Direct N2O5 reactivity measurements at a polluted coastal site
1Department of Atmospheric Sciences, University of Washington, Seattle, USA
2Department of Chemistry, University of Washington, Seattle, USA
3Department of Chemistry and Biochemistry, University of California, San Diego, USA
4Scripps Institution of Oceanography, San Diego, USA
5Cooperative Institute for Research in the Environmental Sciences, University of Colorado, Boulder, USA
Abstract. Direct measurements of N2O5 reactivity on ambient aerosol particles were made during September 2009 at the Scripps Institution of Oceanography (SIO) Pier facility located in La Jolla, CA. N2O5 reactivity measurements were made using a custom flow reactor and the particle modulation technique alongside measurements of aerosol particle size distributions and non-refractory composition. The pseudo-first order rate coefficients derived from the particle modulation technique and the particle surface area concentrations were used to determine the population average N2O5 reaction probability, γ(N2O5), approximately every 50 min. Insufficient environmental controls within the instrumentation trailer led us to restrict our analysis primarily to nighttime measurements. Within this subset of data, γ(N2O5) ranged from <0.001 to 0.029 and showed significant day-to-day variations. We compare these data to a recent parameterization that utilizes aerosol composition measurements and an aerosol thermodynamics model. The parameterization captures several aspects of the measurements with similar general trends over the time series. However, the parameterization persistently overestimates the measurements by a factor of 1.5–3 and does not illustrate the same extent of variability. Assuming chloride is internally mixed across the particle population leads to the largest overestimates. Removing this assumption only partially reduces the discrepancies, suggesting that other particle characteristics that can suppress γ(N2O5) are important, such as organic coatings or non-aqueous particles. The largest apparent driver of day-to-day variability in the measured γ(N2O5) at this site was the particle nitrate loading, as inferred from both the measured particle composition and the parameterizations. The relative change in measured γ(N2O5) as a function of particle nitrate loading appears to be consistent with expectations based on laboratory data, providing direct support for the atmospheric importance of the so-called "nitrate effect".