References

ACP

Atmospheric Chemistry and Physics

ACP

Atmos. Chem. Phys.

1680-7324

Copernicus Publications

Göttingen, Germany

10.5194/acp-7-4171-2007

Observations of OH and HO2 radicals in coastal Antarctica

Bloss

W. J.

¹ ³ Lee

J. D.

¹ ⁴ Heard

D. E.

¹ Salmon

R. A.

² Bauguitte

S. J.-B.

² Roscoe

H. K.

² Jones

A. E.

School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK

British Antarctic Survey, Madingley Road, Cambridge, CB3 0ET, UK

now at: School of Geography, Earth & Environmental Sciences, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK

now at: Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK

16 08 2007

7 16 4171 4185

2007

This work is licensed under the Creative Commons Attribution-NonCommercial-ShareAlike 2.5 Generic License. To view a copy of this licence, visit https://creativecommons.org/licenses/by-nc-sa/2.5/

This article is available from https://acp.copernicus.org/articles/7/4171/2007/acp-7-4171-2007.html

The full text article is available as a PDF file from https://acp.copernicus.org/articles/7/4171/2007/acp-7-4171-2007.pdf

OH and HO2 radical concentrations have been measured in the boundary layer of coastal Antarctica for a six-week period during the austral summer of 2005. The measurements were performed at the British Antarctic Survey's Halley Research Station (75° 35' S, 26° 19' W), using the technique of on-resonance laser-induced fluorescence to detect OH, with HO2 measured following chemical conversion through addition of NO. The mean radical levels were 3.9×105 molecule cm−3 for OH, and 0.76 ppt for HO2 (ppt denotes parts per trillion, by volume). Typical maximum (local noontime) levels were 7.9×105 molecule cm−3 and 1.50 ppt for OH and HO2 respectively. The main sources of HOx were photolysis of O3 and HCHO, with potentially important but uncertain contributions from HONO and higher aldehydes. Of the measured OH sinks, reaction with CO and CH4 dominated, however comparison of the observed OH concentrations with those calculated via the steady state approximation indicated that additional co-reactants were likely to have been present. Elevated levels of NOx resulting from snowpack photochemistry contributed to HOx cycling and enhanced levels of OH, however the halogen oxides IO and BrO dominated the CH3O2 – HO2 – OH conversion in this environment, with associated ozone destruction.

References 1

Anderson, P. S.: Behaviour of tracer diffusion in simple atmospheric boundary layer models, Atmos. Chem. Phys. Discuss. 6, 13 111–13 138, 2006.

Aschmutat, U., Hessling, M., Holland, F. and Hofzumahaus, A.: A tuneable source of hydroxyl (OH) and hydroperoxy (HO$_2)$ radicals: In the range between 10$^6$ and 10$^9$ cm−3, Physico-Chemical Behaviour of Atmospheric Pollutants, edited by: Angeletti, G. and Restelli, C., Proc. EUR 15609, 811–816, 1994.

Bauguitte, S. J.-B., Bloss, W. J., Clemitshaw, K. C., Evans, M. J., Jones, A. E., Lee, J. D., Mills, G., Saiz-Lopez, A., Salmon, R. A., Roscoe, H. K., and Wolff, E. W.: An overview of year-round NOx measurements during the CHABLIS campaign: can sources and sinks estimates unravel observed diurnal cycles?, Geophys. Res. Abstr., 8, 09054, 2006.

Berresheim, H., Plass-Dülmer, C., Elste, T., Mihalopoulos, N., and Rohrer, F.: OH in the coastal boundary layer of Crete during MINOS: Measurements and relationship with ozone photolysis, Atmos. Chem. Phys., 3, 639–649, 2003.

Bloss, W. J., Gravestock, T. J., Heard, D. E., Ingham, T., Johnson, G. P., and Lee, J. D.: Application of a compact all-solid-state laser system to the in situ detection of atmospheric OH, HO2, NO and IO by laser-induced fluorescence, J. Environ. Monit. 5, 21–28, 2003.

