Hydrogen Peroxide, Organic Peroxides and Higher Carbonyl Compounds Determined during the BERLIOZ Campaign

Gas-phase H^sub 2^O^sub 2^, 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 s...

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Published in:Journal of atmospheric chemistry 2002-05, Vol.42 (1), p.443-463
Main Authors: Moortgat, G K, Grossmann, D, Boddenberg, A, Dallmann, G, Ligon, AP, Turner, W V, Gaeb, S, Slemr, F, Wieprecht, W, Acker, K, Kibler, M, Schlomski, S, Baechmann, K
Format: Article
Language:English
Subjects:
Carbon
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Summary:Gas-phase H^sub 2^O^sub 2^, 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 (H^sub 2^O^sub 2^),methyl hydroperoxide (MHP, CH^sub 3^OOH) and occasionally hydroxymethyl hydroperoxide (HMHP, HOCH^sub 2^OOH) 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 H^sub 2^O^sub 2^ was formed throughrecombination reactions of HO^sub 2^ radicals, but there is some evidencethat H^sub 2^O^sub 2^ is also formed from ozonolysis ofanthropogenic and/or biogenic alkenes. Diurnal variations of mixing ratios of various carbonyl compounds are reported: alkanals (C^sub 2^ to C^sub 10^,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.[PUBLICATION ABSTRACT]
ISSN:0167-7764
1573-0662
DOI:10.1023/A:1015743013107