• Aerosol Chemistry Resolved by Mass Spectrometry: Linking Field Measurements of Cloud Condensation Nuclei Activity to Organic Aerosol Composition

      Vogel, Alexander; Schneider, Johannes; Mueller-Tautges, Christina; Phillips, Gavin J.; Poehlker, Mira L.; Rose, Diana; Zuth, Christoph; Makkonen, Ulla; Hakola, Hannele; Crowley, John N.; et al. (American Chemical Society, 2016-10-06)
      Aerosol hygroscopic properties were linked to its chemical composition by using complementary online mass spectrometric techniques in a comprehensive chemical characterization study at a rural mountaintop station in central Germany in August 2012. In particular, atmospheric pressure chemical ionization mass spectrometry ((−)APCI-MS) provided measurements of organic acids, organosulfates, and nitrooxy-organosulfates in the particle phase at 1 min time resolution. Offline analysis of filter samples enabled us to determine the molecular composition of signals appearing in the online (−)APCI-MS spectra. Aerosol mass spectrometry (AMS) provided quantitative measurements of total submicrometer organics, nitrate, sulfate, and ammonium. Inorganic sulfate measurements were achieved by semionline ion chromatography and were compared to the AMS total sulfate mass. We found that up to 40% of the total sulfate mass fraction can be covalently bonded to organic molecules. This finding is supported by both on- and offline soft ionization techniques, which confirmed the presence of several organosulfates and nitrooxy-organosulfates in the particle phase. The chemical composition analysis was compared to hygroscopicity measurements derived from a cloud condensation nuclei counter. We observed that the hygroscopicity parameter (κ) that is derived from organic mass fractions determined by AMS measurements may overestimate the observed κ up to 0.2 if a high fraction of sulfate is bonded to organic molecules and little photochemical aging is exhibited.
    • Estimating N2O5 uptake coefficients using ambient measurements of NO3, N2O5, ClNO2 and particle-phase nitrate

      Phillips, Gavin J.; Thieser, Jim; Tang, Mingjin; Sobanski, Nicolas; Schuster, Gerhard; Fachinger, Johannes; Drewnick, Frank; Borrmann, Stephan; Bingemer, Heinz; Lelieveld, Jos; et al. (Copernicus Publications, 2016-10-27)
      We present an estimation of the uptake coefficient (γ) and yield of nitryl chloride (ClNO2) (f) for the heterogeneous processing of dinitrogen pentoxide (N2O5) using simultaneous measurements of particle and trace gas composition at a semi-rural, non-coastal, mountain site in the summer of 2011. The yield of ClNO2 varied between (0.035 ± 0.027) and (1.38 ± 0.60) with a campaign average of (0.49 ± 0.35). The large variability in f reflects the highly variable chloride content of particles at the site. Uptake coefficients were also highly variable with minimum, maximum and average γ values of 0.004, 0.11 and 0.028 ± 0.029, respectively, with no significant correlation with particle composition, but a weak dependence on relative humidity. The uptake coefficients obtained are compared to existing parameterizations based on laboratory datasets and with other values obtained by analysis of field data.