Many important environmental pollutants are strongly adsorbing hydrophobic compounds. Because of their potential to adsorb to dissolved organic matter (DOM), their partition coefficient Kd may be underestimated by the conventional approach due to incomplete phase separation. In this study, solid-phase microextraction (SPME) was compared with liquid-liquid partition (LLP) for measuring Kd of bifenthrin and permethrin isomers on sediments. Due to its selective detection of the freely dissolved concentration, SPME gave Kd values 0.6-4.4-fold greater than those obtained by LLP in creek and field sediments and 3.6-21.7-fold greater in nursery runoff sediments. Underestimation by the conventional method was attributed to adsorption to DOM that was not excluded from the aqueous phase by centrifugation. The degree of underestimation was dependent on the source and amount of DOM and may be generally significant for compounds that have DOM adsorption coefficient (KDOM) > 10(4). This study provides evidence that the existing Kd values for many hydrophobic pollutants may be underestimated, and SPME may be a viable, efficacious tool for evaluating the underestimation.