Partitioning, Extractability, and Formation of Nonextractable PAH Residues in Soil. 1. Compound Differences in Aging and Sequestration

This study was carried out to assess the influence of physicochemical properties on PAH sequestration in sterile sewage sludge-amended arable soil. Radiolabeled phenanthrene (14C-9-Phe), pyrene (14C-4,5,9,10-Pyr), and benzoapyrene (14C-7-BaP) were spiked and aged for up to 525 days in sterile soil microcosms. The degree of compound sequestration at various sampling times was determined by their extractability with organic solvents and release from soil residues by base saponification extraction. The amount of PAH extractable by butanol and dichloromethane decreased with compound aging in the soil. The decrease in PAH extractability with aging, and the formation of nonextractable bound residues, increased with compound molecular weight, KOW and KOC. The amount of total extractable PAH determined by sequential dichloromethane soxtec and methanolic saponification extraction decreased from 98%, 97%, and 94% at day 10 to 95%, 91%, and 77%, respectively for 14C-9-Phe, 14C-4,5,9,10-Pyr, and 14C-7-BaP after 525 days aging. During the same aging period there was an increase in the amount of PAH released from the soil by base saponification extraction, suggesting a progressive diffusion of PAHs into hydrolyzable and recalcitrant organic matter and mineral phases of soil. Calculated half-lives for the apparent loss of PAHs by sequestration in this experiment were dependent on the method used to extract them from soil. These half-lives ranged from 96 to 1,789 days depending on the compound, and are in agreement with values obtained from previous spiking experiments using nonsterile soils. These results suggest that a considerable fraction of PAHs assumed degraded in previous studies may have been sequestered within the organic carbon and, to a lesser extent, mineral phases of soil.