ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-11-25909-2011 The global atmospheric budget of ethanol revisited Kirstine W. V. 1 2 Galbally I. E. 2 School of Applied Sciences & Engineering, Monash University, Churchill, Victoria 3840, Australia Centre for Australian Weather and Climate Research, CSIRO Marine & Atmospheric Research, Aspendale, Victoria 3195, Australia 16 09 2011 11 9 25909 25936 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys-discuss.net/11/25909/2011/acpd-11-25909-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/11/25909/2011/acpd-11-25909-2011.pdf

Ethanol is an important biogenic volatile organic compound, which is increasingly used as a fuel for motor vehicles; therefore, an improved understanding of its atmospheric cycle is important. In this paper we use three sets of observational data, measured emissions of ethanol from living plants, measured concentrations of ethanol in the atmosphere and measured hydroxyl concentrations in the atmosphere (by methyl chloroform titration), to make two independent estimates related to the rate of cycling of ethanol through the atmosphere. The observational bases are small and the uncertainties large; however, the measurements identified above are the only experimentally determined information available on atmospheric ethanol. In the first estimate, simple calculations give the emission rate of ethanol from living plants as 26 (range, 10–38) Tg y<sup>−1</sup>. This contributes significantly to the total global ethanol source of 42 (range, 25–56) Tg y<sup>−1</sup>. In the second estimate, the total losses of ethanol from the global atmosphere are 70 (range, 50–90) Tg y<sup>−1</sup>, with about three-quarters of the ethanol removed by reaction with hydroxyl radicals in the gaseous and aqueous phases of the atmosphere, and the remainder lost through wet and dry deposition to land. These values of both the source of ethanol from living plants and the removal of atmospheric ethanol via oxidation by hydroxyl radicals (derived entirely from observations) are significantly larger than those in recent literature. We suggest that a revision of the estimate of global ethanol emissions from plants to the atmosphere to a value comparable with this analysis is warranted.

 References Anderson, J. G.: Ethanol fuel use in Brazil: air quality impacts, Energy Environ. Sci., 2, 1015–1037, 2009. Beale, R., Liss, P. S., and Nightingale, P. D.: First ocean measurements of ethanol and propanol, Geophys. Res. Lett., 37, L24607, http://dx.doi.org/10.1029/2010GL045534doi:10.1029/2010GL045534, 2010. Boudries, H., Bottenheim, J.W., Guimbaud, C., Grannas, A.M., Shepson, P.B., Houdier, S., Perrier, S., and Dominé, F.: Distribution and trends of oxygenated hydrocarbons in the high Arctic derived from measurements in the atmosphere boundary layer and interstitial snow air during ALERT2000 field campaign, Atmos. Environ., 36, 2573–2583, 2002. Chawanakul, S., Chaiprasert, P., Towprayoon, S., and Tanticharoen, M.: Contributions of available substrates and activities of trophic microbial community to methanogenesis in vegetative and reproductive rice rhizospheric soil, J. Environ. Biol., 30, 119–127, 2009. Chung, M. Y., Beene, M., Ashkan, S., Krauter, C., and Hasson, A. S.: Evaluation of non-enteric sources of non-methane volatile organic compound (NMVOC) emissions from dairies, Atmos. Environ., 44, 786–794, 2010. Cullen, A. C. and Frey, H. C.: Probabilistic Techniques in Exposure Assessment, Plenum Press, NY, USA, 1999. de Gouw, G. A., Middlebrook, A M , Warneke, C , Goldan, P D., Kuster, W C., Roberts, J M., Fehsenfeld, F