The cone calorimeter is a standard test method for material behaviour in fires. The principle of the cone calorimeter is to use an electric radiant heater to raise the temperature of the combustion zone and ignite the fuel. 35 kW/m2 was used in the present work, as this has been previously shown to be sufficient to establish fully developed combustion of biomass materials such as wood. As one of the main fire loads is wood and wood is the dominant biomass for energy generation, it is reasonable to use the cone calorimeter to characterize the combustion of biomass on a small scale and pine was used in the present work. The cone calorimeter was used in the controlled atmosphere mode with an enclosure around the test biomass that enabled the air flow for biomass combustion to be controlled at 19.2 g/m2s, which corresponds to a combustion heat release rate HRR of 57 kW/m2, assuming all the oxygen in the air is consumed. This air flow will be shown to generate rich combustion at a metered equivalence ratio, Ø, of about 2, which is comparable with the first gasification stage of biomass two stage burning in log burners and pellet burners, where air is added downstream of the gasification stage of biomass combustion. Soot emissions are generated in this rich gasification stage burning and potentially oxidized in the oxidation second stage burning. The rich burning gasification zone particulate emissions were analysed for number size distribution using the Cambustion DMS 500 particle size analyser. The exit from the controlled combustion zone was extended in a 75 mm diameter chimney where a mean gas sample was taken. A heated Gasmet FTIR was used for gas composition analysis, using a heated sample line, filter and pump from the sample point to the analyser. The particles emitted were sampled after the second stage combustion from entrained air into the chimney discharge gases into a dilution tunnel with a fixed gas flow rate of 24 l/s, which gave a dilution ratio of the primary combustion gases of 150/1 which is required for nano-particle size analysis. A Cambustion DMS500 electrical mobility particle number and size instrument was used with size resolution from 5 to 1000 nm. The present results show that in the rich burning first stage chimney sample there were very high levels of 20 nm nanoparticles, 1 × 1010/cc, and an accumulation mode peak at 200 nm. The presence of the 20 nm particles makes the particulate emissions extremely toxic.