Isomer-selective biodegradation of high-molecular-weight azaarenes in PAH-contaminated environmental samples.

Polycyclic aromatic nitrogen heterocycles, or azaarenes, normally co-occur with polycyclic aromatic hydrocarbons (PAHs) in contaminated soils. We recently reported that nontarget analysis using high resolution mass spectrometry of samples from four PAH-contaminated sites revealed a previously unrecognized diversity and abundance of azaarene isomers and their methylated derivatives. Here we evaluated their biodegradability by natural microbial communities from each site in aerobic microcosm incubations under biostimulated conditions. The removal of total quantifiable azaarenes ranged from 15 to 85%, and was related to the initial degree of weathering for each sample. While three-ring azaarenes were readily biodegradable, the five-ring congeners were the most recalcitrant. Microbial-mediated removal of four-ring congeners varied for different isomers, which might be attributed to the position of the nitrogen atom that also influences the physicochemical properties of azaarenes and possibly the susceptibility to transformation by relevant microbial enzymes. The presence of methyl groups also influenced azaarene biodegradability, which decreased with increasing degree of methylation. Several oxidation products of azaarenes were detected, including ketones and dioxygenated derivatives of three- and four-ring compounds. Our results indicate the susceptibility of some azaarenes to bioremediation, while suggesting the potential implications for risk from the persistence of less-biodegradable isomers and the formation of oxidized-azaarene derivatives.