Articles | Volume 15, issue 12
Atmos. Chem. Phys., 15, 6851–6866, 2015
https://doi.org/10.5194/acp-15-6851-2015
Atmos. Chem. Phys., 15, 6851–6866, 2015
https://doi.org/10.5194/acp-15-6851-2015

Research article 23 Jun 2015

Research article | 23 Jun 2015

Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications

Q. Q. Wu1, L. B. Huang1, H. Liang1, Y. Zhao1,a, D. Huang1,b, and Z. M. Chen1 Q. Q. Wu et al.
  • 1State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China
  • anow at: Department of Chemistry, University of California, Irvine, CA 92697, USA
  • bnow at: Department of Earth Sciences, Zhejiang University, Hangzhou, Zhejiang Province 310027, China

Abstract. Hydrogen peroxide (H2O2) and organic peroxides play important roles in the cycle of oxidants and the formation of secondary aerosols in the atmosphere. Recent field observations have suggested that the budget of peroxyacetic acid (PAA, CH3C(O)OOH) is potentially related to the aerosol phase processes, especially to secondary aerosol formation. Here, we present the first laboratory measurements of the uptake coefficient of gaseous PAA and H2O2 onto ambient fine particulate matter (PM2.5) as a function of relative humidity (RH) at 298 K. The results show that the PM2.5, which was collected in an urban area, can take up PAA and H2O2 at the uptake coefficient (γ) of 10−4, and both γPAA and γH2O2 increase with increasing RH. The value of γPAA at 90 % RH is 5.4 ± 1.9 times that at 3 % RH, whereas γH2O2 at 90 % RH is 2.4 ± 0.5 times that at 3 % RH, which suggests that PAA is more sensitive to the RH variation than H2O2 is. Considering the larger Henry's law constant of H2O2 than that of PAA, the smaller RH sensitivity of the H2O2 uptake coefficient suggests that the enhanced uptake of peroxide compounds on PM2.5 under humid conditions is dominated by chemical processes rather than dissolution. Considering that mineral dust is one of the main components of PM2.5 in Beijing, we also determined the uptake coefficients of gaseous PAA and H2O2 on authentic Asian Dust storm (ADS) and Arizona Test Dust (ATD) particles. Compared to ambient PM2.5, ADS shows a similar γ value and RH dependence in its uptake coefficient for PAA and H2O2, while ATD gives a negative dependence on RH. The present study indicates that, in addition to the mineral dust in PM2.5, other components (e.g., soluble inorganic salts) are also important to the uptake of peroxide compounds. When the heterogeneous reaction of PAA on PM2.5 is considered, its atmospheric lifetime is estimated to be 3.0 h on haze days and 7.1 h on non-haze days, values that are in good agreement with the field observations.

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Short summary
The present study provides the first measurement for the uptake coefficient of gaseous peroxide compounds including peroxyacetic acid and hydrogen peroxide on the ambient particles (PM2.5 and Asian Storm Dust) over a wide range of relative humidity. The measured uptake coefficient values suggest that the heterogeneous reaction on the ambient particles plays an important role in the atmospheric budgets of peroxide compounds and potentially affects the components of aerosols in the atmosphere.
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