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Abstract. Emission of organic aerosol (OA) from wood combustion is not well constrained; understanding the governing factors of OA emissions would aid in explaining the reported variability. Pyrolysis of the wood during combustion is the process that produces and releases OA precursors. We performed controlled pyrolysis experiments at representative combustion conditions. The conditions changed were the temperature, wood length, wood moisture content, and wood type. The mass loss of the wood, the particle concentrations, and light-gas concentrations were measured continuously. The experiments were repeatable as shown by a single experiment, performed nine times, in which the real-time particle concentration varied by a maximum of 20 %. Higher temperatures increased the mass loss rate and the released concentration of gases and particles. Large wood size had a lower yield of particles than the small size because of higher mass transfer resistance. Reactions outside the wood became important between 500 and 600 ∘C. Elevated moisture content reduced product formation because heat received was shared between pyrolysis reactions and moisture evaporation. The thermophysical properties, especially the thermal diffusivity, of wood controlled the difference in the mass loss rate and emission among seven wood types. This work demonstrates that OA emission from wood pyrolysis is a deterministic process that depends on transport phenomena.

Abstract. Wood pyrolysis is a distinct process that precedes combustion and contributes to biomass and biofuel burning gas-phase and particle-phase emissions. Pyrolysis is defined as the thermochemical degradation of wood, the products of which can be released directly or undergo further reaction during gas-phase combustion. To isolate and study the processes and emissions of pyrolysis, a custom-made reactor was used to uniformly heat small blocks of wood in a nitrogen atmosphere. Pieces of maple, Douglas fir, and oak wood (maximum of 155 cm3) were pyrolyzed in a temperature-controlled chamber set to 400, 500, or 600 ∘C. Real-time particle-phase emissions were measured with a soot particle aerosol mass spectrometer (SP-AMS) and correlated with simultaneous gas-phase emission measurements of CO. Particle and gas emissions increased rapidly after inserting a wood sample, remained high for tens of minutes, and then dropped rapidly leaving behind char. The particulate mass-loading profiles varied with elapsed experiment time, wood type and size, and pyrolysis chamber temperature. The chemical composition of the emitted particles was organic (C, H, O), with negligible black carbon or nitrogen. The emitted particles displayed chemical signatures unique to pyrolysis and were notably different from flaming or smoldering wood combustion. The most abundant fragment ions in the mass spectrum were CO+ and CHO+, which together made up 23 % of the total aerosol mass on average, whereas CO2+ accounted for less than 4 %, in sharp contrast with ambient aerosol where CO2+ is often a dominant contributor. The mass spectra also showed signatures of levoglucosan and other anhydrous sugars. The fractional contribution of m/z 60, traditionally a tracer for anhydrous sugars including levoglucosan, to total loading (f60) was observed to be between 0.002 and 0.039, similar to previous observations from wildfires and controlled wood fires. Atomic ratios of oxygen and hydrogen to carbon, O:C and H:C as calculated from AMS mass spectra, varied between 0.41–0.81 and 1.06–1.57, respectively, with individual conditions lying within a continuum of O:C and H:C for wood's primary constituents: cellulose, hemicellulose, and lignin. This work identifies the mass spectral signatures of particle emissions directly from pyrolysis, including f60 and the CO+/CO2+ ratio, through controlled laboratory experiments in order to help in understanding the importance of pyrolysis emissions in the broader context of wildfires and controlled wood fires.

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Semi-volatile secondary organic aerosols (SOA) comprise a major fraction of ambient particle pollutants. The partitioning of SOA in the atmosphere has commonly been assumed to be fast enough that it could be computed solely from thermodynamic equilibrium considerations e.g., using Raoult's Law. This simplifying assumption has been called into question by recent studies of single SOA particles evaporating in a zero-vapor concentration environment, which reported unexpectedly slow evaporation relative to atmospheric timescales. In this work we directly investigated the phase equilibration kinetics of systems of SOA particles under realistic atmospheric conditions. SOA was generated in an oxidation flow reactor (OFR) from engine exhaust or α-pinene and mixed with clean air in an atmospheric pressure smog chamber (32&amp;thinsp;°C) to induce evaporation. The evolution of the particle size distribution was monitored over time as the aerosol system returned to phase equilibrium under different particle concentrations (2.5 and 5&amp;thinsp;µg&amp;thinsp;m^&amp;minus;3) and humidity conditions (<&amp;thinsp;10&amp;thinsp;% and 60&amp;thinsp;%). We found that under typical ambient conditions, and independent of relative humidity and precursor origin (engine exhaust vs. α-pinene), SOA reestablished equilibrium with the vapor phase within minutes, and that the evolution of particle size was well-fit by a computational model treating the particle phase as well-mixed. The effective thermodynamic saturation concentration of the SOA was found to be in the range 0.02&amp;ndash;0.11&amp;thinsp;µg&amp;thinsp;m^&amp;minus;3 at 20&amp;thinsp;°C, assuming an enthalpy of vaporization of 150&amp;thinsp;kJ&amp;thinsp;mol^&amp;minus;1. The effective evaporation coefficient was found to be in the range 0.1&amp;ndash;0.2 using a gas diffusion coefficient of 5&amp;thinsp;×&amp;thinsp;10^&amp;minus;6&amp;thinsp;m²&amp;thinsp;s^&amp;minus;1. Unlike previous single-particle studies, this data suggests that under most loading conditions, anthropogenic and biogenic SOA can rapidly attain phase equilibrium in the atmosphere and that their partitioning can be modeled assuming thermodynamic equilibrium.