References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-7-4733-2007

Retrieval of stratospheric and tropospheric BrO columns from multi-axis DOAS measurements at Reunion Island (21° S, 56° E)

Theys

¹ Van Roozendael

¹ Hendrick

¹ Fayt

¹ Hermans

¹ Baray

J.-L.

² Goutail

³ Pommereau

J.-P.

³ De Mazière

Belgium Institute for Space Aeronomy (IASB-BIRA), Brussels, Belgium

Laboratoire de L'Atmosphère et des Cyclones (LACy), UMR-CNRS, St-Denis, La Réunion, France

Service d'Aéronomie, Verrières-le-Buisson, France

18 09 2007

7 18 4733 4749

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Spectral measurements of BrO using zenith-sky and off-axis viewing geometries are combined in a linear multiple regression retrieval algorithm to provide stratospheric and tropospheric BrO vertical columns. One year of measurement data are investigated over Reunion-Island (20.9° S, 55.5° E), from August 2004 to June 2005. A comparison between the stratospheric columns retrieved at 45°, 80°, 85°, 87.5° and 92.5° solar zenith angles and photochemical simulations initialized by chemical fields from the 3-D-CTM SLIMCAT and further constrained by observed NO2 profiles shows a good agreement only by considering a contribution from the very short-lived organic bromine substances to the stratospheric inorganic bromine budget, of 6 to 8 pptv. Furthermore, stratospheric BrO profiles retrieved from late twilight zenith-sky observations are consistent with a total inorganic bromine (Bry) loading of approximately 23 pptv. This represents 6 to 7 pptv more than can be supplied by long-lived organic bromine sources, and therefore supports an added contribution from very short-lived organic bromine substances as recently suggested in several other studies. Moreover strong evidences are presented for the existence of a substantial amount of BrO in the tropical free-troposphere, around 6 km altitude, possibly supplied by the decomposition of short-lived biogenic bromine organic compounds. Tropospheric BrO vertical columns of 1.1±0.45×1013 molec/cm² are derived for the entire observation period. Comparisons between ground-based BrO vertical columns and total BrO columns derived from SCIAMACHY (onboard the ENVISAT satellite) nadir observations in a latitudinal band centered around 21° S present a good level of consistency, which further strengthens the conclusions of our study.

References 1

Aliwell, S. R., Van Roozendael, M., Johnston, P. V., Richter, A., Wagner, T., et al.: Analysis for BrO in zenith-sky spectra: An intercomparison exercise for analysis improvement, J. Geophys. Res., 107, D140, doi:10.1029/2001JD000329, 2002.

Anderson, G. P., Clough, S. A., Kneizys, F. X., Chetwynd, J. H., and Shettle, E. P.: AFGL atmospheric constituent profiles (0–120 km), Tech. Rep. AFGL-TR-86-0110, Air Force Geophys. Lab., Hascom Air Force Base, Mass., 1986.

Arpag, K. H., Johnston, P. V., Miller, H. L., Sander, R. W., and Solomon, S.: Observations of stratospheric BrO column over Colorado, 40° N, J. Geophys. Res., 99, 8175–8181, 1994.

Bobrowski, N., Höninger, G., Galle, B., and Platt, U.: Detection of bromine monoxide in a volcanic plume, Nature, 423, 273–276, 2003.

Bogumil, K., Orphal, J., Homann, T., Voigt, S., Spietz, P., Fleischmann, O. C., Vogel, A., Hartmann, M., Bovensmann, H., Frerik, J., and Burrows, J. P.: Measurements of molecular absorption spectra with the SCIAMACHY Pre-Flight Model: Instrument characterization and reference spectra for atmospheric remote sensing in the 230–2380 nm region, J. Photochem. Photobiol. A, 157, 167–184, 2003.

