References

AMTD

Atmospheric Measurement Techniques Discussions

AMTD

1867-8610

Copernicus GmbH

Göttingen, Germany

10.5194/amtd-4-1853-2011

A sublimation technique for high-precision measurements of δ13CO2 and mixing ratios of CO2 and N2O from air trapped in ice cores

Schmitt

¹ ² Schneider

¹ Fischer

¹ ²

Climate and Environmental Physics, Physics Institute, & Oeschger Centre for Climate Change Research, University of Bern, Sidlerstrasse 5, 3012 Bern, Switzerland

Alfred Wegener Institute for Polar and Marine Research, Bremerhaven, Germany

16 03 2011

4 2 1853 1892

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In order to provide high precision stable carbon isotope ratios (δ13CO2 or δ13C on CO2) from small bubble and clathrate ice core samples we developed a new method based on vacuum sublimation extraction of the CO2 and gas chromatography-isotope ratio mass spectrometry (GC-IRMS). In a first step the trapped air is quantitatively released from ~30 g of ice and CO2 together with N2O are separated from the bulk air components and stored in a miniature glass tube. In an off-line step, the extracted sample is introduced into a helium carrier flow using a minimised tube cracker device. Prior to measurement, N2O and organic sample contaminants are gas chromatographically separated from CO2. Pulses of a CO2/N2O mixture are admitted to the tube cracker and follow the path of the sample through the system. This allows an identical treatment and comparison of sample and standard peaks. The ability of the method to reproduce δ13C from bubble and clathrate ice is verified on different ice cores. We achieve reproducibilities for bubble ice between 0.05&permil; and 0.07&permil; and for clathrate ice between 0.05&permil; and 0.09&permil; (dependent on the ice core used). A comparison of our data with measurements on bubble ice from the same ice core but using a mechanic extraction device shows no significant systematic offset. In addition to δ13C, the CO2 and N2O mixing ratios can be volumetrically derived with a precision of 2 ppmv and 8 ppbv, respectively.

References 1

Ahn, J. H., Brook, E. J., and Howell, K.: A high-precision method for measurement of paleoatmospheric CO2 in small polar ice samples, J. Glaciol., 55, 499–506, 2009.

Anklin, M., Barnola, J.-M., Schwander, J., Stauffer, B., and Raynaud, D.: Processes affecting the CO2 concentrations measured in Greenland ice, Tellus, 47, 461–470, 1995.

Barnes, P. R. F., Wolff, E. W., Mallard, D. C., and Mader, H. M.: SEM Studies of the Morphology and Chemistry of Polar Ice, Microsc. Res. Techniq., 62, 62–69, 2003.

Behrens, M., Schmitt, J., Richter, K.-U., Bock, M., Richter, U., Levin, I., and Fischer, H.: A gas chromatography/combustion/isotope ratio mass spectrometry system for high-precision $\delta ^13$C measurements of atmospheric methane extracted from ice core samples, Rapid. Commun. Mass Spectrom., 22, 3261–3269, 2008.

Bock, M., Schmitt, J., Behrens, M., Möller, L., Schneider, R., Sapart, C., and Fischer, H.: A gas chromatography/pyrolysis/isotope ratio mass spectrometry system for high-precision $\delta $D measurements of atmospheric methane extracted from ice cores, Rapid. Commun. Mass Spectrom., 24, 621–633, 2010.

Broecker, W. S. and Clark, E.: Holocene atmospheric CO2 increase as viewed from the seafloor, Global Biogeochem. Cy., 17, 1052, http://dx.doi.org/10.1029/2002GB001985doi:10.1029/2002GB001985, 2003.

Brovkin, V., Hofmann, M., Bendtsen, J., and Ganopolski, A.: Ocean biology could control atmospheric $\delta ^13$C during glacial-interglacial cycle, G-Cubed, 3, 1–15, 2002.

Caldwell, W. E., Odom, J. D., and Williams, D. F.: Glass-Sample Tube Breaker, Anal. Chem., 55, 1175–1176, 1983.

Des Marais, D. J. and Hayes, J. M.: Tube Cracker for Opening Glass-Sealed Ampoules under Vacuum, Anal. Chem., 48, 1651–1652, 1976.

Elsig, J.: New insights into the global carbon cycle from measurements of CO2 stable isotopes: methodological improvements and interpretation of a new EPICA Dome C ice core $\delta ^13$C record, Dissertation, University of Bern, 2009.

Elsig, J., Schmitt, J., Leuenberger, D., Schneider, R., Eyer, M., Leuenberger, M., Joos, F., Fischer, H., and Stocker, T. F.: Stable isotope constraints on Holocene carbon cycle changes from an Antarctic ice core, Nature, 461, 507–510, 2009.

Elsig, J. and Leuenberger, M. C.: C-13 and O-18 fractionation effects on open splits and on the ion source in continuous flow isotope ratio mass spectrometry, Rapid. Commun. Mass Spectrom., 24, 1419–1430, http://dx.doi.org/10.1002/rcm.4531doi:10.1002/rcm.4531, 2010.

