Location of Repository

Coupling of HOx, NOx and halogen chemistry in the Antarctic boundary layer

By W.J. Bloss, M. Camredon, J.D. Lee, D.E. Heard, J.M.C. Plane, A. Saiz-Lopez, Stephane J.-B Bauguitte, Rhian Anya Salmon and Anna E. Jones


A modelling study of radical chemistry in the coastal Antarctic boundary layer, based upon observations performed in the course of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) campaign at Halley Research Station in coastal Antarctica during the austral summer 2004/2005, is described: a detailed zero-dimensional photochemical box model was used, employing inorganic and organic reaction schemes drawn from the Master Chemical Mechanism, with additional halogen (iodine and bromine) reactions added. The model was constrained to observations of long-lived chemical species, measured photolysis frequencies and meteorological parameters, and the simulated levels of HOx, NOx and XO compared with those observed. The model was able to replicate the mean levels and diurnal variation in the halogen oxides IO and BrO, and to reproduce NOx levels and speciation very well. The NOx source term implemented compared well with that directly measured in the course of the CHABLIS experiments. The model systematically overestimated OH and HO2 levels, likely a consequence of the combined effects of (a) estimated physical parameters and (b) uncertainties within the halogen, particularly iodine, chemical scheme. The principal sources of HOx radicals were the photolysis and bromine-initiated oxidation of HCHO, together with O(1D) + H2O. The main sinks for HOx were peroxy radical self- and cross-reactions, with the sum of all halogen-mediated HOx loss processes accounting for 40% of the total sink. Reactions with the halogen monoxides dominated CH3O2-HO2-OH interconversion, with associated local chemical ozone destruction in place of the ozone production which is associated with radical cycling driven by the analogous NO reactions. The analysis highlights the need for observations of physical parameters such as aerosol surface area and boundary layer structure to constrain such calculations, and the dependence of simulated radical levels and ozone loss rates upon a number of uncertain kinetic and photochemical parameters for iodine species.\u

Topics: Glaciology, Chemistry, Atmospheric Sciences
Publisher: Copernicus Publications
Year: 2010
DOI identifier: 10.5194/acp-10-10187-2010
OAI identifier: oai:nora.nerc.ac.uk:12755

