References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-8-20113-2008

Atmospheric oxygen and carbon dioxide observations from two European coastal stations 2000–2005: continental influence, trend changes and APO climatology

Sirignano

¹ Neubert

R. E. M.

¹ Meijer

H. A. J.

¹ Rödenbeck

Centre for Isotope Research, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands

Max-Planck-Institute for Biogeochemistry, Hans-Knoell-Straße 10, 07745, Jena, Germany

28 11 2008

8 6 20113 20154

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Seeking for baseline conditions has biased the carbon dioxide (CO2) monitoring networks towards remote marine stations, missing part of the variability that is due to regional anthropogenic as well as land biota activity. We present here a five-year record of atmospheric CO2 mixing ratios and oxygen/nitrogen ratios (O2/N2) from the coastal stations Lutjewad (LUT), the Netherlands and Mace Head (MHD), Ireland, derived from flask samples. Oxygen mixing ratios, concurrently measured with CO2, help determine regional CO2 fluxes by separating land fluxes from sea fluxes. Mace Head is the closest marine baseline station to Lutjewad, located at the same latitude, and therefore is taken as a reference. During the period of this study, we observed an average increase of CO2 in the atmosphere of (1.7±0.2) μmol*(mol dry air)−1 per year, and a change of the O2 fraction of (−20±1) per meg per year. The observed acceleration of the oxygen decrease during the study period seems to confirm the existence of a net oxygen sink other than the combustion processes alone. The difference between the CO2 summer minimum and the winter maximum is 14.4 μmol*(mol dry air)−1 and 16.1 μmol*(mol dry air)−1 at Mace Head and Lutjewad, respectively, while the opposite variation in the O2 signal equals 113 per meg and 153 per meg, respectively. We also studied the APO (atmospheric potential oxygen) tracer at both stations. By this analysis, evidence has been found that we need to be careful when using APO close to anthropogenic CO2 sources. It could be biased by combustion-derived CO2, and models have to take into account daily and seasonal variations in the anthropogenic CO2 production in order to be able to simulate APO over the continents.

References 1

Balkanski, Y., Monfray, P., Battle, M., and Heimann, M.: Ocean primary production derived from satellite data: An evaluation with atmospheric oxygen measurements, Global Biogeochem. Cy., 13, 257–271, 1999.

Battle, M., Bender, M. L., Tans, P. P., White, J. W. C., Ellis, J. T., Conway, T., and Francey, R. J.: Global carbon sinks and their variability inferred from atmospheric O2 and $\delta $13C, Science, 287, 2467–2470, 2000.

Battle, M., Fletcher, S. M., Bender, M. L., Keeling, R. F., Manning, A. C., Gruber, N., Tans, P. P., Hendricks, M. B., Ho, D. T., Simonds, C., Mika, R., and Paplawsky, B.: Atmospheric Potential Oxygen: New observations and their implications for some atmospheric and oceanic models, Global Biogeochem. Cy., 20, GB1010, doi:10.1029/2005GB002534, 2006.

Bender, M., Ellis, T., Tans, P., Francey, R., and Lowe, D.: Variability in the O2/N2 ratio of southern hemisphere air, 1991–1994: Implications for the Carbon cycle, Global Biogeochem. Cy., 10, 9–21, 1996.

Bender, M. L., Tans, P. P., Ellis, J. T., Orchardo, J., and Habfast, K.: A high-precision isotope ratio mass spectrometry method for measuring the O2/N2 ratio of air, Geochim. Cosmochim. Ac., 58, 4751–4758, 1994.

Bousquet, P., Gaudry, A., Ciais, P., Kazan, V., Monfray, P., Simmonds, P. G., Jennings, S. G., and O'Connor, T. C.: Atmospheric CO2 concentration variations recorded at Mace Head, Ireland from 1992 to 1994, Phys. Chem. Earth, 21, 477–481, 1996.

BP Statistical Review of World Energy June 2008, BP p.l.c., London, UK (also available from http://www.bp.com/statisticalreview), 2008.

Ciais, P., Tans, P. P., White, J. W. C., Trolier, M., Francey, R. J., Berry, J. A., Randall, D. R., Sellers, P. J., Collatz, J. G., and Schimel, D. S.: Partitioning of ocean and land uptake of CO2 as inferred by $\delta $13C measurements from the NOAA Climate Monitoring and Diagnostics Laboratory Global Air Sampling Network, J. Geophys. Res., 100, 5051–5070, 1995.

