Aerosolomics based approach to discover source molecular markers: A case study for discriminating residential wood heating vs garden green waste burning emission sources.

Biomass burning is a significant source of particulate matter (PM) in ambient air and its accurate source apportionment is a major concern for air quality. The discrimination between residential wood heating (RWH) and garden green waste burning (GWB) particulate matter (PM) is rarely achieved. The objective of this work was to evaluate the potential of non-targeted screening (NTS) analyses using HRMS (high resolution mass spectrometry) data to reveal discriminating potential molecular markers of both sources. Two residential wood combustion appliances (wood log stove and fireplace) were tested under different output conditions and wood moisture content. GWB experiments were carried out using two burning materials (fallen leaves and hedge trimming). PM samples were characterized using NTS approaches with both LC- and GC-HRMS (liquid and gas chromatography-HRMS). The analytical procedures were optimized to detect as many species as possible. Chemical fingerprints obtained were compared combining several multivariate statistical analyses (PCA, HCA and PLS-DA). Results showed a strong impact of the fuel nature and the combustion quality on the chemical fingerprints. 31 and 4 possible markers were discovered as characteristic of GWB and RWH, respectively. Complementary work was attempted to identify potential molecular formulas of the different potential marker candidates. The combination of HRMS NTS chemical characterization with multivariate statistical analyses shows promise for uncovering organic aerosol fingerprinting and discovering potential PM source markers.

Emission factors and chemical characterization of particulate emissions from garden green waste burning.

This work provides an evaluation of the emission factors (EFs) of typical garden waste burning (fallen leaves and hedge trimming) in terms of particulate matter (PM), elemental and organic carbon (EC-OC) together with a detailed chemical characterization of 88 particle-bound organic species including polycyclic aromatic hydrocarbons (PAHs), levoglucosan and its isomers, lignin breakdown products (methoxyphenols), cholesterol, alkanes, polyols and sugars. Furthermore, wood-log based burning experiments have been performed to highlight key indicators or chemical patterns of both, green waste and wood burning (residential heating) sources, that may be used for PM source apportionment purposes. Two residential log wood combustion appliances, wood stove (RWS) and fireplace, under different output conditions (nominal and reduced) and wood log moisture content (mix of beech, oak and hornbeam), have been tested. Open wood burning experiments using wood logs were also performed. Green waste burning EFs obtained were comparable to the available literature data for open-air biomass burning. For PM and for most of the organic species studied, they were about 2 to 30 times higher than those observed for wood log combustion experiments. Though, poor performance wood combustions (open-air wood log burning, fireplace and RWS in reduced output) showed comparable EFs for levoglucosan and its isomers, methoxyphenols, polyols, PAHs and sugars. Toxic PAH equivalent benzo[a]pyrene EFs were even 3-10 times higher for the fireplace and open-air wood log burning. These results highlighted the impact of the nature of the fuel burnt and the combustion performances on the emissions. Different chemical fingerprints between both biomass burning sources were highlighted with notably a predominance of odd high-molecular weight n-alkanes (higher carbon preference index, CPI), lower levoglucosan/mannosan ratio and lower sinapylaldehyde abundance for green waste burning. However, the use of such indicators seems limited, especially if applied alone, for a clear discrimination of both sources in ambient air.