Emission of bromine and iodine from Mount Etna volcano

Constraining fluxes of volcanic bromine and iodine to the atmosphere is important given the significant role these species play in ozone depletion. However, very few such measurements have been made hitherto, such that global volcanic fluxes are poorly constrained. Here we extend the data set of volcanic Br and I degassing by reporting the first measurements of bromine and iodine emissions from Mount Etna.
These data were obtained using filter packs and contemporaneous ultraviolet spectroscopic SO2 flux measurements, resulting in time-averaged emission rates of 0.7 kt yr 1 and 0.01 kt yr 1 for Br and I,
respectively, from April to October 2004, from which we estimate global Br and I fluxes of order 13 (range, 3â 40) and 0.11 (range, 0.04â 6.6) kt yr 1. Observed changes in plume composition highlight the coherent geochemical behavior of HCl, HF, HBr, and HI during magmatic degassing, and strong fractionation of these species with respect to SO2.

Aiuppa, A., C. Federico, A. Paonita, G. Pecoraino, and M. Valenza (2002), S, Cl and F degassing as an indicator of volcanic dynamics: The 2001 eruption of Mount Etna, Geophys. Res. Lett., 29(11), 1559, doi:10.1029/2002GL015032.


Aiuppa, A., M. Burton, F. Mure`, and S. Inguaggiato (2004a), Intercomparison of volcanic gas monitoring methodologies performed on Vulcano Island, Italy, Geophys. Res. Lett., 31, L02610, doi:10.1029/2003GL018651.

Aiuppa, A., C. Federico, G. Giudice, S. Gurrieri, A. Paonita, and M. Valenza (2004b), Plume chemistry provides insights into the mechanisms of sulfur and halogen degassing at basaltic volcanoes, Earth Planet. Sci. Lett., 222, 469-483.

Allard, P. (1997), Endogenous magma degassing and storage at Mount Etna, Geophys. Res. Lett., 24, 2219-2222.

Allard, P., et al. (1991), Eruptive and diffuse emissions of CO2 from Mount Etna, Nature, 351, 387-391.

Allard, P., M. Burton, and F. Mure` (2004), Spectroscopic evidence for a lava fountain driven by previously accumulated magmatic gases, Nature, 433, 407-410.

Andres, R. J., and A. D. Kasgnoc (1998), A time-averaged inventory of subaerial volcanic sulfur emissions, J. Geophys. Res., 103(D19), 25,251-262.

Berresheim, H., and W. Jaeschke (1983), The contribution of volcanoes to the global atmospheric sulfur budget, J. Geophys. Res., 88, 3732-3740.

Bluth, G. J. S., C. C. Schnetzler, A. J. Kreuger, and L. S. Walter (1993), The contribution of explosive volcanism to global sulfur dioxide concentrations, Nature, 366, 327-329.

Bobrowski, N., G. Ho¨nninger, B. Galle, and U. Platt (2003), Detection of bromine monoxide in a volcanic plume, Nature, 423, 273-276.

Bobrowski, N., I. Louban, O. I. Whaba, A. Aiuppa, and S. Inguaggiato (2005), Halogen chemistry in a volcanic plume, Geophys. Res. Abstr., 7, 09701.

Bureau, H., H. Keppler, and N. Metrich (2000), Volcanic degassing of bromine and iodine: Experimental fluid/melt partitioning data and applications to stratospheric chemistry,
Earth. Planet. Sci. Lett., 183, 51-90.

Cadle, R. D. (1975), Volcanic emissions of halides and sulfur compounds to the troposphere and stratosphere, J. Geophys. Res., 80, 1650-1652.

Cadle, R. D. (1980), A comparison of volcanic with other fluxes of atmospheric trace gas constituents, Rev. Geophys., 18, 746-752.

Caltabiano, T., M. Burton, S. Giammanco, P. Allard, N. Bruno, F. Mure`, and R. Romano (2004), Volcanic gas emissions from the summit craters and flanks of Mt. Etna, 1987-2000, in Mt. Etna: Volcano Laboratory, Geophys. Monogr. Ser., vol. 143, edited by A. Bonaccorso et al., pp. 111-128,AGU, Washington, D. C.

