A biogenic source of oxalic acid and glyoxal in marine boundary layer

We present the results of oxalic acid aerosol measurements samples performed at Mace Head (Ireland, 53°20'N, 9°54'W) and Amsterdam Island (Indian Ocean, 37°48'S, 77°34'E), supporting the existence of a biogenic source of oxalic acid over the oceans. Aerosol oxalic acid was detected in clean marine air masses in concentrations ranging from 2.7 to 39 ng m-3, at Mace Head, and from 0.31 to 17 ng m-3, at Amsterdam Island. In both hemispheres, oxalic acid concentration showed a clear seasonal trend, with maxima in spring-summer and minima in the fall-winter period, in analogy with other marine biogenic aerosol components (e.g., MSA and amines). Oxalic acid was distributed along the whole aerosol size spectrum, with the major contribution given by the 1.0-2.0 μm size range, and by the lower accumulation mode (0.25-0.5 μm). Given the observed size distributions, marine aerosol oxalic acid can be assumed as the result of the combination of different formation processes, among which in-cloud oxidation of gaseous precursors [1] and photochemical degradation of biogenic unsaturated fatty acids [2] are likely the most important. Among aerosol oxalic acid precursors, glyoxal is the most likely candidate in the marine boundary layer, as a source of glyoxal over the oceans has recently been discovered by satellite observations [3] and confirmed by in situ measurements [4]. In support of this hypothesis, SCIAMACHY satellite retrieved glyoxal column concentrations, over the two sampling sites, resulted characterized by a clear seasonal trend, resembling the aerosol oxalic acid one. [1] Warneck, Atmospheric Environment, 37, 2423-2427, 2003. [2] Kawamura & Sakaguchi, J. Geophys. Res., 104, D3, 3501-3509, 1999. [3] Fu et al., J. Geophys. Res., 113, D15303, doi:10.1029/2007JD009505, 2008 [4] Sinreich et al., Atmos. Chem. Phys. Discuss., 10, 15075-15107, 2010.