Ciais, P., Reichstein, M., Viovy, N., Granier, A., Ogée, J., Allard, V., Aubinet, M., Buchmann, N., Bernhofer, C., Carrara, A., Chevallier, F., De Noblet, N., Friend, A. D., Friedlingstein, P., Grünwald, T., Heinesch, B., Keronen, P., Knohl, A., Krinner, G., Loustau, D., Manca, G., Matteucci, G., Miglietta, F., Ourcival, J. M., Papale, D., Pilegaard, K., Rambal, S., Seufert, G., Soussana, J. F., Sanz, M. J., Schulze, E. D., Vesala, T., and Valentini, R.: Europe-wide reduction in primary productivity caused by the heat and drought in 2003, Nature, 437, 529–533, 2005.

Ciais, P., Manning, A. C., Reichstein, M., Zaehle, S., and Bopp, L.: Nitrification amplifies the decreasing trends of atmospheric oxygen and implies a larger land carbon uptake, Global Biogeochem. Cy., 21, GB2030, doi:10.1029/2006GB002799, 2007.

Cleveland, R. B., Cleveland, W. S., McRae, J. E., and Terpenning, I.: STL: A seasonal-trend decomposition procedure based on Loess, Journal of Official Statistics, 6, 3–73, 1990.

Denning, A. S., Takahashi, T., and Friedlingstein, P.: Keynote perspective. Can a strong atmospheric CO2 rectifier effect be reconciled with a "reasonable" Carbon budget?, Tellus B, 51, 249–253, 1999.

Derwent, R. G., Ryall, D. B., Manning, A. J., Simmonds, P. G., O'Doherty, S., Biraud, S., Ciais, P., Ramonet, M., and Jennings, S. G.: Continuous observations of carbon dioxide at Mace Head, Ireland from 1995 to 1999 and its net European ecosystem exchange, Atmos. Environ., 36, 2799–2807, 2002.

Friedrich, R., Freibauer, A., Gallmann, E., Giannouli, M., Koch, D., Peylin, P., Pye, S., Riviere, E., San Jose, R., Winiwarter, W., Blank, P., Kühlwein, J., Pregger, T., Reis, S., Scholz, Y., Theloke, J., and Vabitsch, A.: Temporal and spatial resolution of greenhouse gas emissions in Europe, Report of a Carbo Europe workshop held at Stuttgart, Germany, 26–27~June~2003, 36 pp., 2003.

Gamnitzer, U., Karstens, U., Kromer, B., Neubert, R. E. M., Meijer, H. A. J., Schroeder, H., and Levin, I.: Carbon monoxide: A quantitative tracer for fossil fuel CO2, J. Geophys. Res., 111, D22302, doi:10.1029/2005JD006966, 2006.

Garcia, H. E., and Keeling, R. F.: On the global oxygen anomaly and air-sea flux, J. Geophys. Res. Atmos., 106, 31155–31166, 2001.

Gloor, M., Gruber, N., Hughes, T. M. C., and Sarmiento, J. L.: Estimating net air-sea fluxes from ocean bulk data: Methodology and application to the heat cycle, Global Biogeochem. Cy., 15, 767–782, 2001.

Gruber, N., Gloor, M., Fan, S.-M., and Sarmiento, J. L.: Air-sea flux of oxygen estimated from bulk data: Implications for the marine and atmospheric oxygen cycles, Global Biogeochem. Cy., 15, 783–803, 2001.

IPCC: Climate Change 2007: The Physical Science Basis, in: Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K. B., Tignor, M., and Miller, H. L., Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, 996 pp., 2007.

Keeling, C. D. and Whorf, T. P.: Atmospheric CO2 records from sites in the SIO air sampling network. In Trends: A Compendium of Data on Global Change. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, US Department of Energy, Oak Ridge, Tenn., USA, 2005.

Keeling, R. F., Najjar, R., Bender, M., and Tans, P. P.: What atmospheric oxygen measurements can tell us about the global carbon cycle, Global Biogeochem. Cy., 7, 37–67, 1993.

Keeling, R. F.: Development of an interferometric oxygen analyzer for precise measurement of atmospheric O2 mole fraction, PhD Thesis, Harvard University, USA, 1988.

Keeling, R. F. and Shertz, S. R.: Seasonal and interannual variations in atmospheric oxygen and implications for the global carbon cycle, Nature, 358, 723–727, 1992.

Keeling, R. F., Piper, S. C., and Heimann, M.: Global and hemispheric CO2 sinks deduced from changes in atmospheric O2 concentration, Nature, 381, 218–221, 1996.

Keeling, R. F., Stephens, B. B., Najjar, R. G., Doney, S. C., Archer, D., and Heimann, M.: Seasonal variations in the atmospheric O2/N2 ratio in relation to the kinetics of air-sea gas exchange, Global Biogeochem. Cy., 12, 141–163, 1998.

