Fine and coarse modes of dicarboxylic acids in the Arctic aerosols collected during the Polar Sunrise Experiment 1997

Abstract

[1] Fine (<1 mm) and coarse (>1 mm) aerosol particles were collected at Alert, Canada (82°27 0 N, 62°30 0 W), during the Arctic spring as part of the Polar Sunrise Experiment 1997 and were analyzed for low molecular weight dicarboxylic acids (C 2 -C 11 ) using gas chromatography with flame ionization detector (GC-FID) and GC/mass spectrometry (GC/MS). More than 80% of total diacids were detected in the fine fraction, suggesting the production by gas-to-particle conversion in the Arctic. In both fractions, oxalic acid was the dominant diacid species followed by succinic and malonic acids. Shorter chain diacids (C 2 -C 5 ) showed the concentration maximum on 5-7 April; however, longer chain diacids (<C 6 ) did not show a clear peak in the same periods. A significant depletion of ozone was observed during the experiment, where an anticorrelation was found between the concentrations of ozone and shorter chain diacids (C 2 -C 5 ) in both fine and coarse aerosols. During this event, we also observed the enhanced concentration of filterable bromine in both modes. Peaks of dicarboxylic acids in both coarse and fine aerosols during ozone depletion events indicate that heterogeneous reactions are occurring on coarse particle and possibly on fine particles as well. Dicarboxylic acids may be produced by the oxidation of precursor compounds such as glyoxal and glyoxylic and other w-oxocarboxylic acids that contain aldehyde (hydrated form) group, being involved with ozone and halogen chemistry in the Arctic marine boundary layer.

High abundances of water-soluble dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in the mountaintop aerosols over the North China Plain during wheat burning season

“…In general, their molecular distributions are characterized by the predominance of oxalic acid (C 2 ), followed by malonic (C 3 ) and succinic (C 4 ) acids. LMW dicarboxylic acids have been reported in urban (Kawamura and Ikushima, 1993;Sempéré and Kawamura, 1994;Rohrl and Lammel, 2001;Wang et al, 2002;Yao et al, 2002;Rompp et al, 2006;Kitanovski et al, 2011), mountainous (Legrand et al, 2007), marine (Kawamura and Sakaguchi, 1999;Mochida et al, 2003a, b) and Arctic and Antarctic atmospheres (Kawamura et al, 1996a, b;Kerminen et al, 1999;Narukawa et al, 2002Narukawa et al, , 2003. In general, concentrations of LMW diacids were found to be higher in Asian cities and its coastal regions in the Asian Pacific region .…”

Organic aerosol and global climate modelling: a review

“…This new reaction pathway involves reactions of Criegee intermediates in the condensed phase with aldehydes, ketones and alkenes and it does not involve acidity. Kawamura et al (1995Kawamura et al ( , 1996Kawamura et al ( , 2005 and Narukawa et al (2003) provide experimental evidence that Br chemistry in the Arctic transforms unsaturated diacids to smaller saturated acids. Ozonolysis of oleic and linoleic acid is shown to contribute to activation of particles to cloud droplets (Broekhuizen et al, 2005).…”

Diurnal changes in the distribution of dicarboxylic acids, ketocarboxylic acids and dicarbonyls in the urban Tokyo atmosphere

“…They are also present in the remote marine aerosols from the Pacific Kawamura, 1994, 2003;Kawamura and Sakaguchi, 1999;Mochida et al, 2003a,b) and Atlantic (Barboukas et al, 2000) and in the polar aerosols from the Arctic (Li and Winchester, 1993;Kawamura et al, 1996a;Kerminen et al, 1999;Hara et al, 2002;Narukawa et al, 2003) and Antarctic (Kawamura et al, 1996b). Because LMW diacids are very water soluble, their existence on the aerosol surface alters the chemical and physical properties of atmospheric aerosols and enhances the capability of aerosols as cloud condensation nuclei (Saxena et al, 1995).…”