Polar semi-volatile organic compounds in biomass burning emissions and their chemical transformations during aging in an oxidation flow reactor

Abstract. Semi-volatile organic compounds (SVOCs) emitted from open biomass-burning (BB) can contribute to chemical and physical properties of atmospheric aerosols and also may cause adverse health effects. The polar fraction of SVOCs constitutes a significant part of BB organic aerosols, and thus it is important to characterize the chemical composition and reactivity of this fraction. In this study, globally and regionally important representative fuels (Alaskan peat, Moscow peat, Pskov peat, Eucalyptus, Malaysian peat, and Malaysian agricultural peat) were burned under controlled conditions using the combustion chamber facility at the Desert Research Institute (DRI). Gas- and particulate-phase biomass-burning emissions were aged in an oxidation flow reactor (OFR) to mimic 5–7 days of atmospheric aging. Fresh and OFR-aged biomass-burning aerosols were collected on Teflon impregnated glass fiber filters (TIGF) in tandem with XAD resin media for organic compound (OC) speciation. The polar fraction extracted with dichloromethane and acetone was analyzed with gas chromatography mass spectrometry (GC-MS) for 84 polar organic compounds – including mono and dicarboxylic acids, methoxylated phenols, aromatic acids, anhydrosugars, resin acids, and sterols. For all these compounds, fuel-based emission factors (EFs) were calculated for fresh and OFR-aged samples. The carbon mass of the quantified polar compounds was found to constitute 5 % to 7 % of the total OC mass. High abundance of methoxyphenols (239 mg kg−1 for Pskov peat; 22.6 % of total GC-MS characterized mass) and resin acids (118 mg kg−1 for Pskov peat; 14.5 % of total GC-MS characterized mass) was found in peat burning emissions (smoldering combustion). Concentration of some organic compounds (e.g., tetracosanoic acid) with molecular weight (MW) above 350 g mol−1 decreased after the OFR aging, while abundances of low MW compounds (e.g., hexanoic acid) increased. This indicated a significant extent of fragmentation reactions in the OFR. Methoxyphenols decreased after OFR aging, while a significant increase (3.7 to 8.6 times) in abundance of dicarboxylic acids emission factors (EFs), especially maleic acid (10 to 60 times), was observed. EFs for fresh and ratios from fresh-to-aged BB samples reported in this study can be used to perform source apportionment and predict processes occurring during atmospheric transport.