Bovensmann, H., Burrows, J. P., Buchwitz, M., Frerick, J., No\"el, S., Rozanov, V. V., Chance, K. V., and Goede, A. P. H.: SCIAMACHY: Mission objectives and Measurement Modes, J. Atmos. Sci., 56, 127–150, 1999.

Carpenter, L. J. and Liss, P. S.: On temperature sources of bromoform and other reactive organic bromine gases, J. Geophys. Res. D., 105(D16), 20 539–20 547, 2000.

Chipperfield, M. P.: Multiannual simulations with a three-dimensional chemical transport model, J. Geophys. Res., 104(D1), 1781–1805, 1999.

Chipperfield, M. P.: New Version of the TOMCAT/SLIMCAT Off-Line Chemical Transport Model: Intercomparison of Stratospheric Tracer Experiments, Q. J. Roy. Meteor. Soc., 132, 1179–1203, doi:10.1256/qj.05.51, 2006.

Dorf, M., Bösch, H., Butz, A., Camy-Peyret, C., Chipperfield, M., Engel, A., Goutail,F., Grunow, K., Hendrick, F., Hrechanyy, S., Naujokat, B., Pommereau, J.-P., Van Roozendael, M., Sioris, C., Stroh, F., Weidner, F., and Pfeilsticker, K.: Balloon-borne stratospheric BrO measurements: Intercomparisons with ENVISAT/SCIAMACHY BrO limb profiles, Atmos. Chem. Phys., 6, 2483–2501, 2006a.

Dorf, M., Butler, J. H., Butz, A., Camy-Peyret, C., Chipperfield, M. P., Kritten, L., Montzka, S. A., Simmes, B., Weidner, F., and Pfeilsticker, K.: Long-term observations of stratospheric bromine reveal slow down in growth, Geophys. Res. Lett., 33, L24803, doi:10.1029/2006GL027714, 2006b.

Errera, Q. and Fonteyn, D.: Four-dimensional variational chemical assimilation of CRISTA stratospheric measurements, J. Geophys. Res., 106(D11), 12 253–12 265, 2001.

Feng, W., Chipperfield, M. P., Dorf, M., Pfeilsticker, K., and Ricaud, P.: Mid-latitude ozone changes: studies with a 3-D CTM forced by ERA-40 analyses, Atmos. Chem. Phys., 7, 2357–2369, 2007.

Fietkau, S., Medeke, T., Richter, A., Sheode, N., Sinnhuber, B.-M., Wittrock, F., Theys, N., Van Roozendael, M., and Burrows, J. P.: Ground-based measurements of tropospheric and stratospheric bromine monoxide above Nairobi (1° S, 36° E), Atmos. Chem. Phys. Discuss., 7, 6527–6555, 2007.

Fish, D. J., Jones, R. L., and Strong, E. K.: Mid-latitude observations of the diurnal variation of stratospheric BrO, J. Geophys. Res., 100, 18 863–18 871, 1995.

Fitzenberger, R., Bösch, R., Camy-Peyret, C., Chipperfiel, M. P., Harder, H., Platt, U., Sinnhuber, B.-M., Wagner, T., and Pfeilsticker, K.: First profile measurements of tropospheric BrO, Geophys. Res. Lett., 27, 2921–2924, 2000.

Frieß, U., Hollwedel, J., König-Langlo, G., Wagner, T., and Platt, U.: Dynamics and chemistry of tropospheric bromine explosion events in the Antarctic coastal region, J. Geophys. Res., 109, D06305, doi:10.1029/2003JD004133, 2004.

Frieß, U., Monks, P. S., Remedios, J. J., Rozanov, A., Sinreich, R., Wagner, T., and Platt, U.: MAX-DOAS O4 measurements: A new technique to derive information on atmospheric aerosols: 2. Modeling studies, J. Geophys. Res., 111, D14203, doi:10.1029/2005JD006618, 2006.

Grainger, J. F. and Ring, J.: Anomalous Fraunhofer line profiles, Nature, 193, 762, 1962.

