Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 10 3 2010 10.5194/acp-10-1203-2010 http://www.atmos-chem-phys.net/10/1203/2010/ http://www.atmos-chem-phys.net/10/1203/2010/acp-10-1203-2010.html http://www.atmos-chem-phys.net/10/1203/2010/acp-10-1203-2010.pdf 1203 1214 2010-02-03 A 15 year record of high-frequency, in situ measurements of hydrogen at Mace Head, Ireland A. Grant aoife.grant@bristol.ac.uk C. S. Witham P. G. Simmonds A. J. Manning S. O'Doherty School of Chemistry, University of Bristol, UK Met Office, FitzRoy Road, Exeter, Devon, UK Continuous high-frequency measurements of atmospheric molecular hydrogen have been made at Mace Head atmospheric research station on the west coast of Ireland from March 1994 to December 2008. The presented data provides information on long term trends and seasonal cycles of hydrogen in background northern hemispheric air. Individual measurements have been sorted using a Lagrangian dispersion model to separate clean background air from regionally polluted European air masses and those transported from southerly latitudes. No significant trend was observed in background northern hemispheric air over the 15 year record, elevations in yearly means were accounted for from large scale biomass burning events. Seasonal cycles show the expected pattern with maxima in spring and minima in late autumn. The mean hydrogen mole fraction in baseline northern hemispheric air was found to be 500.1 ppb. Air transported from southerly latitudes showed an elevation from baseline mean of 11.0 ppb, reflecting both the latitudinal gradient of hydrogen, with higher concentrations in the Southern Hemisphere, and the photochemical source of hydrogen from low northern latitudes. European polluted air masses arriving at Mace Head showed mean elevation of 5.3 ppb from baseline air masses, reflecting hydrogen's source from primary emissions like fossil fuel combustion. Forward modelling of transport of hydrogen to Mace Head suggests that the ratio of hydrogen to carbon monoxide in primary emissions is considerably less in non-traffic sources than traffic sources. Barnes, D. H., Wofsy, S. C., Fehlau, B. P., Gottlieb, E. W., Elkins, J. W., Dutton, G. S., and Novelli, P. C.: Hydrogen in the atmosphere: Observations above a forest canopy in a polluted environment, J. Geophys. Res., 108, 4197, doi:10.1029/2001JD001199, 2003. Brayshaw, D. J., Hoskins, B., and Blackburn, M.: The basic ingredients of the North Atlantic Storm Track, Part I: Land-sea contrast and orography, J. Atmos. Sci., 66, 2539–2558, 2009. Conrad, R. and Seiler, W.: Influence of Temperature, Moisture, and Organic Carbon on the Flux of H₂ and CO Between Soil and Atmosphere: Field Studies in Subtropical Regions, J. Geophys. Res., 90, 5699–5709, 1985. Creilson, J. K., Fishman, J., and Wozniak, A. E.: Intercontinental transport of tropospheric ozone: a study of its seasonal variability across the North Atlantic utilizing tropospheric ozone residuals and its relationship to the North Atlantic Oscillation, Atmos. Chem. Phys., 3, 2053–2066, 2003. Cunnold, D. M., Weiss, R. F., Prinn, R. G., Hartley, D., Simmonds, P. G., Fraser, P. J., Miller, B., Alyea, F. N., and Porter, L.: GAGE/AGAGE measurements indicating reductions in global emissions of CCl3F and CCl2F2 in 1992–1994, J. Geophys. Res., 102, 1259, doi:1210.1029/1296JD02973, 1997. Derwent, R. G., Simmonds, P. G., Seuring, S., and Dimmer, C.: Observation and interpretation of the seasonal cycles in the surface concentrations of ozone and carbon monoxide at Mace Head, Ireland from 1990 to 1994, Atmos. Environ., 32, 145–157, 1998. Derwent, R. G., Simmonds, P. G., Manning, A. J., O'Doherty, S., and Spain, G.: Methane emissions from peat bogs in the vicinity of the Mace Head Atmospheric Research Station over a 12-year period, Atmos. Environ., 43, 2328–2335, 2009. Duncan, B. N., Martin, R. V., Staudt, A. C., Yevich, R., and Logan, J. A.: