References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-6-5589-2006

Measurement-based modeling of bromine chemistry in the boundary layer: 1. Bromine chemistry at the Dead Sea

Tas

¹ Peleg

¹ Pedersen

D. U.

¹ Matveev

¹ Pour Biazar

² Luria

Institute of Earth Sciences, Hebrew University of Jerusalem, Israel

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

14 12 2006

6 12 5589 5604

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.net/6/5589/2006/acp-6-5589-2006.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/6/5589/2006/acp-6-5589-2006.pdf

The Dead Sea is an excellent natural laboratory for the investigation of Reactive Bromine Species (RBS) chemistry, due to the high RBS levels observed in this area, combined with anthropogenic air pollutants up to several ppb. The present study investigated the basic chemical mechanism of RBS at the Dead Sea using a numerical one-dimensional chemical model. Simulations were based on data obtained from comprehensive measurements performed at sites along the Dead Sea. The simulations showed that the high BrO levels measured frequently at the Dead Sea could only partially be attributed to the highly concentrated Br− present in the Dead Sea water. Furthermore, the RBS activity at the Dead Sea cannot solely be explained by a pure gas phase mechanism. This paper presents a chemical mechanism which can account for the observed chemical activity at the Dead Sea, with the addition of only two heterogeneous processes: the "Bromine Explosion" mechanism and the heterogeneous decomposition of BrONO2. Ozone frequently dropped below a threshold value of ~1 to 2 ppbv at the Dead Sea evaporation ponds, and in such cases, O3 became a limiting factor for the production of BrOx (BrO+Br). The entrainment of O3 fluxes into the evaporation ponds was found to be essential for the continuation of RBS activity, and to be the main reason for the jagged diurnal pattern of BrO observed in the Dead Sea area, and for the positive correlation observed between BrO and O3 at low O3 concentrations. The present study has shown that the heterogeneous decomposition of BrONO2 has a great potential to affect the RBS activity in areas influenced by anthropogenic emissions, mainly due to the positive correlation between the rate of this process and the levels of NO2. Further investigation of the influence of the decomposition of BrONO2 may be especially important in understanding the RBS activity at mid-latitudes.

References 1

Aranda, A., Bras, G. L., LaVerdet, G., and Poulet, G.: The BrO + CH3O2 reaction: kinetics and role in the atmospheric ozone budget, Geophys. Res. Lett., 24, 2745–2748, 1997.

Andreae, T. W., Andreae, M. O., Ichoku, C., Maenhaut, W., Cafmeyer, J., Karnieli, A., and Orlovsky, L.: Light scattering by dust and anthropogenic aerosol at remote site in the Negev desert, Israel, J. Geophys. Res., 107(D2), 4008, doi:10.1029/2001JD900252, 2002.

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/, 2002.

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.

Bedjanian, Y., Riffault, V., Le Bras, G., and Poulet, G.: Kinetics and Mechanism of the OH and OD Reactions with BrO, J. Phys. Chem. A, 105, 6154–6166, 2001.

Behnke, W., Elend, M., Kruger, U., and Zetzsch, C.: The Influence of NaBr/NaCl Ratio on the Br -Catalysed Production of Halogenated Radicals, J. Atmos. Chem., 34, 87–99, 1999.

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.

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.

Bloss, W. J., Rowley, D. M., Cox, R. A., and Jones, L. J.: Rate coefficient for the BrO+HO2 raction at 298 K, Phys. Chem. Chem. Phys, 3639–3647, 2002.

Evans, M. J., Jacob, D. J., Atlas, E., Cantrell, C. A., Eisele, F., Flocke, F., Fried, A., Mauldin, R. L., Ridley, B. A., Wert, B., Talbot, R., Blake, D., Heikes, B., Snow, J., Welega, J., Weinheimer, A. J., and Dibb, J.: Coupled evolution of BrOX-ClOX-HOX-NOX chemistry during bromine-catalyzed ozone depletion events in the arctic boundary layer, J. Geophys. Res., 108(D4), 8368, doi:10.1029/2002JD002732, 2003.

Erlick, C. and Frederick, E.: Effects of aerosols on the wavelength dependence of the atmospheric transmission in the ultraviolet and visible 2. Continental and urban aerosols in clear skies, J. Geophys. Res., 103(D18), 23 275–23 285, 1998.

Fan, S.-M. and Jacob, D. J.: Surface ozone depletion in Arctic spring sustained by bromine reactions on aerosols, Nature, 359, 522–524, 1992.

