Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 11 2009 10.5194/acp-9-3491-2009 http://www.atmos-chem-phys.net/9/3491/2009/ http://www.atmos-chem-phys.net/9/3491/2009/acp-9-3491-2009.html http://www.atmos-chem-phys.net/9/3491/2009/acp-9-3491-2009.pdf 3491 3503 2009-06-02 Inter-comparison of four different carbon monoxide measurement techniques and evaluation of the long-term carbon monoxide time series of Jungfraujoch C. Zellweger christoph.zellweger@empa.ch C. Hüglin J. Klausen M. Steinbacher M. Vollmer B. Buchmann Empa, Swiss Federal Laboratories for Materials Testing and Research, Laboratory for Air Pollution/Environmental Technology, 8600 Dübendorf, Switzerland Despite the importance of carbon monoxide (CO) for the overall oxidative capacity of the atmosphere, there is still considerable uncertainty in ambient measurements of CO. To address this issue, an inter-comparison between four different measurement techniques was made over a period of two months at the high-alpine site Jungfraujoch (JFJ), Switzerland. The measurement techniques were Non-dispersive Infrared Absorption (NDIR), Vacuum UV Resonance Fluorescence (VURF), gas chromatographic separation with a mercuric oxide reduction detector (GC/HgO), and gas chromatographic separation followed by reduction on a nickel catalyst and analysis by a flame ionization detector (GC/FID). The agreement among all techniques was better than 2% for one-hourly averages, which confirmed the suitability of the NDIR method for CO measurements even at remote sites. The inter-comparison added to the validation of the 12-year record (1996–2007) of continuous CO measurements at JFJ. To date this is one of the longest time series of continuous CO measurements in the free troposphere over Central Europe. This data record was further investigated with a focus on trend analysis. A significant negative trend was observed at JFJ showing a decrease of 21.4±0.3% over the investigated period, or an average annual decrease of 1.78%/yr (2.65±0.04 ppb/yr). These results were compared with emission inventory data reported to the Long-range Transboundary Air Pollution (LRTAP) Convention. It could be shown that long range transport significantly influences the CO levels observed at JFJ, with air masses of non-European origin contributing at least one third of the observed mole fractions. Chevalier, A., Gheusi, F., Attié, J. L., Delmas, R., Zbinden, R., Athier, G., and Cousin, J. M.: Carbon monoxide observations from ground stations in France and Europe and long trends in the free troposphere, Atmos. Chem. Phys. Discuss., 8, 3313–3356, 2008. Daniel, J. S. and Solomon, S.: On the climate forcing of carbon monoxide, J. Geophys. Res. Atmos., 103, 13249–13260, 1998. Dils, B., Mahieu, E., Demoulin, P., Steinbacher, M., Buchmann, B., and De Maziere, M.: Ground-based CO observations at Jungfraujoch: Comparison between FTIR and NDIR measurements, in preparation, 2009. Duncan, B. N., Logan, J. A., Bey, I., Megretskaia, I. A., Yantosca, R. M., Novelli, P. C., Jones, N. B., and Rinsland, C. P.: Global budget of CO, 1988–1997: Source estimates and validation with a global model, J. Geophys. Res. Atmos., 112, D22301, doi:10.1029/2007JD008459, 2007. EEA: Annual European Community LRTAP Convention Emission Inventory report 1990-2005, Technical report No 14/2007, EEA (European Environment Agency)14/2007, 2007. Folini, D., Ubl, S., and Kaufmann, P.: Lagrangian particle dispersion modeling for the high Alpine site Jungfraujoch, J. Geophys. Res. Atmos., 113, D18111, doi:10.1029/2007jd009558, 2008. Forrer, J., Ruttimann, R., Schneiter, D., Fischer, A., Buchmann, B., and Hofer, P.: Variability of trace gases at the high-Alpine site Jungfraujoch caused by meteorological transport processes, J. Geophys. Res. Atmos., 105, 12241–12251, 2000. Fried, A., Henry, B., Parrish, D. D., Carpenter, J. R., and Buhr, M. P.: Intercomparison of Tunable Diode-Laser and Gas Filter Correlation-Measurements of Ambient Carbon-Monoxide, Atmos. Environ. A-Gen., 25, 2277–2284, 1991. GAWSIS: GAW Station Information System: