Biogeosciences www.biogeosciences.net 1726-4170 1726-4189 5 6 2008 10.5194/bg-5-1551-2008 http://www.biogeosciences.net/5/1551/2008/ http://www.biogeosciences.net/5/1551/2008/bg-5-1551-2008.html http://www.biogeosciences.net/5/1551/2008/bg-5-1551-2008.pdf 1551 1558 2008-11-14 No detectable aerobic methane efflux from plant material, nor from adsorption/desorption processes M. U. F. Kirschbaum A. Walcroft Landcare Research, Private Bag 11052, Palmerston North 4442, New Zealand In early 2006, Keppler et al. (Nature, 439:187–191) reported a novel finding that plant leaves, and even simple organic materials, can release methane under aerobic conditions. We investigated here whether the reported methane release might simply arise from methane desorption from sample surfaces after prior exposure to higher methane concentrations. We exposed standard cellulose filter papers (i.e. organic material with a high surface area) to atmospheric methane concentration and then transferred them to a low-methane atmosphere. Our results suggest that any desorption flux was extremely small (−0.0001±0.0019 ngCH4 kgDW−1 s−1) and would play no quantitatively significant role in modifying any measured methane fluxes. We also incubated fresh detached leaves of several species and intact Zea mays seedlings under aerobic and low-light conditions. After correcting for a small measured methane influx into empty chambers, measured rates of methane emission by plant materials were zero or, at most, very small, ranging from −0.25±1.1 ngCH4 kgDW−1 s−1 for Zea mays seedlings to 0.10±0.08 ngCH4 kgDW−1 s−1 for a mixture of freshly detached grasses. These rates were much smaller than the rates originally reported by Keppler et al. (2006). Beerling, D. J., Gardiner, T., Leggett, G., McLeod, A., and Quick, W. P.: Missing methane emissions from leaves of terrestrial plants, Global Change Biol., 14, 1–6, 2008. Biloe, S., Goetz, V., and Guillot, A.: Optimal design of an activated carbon for an adsorbed natural gas storage system, Carbon, 40, 1295–1308, 2002. Carpita, N., Sabularse, D., Montezinos, D., and Delmer, D. P.: Determination of the pore size of cell walls of living plant cells, Science, 205, 1144–1147, 1979. Carpita, N. C. and Gibeaut, D. M.: Structural models of primary cell walls in flowering plants: consistency of molecular structure with the physical properties of the walls during growth, The Plant Journal, 3, 1–30, 1993. Celzard, A. and Fierro, V.: Preparing a suitable material designed for methane storage: A comprehensive report, Energy and Fuels, 19, 573–583, 2005. Cheng, A.-L. and Huang, W.-L.: Selective adsorption of hydrocarbon gases on clays and organic matter, Org. Geochem., 35, 413–423, 2004. Crutzen, P. J., Sanhueza, E., and Brenninkmeijer, C. A. M.: Methane production from mixed tropical savanna and forest vegetation in Venezuela, Atmos. Chem. Phys. Discuss., 6, 3093-3097, 2006. do Carmo, J. B., Keller, M., Dias, J. D., de Camargo, P. B., and Crill, P.: A source of methane from upland forests in the Brazilian Amazon, Geophys. Res. Lett., 33, L04809, doi:10.1029/2005GL025436, 2006. Dueck, T. A., de Visser, R., Poorter, H., Persijn, S., Gorissen, A., de Visser, W., Schapendonk, A., Verhagen, J., Snel, J., Harren, F. J. M., Ngai, A. K. Y., Verstappen, F., Bouwmeester, H., Voesenek, L. A. C. J., and van der Werf, A.: No evidence for substantial aerobic methane emission by terrestrial plants: A $^13$C-labelling approach, New Phytol., 175, 29–35, 2007. Ferretti, D. F., Miller, J. B., White, J. W. C., Lassey, K. R., Lowe, D. C., and Etheridge, D. M.: Stable isotopes provide revised global limits of aerobic methane emissions from plants, Atmos. Chem. Phys., 7, 237–241, 2007. Frankenberg, C., Bergamaschi, P., Butz, A., Houweling, S., Meirink, J. F., Notholt, J., Petersen, A. K., Schrijver, H., Warneke, T., and Aben, I.: Tropical methane emissions: A revised view from SCIAMACHY onboard ENVISAT, Geophys. Res. Lett., 35, L15811, doi:10.1029/2008GL034300, 2008. Frankenberg, C., Meirink, J. F., Bergamaschi, P., Goede, A. P. H., Heimann, M., Körner, S., Platt, U., van Weele, M., and Wagner, T.: Satellite chartography of atmospheric methane from SCIAMACHY onboard ENVISAT: Analysis of the years 2003 and 2004, J. Geophys. Res., 111, D07303, doi:10.1029/2005JD006235, 2006. Frankenberg, C., Meirink, J. F., van Weele, M., Platt, U., and Wagner, T.: Assessing methane emissions from global space-borne observations, Science, 308, 1010–1014, 2005. García-Pérez, E., Parra, J. B., Ania, C. O., García-Sánchez, A., van Baten, J. M., Krishna, R., Dubbeldam, D., and Calero, S.: A computational study of CO2, N2, and CH4 adsorption in zeolites, Adsorption, 13, 469–476, 