Divergent Transport Dynamics of Alkylated versus Unsubstituted Polycyclic Aromatic Hydrocarbons at the Air-Water and Sediment-Water Interfaces at a Legacy Creosote Site.

Alkylated polycyclic aromatic hydrocarbons (PAHs) are abundant constituents of many PAH mixtures and contribute to risk at contaminated sites. Despite their abundance, the movement of alkylated PAHs remains understudied relative to unsubstituted PAHs. In the present study, passive sampling devices were deployed in the air, water, and sediments at 11 locations across multiple seasons to capture spatial and temporal variability in the abundance and movement of alkylated PAHs at a Brownsfield creosote site in Oregon, USA. Freely dissolved concentrations of 18 alkyl homologous series were quantified by gas chromatography-triple quadrupole mass spectrometry. Alkylated PAHs were consistently more abundant than unsubstituted PAHs in all sampled media (sum PAH and APAH concentrations 43-96% alkyl PAHs). Models of diffusive and advective flux revealed abundant 2 and 3-ring alkyl PAHs exhibited seasonal differences in movement, particularly across the air-water interface. The novel application of these methods to freely dissolved alkylated PAH homologues revealed that, in many instances, alkylated PAHs, particularly C3 and C4 homologues, moved in the opposite direction as unsubstituted PAHs across both the air-water and sediment-water interfaces. These findings reinforce the need to characterize alkylated PAHs and seasonal variability and can inform future sampling at contaminated sites.