the Extraction and Quantification of Marine Surfactants from Seawater through Solid Phase Extraction and Subsequent Colorimetric Analyses

Surfactants are amphiphilic molecules that adsorb to interfaces and affect the interfacial tension. Surfactants in seawater can impact gas-exchange, surface properties, and the composition and fate of sea spray aerosol. The accurate quantification of surfactants and their classes is crucial to constraining the effect of surfactants in seawater and their role in air-sea exchanges. Here, we evaluate and optimize a solid phase extraction (SPE) method paired with colorimetry and UV-vis spectroscopy to quantify the concentrations of anionic, cationic, and nonionic surfactants in seawater. We compare tandem SPE with two-step SPE and different elution volumes and evaluate the impact of different interferents. Improved extraction efficiencies were obtained with an 8 mL acetonitrile elution and with separate ENVI-18 and ENVI-Carb extractions, instead of tandem. With complex surfactant mixtures, the presence of anionic surfactants interfered with the quantification of cationic surfactants and caused underestimations of up to 83%. Using a two-step extraction and analyzing each seawater SPE extract separately during colorimetric quantification help avoid the effects of interferents and ensure more representative quantification of surfactants. With this method, average seawater surfactant concentrations ranged from 0.04 to 0.06 μM. At the highest concentrations, the class composition comprised 23% anionic, 21% cationic, and 56% nonionic surfactants.