Fickert, S., Adams, J. W., and Crowley, J. N.: Activation of Br2 and BrCl via uptake of HOBr onto aqueous salt solutions, J. Geophys. Res., 04(D19), 23 719–23 727, 1999.

Formenti, P., Andreae, M. O., Andreae, T. W., Ichoku, C., Schebeske G., Kettle, J., Maenhaut, W., Ptasinsky, J., Karnieli A., and Leliveld, J.: Physical and chemical characteristics of aerosols over the Negev Desert (Israel) during summer 1996, J. Geophys. Res., 106(D5), 4871–4890, 2001.

Gilles, M. K., McCabe, D. C., Burkholder, J. B., and Ravishankara, A. R.: Measurement of the Rate Coefficient for the Reaction of OH with BrO, J. Phys. Chem. A., 105, 5849–5853, 2001.

Gong, S. L., Barrie, L. A., and Blanchey, J.-P.: Modeling sea-salt aerosols in the atmosphere 1. Model development, J. Geophys. Res., 102(D3), 3805–3818, 1997.

Gras, J. L. and Ayers, G. P.: marine aerosol at southern mid-latitudes, J. Geophys. Res., 88(C15), 10 661–10 666, 1983.

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.

Hanson, D. R., Ravishankara, A. R., and Lovejoy, E. R.: Reaction of BrONO2 with H2O on submicron sulfuric acid aerosol and implications for the lower stratosphere, J. Geophys. Res., 101(D4), 9063–9069, 1996.

Harry, S., Peter, K., and Ruggaber, A.: Uncertaities in modeled UV irradiancesdue to limited accuracy and availability of input data, J. Geophys. Res., 102(D8), 9419–9429, 1997.

Harwood, M. H. and Burkholder, J. B.: Photodissociation of BrONO2 and N2O$_5$: Quantum yields for NO3 production at 248, 308, and 352.5 nm, J. Phys. Chem. A., 102(8), 1309–1317, 1998.

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.

Honninger, 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.

Leser, H., Honinger, 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.

Li, Z. and Tao, Z.: A kinetic study on reactions of OBrO with NO, OClO, and ClO at 298 K, Cem. Phys. Lett., 306, 17–123, 1999.

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

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.

McNider, R. T. and Pielke, R. A.: Diurnal boundary-layer development over sloping terrain, J. Atmos. Sci., 38, 2198–2212, 1981.

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, 15 131–15 145, 2000.

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.

Niemi, T. M., Ben-Avraham, Z., and Gat, J. R.: The Dead Sea: The Lake and Its Setting, Oxford Monogr. Geol. Geophys., vol. 36, Oxford Univ. Press, New York, 1997.

Platt, U. and Honninger, 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., and Crutzen, P. J.: 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.

Ruggaber, A., Dulgi, R., and Nakajima, T.: Modelling Radiation Quantities and Photolysis Frequencies in the Troposphere, J. Atmos. Chem., 18, 171–210, 1994.

Sander, R. and Crutzen, P. J.: Model study indicating halogen activation and ozone destruction in polluted air masses transported to the sea, J. Geophys. Res., 101(D4), 9121–9138, 1996.

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(18), 2857–2860, 1999.

Schwander, H., Koepke, P., and Ruggaber, A.: Uncertainties in modeled UV irradiances due to limited accuracy and availability of input data, J. Geophys. Res., 102, 9419–9429, 1997.

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.

Sverdrup, H. U., Johnson, M. W., and Fleming, R. H.: The Oceans, Their Physics, Chemistry and General Biology, Prentice-Hal, Englewood Cliffs, N. J., 1942.

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.

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., von Kuhlman, 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.

Wanger, A., Peleg, M., Sharf, G., Mahrer, Y., Dayan, U., Kallos, G., Kotroni, V., Lagouvardos, K., Varinou, M., Papadopoulos, A., and Luria, M.: Some observational and modeling evidence of long-range transport of air pollutants from Europe toward Israeli coast, J. Geophys. Res., 105(D6), 7177–7186, 2000.

Wayne, R. P., Poulet, G., Biggs, P., Burrows, J. P., Cox, R. A., Crutzen, P. J., Haymann, G. D., Jenkin, M. E., Bras, G. L., Moortgat, G. K., Platt, U., and Schindler, R. N.: Halogen oxides: radicals, sources and reservoirs in the laboratory and in the atmosphere, Atmos. Environ., 29, 2675–2884, 1995.

Zingler, J. and Platt, U.: Iodine oxide in the Dead Sea Valley: Evidence for inorganic sources of boundary layer IO, J. Geophys. Res., 110, D07307, doi:10.1029/2004JD004993, 2005.