Biomass burning emits teragrams (1012 g) of gaseous organic compounds to the atmosphere. In-plume chemistry leads to the formation of secondary pollutants and short-lived climate forcers, including ozone and particulate matter (PM). Accurate predictions of the spatial and temporal distribution of biomass burning PM, and therefore subsequent effects on air quality and climate, are precluded by incomplete identification of the precursor compounds contributing to secondary PM (formed in the atmosphere) and the relevant formation mechanisms, as well as their model representation. Here we propose to leverage our ongoing efforts to use two-dimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-TOFMS) for improved speciation of the volatile organic compounds emitted by biomass burning. Specifically we propose to use filter-based collection and extraction, followed by derivatization, to expand the polarity and volatility range of observed compounds. We further propose to use Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) to analyze a fraction of the extracts (prior to derivatization). While the molecular-level (compound structure) identification of compounds afforded by GCxGC-TOFMS is critical for developing emissions inventories and predictive modeling capabilities, the FTICR-MS will provide a vastly expanded view of the compositional range of volatile to semi-volatile organic compounds in biomass burning smoke samples. The FTICR-MS results will enable improved compound identification and chromatographic interpretation of GCxGC-TOFMS data. The proposed research is directly aligned with the EMSL mission to lead molecular-level discoveries that translate to predictive understanding of national energy and environmental challenges. Here, the molecular-level discoveries are the individual gas-phase organic compounds emitted and formed in biomass burning plumes, which will lead to improved emissions inventories and model representation of PM formation; and thus advancements in the predictive understanding of biomass burning PM and its impacts on chemistry and climate, including as relevant for air quality and energy planning purposes.