Interannual and seasonal variability of biomass burning emissions constrained by satellite observations, J. Geophys. Res., 108, 4100, doi:10.1029/2002JD002378, 2003. Ehhalt, D. H. and Rohrer, F.: The tropospheric cycle of H2: A critical review, Tellus B, 61, 500–535, 2009. Glueckauf, E. and Kitt, G. P.: The hydrogen content of atmospheric air at ground level, Q. J.e Roy. Meteor. Soc., 83, 522–528, 1957. Hammer, S., Vogel, F., Kaul, M., and Levin, I.: The H₂/CO ratio of emissions from combustion sources: comparison of top-down with bottom-up measurements in southwest Germany, Tellus B, 61, 547–-555, 2009. Hauglustaine, D. A. and Ehhalt, D. H.: A three-dimensional model of molecular hydrogen in the troposphere, J. Geophys. Res., 107, 4330, doi:10.1029/2001JD001156, 2002. Jaffe, D., Bertschi, I., Jaegte, L., Novelli, P. C., Reid, J. S., Tanimoto, H., Vingarzan, R., and Westphal, D. L.: Large-scale transport of Siberian biomass burning emissions and impact on surface ozone in Western North America., Geophys. Res. Lett., 31, 16106, doi:10.1029/2004GL020093, 2004. Jones, A. R., Thomson, D. J., Hort, M., and Devenish, B.: The UK Met Office's next-generation atmospheric dispersion model, NAME III, in: Air Pollution Modeling and its Application XVII Proceedings of the 27th NATO/CCMS International Technical Meeting on Air Pollution Modelling and its Application, edited by: Borrego, C. and Norman, A.-L., 580–589, 2007, Khalil, M. A. K., and Rasmussen, R. A.: The global cycle of carbon monoxide: Trends and mass balance, Chemosphere, 20, 227-242, 1990. Lallo, M., Aalto, T., Laurila, T., and Hatakka, J.: Seasonal variations in hydrogen deposition to boreal forest soil in southern Finland, Geophys. Res. Lett., 35, L04402, doi:10.1029/2007GL032357, 2008. Langenfelds, R. L., Francey, R. J., Pak, B. C., Steele, L. P., Lloyd, J., Trudinger, C. M., and Allison, C. E.: Interannual growth rate variations of atmospheric CO₂ and its delta C-13, H-2, CH₄, and CO between 1992 and 1999 linked to biomass burning. , Global Biogeochem. Cy., 16, 1048, doi:10.1029/2001GB001466, 2002. Manning, A. J., Ryall, D. B., Derwent, R. G., Simmonds, P., and O'Doherty, S.: Estimating European emissions of ozone-depleting and greenhouse gases using observations and a modeling back-attribution technique, J. Geophys. Res., 108, 4405, doi:10.1029/2002JD002312, 2003. Novelli, P. C., Lang, P. M., Masarie, K. A., Hurst, D. F., Myers, R., and W., E. J.: Molecular hydrogen in the troposphere: Global distribution and budget, J. Geophys. Res., 104, 30427–30444, 1999. Price, H., Jaeglé, L., Rice, A., Quay, P., Novelli, P. C., and Gammon, R.: Global budget of molecular hydrogen and its deuterium content: Constraints from ground station, cruise, and aircraft observations, J. Geophys. Res., 112, D22108, doi:10.1029/2006JD008152, 2007. Prinn, R. G., Weiss, R. F., Fraser, P. J., Simmonds, P. G., Cunnold, D. M., Alyea, F. N., O'Doherty, S., Salameh, P., Miller, B. R., Huang, J., Wang, R. H. J., Hartley, D. E., Harth, C., Steele, L. P., Sturrock, G., Midgley, P. M., and McCulloch, A.: A history of chemically and radiatively important gases in air deduced from ALE/GAGE/AGAGE, J. Geophys. Res., 105, 17751, doi:10.1029/2000JD900141, 2000. Rahn, T., Eiler, J. M., Kitchen, N., Fessenden, J. E., and Randerson, J. T.: Concentration and $\delta $D of molecular hydrogen in boreal forests: Ecosystem-scale systematics of atmospheric H2, Geophys. Res. Lett., 29, 1888, doi:10.1029/2002GL015118, 2002. Rhee, T. S., Brenninkmeijer, C. A. M., and Röckmann, T.: The overwhelming role of soils in the global atmospheric hydrogen cycle, Atmos. Chem. Phys., 6, 1611–1625, 2006. Sanderson, M. G., Collins, W. J., Derwent, R. G., and Johnson, C. E.: Simulation of Global Hydrogen Levels Using a Lagrangian Three-Dimensional Model, J. Atmos. Chem., 43, 15–28, 2003. Schmidt, M., Hanselmann, U., Wollschlager, U., Hammer, S., and Levin, I.: Investigation