Carroll, M. R., and J. D. Webster (1994), Solubilities of sulfur,noble gases, nitrogen, chlorine and fluorine in magmas, in Volatiles in Magmas, edited by M. R. Carroll and J. R. Halloway, Rev. Mineral., 30, 231-279.

Coffey, M. T. (1996), Observation of the impact of volcanic activity on stratospheric chemistry, J. Geophys. Res., 101,6767-6780.

Daniel, J. S., S. Solomon, R. W. Portmann, and R. R. Garcia (1999), Stratospheric ozone estruction: The importance of bromine relative to chlorine, J. Geophys. Res., 104, 23,871-880.

Francis, P., M. R. Burton, and C. Oppenheimer (1998), Remote measurements of volcanic gas compositions by solar occultation spectroscopy, Nature, 396, 567-570.

Galle, B., C. Oppenheimer, A. Geyer, A. J. S. McGonigle, M. Edmonds, and L. A. Horrocks (2003), A miniaturised ultraviolet spectrometer for remote sensing of SO2 fluxes: A new tool for volcano surveillance, J. Volcanol. Geotherm. Res., 119, 241-254.

Gerlach, T. M. (1991), Present-day CO2 emissions from volcanoes, Eos Trans. AGU, 72, 249, 254-255.

Gerlach, T. M. (2004), Volcanic sources of tropospheric ozonedepleting trace gases, Geochem. Geophys. Geosyst., 5,Q09007,doi:10.1029/2004GC000747.

Goff, F., and G. M. McMurtry (2000), Tritium and stable isotopes of magmatic water, J. Volcanol. Geotherm. Res., 97,347-396.

Halmer, M. M., H.-U. Schmincke, and H.-F. Graf (2002), The annual volcanic gas input into the atmosphere, in particular into the stratosphere: A global data set for the past 100 years,
J. Volcanol. Geotherm. Res., 115, 511-528.

Hilton, D. R., T. P. Fischer, and B. Marty (2002), Noble gases in subduction zones and volatile recycling, in Noble Gases in Geochemistry and Cosmochemistry, Rev. Mineral. Geochem.,vol. 47, edited by C. Ballentine, D. Porcelli, and R. Wieler, pp. 319-362, Mineral. Soc. of Am., Washington, D. C.

Hinkley, T. K., P. J. Lamothe, S. A. Wilson, D. L. Finnegan, and T. M. Gerlach (1999), Metal emissions from Kilauea, and a suggested revision of the estimated world-wide metal output by quiescent degassing of volcanoes, Earth Planet. Sci. Lett., 170, 315-325.

Honda, F. (1970), Geochemical study of iodine in volcanic gases. II. Behaviour of iodine in volcanic gases, Geochem. J., 3, 201-211.

Honda, F., Y. Mizutani, T. Sugiura, and S. Oana (1966), A geochemical study of iodine in volcanic gases, Bull. Chem. Soc. Jpn., 39, 2690-2695.

Khalil, M. A., R. A. Rasmussen, and R. Gunawardena (1993), Atmospheric methyl bromide emissions: Trends and global mass balance, J. Geophys. Res., 98, 2887-2896.

Mather, T., D. M. Pyle, and C. Oppenheimer (2003),
Tropospheric volcanic aerosols, in Volcanism and the Earth-Atmosphere, Geophys. Monogr. Ser., vol. 139, edited by A. Robock and C. Oppenheimer, pp. 189-212, AGU,Washington, D. C.

McElroy, M. B., R. J. Salawitch, S. C. Wofsy, and J. A. Logan (1986), Reduction of Antarctic ozone due to synergistic interactions of chlorine and bromine, Nature, 321, 759-762.