Langenfelds, R. L., Francey, R. J., Steele, L. P., Battle, M., Keeling, R. F., and Budd, W. F.: Partitioning of the global fossil CO2 sink using a 19-year trend in atmospheric O2, Geophys. Res. Lett., 26, 1897–1900, 1999.

Le Quéré, C., Aumont, O., Bopp, L., Bousquet, P., Ciais, P., Francey, R., Heimann, M., Keeling, C. D., Keeling, R. F., Kheshgi, H., Peylin, P., Piper, S. C., Prentice, I. C., and Rayner, P. J.: Two decades of ocean CO2 sink and variability, Tellus B, 55, 649–656, 2003.

Le Quéré, C., Rödenbeck, C., Buitenhuis, E. T., Conway, T. J., Langenfelds, R., Gomez, A., Labuschagne, C., Ramonet, M., Nakazawa, T., Metzl, N., Gillett, N., and Heimann, M.: Saturation of the Southern Ocean CO2 sink due to recent Climate Change, Science, 316, 5832, doi:10.1126/science.1136188, 2007.

Levin, I., Hammer, S., Kromer, B., and Meinhardt, F.: Radiocarbon observations in atmospheric CO2: Determining fossil fuel CO2 over Europe using Jungfraujoch observations as background, Sci. Total Environ., 391, 211–216, 2008.

Levin, I. and Karstens, U.: Inferring high-resolution fossil fuel CO2 records at continental sites from combined 14CO2 and CO observations, Tellus B, 59, 245–250, 2007.

Levitus, S., Antonov, J. I., Boyer, T. P., and Stephens, C.: Warming of the world ocean, Science, 287, 2225–2229, 2000.

Manning, A. C., Keeling, R. F., Katz, L. E., Paplawsky, W. J., and McEvoy, E. M.: Interpreting the seasonal cycles of atmospheric oxygen and carbon dioxide concentrations at American Samoa Observatory, Geophys. Res. Lett., 30, 1333, doi:10.1029/2001GL014312, 2003.

Manning, A. C. and Keeling, R. F.: Global oceanic and land biotic carbon sinks from the Scripps atmospheric oxygen flask sampling network, Tellus B, 58, 95–116, 2006.

Marland, G., Boden, T. A., and Andres., R. J.: Global, regional, and national CO2 emissions, In Trends: A Compendium of Data on Global Change. Carbon Dioxide Information Analysis Center, Oak Ridge National Laboratory, US Department of Energy, Oak Ridge, Tenn., USA, 2005.

Meijer, H. A. J., Smid, H. M., Perez, E., and Keizer, M. G.: Isotopic characterisation of anthropogenic CO2 emissions using isotopic and radiocarbon analysis, Phys. Chem. Earth, 21, 483–487, 1996.

Nakazawa, T., Ishizawa, M., Higuchi, K., and Trivett, N. B. A.: Two curve fitting methods applied to CO2 flask data, Environmetrics, 8, 197–218, 1997.

Neubert, R. E. M., Spijkervet, L. L., Schut, J. K., Been, H. A., and Meijer, H. A. J.: A computer-controlled continuous air drying and flask sampling system, J. Atmos. Ocean. Tech., 21, 651–659, 2004.

Neubert, R. E. M., Weber, P., Gerritsma, R., and Meijer, H. A. J.: The Atmospheric CO2 and greenhouse gas monitoring activities at Lutjewad, The Netherlands, in: Report of the twelfth WMO/IAEA meeting of experts on Carbon Dioxide concentration and related tracer measurement techniques, Toronto, Canada, 15–18/9/2003, edited by: Worthy, D. and Huang, L., WMO-TD No. 1275, WMO-GAW No.161, 203–209, Geneve, Switzerland, 2005.

Olivier, J. G. J. and Berdowski, J. J. M.: Global emission sources and sinks., in: The climate system, edited by: Berdowski, J., Guicherit, R., and Heij, B. J., A. A. Balkema Publishers/Swets & Zeitlinger Publishers, Lisse, The Netherlands, 33–78, 2001.

Press, W. H., Flannery, B. P., Teukolsky, S. A., and Vetterling, W. T.: General linear least squares fit, in: Numerical recipes in C: The art of scientific computing, Cambridge University Press, Cambridge, UK, 671–681, 1992.

Randerson, J. T., Masiello, C. A., Still, C. J., Rahn, T., Poorter, H., and Field, C. B.: Is carbon within the global terrestrial biosphere becoming more oxidized? Implications for trends in atmospheric O2, Glob. Change Biol., 12, 260–271, 2006.