Greenblatt, G. D., Orlando, J. J., Burkholder, J. B., and Ravishankara, A. R.: Absorption measurements of oxygen between 330 and 1140 nm, J. Geophys. Res., 95, 18 577–18 582, 1990.

Hausmann, M. and Platt, U.: Spectroscopic measurement of bromine oxide and ozone in the high Arctic during Polar Sunrise Experiment 1992, J. Geophys. Res., 99, 25 399–25 414, 1994.

Hebestreit, K., Stutz, J., Rosen, D., Matveiv, V., Peleg, M., Luria, M., and Platt, U.: DOAS measurements of tropospheric bromine oxide in mid-latitudes, Science, 283, 55–57, 1999.

Heckel, A., Richter, A., Tarsu, T., Wittrock, F., Hak, C., Pundt, I., Junkermann, and Burrows, J. P.: MAX-DOAS measurements of formaldehyde in the Po-Valley, Atmos. Chem. Phys., 5, 909–918, 2005.

Hendrick, F., Barret, B., Van Roozendael, M., Boesch, H., Butz, A., De Mazière, M., Goutail, F., Hermans, C., Lambert, J.-C., Pfeilsticker, K., and Pommereau, J.-P.: Retrieval of nitrogen dioxide stratospheric profiles from ground-based zenith-sky UV-visible observations: validation of the technique through correlative comparisons, Atmos. Chem. Phys., 4, 2091–2106, 2004.

Hendrick, F., Van Roozendael, M., Kylling, A., Petritoli, A., Rozanov, A., Sanghavi, S., Schofield, R., von Friedeburg, C., Wagner, T., Wittrock, F., Fonteyn. D., and De Mazière, M.: Intercomparison exercise between different radiative transfer models used for the interpretation of ground-based zenith-sky and multi-axis DOAS observations, Atmos. Chem. Phys., 6, 93–108, 2006.

Hendrick, F., Van Roozendael, M., Chipperfield, M. P., Dorf, M., Goutail, F., Yang, X., Fayt, C., Hermans, C., Pfeilsticker, K., Pommereau, J.-P., Pyle, J. A., Theys, N., and De Mazière, M.: Retrieval of stratospheric and tropospheric BrO profiles and columns using ground-based zenith-sky DOAS observations at Harestua, 60° N, Atmos. Chem. Phys. Discuss., 7, 8663–8708, 2007.

Hönninger, G. and Platt, U.: Observations of BrO and its vertical distribution during surface ozone depletion at Alert, Atmos. Environ., 36, 2481–2489, 2002.

Koelemeijer, R. B. A., de Haan, J. F., and Stammes, P.: A database of spectral surface reflectivity in the range 335–772 nm derived from 5.5 years of GOME observations, J. Geophys. Res.-Atm., 108(D2), 4070, doi:10.1029/2002JD002429, 2003.

Kreher, K., Johnston, P. V., Wood, S. W., Nardi, B., and Platt, U.: Ground-based measurements of tropospheric and stratospheric BrO at Arrival Heights, Antartica, Geophys. Res. Lett., 24, 3021–3024, 1997.

Kurucz, R. L., Furenlid, I., Brault, J., and Testerman, L.: Solar flux atlas from 296 nm to 1300 nm, National Solar Observatory Atlas No. 1, 1984.

Lary, D. J.: Gas phase atmospheric bromine photochemistry, J. Geophys. Res., 101, 1505–1516, 1996a.

Lary, D. J., Chipperfield, M. P., Toumi, R., and Lenton, T.: Heterogeneous atmospheric bromine photochemistry, J. Geophys. Res., 101, 1489–1504, 1996b.

Lary, D. J.: Halogens and the chemistry of the free troposphere, Atmos. Chem. Phys., 5, 227–237, 2005.