Bloss, W. J., Lee, J. D., Johnson, G. P., Sommariva, R., Heard, D. E., Saiz-Lopez, A., Plane, J. M. C., McFiggans, G., Coe, H., Flynn, M., Williams, P., Rickard, A. R., and Fleming, Z. L.: Impact of halogen monoxide chemistry upon boundary layer OH and HO2 concentrations at a coastal site, Geophys. Res. Lett., 32, L06814, https://doi.org/10.1029/2004GL022084, 2005a.

Bloss, W. J., Evans, M. J., Lee, J. D., Sommariva, R., Heard, D. E., and Pilling, M. J.: The oxidative capacity of the troposphere: Coupling of field measurements of OH and a global chemistry transport model, Faraday Discuss.,130, 425–436, 2005b. %

%Bloss, W. J., Lee, J. D., Heard, D. E., Saiz-Lopez, A., Plane, J. M. C., %Salmon, R. A., Bauguitte, S. J.-B., Roscoe, H. K., and Jones, A. E.: Box %Model Studies of Radical Chemistry in the Coastal Antarctic Boundary Layer, %in preparation\blackbox\bf status?, 2007.

Boudries, H., Bottenheim, J. W., Guimbaud, C., Grannas, A. M., Shepson, P. B., Houdier, S., Perrier, S., and Dominé, F.: Distribution and trends of oxygenated hydrocarbons in the high Arctic derived from measurements in the atmospheric boundary layer and interstitial snow air during the ALERT2000 field campaign, Atmos. Environ., 36, 2573–2583, 2002.

Brauers, T., Hausmann, M., Bister, A., Kraus, A., and Dorn, H. P.: OH radicals in the boundary layer of the Atlantic Ocean 1. Measurements by long-path laser absorption spectroscopy, J. Geophys. Res., 106, 7399–7414, 2001.

Cantrell, C. A., Zimmer, A., and Tyndall, G.S.: Absorption cross sections for water vapour from 183 to 193 nm, Geophys. Res. Lett., 24, 17, 2195–2198, 1997.

Chen, G., Davis, D., Crawford, J., Nowak, J.B., Eisele, F., Mauldin III, R.L., Tanner, D., Buhr, M., Shetter, R., Lefer, B., Arimoto, R., Hogan, A., and Blake, D.: An Investigation of South Pole HOx Chemistry: Comparison of Model Results with ISCAT Observations, Geophys. Res. Lett., 28, 3633–3636, 2001.

Chen, G., Davis, D., Crawford, J., Hutterli, L. M., Huey, L. G., Slusher, D., Mauldin, L., Eisele, F., Tanner, D., Dibb, J., Buhr, M., McConnell, J., Lefer, B., Shetter, R., Blake, D., Song, C. H., Lombardo, K., and Arnoldy, J.: A reassessment of HOx South Pole chemistry based on observations recorded during ISCAT 2000, Atmos. Environ., 38, 5451–5461, 2004.

Clemitshaw, K. C.: A Review of Instrumentation and Measurement Techniques for Ground-Based and Airborne Field Studies of Gas-Phase Tropospheric Chemistry, Critical Reviews in Environmental Science and Technology, 34, 1–108, 2004.

Clemitshaw, K. C.: Coupling between Tropospheric Photochemistry of Nitrous Acid (HONO) and Nitric Acid (HNO$_3)$, Environ. Chem., 3, 31–34, 2006.

Creasey, D. J., Heard, D. E., and Lee, J. D.: Absorption cross-section measurements of water vapour and oxygen at 185 nm. Implications for the calibration of field instruments to measure OH, HO2 and RO2 radicals, Geophys. Res. Lett. 27(11), 1651–1654, 2000

Creasey, D. J., Evans, G. E., Heard, D. E., and Lee, J. D.: Measurements of OH and HO2 concentrations in the Southern Ocean marine boundary layer, J. Geophys. Res. 108, 4475, https://doi.org/10.1029/2002JD003206, 2003.

