Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 5 2009 10.5194/acpd-9-19683-2009 http://www.atmos-chem-phys-discuss.net/9/19683/2009/ http://www.atmos-chem-phys-discuss.net/9/19683/2009/acpd-9-19683-2009.html http://www.atmos-chem-phys-discuss.net/9/19683/2009/acpd-9-19683-2009.pdf 19683 19712 2009-09-23 Acetaldehyde in the Alaskan subarctic snow pack F. Domine florent@lgge.obs.ujf-grenoble.fr S. Houdier A.-S. Taillandier W. R. Simpson CNRS-INSU, Laboratoire de Glaciologie et Géophysique de l'Environnement, BP 96, 38402 Saint-Martin d'Hères Cedex, France Université Joseph Fourier – Grenoble I, France Geophysical Institute, University of Alaska Fairbanks, Alaska, USA Department of Chemistry, University of Alaska Fairbanks, USA Acetaldehyde is a reactive intermediate in hydrocarbon oxidation. It is both emitted and taken up by snowpacks and photochemical and physical processes are probably involved. Understanding the reactivity of acetaldehyde in snow and its processes of physical and chemical exchanges requires the knowledge of its incorporation mechanism in snow crystals. We have performed a season-long study of the evolution of acetaldehyde concentrations in the subarctic snowpack near Fairbanks (65° N), central Alaska, which is subjected to a vigorous metamorphism due to persistent elevated temperature gradients in the snowpack, between 20 and 200°C m<sup>−1</sup>. The snowpack therefore almost entirely transforms into depth hoar. We have also analyzed acetaldehyde in a manipulated snowpack where temperature gradients were suppressed. Snow crystals there transformed much more slowly and their original shapes remained recognizable for months. The specific surface area of snow layers in both types of snowpacks was also measured. We deduce that acetaldehyde is not adsorbed onto the surface of snow crystals and that most of the acetaldehyde is probably not dissolved in the ice lattice of the snow crystals. We propose that most of the acetaldehyde measured is either trapped or dissolved within organic aerosol particles trapped in snow, or that acetaldehyde is formed by the hydrolysis of organic precursors contained in organic aerosols trapped in the snow, when the snow is melted for analysis. These precursors are probably aldehyde polymers formed within the aerosol particles by acid catalysis, but might also be biological molecules. In a laboratory experiment, acetaldehyde-di-n-hexyl acetal, representing a potential acetaldehyde precursor, was subjected to our analytical procedure and reacted to form acetaldehyde. This confirms our suggestion that acetaldehyde in snow could be produced during the melting of snow for analysis. Albert, M R., Grannas, A M., Bottenheim, J., Shepson, P B., and Perron, F E.: Processes and properties of snow-air transfer in the high Arctic with application to interstitial ozone at Alert, Canada, Atmos. Environ., 36, 2779–2787, 2002. Ariya, P A. and Amyot, M.: New Directions: The role of bioaerosols in atmospheric chemistry and physics, Atmos. Environ., 38, 1231–1232, 2004. Ariya, P A., Sun, J., Eltouny, N A., Hudson, E D., Hayes, C T., and Kos, G.: Physical and chemical characterization of bioaerosols~– Implications for nucleation processes, Int. Rev. Phys. Chem., 28, 1–32, 2009. 