References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-12-5319-2012

An isotopic analysis of ionising radiation as a source of sulphuric acid

Enghoff

M. B.

¹ Bork

¹ ² ⁴ Hattori

³ Meusinger

⁴ Nakagawa

⁵ Pedersen

J. O. P.

¹ Danielache

³ ⁶ Ueno

⁶ Johnson

M. S.

⁴ Yoshida

³ ⁵ Svensmark

National Space Institute, Technical University of Denmark, 2100, Copenhagen Ø, Denmark

Division of Atmospheric Science, Department of Physics, P.O. Box 64, 00014 University of Helsinki, Finland

Department of Environmental Science and Technology, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Yokohama, 226-8502, Japan

University of Copenhagen, Department of Chemistry, 2100, Copenhagen Ø, Denmark

Department of Environmental Chemistry and Engineering, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Yokohama, 226-8502, Japan

Department of Earth and Planetary Science, Tokyo Institute of Technology, Meguro-ku, Tokyo, 152-8551, Japan

19 06 2012

12 12 5319 5327

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Sulphuric acid is an important factor in aerosol nucleation and growth. It has been shown that ions enhance the formation of sulphuric acid aerosols, but the exact mechanism has remained undetermined. Furthermore some studies have found a deficiency in the sulphuric acid budget, suggesting a missing source. In this study the production of sulphuric acid from SO2 through a number of different pathways is investigated. The production methods are standard gas phase oxidation by OH radicals produced by ozone photolysis with UV light, liquid phase oxidation by ozone, and gas phase oxidation initiated by gamma rays. The distributions of stable sulphur isotopes in the products and substrate were measured using isotope ratio mass spectrometry. All methods produced sulphate enriched in 34S and we find an enrichment factor (δ34S) of 8.7 ± 0.4&permil; (1 standard deviation) for the UV-initiated OH reaction. Only UV light (Hg emission at 253.65 nm) produced a clear non-mass-dependent excess of 33S. The pattern of isotopic enrichment produced by gamma rays is similar, but not equal, to that produced by aqueous oxidation of SO2 by ozone. This, combined with the relative yields of the experiments, suggests a mechanism in which ionising radiation may lead to hydrated ion clusters that serve as nanoreactors for S(IV) to S(VI) conversion.

References 1

Bao, H., Rumble, D., and Lowe, D R.: The five stable isotope compositions of Fig Tree barites: Implications on sulfur cycle in ca. 3.2 Ga oceans, Geochim. Cosmochim. Ac., 71, 4868–4879, http://dx.doi.org/10.1016/j.gca.2007.05.032doi:10.1016/j.gca.2007.05.032, 2007.

Baroni, M., Thiemens, M., Delmas, R., and Savarino, J.: Mass-Independent Sulfur Isotopic Compositions in Stratospheric Volcanic Eruptions, Science, 315, 84–87, http://dx.doi.org/10.1126/science.1131754doi:10.1126/science.1131754, 2007.

Bazilevskaya, G A., Usoskin, I G., Flueckiger, E O., Harrison, R G., Desorgher, L., Buetikofer, R., Krainev, M B., Makhmutov, V S., Stozhkov, Y I., Svirzhevskaya, A K., Svirzhevsky, N S., and Kovaltsov, G A.: Cosmic ray induced ion production in the atmosphere, Space Sci. Rev., 137, 149–173, http://dx.doi.org/10.1007/s11214-008-9339-ydoi:10.1007/s11214-008-9339-y, 2008.

Berndt, T., Böge, O., and Stratmann, F.: Formation of atmospheric \chemH_2SO_4/H_2O particles in the absence of organics: A laboratory study, Geophys. Res. Lett., 33, L15817, http://dx.doi.org/10.1029/2006GL026660doi:10.1029/2006GL026660, 2006.

Bork, N., Kurtén, T., Enghoff, M. B., Pedersen, J. O. P., Mikkelsen, K. V., and Svensmark, H.: Ab initio studies of O$_2^-$(H2O)$_n$ and O$_3^-$(H2O)$_n$ anionic molecular clusters, $n\leq12$, Atmos. Chem. Phys., 11, 7133–7142, http://dx.doi.org/10.5194/acp-11-7133-2011doi:10.5194/acp-11-7133-2011, 2011a.

