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Jaeglé et al. 2000
Jaeglé, L., Jacob, D.J., Brune, W.H., Faloona, I., Tan, D., Heikes, B.G., Kondo, Y., Sachse, G.W., Anderson, B., Gregory, G.L., Singh, H.B., Pueschel, R., Ferry, G., Blake, D.R. and Shetter, R.E. (2000). Photochemistry of HOx in the upper troposphere at northern midlatitudes. Journal of Geophysical Research 105: doi: 10.1029/1999JD901016. issn: 0148-0227.

The factors controlling the concentrations of HOx radicals (=OH+peroxy) in the upper troposphere (8--12 km) are examined using concurrent aircraft observations of OH, HO2, H2O2, CH3OOH, and CH2O made during the Subsonic Assessment Ozone and Nitrogen Oxide Experiment (SONEX) at northern midlatitudes in the fall. These observations, complemented by concurrent measurements of O3, H2O, NO, peroxyacetyl nitrate (PAN), HNO3, CH4, CO, acetone, hydrocarbons, actinic fluxes, and aerosols, allow a highly constrained mass balance analysis of HOx and of the larger chemical family HOy(=HOx+2H2O2+2CH3OOH+HNO2+HNO4). Observations of OH and HO2 are successfully simulated to within 40% by a diel steady state model constrained with observed H2O2 and CH3OOH. The model captures 85% of the observed HOx variance, which is driven mainly by the concentrations of NOx(=NO+NO2) and by the strength of the HOx primary sources. Exceptions to the good agreement between modeled and observed HOx are at sunrise and sunset, where the model is too low by factors of 2--5, and inside cirrus clouds, where the model is too high by factors of 1.2--2. Heterogeneous conversion of NO2 to HONO on aerosols (&ggr;NO2=10-3) during the night followed by photolysis of HONO could explain part of the discrepancy at sunrise. Heterogeneous loss of HO2 on ice crystals (&ggr;ice_HO2=0.025) could explain the discrepancy in cirrus. Primary sources of HOx from O(1D)+H2O and acetone photolysis were of comparable magnitude during SONEX. The dominant sinks of HOy were OH+HO2 (NOx50 pptv). Observed H2O2 concentrations are reproduced by model calculations to within 50% if one allows in the model for heterogeneous conversion of HO2 to H2O2 on aerosols (&ggr;HO2=0.2). Observed CH3OOH concentrations are underestimated by a factor of 2 on average. Observed CH2O concentrations were usually below the 50 pptv detection limit, consistent with model results; however, frequent occurrences of high values in the observations (up to 350 pptv) are not captured by the model. These high values are correlated with high CH3OH a

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Abstract

Keywords
Atmospheric Composition and Structure, Constituent sources and sinks, Atmospheric Composition and Structure, Troposphere—composition and chemistry, Atmospheric Composition and Structure, Troposphere—constituent transport and chemistry, Mathematical Geophysics, Modeling, Atmospheric Composition and Structure, Cloud physics and chemistry
Journal
Journal of Geophysical Research
http://www.agu.org/journals/jb/
Publisher
American Geophysical Union
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