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. Betterton, E A. and Hoffmann, M R.: Henry law constants of some environmentally important aldehydes, Environ. Sci. Technol., 22, 1415–1418, 1988. Bottenheim, J W., Gallant, A G., and Brice, K A.: Measurements of \chemNO_y species and \chemO_3 at 82-degrees-n latitude, Geophys. Res. Lett., 13, 113–116, 1986. Boudries, H., Bottenheim, J W., Guimbaud, C., Grannas, A M., Shepson, P B., Houdier, S., Perrier, S., and Domine, F.: Distribution and trends of oxygenated hydrocarbons in the high Arctic derived from measurements in the atmospheric boundary layer and interstitial snow air during the ALERT2000 field campaign, Atmos. Environ., 36, 2573–2583, 2002. Burkhart, J F., Hutterli, M A., and Bales, R C.: Partitioning of formaldehyde between air and ice at $-35$ degrees C to $-5$ degrees C, Atmos. Environ., 36, 2157–2163, 2002. Colbeck, S C.: An overview of seasonal snow metamorphism, Rev. Geophys., 20, 45–61, 1982. Couch, T L., Sumner, A L., Dassau, T M., Shepson, P B., and Honrath, R E.: An investigation of the interaction of carbonyl compounds with the snowpack, Geophys. Res. Lett., 27, 2241–2244, 2000. Decesari, S., Fuzzi, S., Facchini, M C., Mircea, M., Emblico, L., Cavalli, F., Maenhaut, W., Chi, X., Schkolnik, G., Falkovich, A., Rudich, Y., Claeys, M., Pashynska, V., Vas, G., Kourtchev, I., Vermeylen, R., Hoffer, A., Andreae, M O., Tagliavini, E., Moretti, F., and Artaxo, P.: Characterization of the organic composition of aerosols from Rondônia, Brazil, during the LBA-SMOCC 2002 experiment and its representation through model compounds, Atmos. Chem. Phys., 6, 375–402, 2006. Dibb, J E. and Arsenault, M.: Shouldn't snowpacks be sources of monocarboxylic acids?, Atmos. Environ., 36, 2513–2522, 2002. Domine, F., Thibert, E., Silvente, E., Legrand, M., and Jaffrezo, J L.: Determining past atmospheric \chemHCl mixing ratios from ice core analyses, J. Atmos. Chem., 21, 165–186, 1995. Domine, F. and Thibert, E.: Mechanism of incorporation of trace gases in ice grown from the gas phase, Geophys. Res. Lett., 23, 3627–3630, 1996. Domine, F., Cabanes, A., and Legagneux, L.: Structure, microphysics, and surface area of the Arctic snowpack near Alert during the ALERT 2000 campaign, Atmos. Environ., 36, 2753–2765, 2002. Domine, F. and Shepson, P B.: Air-snow interactions and atmospheric chemistry, Science, 297, 1506–1510, 2002. Domine, F., Taillandier, A S., and Simpson, W R.: A~parameterization of the specific surface area of seasonal snow for field use and for models of snowpack evolution, J. Geophys. Res.-Earth, 112, F02031, doi:10.1029/2006jf000512, 2007. Gattinger, A., Gunther, A., Schloter, M., and Munich, J C.: Characterisation of Archaea in soils by polar lipid analysis, Acta Biotechnol., 23, 21–28, 2003. Grannas, A M., Shepson, P B., Guimbaud, C., Sumner, A L., Albert, M., Simpson, W., Domine, F., Boudries, H., Bottenheim, J., Beine, H J., Honrath, R., and Zhou, X L.: A~study of photochemical and physical processes affecting carbonyl compounds in the Arctic atmospheric boundary layer, Atmos. Environ., 36, 2733–2742, 2002. Grannas, A M., Shepson, P B., and Filley, T R.: Photochemistry and nature of organic matter in Arctic and Antarctic snow, Global Biogeochem. Cy., 18, GB1006, doi:10.1029/2003gb002133, 2004. Grannas, A M., Jones, A E., Dibb, J., Ammann, M., Anastasio, C., Beine, H J., Bergin, M., Bottenheim, J., Boxe, C S., Carver, G., Chen, G., Crawford, J H., Dominé, F., Frey, M M., Guzmán, M I., Heard, D E., Helmig, D., Hoffmann, M R., Honrath, R E., Huey, L G., Hutterli, M., Jacobi, H W., Klán, P., Lefer, B., McConnell, J., Plane, J., Sander, R., Savarino, J., Shepson, P B., Simpson, W R., Sodeau, J R., von Glasow, R., Weller, R., Wolff, E W., and Zhu, T.: An overview of snow photochemistry: evidence, mechanisms and impacts, Atmos. Chem. Phys., 7, 4329–4373, 2007. Guimbaud, C., Grannas, A M., Shepson, P B., Fuentes, J D., Boudries, H., Bottenheim, J W., Domine, F., Houdier, S., Perrier, S., Biesenthal, T B., and Splawn, B G.: Snowpack processing of acetaldehyde and acetone in the Arctic atmospheric boundary layer, Atmos. Environ., 36, 2743–2752, 2002. Hanot, L. and Domine, F.: Evolution of the