References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-8-7725-2008

Measurement-based modeling of bromine chemistry at the Dead Sea boundary layer – Part 2: The influence of NO2 on bromine chemistry at mid-latitude areas

Tas

¹ ² Peleg

¹ Pedersen

D. U.

¹ Matveev

¹ Biazar

A. P.

³ Luria

Institute of Earth Sciences, Hebrew University of Jerusalem, Israel

Atmospheric Chemistry Division, Max-Planck-Institut für Chemie, Mainz, Germany

Earth System Science Center, University of Alabama in Huntsville, Huntsvile, AL 35899 USA

21 04 2008

8 2 7725 7753

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys-discuss.net/8/7725/2008/acpd-8-7725-2008.html

The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/8/7725/2008/acpd-8-7725-2008.pdf

Understanding the interaction between anthropogenic air pollution and Reactive Halogen Species (RHS) activity has had only limited support of direct field measurements, due to the fact that past field measurements of RHS have been mainly performed in Polar Regions. The present paper investigates the interaction between NO2 and Reactive Bromine Species (RBS) activity by model simulations based on extensive field measurements performed in the Dead Sea area, as described in a companion paper (Tas et al., 2006). The Dead Sea is an excellent natural laboratory for this investigation since elevated concentrations of BrO (up to more than 150 pptv) are frequently observed, while the average levels of NO2 are around several ppb. The results of the present study show that under the chemical mechanisms that occur at the Dead Sea, higher levels of NO2 lead to higher daily average concentrations of BrOX, as a result of an increase in the rate of the heterogeneous decomposition of BrONO2 that in turn causes an increase in the rate of the "Bromine Explosion" mechanism. The present study has shown that the influence of NO2 on BrOX production clearly reflects an enhancement of RBS activity caused by anthropogenic activity. However, above a certain threshold level of NO2 (daily average mixing ratios of 0.2 ppbv during RBS activity), the daily average concentrations of BrOX decrease for a further increase in the NO2 concentrations.

References 1

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Kerr, J. A., Rossi, M. J., and Troe, J.: Summary of Evaluated Kinetic and Photochemical Data for Atmospheric Chemistry, IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry, Web Version, http://www.iupac-kinetic.ch.cam.ac.uk/, 2003.

Barrie, L. A., Bottenheim, J. W., Schnell, R. C., Crutzen, P. J., and Rasmussen, R. A.: Ozone destruction and photochemical reactions at polar sunrise in the lower Arctic atmosphere, Nature, 334, 138–141, 1988.

Biazar, A. P.: The role of natural nitrogen oxides in ozone production in the southern environment, Dissertation, The Department of Atmospheric Sciences, The University of Alabama in Huntsville, 1995.

Beine, H. J., Jaffe, D. A., Stordal F., Engardt, M., Solberg, S., Schmidbauer, N., and Holmen, K.: NOx during ozone depletion events in the arctic troposphere at Ny-Alesund, Svalbard, Tellus, 494, 556–565, 1997.

De Haan, D. O., Brauers, T., Oum, K., Stutz, J., Nordmeyer, T. and B. J., Finlayson-Pitts, Heterogeneous chemistry in the troposphere: experimental approaches and applications of the chemistry of sea salt particles, Int. Rev. Phys. Chem.,18, 343–385, 1999.

Hanson, D. R. and Ravishankara, A. R.: Heterogeneous chemistry of Bromine species in sulfuric acid under stratospheric conditions, J. Geophys. Res., 22(4), 385–388, 1995.

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), 399–413, 1994.

Hebestreit, K., Stutz, J., Rosen, D., Matveev, V., Peleg, M., Luria, M., and Platt, U.: First DOAS Measurements of Tropospheric Bromine Oxide in Mid Latitudes, Science, 283, 55–57, 1999.

Hoenninger, G., Bobrowski, N., Palenque, E. R., Torrez, R., and Platt, U.: Reactive bromine and sulfur emissions at Salar de Uyuni, Bolivia, Geophys. Res. Lett., 31, L04101, doi:10.1029/2003GL018818, 2004.

Kreher, K., Johnston, P. V., Wood, S. W., Nardi, B., and Platt, U.: Ground-based measurements of tropospheric and stratospheric BrO at Arrival Heights (78° S), Antarctica, Geophys. Res. Lett., 24(23), 3021–3024, 1997.

Lehrer, E., Hoenninger, G., and Platt, U.: A one dimensional model study of the mechanism of halogen liberation and vertical transport in the polar troposphere, Atmos. Chem. Phys., 4, 2427–2440, 2004.

Leser, H., Hoeninger, G., and Platt, U.: Max-DOAS measurements of BrO and NO2 in the marine boundary layer, Geophys. Res. Lett., 31, 1537, doi:10.1029/2002GL015811, 2003.

Matveev, V., Hebestreit, K., Peleg, M., Rosen, D. S., Tov-Alper, D., Stutz, J., Platt, U., Blake, D., and Luria, M.: Bromine Oxide- Ozone interaction over the Dead Sea, J. Geophys. Res., 106(D10), 10 375–10 387, 2001.

Michalowski, B. A., Francisco, J. S., Li, S. M., Barrie, L. A., Bottenheim, J. W., and Shepson, P. B.: A computer model study of multiphase chemistry in the Arctic boundary layer during polar sunrise, J. Geophys. Res., 105(D12), 25 355–25 368, 2000.

