Availability of polycyclic aromatic hydrocarbons from lampblack‐impacted soils at former oil‐gas plant sites in California, USA

Lampblack‐impacted soils at former oil‐gas plant sites in California, USA, were characterized to assess the sorption of polycyclic aromatic hydrocarbons (PAHs) and the concentration‐dependent effects of a residual oil tar phase on sorption mechanism and availability of PAHs. Nuclear magnetic resonance spectroscopy demonstrated similar aromaticity for both lampblack carbon and the oil tar phase, with pronounced resonance signals in the range of 100 to 150 ppm. Scanning‐electron microscopic images revealed a physically distinct oil tar phase, especially at high concentrations in lampblack, which resulted in an organic‐like film structure when lampblack particles became saturated with the oil tar. Sorption experiments were conducted on a series of laboratory‐prepared lampblack samples to systematically evaluate influences of an oil tar phase on PAH sorption to lampblack. Results indicate that the sorption of PAHs to lampblack exhibits a competition among sorption phases at low oil tar contents when micro‐ and mesopores are accessible. When the oil tar content increases to more than 5 to 10% by weight, this tar phase fills small pores, reduces surface area, and dominates PAH sorption on lampblack surface. A new PAH partitioning model, K d = K LB‐C (1‐ f tar )° + f tar K tar (α = empirical exponent), incorporates these effects in which the control of PAH partitioning transits from being dominated by sorption in lampblack ( K LB‐C ) to absorption in oil tar ( K tar ), depending on the fraction of tar ( f tar ). This study illustrates the importance of understanding interactions among PAHs, oil tar, and lampblack for explaining the differences in availability of PAHs among site soils and, consequently, for refining site‐specific risk assessment and establishing soil cleanup levels.