Bork, N., Kurtén, T., Enghoff, M. B., Pedersen, J. O. P., Mikkelsen, K. V., and Svensmark, H.: Structures and reaction rates of the gaseous oxidation of SO2 by an O$_3^-$(H2O)$_0-5$ cluster – a density functional theory investigation, Atmos. Chem. Phys., 12, 3639–3652, http://dx.doi.org/10.5194/acpd-11-29647-2011doi:10.5194/acpd-11-29647-2011, 2011b.

Boy, M., Kulmala, M., Ruuskanen, T. M., Pihlatie, M., Reissell, A., Aalto, P. P., Keronen, P., Dal Maso, M., Hellen, H., Hakola, H., Jansson, R., Hanke, M., and Arnold, F.: Sulphuric acid closure and contribution to nucleation mode particle growth, Atmos. Chem. Phys., 5, 863–878, http://dx.doi.org/10.5194/acp-5-863-2005doi:10.5194/acp-5-863-2005, 2005.

Brenninkmeijer, C. A M., Janssen, C., Kaiser, J., Röckmann, T., Rhee, T S., and Assonov, S S.: Isotope Effects in the Chemistry of Atmospheric Trace Compounds, Chem. Rev., 103, 5125–5162, http://dx.doi.org/10.1021/cr020644kdoi:10.1021/cr020644k, 2003.

Curtius, J.: Nucleation of atmospheric aerosol particles, CR Phys., 7, 1027–1045, http://dx.doi.org/10.1016/j.crhy.2006.10.018doi:10.1016/j.crhy.2006.10.018, 2006.

Danielache, S O., Hattori, S., Johnson, M. S., Ueno, Y., Nanbu, S., and Yoshida, N.: Photoabsorption cross-section measurements of $^32$S, $^33$S, $^34$S and $^36$S sulfur dioxide for the B1B1-X1A1 absorption band, J. Geophys. Res., submitted, 2012.

Danielache, S O., Eskebjerg, C., Johnson, M S., Ueno, Y., and Yoshida, N.: High-precision spectroscopy of $^32$S, $^33$S, and $^34$S sulfur dioxide: Ultraviolet absorption cross sections and isotope effects, J. Geophys. Res., 113, D17314, http://dx.doi.org/10.1029/2007JD009695doi:10.1029/2007JD009695, 2008.

Enghoff, M. B. and Svensmark, H.: The role of atmospheric ions in aerosol nucleation – a review, Atmos. Chem. Phys., 8, 4911–4923, http://dx.doi.org/10.5194/acp-8-4911-2008doi:10.5194/acp-8-4911-2008, 2008.

Enghoff, M B., Pedersen, J. O P., Bondo, T., Johnson, M S., Paling, S., and Svensmark, H.: Evidence for the Role of Ions in Aerosol Nucleation, J. Phys. Chem. A, 112, 10305–10309, http://dx.doi.org/10.1021/jp806852ddoi:10.1021/jp806852d, 2008.

Farquhar, J., Bao, H., and Thiemens, M.: Atmospheric Influence of Earth's Earliest Sulfur Cycle, Science, 289, 756–758, http://dx.doi.org/10.1126/science.289.5480.756doi:10.1126/science.289.5480.756, 2000a.

Farquhar, J., Jackson, T L., and Thiemens, M H.: A $^33$S enrichment in ureilite meteorites: Evidence for a nebular sulfur component, Geochim. Cosmochim. Ac., 64, 1819–1825, http://dx.doi.org/10.1016/S0016-7037(00)00356-2doi:10.1016/S0016-7037(00)00356-2, 2000b.

Farquhar, J., Savarino, J., Airieau, S., and Thiemens, M H.: Observation of wavelength-sensitive mass-independent sulfur isotope effects during SO2 photolysis: Implications for the early atmosphere, J. Geophys. Res., 106, 32829–32839, http://dx.doi.org/10.1029/2000JE001437doi:10.1029/2000JE001437, 2001.

Fehsenfeld, F C. and Ferguson, E E.: Laboratory studies of negative ion reactions with atmospheric trace constituents, J. Chem. Phys., 61, 3181–3193, http://dx.doi.org/10.1063/1.1682474doi:10.1063/1.1682474, 1974.

