References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-12-407-2012

Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

Harris

¹ Sinha

¹ ² Hoppe

¹ Crowley

J. N.

³ Ono

⁴ Foley

⁵

Abteilung Partikelchemie, Max-Planck-Institut für Chemie, Becherweg 27, 55128 Mainz, Germany

Department of Earth Sciences, IISER Mohali, Sector 81, SAS Nagar, Manauli P.O. 140306, India

Abteilung Luftchemie, Max-Planck-Institut für Chemie, Becherweg 27, 55128 Mainz, Germany

Department of Earth, Atmospheric, and Planetary Sciences, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA

Earth System Science Research Center, Institute for Geosciences, University of Mainz, Becherweg 21, 55128 Mainz, Germany

06 01 2012

12 1 407 423

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The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007)−((4±5)×10−5) T(°C). The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019)−((8.7±3.5) ×10−5)T(°C). The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV) in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043) at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

References 1

Alexander, B., Savarino, J., Barkov, N I., Delmas, R J., and Thiemens, M H.: Climate driven changes in the oxidation pathways of atmospheric sulfur, Geophys. Res. Lett., 29, 1685, http://dx.doi.org/10.1029/2002GL014879doi:10.1029/2002GL014879, 2002.

Alexander, B., Thiemens, M H., Farquhar, J., Kaufman, A J., Savarino, J., and Delmas, R J.: East Antarctic ice core sulfur isotope measurements over a complete glacial-interglacial cycle, J. Geophys. Res.-Atmos., 108, 4786, http://dx.doi.org/10.1029/2003JD003513doi:10.1029/2003JD003513, 2003.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I –gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, http://dx.doi.org/10.5194/acp-4-1461-2004doi:10.5194/acp-4-1461-2004, 2004.

Baroni, M., Thiemens, M H., Delmas, R J., and Savarino, J.: Mass-independent sulfur isotopic compositions in stratospheric volcanic eruptions, Science, 315, 84–87, 2007.

Baroni, M., Savarino, J., Cole-Dai, J H., Rai, V K., and Thiemens, M H.: Anomalous sulfur isotope compositions of volcanic sulfate over the last millennium in Antarctic ice cores, J. Geophys. Res.-Atmos., 113, D20112, http://dx.doi.org/10.1029/2008JD010185doi:10.1029/2008JD010185, 2008.

Benson, D R., Young, L H., Kameel, F R., and Lee, S H.: Laboratory-measured nucleation rates of sulfuric acid and water binary homogeneous nucleation from the SO2 + OH reaction, Geophys. Res. Lett., 35, L11801, http://dx.doi.org/10.1029/2008GL033387doi:10.1029/2008GL033387, 2008.

Berresheim, H., Elste, T., Tremmel, H G., Allen, A G., Hansson, H C., Rosman, K., Dal~Maso, M., Makela, J M., Kulmala, M., and O'Dowd, C D.: Gas-aerosol relationships of H2SO4, MSA, and OH: Observations in the coastal marine boundary layer at Mace Head, Ireland, J. Geophys. Res.-Atmos., 107, 8100, http://dx.doi.org/10.1029/2000JD000229doi:10.1029/2000JD000229, 2002.

Bevington, P. and Robinson, D.: Data Reduction and Error Analysis for the Physical Sciences, Mc-Graw Hill, 23–28, 1992.

Botha, C F., Hahn, J., Pienaar, J J., and Vaneldik, R.: Kinetics and mechanism of the oxidation of sulfur(IV) by ozone in aqueous solutions, Atmos. Environ., 28, 3207–3212, 1994.

Bower, K N. and Choularton, T W.: Cloud processing of the Cloud Condensation Nucleus spectrum and its climatological consequences, Q. J. Roy. Meteorol. Soc., 119, 655–679, 1993.

Calhoun, J. A., Bates, T. S. and Charlson, R. J.: Sulfur Isotope Measurements of Submicrometer Sulfate Aerosol-Particles over the Pacific-Ocean. Geophys. Res. Lett., 18, 1877–1880, 1991.

Cantrell, C A., Zimmer, A., and Tyndall, G S.: Absorption cross sections for water vapor from 183 to 193 nm, Geophys. Res. Lett., 24, 2195–2198, 1997.

Caron, F., Tessier, A., Kramer, J R., Schwarcz, H P., and Rees, C E.: Sulfur and oxygen isotopes of sulfate in precipitation and lakewater, Quebec, Canada, Appl. Geochem., 1, 601–606, 1986.

