Origin of C₂–C₅dicarboxylic acids in the European atmosphere inferred from year‐round aerosol study conducted at a west‐east transect

Abstract

[1] An atmospheric study of C 2 -C 5 dicarboxylic acids was conducted over two years at seven sites located from the Azores to eastern continental European sites. The lowest concentrations of total C 2 -C 5 diacids are observed at the Azores (Portugal) and at 4360 m elevation in the Alps ($50 ng m À3 ), and the highest (400 ng m À3) are observed at the rural K-puszta site (Hungary). Quasi-absent at surface sites, the seasonal cycle of total diacids is characterized by a pronounced summer maximum at elevated sites, the highest summer level (510 ng m À3) being observed at the forested mountain site of Schauinsland (Germany). Whatever site and season, oxalic acid is always the most abundant diacid with a relative abundance higher than 60%. The climatology of C 2 -C 5 diacids in Europe is discussed versus environmental conditions at sites (marine/ continental, rural/forested, boundary layer/free troposphere, and winter/summer). Observations are used to discuss the possible sources of C 2 -C 5 diacids, with special emphasis on their primary versus secondary and natural versus anthropogenic origin. At surface sites in winter, fast secondary productions in wood burning plumes in addition to secondary production from volatile organic carbon (VOC) species emitted by vehicles seem to be important contributors. In summer the impact of anthropogenic sources is weakened and biogenic emissions from vegetation (unsaturated fatty acids, isoprene, oxygenated VOCs, and eventually monoterpenes) likely represent major precursors of diacids. At the Azores, diacids are not only related to long-range transport from continents but also to marine biogenic emissions from phytoplankton, particularly in summer.Citation: Legrand, M., S. Preunkert, T. Oliveira, C. A. Pio, S. Hammer, A. Gelencsér, A. Kasper-Giebl, and P. Laj (2007), Origin of C 2 -C 5 dicarboxylic acids in the European atmosphere inferred from year-round aerosol study conducted at a west-east transect,

Diurnal and temporal variations of water-soluble dicarboxylic acids and related compounds in aerosols from the northern vicinity of Beijing: Implication for photochemical aging during atmospheric transport

“…Oxalic acid (C 2 ) is usually the dominant organic species in aerosols (Kawamura and Sakaguchi, 1999). Diacids are emitted primarily from combustion of fossil fuels, i.e., motor exhausts and coal burning, and biomass burning (Graham et al, 2002;Kawamura and Kaplan, 1987;Kundu et al, 2010a, b;Narukawa et al, 1999), but more importantly produced by the secondary oxidation of anthropogenic and biogenic volatile organic compounds (VOCs) in the atmosphere (Glasius et al, 2000;Kawamura et al, 1996a;Legrand et al, 2007). Aqueous-phase production of C 2 is also important in aerosol/cloud/fog droplets (Warneck, 2003).…”

A Preparative 2D-Chromatography Method for Compound-Specific Radiocarbon Analysis of Dicarboxylic Acids in Aerosols

“…DCAs are found at rural (Legrand et al 2007), urban (Kawamura and Ikushima 1993), and marine sites (Kawamura and Usukura 1993), which raises questions about their sources, precursors, and formation processes. Moreover, DCAs may play a role as cloud condensation nuclei (Hori et al 2003).…”

“…Recent studies have revealed a strong diurnal correlation of ozone with the oxalic acid content of aerosols (Fisseha et al 2009) and many other investigations concluded that this low-molecular weight DCA is produced mainly through oxidation of volatile organic compounds (VOCs). A brief summary of proposed precursors and formation processes of C 2 to C 6 diacids is given in Legrand et al (2007).…”

Intercomparison of the measurements of oxalic acid in aerosols by gas chromatography and ion chromatography

“…First, with GC the homologous series of dicarboxylic acids (C 2 -C 10 ), ketocarboxylic acids, and α-dicarbonyls can be measured (Kawamura et al, 1996a(Kawamura et al, , 2005 whereas the IC method usually measures only oxalate (Barboukas et al, 2000). If a gradient elusion technique is utilized, other species such as malonate and succinate can be determined with IC (e.g., Legrand et al, 2005Legrand et al, , 2007. Second, GC is combined on-line to mass spectrometry to obtain mass spectra of various compounds.…”

“…Oxalic acid (C 2 ) and other low molecular weight dicarboxylic acids are the most abundant organic compound class in atmospheric aerosols from many locations on the globe including urban (Kawamura and Kaplan, 1987;Kawamura and Ikushima, 1993;Yao et al, 2004;Huang et al, 2005;Kawamura et al, 2005;Ho et al, 2007;Aggarwal and Kawamura, 2008;Hsieh et al, 2008;Miyazaki et al, 2009), remote continental (Legrand et al, 2005(Legrand et al, , 2007Kundu et al, 2010), coastal (Mochida et al, 2003a;Kawamura et al, 2004) and remote marine (Kawamura and Usukura, 1993;Kawamura and Sakaguchi, 1999;Mochida et al, 2003b;Sempéré and Kawamura, 2003) and polar regions (Li and Winchester, 1993;Kawamura et al, 1996a,b;Kerminen et al, 1999;Narukawa et al, 2003) and are abundantly present in wet precipitation samples (Sempéré and Kawamura, 1994;Kawamura et al, 2001).…”