Hostname: page-component-78c5997874-94fs2 Total loading time: 0 Render date: 2024-11-10T19:47:03.856Z Has data issue: false hasContentIssue false
  • English
  • Français

The effect of the novel HO2 + NO → HNO3 reaction channel at South Pole, Antarctica

Published online by Cambridge University Press:  06 March 2012

C.S. Boxe ,
P.D. Hamer ,
W. Ford ,
M. Hoffmann  and
D.E. Shallcross
C.S. Boxe*
Affiliation:
Earth and Space Science Division, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109, USA
P.D. Hamer
Affiliation:
Earth and Space Science Division, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109, USA
W. Ford
Affiliation:
Computation and Neural Systems, California Institute of Technology, 1200 East California Boulevard, Pasadena, CA 91125, USA
M. Hoffmann
Affiliation:
Environmental Science and Engineering, California Institute of Technology, 1200 East California Boulevard, Pasadena, CA 91125, USA
D.E. Shallcross
Affiliation:
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 ITS, UK
*
boxeman3@gmail.com
Get access Rights & Permissions [Opens in a new window]

Abstract

It is well established that the reaction of HO2 with NO plays a central role in atmospheric chemistry, by way of OH/HO2 recycling and reduction of ozone depletion by HOx cycles in the stratosphere and through ozone production in the troposphere. Utilizing a photochemical box model, we investigate the impact of the recently observed HNO3 production channel (HO2+NO → HNO3) on NOx (NO + NO2), HOx (OH + HO2), HNO3, and O3 concentrations in the boundary layer at the South Pole, Antarctica. Our simulations exemplify decreases in peak O3, NO, NO2, and OH and an increase in HNO3. Also, mean OH is in better agreement with observations, while worsening the agreement with O3, HO2, and HNO3 concentrations observed at the South Pole. The reduced concentrations of NOx are consistent with expected decreases in atmospheric NOx lifetime as a result of increased sequestration of NOx into HNO3. Although we show that the inclusion of the novel HNO3 production channel brings better agreement of OH with field measurements, the modelled ozone and HNO3 are worsened, and the changes in NOx lifetime imply that snowpack NOx emissions and snowpack nitrate recycling must be re-evaluated.

Keywords

boundary layerice photochemistrynitric acidNOxozonepolar chemistry
Type
Physical Science
Information
Antarctic Science , Volume 24 , Issue 4 , 17 July 2012 , pp. 417 - 425
Copyright
Copyright © Antarctic Science Ltd 2012