C., Worsnop, D R., Canagaratna, M R., Pszenny, A A P , Keene, W C., Marchewka, M , Bertman, S B., and Bates, T S.: Budget of organic carbon in a polluted atmosphere: results from the New England Air Quality Study in 2002, J. Geophys. Res., 110, D16305, http://dx.doi.org/10.1029/2004JD005623doi:10.1029/2004JD005623, 2005. Ervens, B., Gligorovski, S., and Herrmann, H.: Temperature-dependent rate constants for hydroxyl radical reactions with organic compounds in aqueous solution, Phys. Chem. Chem. Phys., 5, 1811–1824, 2003. Esser, G.: Implications of climate change for production and decomposition in grasslands and coniferous forests, Ecol. Appl., 2, 47–54, 1992. Fehsenfeld, F., Calvert, J., Fall, R., Goldan, P., Guenther, A. B., Hewitt, C. N., Lamb, B., Liu, S., Trainer, M., Westberg, H. and Zimmerman, P.: Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry, Global Biogeochem. Cy., 6, 389–430, 1992. Filipy, J., Rumburg, B., Mount, G., Westberg, H., and Lamb, B.: Identification and quantification of volatile organic compounds from a dairy, Atmos. Environ., 40, 1480–1494, 2006. Fukui, Y. and Doskey, P. V.: Air-surface exchange of nonmethane organic compounds at a grassland site: seasonal variations and stressed emissions, J. Geophys. Res., 103, 13153–13168, 1998. Galbally, I. E. and Kirstine, W.: The production of methanol by flowering plants and the global cycle of methanol, J. Atmos. Chem., 43, 195–229, 2002. Gilman, J. B., Kuster, W. C., Goldan, P. D., Herndon, S. C., Zahniser, M. S., Tucker, S. C., Brewer, W. A., Lerner, B. M., Williams, E. J., Harley, R. A., Fehsenfeld, F. C., Warneke, C., and de Gouw, J.: Measurements of volatile organic compounds during the 2006 TexAQS/GoMACCS campaign: industrial influences, regional characteristics, and diurnal dependencies of the OH reactivity, J. Geophys. Res., 114, D00F06, http://dx.doi.org/10.1029/2008JD011525doi:10.1029/2008JD011525, 2009. Goldan, P. D., Kuster, W. C., and Fehsenfeld, F. C.: Hydrocarbon measurements in the southeastern United States: the rural oxidants in the southern environment (ROSE) program 1990, J. Geophys. Res., 100, 25945–25963, 1995a. Goldan, P. D., Trainer, M., Kuster, W. C., Parrish, D. D., Carpenter, J., Roberts, J. M., Yee, J. E., and Fehsenfeld, F. C.: Measurements of hydrocarbons, oxygenated hydrocarbons, carbon monoxide, and nitrogen oxides in an urban basin in Colorado: implications for emission inventories, J. Geophys. Res., 100, 22771–22783, 1995b. Grabmer, W., Kreuzwieser, J., Wisthaler, A., Cojocariu, C., Graus, M., Rennenberg, H., Steigner, D., Steinbrecher, R., and Hansel, A.: VOC emissions from Norway spruce (\textitPicea abies L. [Karst]) twigs in the field – results of a dynamic enclosure study, Atmos. Environ., 40, S128–S137, 2006. Guenther, A., Zimmerman, P., and Wildermuth, K.: Natural volatile organic compound emission rate estimates for U.S. woodland landscapes, Atmos. Environ., 28, 1197–1210, 1994. Helmig, D., Klinger, L. F., Guenther, A., Vierling, L., Geron, C., and Zimmerman, P.: Biogenic volatile organic compound emissions (BVOCs) I. Identifications from three continental sites in the U.S., Chemosphere, 38, 2163–2187, 1999. Herrmann, H., Ervens, B., Nowacki, P., Wolke, R., and Zellner, R.: A chemical aqueous phase radical mechanism for tropospheric chemistry, Chemosphere, 38, 1223–1232, 1999. 