Leser, H., Höninger, G., and Platt, U.: Max-DOAS measurements of BrO and NO2 in the marine boundary layer, Geophys. Res. Lett., 30, 1537, doi:10.1029/2002GL015811, 2003.

Mayer, B. and Kylling, A.: Technical note: The libRadtran software package for radiative transfer calculations – description and examples of use, Atmos. Chem. Phys., 5, 1855–1877, 2005.

Meller, R. and Moortgat, G. K.: Temperature dependence of the absorption cross-sections of formaldehyde between 223 and 323 K in the wavelength range 225–375 nm, J. Geophys. Res., 105, 7089–7101, 2000.

Middleton, W. E. K.: Vision through the Atmosphere, Univ. of Toronto Press, Toronto, 1952.

Platt, U.: Differential optical absorption spectroscopy (DOAS), Air Monit. By Spectr. Techniques, edited by: Sigrist, M. W., Chemical Analysis Series, 127, 27–84, John Wiley & Sons, Inc., 1994.

Pfeilsticker, K., Sturges, W. T., Bösch, H., Camy-Peyret, C., Chipperfield, M. P., Engel, A., Fitzenberger, R., Müller, M., Payan, S., and Sinnhuber, B.-M.: Lower stratospheric organic and inorganic bromine budget for the arctic winter 1998/99, Geophys. Res. Lett., 27, 3305–3308, 2000.

Preston, K. E., Jones, R. L., and Roscoe, H. K.: Retrieval of NO2 profiles from ground-based UV-visible measurements – method and validation, J. Geophys. Res., 102, 19 089–19 097, 1997.

Pundt, I., Van Roozendael, M., Wagner, T., Richter, A., Chipperfield, M., Burrows, J. P., Fayt, C., Hendrick, F., Pfeilsticker, K., Platt, U., and Pommereau, J.-P.: Simultaneous UV-vis measurementsof BrO from balloon, satellite and ground: implications for tropospheric BrO, in Proc. Fifth European Symp. on polar stratospheric ozone 1999, Air Poll. Res. Report 73, EUR 19340, European Commission, Brussels, Belgium, edited by: Harris, N. R. P., Guirlet, M., and Amanatidis, G. T., p. 316–319, 2000.

Pundt, I., Pommereau, J.-P., Chipperfield, M. P., Van Roozendael, M., and Goutail, F.: Climatology of the stratospheric BrO vertical distribution by balloon-borne UV-visible spectrometry, J. Geophys. Res., 107(D24), 4806, doi:10.1029/2002JD002230, 2002.

Richter, A., Wittrock, F., Eisinger, M., and Burrows, J. P.: GOME observations of tropospheric BrO in Northern Hemispheric spring and summer 1997, Geophys. Res. Lett., 25, 2683–2686, 1998.

Richter, A., Eisinger, M., Ladstätter-Weissenmayer, A., and Burrows, J. P.: DOAS zenith-sky observations, 2, seasonal variation of BrO over Bremen (53° N) 1994–1995, J. Atmos. Chem., 32, 83–99, 1999.

Richter, A., Wittrock, F., Ladstätter-Weissenmayer, A., and Burrows, J. P.: GOME measurements of stratospheric and tropospheric BrO, Adv. Space Res., 29, 1667–1672, 2002.

Rodgers, C. D.: Inverse Methods for Atmospheric Sounding, Theory and Practice, World Scientific Publishing, Singapore-New-Jersey-London-Hong Kong, 2000.

Rozanov, A., Rozanov, V., and Burrows, J. P.: A numerical radiative transfer model for a spherical planetary atmosphere: Combined differential integral approach involving the Piccard iterative approximation, J. Quant. Spectrosc. Radiat. Trans., 69, 491–512, 2001.

Salawitch, R. J., Weisenstein, D. K., Kovalenko, L. J., Sioris, C. E., Wennberg, P. O., Chance, K., Ko, M. K. W., and McLinden, C. A.: Sensitivity of ozone to bromine in the lower stratosphere, Geophys. Res. Lett., 32, L05811, doi:10.1029/2004GL021504, 2005.

