Polycyclic aromatic compounds (PACs) threaten the health of aquatic ecosystems. In northeastern Alberta, Canada, decades of oil sands mining and upgrading activities have increased PAC delivery into freshwaters. This PAC pollution adds to natural inputs from river erosion of bitumen-bearing McMurray Formation outcrops and wildfire inputs. Quantifying these petrogenic and pyrogenic PAC inputs, which is key for understanding industrial impacts, remains a challenge. To distinguish petrogenic from pyrogenic inputs, we characterized river water PACs before and after the 2016 Fort McMurray wildfire, one of the largest natural disasters in Canadian history. Samples of wildfire ash and outcropping bitumen allow us to distinguish between these important PAC sources. River PAC concentrations ranged over multiple orders of magnitude (10s–10 000s ng/L). Petrogenic PACs dominated most of the postfire period with only short-term episodes of pyrogenic signatures in burned watersheds due to the wash-in of ash from the watershed. Wildfire PAC inputs during these events resulted in exceptional increases in concentrations that met or exceeded high (petrogenic) background concentrations, driven by the natural erosion of outcropping bitumen. Our dataset offers the first quantification of these two important PAC sources in this industrialized region and provides new insight into the impacts of increasing wildfire frequency and severity across the Boreal Forest.