Forster, P., Ramaswamy, V., Artaxo, P., Berntsen, T., Betts, R., Fahey, D W., Haywood, J., Lean, J., Lowe, D C., Myhre, G., Nganga, J., Prinn, R., Raga, G., Schulz, M., and Van~Dorland, R.: Changes in Atmospheric Constituents and in Radiative Forcing, in: Climate Change 2007: The Physical Science Basis. Contribution of Working Group 1 to the Fourth Assessment Report of the Intergovenrmental Panel on Climate Change, edited by: Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K. B., Tignor, M., and Miller, H. L., Cambridge University Press, 2007.

Gao, Y Q. and Marcus, R A.: Strange and Unconventional Isotope Effects in Ozone Formation, Science, 293, 259–263, http://dx.doi.org/10.1126/science.1058528doi:10.1126/science.1058528, 2001.

Guo, Z., Li, Z., Farquhar, J., Kaufman, A J., Wu, N., Li, C., Dickerson, R R., and Wang, P.: Identification of sources and formation processes of atmospheric sulfate by sulfur isotope and scanning electron microscope measurements, J. Geophys. Res., 115, D00K07, http://dx.doi.org/10.1029/2009JD012893doi:10.1029/2009JD012893, 2010.

Harris, E., Sinha, B., Hoppe, P., Crowley, J N., Ono, S., and Foley, S.: Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis, Atmos. Chem. Phys., 12, 407–424, http://dx.doi.org/10.5194/acp-12-407-2012doi:10.5194/acp-12-407-2012, 2012.

Hirsikko, A., Nieminen, T., Gagne, S., Lehtipalo, K., Manninen, H E., Ehn, M., Horrak, U., Kerminen, V.-M., Laakso, L., McMurry, P H., Mirme, A., Mirme, S., Petaja, T., Tammet, H., Vakkari, V., Vana, M., and Kulmala, M.: Atmospheric ions and nucleation: a review of observations, Atmos. Chem. Phys., 11, 767–798, http://dx.doi.org/10.5194/acp-11-767-2011doi:10.5194/acp-11-767-2011, 2011.

Jefferson, A., Tanner, D J., Eisele, F L., and Berresheim, H.: Sources and sinks of H2SO4 in the remote Antarctic marine, J. Geophys. Res., 103, 1639–1645, http://dx.doi.org/10.1029/97JD01212doi:10.1029/97JD01212, 1998.

Johnson, M S., Feilberg, K L., von Hessberg, P., and Nielsen, O J.: Isotopic processes in atmospheric chemistry, Chem. Soc. Rev., 31, 313–323, http://dx.doi.org/10.1039/b108011ndoi:10.1039/b108011n, 2002.

Johnston, D T.: Multiple sulfur isotopes and the evolution of Earth's surface sulfur cycle, Earth-Sci. Rev., 106, 161–183, http://dx.doi.org/10.1016/j.earscirev.2011.02.003doi:10.1016/j.earscirev.2011.02.003, 2011.

Kazil, J., Harrison, R G., and Lovejoy, E R.: Tropospheric New Particle Formation and the Role of Ions, Space Sci. Rev., 137, 241–255, http://dx.doi.org/10.1007/s11214-008-9388-2doi:10.1007/s11214-008-9388-2, 2008.

Kirkby, J., Curtius, J., Almeida, J., Dunne, E., Duplissy, J., Ehrhart, S., Franchin, A., Gagne, S., Ickes, L., Kuerten, A., Kupc, A., Metzger, A., Riccobono, F., Rondo, L., Schobesberger, S., Tsagkogeorgas, G., Wimmer, D., Amorim, A., Bianchi, F., Breitenlechner, M., David, A., Dommen, J., Downard, A., Ehn, M., Flagan, R C., Haider, S., Hansel, A., Hauser, D., Jud, W., Junninen, H., Kreissl, F., Kvashin, A., Laaksonen, A., Lehtipalo, K., Lima, J., Lovejoy, E R., Makhmutov, V., Mathot, S., Mikkila, J., Minginette, P., Mogo, S., Nieminen, T., Onnela, A., Pereira, P., Petaja, T., Schnitzhofer, R., Seinfeld, J H., Sipila, M., Stozhkov, Y., Stratmann, F., Tome, A., Vanhanen, J., Viisanen, Y., Vrtala, A., Wagner, P E., Walther, H., Weingartner, E., Wex, H., Winkler, P M., Carslaw, K S., Worsnop, D R., Baltensperger, U., and Kulmala, M.: Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation, Nature, 476, 429–433, http://dx.doi.org/10.1038/nature10343doi:10.1038/nature10343, 2011.

