Modelling PAHs adsorption and sequestration in freshwater and marine sediments

Chemical sequestration is a natural process taking place in sediments and soils which reduces the availability of hydrophobic compounds such as polycyclic aromatic hydrocarbons (PAHs). The rate of sequestration following the release of PAHs into the aquatic environment is still unexplored. To measure kinetic parameters and investigate governing factors of adsorption and sequestration of individual PAHs, natural sediment slurries were spiked with [2H]-PAHs and periodically extracted with a high molecular weight surfactant solution to determine changes in the available fraction over periods of 7-28 days. Dissolved and/or colloidal [2H]-PAHs were first adsorbed on particles within 4-7 days. Adsorbed molecules became slowly sequestered into sediment particles and were gradually more difficult to extract over a period of 17-20 days. An empirical model based on a three-compartment dynamic system was developed to quantify the sequestration rate constants of a group of seven selected PAHs. The sequestration process was assumed to be a first-order consecutive and irreversible two-stage reaction. The model was tested with lowly contaminated marine sediment and moderately contaminated freshwater sediment. Adsorption rate constants ranged between 0.056 h(-1) and 0.017 h(-1) and were approximately ten times higher than sequestration rate constants. Light PAHs were faster to enter into the sequestration process whereas colloidal dispersion of heavier less soluble PAHs reduced their adsorption rates. Although quite simple, this model was efficient to compute kinetic parameters for most PAHs studied and predict that only a small proportion of adsorbed PAHs would remain extractable after one month.