Bulk and molecular-level composition of primary organic aerosol from wood, straw, cow dung, and plastic burning

Abstract

During the past decades, the source apportionment of organic aerosol (OA) in ambient air has been improving substantially. The database of source retrieval model-resolved mass spectral profiles for different sources has been built with the aerosol mass spectrometer (AMS). However, distinguishing similar sources (such as wildfires and residential wood burning) remains challenging, as the hard ionization of the AMS mostly fragments compounds and therefore cannot capture detailed molecular information. Recent mass spectrometer technologies of soft ionization and high mass resolution have allowed for aerosol characterization at the molecular formula level. In this study, we systematically estimated the emission factors and characterized the primary OA (POA) chemical composition with the AMS and the extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) for the first time from a variety of solid fuels, including beech logs, spruce and pine logs, spruce and pine branches and needles, straw, cow dung, and plastic bags. The emission factors of organic matter estimated by the AMS and hydrocarbon gases estimated by the total hydrocarbon analyzer are 16.2 ± 10.8 g kg−1 and 30.3 ± 8.5 g kg−1 for cow dung burning, which is generally higher than that of wood (beech, spruce, and pine), straw, and plastic bag burning (in the range from 1.1 to 6.2 g kg−1 and 14.1 to 19.3 g kg−1). The POA measured by the AMS shows that the f60 (mass fraction of 60) varies from 0.003 to 0.04 based on fuel types and combustion efficiency for wood (beech, spruce, and pine) and cow dung burning. On a molecular level, the dominant compound of POA from wood, straw, and cow dung is C6H10O5 (mainly levoglucosan), contributing ∼ 7 % to ∼ 30 % of the total intensity, followed by C8H12O6 with fractions of ∼ 2 % to ∼ 9 %. However, as they are prevalent in all burning of biomass material, they cannot act as tracers for the specific sources. By using the Mann–Whitney U test among the studied fuels, we find specific potential new markers for these fuels from the measurement of the AMS and EESI-TOF. Markers from spruce and pine burning are likely related to resin acids (e.g., compounds with 20–21 carbon atoms). The product from the pyrolysis of hardwood lignins is found especially in beech log burning. Nitrogen-containing species are selected markers primarily for cow dung open burning. These markers in the future will provide support for the source apportionment.