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Atkinson, R., Baulch, D.L., Cox, R.A., Crowley, J.N., Hampson, R.F., Hynes, R.G., Jenkin, M.E., Rossi, M.J.Troe, J. 2004. Evaluated kinetic and photochemical data for atmospheric chemistry: volume I - gas phase reactions of Ox, HOx, NOx and SOx species. Atmospheric Chemistry and Physics, 4, 1461–1738.CrossRefGoogle Scholar
Bock, J.Jacobi, H.W. 2010. Development of a mechanism for nitrate photochemistry in snow. Journal of Physical Chemistry A, 114, 1790–1796.CrossRefGoogle ScholarPubMed
Boxe, C.S. 2005. Nitrate photochemistry and interrelated chemical phenomena in ice: influence of the quasi-liquid layer (QLL). PhD thesis, California Institute of Technology, 225 pp. [Unpublished.]Google Scholar
Boxe, C.S.Saiz-Lopez, A. 2008. Multiphase modeling of nitrate photochemistry in the quasi-liquid layer (QLL): implications for NOx release from the Arctic and coastal Antarctic snowpack. Atmospheric Chemistry and Physics, 8, 4855–4864.CrossRefGoogle Scholar
Boxe, C.S.Saiz-Lopez, A. 2009. Influence of thin liquid films on polar chemistry: implications for Earth and planetary science. Polar Science, 3, 73–81.CrossRefGoogle Scholar
Boxe, C.S., Colussi, A.J., Hoffmann, M.R., Tan, D., Mastromarino, J., Case, A.T., Sandholm, S.T.Davis, D.D. 2003. Multiscale ice fluidity in NOx photodesorption from frozen nitrate solutions. Journal of Physical Chemistry A, 107, 11 409–11 413.CrossRefGoogle Scholar
Butkovskaya, N.I., Kukui, A.Le Bras, G. 2007. HNO3 Forming channel of the HO2 + NO reaction as a function of pressure and temperature in the ranges of 72–600 torr and 223–323 K. Journal of Physical Chemistry A, 111, 9047–9053.CrossRefGoogle ScholarPubMed
Butkovskaya, N.I., Kukui, A., Pouvelse, N.Le Bras, G. 2005. Formation of nitric acid in the gas-phase HO2 + NO reaction: effects of temperature and water vapor. Journal of Physical Chemistry A, 109, 6509–6520.CrossRefGoogle ScholarPubMed
Cariolle, D., Evans, M.J., Chipperfield, M.P., Butkovskaya, N., Kukui, A.Le Bras, G. 2008. Impact of the new HNO3-forming channel of the HO2 + NO reaction on tropospheric HNO3, NOx, HOx and ozone. Atmospheric Chemistry and Physics, 8, 1–8.Google Scholar
Carver, G.D., Brown, P.D.Wild, O. 1997. The ASAD atmospheric chemistry integration package and chemical reaction database. Computer Physics Communications, 105, 197–215.CrossRefGoogle Scholar
Chen, G. et al. . 2001. An investigation of South Pole HOx chemistry: comparison of model results with ISCAT observations. Geophysical Research Letters, 28, 3633–3636.CrossRefGoogle Scholar
Chen, G. et al. . 2004. A reassessment of HOx South Pole chemistry based on observations recording during ISCAT 2000. Atmospheric Environment, 38, 5451–5461.CrossRefGoogle Scholar
Cotter, E.S.N., Jones, A.E., Wolff, E.W.Bauguitte, S.J.-B. 2003. What controls photochemical NO and NO2 production from Antarctic snow? Laboratory investigation assessing the wavelength and temperature dependence. Journal of Geophysical Research, 10.1029/2002JD002602.CrossRefGoogle Scholar
Crawford, J.H. et al. . 2001. Evidence for the photochemical production of ozone at the South Pole surface. Geophysical Research Letters, 28, 3641–3644.CrossRefGoogle Scholar
Davis, D., Chen, G., Buhr, M., Crawford, J., Lenschow, D., Lefer, B., Shetter, R., Eisele, F., Mauldin, L.Hogan, A. 2004. South Pole NOx chemistry: an assessment of factors controlling variability and absolute levels. Atmospheric Environment, 38, 5375–5388.CrossRefGoogle Scholar
Davis, D. et al. . 2001. Unexpected high levels of NO observed at South Pole. Geophysical Research Letters, 28, 3625–3628.CrossRefGoogle Scholar
Davis, D. et al. . 2008. A reassessment of Antarctic plateau reactive nitrogen based on ANTCI 2003 airborne and ground based measurements. Atmospheric Environment, 42, 2831–2848.CrossRefGoogle Scholar
Dibb, J.E., Huey, L.G., Slusher, D.L.Tanner, D.J. 2004. Soluble reactive nitrogen oxides at South Pole during ISCAT 2000. Atmospheric Environment, 38, 5399–5409.CrossRefGoogle Scholar
Frey, M.M., Stewart, R.W., McConnell, J.R.Bales, R.C. 2005. Atmospheric hydroperoxides in West Antarctica: links to stratospheric ozone and atmospheric oxidation capacity. Journal of Geophysical Research, 10.1029/2005JD006110.CrossRefGoogle Scholar
