[1] For the 2008 Beijing Olympic Games full-scale control (FSC) of atmospheric pollution was implemented to improve the air quality from 20 July to 20 September 2008, resulting in a significant decrease in the emission of pollutants in urban Beijing, especially vehicular emissions. The combination of reduced emissions and weather condition changes provided us with a unique opportunity to investigate urban atmospheric chemistry. Hydrogen peroxide (H 2 O 2 ) and organic peroxides play significant roles in atmospheric processes, such as the cycling of HO x radicals and the formation of secondary sulfate aerosols and secondary organic aerosols. We measured atmospheric H 2 O 2 and organic peroxides in urban Beijing, at the Peking University campus, from 12 July to 30 September, before and during the FSC. The major peroxides observed were H 2 O 2 , methyl hydroperoxide (MHP), and peroxyacetic acid (PAA), having maximal mixing ratios of 2.34, 0.95, and 0.17 ppbv (parts per billion by volume), respectively. Other organic peroxides were detected occasionally, such as bis-hydroxymethyl hydroperoxide, hydroxymethyl hydroperoxide, ethyl hydroperoxide, and 1-hydroxyethyl hydroperoxide. On sunny days the concentrations of H 2 O 2 , MHP, and PAA exhibited pronounced diurnal variations, with a peak in the afternoon (1500-1900) and, occasionally, a second peak in the evening (2000-0200). The night peaks can be attributed to local night production from the ozonolysis of alkenes, coupled with the reaction between NO 3 radicals and organic compounds. Sunny-day weather dominated during 16-26 July, and we found that the concentrations of H 2 O 2 , MHP, and PAA increased strikingly on 22-26 July, compared with the concentrations during 16-19 July. This effect was mainly attributed to the NO x (NO and NO 2 ) decline because of the FSC, due to (i) the suppressing effect of NO and NO 2 on the production of peroxides and (ii) the indirect effect of reduced NO x on the concentration of peroxides via O 3 production in the volatile organic compound-sensitive area. Although the time period from 29 July to 15 August fell within the FSC, the concentrations of H 2 O 2 , MHP, and PAA decreased significantly. This can be explained by a combination of chemical and physical factors during this period, when rainy-and cloudy-day weather dominated. Weaker irradiation and lower temperatures resulted in a lower photochemical production of peroxides; the higher humidity resulted in their greater loss through their aqueous-phase oxidation of S(IV) and through heterogeneous removal, and lower temperatures and higher nighttime humidity resulted in a quicker surface deposition of peroxides. Furthermore, our observations seem to imply that the heterogeneous removal of H 2 O 2 is faster than that of MHP, as indicated by the strong negative correlation between the H 2 O 2 -to-MHP ratio and the aerosol surface area.

Abstract. Field measurements of atmospheric peroxides were obtained during the summer on two consecutive years over urban Beijing, which highlighted the impacts of aerosols on the chemistry of peroxide compounds and hydroperoxyl radicals (HO2). The major peroxides were determined to be hydrogen peroxide (H2O2), methyl hydroperoxide (MHP), and peroxyacetic acid (PAA). A negative correlation was found between H2O2 and PAA in rainwater, providing evidence for a conversion between H2O2 and PAA in the aqueous phase. A standard gas phase chemistry model based on the NCAR Master Mechanism provided a good reproduction of the observed H2O2 profile on non-haze days but greatly overpredicted the H2O2 level on haze days. We attribute this overprediction to the reactive uptake of HO2 by the aerosols, since there was greatly enhanced aerosol loading and aerosol liquid water content on haze days. The discrepancy between the observed and modeled H2O2 can be diminished by adding to the model a newly proposed transition metal ion catalytic mechanism of HO2 in aqueous aerosols. This confirms the importance of the aerosol uptake of HO2 and the subsequent aqueous phase reactions in the reduction of H2O2. The closure of HO2 and H2O2 between the gas and aerosol phases suggests that the aerosols do not have a net reactive uptake of H2O2, because the conversion of HO2 to H2O2 on aerosols compensates for the H2O2 loss. Laboratory studies for the aerosol uptake of H2O2 in the presence of HO2 are urgently required to better understand the aerosol uptake of H2O2 in the real atmosphere.

Abstract. The ozonolysis of alkenes is considered to be an important source of atmospheric peroxides, which serve as oxidants, reservoirs of HOx radicals, and components of secondary organic aerosols (SOAs). Recent laboratory investigations of this reaction identified hydrogen peroxide (H2O2) and hydroxymethyl hydroperoxide (HMHP) in ozonolysis of isoprene. Although larger hydroxyalkyl hydroperoxides (HAHPs) were also expected, their presence is not currently supported by experimental evidence. In the present study, we investigated the formation of peroxides in the gas phase ozonolysis of isoprene at various relative humidities on a time scale of tens of seconds, using a quartz flow tube reactor coupled with the online detection of peroxides. We detected a variety of conventional peroxides, including H2O2, HMHP, methyl hydroperoxide, bis-hydroxymethyl hydroperoxide, and ethyl hydroperoxide, and interestingly found three unknown peroxides. The molar yields of the conventional peroxides fell within the range of values provided in the literature. The three unknown peroxides had a combined molar yield of ~ 30% at 5% relative humidity (RH), which was comparable with that of the conventional peroxides. Unlike H2O2 and HMHP, the molar yields of these three unknown peroxides were inversely related to the RH. On the basis of experimental kinetic and box model analysis, we tentatively assigned these unknown peroxides to C2−C4 HAHPs, which are produced by the reactions of different Criegee intermediates with water. Our study provides experimental evidence for the formation of large HAHPs in the ozonolysis of isoprene (one of the alkenes). These large HAHPs have a sufficiently long lifetime, estimated as tens of minutes, which allows them to become involved in atmospheric chemical processes, e.g., SOA formation and radical recycling.