As part of the Fire Lab at Missoula Experiments (FLAME) in 2006–2007, we examined hygroscopic properties of particles emitted from open combustion of 33 select biomass fuels. Measurements of humidification growth factors for subsaturated water relative humidity (RH) conditions were made with a hygroscopic tandem differential mobility analyzer (HTDMA) for dry particle diameters of 50, 100 and 250 nm. Results were then fit to a single-parameter model to obtain the hygroscopicity parameter, κ. Particles in freshly emitted biomass smoke exhibited a wide range of hygroscopicity (individual modes with 02.5 filter samples. Despite aerosol heterogeneity, reconstructions of κ using PM2.5 bulk chemical composition data fell along a 1:1 line with measured ensemble κ values.