Suggested articles



  1. (2005). A discharge-flow study of the kinetics of the reactions of IO with CH3O2 and CF3O2,
  2. (2000). A larger pool of ozone-forming carbon compounds in urban atmospheres,
  3. (2008). A mechanism for biologicallyinduced iodine emissions from sea-ice, doi
  4. (2000). A modelling study of iodine chemistry in the marine boundary layer,
  5. (2000). A reassessment of HOx South Pole chemistry based on observations recorded during ISCAT
  6. (2002). A study of photochemical and physical processes affecting carbonyl compounds in the Arctic atmospheric boundary layer, doi
  7. (2010). Acetaldehyde in the Alaskan subarctic snowpack,
  8. (2002). Acetaldeyhde and acetone in the Arctic snowpack during the ALERT2000 cmapgin. Snowpack composition, incorporation processes and atmospheric impact.
  9. (2007). An assessment of the polar HOx photochemical budget based on 2003 Summit Greenland field observations,
  10. (2006). An Experimental and
  11. (2001). An Investigation of South Pole HOx Chemistry:
  12. (2007). An overview of snow photochemistry: evidence, mechanisms and impacts,
  13. (1999). Atmosphereto-snow-to-firn transfer studies of HCHO at Summit,
  14. (2001). Behavior of OH and HO2 radicals during the Observations at a Remote Island of Okinawa (ORION99) field campaign: 1. Observation using a laser-induced fluorescence instrument,
  15. (2010). Bloss et al.: Coupling of HOx, NOx and halogen chemistry 10207 Antarctic Tropospheric Chemistry Investigation (ANTCI)
  16. (2010). Bloss et al.: Coupling of HOx, NOx and halogen chemistry 10209
  17. (2007). Boundary layer halogens in coastal Antarctica, doi
  18. (2002). C.: A Study of the Recombination of IO with NO2 and the Stability of INO3: Implications for the Atmospheric Chemistry of Iodine,
  19. (2008). Chemistry of the antarctic boundary layer and the interface with snow: an overview of the CHABLIS campaign,
  20. (1998). Climatology of the three coastal Antarctic stations Dumont d’Urville,
  21. (2003). Coupled evolution of BrOx -ClOx -HOx-NOx chemistry during bromine catalyzed ozone depletion events in the arctic boundary layer,
  22. (2006). Coupling between the Tropospheric Photochemistry of Nitrous Acid (HONO) and Nitric Acid (HNO3),
  23. (1996). Dimethyl sulphide, methane sulphonic acid and the physiochemical aerosol properties in Atlantic air from the United Kingdom to Halley Bay,
  24. (2008). DMS and MSA measurements in the Antarctic Boundary Layer: impact of
  25. (2007). Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III gas phase reactions of inorganic halogens,
  26. (1999). Evidence of NOx production within or upon ice particles in the Greenland snowpack, doi
  27. (2005). Formation Pathways and Composition of Iodine Oxide Ultra-Fine Particles, doi
  28. (2010). Glaciochemistry of Polar Ice www.atmos-chem-phys.net/10/10187/2010/ Atmos.
  29. (2000). Heterogeneous chemistry and tropsopheric ozone,
  30. (2001). Heterogeneous reaction of HOI with sodium halide salts,
  31. (2007). Heterogeneous reactions of HOI, ICl and IBr on sea salt and sea salt proxies,
  32. (2005). Impact of Halogen Monoxide Chemistry upon Boundary Layer OH and HO2 concentrations at a Coastal Site,
  33. (2010). In situ measurements of bromine oxide at two www.atmos-chem-phys.net/10/10187/2010/ Atmos.
  34. (2007). Kinetic and Mechanistic
  35. (2006). Kinetic Study of IO Radical with RO2 (R = CH3, C2H5, and CF3) Using Cavity Rind-Down Spectroscopy, doi
  36. (2001). Kinetics and
  37. Laboratory studies of the homogeneous nucleation of iodine oxides,
  38. (2006). Laser induced fluorescence studies of iodine oxide chemistry,
  39. (2008). LIF Studies of Iodine Oxide Chemistry Part 3.
  40. (2008). Measurement and interpretation of gas phase formaldehyde concentrations obtained during the CHABLIS campaign in coastal Antarctica, doi
  41. (2004). Missing OH Reactivity in a Forest: Evidence for Unknown Reactive Biogenic VOCs,
  42. (1999). Modeling OH, HO2 and RO2 radicals in the marine boundary layer 1. Model construction and comparison with field measurements,
  43. (2008). Multiphase modeling of nitrate photochemistry in the quasi-liquid layer (QLL): implications for NOx release from the Arctic and coastal Antarctic snowpack,
  44. (2003). Observations of HONO by laser-induced fluorescence at the South Pole during ANTCI
  45. (2000). Observations of summertime NO fluxes and boundarylayer height at the South Pole during ISCAT
  46. (2007). OH and halogen atom influence on the variability of nonmethane hydrocarbons in the Antarctic Boundary Layer,
  47. (1998). OH Photochemistry and methane sulphonic acid formation in the coastal Antarctic boundary layer,
  48. (1999). OIO and the Atmospheric Cycle of Iodine,
  49. (2007). On the photochemistry of IONO2: absorption cross section (240–370 nm) and photolysis product yields at 248 nm,
  50. (2007). On the vertical distribution of boundary layer halogens over coastal Antarctica: implications for O3, HOx, NOx and the Hg lifetime,
  51. (2009). Photochemistry of OIO: Laboratory study and atmospheric implications,
  52. (2008). Quantum chemical calculations on a selection of iodine containing species (IO,
  53. (1996). Rate Coefficients for the Thermal Decomposition of BrONO2 and the Heat of Formation of
  54. (1994). Reaction of Chlorine Atoms with Methyl and Ethylperoxy Radicals,
  55. (2005). Sources and sinks of acetone, methanol, and acetaldehyde in North Atlantic marine air,
  56. (2010). South Pole Antarctica observations and modeling results: New insights on HOx radical and sulfur chemistry,
  57. (2009). Summertime NOx measurements during the CHABLIS campaign: can source and sink estimates unravel observed diurnal cycles?,
  58. (2010). Technical Note: Formal blind intercomparison of HO2 measurements in the atmosphere simulation chamber SAPHIR during the HOxComp campaign,
  59. (2005). The absorption cross-section and photochemistry of OIO,
  60. (1997). The BrO + CH3O2 reaction: Kinetics and role in the atmospheric ozone budget,
  61. (1988). The calculation of photolysis rates for use in global tropospheric modelling studies,
  62. (2007). The multi-seasonal NOy budget in coastal Antarctica and its link with surface snow and ice core nitrate: results from the CHABLIS campaign,
  63. (1998). The role of solar radiation in atmospheric chemistry,
  64. (2002). The UV-visible absorption cross-sections of IONO2,
  65. (2004). Validation of the calibration of a laser-induced fluorescence instrument for the measurement of OH radicals in the atmosphere,
  66. (1999). Variability of formaldehyde in the Antarctic troposphere,
  67. (2002). Vertical fluxes of NOx, HONO, and HNO3 above the snowpack at Summit, doi
  68. (2003). What controls photochemical NO and NO2 production from Antarctic snow ? Laboratory investigation assessing the wavelength and temperature dependence.

To submit an update or takedown request for this paper, please submit an Update/Correction/Removal Request.