Determination of poly(dimethyl)siloxane–water partition coefficients for selected hydrophobic organic chemicals using 14C-labeled analogs

Aqueous solutions of 14C-labeled analogs of seven hydrophobic organic chemicals (HOCs) were subject to solid-phase microextraction (SPME) under static conditions to assess their multi-compartment distribution and to compare poly(dimethyl)siloxane (PDMS)–water partition coefficients (Kf values) with previously reported values. To accomplish this, a protocol for quantitative desorption of radiolabelled HOCs from SPME fibers using hexane was developed. Time series extractions indicated that loading of SPME fibers had reached steady-state by day 8 for PCBs 52, 77 and 153, phenanthrene, benzo[a]pyrene, p,p′-DDT and p,p′-DDE. The recovery of spiked radioactivity among the (residual) aqueous phase, the PDMS coating, and all remaining wetted experimental surfaces ranged between 80 and 120%. Kf values based on 14C-labeled analogs were in good agreement with previously published values that were determined at (or closely approaching) equilibrium conditions and without significant chemical depletion and/or uncorrected system losses. Because it allows for the direct determination of HOCs associated with the residual aqueous and experimental surface compartments, the use of radiolabelled HOC analogs is a powerful tool in discriminating among competing sorptive compartments encountered in most SPME fiber calibration methodologies employed to date.