Molecular Characterization of Free Tropospheric Aerosol Collected at the Pico Mountain Observatory

Tuesday, 16 December 2014
Katja Dzepina1, Claudio Mazzoleni1, Paulo JLCS Fialho2, Swarup China1, Bo Zhang1, Robert Chris Owen1,3, Detlev Helmig4, Jacques Hueber4, Sumit Kumar1,5, Judith A Perlinger1, Louisa J Kramer1, Michael Dziobak1, Marian Ampadu1, Seth C Olsen6,7, Donald J Wuebbles8 and Lynn R Mazzoleni1, (1)Michigan Technological University, Houghton, MI, United States, (2)University of the Azores, Azores, Portugal, (3)Environmental Protection Agency Research Triangle Park, Research Triangle Park, NC, United States, (4)University of Colorado at Boulder, Boulder, CO, United States, (5)National Center for Medium Range Weather Forecasting, Noida, India, (6)UIUC, Urbana, IL, United States, (7)Xyratex International Ltd, Sacramento, CA, United States, (8)Pacific Northwest Natl Lab, Richland, WA, United States
Long-range transported free tropospheric aerosol was sampled at the Pico Mountain Observatory (38°28’15’’N, 28°24’14’’W; 2225 m amsl) on Pico Island of the Azores archipelago in the North Atlantic ~3900 km east and downwind of North America. Filter-collected aerosol during summer 2012 was analyzed for organic and elemental carbon, and inorganic ions. The average ambient concentration of aerosol was 0.9 μg m-3. Organic aerosol contributed the majority of mass (57%), followed by sulfate (21%) and nitrate (17%). Filter-collected aerosol was positively correlated with continuous aerosol measurements of black carbon, light scattering and number concentration. Water-soluble organic compounds (WSOC) from 9/24 and 9/25 aerosol samples collected during a pollution event were analyzed using ultrahigh-resolution FT-ICR MS. FLEXPART retroplume analysis shows the air masses were very aged (> 12 days). About 4000 molecular formulas were assigned to each of the mass spectra between m/z 100-1000. The majority of the assigned molecular formulas have unsaturated structures with CHO and CHNO elemental compositions. WSOC have an average O/C ratio of ~0.45, relatively low compared to O/C ratios of other aged aerosol which might be the result of evaporation and fragmentation during long-range transport. The increase in aerosol loading during 9/24 was linked to biomass burning emissions from North America by FLEXPART retroplumes and MODIS fire counts. This was confirmed with WSOC biomass burning markers and with the morphology and mixing state of particles as determined by scanning electron microscopy. The presence of markers characteristic of aqueous-phase reactions of biomass burning phenolic species suggests that the aerosol collected at Pico had undergone cloud processing. The air masses on 9/25 were more aged (~15 days) and influenced by marine emissions, as indicated by organosulfates and species characteristic for marine aerosol (e.g. fatty acids). The change in air masses for the two samples was corroborated by the changes in ozone, ethane, propane, morphology of particles, as well as by the FLEXPART retroplumes. In this presentation we will report the first detailed molecular characterization of free tropospheric aged aerosol intercepted at the Pico Mountain Observatory.