Kulmala, M.: How Particles Nucleate and Grow, Science, 202, 1000–1001, http://dx.doi.org/10.1126/science.1090848doi:10.1126/science.1090848, 2003.

Kurtén, T., Loukonen, V., Vehkamäki, H., and Kulmala, M.: Amines are likely to enhance neutral and ion-induced sulfuric acid-water nucleation in the atmosphere more effectively than ammonia, Atmos. Chem. Phys., 8, 4095–4103, http://dx.doi.org/10.5194/acp-8-4095-2008doi:10.5194/acp-8-4095-2008, 2008.

Leung, F Y., Colussi, A J., and Hoffmann, M R.: Sulfur isotopic fractionation in the gas-phase oxidation of sulfur dioxide initiated by hydroxyl radicals, J. Phys. Chem. A, 105, 8073–8076, http://dx.doi.org/10.1021/jp011014+doi:10.1021/jp011014+, 2001.

Lovejoy, E R., Curtius, J., and Froyd, K D.: Atmospheric ion-induced nucleation of sulfuric acid and water, J. Geophys. Res., 109, 1–11, http://dx.doi.org/10.1029/2003JD004460doi:10.1029/2003JD004460, 2004.

Manninen, H E., Nieminen, T., Asmi, E., Gagne, S., Hakkinen, S., Lehtipalo, K., Aalto, P., Vana, M., Mirme, A., Mirme, S., Horrak, U., Plass-Duelmer, C., Stange, G., Kiss, G., Hoffer, A., Toeroe, N., Moerman, M., Henzing, B., de~Leeuw, G., Brinkenberg, M., Kouvarakis, G N., Bougiatioti, A., Mihalopoulos, N., O'Dowd, C., Ceburnis, D., Arneth, A., Svenningsson, B., Swietlicki, E., Tarozzi, L., Decesari, S., Facchini, M C., Birmili, W., Sonntag, A., Wiedensohler, A., Boulon, J., Sellegri, K., Laj, P., Gysel, M., Bukowiecki, N., Weingartner, E., Wehrle, G., Laaksonen, A., Hamed, A., Joutsensaari, J., Petaja, T., Kerminen, V M., and Kulmala, M.: EUCAARI ion spectrometer measurements at 12 European sites – analysis of new particle formation events, Atmos. Chem. Phys., 10, 7907–7927, http://dx.doi.org/10.5194/acp-10-7907-2010doi:10.5194/acp-10-7907-2010, 2010.

Müller, R. and Crutzen, P J.: A Possible Role of Galactic Cosmic Rays in Chlorine Activation During Polar Night, J. Geophys. Res., 98, 20483–20490, http://dx.doi.org/10.1029/93JD02455doi:10.1029/93JD02455, 1993.

Ono, S., Eigenbrode, J L., Pavlov, A A., Kharecha, P., Rumble~III, D., Kasting, J F., and Freeman, K H.: New insights into Archean sulfur cycle from mass-independent sulfur isotope records from the Hamersley Basin, Australia, Earth Planet. Sc. Lett., 213, 15–30, http://dx.doi.org/10.1016/S0012-821X(03)00295-4doi:10.1016/S0012-821X(03)00295-4, 2003.

Ono, S., Wing, B., Johnston, D., Farquhar, J., and Rumble, D.: Mass-dependent fractionation of quadruple stable sulfur isotope system as a new tracer of sulfur biogeochemical cycles, Geochim. Cosmochim. Ac., 70, 2238–2252, http://dx.doi.org/10.1016/j.gca.2006.01.022doi:10.1016/j.gca.2006.01.022, 2006.

Pavlov, A A., Mills, M J., and Toon, O B.: Mystery of the volcanic mass-independent sulfur isotope fractionation signature in the Antarctic ice core, Geophys. Res. Lett., 32, L12816, http://dx.doi.org/10.1029/2005GL022784doi:10.1029/2005GL022784, 2008.

Raes, F., Janssens, A., and Eggermont, G.: A synergism between ultraviolet and gamma radiation in producing aerosol particles from \chemSO_2-H_2SO_4 laden atmospheres, Atmos. Environ., 19, 1069–1073, http://dx.doi.org/10.1016/0004-6981(85)90191-Xdoi:10.1016/0004-6981(85)90191-X, 1985.

Rees, C E.: Steady-state model for sulfur isotope fractionation in bacterial reduction processes, Geochim. Cosmochim. Ac., 37, 1141–1162, http://dx.doi.org/10.1016/0016-7037(73)90052-5doi:10.1016/0016-7037(73)90052-5, 1973.