McGonigle, A. J. S., C. Oppenheimer, A. R. Hayes, B. Galle, M. Edmonds, T. Caltabiano, G. Salerno, M. Burton, and T. A. Mather (2003), Sulphur dioxide fluxes from Mount Etna, Vulcano, and Stromboli measured with an automated scanning ultraviolet spectrometer, J. Geophys. Res., 108(B9), 2455, doi:10.1029/2002JB002261.

Métrich, N., and R. Clocchiatti (1996), Sulfur abundance and its speciation in oxidized alkaline melts, Geochim. Cosmochim. Acta, 60, 4151-4160.

Muranatsu, Y., and K. H. Wedepohl (1998), The distribution of iodine in the Earth's crust, Chem. Geol., 147, 201-216.

Nriagu, J. O. (1989), A global assessment of natural sources of atmospheric trace metals, Nature, 338, 47-49.

Pyle, D. M., and T. A. Mather (2003), The importance of volcanic emissions for the global atmospheric mercury cycle, Atmos. Environ., 37, 5115-5124.

Sachs, P. M., and E. Harms (1998), The injection of bromine into the atmosphere by the plinian Laacher See eruption (Germany), 12000 BP relevance for the global stratospheric layer, Eos Trans. AGU, 79(45), Fall Meet. Suppl., F936.

Schauffler, S. M., E. L. Atlas, F. Klocke, R. A. Lueb, V. Stroud, and W. Travnicek (1998), Measurements of bromine-containing organic compounds at the tropical troposphere, Geophys. Res. Lett., 25, 317-320.

Schwandner, F. M., T. M. Seward, A. P. Gize, P. A. Hall, and V. J. Dietrich (2004), Diffuse emission of organic trace gases from the flank and crater of a quiescent active volcano (Vulcano, Aeolian Islands, Italy), J. Geophys. Res., 109, D04301, doi:10.1029/2003JD003890.

Shallcross, D. E., K.-Y. Wang, and C. H. Dimmer (2003), Biogeochemical cycles and residence times, in Handbook of Atmospheric Science, edited by C. N. Hewitt and A. Jackson, Blackwell, Malden, Mass.

Snyder, G. T., and U. Fehn (2002), Origin of iodine in volcanic fluids: 129I results from the Central American volcanic arc, Geochim. Cosmochim. Acta, 21, 3827-3838.

Snyder, G. T., U. Fehn, and F. Goff (2002), Iodine isotope ratios and halide concentrations in fluids of The Satsuma-Iwojima volcano, Japan, Earth Planets Space, 54, 265-273.

Stoiber, R. E., S. N. Williams, and B. Huebert (1987), Annual contribution of sulphur dioxide to the atmosphere by volcanoes, J. Volcanol. Geotherm. Res., 33, 1-8.

Sugiura, T., Y. Mizutani, and S. Oana (1963), Fluorine, chlorine, bromine and iodine in volcanic gases, J. Earth. Sci. Nagoya Univ., 11, 272.

Symonds, R., W. I. Rose, and M. H. Reed (1988), Contribution of Cl- and F-bearing gases to the atmosphere by volcanoes, Nature, 334, 415-418.

Symonds, R., Y. Mizutani, and P. H. Briggs (1996), Long term geochemical surveillance of fumaroles of Showa-Shinzan dome, Usu volcano, Japan, J. Volcanol. Geotherm. Res., 73, 177-211.

Tedesco, D., and J. P. Toutain (1991), Chemistry and emission rate of volatiles from white Island volcano (New Zealand), Geophys. Res. Lett., 18, 113-116.

von Glasow, R., and P. J. Crutzen (2003), Tropospheric halogen chemistry, in Treatise on Geochemistry, vol. 4, edited by R. F. Keeling, pp. 88-132, Elsevier, New York.

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

Williams, S. N., S. J. Schaefer, V. Calvache, and D. Lopez (1992), Global carbon dioxide emission to the atmosphere by volcanoes, Geochim. Cosmochim. Acta, 56, 1765-1770.

Yung, Y. L., J. P. Pinto, R. T. Watson, and S. P. Sander (1980), Atmospheric bromine and ozone perturbations in the lower stratosphere, J. Atmos. Sci., 37, 339-353.