Possible Chemical Transformations in Snow and Ice Induced by Solar (UV PHOTONS) and Cosmic Irradiation (MUONS)

  • Michael R. Hoffmann
Part of the NATO ASI Series book series (volume 43)

Abstract

Over the last decade there has been a growing interest in the chemical composition of the snow packs in the polar regions (Bales and Wolff, 1995). Delmas (Delmas, 1992; Delmas, 1994) has noted that “information recorded in polar ice cores over the last several hundred millennia is invaluable to studies aimed at understanding the pre-industrial environmental system and anticipating the future evolution of the climate and the atmosphere.” For example, the isotopie composition of the ice (H20) matrix is a reliable paleothermometer. From the analysis of deep Antarctic and Greenland ice cores the ice age environmental conditions appeared to correspond to about 6 °C cooler temperatures and atmospheric CO2 and CH4 levels lower by factors of nearly 2 and 4, respectively. The biogeochemical cycles of S and N also appear to be affected by climatic changes that result in modifications in the source intensity and the transport of gaseous precursors. Even though atmospheric sulfate is derived principally from marine biogenic sources (i.e., dimethyl sulfide emission), cataclysmic volcanic eruptions can contribute sporadically to the atmospheric sulfur budget through large point source emissions of SO2. These events are ultimately detected in polar ice as H2SO4 spikes. Nitrate, which is the next most abundant anion found in polar snowfall, exhibits concentration changes that are poorly understood, but which could be linked with the polar ozone hole formation. In addition to ions derived primarily from gas-to-particle conversions,