Davis, D., Nowak. J. B., Chen, G., Buhr, M., Arimoto, R., Hogan, A., Eisele, F., Mauldin, L., Tanner, D., Shetter, R., Lefer, B., and McMurry, P.: Unexpected High Levels of NO Observed at South Pole, Geophys. Res. Lett., 28, 3625–3628, 2001.

Davis, D., Chen, G., Buhr, M., Crawford, J., Lenschow, D., Lefer, B., Shetter, R., Eisele, F., Mauldin, L., and Hogan, A.: South Pole NOx Chemistry: an assessment of factors controlling variability and absolute levels, Atmos. Environ., 38, 5375–5388, 2004.

Davison, B., Hewitt, C. N., O'Dowd, C., Lowe, J. A., Smith, M. H., Schwikowski, M., Baltensperger, U. and Harrison, R. M., Dimetyl sulphide, methane sulphonic acid and the physiochemical aerosol properties in Atlantic air from the United Kingdom to Halley Bay, J. Geophys. Res. 101, 22 855–22 867, 1996.

Dibb, J. E., Huey, L. G., Slusher, D. L., and Tanner, D. J.: Soluble reactive nitrogen oxides at South Pole during ISCAT 2000, Atmos. Environ., 38, 5399–5409, 2004.

Dubey, M. K., Hanisco, T. F., Wennberg, P. O., and Anderson, J. G.: Monitoring potential photochemical interference in laser-induced fluorescence measurements of atmospheric OH, Geophys. Res. Lett., 23, 3215–3218, 1996.

Ehhalt, D. H. and Rohrer, F.: Dependence of the OH concentration on solar UV, J. Geophys. Res. 105, 3565–3571, 2000.

Grannas, A., M., Shepson, P. B., Guimbaud, C., Sumner, A. L., Albert, M., Simpson, W., Domine, F., Boudries, H., Bottenheim, J., Beine, H. J., Honrath, R., and Zhou, X.: A study of photochemical and physical processes affecting carbonyl compounds in the Arctic atmospheric boundary layer, Atmos. Environ., 36, 2733–2742, 2002.

Grannas, A. M., Shepson, P. B., and Filley, T. R.: Photochemistry and nature of organic matter in Arctic and Antarctic snow, Glob. Biogeochem. Cycles, 18, GB1006, https://doi.org/10.1029/2003GB002133, 2004.

Guimbaud, C., Grannas, A. M., Shepson, P. B., Fuentes, J. D., Boudries, H., Bottenheim, J. W., Dominé, F., Houdier, S., Perrier, S., Biesenthal, T. B. and Splawn, B. G.: Snowpack processing of acetaldehyde and acetone in the Arctic atmospheric boundary layer, Atmos. Environ., 36, 2743–2752, 2002.

Hard, T. M., O'Brien, R. J., Chan, Y. C., and Mehrabzadeh, A. A.: Tropospheric Free Radical Determination by FAGE, Environ. Sci. Tech., 18, 768–777, 1984.

Heard, D. E. and Pilling, M. J.: Measurement of OH and HO2 in the Troposphere, Chem. Rev. 103, 5163–5198, 2003.

Honrath, R. E., Peterson, M. C., Guo, S., Dibb, J. E., Shepson, P. B., and Campbell, B.: Evidence of NOx production within or upon ice particles in the Greenland snowpack, Geophys. Res. Lett., 26, 695–698, 1999.

Hofzumahaus, A., Aschmutat, U., Heßling, M., Holland, F., and Ehhalt, D. H.: The measurement of tropospheric OH radicals by laser-induced fluorescence spectroscopy during the POPCORN field campaign, Geophys. Res. Lett., 23, 2541–2544, 1996.

Holland, F., Hofzumahaus, A., Schäfer, R., Kraus, A., and Pätz, H. W.: Measurements of OH and HO2 radical concentrations and photolysis frequencies during BERLIOZ, J. Goephys. Res., 108(D4), 8246, https://doi.org/10.1029/2001JD001393, 2003.

