Thermal analysis of aerosol size distributions provided size resolved volatility up to temperatures of 400°C during extensive flights over North America (NA) for the INTEX/ICARTT experiment in summer 2004. Biomass burning and pollution plumes identified from trace gas measurements were evaluated for their aerosol physiochemical and optical signatures. Measurements of soluble ionic mass and refractory black carbon (BC) mass, inferred from light absorption, were combined with volatility to identify organic carbon at 400°C (VolatileOC) and the residual or refractory organic carbon, RefractoryOC. This approach characterized distinct constituent mass fractions present in biomass burning and pollution plumes every 5–10 min. Biomass burning, pollution and dust aerosol could be stratified by their combined spectral scattering and absorption properties. The “nonplume” regional aerosol exhibited properties dominated by pollution characteristics near the surface and biomass burning aloft. VolatileOC included most water-soluble organic carbon. RefractoryOC dominated enhanced shortwave absorption in plumes from Alaskan and Canadian forest fires. The mass absorption efficiency of this RefractoryOC was about 0.63 m2 g−1 at 470 nm and 0.09 m2 g−1 at 530 nm. Concurrent measurements of the humidity dependence of scattering, γ, revealed the OC component to be only weakly hygroscopic resulting in a general decrease in γ with increasing OC mass fractions. Under ambient humidity conditions, the systematic relations between physiochemical properties and γ lead to a well-constrained dependency on the absorption per unit dry mass for these plume types that may be used to challenge remotely sensed and modeled optical properties.