surface area of a~snow layer, Environ. Sci. Technol., 33, 4250–4255, 1999. Houdier, S., Legrand, M., Boturyn, D., Croze, S., Defrancq, E., and Lhomme, J.: A~new fluorescent probe for sensitive detection of carbonyl compounds, Anal. Chim. Acta, 382, 253–263, 1999. Houdier, S., Perrier, S., Defrancq, E., and Legrand, M.: A~new fluorescent probe for sensitive detection of carbonyl compounds: sensitivity improvement and application to environmental water samples, Anal. Chim. Acta, 412, 221–233, 2000. Houdier, S., Perrier, S., Domine, F., Cabanes, A., Legagneux, L., Grannas, A M., Guimbaud, C., Shepson, P B., Boudries, H., and Bottenheim, J W.: Acetaldehyde and acetone in the Arctic snowpack during the ALERT2000 campaign. Snowpack composition, incorporation processes and atmospheric impact, Atmos. Environ., 36, 2609–2618, 2002. Hutterli, M A., Rothlisberger, R., and Bales, R C.: Atmosphere-to-snow-to-firn transfer studies of \chemHCHO at Summit, Greenland, Geophys. Res. Lett., 26, 1691–1694, 1999. Hutterli, M A., Bales, R C., McConnell, J R., and Stewart, R W.: \chemHCHO in Antarctic snow: Preservation in ice cores and air-snow exchange, Geophys. Res. Lett., 29, 1235, doi:10.1029/2001GL014256, 2002. Jacobi, H W., Frey, M M., Hutterli, M A., Bales, R C., Schrems, O., Cullen, N J., Steffen, K., and Koehler, C.: Measurements of hydrogen peroxide and formaldehyde exchange between the atmosphere and surface snow at Summit, Greenland, Atmos. Environ., 36, 2619–2628, 2002. Jang, M S., Czoschke, N M., Lee, S., and Kamens, R M.: Heterogeneous atmospheric aerosol production by acid-catalyzed particle-phase reactions, Science, 298, 814–817, 2002. Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., Prevot, A S H., Fisseha, R., Weingartner, E., Frankevich, V., Zenobi, R., and Baltensperger, U.: Identification of polymers as major components of atmospheric organic aerosols, Science, 303, 1659–1662, 2004. King, T E. and Cheldelin, V H.: Pyruvic carboxylase of acetobacter-suboxydans, J. Biol. Chem., 208, 821–831, 1954. Koga, Y. and Morii, H.: Biosynthesis of ether-type polar lipids in archaea and evolutionary considerations, Microbiol. Mol. Biol. R., 71, 97–120, 2007. Lary, D J. and Shallcross, D E.: Central role of carbonyl compounds in atmospheric chemistry, J. Geophys. Res.-Atmos., 105, 19771-19778, 2000. Legagneux, L., Cabanes, A., and Domine, F.: Measurement of the specific surface area of 176 snow samples using methane adsorption at 77 \unitK, J. Geophys. Res.-Atmos., 107, D4335, doi:10.1029/2001jd001016, 2002. Li, S M., Macdonald, A M., Leithead, A., Leaitch, W R., Gong, W M., Anlauf, K G., Toom-Sauntry, D., Hayden, K., Bottenheim, J., and Wang, D.: Investigation of carbonyls in cloudwater during ICARTT, J. Geophys. Res.-Atmos., 113, D17206, doi:10.1029/2007jd009364, 2008. Mabilia, R., Di Palo, V., Cassardo, C., Ciuchini, C., Pasini, A., and Possanzini, M.: Measurements of lower carbonyls and hydrocarbons at Ny-Alesund, svalbard, Ann. Chim.-Rome, 97, 1027–1037, 2007. Mauldin, R L., Eisele, F L., Tanner, D J., Kosciuch, E., Shetter, R., Lefer, B., Hall, S R., Nowak, J B., Buhr, M., Chen, G., Wang, P., and Davis, D.: Measurements of \chemOH, \chemH_2SO_4, and MSA at the South Pole during ISCAT, Geophys. Res. Lett., 28, 3629–3632, 2001. Michelsen, R R., Ashbourn, S F M., and Iraci, L T.: Dissolution, speciation, and reaction of acetaldehyde in cold sulfuric acid, J. Geophys. Res.