• Aging and condensed phase chemistry affects the hygroscopicity of ambient SOA

      Vogel, Alexander; Müller-Tautges, Christina; Krueger, Mira; Rose, Diana; Schneider, Johannes; Phillips, Gavin J.; Makkonen, Ulla; Hakola, Hannele; Crowley, John N.; Poeschl, Ulrich; et al. (European Aerosol Assembly, 2015-09-30)
      Secondary inorganic and organic aerosol particles are ubiquitous constituents in the atmosphere. They are largely produced through the photo-oxidation of gaseous precursor molecules, such as SO2, NOx and VOCs, from both anthropogenic and natural sources. Once grown to atmospherically relevant sizes, they can act as cloud condensation nuclei (CCN) and thus affect earth’s climate (IPCC, 2013). However, their chemical composition can vary considerably over their atmospheric lifetime (up to one week) as a result of which, their physico-chemical properties may change significantly due to chemical transformation processes (Jimenez et al., 2009). One of these properties is hygroscopicity, which largely depends on the chemical composition. Linking both, measured chemical composition and hygroscopicity helps to advance our current understanding of the hygroscopicity parametrisation. In this work we investigated how photochemical aging of the organic aerosol fraction and chemical reactions between inorganic and organic compounds can affect the hygroscopicity parameter κ (Petters and Kreidenweis, 2007). The measurements were conducted at the semi-rural Taunus Observatory/ Germany during summer 2012. An extensive suite of particle phase characterizing instrumentation was applied for the detailed composition analysis of submicron aerosol: We used online atmospheric pressure chemical ionization mass spectrometry (APCI-MS) (Vogel et al., 2013), aerosol mass spectrometry (AMS), and filter sampling for laboratory based analysis using ultrahigh performance liquid chromatography coupled to electrospray ionization ultrahigh resolution (OrbitrapTM) mass spectrometry (UHPLC/ESI-UHRMS). The AMS allows quantification of total organics, sulfate and nitrate, whereas the APCI-MS can identify single organic species (organic acids, organosulfates, nitrooxy-organosulfates), both at a high measurement frequencies (< 1 minute). The UHPLC/ESI-UHRMS analysis of filter samples provides vital information helping to understand the complex online spectra of the APCI-MS by the unambiguous determination of the elemental composition of different organic compounds. Furthermore, we used a MARGA (Monitor for Aerosols and Gases in Ambient Air) to measure the concentration of purely inorganic sulfate in PM10. Finally a CCN counter coupled to a differential mobility analyser (DMA) and to a condensation particle counter (CPC) was used to measure size-resolved CCN efficiency spectra and to derive the hygroscopicity parameter κ. We determined the κ-value of the ambient aerosol from size resolved chemical composition measurements by the AMS and compared it to the measured values of the CCN efficiency spectra. The relative evolution of the aerosol aging was determined by measuring the ratio of two biogenic acids: the aging product 1,2,3-methyl-butane-tricarboxylic acid (MBTCA) and the first generation oxidation product pinic acid by the online APCI-MS. The occurrence of organosulfates and nitrooxy-organosulfates was observed by the ultrahigh resolution MS analysis and the online APCI-MS. Comparison of the total sulfate concentration measured by the AMS with the sulfate measurements by the MARGA allowed for the determination of the fraction of sulfate which is bonded to organic molecules. We observed that photochemical aging and the formation of (hydrophobic) nitrooxy-organosulfates is responsible for the observed bias between the predicted and measured κ-value.
    • ClNO2 and nitrate formation via N2O5 uptake to particles: Derivation of N2O5 uptake coefficients from ambient datasets

      Phillips, Gavin J.; Thieser, Jim; Tang, Mingjin; Sobanski, Nicolas; Fachinger, Johannes; Drewnick, Frank; Lelieveld, Jos; Crowley, John N.; Max Planck Institute for Chemistry; University of Chester (Copernicus Publications, 2015-02-25)
      We present estimates of the uptake coefficient of N2O5 using ambient measurements of the trace gases N2O5 and ClNO2 and particle composition and surface area at the Kleiner Feldberg observatory, near Frankfurt, SW Germany, during the PARADE campaign (summer 2011). Three methods used to extract gamma(N2O5) from the datasets were found to be in reasonable agreement, generating values between 0.001 and 0.4. Gamma (N2O5) displayed a significant dependence on relative humidity (RH), the largest values obtained, as expected, at high RH. No significant dependence of gamma(N2O5) on particle organic content or sulphate-to-organic ratio was observed. The variability in gamma(N2O5) is however large, indicating that humidity is not the sole factor determining the uptake coefficient. There is also an indication that the yield of ClNO2 with respect to N2O5 uptake is larger with lower concentrations of PM1 total organics. Our results will be compared to existing uptake coefficients from laboratory studies and those derived from field observations.
    • Oxidation processes in the eastern Mediterranean atmosphere: evidence from the modelling of HOx measurements over Cyprus

      Mallik, Chinmay; Tomsche, Laura; Bourtsoukidis, Efstratios; Crowley, John N.; Derstroff, Bettina; Fischer, Horst; Hafermann, Sascha; Hueser, Imke; Javed, Umar; Kessel, Stephan; et al. (Copernicus Publications, 2018-07-31)
      The Mediterranean is a climatically sensitive region located at the crossroads of air masses from three continents: Europe, Africa, and Asia. The chemical processing of air masses over this region has implications not only for the air quality but also for the long-range transport of air pollution. To obtain a comprehensive understanding of oxidation processes over the Mediterranean, atmospheric concentrations of the hydroxyl radical (OH) and the hydroperoxyl radical (HO2) were measured during an intensive field campaign (CYprus PHotochemistry EXperiment, CYPHEX-2014) in the northwest of Cyprus in the summer of 2014. Very low local anthropogenic and biogenic emissions around the measurement location provided a vantage point to study the contrasts in atmospheric oxidation pathways under highly processed marine air masses and those influenced by relatively fresh emissions from mainland Europe. The CYPHEX measurements were used to evaluate OH and HO2 simulations using a photochemical box model (CAABA/MECCA) constrained with CYPHEX observations of O3, CO, NOx, hydrocarbons, peroxides, and other major HOx (OH+HO2) sources and sinks in a low-NOx environment (<100pptv of NO). The model simulations for OH agreed to within 10% with in situ OH observations. Model simulations for HO2 agreed to within 17% of the in situ observations. However, the model strongly under-predicted HO2 at high terpene concentrations, this under-prediction reaching up to 38% at the highest terpene levels. Different schemes to improve the agreement between observed and modelled HO2, including changing the rate coefficients for the reactions of terpene-generated peroxy radicals (RO2) with NO and HO2 as well as the autoxidation of terpene-generated RO2 species, are explored in this work. The main source of OH in Cyprus was its primary production from O3 photolysis during the day and HONO photolysis during early morning. Recycling contributed about one-third of the total OH production, and the maximum recycling efficiency was about 0.7. CO, which was the largest OH sink, was also the largest HO2 source. The lowest HOx production and losses occurred when the air masses had higher residence time over the oceans.