The uptake kinetics of fluorene, phenanthrene, fluoranthene, pyrene, and benzo[e]pyrene by solid-phase microextraction fibers was studied in the presence of dissolved organic matter (DOM) obtained from sediment pore water and resulted in increased fiber absorption and desorption rate coefficients. Compared to the control without DOM, these rate coefficients were increased at a DOM concentration of 36.62 mg/L by a factor of 1.27 to 2.21 and 1.31 to 2.10 for fluorene and benzo[e]pyrene, respectively. The calculated values for the fiber absorption and desorption rate coefficients show that diffusion through an unstirred boundary layer (UBL) surrounding the fiber probably forms the rate-limiting step of the process. The mineralization of aqueous-phase phenanthrene and pyrene by a representative polycyclic aromatic hydrocarbon (PAH)-degrading bacterium (Mycobacterium gilvum VM552) also was found to be enhanced by DOM. The initial degradation rates of phenanthrene (9.03 (microg/L) and pyrene (1.96 microg/L) were significantly higher compared to the control values and were enhanced by a factor of 1.32 and 1.26 at a DOM concentration of 43.14 and 42.15 mg/L, respectively. We suggest that such an enhancement results from the combination of faster uptake kinetics of the water-dissolved compounds in the UBL surrounding microbial cells and direct access of the bacteria to DOM-associated PAHs. These enhanced kinetic effects of DOM may have strong implications in sediment processes like desorption, nonequilibrium exposure, and biodegradation.