Castleman, A W., Munkelwitz, H R., and Manowitz, B.: Isotopic Studies of Sulfur Component of Stratospheric Aerosol Layer, Tellus, 26, 222–234, 1974.

Chin, M., Jacob, D J., Gardner, G M., ForemanFowler, M S., Spiro, P A., and Savoie, D L.: A global three-dimensional model of tropospheric sulfate, J. Geophys. Res.-Atmos., 101, 18667–18690, 1996.

Chmielewski, A G., Derda, M., Wierzchnicki, R., and Mikolajczuk, A.: Sulfur isotope effects for the SO2(g)-SO2(aq) system, Nukleonika, 47, S69–S70, 2002.

Derda, M., Chmielewski, A. G., and Licki, J.: Sulphur isotope compositions of components of coal and S-isotope fractionation during its combustion and flue gas desulphurization, Isotopes in Environmental and Health Studies, 43, 57-63, 2007.

Ding, T., Valkiers, S., Kipphardt, H., De~Bievre, P., Taylor, P. D P., Gonfiantini, R., and Krouse, R.: Calibrated sulfur isotope abundance ratios of three IAEA sulfur isotope reference materials and V-CDT with a reassessment of the atomic weight of sulfur, Geochimi. Cosmochim. Acta, 65, 2433–2437, 2001.

Egiazarov, A C., Kaviladze, M., Kerner, M N., Oziashvili, E L., Ebralidze, A., and Esakiya, A D.: Separation of Sulfur Isotopes by Chemical Exchange, Isotopenpraxis: Isotopes in Environmental and Health Studies, 7, 379–383, 1971.

Eriksen, T E.: Sulfur Isotope Effects 1. Isotopic Exchange Coefficient for Sulfur Isotopes 34S-32S in System SO2(g)-HSO3(aq) at 25, 35, and 45 Degrees C, Acta Chem. Scand., 26, 573, 1972a.

Eriksen, T E.: Sulfur Isotope Effects 2. Isotopic Exchange Coefficients for Sulfur Isotopes 34S-32S in System SO2(g)-Aqueous Solutions of SO2, Acta Chem. Scand., 26, 581, 1972b.

Eriksen, T E.: Sulfur Isotope Effects 3. Enrichment of 34S by Chemical Exchange between SO2(g) and Aqueous Solutions of SO2, Acta Chem. Scand., 26, 975, 1972c.

Eriksen, T E.: Sulfur Isotope Effects 4. Sulfur Isotope Effects in Anion-Exchange Systems, Acta Chem. Scand., 26, 980, 1972d.

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.-Plan., 106, 32829–32839, 2001.

Goldstein, D. E., N., Echlin, P., Joy, D., Fiori, C., and Lifshin, E.: Scanning Electron Microscopy and X-ray Microanalysis, Plenum Press, New York, USA, 53–122, 1981.

Groener, E. and Hoppe, P.: Automated ion imaging with the NanoSIMS ion microprobe, Appl. Surf. Sci., 252, 7148–7151, http://dx.doi.org/10.1016/j.apsusc.2006.02.280doi:10.1016/j.apsusc.2006.02.280, 2006.

Hanson, D R. and Eisele, F.: Diffusion of H2SO4 in humidified nitrogen: Hydrated H2SO4, J. Phys. Chem. A, 104, 1715–1719, 2000.

Hattori, S., Danielache, S., Johnson, M., Schmidt, J., Kjaergaard, H., Toyoda, S., Ueno, Y., and Yoshida, N.: Ultraviolet absorption cross sections of carbonyl sulfide isotopologues OC32S, OC33S, OC34S and O13CS: isotopic fractionation in photolysis and atmospheric implications, Atmos. Chem. Phys., 11, 10293–10303, http://dx.doi.org/10.5194/acp-11-10293-2011doi:10.5194/acp-11-10293-2011, 2011.

Herrmann, H., Ervens, B., Jacobi, H W., Wolke, R., Nowacki, P., and Zellner, R.: CAPRAM2.3: A chemical aqueous phase radical mechanism for tropospheric chemistry, J. Atmos. Chem., 36, 231–284, 2000.

Hoppe, P.: NanoSIMS: A new tool in cosmochemistry, Appl. Surf. Sci., 252, 7102–7106, 2006.