http://gaw.empa.ch/gawsis, access: May 15, 2009. Gerbig, C., Schmitgen, S., Kley, D., Volz-Thomas, A., Dewey, K., and Haaks, D.: An improved fast-response vacuum-UV resonance fluorescence CO instrument, J. Geophys. Res. Atmos., 104, 1699–1704, 1999. Henne, S., Furger, M., Nyeki, S., Steinbacher, M., Neininger, B., de Wekker, S. F. J., Dommen, J., Spichtinger, N., Stohl, A., and Prévôt, A. S. H.: Quantification of topographic venting of boundary layer air to the free troposphere, Atmos. Chem. Phys., 4, 497–509, 2004. Hoell, J. M., Gregory, G. L., McDougal, D. S., Sachse, G. W., Hill, G. F., Condon, E. P., and Rasmussen, R. A.: Airborne Intercomparison of Carbon-Monoxide Measurement Techniques, J. Geophys. Res. Atmos., 92, 2009–2019, 1987. Holloway, J. S., Jakoubek, R. O., Parrish, D. D., Gerbig, C., Volz-Thomas, A., Schmitgen, S., Fried, A., Wert, B., Henry, B., and Drummond, J. R.: Airborne intercomparison of vacuum ultraviolet fluorescence and tunable diode laser absorption measurements of tropospheric carbon monoxide, J. Geophys. Res. Atmos., 105, 24251–24261, 2000a. Holloway, T., Levy, H., and Kasibhatla, P.: Global distribution of carbon monoxide, J. Geophys. Res. Atmos., 105, 12123–12147, 2000b. Kaiser, A., Schelfinger, H., Spangl, W., Weiss, A., Gilge, S., Fricke, W., Ries, L., Cemas, D., and Jesenovec, B.: Transport of nitrogen oxides, carbon monoxide and ozone to the Alpine Global Atmosphere Watch stations Jungfraujoch (Switzerland), Zugspitze and Hohenpeissenberg (Germany), Sonnblick (Austria) and Mt. Krvavec (Slovenia), Atmos. Environ., 41, 9273–9287, 2007. Khalil, M. A. K. and Rasmussen, R. A.: Carbon-Monoxide in the Earths Atmosphere – Indications of a Global Increase, Nature, 332, 242–245, 1988. Khalil, M. A. K. and Rasmussen, R. A.: Global Decrease in Atmospheric Carbon-Monoxide Concentration, Nature, 370, 639–641, 1994. Levy, H., Kasibhatla, P. S., Moxim, W. J., Klonecki, A. A., Hirsch, A. I., Oltmans, S. J., and Chameides, W. L.: The global impact of human activity on tropospheric ozone, Geophys. Res. Lett., 24, 791–794, 1997. Logan, J. A., Prather, M. J., Wofsy, S. C., and McElroy, M. B.: Tropospheric Chemistry – a Global Perspective, Journal of Geophysical Research-Oceans and Atmospheres, 86, 7210–7254, 1981. Luterbacher, J., Dietrich, D., Xoplaki, E., Grosjean, M., and Wanner, H.: European seasonal and annual temperature variability, trends, and extremes since 1500, Science, 303, 1499–1503, 2004. Meszaros, T., Haszpra, L., and Gelencser, A.: Tracking changes in carbon monoxide budget over Europe between 1995 and 2000, Atmos. Environ., 39, 7297–7306, 2005. Novelli, P. C., Masarie, K. A., Tans, P. P., and Lang, P. M.: Recent Changes in Atmospheric Carbon-Monoxide, Science, 263, 1587–1590, 1994. Novelli, P. C., Masarie, K. A., and Lang, P. M.: Distributions and recent changes of carbon monoxide in the lower troposphere, J. Geophys. Res. Atmos., 103, 19015–19033, 1998. Novelli, P. C.: CO in the atmosphere: measurement techniques and related issues, Chemosphere – Global Change Science, 1, 115–126, 1999. Novelli, P. C., Masarie, K. A., Lang, P. M., Hall, B. D., Myers, R. C., and Elkins, J. W.: Re-analysis of tropospheric CO trends: Effects of the 1997–1998 wild fires, J. Geophys. Res.-Atmos., 108, 4464, doi:4410.1029/2002JD003031, 2003. Pfister, G., Petron, G., Emmons, L. K., Gille, J. C., Edwards, D. P., Lamarque, J. F., Attie, J. L., Granier, C., and Novelli, P. C.: Evaluation of CO simulations and the analysis of the CO budget for Europe, J. Geophys. Res. Atmos., 109, doi:10.1029/2004JD004691, 2004. Reimann, S., Manning, A. J., Simmonds, P. G., Cunnold, D. M., Wang, R. H. J., Li, J., McCulloch, A., Prinn, R. G., Huang, J., Weiss, R. F., Fraser, J., O'Doherty, S., Greally, B. R., Stemmler, K., Hill, M., and Folini, D.: Low European methyl chloroform emissions inferred from long-term atmospheric measurements, Nature, 433, 506–508, 2005. Tanimoto, H., Sawa, Y., Matsueda, H., Yonemura, S., Wada, A., Mukai, H., Wang, T., Poon, S., Wong, A., Lee, G., Jung, J. Y., Kim, K. R., Lee, M., Lin, N. H., Wang, J. L., Ou-Yang, C. F., and