Salawitch, R. J.: Atmospheric chemistry: biogenic bromine, Nature, 439, 275–277, 2006.

Sander, S. P., Friedl, R. R., Ravishankara, A. R., et al.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation no. 15, NASA JPL Publication no. 06-2, 2006.

Schofield, R., Kreher, K., Connor, B. J., Johnston, P. V., Thomas, A., Shooter, D., Chipperfield, M. P., Rodgers, C. D., and Mount, G. H.: Retrieved tropospheric and stratospheric BrO columns over Lauder, New Zealand., J. Geophys. Res., 109, D14304, doi:10.1029/2003JD004463, 2004a.

Schofield, R., Connor, B. J., R., Kreher, K., Johnston, P. V., and Rodgers, C. D.: The retrieval of profile and chemical information from ground-based UV-visible spectroscopic measurements, J. Quant. Spectrosc. Radiat. Trans., 86, 115–131, 2004b.

Schofield, R., Johnston, P. V., Thomas, A., Kreher, K., Connor, B. J., Wood, S., Shooter, D., Chipperfield, M. P., Richter, A., von Glasow, R., and Rodgers, C. D.: Tropospheric and stratospheric BrO columns over Arrival Heights, Antartica, 2002, J. Geophys. Res., 111, D22310, doi:10.1029/2005JD007022, 2006.

Simpson, W. R., von Glasow, R., Riedel, K., Anderson, P., Ariya, P., Bottenheim, J., Burrows, J., Carpenter, L., Frieß, U., Goodsite, M. E., Heard, D., Hutterli, M., Jacobi, H.-W., Kaleschke, L., Neff, B., Plane, J., Platt, U., Richter, A., Roscoe, H., Sander, R., Shepson, P., Sodeau, J., Steffen, A., Wagner, T., and Wolff, E.: Halogens and their role in polar boundary-layer ozone depletion, Atmos. Chem. Phys., 7, 4375–4418, 2007.

Sinnhuber, B.-M., Arlander, D. W., Bovensmann, H., et al.: Comparison of measurements and model calculations of stratospheric bromine monoxide, J. Geophys. Res., 107(D19), 4398, doi:10.1029//2001JD000940, 2002.

Sinnhuber, B.-M., Rozanov, A., Sheode, N., Afe, O. T., Richter, A., Sinnhuber, M., Wittrock, F., and Burrows, J. P.: Global observations of stratospheric bromine monoxide from SCIAMACHY, Geophys. Res. Lett., 32, L20810, doi:10.1029/2005GL023839, 2005.

Sioris, C. E., Kovalenko, L. J., McLinden, C. A., Salawitch, R. J., Van Roozendael, M., Goutail, F., Dorf, M., Pfeilsticker, K., Chance, K., von Savigny, C., Liu, X., Kurosu, T. P., Pommereau, J.-P., Bösch, H., and Frerick, J.: Latitudinal and vertical distribution of bromine monoxide in the lower stratosphere from Scanning Imaging Absorption Spectrometer for Atomspheric Chartography limb scattering measurements, J. Geophys. Res., 111, D14301, doi:10.1029/2005JD006479, 2006.

Vandaele, A.-C., Hermans, C., Simon, P. C., Carleer, M., Colin, R., Fally, S., Mérienne, M.-F., Jenouvrier, A., and Coquart, B.: Measurements of the NO2 absorption cross-section from 42 000 cm−1 to 10 000 cm−1 (238–1000 nm) at 220 K and 294 K, J. Quant. Spectrosc. Radiat. Trans., 59, 171–184, 1997.

Van Roozendael, M., Fayt, C., Lambert, J.-C., Pundt, I., Wagner, T., Richter, A., and Chance, K.: Development of a bromine oxide product from GOME, European Symposium on Atmosph. Measurements from Space, ESA WPP-161, 543–547, 1999.