Eyer, M.: Highly resolved $\delta ^13$C measurements on CO2 in air from Antarctic ice cores, Dissertation, University of Bern, 2004.

Ferretti, D. F., Lowe, D. C., Martin, R. J., and Brailsford, G. W.: A new gas chromatograph-isotope ratio mass spectrometry technique for high-precision, N2O-free analysis of $\delta ^13$C and $\delta ^18$O in atmospheric CO2 from small air samples, J. Geophys. Res., 105, 6709–6718, 2000.

Fischer, H., Wahlen, M., Smith, J., Mastroianni, D., and Deck, B.: Ice core records of atmospheric CO2 around the last three glacial terminations, Science, 283, 1712–1714, 1999.

Fischer, H., Wahlen, M., and Smith, H. J.: Reconstruction of glacial/interglacial changes in the global carbon cycle from CO$_2 $ and $\delta ^13$CO2 in Antarctic ice cores., Memoirs of the National Institute for Polar Research, 57, 121–138, 2003.

Francey, R. J., Allison, C. E., Etheridge, D. M., Trudinger, C. M., Enting, I. G., Leuenberger, M., Langenfelds, R. L., Michel, E., and Steele, L. P.: A 1000-year high precision record of $\delta ^13$C in atmospheric CO2, Tellus, 51B, 170–193, 1999.

Güllük, T., Slemr, F., and Stauffer, B.: Simultaneous measurement of CO2, CH4, and N2O in air extracted by sublimation from Antarctica ice cores: Confirmation of the data obtained using other extraction techniques, J. Geophys. Res., 103, 15971–15978, 1998.

Hall, J. A., Barth, J. A. C., and Kalin, R. M.: Routine Analysis by High Precision Gas Chromatography/Mass Selective Detector/Isotope Ratio Mass Spectrometry to 0.1 Parts Per Mil, Rapid. Commun. Mass Spectrom., 13, 1231–1236, 1999.

Indermühle, A., Stocker, T. F., Joos, F., Fischer, H., Smith, H. J., Wahlen, M., Deck, B., Mastroianni, D., Tschumi, J., Blunier, T., Meyer, R., and Stauffer, B.: Holocene carbon-cycle dynamics based on CO2 trapped in ice at Taylor Dome, Antarctica, Nature, 398, 121–126, 1999.

Kawamura, K., Nakazawa, T., Aoki, S., Sugawara, S., Fujii, Y., and Watanabe, O.: Atmospheric CO2 variations over the last three glacial-interglacial climatic cycles deduced from the Dome Fuji deep ice core, Antarctica using a wet extraction technique, Tellus B, 55, 126–137, 2003.

Köhler, P. and Fischer, H.: Simulating changes in the terrestrial biosphere during the last glacial/interglacial transition, Global Planet. Change, 43, 33–55, 2004.

Leckrone, K. J. and Hayes, J. M.: Efficiency and Temperature Dependence of Water Removal by Membrane Dryers, Anal. Chem., 69, 911–918, 1997.

Leckrone, K. J. and Hayes, J. M.: Water-Induced Errors in Continuous-Flow Carbon Isotope Ratio Mass Spectrometry, Anal. Chem., 70, 2737–2744, 1998.

Leuenberger, M., Siegenthaler, U., and Langway, C. C.: Carbon isotope composition of atmospheric CO2 during the last ice age from an Antarctic ice core, Nature, 357, 488–490, 1992.

Leuenberger, M. C., Eyer, M., Nyfeler, P., Stauffer, B., and Stocker, T. F.: High-resolution $\delta ^13$C measurement on ancient air extracted from less than 10 cm3 of ice, Tellus, 55B, 138–144, 2003.

Lourantou, A., Chappellaz, J., Barnola, J. M., Masson-Delmotte, V., and Raynaud, D.: Changes in atmospheric CO2 and its carbon isotopic ratio during the penultimate deglaciation, Quaternary Sci. Rev., 29, 1983–1992, 2010a.

Lourantou, A., Lavric, J. V., Köhler, P., Barnola, J. M., Paillard, D., Michel, E., Raynaud, D., and Chappellaz, J.: Constraint of the CO2 rise by new atmospheric carbon isotopic measurements during the last deglaciation, Global Biogeochem. Cy., 24, 1–15, 2010b.

Lüthi, D., Le Floch, M., Bereiter, B., Blunier, T., Barnola, J. M., Siegenthaler, U., Raynaud, D., Jouzel, J., Fischer, H., Kawamura, K., and Stocker, T. F.: High-resolution carbon dioxide concentration record 650 000–800 000 years before present, Nature, 453, 379–382, 2008.

