Characterization of the South Atlantic marine boundary layer aerosol using an aerodyne aerosol mass spectrometer

Abstract

Measurements of the submicron fraction of the atmospheric aerosol in the marine boundary layer were performed from January to March 2007 (Southern Hemisphere summer) onboard the French research vessel Marion Dufresne in the Southern Atlantic and Indian Ocean (20° Sĝ€"60° S, 70° Wĝ€"60° E). We used an Aerodyne High-Resolution-Time-of-Flight AMS to characterize the chemical composition and to measure species-resolved size distributions of non-refractory aerosol components in the submicron range. Within the "standard" AMS compounds (ammonium, chloride, nitrate, sulfate, organics) "sulfate" is the dominant species in the marine boundary layer with concentrations ranging between 50 ng m −3 and 3 μg m−3. Furthermore, what is seen as "sulfate" by the AMS is likely comprised mostly of sulfuric acid. Another sulfur containing species that is produced in marine environments is methanesulfonic acid (MSA). There have been previously measurements of MSA using an Aerodyne AMS. However, due to the use of an instrument equipped with a quadrupole detector with unit mass resolution it was not possible to physically separate MSA from other contributions to the same m/z. In order to identify MSA within the HR-ToF-AMS raw data and to extract mass concentrations for MSA from the field measurements the standard high-resolution MSA fragmentation patterns for the measurement conditions during the ship campaign (e.g. vaporizer temperature) needed to be determined. To identify characteristic air masses and their source regions backwards trajectories were used and averaged concentrations for AMS standard compounds were calculated for each air mass type. Sulfate mass size distributions were measured for these periods showing a distinct difference between oceanic air masses and those from African outflow. While the peak in the mass distribution was roughly at 250 nm (vacuum aerodynamic diameter) in marine air masses, it was shifted to 470 nm in African outflow air. Correlations between the mass concentrations of sulfate, organics and MSA show a narrow correlation for MSA with sulfate/sulfuric acid coming from the ocean, but not with continental sulfate.