References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-7-17599-2007

Aqueous-phase ozonolysis of methacrolein and methyl vinyl ketone: a potentially important source of atmospheric aqueous oxidants

Chen

Z. M.

¹ Wang

H. L.

¹ Zhu

L. H.

¹ Wang

C. X.

¹ Jie

C. Y.

¹ Hua

State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China

05 12 2007

7 6 17599 17623

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Recent studies indicate that isoprene could contribute a considerable amount of aerosol through aqueous-phase acid-catalyzed oxidation with hydrogen peroxide (H2O2), although the source of H2O2 is unclear. The present study revealed a potentially important route to the formation of aqueous oxidants, including H2O2, from the aqueous-phase ozonolysis of methacrolein (MAC) and methyl vinyl ketone (MVK). Laboratory simulation was used to perform the atmospheric aqueous-phase ozonolysis at different pHs and temperatures. Unexpectedly high molar yields of the products, including hydroxylmethyl hydroperoxide (HMHP), formaldehyde (HCHO) and methylglyoxyl (MG), of both of these reaction systems have been seen. Moreover, these yields are almost independent of pH and temperature and are as follows: (i) for MAC–O3, 70.3±6.3% HMHP, 32.3±5.8% HCHO and 98.6±5.4% MG; and (ii) for MVK–O3, 68.9±9.7% HMHP, 13.3±5.8% HCHO and 75.4±7.9% MG. A yield of 24.2±3.6% pyruvic acid has been detected for MVK–O3. HMHP is unstable in the aqueous phase and can transform into H2O2 and HCHO with a yield of 100%. We suggest that the aqueous-phase ozonolysis of MAC and MVK can contribute a considerable amount of oxidants in a direct and indirect mode to the aqueous phase and that these compounds might be the main source of aqueous-phase oxidants. The formation of oxidants in the aqueous-phase ozonolysis of MAC and MVK effectively confirms the formation of aerosols from the aqueous-phase acid-catalyzed reaction of H2O2 with isoprene, even if there are no other sources of oxidants.

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