Wu, C. F.: Evaluation of standards and methods for continuous measurements of carbon monoxide at ground-based sites in Asia, Papers in Meteorology and Geophysics, 58, 85–93, 2007. Tanimoto, H., Sawa, Y., Yonemura, S., Yumimoto, K., Matsueda, H., Uno, I., Hayasaka, T., Mukai, H., Tohjima, Y., Tsuboi, K., and Zhang, L.: Diagnosing recent CO emissions and ozone evolution in East Asia using coordinated surface observations, adjoint inverse modeling, and MOPITT satellite data, Atmos. Chem. Phys., 8, 3867–3880, 2008. Thoning, K. W., Tans, P. P., and Komhyr, W. D.: Atmospheric Carbon-Dioxide at Mauna Loa Observatory. 2. Analysis of the NOAA GMCC Data, 1974–1985, J. Geophys. Res. Atmos., 94, 8549–8565, 1989. Tressol, M., Ordonez, C., Zbinden, R., Brioude, J., Thouret, V., Mari, C., Nedelec, P., Cammas, J. P., Smit, H., Patz, H. W., and Volz-Thomas, A.: Air pollution during the 2003 European heat wave as seen by MOZAIC airliners, Atmos. Chem. Phys., 8, 2133–2150, 2008. Tsutsumi, Y. and Matsueda, H.: Relationship of ozone and CO at the summit of Mt. Fuji (35.35 degrees N, 138.73 degrees E, 3776 m above sea level) in summer 1997, Atmos. Environ., 34, 553–561, 2000. Vestreng, V., Breivik, K., Adams, M., Wagener, A., Goodwin, J., Rozovskkaya, O., and Pacyna, J. M.: Inventory Review 2005, Emission Data reported to LRTAP Convention and NEC Directive, Initial review of HMs and POPs. Technical report MSC-W 1/2005, ISSN 0804-2446Technical report MSC-W 1/2005, ISSN 0804-2446, 2005. 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, doi:10.1016/j.atmosenv.2007.06.037, 2007. Whalley, L. K., Lewis, A. C., McQuaid, J. B., Purvis, R. M., Lee, J. D., Stemmler, K., Zellweger, C., and Ridgeon, P.: Two high-speed, portable GC systems designed for the measurement of non-methane hydrocarbons and PAN: Results from the Jungfraujoch High Altitude Observatory, J. Environ. Monit., 6, 234–241, 2004. Wild, O. and Prather, M. J.: Excitation of the primary tropospheric chemical mode in a global three-dimensional model, J. Geophys. Res. Atmos., 105, 24647–24660, 2000. Wotawa, G., Novelli, P. C., Trainer, M., and Granier, C.: Inter-annual variability of summertime CO concentrations in the Northern Hemisphere explained by boreal forest fires in North America and Russia, Geophys. Res. Lett., 28, 4575–4578, 2001. York, D.: Least-Squares Fitting of a Straight Line, Can. J. Physics, 44, 1079–1086, 1966. Yurganov, L. N., Blumenstock, T., Grechko, E. I., Hase, F., Hyer, E. J., Kasischke, E. S., Koike, M., Kondo, Y., Kramer, I., Leung, F. Y., Mahieu, E., Mellqvist, J., Notholt, J., Novelli, P. C., Rinsland, C. P., Scheel, H. E., Schulz, A., Strandberg, A., Sussmann, R., Tanimoto, H., Velazco, V., Zander, R., and Zhao, Y.: A quantitative assessment of the 1998 carbon monoxide emission anomaly in the Northern Hemisphere based on total column and surface concentration measurements, J. Geophys. Res. Atmos., 109, doi:10.1029/2004JD004559, 2004. 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. Zander, R., Demoulin, P., Ehhalt, D. H., Schmidt, U., and Rinsland, C. P.: Secular Increase of the Total Vertical Column Abundance of Carbon-Monoxide above Central-Europe since 1950, J. Geophys. Res. Atmos., 94, 11021–11028, 1989. Zander, R., Mahieu, E., Demoulin, P., Duchatelet, P., Roland, G., Servais, C., Maziere, M. D., Reimann, S., and Rinsland, C. P.: Our changing atmosphere: Evidence based on long-term infrared solar observations at the Jungfraujoch since 1950, Sci. Total Environ., 391, 184–195, 2008. Zellweger, C., Ammann, M., Buchmann, B., Hofer, P., Lugauer, M., Ruttimann, R., Streit, N., Weingartner, E., and Baltensperger, U.: Summertime NOy speciation at the Jungfraujoch, 3580 m above sea level, Switzerland, J. Geophys. Res. Atmos., 105, 6655–6667, 2000. Zellweger, C., Forrer, J., Hofer, P., Nyeki, S., Schwarzenbach, B., Weingartner, E., Ammann, M., and Baltensperger, U.: Partitioning of reactive nitrogen (NOy) and dependence on meteorological conditions in the lower free troposphere, Atmos. Chem. Phys., 3, 779–796, 2003.