Sources of nitrate in stratocumulus cloud water: Airborne measurements during the 2011 E-PEACE and 2013 NiCE studies

This study examines the sources of NO3- in stratocumulus clouds over the eastern Pacific Ocean off the California coast using airborne and surface measurement data from the Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE; 2011) and Nucleation in California Experiment (NiCE; 2013). Average NO3- air-equivalent concentrations in cloud water samples categorized as having been influenced by ship exhaust (2.5 mu g m(-3)), strong marine emissions (2.5 mu g m(-3)) and fires (2.0 mu g m(-3)) were more than twice that in the background cloud water (0.9 mu g m(-3)). During periods when biomass burning plumes resided above cloud top, 16 of 29 cloud water samples were impacted due to instability in the entrainment interface layer with NO3- levels reaching as high as 9.0 mu g m(-3). Nucleation scavenging of chloride depleted sea-salt is a source of cloud water NO3-, with the lowest Cl-:Na+ ratio (1.5) observed in ship-influenced samples. Surface aerosol measurements show that NOT concentrations peak in the particle diameter range of 1.0-5.6 mu m, similar to Na, Cl- and Si, suggesting that drop activation of crustal particles and sea salt could be an important source of NO3- in cloud water. The contrasting behavior of NOT and SO42- is emphasized by the NO3-:SO42- mass concentration ratio which is highest in cloud water (by more than a factor of two) followed by above cloud aerosol, droplet residual particles, and below cloud aerosol. Trends of a decreasing NO3-:SO42- ratio with altitude in clouds are confirmed by parcel model studies due to the higher rate of in-cloud sulfate formation as compared to HNO3 uptake by droplets. (C) 2014 Elsevier Ltd. All rights reserved.