Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications
Hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) 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, CH<sub>3<...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2015-06-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | http://www.atmos-chem-phys.net/15/6851/2015/acp-15-6851-2015.pdf |
| _version_ | 1811339228233072640 |
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| author | Q. Q. Wu L. B. Huang H. Liang Y. Zhao D. Huang Z. M. Chen |
| author_facet | Q. Q. Wu L. B. Huang H. Liang Y. Zhao D. Huang Z. M. Chen |
| author_sort | Q. Q. Wu |
| collection | DOAJ |
| description | Hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) 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, CH<sub>3</sub>C(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 H<sub>2</sub>O<sub>2</sub> onto ambient fine particulate matter
(PM<sub>2.5</sub>) as a function of relative humidity (RH) at 298 K. The results
show that the PM<sub>2.5</sub>, which was collected in an urban area, can take up
PAA and H<sub>2</sub>O<sub>2</sub> at the uptake coefficient (γ) of 10<sup>−4</sup>,
and both γ<sub>PAA</sub> and γ<sub>H<sub>2</sub>O<sub>2</sub></sub> increase
with increasing RH. The value of γ<sub>PAA</sub> at 90 % RH is
5.4 ± 1.9 times that at 3 % RH, whereas
γ<sub>H<sub>2</sub>O<sub>2</sub></sub> 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 H<sub>2</sub>O<sub>2</sub> is. Considering the larger Henry's law constant of
H<sub>2</sub>O<sub>2</sub> than that of PAA, the smaller RH sensitivity of the
H<sub>2</sub>O<sub>2</sub> uptake coefficient suggests that the enhanced uptake of
peroxide compounds on PM<sub>2.5</sub> under humid conditions is dominated by
chemical processes rather than dissolution. Considering that mineral dust is
one of the main components of PM<sub>2.5</sub> in Beijing, we also determined the
uptake coefficients of gaseous PAA and H<sub>2</sub>O<sub>2</sub> on authentic Asian Dust
storm (ADS) and Arizona Test Dust (ATD) particles. Compared to ambient
PM<sub>2.5</sub>, ADS shows a similar γ value and RH dependence in its
uptake coefficient for PAA and H<sub>2</sub>O<sub>2</sub>, while ATD gives a negative
dependence on RH. The present study indicates that, in addition to the
mineral dust in PM<sub>2.5</sub>, other components (e.g., soluble inorganic salts)
are also important to the uptake of peroxide compounds. When the
heterogeneous reaction of PAA on PM<sub>2.5</sub> 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. |
| first_indexed | 2024-04-13T18:23:10Z |
| format | Article |
| id | doaj.art-0f3f9cf62e634afeaada893362587adb |
| institution | Directory Open Access Journal |
| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-04-13T18:23:10Z |
| publishDate | 2015-06-01 |
| publisher | Copernicus Publications |
| record_format | Article |
| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-0f3f9cf62e634afeaada893362587adb2022-12-22T02:35:21ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242015-06-0115126851686610.5194/acp-15-6851-2015Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implicationsQ. Q. Wu0L. B. Huang1H. Liang2Y. Zhao3D. Huang4Z. M. Chen5State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, ChinaState Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, ChinaState Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, ChinaState Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, ChinaState Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, ChinaState Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, ChinaHydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) 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, CH<sub>3</sub>C(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 H<sub>2</sub>O<sub>2</sub> onto ambient fine particulate matter (PM<sub>2.5</sub>) as a function of relative humidity (RH) at 298 K. The results show that the PM<sub>2.5</sub>, which was collected in an urban area, can take up PAA and H<sub>2</sub>O<sub>2</sub> at the uptake coefficient (γ) of 10<sup>−4</sup>, and both γ<sub>PAA</sub> and γ<sub>H<sub>2</sub>O<sub>2</sub></sub> increase with increasing RH. The value of γ<sub>PAA</sub> at 90 % RH is 5.4 ± 1.9 times that at 3 % RH, whereas γ<sub>H<sub>2</sub>O<sub>2</sub></sub> 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 H<sub>2</sub>O<sub>2</sub> is. Considering the larger Henry's law constant of H<sub>2</sub>O<sub>2</sub> than that of PAA, the smaller RH sensitivity of the H<sub>2</sub>O<sub>2</sub> uptake coefficient suggests that the enhanced uptake of peroxide compounds on PM<sub>2.5</sub> under humid conditions is dominated by chemical processes rather than dissolution. Considering that mineral dust is one of the main components of PM<sub>2.5</sub> in Beijing, we also determined the uptake coefficients of gaseous PAA and H<sub>2</sub>O<sub>2</sub> on authentic Asian Dust storm (ADS) and Arizona Test Dust (ATD) particles. Compared to ambient PM<sub>2.5</sub>, ADS shows a similar γ value and RH dependence in its uptake coefficient for PAA and H<sub>2</sub>O<sub>2</sub>, while ATD gives a negative dependence on RH. The present study indicates that, in addition to the mineral dust in PM<sub>2.5</sub>, other components (e.g., soluble inorganic salts) are also important to the uptake of peroxide compounds. When the heterogeneous reaction of PAA on PM<sub>2.5</sub> 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.http://www.atmos-chem-phys.net/15/6851/2015/acp-15-6851-2015.pdf |
| spellingShingle | Q. Q. Wu L. B. Huang H. Liang Y. Zhao D. Huang Z. M. Chen Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications Atmospheric Chemistry and Physics |
| title | Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications |
| title_full | Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications |
| title_fullStr | Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications |
| title_full_unstemmed | Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications |
| title_short | Heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions: kinetics, mechanism and implications |
| title_sort | heterogeneous reaction of peroxyacetic acid and hydrogen peroxide on ambient aerosol particles under dry and humid conditions kinetics mechanism and implications |
| url | http://www.atmos-chem-phys.net/15/6851/2015/acp-15-6851-2015.pdf |
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