Articles | Volume 8, issue 1
Atmos. Meas. Tech., 8, 125–147, 2015
Atmos. Meas. Tech., 8, 125–147, 2015

Research article 09 Jan 2015

Research article | 09 Jan 2015

An intercomparison study of analytical methods used for quantification of levoglucosan in ambient aerosol filter samples

K. E. Yttri1, J. Schnelle-Kreis2, W. Maenhaut3,6, G. Abbaszade2, C. Alves4, A. Bjerke1, N. Bonnier14, R. Bossi5, M. Claeys6, C. Dye1, M. Evtyugina4, D. García-Gacio7, R. Hillamo8, A. Hoffer9, M. Hyder10,15, Y. Iinuma11, J.-L. Jaffrezo12, A. Kasper-Giebl13, G. Kiss9, P. L. López-Mahia7, C. Pio4, C. Piot12,16, C. Ramirez-Santa-Cruz13, J. Sciare14, K. Teinilä8, R. Vermeylen6, A. Vicente4, and R. Zimmermann2 K. E. Yttri et al.
  • 1NILU – Norwegian Institute for Air Research, P.O. Box 100, 2027 Kjeller, Norway
  • 2Helmholtz Zentrum München, Cooperation group Comprehensive Molecular Analytics, 85764 Neuherberg, Germany
  • 3Department of Analytical Chemistry, Ghent University, 9000 Gent, Belgium
  • 4Centre for Environmental and Marine Studies, Department of Environment, University of Aveiro, 3810-193 Aveiro, Portugal
  • 5Department of Environmental Science, Aarhus University, Frederiksborgvej 399, 4000 Roskilde, Denmark
  • 6Department of Pharmaceutical Sciences, University of Antwerp, Campus Drie Eiken, 2610 Antwerp, Belgium
  • 7Group of Analytical Chemistry (QANAP), Institute of Environment (IUMA), Department of Analytical Chemistry, Faculty of Sciences, University of A Coruña, Campus de A Coruña, 15071 A Coruña, Spain
  • 8Finnish Meteorological Institute, Atmospheric Composition Research, Aerosol Research, Erik Palménin Aukio 1, 00560, Helsinki, Finland
  • 9MTA-PE Air Chemistry Research Group, P.O. Box 158, 8201Veszprém, Hungary
  • 10Center for Analysis and Synthesis, Department of Chemistry, Lund University, Sweden
  • 11Leibniz-Institut für Troposphärenforschung, Permoserstr. 15, 04138 Leipzig, Germany
  • 12Univ. Grenoble Alpes, LGGE, 38000 Grenoble, France, CNRS, LGGE, 38000 Grenoble, France
  • 13Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164, 1060 Vienna, Austria
  • 14Laboratoire des Sciences du Climat et de l'Environnement, CEA-CNRS-UVSQ, 91190 Gif-sur-Yvette, France
  • 15Pakistan Space and Upper Atmosphere research commission (SUPARCO), Lahore, Pakistan
  • 16Université de Savoie, LCME, 73376 Le Bourget du lac, France

Abstract. The monosaccharide anhydrides (MAs) levoglucosan, galactosan and mannosan are products of incomplete combustion and pyrolysis of cellulose and hemicelluloses, and are found to be major constituents of biomass burning (BB) aerosol particles. Hence, ambient aerosol particle concentrations of levoglucosan are commonly used to study the influence of residential wood burning, agricultural waste burning and wildfire emissions on ambient air quality. A European-wide intercomparison on the analysis of the three monosaccharide anhydrides was conducted based on ambient aerosol quartz fiber filter samples collected at a Norwegian urban background site during winter. Thus, the samples' content of MAs is representative for BB particles originating from residential wood burning. The purpose of the intercomparison was to examine the comparability of the great diversity of analytical methods used for analysis of levoglucosan, mannosan and galactosan in ambient aerosol filter samples. Thirteen laboratories participated, of which three applied high-performance anion-exchange chromatography (HPAEC), four used high-performance liquid chromatography (HPLC) or ultra-performance liquid chromatography (UPLC) and six resorted to gas chromatography (GC). The analytical methods used were of such diversity that they should be considered as thirteen different analytical methods. All of the thirteen laboratories reported levels of levoglucosan, whereas nine reported data for mannosan and/or galactosan. Eight of the thirteen laboratories reported levels for all three isomers.

The accuracy for levoglucosan, presented as the mean percentage error (PE) for each participating laboratory, varied from −63 to 20%; however, for 62% of the laboratories the mean PE was within ±10%, and for 85% the mean PE was within ±20%. For mannosan, the corresponding range was −60 to 69%, but as for levoglucosan, the range was substantially smaller for a subselection of the laboratories; i.e. for 33% of the laboratories the mean PE was within ±10%. For galactosan, the mean PE for the participating laboratories ranged from −84 to 593%, and as for mannosan 33% of the laboratories reported a mean PE within ±10%.

The variability of the various analytical methods, as defined by their minimum and maximum PE value, was typically better for levoglucosan than for mannosan and galactosan, ranging from 3.2 to 41% for levoglucosan, from 10 to 67% for mannosan and from 6 to 364% for galactosan. For the levoglucosan to mannosan ratio, which may be used to assess the relative importance of softwood versus hardwood burning, the variability only ranged from 3.5 to 24 .

To our knowledge, this is the first major intercomparison on analytical methods used to quantify monosaccharide anhydrides in ambient aerosol filter samples conducted and reported in the scientific literature. The results show that for levoglucosan the accuracy is only slightly lower than that reported for analysis of SO42- (sulfate) on filter samples, a constituent that has been analysed by numerous laboratories for several decades, typically by ion chromatography and which is considered a fairly easy constituent to measure. Hence, the results obtained for levoglucosan with respect to accuracy are encouraging and suggest that levels of levoglucosan, and to a lesser extent mannosan and galactosan, obtained by most of the analytical methods currently used to quantify monosaccharide anhydrides in ambient aerosol filter samples, are comparable.

Finally, the various analytical methods used in the current study should be tested for other aerosol matrices and concentrations as well, the most obvious being summertime aerosol samples affected by wildfires and/or agricultural fires.