Atmospheric Chemistry and Physics
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10.5194/acp-7-1347-2007
http://www.atmos-chem-phys.net/7/1347/2007/
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http://www.atmos-chem-phys.net/7/1347/2007/acp-7-1347-2007.pdf
1347
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2007-02-27
Characterizing ozone production in the Mexico City Metropolitan Area: a case study using a chemical transport model
W. Lei
wflei@mit.edu
B. de Foy
M. Zavala
R. Volkamer
L. T. Molina
Department of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, MA, USA
Molina Center for Energy and the Environment, CA, USA
Saint Louis University, MO, USA
Department of Chemistry and Biochemistry, University of California, San Diego, CA, USA
An episodic simulation is conducted to characterize midday (12:00–17:00 CDT) ozone
(O<sub>3</sub>) photochemical production and to investigate its sensitivity to
emission changes of ozone precursors in the Mexico City Metropolitan Area
(MCMA) during an "O<sub>3</sub>-South" meteorological episode using the
Comprehensive Air Quality Model with extensions (CAMx). High O<sub>x</sub>
(O<sub>3</sub>+NO<sub>2</sub>) photochemical production rates of 10–80 ppb/h are
predicted due to the high reactivity of volatile organic compounds (VOCs) in
which alkanes, alkenes, and aromatics exert comparable contributions. The
predicted ozone production efficiency is between 4–10 O<sub>3</sub> molecules per
NO<sub>x</sub> molecule oxidized, and increases with VOC-to-NO<sub>2</sub> reactivity
ratio. Process apportionment analyses indicate significant outflow of
pollutants such as O<sub>3</sub> and peroxyacetyl nitrate (PAN) from the urban
area to the surrounding regional environment. PAN is not in chemical-thermal
equilibrium during the photochemically active periods. Sensitivity studies
of O<sub>3</sub> production suggest that O<sub>3</sub> formation in the MCMA urban
region with less chemical aging (NO<sub>z</sub>/NO<sub>y</sub><0.3) is VOC-limited.
Both the simulated behavior of O<sub>3</sub> production and its sensitivities to
precursors suggest that midday O<sub>3</sub> formation during this episode is
VOC-sensitive in the urban region on the basis of the current emissions
inventory estimates, and current NO<sub>x</sub> levels depress the O<sub>3</sub>
production.
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