Investigating the influences of SO2 and NH3 levels on isoprene-derived secondary organic aerosol formation using conditional sampling approaches
1Department of Environmental Sciences and Engineering, Gillings School of Global Public Health, The University of North Carolina at Chapel Hill, Chapel Hill, NC, USA
2Electric Power Research Institute, Washington, DC, USA
3Atmospheric Research & Analysis, Inc., Cary, NC, USA
4Electric Power Research Institute, Palo Alto, CA, USA
Abstract. Filter-based PM2.5 samples were chemically analyzed to investigate secondary organic aerosol (SOA) formation from isoprene in a rural atmosphere of the southeastern US influenced by both anthropogenic sulfur dioxide (SO2) and ammonia (NH3) emissions. Daytime PM2.5 samples were collected during summer 2010 using conditional sampling approaches based on pre-defined high and low SO2 or NH3 thresholds. Known molecular-level tracers for isoprene SOA formation, including 2-methylglyceric acid, 3-methyltetrahydrofuran-3,4-diols, 2-methyltetrols, C5-alkene triols, dimers, and organosulfate derivatives, were identified and quantified by gas chromatography coupled to electron ionization mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS). Mass concentrations of six isoprene low-NOx SOA tracers contributed to 12–19% of total organic matter (OM) in PM2.5 samples collected during the sampling period, indicating the importance of the hydroxyl radical (OH)-initiated oxidation (so-called photooxidation) of isoprene under low-NOx conditions that leads to SOA formation through reactive uptake of gaseous isoprene epoxydiols (IEPOX) in this region. IEPOX-derived SOA tracers were enhanced under high-SO2 sampling scenarios, suggesting that SO2 oxidation increases aerosol acidity of sulfate aerosols needed for enhancing heterogeneous oxirane ring-opening reactions of IEPOX. No clear associations between isoprene SOA formation and high and low NH3 conditional samples were found. Furthermore, weak correlations between aerosol acidity and mass of IEPOX SOA tracers suggests that IEPOX-derived SOA formation might be modulated by other factors as well in addition to aerosol acidity. Positive correlations between sulfate aerosol loadings and IEPOX-derived SOA tracers for samples collected under all conditions indicates that sulfate aerosol could be a surrogate for surface area in the uptake of IEPOX onto preexisting aerosols.