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. Holzinger, R., Sandoval-Soto, L., Rottenberger, S., Crutzen, P.J., and Kesselmeier, J.: Emissions of volatile organic compounds from \textitQuercus ilex L. measured by Proton Transfer Reaction Mass Spectrometry under different environmental conditions, J. Geophys. Res., 105, 20573–20579, 2000. Jiménez, E., Gilles, M. K., and Ravishankara, A. R.: Kinetics of the reactions of the hydroxyl radical with CH<sub>3</sub>OH and C<sub>2</sub>H$_5$OH between 235 and 360 K, J. Photochem. Photobiol. A, 157, 237–245, 2003. Jonsson, A., Persson, K. A., and Grigoriadis, V.: Measurements of some low molecular-weight oxygenated, aromatic, and chlorinated hydrocarbons in ambient air and in vehicle emissions, Environ. Internat., 11, 383–392, 1985. Junge, C. E.: Residence time and variability of tropospheric trace gases, Tellus, 26, 477–488, 1974. Kimmerer, T. W. and MacDonald, R. C.: Acetaldehyde and ethanol biosynthesis in leaves of plants, Plant Physiol., 84, 1204–1209, 1987. Kirstine, W. and Galbally, I.E.: Ethanol in the environment – a critical review of its roles as a natural product, a biofuel and a potential environmental pollutant, Crit. Rev. Environ. Sci. Technol., accepted, 2011. Kirstine, W., Galbally, I. E., Ye, Y., and Hooper, M. A.: Emissions of volatile organic compounds (primarily oxygenated species) from pasture, J. Geophys. Res., 103, 10605–10620, 1998. Kreuzwieser, J., Papadopoulou, E., and Rennenberg, H.: Interaction of flooding with carbon metabolism of forest trees, Plant Biol., 6, 299–306, 2004. Legreid, G., Lööv, J. B., Staehelin, J., Hueglin, C., Hill, M., Buchmann, B., Prevot, A. S. H., and Reimann, S.: Oxygenated volatile organic compounds (OVOCs) at an urban background site in Zürich (Europe): seasonal variation and source allocation, Atmos. Environ., 41, 8409–8423, 2007. Legreid, G., Folini, D., Staehelin, J., Lööv, J. B., Steinbacher, M., and Reimann, S.: Measurements of organic trace gases including oxygenated volatile organic compounds at the high altitude site Jungfraujoch (Switzerland): seasonal variation and source allocations, J. Geophys. Res., 113, D05307, http://dx.doi.org/10.1029/2007JD008653doi:10.1029/2007JD008653, 2008. Leibrock, E. and Slemr, J.: Method for measurement of volatile oxygenated hydrocarbons in ambient air, Atmos. Environ., 31, 3329–3339, 1997. Lelieveld, J. and Crutzen, P. J.: The role of clouds in tropospheric photochemistry, J. Atmos. Chem., 12, 229–267, 1991. Lelieveld, J., Crutzen, P. J., and Rodhe, H.: Zonal average cloud characteristics for global atmospheric chemistry modelling, GLOMAC Report CM-76, UDC 551.510.4, International Meteorological Institute of Stockholm, 1989. Leriche, M., Voisin, D., Chaumerliac, N., Monod, A., and Aumont, B.: A model for tropospheric multiphase chemistry: application to one cloudy event during the CIME experiment, Atmos. Environ., 34, 5015–5036, 2000. MacDonald, R. C. and Kimmerer, T. W.: Metabolism of transpired ethanol by eastern cottonwood (\textitPopulus deltoides Bartr.), Plant Physiol., 102, 173–179, 1993. Metje, M. and Frenzel, P.: Effect of temperature on anaerobic ethanol oxidation and methanogenesis in acidic peat from a northern wetland, Appl. Environ. Microbiol., 71, 8191–8200, 2005. Millet, D. B., Goldstein, A. H., Allan, J. D., Bates, T. S., Boudries, H., Bower, K. N., Coe, H., Ma, Y., McKay, M., Quinn, P. K., Sullivan, A., Weber, R. J., and Worsnop, D. R.: Volatile organic compound measurements at Trinidad Head, California, during ITCT 2K2: analysis of sources, atmospheric composition, and aerosol residence times, J. Geophys. Res., 109, D23S16, http://dx.doi.org/10.1029/2003JD004026doi:10.1029/2003JD004026, 2004. Millet, D. B., Donahue, N. M., Pandis, S. N., Polidori, A., Stanier, C. O., Turpin, B. J., and Goldstein, A. H.: Atmospheric volatile organic compound measurements during Pittsburgh Air Quality Study: