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European Geosciences Union, Atmospheric Chemistry and Physics, 14(10), p. 6551-6567, 2010

DOI: 10.5194/acp-10-6551-2010

European Geosciences Union, Atmospheric Chemistry and Physics Discussions, 2(10), p. 4143-4188

DOI: 10.5194/acpd-10-4143-2010

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Impacts of HONO sources on the photochemistry in Mexico City during the MCMA-2006/MILAGO Campaign

This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

The contribution of HONO sources to the photochemistry in Mexico City is investigated during the MCMA-2006/MILAGO Campaign using the WRF-CHEM model. Besides the homogeneous reaction of NO with OH, four additional HONO sources are considered in the WRF-CHEM model: secondary HONO formation from NO 2 heterogeneous reaction with semivolatile organics, NO 2 reaction with freshly emitted soot, NO 2 heterogeneous reaction on aerosol and ground surfaces. The WRF-CHEM model with the five HONO sources performs reasonably well in tracking the observed diurnal variation of HONO concentrations. The HONO sources included are found to significantly improve the HO x (OH+HO 2 ) simulations during daytime and the partition of NO/NO 2 in the morning. The HONO sources also accelerate the accumulation of O 3 concentrations in the morning by about 2 h and subsequently result in a noticeable enhancement of O 3 concentrations over the course of the day with a midday average of about 6 ppb. Furthermore, these HONO sources play a very important role in the formation of secondary aerosols in the morning. They substantially enhance the secondary organic aerosol concentrations by a factor of 2 on average in the morning, although they contribute less during the rest of the day. The simulated particle-phase nitrate and ammonium are also substantially enhanced in the morning when the four HONO sources are included, in good agreement with the measurements. The impact of the HONO sources on the sulfate aerosols is negligible because of the inefficient conversion of H 2 SO 4 from SO 2 reacting with OH.