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Scripps Carbon Dioxide and Oxygen Programs Ralph F Scripps Carbon Dioxide and Oxygen Programs Ralph F. Keeling, PI, Scripps Institution of Oceanography, UCSD, La Jolla, CA Scripps CO2 Program - www.scrippsco2.ucsd.edu Scripps O2 Program - http://bluemoon.ucsd.edu Ralph Keeling - [email protected] CO TREND O TREND CO EXTRACTION RACK INTRODUCTION 4 2 5 2 9 2 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06 0 0 System for extracting CO2 -50 -50 from flasks into glass am- ALT -100 -100 poules. CO is trapped cryo- The Scripps CO2 program was initiated in 1956 by Charles David Keeling and 2 82N operated under his direction until his passing in 2005. It is currently being con- -150 -150 genically from the air using -200 -200 liquid nitrogen, and then tinued by Ralph F. Keeling, who also runs the parallel Scripps O2 program. The -250 transferred into a 1/4" O.D. combined programs are sustaining the longest continuous measurements of -300 glass tube. The tube is then changes in atmospheric carbon dioxide concentration, the isotopes of CO , and -100 -350 sealed using an electronic 2 CBA -150 -400 heating element. Examples of 55N -200 the atmospheric O2 concentration (as O2/N2 ratio). The program involves flask -450 the glass ampoules are shown collections made through cooperative programs with field stations at roughly a 0 -250 in the insert. The system -50 -300 allows for up to six flask to be dozen stations around the world. The emphasis in the program is in the detec- LJO -100 -350 33 N extracted in series. The tion of global and hemispheric trends in these species. -150 -400 archived samples have been -200 -450 used in support of 14C/12C -50 -250 O MLO analyses and for retrospective 2 Glass Ampoules -100 -300 /N 20 N cross-checks on the calibra- -150 -350 2 13 12 18 16 SCRIPPS SAMPLING NETWORK ratio (per meg) tion of C/ C and O/ O 1 -50 -400 ratios. KUM -100 -450 Concentration (ppm) 2 20 N ALT -150 -300 CO -200 PTB -350 SMO -100 -400 14 S -150 -300 CBA -200 -350 LJO CGO -50 -400 BCS MLO 41 S -100 -300 KUM GOALS & METHODS -150 -350 CHR -400 SAM Our measurements are pertinent to assessing global and hemispheric sources -150 -300 KER PSA -200 -350 and sinks of CO and their changes from year to year. The records are also rel- 65 S 2 CGO NZD -50 -250 -400 evant source/sink estimates on finer spatial scales, and are among the first -100 -300 PSA -150 -350 places to look for evidence of climate feedbacks or other "surprises" in the re- SPO 90S -200 -400 cords. SPO -250 -300 -300 -350 -350 For more than decade, the program has been archiving CO2 from air samples in Scripps CO2 Program Scripps O2/N2 Program -400 -400 sealed glass ampoules for retrospective analysis. As an example of an applica- 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06 Station symbols: ALT = Alert; PTB = Point Barrow; CBA = Cold Bay; LJO = La Jolla; tion, these archives have recently allowed the generation of time series of the BCS = Baja California Sur ; KUM = Cape Kumukahi ; MLO = Mauna Loa Observatory; radiocarbon 14C/12C content of atmospheric CO , which is relevant for assessing The concentration of atmospheric CO (ppm = μmol mol-1) at six of the eleven stations in 2 CHR = Christmas Island ; SAM = Samoa; KER = Kermadec; CGO = Cape Grim; 2 Atmospheric O concentration (reported as O /N ratio) from flasks collected in the Scripps 2 2 2 the distribution of carbon between reservoirs and the rates of fossil-fuel burn- NZD = New Zealand ; PSA = Palmer Station ; SPO = South Pole the Scripps CO2 sampling network. The oscillating curves are fits of monthly mean con- O2 sampling network. Each point represents monthly mean. The O2 trends tend to mirror the centration to a spline function and four harmonic terms. The dots denote monthly mean CO trends, with an opposing seasonal cycle and long-term trend. The rate of O loss helps to ing. concentrations. 2 2 establish the relative magnitude of the land and ocean sinks for CO2 globally. The seasonal cycle contains information about rates of metabolic activity in both the land and ocean bio- The O program has also expanded recently to include measurements of the Ar spheres. 2 concentration (as Ar/N2 ratio). This ratio varies as the ocean warms and cools due to thermally-driven ingassing and outgassing of Ar and N2 by the oceans. 