Raupach, M. R., Marland, G., Ciais, P., Le Quéré, C., Canadell, J. G., Klepper, G., and Field, C. B.: Global and regional drivers of accelerating CO2 emissions, P. Natl. Acad. Sci. USA, 104, 10 288–10 293, doi:10.1073/pnas.0700609104, 2007.

Rayner, P. J., Enting, I. G., Francey, R. J., and Langenfelds, R. L.: Reconstructing the recent carbon cycle from atmospheric CO2, $\delta ^13$C and O2/N2 observations, Tellus B, 51, 213–232, 1999.

Rödenbeck, C.: Estimating CO2 sources and sinks from atmospheric mixing ratio measurements using a global inversion of atmospheric transport, Max-Planck-Institute for Biogeochemistry, Technical Reports Nr 6, Jena, Germany, 53 pp., ISSN 1615–7400, 2005.

Schmidt, M., Graul, R., Sartorius, H., and Levin, I.: Carbon dioxide and methane in continental Europe: a climatology and $^222$Radon-based emission estimates, Tellus B, 48, 457–473, 1996.

Severinghaus, J. P.: Studies of the terrestrial O2 and Carbon Cycles in sand dune gases and in Biosphere 2, PhD Thesis, Columbia University, New York, 148 pp., 1995.

Stephens, B. B., Keeling, R. F., Heimann, M., Six, K. D., Murnane, R., and Caldeira, K.: Testing global ocean carbon models using measurements of atmospheric O2 and CO2 concentration, Global Biogeochem. Cy., 12, 213–230, 1998.

Stephens, B. B.: Field-based atmospheric oxygen measurements and the ocean carbon cycle, PhD Thesis, University of California, San Diego, 221 pp., 1999.

Stephens, B. B., Bakwin, P. S., Tans, P. P., Teclaw, R. M., and Baumann, D. D.: Application of a differential fuel-cell analyzer for measuring atmospheric oxygen variations, J. Atmos. Ocean. Tech., 24, 82–94, 2007.

Sturm, P., Leuenberger, M., Sirignano, C., Neubert, R. E. M., Meijer, H. A. J., Langenfelds, R. L., Brand, W. A., and Tohjima, Y.: Permeation of atmospheric gases through polymer O-rings used in flasks for air sampling, J. Geophys. Res., 109, D04309, doi:10.1029/2003JD004073, 2004.

Sturm, P., Leuenberger, M., Moncrieff, J., and Ramonet, M.: Atmospheric O2, CO2 and $\delta $13C measurements from aircraft sampling over Griffin Forest, Perthshire, UK, Rapid Commun. Mass Sp., 19, 2399–2406, 2005a.

Sturm, P., Leuenberger, M., and Schmidt, M.: Atmospheric O2, CO2 and $\delta ^13$C observations from the remote sites Jungfraujoch, Switzerland, and Puy de Dôme, France, Geophys. Res. Lett., 32, L17811, doi:10.1029/2005GL023304, 2005b.

Sturm, P., Leuenberger, M., Valentino, F. L., Lehmann, B., and Ihly, B.: Measurements of CO2, its stable isotopes, O2/N2, and $^222$Rn at Bern, Switzerland, Atmos. Chem. Phys., 6, 1991–2004, 2006.

Takahashi, T., Sutherland, S. C., Sweeney, C., Poisson, A., Metzl, N., Tilbrook, B., Bates, N., Wanninkhof, R., Feely, R. A., and Sabine, C.: Global sea-air CO2 flux based on climatological surface ocean $p$CO2, and seasonal biological and temperature effects, Deep Sea Res. Pt II, 49, 1601–1622, 2002.

Tans, P. P., Conway, T. J., and Nakazawa, T.: Latitudinal distribution of the sources and sinks of atmospheric carbon dioxide derived from surface observations and an atmospheric transport model, J. Geophys. Res., 92, 5151–5172, 1989.

Tans, P. P., Fung, I. Y., and Takahashi, T.: Observational constraints on the global atmospheric CO2 budget, Science, 247, 1431–1438, 1990.

Valentino, F. L., Leuenberger, M., Uglietti, C., and Sturm, P.: Measurements and trend analysis of O2, CO2 and $\delta ^13$C of CO2 from the high altitude research station Junfgraujoch, Switzerland – A comparison with the observations from the remote site Puy de Dôme, France, Sci. Total Environ., 391, 203–210, 2008.

Zhao, C. L. and Tans, P. P.: Estimating uncertainty of the WMO mole fraction scale for carbon dioxide in air, J. Geophys. Res., 111, D08S09, doi:10.1029/2005JD006003, 2006.