Temperature-dependent sorption of polycyclic aromatic hydrocarbons on natural and treated sediments

In aqueous environment temperature is considered to play a significant role in the sorption process of polycyclic aromatic hydrocarbons (PAHs) and its influence on the sorption equilibrium is indicative of sorption energies and mechanisms. In this study, sorptions of five PAHs on three heterogeneous sorbents including one river sediment (YHR), one estuary sediment (YRD) and one treated sediment with organic matter removed (IM) were carried out at a range of temperature from 5 °C to 35 °C. Stronger sorptions were observed at lower temperatures, with the equilibrium sorption coefficient K_d increasing 2-5 times as the temperature decreases 30 °C. The increase of K_d value was attributed primarily to the change of PAH water solubility, which predicted 40-75% of the increase of K_d in the sorption process. To provide insight into the sorption mechanism, enthalpy change (ΔH_S) for the sorption process was calculated and the values were observed to be negative for all of the interactions, suggesting that the exothermal sorption of PAHs inversely dependents on temperature. Based on the values of ΔH_S, van der Waals forces were inferred as the main sorption mechanism for the PAHs, especially on the YHR sediment which contained more organic matter. For sorption of larger size PAHs on the sorbents with low organic matter, specific interactions were deduced to contribute to the overall sorption.