2007. Ghyczy, M., Torday, C., Kaszaki, J., Szabó, A., Czóbel, M., and Mihály, B.: Hypoxia-induced generation of methane in mitochondria and eukaryotic cells – an alternative approach to methanogenesis, Cell. Physiol. Biochem., 21, 251–258, 2008. Harrison, D., Seakins, P. W., and Lewis, A. C.: Simultaneous monitoring of atmospheric methane and speciated nonmethane hydrocarbon concentrations using Peltier effect sub-ambient pre-concentration and gas chromatography, J. Environ. Monitor., 2, 59–63, 2000. Higaki, S., Oya, Y., and Makide, Y.: Emission of methane from stainless steel surface investigated by using tritium as a radioactive tracer, Chem. Lett., 35, 292–293, 2006. Keppler, F., Hamilton, J. T. G., Braß, M., and Röckmann, T.: Methane emissions from terrestrial plants under aerobic conditions, Nature, 439, 187–191, 2006. Keppler, F., Hamilton, J. T. G., McRoberts, W. C., Vigano, I., Braß, M., and Röckmann, T.: Methoxyl groups of plant pectin as a precursor of atmospheric methane: Evidence from deuterium labelling studies, New Phytol., 178, 808–814, 2008. Kirschbaum, M. U. F., Bruhn, D., Etheridge, D. M., Evans, J. R., Farquhar, G. D., Gifford, R. M., Paul, K. I., and Winters, A. J.: A comment on the quantitative significance of aerobic methane release by plants, Funct. Plant Biol., 33, 521–530, 2006. Kirschbaum, M. U. F., Niinemets, U., Bruhn, D., and Winters, A. J.: How important is aerobic methane release by plants?, Functional Plant Science and Biotechnology, 1, 138–145, 2007. Lozano-Castello, D., Alcaniz-Monge, J., de la Casa-Lillo, M. A., Cazorla-Amoros, D., and Linares-Solano, A.: Advances in the study of methane storage in porous carbonaceous materials, Fuel, 81, 1777–1803, 2002. McLeod, A. R., Fry, S. C., Loake, G. J., Messenger, D. J., Reay, D. S., Smith, K. A., and Yun, B.-W.: Ultraviolet radiation drives methane emissions from terrestrial plant pectins, New Phytol., 180, 124–132, doi:10.1111/j.1469-8137.2008.02571.x, 2008. Pignatello, J. J. and Xing, B.: Mechanisms of slow sorption of organic chemicals to natural particles, Environ. Sci. Technol., 30, 1–11, 1996. Pollmann, J., Helmig, D., Hueber, J., Tanner, D., and Tans, P. P.: Evaluation of solid adsorbent materials for cryogen-free trapping – gas chromatographic analysis of atmospheric C2-C6 non-methane hydrocarbons, J. Chromato. A, 1134, 1–15, 2006. Ramaswamy, V., Boucher, O., Haigh, J., Hauglustaine, D., Haywood, J., Myhre, G., Nakajima, T., Shi, G. Y., and Solomon, S.: Radiative forcing of climate change, in: Climate Change 2001: The Scientific Basis, Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Houghton, J. T., Ding, Y., Griggs, D. J., Noguer, M., van der Linden, P. J., Dai, X., Maskell, K., and Johnson, C. A., Cambridge University Press, Cambridge, UK, 349–416, 2001. R Development Core Team: R-A language and environment for statistical computing, version 2.7.1. R Foundation for Statistical Computing, Vienna, Austria, ISBN 3-900051-07-0 (http://www.R-project.org), 2008. Saha, B. B ., Koyama, S., El-Sharkawy, I. I., Habib, K., Srinivasan, K., and Dutta, P.: Evaluation of adsorption parameters and heats of adsorption through desorption measurements, Journal of Chemical Engineering Data, 52, 2419–2424, 2007. Sanhueza, E. and Donoso, L.: Methane emission from tropical savanna \textitTrachypogon sp. grasses, Atmos. Chem. Phys., 6, 5315–5319, 2006. Shao, X., Wang, W., Xue, R., and Shen, Z.: Adsorption of methane and hydrogen on mesocarbon microbeads by experiment and molecular simulation, J. Phys.l Chem. B, 108, 2970–2978, 2004. Thammakhet, C., Thavarungkul, P., Brukh, R., Mitra, S., and Kanatharana, P.: Microtrap modulated flame ionization detector for on-line monitoring of methane, J. Chromatogr. A, 1072, 243–248, 2005. Vigano, I., van Weelden, H., Holzinger, R., Keppler, F., McLeod, A., and Röckmann, T.: Effect of UV radiation and temperature on the emission of methane from plant biomass and structural components, Biogeosciences, 5, 937–947, 2008. Walton, K. S., Cavalcante, C. L., and Levan, M. D.: Adsorption equilibrium of alkanes on a high surface area activated carbon prepared from Brazilian coconut shells, Adsorption, 11, 107–111, 2005. Wang, Z.-P., Han, X.-G., Wang, G. G., Song, Y. and, Gulledge, J.: Aerobic methane emission from plants in the inner Mongolia steppe, Environ. Sci. Technol., 42, 62–68, 2008. Wegrzyn, J. and Gurevich, M.: Adsorbent storage of natural gas, Appl. Energ., 55, 71–83, 1996. Zhang, T. and Krooss, B. M.: Experimental investigation on the carbon isotope fractionation of methane during gas migration by diffusion through sedimentary rocks at elevated temperature and pressure, Geochim. et Cosmochim. Ac., 65, 2723–2742, 2001.