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

Abstract

Abstract. Gas-phase H 2 O 2 , organic peroxides and carbonyl compounds were 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 2 O 2 ), methyl hydroperoxide (MHP, CH 3 OOH) and occasionally hydroxymethyl hydroperoxide (HMHP, HOCH 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 on O-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 2 O 2 was formed through recombination reactions of HO 2 radicals, but there is some evidence that H 2 O 2 is also formed from ozonolysis of anthropogenic and/or biogenic alkenes. Diurnal variations of mixing ratios of various carbonyl compounds are reported: alkanals (C 2 to C 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.

Atmospheric hydrogen peroxide and organic hydroperoxides during PRIDE-PRD'06, China: their concentration, formation mechanism and contribution to secondary aerosols

“…The mean values at night (20:00-02:00 LT) were 0.74±0.62 ppbv for H 2 O 2 and 0.19±0.10 ppbv for MHP. The mixing ratios of H 2 O 2 and MHP are in agreement with those reported in the literature with H 2 O 2 ranging between 0.5 ppbv and 5 ppbv and MHP ranging between several pptv and 2.7 ppbv worldwide respectively (Hellpointner and Gäb, 1989;Hewitt and Kok, 1991;Das and Aneja, 1994;Watkins et al, 1995a, b;Jackson and Hewitt, 1996;Sauer et al, 1997Sauer et al, , 2001O'Sullivan et al 1999;Morgan and Jackson, 2002;Moortgat et al, 2002;Grossmann et al, 2003;Lee et al, 1993Lee et al, , 1995Lee et al, , 1998Lee et al, , 2000Lee et al, , 2008François et al, 2005;Xu and Chen, 2005;Walker et al, 2006;Kim et al, 2007).…”

Contribution of human-related sources to indoor volatile organic compounds in a university classroom

“…Ion signal at m/z 75 may represent hydroxyacetone (Wisthaler and Weschler, 2010), which is a pro- duct of the oxidation (mainly by OH radicals) of isoprene (Grosjean et al, 1993;Paulot et al, 2009). The daytime indoor concentration of m/z 75 ranged from 0.2 to 1.2 ppb (Figure 5b), with a ventilation/infiltration factor contribution of 0.1-0.7 ppb, while outdoor hydroxyacetone concentrations range from 0 to 0.4 ppb in rural and forested areas (Matsunaga, 2004;Moortgat et al, 2002;Ortiz et al, 2006;Zhou et al, 2009). The concentration of m/z 75 may be higher in the classroom because it included other compounds that have the same nominal molecular mass as hydroxyacetone.…”

Measurements of OH and HO<sub>2</sub> yields from the gas phase ozonolysis of isoprene

“…The reactions have been recogCorrespondence to: P. W. Seakins (p.w.seakins@leeds.ac.uk) nised as a major source of organic acids and organic hydroperoxides in the atmosphere (Horie et al, 1994;Becker et al, 1993Becker et al, , 1990Baker et al, 2002;Gäb et al, 1995;Hewitt and Kok, 1991;Moortgat et al, 2002;Neeb et al, 1997;Sauer et al, 1999;Simonaitis et al, 1991) and the ozonolysis of biogenic alkenes, typically terpenes, has been known to form particulate products which serve as the precursors to secondary organic aerosols (Donahue et al, 2007). Finally, the reaction provides a direct means for the oxidation of unsaturated non-methane hydrocarbons (NMHC) that competes with OH radical and NO 3 radical initiated processes which also give rise to intermediates that are of atmospheric significance.…”