Grannas, A. et al. . 2007. An overview of snow photochemistry: evidence, mechanisms, and impacts. Atmospheric Chemistry and Physics, 7, 4329–4373.CrossRefGoogle Scholar
Hamer, P.D., Shallcross, D.E.Frey, M.M. 2007. Modelling the impact of oxygenated VOC and meteorology upon the boundary layer photochemistry at the South Pole. Atmospheric Science Letters, 8, 14–20.CrossRefGoogle Scholar
Hamer, P.D., Shallcross, D.E., Yabushita, A.Kawasaki, M. 2008. Modelling the impact of possible snowpack emissions of O(3P) and NO2 on photochemistry in the South Pole boundary layer. Environmental Chemistry, 5, 268–273.CrossRefGoogle Scholar
Huey, L.G. et al. . 2004. CIMS measurements of HNO3 and SO2 at the South Pole during ISCAT 2000. Atmospheric Environment, 38, 5411–5421.CrossRefGoogle Scholar
Hutterli, M.A., McConnell, J.R., Chen, G., Bales, R.C., Davis, D.D.Lenschow, D.H. 2004. Formaldehyde and hydrogen peroxide in air, snow and interstitial air at South Pole. Atmospheric Environment, 38, 5439–5450.CrossRefGoogle Scholar
Jacobi, H.-W.Hilker, B. 2007. A mechanism for the photochemical transformation of nitrate in snow. Journal of Photochemistry and Photobiology A Chemistry, 185, 371–382.CrossRefGoogle Scholar
Jenkin, M.E., Saunders, S.M.Philling, M.J. 1997. The tropospheric degradation of volatile organic compounds: a protocol for mechanism development. Atmospheric Environment, 31, 81–104.CrossRefGoogle Scholar
Jones, A.E.Wolff, E.W. 2003. An analysis of the oxidation potential of the South Pole boundary layer and the influence of stratospheric ozone depletion. Journal of Geophysical Research, 10.1029/2003JD003379.CrossRefGoogle Scholar
Jones, A.E., Weller, R., Wolff, E.W.Jacobi, H.W. 2000. Speciation and rate of photochemical NO and NO2 production in Antarctic snow. Geophysical Research Letters, 27, 345–348.CrossRefGoogle Scholar
Jones, A.E. et al. . 2001. Measurements of NOx emissions from the Antarctic snowpack. Geophysical Research Letters, 28, 1499–1502.CrossRefGoogle Scholar
Lefer, B.L., Hall, S.R., Cinquini, L.Shetter, R.E. 2001. Photolysis frequency measurements at the South Pole during ISCAT-98. Geophysical Research Letters, 28, 3637–3640.CrossRefGoogle Scholar
Martin, R.V., Sauvage, B., Folkins, I., Sioris, C.E., Boone, C., Bernath, P.Ziemke, J. 2007. Spaced-based constraints on the production of nitric oxide by lightning. Journal of Geophysical Research, 10.1029/2006JD007831.CrossRefGoogle Scholar
Matsuki, H., Yoshikawa, K.J., Yanagisawa, Y.Kasuga, H. 2002. Measurement of atmospheric NO2 concentrations in Antarctica with NO2 filter badge and tube. Tokai Journal of Experimental and Clinical Medicine, 27, 35–42.Google ScholarPubMed
Mauldin, L., Kosciuch, E., Henry, B., Eisele, F., Shetter, R., Lefer, B., Chen, G., Davis, D., Huey, G.Tanner, D. 2004. Measurements of OH, HO2 + RO2, H2SO4, and MSA at the South Pole during ISCAT 2000. Atmospheric Environment, 38, 5423–5437.CrossRefGoogle Scholar
Oncley, S.P., Buhr, M., Lenschow, D.H., Davis, D.Semmer, S.R. 2004. Observations of summertime NO fluxes and boundary-layer height at the South Pole during ISCAT 2000 using scalar similarity. Atmospheric Environment, 38, 5389–5398.CrossRefGoogle Scholar
Sander, S.P.et al. 2006. Chemical kinetics and photochemical data for use in atmospheric studies. Evaluation no. 15. JPL Publication 06-02. Pasadena, CA: NASA. http://jpldataeval.jpl.nasa.gov/pdf/JPL_15_AllInOne.pdf.Google Scholar
Wang, Y.H., Choi, Y., Zeng, T., Davis, D., Buhr, M., Huey, L.G.Neff, W. 2008. Assessing the photochemical impact of snow NOx emissions over Antarctica during ANTCI 2003. Atmospheric Environment, 42, 2849–2863.CrossRefGoogle Scholar
Wayne, R.P. 2000. Chemistry of atmospheres. Oxford: Oxford University Press, 806 pp.Google Scholar
Wolff, E.W., Jones, A.E., Martin, T.J.Grenfell, T.C. 2002. Modelling photochemical NOx production and nitrate loss in the upper snowpack of Antarctica. Geophysical Research Letters, 10.1029/2002GL015823.CrossRefGoogle Scholar
Yabushita, A., Kawanaka, N., Kawasaki, M., Hamer, P.D.Shallcross, D.E. 2007. Release of oxygen atoms and nitric oxide molecules from the ultraviolet photodissociation of nitrate adsorbed on water ice films at 100 K. Journal of Physical Chemistry A, 111, 8629–8634.CrossRefGoogle Scholar