Huygen, C.: The sampling of sulfur dioxide in air with impregnated filter paper, Anal. Chim. Acta, 28, 349–360, 1963.

IPCC: Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, 2007, Cambridge University Press, http://www.ipcc.ch/publications_and_data/ar4/wg1/en/contents.html, 2007.

Krouse, H R. and Grinenko, V A.: Stable isotopes : natural and anthropogenic sulphur in the environment, vol 43, Wiley, Chichester, UK, 1991.

Krouse, H., Grinenko, L., Grinenko, V., Newman, L., Forrest, J., Nakai, N., Tsuji, Y., Yatsumimi, T., Takeuchi, V., Robinson, B., Stewart, M., Gunatilaka, A., Plumb, L., Smith, J., Buzek, F., Cerny, J., Sramek, J., Menon, A., Iyer, G., Venkatasubramanian, V., Egboka, B., Irogbenachi, M. and Eligwe, C.: Stable Isotopes: Natural and Anthropogenic Sulphur in the Environment, chap 8. Case Studies and Potential Applications, John Wiley and Sons, 307–416, 1991.

Kulmala, M., Vehkamaki, H., Petaja, T., Maso, M D., Lauri, A., Kerminen, V M., Birmili, W., and McMurry, P H.: Formation and growth rates of ultrafine atmospheric particles: a review of observations, J. Aerosol Sci., 35, 143–176, 2004.

Kulmala, M., Riipinen, I., Sipila, M., Manninen, H. E., Petaja, T., Junninen, H., Maso, M. D., Mordas, G., Mirme, A., Vana, M., Hirsikko, A., Laakso, L., Harrison, R. M., Hanson, I., Leung, C., Lehtinen, K. E. J., and Kerminen, V. M.: Toward direct measurement of atmospheric nucleation, Science, 318, 89–92, 2007.

Lai, A C.: Investigation of Electrostatic Forces on Particle Deposition in a Test Chamber, Indoor Built Environ., 15, 179–186, 2006.

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, 2001.

Leung, F Y., Colussi, A J., Hoffmann, M R., and Toon, G C.: Isotopic fractionation of carbonyl sulfide in the atmosphere: Implications for the source of background stratospheric sulfate aerosol, Geophys. Res. Lett., 29, 1474, doi:10.1029/2001g1013955, 2002.

Lin, Y., Sim, M. S., and Ono, S.: Multiple-sulfur isotope effects during photolysis of carbonyl sulfide, Atmos. Chem. Phys., 11, 10283–10292, http://dx.doi.org/10.5194/acp-11-10283-2011doi:10.5194/acp-11-10283-2011, 2011.

Luz, B. and Barkan, E.: The isotopic ratios O-17/O-16 and O-18/O-16 in molecular oxygen and their significance in biogeochemistry, Geochim. Cosmochim. Acta, 69, 1099–1110, 2005.

Lyons, J R.: Atmospherically-derived mass-independent sulfur isotope signatures, and incorporation into sediments, Chem. Geol., 267, 164–174, 2009.

Mariotti, A., Germon, J C., Hubert, P., Kaiser, P., Letolle, R., Tardieux, A., and Tardieux, P.: Experimental-determination of Nitrogen Kinetic Isotope Fractionation - Some Principles – Illustration For the Denitrification and Nitrification Processes, Plant Soil, 62, 413–430, 1981.

Mayer, B., Feger, K. H., Giesemann, A., and Jäger, H.-J.: Interpretation of sulfur cycling in two catchments in the Black Forest (Germany) using stable sulfur and oxygen isotope data, Biogeochemistry, 30, 31–58, 1995.

Mertes, S., Lehmann, K., Nowak, A., Massling, A., and Wiedensohler, A.: Link between aerosol hygroscopic growth and droplet activation observed for hill-capped clouds at connected flow conditions during FEBUKO, Atmos. Environ., 39, 4247–4256, 2005.

Moore, J., Stanitski, C., and Jurs, P.: Chemistry: The Molecular Science, Brooks/Cole, Thomson Learning, USA, A.31–A.32, 2005.

Mukai, H., Tanaka, A., Fujii, T., Zeng, Y Q., Hong, Y T., Tang, J., Guo, S., Xue, H S., Sun, Z L., Zhou, J T., Xue, D M., Zhao, J., Zhai, G H., Gu, J L., and Zhai, P Y.: Regional characteristics of sulfur and lead isotope ratios in the atmosphere at several Chinese urban sites, Environ. Sci. Technol., 35, 1064–1071, 2001.