Van Roozendael, M., Wagner, T., Richter, A., Pundt, I., Arlander, D., Burrows, J. P., Chipperfield, M., Fayt, C., Johnston, P. V., Lambert, J.-C., Kreher, K., Pfeilsticker, K., Platt, U., Pommereau, J.-P., Sinnhuber, B.-M., Tornkvist, K. K., and Wittrock, F.: Intercomparison of BrO measurements from ERS-2 GOME, ground-based and balloon platforms, Adv. Space Res., 29, 1661–1666, 2002.

Van Roozendael, M., De Smedt, I., Fayt, C., Wittrock, F., Richter, A., and Afe, O.: First validation of SCIAMACHY BrO columns, in Proc. Second Workshop on the Atmospheric Chemistry Validation of ENVISAT (ACVE-2), Frascati, Italy, 3–7 May 2004.

von Glasow, R., von Kuhlmann, R., Lawrence, M. G., Platt, U., and Crutzen, P. J.: Impact of reactive bromine chemistry in the troposphere, Atmos. Chem. Phys., 4, 2481–2497, 2004.

Vountas, M., Rozanov, V. V., and Burrows, J. P.: Ring effect: Impact of rotational raman scattering on radiative transfer in earth's atmosphere, J. Quant. Spectrosc. Radiat. Trans., 60, 943–961, 1998.

Wagner, T. and Platt, U.: Satellite mapping of enhanced BrO concentrations in the troposphere, Nature, 395, 486–490, 1998.

Wagner, T., Dix, D., von Friedeburg, C., Friess, U., Sanghavi, S., Sinreich, R., and Platt, U.: MAX-DOAS O4 measurements: A new technique to derive information an atmospheric aerosols-Principles and information content, J. Geophys. Res., 109, D22205, doi:10.1029/2004JD004904, 2004.

Wamsley, P. R., Elkins, J. W., Fahey, D. W., Dutton, G. S., Volk, C. M., Myers, R. C., Montzka, S. A., Butler, J. H., Clarke, A. D., Fraser, P. J., Steele, L. P., Lucarelli, M. P., Atlas, E. L., Schauffler, S. M., Blake, D. R., Rowland, F. S., Sturges, W. T., Lee, J. M., Penkett, S. A., Engel, A., Stimpfle, R. M., Chan, K. R., Weisenstein, D. K., Ko, M. K. W., and Salawitch, R. J.: Distribution of halon-1211 in the upper troposphere and lower stratosphere and the 1994 total bromine budget, J. Geophys. Res., 103(D1), 1513–1526, 1998.

WMO: Global ozone research and monitoring project, in: Scientific Assessment of Ozone Depletion: 1998, Rep. 44, Geneva, 1998.

WMO: Global ozone research and monitoring project, in: Scientific Assessment of Ozone Depletion: 2002, Rep. 47, Geneva, 2003.

Wilmouth, D. M., Hanisco, T. F., Donahue, N. M., and Anderson, J. G.: Fourier transform ultraviolet spectroscopy of the A$^2\Pi _3/2 \leftarrow$X$^2\Pi _3/2$ transition of BrO, J. Phys. Chem. A., 103, 8935–8945, 1999.

Wittrock, F., Oetjen, H., Richter, A., Fietkau, S., Medeke, T., Rozanov, A., and Burrows, J. P.: Max-DOAS measurements of atmospheric trace gases in Ny-Ålesund – Radiative transfer studies and their application, Atmos. Chem. Phys., 4, 955–966, 2004.

Yang, X., Cox, R. A., Warwick, N. J., Pyle, J. A., Carver, G. D., O'Connor, F. M., and Savage, N. H.: Tropospheric bromine chemistry and its impact on ozone: A model study, J., Geophys. Res., 110, D23311, doi:10.1029/2005JD006244, 2005.