of parameters controlling the soil sink of atmospheric molecular hydrogen, Tellus B, 61, 416–423, 2008. Schmidt, U.: Molecular hydrogen in the atmosphere, Tellus, 26, 78–90, 1974. Schmitt, S., Hanselmann, A., WollschlÄGer, U., Hammer, S., and Levin, I.: Investigation of parameters controlling the soil sink of atmospheric molecular hydrogen, Tellus B, 9999, 61, 416–423, 2009. Schultz, M. G., Diehl, T., Brasseur, G. P., and Zittel, W.: Air pollution and climate-forcing impacts of a global hydrogen economy, Science, 302, 624–627, 2003. Seiler, W. and Conrad, R.: Contribution of Tropical Ecosystems to the Global Budgets of Trace Gases, especially CH₄, H₂, CO and N₂O., in: The Geophysiology of Amazonia, Vegatation and Climate Interactions, John Wiley and Sons, New York, 133–151, 1987. Simmonds, P. G., Derwent, R. G., O'Doherty, S., Ryall, D. B., Steele, L. P., Langenfelds, R. L., Salameh, P., Wang, H. J., Dimmer, C. H., and Hudson, L. E.: Continuous high-frequency observations of hydrogen at the Mace Head baseline atmospheric monitoring station over the 1994–1998 period, J. Geophys. Res., 105, 12105–12121, 2000. Simmonds, P. G., Manning, A. J., Derwent, R. G., Ciais, P., Ramonet, M., Kazan, V., and Ryall, D.: A burning question, Can recent growth rate anomalies in the greenhouse gases be attributed to large-scale biomass burning events?, Atmos. Environ., 39, 2513–2517, 2005. Simmonds, P. G.: Hydrogen deposition to peat soil at Mace Head, Ireland, 2010. Steinbacher, M., Fischer, A., Vollmer, M. K., Buchmann, B., Reimann, S., and Hueglin, C.: Perennial observations of molecular hydrogen (H₂) at a suburban site in Switzerland, Atmos. Environ., 41, 2111–2124, 2007. Stohl, A., Berg, T., Burkhart, J. F., Fj\'æraa, A. M., Forster, C., Herber, A., Hov, Ø., Lunder, C., McMillan, W. W., Oltmans, S., Shiobara, M., Simpson, D., Solberg, S., Stebel, K., Ström, J., Tørseth, K., Treffeisen, R., Virkkunen, K., and Yttri, K. E.: Arctic smoke – record high air pollution levels in the European Arctic due to agricultural fires in Eastern Europe in spring 2006, Atmos. Chem. Phys., 7, 511–534, 2007. Tromp, T. K., Shia, R.-L., Allen, M., Eiler, J. M., and Yung, Y. L.: Potential environmental impact of a hydrogen economy on the stratosphere, Science, 300, 1740–1742, 2003. Vollmer, M. K., Juergens, N., Steinbacher, M., Reimann, S., Weilenmann, M., and Buchmann, B.: Road vehicle emissions of molecular hydrogen (H₂) from a tunnel study, Atmos. Environ., 41, 8355–-8369, 2007. Warwick, N. J., Bekki, S., Nisbet, E. G., and Pyle, J. A.: Impact of a hydrogen economy on the stratosphere and troposphere studied in a 2-D model, Geophys. Res. Lett., 31, L05107, doi:10.1029/2003GL019224, 2004. Xiao, X., Prinn, R. G., Simmonds, P., Novelli, P. C., Huang, L., Langenfelds, R. L., O'Doherty, S., Krummel, P. B., Fraser, P. J., Porter, L. W., Weiss, R. F., Salameh, P., and Wang, H. J.: Optimal estimation of the soil uptake rate of molecular hydrogen from the Advanced Global Atmospheric Gases Experiment and other measurements, J. Geophys. Res., 112, D07303, doi:10.1029/2006JD007241, 2007. Yonemura, S., Kawashima, S., and Tsuruta, H.: Continuous measurements of CO and H₂ deposition velocities onto an andisol: uptake control by soil moisture, Tellus B, 51, 688–700, 1999. Yonemura, S., Kawashima, S., and Tsuruta, H.: Carbon monoxide, hydrogen, and methane uptake by soils in a temperate arable field and a forest., J. Geophys. Res., 105, 14347–14362, 2000. Yurganov, L. N., Duchatelet, P., Dzhola, A. V., Edwards, D. P., Hase, F., Kramer, I., Mahieu, E., Mellqvist, J., Notholt, J., Novelli, P. C., Rockmann, A., Scheel, H. E., Schneider, M., Schulz, A., Strandberg, A., Sussmann, R., Tanimoto, H., Velazco, V., Drummond, J. R., and Gille, J. C.: Increased northern hemispheric carbon monoxide burden in the troposphere in 2002 and 2003 detected from the ground and from space, Atmos. Chem. Phys., 5, 563–573, 2005.