Boreal forest fire emissions in fresh Canadian smoke plumes: C₁-C₁₀ volatile organic compounds (VOCs), CO₂, CO, NO₂, NO, HCN and CH₃CN

Abstract. Boreal regions comprise about 17 % of the global land area, and they both affect and are influenced by climate change. To better understand boreal forest fire emissions and plume evolution, 947 whole air samples were collected aboard the NASA DC-8 research aircraft in summer 2008 as part of the ARCTAS-B field mission, and analyzed for 79 non-methane volatile organic compounds (NMVOCs) using gas chromatography. Together with simultaneous measurements of CO₂, CO, CH₄, CH₂O, NO₂, NO, HCN and CH₃CN, these measurements represent the most comprehensive assessment of trace gas emissions from boreal forest fires to date. Based on 105 air samples collected in fresh Canadian smoke plumes, 57 of the 80 measured NMVOCs (including CH₂O) were emitted from the fires, including 45 species that were quantified from boreal forest fires for the first time. After CO₂, CO and CH₄, the largest emission factors (EFs) for individual species were formaldehyde (2.1 ± 0.2 g kg⁻¹), followed by methanol, NO₂, HCN, ethene, α-pinene, β-pinene, ethane, benzene, propene, acetone and CH₃CN. Globally, we estimate that boreal forest fires release 2.4 ± 0.6 Tg C yr⁻¹ in the form of NMVOCs, with approximately 41 % of the carbon released as C₁-C₂ NMVOCs and 21 % as pinenes. These are the first reported field measurements of monoterpene emissions from boreal forest fires, and we speculate that the pinenes, which are relatively heavy molecules, were detected in the fire plumes as the result of distillation of stored terpenes as the vegetation is heated. Their inclusion in smoke chemistry models is expected to improve model predictions of secondary organic aerosol (SOA) formation. The fire-averaged EF of dichloromethane or CH₂Cl₂, (6.9 ± 8.6) × 10⁻⁴ g kg⁻¹, was not significantly different from zero and supports recent findings that its global biomass burning source appears to have been overestimated. Similarly, we found no evidence for emissions of chloroform (CHCl₃) or methyl chloroform (CH₃CCl₃) from boreal forest fires. The speciated hydrocarbon measurements presented here show the importance of carbon released by short-chain NMVOCs, the strong contribution of pinene emissions from boreal forest fires, and the wide range of compound classes in the most abundantly emitted NMVOCs, all of which can be used to improve biomass burning inventories in local/global models and reduce uncertainties in model estimates of trace gas emissions and their impact on the atmosphere.