results, interpretation, and quantification of primary and secondary contributions, J. Geophys. Res., 110, D07S07, http://dx.doi.org/10.1029/2004JD004601doi:10.1029/2004JD004601, 2005. Millet, D. B., Goldstein, A. H., Holzinger, R., Williams, B. J., Allan, J. D., Jimenez, J. L., Worsnop, D. R., Roberts, J. M., White, A. B., Hudman, R. C., Bertschi, I. T., and Stolhl, A.: Chemical characteristics of North American surface layer outflow: insights from Chebogue Point, Nova Scotia, J. Geophys. Res., 111, D23S53, http://dx.doi.org/10.1029/2006JD007287doi:10.1029/2006JD007287, 2006. Millet, D. B., Guenther, A., Siegel, D. A., Nelson, N. B., Singh, H. B., de Gouw, J. A., Warneke, C., Williams, J., Eerdekens, G., Sinha, V., Karl, T., Flocke, F., Apel, E., Riemer, D. D., Palmer, P. I., and Barkley, M.: Global atmospheric budget of acetaldehyde: 3-D model analysis and constraints from in-situ and satellite observations, Atmos. Chem. Phys., 10, 3405–3425, http://dx.doi.org/10.5194/acp-10-3405-2010doi:10.5194/acp-10-3405-2010, 2010. Murphy, J. G., Day, D. A., Cleary, P. A., Wooldridge, P. J., Millet, D. B., Goldstein, A. H., and Cohen, R. C.: The weekend effect within and downwind of Sacramento - Part 1: Observations of ozone, nitrogen oxides, and VOC reactivity, Atmos. Chem. Phys., 7, 5327–5339, http://dx.doi.org/10.5194/acp-7-5327-2007doi:10.5194/acp-7-5327-2007, 2007. Naik, V., Fiore, A. M., Horowitz, L. W., Singh, H. B., Wiedinmyer, C., Guenther, A., de Gouw, J. A., Millet, D. B., Goldan, P. D., Kuster, W. C., and Goldstein, A.: Observational constraints on the global atmospheric budget of ethanol, Atmos. Chem. Phys., 10, 5361–5370, http://dx.doi.org/10.5194/acp-10-5361-2010doi:10.5194/acp-10-5361-2010, 2010. Nguyen, H. T., Takenaka, N., Bandow, H., Maeda, Y., de Oliva, S. T., Botelho, M. M., and Tavares, T. M.: Atmospheric alcohols and aldehydes concentrations measured in Osaka, Japan and in São Paulo, Brazil, Atmos. Environ., 35, 3075–3083, 2001. Ngwabie, N. M., Schade, G. W., Custer, T. G., Linke, S., and Hinz, T.: Abundances and flux estimates of volatile organic compounds from a dairy cowshed in Germany, J. Environ. Qual., 37, 565–573, 2008. Niedojadlo, A., Becker, K. H., Kurtenbach, R., and Wiesen, P.: The contribution of traffic and solvent use to the total NMVOC emission in a German city derived from measurement and CMB modelling, Atmos. Environ., 41, 7108–7126, 2007. Potere, D., Schneider, A., Angel, S., and Civco, D. L.: Mapping urban areas on a global scale: which of the eight maps now available is more accurate?, Int. J. Remote Sensing, 30, 6531–6558, 2009. Potter, C. S.: Terrestrial biomass and effects of deforestation on the global carbon cycle, Bioscience, 49, 769–778, 1999. Prinn, R. G., Huang, J., Weiss, R. F., Cunnold, D. M., Fraser, P. J., Simmonds, P. G., McCulloch, A., Harth, C., Salemeh, P., O'Doherty, S., Wang, R. H., Porter, L., and Miller, B. R.: Evidence for substantial variations of atmospheric hydroxyl radicals in the past two decades, Science, 292, 1882–1888, 2001. Riemer, D., Pos, W., Milne, P., Farmer, C., Zika, R., Apel, E., Olszyna, K., Kleindienst, T., Lonneman, W., Bertman, S., Shepson, P., and Starn, T.: Observations of nonmethane hydrocarbons and oxygenated organic compounds at a rural site in the southeastern United States, J. Geophys. Res., 103, 28111–28128, 1998. Rottenberger, S., Kleiss, B., Kuhn, U., Wolf, A., Piedade, M. T. F., Junk, W., and Kesselmeier, J.: The effect of flooding on the exchange of the volatile C<sub>2</sub>-compounds ethanol, acetaldehyde and acetic acid between leaves of Amazonian floodplain tree species and the