PAH sorption mechanism and partitioning behavior in lampblack-impacted soils from former oil-gas plant sites.

Abstract

This study assessed polycyclic aromatic hydrocarbon (PAH) association and aqueous partitioning in lampblack-impacted field soils from five sites in California that formerly housed oil-gas process operations. Lampblack is the solid residue resulting from the decomposition of crude oil at high temperatures in the gas-making operation and is coated or impregnated with oil gasification byproducts, among which PAHs are the compounds of the greatest regulatory concern. A suite of complementary measurements investigated the character of lampblack particles and PAH location and the associated effects on PAH partitioning between lampblack and water. PAH analyses on both whole samples and density-separated components demonstrated that 81-100% of PAHs in the lampblack-impacted soils was associated with lampblack particles. FTIR, 13C NMR, and SEM analyses showed that oil-gas lampblack solids comprise primarily aromatic carbon with soot-like structures. A free-phase aromatic oil may be present in some of the lampblack soils containing high PAH concentrations. Comparable long-term aqueous partitioning measurements were obtained with an air-bridge technique and with a centrifugation/alum flocculation procedure. Large solid/water partition coefficient (Kd) values were observed in samples exhibiting lower PAH and oil levels, whereas smaller Kd values were measured in lampblack samples containing high PAH levels. The former result is in agreement with an oil-soot partitioning model, and the latter is in agreement with a coal tar-water partitioning model. Lampblack containing high PAH levels appears to exhaust the sorption capacity of the soot-carbon, creating a free aromatic oil phase that exhibits partitioning behavior similar to PAHs in coal tar. This study improves mechanistic understanding of PAH sorption on aged lampblack residuals at former oil-gas sites and provides a framework for mechanistic assessment of PAH leaching potential and risk from such site materials.