Romero, A B. and Thiemens, M H.: Mass-independent sulfur isotopic compositions in present-day sulfate aerosols, J. Geophys. Res., 108, 4524, http://dx.doi.org/10.1029/2003JD003660doi:10.1029/2003JD003660, 2003.

Sakai, H., Des~Marais, D J., Ueda, A., and Moore, J G.: Concentrations and isotope ratios of carbon, nitrogen and sulfur in ocean-floor basalts, Geochim. Cosmochim. Ac., 48, 2433–2441, http://dx.doi.org/10.1016/0016-7037(84)90295-3doi:10.1016/0016-7037(84)90295-3, 1984.

Schmidt, J A., Johnson, M S., and Schinke, R.: Isotope effects in N2O photolysis from first principles, Atmos. Chem. Phys., 11, 8965–8975, http://dx.doi.org/10.5194/acp-11-8965-2011doi:10.5194/acp-11-8965-2011, 2011.

Seinfeld, J H. and Pandis, S N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, Second Edn., John Wiley and Sons, 2006.

Sipilä, M., Berndt, T., Petaja, T., Brus, D., Vanhanen, J., Stratmann, F., Patokoski, J., Mauldin, III, R L., Hyvarinen, A.-P., Lihavainen, H., and Kulmala, M.: The Role of Sulfuric Acid in Atmospheric Nucleation, Science, 327, 1243–1246, http://dx.doi.org/10.1126/science.1180315doi:10.1126/science.1180315, 2010.

Svensmark, H., Pedersen, J. O P., Marsh, N D., Enghoff, M B., and Uggerhøj, U I.: Experimental evidence for the role of ions in particle nucleation under atmospheric conditions, P. Roy. Soc. Lond. A Mat., 463, 385–396, http://dx.doi.org/10.1098/rspa.2006.1773doi:10.1098/rspa.2006.1773, 2007.

Tanaka, N., Rye, D M., Xiao, Y., and Lasag, A C.: Use of stable sulfur isotope systematics for evaluating oxidation reaction pathways and in-cloud-scavenging of sulfur-dioxide in the atmosphere, Geophys. Res. Lett., 21, 1519–1522, http://dx.doi.org/10.1029/94GL00893doi:10.1029/94GL00893, 1994.

Thiemens, M H.: History and Applications of Mass-Independent Isotope Effects, Annu. Rev. Earth. Pl. Sc., 34, 217–262, http://dx.doi.org/10.1146/annurev.earth.34.031405.125026doi:10.1146/annurev.earth.34.031405.125026, 2006.

Ueno, Y., Ono, S., Rumble, D., and Maruyama, S.: Quadruple sulfur isotope analysis of ca. 3.5 Ga Dresser Formation: New evidence for microbial sulfate reduction in the Early Archean, Geochim. Cosmochim. Ac., 72, 5675–5691, http://dx.doi.org/10.1016/j.gca.2008.08.026doi:10.1016/j.gca.2008.08.026, 2008.

Ueno, Y., Johnson, M S., Danielache, S O., Eskebjerg, C., Pandey, A., and Yoshida, N.: Geological sulfur isotopes indicate elevated OCS in the Archean atmosphere, solving faint young sun paradox, P. Natl. Acad. Sci. USA, 106, 14784–14789, http://dx.doi.org/10.1073/pnas.0903518106doi:10.1073/pnas.0903518106, 2009.

Yu, F. and Turco, R P.: Ultrafine aerosol formation via ion-mediated nucleation, Geophys. Res. Lett., 27, 883–886, http://dx.doi.org/10.1029/1999GL011151doi:10.1029/1999GL011151, 2000.

Yu, F. and Turco, R P.: From molecular clusters to nanoparticles: Role of \mboxambient ionization in tropospheric aerosol formation, J. Geophys. Res., 106, 4797–4814, http://dx.doi.org/10.1029/2000JD900539doi:10.1029/2000JD900539, 2001.

Zatula, A S., Andersson, P U., Ryding, M J., and Uggerud, E.: Proton mobility and stability of water clusters containing the bisulfate anion, HSO$_4^-$(H2O)$_n$, Phys. Chem. Chem. Phys., 13, 13287–13294, http://dx.doi.org/10.1039/c1cp21070jdoi:10.1039/c1cp21070j, 2011.