Partitioning of crude oil polycyclic aromatic hydrocarbons in aquatic systems

This paper investigates the hypothesis that observed polycyclic aromatic hydrocarbon (PAH) concentrations in an aqueous system are equal to the sum of the organic phase and soluble phase molar concentrations. While the organic phase concentrations are proportional to the PAH mole fraction in the oil, the soluble phase molar concentrations are estimated using Raoult's law. A batch laboratory mixing vessel with a scalable mixing energy was loaded initially at various oil layer thicknesses (0.4-3.2 mm) which correspond to oil surface loadings (40-310 mg/cm2). The vessel was agitated at constant mean shear rates (Gm = 5, 20 s(-1)). Total petroleum hydrocarbon (TPH) samples were taken periodically to estimate the entrainment rate as a function of initial oil layer thickness. TPH concentrations were measured in-situ using a laser scattering instrument (LISST-100) and ex-situ using gravimetric analysis. At a steady-state TPH concentration (>72 h), additional samples were analyzed for PAH concentration using GC/MS analysis. TPH concentrations increased over time according to a first-order kinetic model. Generally, the first-order rate constant and steady-state concentration both increased with increased oil loading and with increased Gm. In addition, measured PAH concentrations correlated well (r2 > 0.96) with those predicted by a partitioning model. These results are useful for assessing the effects of mixing and oil loading conditions on crude oil entrainment and PAH partitioning.