Atmos. Chem. Phys. Discuss., 8, 4877-4909, 2008
© Author(s) 2008. This work is distributed
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Measurements of HNO3 and N2O5 using Ion drift – Chemical Ionization Mass Spectrometry during the MCMA – 2006 Campaign
J. Zheng1, R. Zhang1, E. C. Fortner1,*, L. Molina2, A. C. Aiken3, J. L. Jimenez3, K. Gäggeler4, J. Dommen4, S. Dusanter5, P. S . Stevens5, and X. Tie6
1Dept. Atmospheric Sciences, Texas A & M University, College Station, Texas 77843, TX, USA
2Molina Center for Energy and the Environment, La Jolla, CA, USA
3Dept. Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
4Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, 5232 Villigen, Switzerland
5Dept. Chemistry, Indiana University, Bloomington, IN, USA
6Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, CO, USA
*now at: Dept. Chemistry and Biochemistry, Montana State University, Bozeman, MT, USA

Abstract. An ion drift – chemical ionization mass spectrometry (ID-CIMS) was deployed in Mexico City between 5 and 31 March to measure HNO3 and N2O5 during the 2006 Mexico City Metropolitan Area (MCMA) field campaign. The observation site, T0, was located at the Instituto Mexicano del Petróleo at the center of the Mexico City Basin with major emissions of pollutants from both domestic and industrial sources. Diurnally, HNO3 was less than 200 parts per trillion (ppt) during the night and in the early morning, increased steadily from around 09:00 a.m. central standard time (CST), reached a peak value of 0.5 to 3 parts per billion (ppb) in the early afternoon, and declined sharply to less than half of the peak value near 05:00 p.m. CST. An inter-comparison between the ID-CIMS and an ion chromatograph/mass spectrometer (ICMS) showed a good correlation in the HNO3 measurements (R2=0.75). The HNO3 mixing ratio was found to anti-correlate with aerosol nitrate, suggesting that the gaseous HNO3 concentration was controlled by the gas-particle partitioning process. During most times of the MCMA 2006 field campaign, N2O5 was found to be under the detection limit (about 20 ppt for a 10 s integration time) of the ID-CIMS, because of high NO mixing ratio (>100 ppb) during the night. With one exception on 26 March 2006, about 40 ppt N2O5 was observed during the late afternoon and early evening hours under a cloudy condition, before NO built up at the surface site. The results revealed that during the 2006 MCMA field campaign HNO3 was primarily produced by the reaction of OH with NO2 and regulated by gas/particle partitioning, and HNO3 production from N2O5 hydrolysis during the nighttime was small because of high NO and low O3 concentrations near the surface.

Citation: Zheng, J., Zhang, R., Fortner, E. C., Molina, L., Aiken, A. C., Jimenez, J. L., Gäggeler, K., Dommen, J., Dusanter, S., Stevens, P. S ., and Tie, X.: Measurements of HNO3 and N2O5 using Ion drift – Chemical Ionization Mass Spectrometry during the MCMA – 2006 Campaign, Atmos. Chem. Phys. Discuss., 8, 4877-4909, doi:10.5194/acpd-8-4877-2008, 2008.
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