Huey, L. G., Sjostedt, S., Tanner, D. J., Dibb, J., Chen, G., Lefer, B., Peischl, J., Hutterli, M., Blake, N., Blake, D., Beyersdorf, A., and Ryerson, T.: Measurements of OH and HO2 + RO2 at Summit Greenland, Eos Trans. AGU, 85(47), Fall Meet. Suppl., Abstract A22C-02, 2004.

Hutterli, M. A., Röthlisberger, R., and Bales, R. C.: Atmosphere-to-snow-to-firn transfer studies of HCHO at Summit, Greenland, Geophys. Res. Lett., 26, 1691–1694, 1999.

Jacob, D. J., Field, B. D., Li, Q., Blake, D. R., de Gouw, J., Warneke, C., Hansel, A., Wisthaler, A., Singh, H. B., and Guenther, A.: Global budget of methanol: Constraints from atmospheric observations, J. Geophys. Res., 100, D08303, https://doi.org/10.1029/2004JD005172, 2005.

Jefferson, A., Tanner, D. J., Eisele, F. L., Davis, D. D., Chen, G., Crawford, J., Huey, J. W., Torres, A. L., and Berresheim, H.: OH Photochemistry and methane sulphonic acid formation in the coastal Antarctic boundary layer, J. Geophys. Res., 103, 1647–1656, 1998.

Jones, A. E., Weller, R., Wolff, E. W., and Jacobi, H.-W.: Speciation and Rate of Photochemical NO and NO2 Production in Antarctic Snow, Geophys. Res. Lett., 27, 345–348, 2000. %

%Jones, A. E., \blackbox\bf please name at least 3 authors before using et al. et al.: Chemistry of the Antarctic Boundary Layer and the %Interface with Snow: An overview of the CHABLIS campaign, Atmos. Chem. %Phys. Discuss., in preparation, 2007.

Kanaya, Y., Sadanaga, Y., Nakumura, K., and Akimoto, H.: 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, J. Geophys. Res., 106, 24 197–24 208, 2001.

Legrand, M. and Mayewski, P.: Glaciochemistry of Polar Ice Cores: A Review, Rev. Geophys. 35, 219–243, 1997.

Lewis, A. C., Hopkins, J. R., Carpenter, L. J., Stanton, J., Read, K. A., and Pilling, M. J.: Sources and sinks of acetone, methanol and acetaldehyde in North Atlantic marine air, Atmos. Chem. Phys., 5, 1963–1974, 2005.

Liao, W., Case, A. T., Mastromarino, J., Tan, D., and Dibb, J. E.: Observations of HONO by laser-induced fluorescence at the South Pole during ANTCI 2003, Geophys. Res. Lett., 33, L09810, https://doi.org/10.1029/2005GL025470, 2006.

Madronich, S. and Flocke, S.: The role of solar radiation in atmospheric chemistry, in Handbook of Environmental Chemistry (P. Boule, Ed.), Springer Verlag, Heidelberg, 1–26, 1998.

Mauldin III, R. L., Eisele, F. L., Tanner, D. J., Kosciuch, E., Shetter, R., Lefer, B., Hall, S. R., Nowak, J. B., Buhr, M., Chen, G., Wang, P., and David, D.: Measurements of OH, H2SO4, and MSA at the South Pole during ISCAT, Geophys. Res. Lett., 28, 3629–3632, 2001.

Mauldin III, R. L., Tanner, D., Buhr, M., Shetter, R., Lefer, B., Arimoto, R., Hogan, A. and Blake, D.: An Investigation of South Pole HOx Chemistry: Comparison of Model Results with ISCAT Observations, Geophys. Res. Lett., 28, 3633–3636, 2001.

Mauldin III, R. L., Kosciuch, E., Henry, B., Eisele, F. L., Shetter, R., Lefer, B., Chen, G., Davis, D., Huey, G., and Tanner, D.: Measurements of OH, HO2+RO2, H2SO4 and MSA at the South Pole during ISCAT 2000, Atmos. Environ., 38, 5423–5437, 2004.

