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Hydrogen Peroxide, Organic Peroxides and Higher Carbonyl Compounds Determined during the BERLIOZ Campaign
Authors:G K Moortgat  D Grossmann  A Boddenberg  G Dallmann  A P Ligon  W V Turner  S Gäb  F Slemr  W Wieprecht  K Acker  M Kibler  S Schlomski  K Bächmann
Institution:(1) Division of Atmospheric Chemistry, Max Planck Institut für Chemie (MPI), PO Box 3060, D-55020 Mainz, Germany;(2) Analytische Chemie, Bergische Universität-Gesamthochschule Wuppertal (BUGH) FB 9, Gausstr. 20, D-42119 Wuppertal, Germany;(3) Fraunhofer Institut für Atmosphärische Umweltforschung (IFU), Kreuzeckbahnstr. 19, D-82467 Garmisch-Partenkirchen, Germany;(4) Chair for Atmospheric Chemistry and Air Quality, Brandenburgische Technische Universität Cottbus (BTU), Ernst-Hellmann-Weg, Haus 215, Germany;(5) Institut für Chemie, Technische Universität Darmstadt (TUD), Petersenstr. 8, D-64287 Darmstadt, Germany
Abstract:Gas-phase H2O2, organic peroxides and carbonyl compoundswere determined at various sites from Mid-July to early August 1998 during the BERLIOZ campaign in Germany. The sites were located northwest of Berlin and were chosen to determine pollutants downwind of the city emissions during a summer smog episode. Hydrogen peroxide (H2O2),methyl hydroperoxide (MHP, CH3OOH) and occasionally hydroxymethyl hydroperoxide (HMHP, HOCH2OOH) were quantified in air samples by commercial fluorimetric methods and classical HPLC with post-column derivatisation by horseradish peroxidase/p-hydroxyphenyl acetic acid and fluorimetric detection. Carbonyl compounds were determined in ambient air by a novel method based onO-pentafluorobenzyl hydroxylamine as derivatisation agent.Mixing ratio profiles of the hydroperoxides and the carbonyl compounds are reported for the intensive phase of the campaign, 20–21 July, 1998. Peroxides showed pronounced diurnal variations with peak mixing ratios in the early afternoon. At times, a second maximum was observed in the late afternoon. The major part of the H2O2 was formed throughrecombination reactions of HO2 radicals, but there is some evidencethat H2O2 is also formed from ozonolysis ofanthropogenic and/or biogenic alkenes. Diurnal variations of mixing ratios of various carbonyl compounds are reported: alkanals (C2 to C10,isobutanal), unsaturated carbonyl compounds (methacrolein, methylvinylketone, acrolein), hydroxycarbonyl (glycolaldehyde, hydroxyacetone) and dicarbonyl compounds (glyoxal, methylglyoxal, biacetyl), aromatic compounds (benzaldehyde, o- and m-tolylaldehyde) and pinonaldehyde.
Keywords:H2O2  organic peroxides  carbonyl compounds  city plume  photosmog
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