Fine-mode particulate matter (PM 2.5 ) is a highly detrimental air pollutant, regulated without regard for chemical composition and a chief component of wildfire smoke. As wildfire activity increases with climate change, its growing continental influence necessitates multidisciplinary research to examine smoke's evolving chemical composition far downwind and connect chemical compositionbased source apportionment to potential health effects. Leveraging advanced real-time speciated PM 2.5 measurements, including an aerosol chemical speciation monitor in conjunction with source apportionment and health risk assessments, we quantified the stark pollution enhancements during peak Canadian wildfire smoke transport to New York City over June 6−9, 2023. Interestingly, we also observed lower-intensity, but frequent, multiday wildfire smoke episodes during May−June 2023, which risk exposure misclassification as generic aged organic PM 2.5 via aerosol mass spectrometry given its extensive chemical transformations during 1 to 6+ days of transport. Total smokerelated organic PM 2.5 showed significant associations with asthma exacerbations, and estimates of in-lung oxidative stress were enhanced with chemical aging, collectively demonstrating elevated health risks with increasingly frequent smoke episodes. These results show that avoiding underestimated aged biomass burning PM 2.5 contributions, especially outside of peak episodes, necessitates real-time chemically resolved PM 2.5 monitoring to enable next-generation health studies, models, and policy under farreaching wildfire impacts in the 21st century.