Analysis of freely dissolved alcohol ethoxylate homologues in various seawater matrixes using solid-phase microextraction.

Solid-phase microextraction fibers (SPME) were tested as tools to determine freely dissolved alcohol ethoxylate (AE) surfactants in seawater matrixes. Partitioning of a wide range of AE homologues into a 35-mu m polyacrylate fiber coating was linearly related to aqueous concentrations as low as submicrograms per liter, with high reproducibility. The exposure time needed to reach equilibrium between aqueous phase and the SPME fiber depended on the fiber-water partitioning coefficient (K-fw) of the AE homologue. Specific attention was given to the influence of various matrixes on the analysis via SPME. The presence of sediment increases the uptake kinetics of AE homologues for which diffusion in the aqueous phase is rate limiting. The K-fw in equilibrated systems was not affected by the presence of other homologues, micelles, or varying amounts of sediment phase. SPME is therefore a suitable tool for analysis of AE in sorption studies and sediment toxicity tests. A strong linear relation was observed between K-fw and the hydrophobicity of the AE homologue, using estimated octanol-water partition coefficients. This relation can be used to predict the partitioning coefficient of any AE homologue to the SPME fiber, which facilitates the analysis of complex mixtures.