Penkett, S. A., Monks, P. S., Carpenter, L. J., and Clemitshaw, K. C.: Relationships between ozone photolysis rates and peroxy radical concentrations in clean marine air over the Southern Ocean, J. Geophys. Res., 102, 12 805–12 817, 1997.

Read, K. A., Lewis, A. C., Salmon, R. A., Jones, A. E., and Bauguitte, S.: OH and halogen atom influence on the variability of non-methane hydrocarbons in the Antarctic Boundary Layer, Tellus B, 59, 22–38, 2007.

Rohrer, F. and Berresheim, H.: Strong correlation between levels of tropospheric hydroxyl radicals and solar ultraviolet radiation, Nature, 442, 184–187, 2006.

Saiz-Lopez, A., Mahajan, A. S., Salmon, R. A., Bauguitte, S. J.-B., Jones, A. E., Roscoe, H. K. and Plane, J. M. C, Boundary layer halogens in coastal Antarctica, Science, 317, 348–351, 2007a.

Saiz-Lopez, A., Plane, J. M. C., Mahajan, A. S., Anderson, P. S., Bauguitte, S. J.-B., Jones, A. E., Salmon, R. A., Bloss, W. J., Lee, J. D., and Heard, D. E.: On the vertical distribution of boundary layer halogens over coastal Antarctica: implications for O3, HOx, NOx and the Hg lifetime, Atmos. Chem. Phys. Discuss. 7, 9385–9417, 2007b.

Sander, S. P., Friedl, R. R., Golden, D. M., Kurylo, M. J., Moortgat, G. K., Keller-Rudek, H., Wine, P. H., Ravishankara, A. R., Kolb, C. E., Molina, M. J., Finlayson-Pitts, B. J., Huie, R. E., and Orkin, V. L.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies - Evaluation Number 15, NASA-JPL Publication 06-2, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, 2006.

Sjostedt, S. J., Huey, L. G., Tanner, D. J., Peischl, J., Chen, G., Dibb, J. E., Lefer, B., Hutterli, M. A., Beyersdorf, A. J., Blake, N. J., Blake, D. R.: Peroxy and Hydroxyl Radical Measurements During the Spring 2004 Summit Field Campaign, Eos Trans. AGU, 86(52), Fall Meet. Suppl., Abstract A24A-02, 2005.

Smith, S. C., Lee, J. D., Bloss, W. J., Johnson, G. P., Ingham, T., and Heard, D. E.: Concentrations of OH and HO2 radicals during NAMBLEX: Measurements and steady state analysis, Atmos. Chem. Phys., 6, 1435–1453, 2006.

Sumner, A.-L. and Shepson, P. B.: Snowpack production of formaldehyde and its effect on the Arctic troposphere, Nature, 398, 230–233, 1999.

Tan. D., Faloona, I., Simpas, J. B., Brune, W., Olson, J., Crawford, J., Avery, M., Sachse, G., Vay, S., Sandholm, S., Guan, H.-W., Vaughn, T., Mastromarino, J., Heikes, B., Snow, J., Podolske, J., and Singh, H.: OH and HO2 in the tropical Pacific: Results from PEM-Tropics B, J. Geophys. Res., 106, 32 667–32 681, 2001.

Walker, S. J., Jackson, A. V., Evans, M. J., McQuaid, J. B., and Salmon, R.: Assessment of hydrogen peroxide in the coastal Antarctic boundary layer, Geophys. Res. Abstr., 8, 03740, 2006.

Washida, N., Mori, Y., and I. Tanaka: Quantum Yield of Ozone Formation from Photolysis of the Oxygen molecule at 1849 and 1931 Å, J. Chem. Phys., 54, 1119–1122, 1971.

Zhou, X., Beine, H., Honrath, R. E., Fuentes, J. D., Simpson, W., Shepson, P. B., and Bottenheim, J. W.: Snowpack Photochemical Production of HONO: a Major source of OH in the Arctic Boundary Layer in Springtime, Geophys. Res. Lett., 28, 4087–4090, 2001.