A record of polycyclic aromatic hydrocarbon (PAH) pollution obtained from accreting sediments of the Tamar Estuary, U.K.: evidence for non-equilibrium behaviour of PAH.

Concentrations of polycyclic aromatic hydrocarbons (PAH) were quantified throughout a 210Po-dated inter-tidal sediment core from the Tamar Estuary, U.K. in order to reconstruct the input history and investigate environmental reactivity of PAH in sediments. The profile recorded is similar to those reported in other aquatic sedimentary studies, with an approximately exponential increase in the concentrations of individual PAH from less than 30 ng (g dry sediment)-1 prior to 1940 to between 100 and 1000 ng (g dry sediment)-1 in contemporary surface sediments. This corresponds to an increased input of total PAH from 0.23 to 21 mg m-2 year-1. The PAH composition is dominated by parent compounds rather than alkylated homologues and is characteristic of pyrogenic sources correlating with increased motor vehicle activity and road runoff into the Tamar. There is a remarkable compositional uniformity of PAH throughout the polluted sediment core, indicating that the biogeochemical transformation and exchange processes (sorption/leaching; microbial breakdown; photo-degradation; etc.) which are known to govern the fate of experimentally-added or petroleum-derived PAH, and which exhibit compound discrimination, appear not to affect PAH in the sediments. Using a linear free energy sediment-water exchange model to simulate the repartitioning and exchange of individual PAH between the surface-mixed layer of sediment and water, we demonstrate that the current PAH concentrations in sediments are between 2 and 5 orders of magnitude greater than those expected from equilibrium partitioning with observed water concentrations. This implies that the PAH input to the sediments has been compositionally uniform and that the PAH are chemically inert. Sorptive exchange with the aqueous phase and hence the potential bioavailability of PAH appear restricted by the existence of occluded and other micro-morphologically inert forms of particle-bound PAH.