-Atmos., 109, D23205, doi:10.1029/2004jd005041, 2004. Noziere, B. and Riemer, D D.: The chemical processing of gas-phase carbonyl compounds by sulfuric acid aerosols-2,4-pentanedione, Atmos. Environ., 37, 841–851, 2003. Noziere, B. and Cordova, A.: A~kinetic and mechanistic study of the amino acid catalyzed aldol condensation of acetaldehyde in aqueous and salt solutions, J Phys. Chem. A, 112, 2827–2837, doi:10.1021/jp7096845, 2008. Noziere, B., Dziedzic, P., and Cordova, A.: Products and Kinetics of the Liquid-Phase Reaction of Glyoxal Catalyzed by Ammonium Ions (\chemNH^4+), J Phys. Chem. A, 113, 231–237, doi:10.1021/jp8078293, 2009. Perrier, S., Houdier, S., Domine, F., Cabanes, A., Legagneux, L., Sumner, A L., and Shepson, P B.: Formaldehyde in Arctic snow. Incorporation into ice particles and evolution in the snowpack, Atmos. Environ., 36, 2695–2705, 2002. Perrier, S., Sassin, P., and Domine, F.: Diffusion and solubility of \chemHCHO in ice: preliminary results, Can. J Phys., 81, 319–324, 2003. Petitjean, M., Mirabel, P., and Le Calve, S.: Uptake Measurements of Acetaldehyde on Solid Ice Surfaces and on Solid/Liquid Supercooled Mixtures Doped with \chemHNO_3 in the Temperature Range 203–253 \unitK, J Phys. Chem. A, 113, 5091–5098, 2009. Shepson, P B., Sirju, A P., Hopper, J F., Barrie, L A., Young, V., Niki, H., and Dryfhout, H.: Sources and sinks of carbonyl compounds in the arctic ocean boundary layer: Polar ice floe experiment, J Geophys. Res.-Atmos., 101, 21081–21089, 1996. Snyder, F.: The ether lipid trail: a~historical perspective, BBA-Mol. Cell. Biol. L., 1436, 265–278, 1999. Sokolov, O. and Abbatt, J P D.: Adsorption to ice of n-alcohols (ethanol to 1-hexanol), acetic acid, and hexanal, J Phys. Chem. A, 106, 775–782, 2002. Sommerfeld, R A. and LaChapelle, E.: The classification of snow metamorphism, J Glaciol., 9, 3–17, 1970. Sturm, M. and Johnson, J B.: Natural-convection in the sub-arctic snow cover, J Geophys. Res.-Solid, 96, 11657–11671, 1991. Sturm, M., Holmgren, J., and Liston, G E.: A~seasonal snow cover classification-system for local to global applications, J Climate, 8, 1261–1283, 1995. Sturm, M. and Benson, C S.: Vapor transport, grain growth and depth-hoar development in the subarctic snow, J Glaciol., 43, 42–59, 1997. Sumner, A L. and Shepson, P B.: Snowpack production of formaldehyde and its effect on the Arctic troposphere, Nature, 398, 230–233, 1999. Swanson, A L., Blake, N J., Dibb, J E., Albert, M R., Blake, D R., and Rowland, F S.: Photochemically induced production of \chemCH_3Br, \chemCH_3I, \chemC_2H_5I, ethene, and propene within surface snow at Summit, Greenland, Atmos. Environ., 36, 2671–2682, 2002. Tabazadeh, A.: Organic aggregate formation in aerosols and its impact on the physicochemical properties of atmospheric particles, Atmos. Environ., 39, 5472–5480, 2005. Taillandier, A S., Domine, F., Simpson, W R., Sturm, M., Douglas, T A., and Severin, K.: Evolution of the snow area index of the subarctic snowpack in central Alaska over a~whole season. Consequences for the air to snow transfer of pollutants, Environ. Sci. Technol., 40, 7521–7527, 2006. Taillandier, A S., Domine, F., Simpson, W R., Sturm, M., and Douglas, T A.: Rate of decrease of the specific surface area of dry snow: Isothermal and temperature gradient conditions, J Geophys. Res.-Earth, 112, F03003, doi:10.1029/2006jf000514, 2007. Thibert, E. and Domine, F.: Thermodynamics and kinetics of the solid solution of \chemHCl in ice, J Phys. Chem. B, 101, 3554–3565, 1997. Thibert, E. and Domine, F.: Thermodynamics and kinetics of the solid solution of \chemHNO_3 in ice, J Phys. Chem. B, 102, 4432–4439, 1998. Wood, R. and Healy, K.: liberation of aldehydes from alk-1-enyl glyceryl ethers by acid hydrolysis, Lipids, 5, 661–663, 1970. Yang, J., Honrath, R E., Peterson, M C., Dibb, J E., Sumner, A L., Shepson, P B., Frey, M., Jacobi, H W., Swanson, A., and Blake, N.: Impacts of snowpack emissions on deduced levels of \chemOH and peroxy radicals at Summit, Greenland, Atmos. Environ., 36, 2523–2534, 2002.