Nielsen, H., Pilot, J., Grinenko, L., Grinenko, V., Lein, A., Smith, J., and Pankina, R.: Stable Isotopes: Natural and Anthropogenic Sulphur in the Environment, chap 4. Lithospheric Sources of Sulfur, John Wiley and Sons, 65–132, 1991.

Norman, A L., Anlauf, K., Hayden, K., Thompson, B., Brook, J R., Li, S M., and Bottenheim, J.: Aerosol sulphate and its oxidation on the Pacific NW coast: S and O isotopes in PM$_2.5$, Atmos. Environ., 40, 2676–2689, 2006.

Novak, M., Jackova, I., and Prechova, E.: Temporal Trends in the Isotope Signature of Air-Borne Sulfur in Central Europe, Environ. Sci. Technol., 35, 255–260, 2001.

Nriagu, J O., Rees, C., Mekhtiyeva, V., Lein, A., Fritz, P., Drimmie, R., Pankina, R., Robinson, B., and Krouse, H R.: Stable Isotopes: Natural and Anthropogenic Sulphur in the Environment, chap 6. Hydrosphere, John Wiley and Sons, 177–266, 1991.

Ohizumi, T., Fukuzaki, N., and Kusakabe, M.: Sulfur isotopic view on the sources of sulfur in atmospheric fallout along the coast of the Sea of Japan, Atmos. Environ., 31, 1339–1348, 1997.

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. Acta, 70, 2238–2252, 2006.

Patris, N., Delmas, R. J., Legrand, M., Angelis, M. D., Ferron, F. A., Stievenard, M. and Jouzel, J.: First sulfur isotope measurements in central Greenland ice cores along the preindustrial and industrial periods, J. Geophys. Res.-Atmos., 107, doi:10.1029/2001JD000672, 2002.

Rees, C. and Holt, B.: Stable Isotopes: Natural and Anthropogenic Sulphur in the Environment, chap 3., John Wiley and Sons, 43–64, 1991.

Rees, C E., Jenkins, W J., and Monster, J.: Sulfur Isotopic Composition of Ocean Water Sulfate, Geochim. Cosmochim. Acta, 42, 377–381, 1978.

Rudyak, V. Y., Dubtsov, S. N., and Baklanov, A. M.: Measurements of the temperature dependent diffusion coefficient of nanoparticles in the range of 295-600 K at atmospheric pressure, Journal of Aerosol Science, 40, 833–843, 2009.

Saltzman, E S., Brass, G., and Price, D.: The mechanism of sulfate aerosol formation: Chemical and sulfur isotopic evidence, Geophys. Res. Lett., 10, 513–516, 1983.

Sanusi, A. A., Norman, A.-L., Burridge, C., Wadleigh, M. and Tang, W.-W.: Determination of the S isotope composition of methanesulfonic acid, Anal. Chem., 78, 4964–4968, 2006.

Savarino, J., Lee, C. C W., and Thiemens, M H.: Laboratory oxygen isotopic study of sulfur (IV) oxidation: Origin of the mass-independent oxygen isotopic anomaly in atmospheric sulfates and sulfate mineral deposits on Earth, J. Geophys. Res.-Atmos., 105, 29079–29088, 2000.

Savarino, J., Bekki, S., Cole-Dai, J. H. and Thiemens, M. H.: Evidence from sulfate mass independent oxygen isotopic compositions of dramatic changes in atmospheric oxidation following massive volcanic eruptions Journal of Geophysical Research-Atmospheres, 108, 2003a.

Savarino, J., Romero, A., Cole-Dai, J., Bekki, S. and Thiemens, M. H.: UV induced mass-independent sulfur isotope fractionation in stratospheric volcanic sulfate, Geophys. Res. Lett., 30, 2131, http://dx.doi.org/10.1029/2003GL018134doi:10.1029/2003GL018134, 2003b.

Savarino, J., Romero, A., Cole-Dai, J. and Thiemens, M. H.: UV induced mass-independent sulfur composition in stratospheric volcanic eruptions, Geochim. Cosmochim. Acta, 67, A417–A417, 2003c.

Seinfeld, J H. and Pandis, S N.: Atmospheric Chemistry and Physics, Wiley & Sons, New York, USA, 363–379, 1998.

