Characterization of primary and aged wood burning and coal combustion organic aerosols in an environmental chamber and its implications for atmospheric aerosols

Particulate matter (PM) affects visibility, climate, and public health. Organic matter (OM), a uniquely complex portion of PM, can make up more than half of total atmospheric fine PM mass. We investigated the effect of aging on secondary organic aerosol (SOA) concentration and composition for wood burning (WB) and coal combustion (CC) emissions, two major atmospheric OM sources, using mid-infrared (MIR) spectroscopy and aerosol mass spectrometry (AMS). For this purpose, primary emissions were injected into an environmental chamber and aged using hydroxyl (diurnal aging) and nitrate (nocturnal aging) radicals to reach an atmospherically relevant oxidative age. A time-of-flight AMS instrument was used to measure the high-time-resolution composition of non-refractory fine PM, while fine PM was collected on PTFE filters before and after aging for MIR analysis. AMS and MIR spectroscopy indicate an approximately 3-fold enhancement of organic aerosol (OA) concentration after aging (not wall-loss corrected). The OM:OC ratios also agree closely between the two methods and increase, on average, from 1.6 before aging to 2 during the course of aging. MIR spectroscopy, which is able to differentiate among oxygenated groups, shows a distinct functional group composition for aged WB (high abundance of carboxylic acids) and CC OA (high abundance of non-acid carbonyls) and detects aromatics and polycyclic aromatic hydrocarbons (PAHs) in emissions of both sources. The MIR spectra of fresh WB and CC aerosols are reminiscent of their parent compounds with differences in specific oxygenated functional groups after aging, consistent with expected oxidation pathways for volatile organic compounds (VOCs) of each emission source. The AMS mass spectra also show variations due to source and aging that are consistent with the MIR functional group (FG) analysis. Finally, a comparison of the MIR spectra of aged chamber WB OA with that of ambient samples affected by residential wood burning and wildfires reveals similarities regarding the high abundance of organics, especially acids, and the visible signatures of lignin and levoglucosan. This finding is beneficial for the source identification of atmospheric aerosols and interpretation of their complex MIR spectra.