Diversity and Abundance of High-Molecular-Weight Azaarenes in PAH-Contaminated Environmental Samples

Azaarenes are N-heterocyclic polyaromatic pollutants that co-occur with polycyclic aromatic hydrocarbons (PAHs) in contaminated soils. Despite the known toxicity of some high-molecular-weight azaarenes, their diversity, abundance, and fate in contaminated soils remain to be elucidated. We applied high-resolution mass spectrometry and mass-defect filtering to four PAH-contaminated samples from geographically distant sites and detected 232 azaarene congeners distributed in eight homologous series, including alkylated derivatives and two hitherto unknown series. Four- and five-ring azaarenes were detected among these series, and the most abundant nonalkylated congeners groups (C₁₃H₉N, C₁₅H₉N, C₁₇H₁₁N, C₁₉H₁₁N, and C₂₁H₁₃N) were quantified. The profiles of congener groups varied among different sites. Three-ring azaarenes presented higher concentrations in unweathered sites, while four- and five-ring azaarenes predominated in weathered sites. Known toxic and carcinogenic azaarenes, such as benzo[c]acridine and dibenzo[a,h]acridine, were detected along with their multiple isomers. Our results highlight a previously unrecognized diversity and abundance of azaarenes in PAH-contaminated sites, with corresponding implications for environmental monitoring and risk assessment.