Characterization of gas-phase organics using proton transfer reaction time-of-flight mass spectrometry: fresh and aged residential wood combustion emissions

Abstract

Abstract. Organic gases emitted during the flaming phase of residential wood combustion are characterized individually and by functionality using proton transfer reaction time-of-flight mass spectrometry. The evolution of the organic gases is monitored during photochemical aging. Primary gaseous emissions are dominated by oxygenated species (e.g., acetic acid, acetaldehyde, phenol and methanol), many of which have deleterious health effects and play an important role in atmospheric processes such as secondary organic aerosol formation and ozone production. Residential wood combustion emissions differ considerably from open biomass burning in both absolute magnitude and relative composition. Ratios of acetonitrile, a potential biomass burning marker, to CO are considerably lower ( ∼  0.09 pptv ppbv−1) than those observed in air masses influenced by open burning ( ∼  1–2 pptv ppbv−1), which may make differentiation from background levels difficult, even in regions heavily impacted by residential wood burning. A considerable amount of formic acid forms during aging ( ∼  200–600 mg kg−1 at an OH exposure of (4.5–5.5)  ×  107 molec cm−3 h), indicating residential wood combustion can be an important local source for this acid, the quantities of which are currently underestimated in models. Phthalic anhydride, a naphthalene oxidation product, is also formed in considerable quantities with aging ( ∼  55–75 mg kg−1 at an OH exposure of (4.5–5.5)  ×  107 molec cm−3 h). Although total NMOG emissions vary by up to a factor of  ∼  9 between burns, SOA formation potential does not scale with total NMOG emissions and is similar in all experiments. This study is the first thorough characterization of both primary and aged organic gases from residential wood combustion and provides a benchmark for comparison of emissions generated under different burn parameters.