Keywords

Formaldehyde Dust Cadmium Ozone Chlorine 

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References

  1. Baker, S C, D P Kelly, et al. (1991) Microbial-degradation of methanesulfonic-acid - a missing link in the biogeochemical sulfur cycle. Nature 350: 627–628.CrossRefGoogle Scholar
  2. Bales, R C and E W Wolff (1995) Processes of chemical exchange between the atmosphere and polar snow: key to interpreting natural climate signals in ice cores. EOS, Trans Amer Geophys Union 76:477–482.CrossRefGoogle Scholar
  3. Bednarek, J and A Plonka (1994) ESR studies on reactivity of H02 radicals in polycrystalline ice - nonmonotonic changes of disproportionation rate in the temperature-range 100–200 K. Rad Phys Chem 44:485–489.CrossRefGoogle Scholar
  4. Bednarek, J and S Schlick (1991) Stability of radical intermediates in microscopically heterogeneous media - photolysis of water adsorbed on silica-gel studied by ESR and DSC. J Phys Chem 95: 9940–9944.CrossRefGoogle Scholar
  5. Bernstein, M P, S A Sandford, et al. (1994) Infrared-spectrum of matrix-isolated hexamethylenetetramine in Ar and water at cryogenic temperatures. J Phys Chem 98: 12206–12210.CrossRefGoogle Scholar
  6. Boutron, C F, U Gorlach, et al. (1991) Decrease in anthropogenic lead, cadmium and zinc in greenland snows since the late 1960s. Nature 353:153–156.CrossRefGoogle Scholar
  7. Buxton, G V, C L Greenstock, et al. (1988) Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals in aqueous solution. J Phys Chem Ref Data 17: 513–886.Google Scholar
  8. Carraway, E R, A J Hoffman, et al. (1994) Photocatalytic oxidation of organic-acids on quantum-sized semiconductor colloids. Environ Sci Technol 28: 786–793.CrossRefGoogle Scholar
  9. Davidson, C I, J L Jaffrezo, et al. (1993) Chemical-constituents in the air and snow at Dye-3, Greenland II. Analysis of episodes in April 1989. Atmos Environ 27: 2723–2737.Google Scholar
  10. Davidson, C I, J L Jaffrezo, et al. (1993) Chemical-constituents in the air and snow at Dye-3, Greenland I seasonal-variations. Atmos Environ 27: 2709–2722.Google Scholar
  11. Deangelis, M and M Legrand (1994) Origins and variations of fluoride in greenland precipitation. J Geophys Res 99:1157–1172.CrossRefGoogle Scholar
  12. Delmas, R J (1992) Environmental information from ice cores. Rev Geophys 30:1–21.CrossRefGoogle Scholar
  13. Delmas, R J (1994) Ice records of the past environment. Sci Total Environ 143:17–30.CrossRefGoogle Scholar
  14. Faust, B C and M R Hoffmann (1986) Photoinduced reductive dissolution of hematite by bisulfite. Environ Sci Technol 20: 943–948.CrossRefGoogle Scholar
  15. Faust, B C, M R Hoffmann, et al. (1989) Photocatalytic oxidation of sulfur-dioxide in aqueous suspensions of α-Fe203. J Phys Chem 93: 6371.CrossRefGoogle Scholar
  16. Finlayson-Pitts, B J and J N J Pitts (1986) Atmospheric Chemistry: Fundamentals and Experimental Techniques. New York, John Wiley & Sons. Google Scholar
  17. Fuhrer, K, A Neftel, et al. (1993) Continuous measurements of hydrogen-peroxide, formaldehyde, calcium and ammonium concentrations along the new grip ice core from summit, central greenland. Atmos Environ 27:1873–1880.Google Scholar
  18. Goto, K, T Hondoh, et al. (1986) Determination of diffusion-coefficients of self-interstitials in ice with a new method of observing climb of dislocations by x-ray topography. Japanese J Appl Physics 25: 351–357.CrossRefGoogle Scholar
  19. Graedel, T E and C J Weschler (1981) Chemistry within aqueous atmospheric aerosols and raindrops. Rev Geophys Space Phys 19: 505.CrossRefGoogle Scholar
  20. Hayakawa, S (1969) Cosmic Ray Physics. New York, Wiley-Interscience.Google Scholar
  21. Hoffman, A J, E R Carraway, et al. (1994) Photocatalytic production of H202 and organic peroxides on quantum-sized semiconductor colloids. Environ Sci Technol 28: 776–785.CrossRefGoogle Scholar
  22. Kormann, C, D W Bahnemann, et al. (1988) Photocatalytic production of H202 and organic peroxides in aqueous suspensions of Ti02, ZnO and desert sands. Environ Sci Technol 22: 798–806.CrossRefGoogle Scholar
  23. Laj, P, J M Palais, et al. (1992) Changing sources of impurities to the greenland ice-sheet over the last 250 years. Atmospheric Environment Part A General Topics 26: 2627–2640.CrossRefGoogle Scholar
  24. Legrand, M, C Fenietsaigne, et al. (1992) Spatial and temporal variations of methanesulfonic-acid and non-seasalt sulfate in antarctic ice. J Atmos Chem 14: 245–260.CrossRefGoogle Scholar
  25. Leifer, A (1988) The Kinetics of Environmental Aquatic Photochemistry. Washington, DC, American Chemical Society.Google Scholar
  26. Matheson, M S and L M Dorfman (1969) Pulse Radiolysis. Washington, DC, American Chemical Society.Google Scholar
  27. Neftel, A (1996) The record of gases and reactive species in ice cores and problems of interpretation. This Volume:. Google Scholar
  28. Pehkonen, S, R Siefert, et al. (1993) Photoreduction of iron oyxhydroxides in the presence of important organic compound.s Environ Sci Technol 26: 2056. CrossRefGoogle Scholar
  29. Pehkonen, S O, R L Siefert, et al. (1995) Photoreduction of iron oxyhydroxides and the photooxidation of halogenated acetic acids. Environ Sci Technol 29:1215–1222.CrossRefGoogle Scholar
  30. Perovich, D K and J W Govoni (1991) Absorption-coefficients of ice from 250 to 400 nm. Geophysical Research Letters 18:1233–1235.CrossRefGoogle Scholar
  31. Pursell, C J, J Conyers, et al. (1995) Photochemistry of chlorine dioxide in ice. J Phys Chem 99:10433–10437.CrossRefGoogle Scholar
  32. Rettich, T R (1978) Some photochemical reactions of aqueous nitrous acid, Ph D Thesis, Case Western Reserve University.Google Scholar
  33. Rossi, B (1964) Cosmic Rays New York, Mc-Graw Hill. Google Scholar
  34. Ryan, K G (1992) UV-radiation and photosynthetic production in antarctic sea ice microalgae. J Photochem Photobiol Part B Biol 13:235–240.CrossRefGoogle Scholar
  35. Savarino, J, C F Boutron, et al. (1994) Short-term variations of Pb, Cd, Zn and Cu in recent greenland snow. Atmos Environ 28:1731–1737.CrossRefGoogle Scholar
  36. Schwarzenbach, R P, P M Gschwend, et al. (1993) Environmental Organic Chemistry New York, Wiley-Interscience. Google Scholar
  37. Siefert, R L, S O Pehkonen, et al. (1994) Iron photochemistry of aqueous suspensions of ambient aerosols with added organic acids. Geochem Cosmochim Acta 58: 3271–3279.CrossRefGoogle Scholar
  38. Sigg, A, K Fuhrer, et al. (1994) A continuous analysis technique for trace species in ice cores. Environ Sci Technol 28: 204–209.CrossRefGoogle Scholar
  39. Sigg, A and A Neftel (1991) Evidence for a 50-percent increase in H202 over the past 200 years from a greenland ice core. Nature 351: 557–559.CrossRefGoogle Scholar
  40. Sigg, A, T Staffelbach, et al. (1992) Gas-phase measurements of hydrogen-peroxide in greenland and their meaning for the interpretation of H202 records in ice cores. Atmos Chem 14: 223–232.CrossRefGoogle Scholar
  41. Staffelbach, T, A Neftel, et al. (1991) A record of the atmospheric methane sink from formaldehyde in polar ice cores. Nature 349: 603–605.CrossRefGoogle Scholar
  42. Sturges, WT, GF Cota, et al. (1992) Bromoform emission from arctic ice algae. Nature 358: 660–662.CrossRefGoogle Scholar
  43. Suttie, E D and E W Wolff (1993) The local deposition of heavy-metal emissions from point sources in antarctica. Atmos Environ 27:1833–1841.Google Scholar
  44. Taube, H (1957) Photochemical reactions of ozone in solution. Trans Faraday Soc 53: 656.CrossRefGoogle Scholar
  45. Walker, D C (1983) Muon and Muonium Chemistry Cambridge, Cambridge University Press. Google Scholar
  46. Woafo, P, R Takontchoup, et al. (1995) Soliton mechanism of proton migration in hydrogen-bonded solids. J Phys Chem Solids 56:1277–1283.CrossRefGoogle Scholar
  47. Wolfendale, A W (1973) Cosmic Rays at Ground Level London, The Institute of Physics. Google Scholar
  48. Wolff, E (1992) The influence of global and local atmospheric-pollution on the chemistry of antarctic snow and ice. Marine Pollution Bulletin 25: 274–280.CrossRefGoogle Scholar
  49. Wolff, E W and E D Suttie (1994) Antarctic snow record of southern-hemisphere lead pollution. Geophysical Research Letters 21: 781–784.CrossRefGoogle Scholar
  50. Zafiriou, O C and M B True (1979) Nitrite photolysis in seawater by sunlight Mar Chem. 8: 33. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1996

Authors and Affiliations

  • Michael R. Hoffmann
    • 1
  1. 1.Environmental Engineering Science W.M. Keck Laboratories California Institute of TechnologyPasadenaUSA

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