atmosphere, Biogeosciences, 5, 1085–1100, 2008. Sanderson, M.: UNESCO Sourcebook in Climatology, UNESCO, France, 1990. Schade, G. W. and Goldstein, A. H.: Fluxes of oxygenated volatile organic compounds from a ponderosa pine plantation, J. Geophys. Res., 106, 3111–3123, 2001. Shaw, S. L., Mitloehner, F. M., Jackson, W., Depeters, E. J., Fadel, J. G., Robinson, P. H., Holzinger, R., and Goldstein, A. H.: Volatile organic compound emissions from dairy cows and their waste as measured by proton-transfer-reaction mass spectrometry, Environ. Sci. Technol., 41, 1310–1316, 2007. Singh, H. B., Kanakidou, M., Crutzen, P. J., and Jacob, D. J.: High concentrations and photochemical fate of oxygenated hydrocarbons in the global troposphere, Nature, 378, 50–54, 1995. Singh, H., Chen, Y., Tabazadeh, A. Fukui, Y., Bey, I., Yantosca, R., Jacob, D., Arnold, F., Wohlfrom, K., Atlas, E., Flocke, F., Blake, D, Blake, N., Heikes, B., Snow, J., Talbot, R., Gregory, G., Sachse, G., Vay, S., and Kondo, Y.: Distribution and fate of selected oxygenated organic species in the troposphere and lower stratosphere over the Atlantic, J. Geophys. Res., 105, 3795–3805, 2000. Singh, H., Chen, Y., Staudt, A., Jacob, D., Blake, D, Heikes, B., and Snow, J.: Evidence for the Pacific troposphere for large global sources of oxygenated organic compounds, Nature, 410, 1078–1081, 2001. Singh, H., Salas, L. J., Chatfield, R. B., Czech, E., Fried, A., Walega, J., Evans, M. J., Field, B. D., Jacob, D., Blake, D., Heikes, B., Talbot, R., Sachse, G., Crawford, J. H., Avery, M. A., Sandholm, S., and Fuelberg, H.: Analysis of the atmospheric distribution, sources, and sinks of oxygenated volatile organic chemicals based on measurements over the Pacific during TRACE-P, J. Geophys. Res., 109, D15S07, http://dx.doi.org/10.1029/2003JD003883doi:10.1029/2003JD003883, 2004. Singh, H., Brune, W. H., Crawford, J. H., Jacob, D. J., and Russell, P. B.: Overview of the summer 2004 Intercontinental Chemical Transport Experiment – North America (INTEX-A), J. Geophys. Res., 111, D24S01, http://dx.doi.org/10.1029/2006JD007905doi:10.1029/2006JD007905, 2006. Singh, H. B., Brune, W. H., Crawford, J. H., Flocke, F., and Jacob, D. J.: Chemistry and transport of pollution over the Gulf of Mexico and the Pacific: spring 2006 INTEX-B campaign overview and first results, Atmos. Chem. Phys., 9, 2301–2318, http://dx.doi.org/10.5194/acp-9-2301-2009doi:10.5194/acp-9-2301-2009, 2009. Snider, J. R. and Dawson, G. A.: Tropospheric light alcohols, carbonyls, and acetonitrile: concentrations in the southwestern United States and Henry's law data, J. Geophys. Res., 90, 3797–3805, 1985. Sun, H., Trabue, S. L., Scoggin, K., Jackson, W. A., Pan, Y., Zhao, Y., Malkina, I. L., Koziel, J. A., and Mitloehner, F. M.: Alcohol, volatile fatty acid, phenol, and methane emissions from dairy cows and fresh manure, J. Environ. Qual., 37, 615–622, 2008. von Kuhlmann, R., Lawrence, M. G., Crutzen, P. J., and Rasch, P. J.: A model for the studies of atmospheric ozone and non-methane hydrocarbons: model description and ozone results, J. Geophys. Res., 108, 4294, http://dx.doi.org/10.1029/2002JD002893doi:10.1029/2002JD002893, 2003. Warneke, C., Kato, S., deGouw, J. A., Goldan, P. D., Kuster, W. C., Shao, K., Lovejoy, E. R., Fall, R., and Fehsenfeld, F. C.: Online volatile organic compound measurements using a newly developed proton-transfer ion-trap mass spectrometry instrument during New England Air Quality Study – Intercontinental Transport and Chemical Transformation 2004: Performance, intercomparison, and compound identification, Environ. Sci. Technol., 39, 5390–5397, 2005.