2 MAUNA LOA CO2 RECORD The long-term trend in Ar concentration is expected to be useful for assessing 390 the global ocean warming rate. 6 13C/12C TREND 18O/16O TREND 380 7 18 16 18 370 The O/ O isotopic ratio, expressed as δ O (in per mil, positive upwards) for South Pole (SPO, 90ºS) and Alert (ALT, 82ºN). The 18O/16O ratio is sensi- RECENT CONTRIBUTIONS ) 360 L I tive to the gross (i.e. back and forth) exchanges of M R E CO2 with the land biosphere and to the distribution 350 P Forster, P. et al., 2007. Chapter 2: Changes in Atmospheric Constituents and in Radiative Forcing, Climate ( of water isotopes driven by hydrological cycle. Change 2007, The Physical Science Basis, Contribution of Working Group I to the Fourth Assessment Note the coherent interannual variations at these Report of the Intergovernmental Panel on Climate Change. Cambridge University Press, Cambridge, pp. 340 stations, which is evidently a global phenomenon. 129-234. Concentration (ppm) 2 330 Keeling, R.F., Manning, A.C., Paplawsky, W.J. and Cox, A.C., 2007. On the long-term stability of refer- CO ence gases for atmospheric O2/N2 and CO2 measurements. Tellus 59B: 3-14. 320 Rahmstorf, S., Cazenave, A., Church, J.A., Hansen, J.E., Keeling, R.F., Parker, D.E. and Somerville, 310 R.C.J., 2007. Recent climate observations compared to projections. Science, 316(5825): 709-709. 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010 Manning, A.C. and Keeling, R.F., 2006. Global oceanic and land biotic carbon sinks from the Scripps atmospheric oxygen flask sampling network. Tellus, 58B: 95-116. 8 Ar/N2 TREND 45 Keeling, C.D., Piper, S.C., Bacastow, R.B., Wahlen, M., Whorf, T.P., Heimann, M. and Meijer, H.A., 14 12 The Ar/N2 ratio of the air at La Jolla, California ex- 13 2005. Atmospheric CO2 and CO2 exchange with the terrestrial biosphere and oceans from 1978 to 2000: 3 C/ C TREND 40 pressed as relative deviation from a reference. observations and carbon cycle implications. In: J.R. Ehleringer et al. (Ed.), A History of Atmospheric CO2 35 These data were obtained by using a continuous 140 Observations of 14C/12C ratio ex- and Its Effects on Plants, Animals and Ecosystems. Springer, pp. 83-113. analyser (mass spectrometer) to directly analyze the 130 14 30 La Jolla pressed as ∆ C from CO2 samples air at La Jolla. Blue points: hourly Ar/N2 data from 120 collected at La Jolla. The analyses 25 La Jolla. Black curve: fit to semi-continuous data 110 were made in collaboration with 20 based on a two harmonic function and no trend. 100 Thomas Guilderson at the Center ) (per meg) The Ar/N ratio is potentially useful to trace large- (per mil) 15 2 2 2 for Accelerator Mass Spectrometry 90 The 13C/12C isotopic ratio, expressed as δ13C (in per mil from isotope standard scale warming and cooling of the oceans. The ACKNOWLEDGEMENTS at the Lawrence Livermore Na- 10 80 (Ar/N δ C of CO Ar/N ratio is higher in the summer than the winter PDB), for the same stations as in the CO2 trend figure. The dots indicate 2 14 tional Laboratory. The downward 5 ∆ 70 monthly averages. The oscillating curves are fits similar to those in the CO due to warming of the surface ocean which drives trend is the result of the redistribu- 2 The Scripps CO program is currently jointly supported by U.S. Department of Energy and the U.S. Na- trend figure. Note the expanded time-scale and inverted isotopic scale (the 0 outgassing of Ar due to the temperature dependence 2 60 tion of bomb 14C into the oceans tional Science foundation. The Scripps O program is jointly supported by NOAA and by the U.S. Na- of the Ar solubility. The Ar release is offset by a 2 50 latter so that phasing is seen to be similar to that of the CO2 concentration). −5 and land biosphere. The trend is 13 12 tional Science Foundation. Both programs rely on collaborations with other institutions to gather air The C/ C data contain useful constraints on changes in metabolic activity small opposing N2 release. 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06 07 also influenced by the rate of −10 samples, including Canadian Baseline Program, the NOAA/GMD programs at Mauna Loa Observatory, and sources and sinks of CO with the land biota. Apr04 Jul04 Oct04 Jan05 Apr05 Jul05 Oct05 Jan06 Apr06 Jul06 Oct06 Jan07 Apr07 Jul07 fossil-fuel burning. 2 time American Samoa and Barrow Alaska, the U.S. National Weather Service at Cold Bay, Alaska, the Cape Grim Baseline Station, and the U.S. Antarctic Program..
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