Sinha, B. W., Hoppe, P., Huth, J., Foley, S., and Andreae, M. O.: Sulfur isotope analyses of individual aerosol particles in the urban aerosol at a central European site (Mainz, Germany), Atmos. Chem. Phys., 8, 7217–7238, http://dx.doi.org/10.5194/acp-8-7217-2008doi:10.5194/acp-8-7217-2008, 2008a.

Sinha, V., Williams, J., Crowley, J. N., and Lelieveld, J.: The Comparative Reactivity Method – a new tool to measure total OH Reactivity in ambient air, Atmos. Chem. Phys., 8, 2213–2227, http://dx.doi.org/10.5194/acp-8-2213-2008doi:10.5194/acp-8-2213-2008, 2008b.

Sinha, V., Custer, T G., Kluepfel, T., and Williams, J.: The effect of relative humidity on the detection of pyrrole by PTR-MS for OH reactivity measurements, Int. J. Mass Spectrom., 282, 108–111, 2009.

Sinha, B. W., Hoppe, P., Huth, J., Foley, S., and Andreae, M. O.: Sulfur isotope analysis of individual aerosol particles –a new tool for studying heterogeneous oxidation processes in the marine environment, Atmos. Chem. Phys. Discuss., 9, 3307–3365, http://dx.doi.org/10.5194/acpd-9-3307-2009doi:10.5194/acpd-9-3307-2009, 2009.

Slodzian, G., Chaintreau, M., Dennebouy, R., and Rousse, A.: Precise in situ measurements of isotopic abundances with pulse counting of sputtered ions, Europ. Phys. J.-Appl. Phys., 14, 199–231, 2001.

Slodzian, G., Hillion, F., Stadermann, F J., and Zinner, E.: QSA influences on isotopic ratio measurements, Appl. Surf. Sci., 231–232, 874–877, 2004.

Sofen, E. D., Alexander, B., and Kunasek, S. A.: The impact of anthropogenic emissions on atmospheric sulfate production pathways, oxidants, and ice core $\Delta^17$O(SO$_4^2�$), Atmos. Chem. Phys., 11, 3565–3578, http://dx.doi.org/10.5194/acp-11-3565-2011doi:10.5194/acp-11-3565-2011, 2011.

Stoyan, D.: Stochastik fuer Ingenieure und Naturwissenschaftler, Wiley-VCH, 1998.

Tanaka, N., Rye, D M., Xiao, Y., and Lasaga, 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, 1994.

Tichomirowa, M., Haubrich, F., Klein, M., and Matschullat, J. Regional and temporal (1992-2004) evolution of air-borne sulphur isotope composition in Saxony, southeastern Germany, central Europe. Isotopes in Environmental and Health Studies, 43, 295–305, 2007.

US-EPA: Method 6 – Determination of Sulfur Dioxide Emissions from Stationary Sources, available online at: http://www.epa.gov/ttn/emc/, 2010.

Winterholler, B.: Sulfur Isotope Analysis of Aerosol Particles by NanoSIMS, Ph.D. thesis, Johannes Gutenberg-Universität, Mainz, Germany, 2007.

Winterholler, B., Hoppe, P., Andreae, M O., and Foley, S.: Measurement of sulfur isotope ratios in micrometer-sized samples by NanoSIMS, Appl. Surf. Sci., 252, 7128–7131, 2006.

Winterholler, B., Hoppe, P., Foley, S., and Andreae, M O.: Sulfur isotope ratio measurements of individual sulfate particles by NanoSIMS, Int. J. Mass Spectrom., 272, 63–77, 2008.

Young, L. H., Benson, D. R., Kameel, F. R., Pierce, J. R., Junninen, H., Kulmala, M., and Lee, S.-H.: Laboratory studies of H2SO4/H2O binary homogeneous nucleation from the SO2+OH reaction: evaluation of the experimental setup and preliminary results, Atmos. Chem. Phys., 8, 4997–5016, http://dx.doi.org/10.5194/acp-8-4997-2008doi:10.5194/acp-8-4997-2008, 2008.

Zasypkin, A., Grigor'eva, V., Korchak, V., and Gerschenson, Y.: A formula for summing of kinetic resistances for mobile and stationary media: I.\ Cylindrical reactor, Kin. Catalyst., 38, 842–851, 1997.