Morin, S., Savarino, J., Bekki, S., Gong, S., and Bottenheim, J. W.: Signature of Arctic surface ozone depletion events in the isotope anomaly ($\Delta ^17$O) of atmospheric nitrate, Atmos. Chem. Phys., 7, 1451–1469, 2007.

Mozurkewich, M.: Mechanisms for the release of halogens from sea-salt particles by free radical reactions, J. Geophys. Res, 100(D7), 14 199–14 207, 1995.

Murayama, S., Nakazawa, T., Tanaka, M., Aoki, S., and Kawaguchi, S.: Variations of tropospheric ozone concentrations over Syowa Station, Antarctica, Tellus, 44B, 262–272, 1992.

Platt, U. and Hoenninger, G.: The role of halogen species in the troposphere, Chemosphere, 52, 325–358, 2003.

Platt, U. and Moortgat, G. K.: Heterogeneous and Homogeneous Chemistry of Reactive Halogen Compounds in the Lower Troposphere, J. Atmos. Chem., 34, 1–8, 1999.

Pszenny, A. A. P., Moldanova, J., Keene, W. C., Sander, R., Maben, J. R., Martinez, M., Crutzen, P. J., Perner, D., and Prinn, R. G.: Halogen cycling and aerosol pH in the Hawaiian boundary layer, Atmos. Chem. Phys., 4, 147–168, 2004.

Ridley, B. A. and Orlando, J. J.: Active Nitrogen Surface Ozone Depletion Events at Alert during Spring 1998, J. Atmos. Chem., 44, 1–22, 2003.

Sander, R., Vogt, R., Harris, G. W., and Crutzen, P. J.: Modeling the chemistry of ozone, halogen compounds, and hydrocarbons in the Arctic troposphere during spring, Tellus, 49B, 522–532, 1997.

Sander, R., Rudich, Y., von Glasow, R., and Crutzen, P. J.: The role of BrNO3 in marine tropospheric chemistry: A model study, Geophys. Res. Lett., 26, 2857–2860, 1999.

Stutz, J., Hebestreit, K., Alicke, B., and Platt, U.: Chemistry of halogen oxides in the troposphere: comparison of model calculations with recent field data, J. Atmos. Chem., 34, 65–85, 1999.

Stutz, J., Ackermann, R., Fast, J. D., and Barrie, L.: Atmospheric reactive chlorine and bromine at the Great Salt Lake, Utah, Geophys. Res. Lett., 29, 1380, doi:10.1029/2002GL014812, 2002.

Tang, T. and McConnell, J. C.: Autocatalytic release of bromine from Arctic snow pack during polar sunrise, Geophys. Res. Lett., 23(19), 2633–2636, 1996.

Tas, E., Matveev, V., Zingler, J., Luria, M., and Peleg, M.: Frequency and extent of ozone destruction episodes over the Dead Sea, Israel, Atmos. Environ., 37(34), 4769–4780 ,2003.

Tas, E., Peleg, M., Matveev, V., Zingler, J., and Luria, M.: Frequency and extent of bromine oxide formation over the Dead Sea, J. Geophys. Res., 110(D11), D11304, doi:10.1029/2004JD005665, 2005.

Tas, E., Peleg, M, Pedersen, D. U., Matveev, V., Biazar, A. P., and Luria, M.: Measurement-based modeling of bromine chemistry in the boundary layer: 1. Bromine chemistry at the Dead Sea, Atmos. Chem. Phys., 6, 5589–5604, 2006.

Trainer, M., Williams, E. J., Parish, D. D., Buhr, M. P., Allwine, E. J., Westberg, H. H., Fehsenfeld, F. C., and Liu, S. C.: Models and observations of the impact of natural hydrocarbons on rural ozone, Nature, 329, 705–707, 1987.

Tuckermann, M., Ackermann, R., Golz, C., Lorenzen-Schmidt, H., Senne, T., Stutz, J., Trost, B., Unold, W., and Platt, U.: DOAS-Observation of Halogen Radical-catalysed Arctic Boundary Layer Ozone Destruction During the ARCTOC-Campaigns 1995 and 1996 in Ny-Alesund, Spitsbergen, Tellus, 49B, 533–555, 1997.

Vogt, R., Crutzen, P. J., and Sander, R.: A mechanism for halogen release from sea-salt aerosol in the remote marine boundary layer, Nature, 383, 327–330, 1996.

von Glasow, R., Sander, R., Bott, A., and Crutzen, P. J.: Modeling halogen chemistry in the marine boundary layer 1. Cloud-free MBL, J. Geophys. Res., 107(D17), 4341–4352, 2002.

von Glasow, R., Lawrence, M. G., Sander, R., and Crutzen, P. J.:Modeling the chemical effects of ship exhaust in the cloud-free marine boundary layer, Atmos. Chem. Phys., 3, 233–250, 2003.

Wessel, S., Aoki, S., Winkler, P., Weller, R., Herber, A., Gernandt, H., and Schrems, O.: Tropospheric ozone depletion in Polar regions: A comparison of observations in the Arctic and Antarctic,Tellus 50B, 34–50, 1998.