Application of a static solid-phase microextraction procedure combined with liquid–liquid extraction to determine poly(dimethyl)siloxane–water partition coefficients for selected polychlorinated biphenyls

A static solid-phase microextraction (SPME) procedure combined with liquid–liquid extraction (LLE) was used to determine the poly(dimethyl)siloxane (PDMS)–water partition coefficients (Kf) for selected polychlorinated biphenyl congeners (PCBs), including PCB 1, 15, 28, 47, 101, 153, 180, 202, 206, and 209. The accuracy for the measurements of analyte concentrations in the aqueous phase was ensured with a one-to-one recovery correction strategy employing one 13C-labeled PCB congener as a surrogate standard for each unlabeled PCB counterpart. The effects of coating thickness (7, 30, and 100 μm) and sample volume (130 mL and 2 L) on the Kf values were examined experimentally and confirmed with paired t-tests. Significant dependence of Kf values on coating thickness was found for a few heavily chlorinated congeners only, and was tentatively attributed to the use of the inaccurate effective coating volumes and the structural variation with these PDMS coatings. In addition, no significant differences in the log Kf values of all analytes except for PCB 206 were found between the sample sizes of 130 mL and 2 L for both the 7- and 100-μm coatings. Overall, Kf values obtained with 2-L sample containers were consistently higher than those reported in the literature, which is attributable to the selection of appropriate equilibrium times for SPME and direct measurements of aqueous analyte concentrations with LLE in the present study.