The effects of isoprene and NOx on secondary organic aerosols formed through reversible and irreversible uptake to aerosol water

Isoprene oxidation produces water-soluble organic gases capable of partitioning to aerosol liquid water. The formation of secondary organic aerosols through such aqueous pathways (aqSOA) can take place either reversibly or irreversibly; however, the split between these fractions in the atmosphere is highly uncertain. The aim of this study was to characterize the reversibility of aqSOA formed from isoprene at a location in the eastern United States under substantial influence from both anthropogenic and biogenic emissions. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was characterized in Baltimore, Maryland, USA, using measurements of particulate water-soluble organic carbon (WSOCp) in alternating dry and ambient configurations. WSOCp evaporation with drying was observed systematically throughout the late spring and summer, indicating reversible aqSOA formation during these times. We show through time lag analyses that WSOCp concentrations, including the WSOCp that evaporates with drying, peak 6 to 11 h after isoprene concentrations, with maxima at a time lag of 9 h. The absolute reversible aqSOA concentrations, as well as the relative amount of reversible aqSOA, increased with decreasing NOx / isoprene ratios, suggesting that isoprene epoxydiol (IEPOX) or other low-NOx oxidation products may be responsible for these effects. The observed relationships with NOx and isoprene suggest that this process occurs widely in the atmosphere, and is likely more important in other locations characterized by higher isoprene and/or lower NOx levels. This work underscores the importance of accounting for both reversible and irreversible uptake of isoprene oxidation products to aqueous particles.