Lüthi, D., Bereiter, B., Stauffer, B., Winkler, R., Schwander, J., Kindler, P., Leuenberger, M., Kipfstuhl, S., Capron, E., Landais, A., Fischer, H., and Stocker, T. F.: CO2 and O2/N2 variations in and just below the bubble-clathrate transformation zone of Antarctic ice cores, Earth Planet. Sc. Lett., 297, 226–233, 2010.

Meier-Augenstein, W., Watt, P., and Langhans, C.: Influence of Gas Chromatographic Parameters on Measurement of $^13$C/$^12$C Isotope Ratios by Gas-Liquid Chromatography-Combustion Isotope Ratio Mass spectrometry, J. Chromat. A, 752, 233–241, 1996.

Meier-Augenstein, W.: A Reference Gas Inlet Module for Internal Isotopic Calibration in High Precision Gas-Chromatography, Rapid. Commun. Mass Spectrom., 11, 1775–1780, 1997.

Meier-Augenstein, W.: Review: Applied gas chromatography coupled to isotope ratio mass spectrometry, J. Chromat. A, 842, 351–371, 1999.

Merritt, D. A., Freeman, K. H., Ricci, M. P., Studley, S. A., and Hayes, J. M.: Performance and Optimization of a Combustion Interface for Isotope Ratio Monitoring Gas Chromatography/Mass Spectrometry, Anal. Chem., 67, 2461–2473, 1995.

Monnin, E., Indermühle, A., Dällenbach, A., Flückiger, J., Stauffer, B., Stocker, T. F., Raynaud, D., and Barnola, J.-M.: Atmospheric CO2 concentration over the last termination, Science, 291, 112–114, 2001.

Petit, J. R., Jouzel, J., Raynaud, D., Barkov, N. I., Barnola, J.-M., Basile, I., Bender, M., Chappellaz, J., Davis, M., Delaygue, G., Delmotte, M., Kotlyakov, V. M., Legrand, M., Lipenkov, V. Y., Lorius, C., Pepin, L., Ritz, C., Saltzman, E., and Stievenard, M.: Climate and atmospheric history of the past 420 000 years from the Vostok ice core, Antarctica, Nature, 399, 429–436, 1999.

Ribas-Carbo, M., Still, C., and Berry, J.: Automated system for simultaneous analysis of $^13$C, $^18$O and CO2 concentrations in small air samples, Rapid. Commun. Mass Spectrom., 16, 339–345, 2002.

Rice, A. L., Gotoh, A. A., Ajie, H. O., and Tyler, S. C.: High-precision continuous-flow measurement of $\delta ^13$C and $\delta $D of atmospheric CH4, Anal. Chem., 73, 4104–4110, 2001.

Schilt, A., Baumgartner, M., Schwander, J., Buiron, D., Capron, E., Chappellaz, J., Loulergue, L., Schüpbach, S., Spahni, R., Fischer, H., and Stocker, T. F.: Atmospheric nitrous oxide during the last 140 000 years, Earth Planet. Sc. Lett., 300, 33–43, http://dx.doi.org/10.1016/j.epsl.2010.09.027doi:10.1016/j.epsl.2010.09.027, 2010.

Schmitt, J., Glaser, B., and Zech, W.: Amount-dependent isotopic fractionation during compound-specific isotope analysis, Rapid. Commun. Mass Spectrom., 17, 970–977, 2003.

Schmitt, J.: A sublimation technique for high-precision $\delta ^13$C on CO2 and CO2 mixing ratio from air trapped in deep ice cores, Dissertation, University of Bremen, available at: http://elib.suub.uni-bremen.de/diss/docs/00010568.pdf, 2006.

Siegenthaler, U.: CO2-Konzentrationsmessungen an polaren Eisbohrkernen und Tests mit einer neuen Extraktionsmethode, Diplomarbeit, Bern, unpublished, 2002.

Siegenthaler, U., Monnin, E., Kawamura, K., Spahni, R., Schwander, J., Stauffer, B., Stocker, T. F., Barnola, J.-M., and Fischer, H.: Supporting evidence from the EPICA Dronning Maud Land ice core for atmospheric CO2 changes during the past millennium, Tellus, 57, 51–57, 2005a.

Siegenthaler, U., Stocker, T. F., Monnin, E., Lüthi, D., Schwander, J., Stauffer, B., Raynaud, D., Barnola, J. M., Fischer, H., Masson-Delmotte, V., and Jouzel, J.: Atmospheric science: Stable carbon cycle-climate relationship during the late Pleistocene, Science, 310, 1313, http://dx.doi.org/10.1126/science.1120130doi:10.1126/science.1120130, 2005b.

Smith, H. J., Fischer, H., Wahlen, M., Mastroianni, D., and Deck, B.: Dual modes of the carbon cycle since the Last Glacial Maximum, Nature, 400, 248–250, 1999.

Werner, R. A. and Brand, W. A.: Referencing strategies and techniques in stable isotope ratio analysis, Rapid. Commun. Mass Spectrom., 15, 501–519, 2001.

Wilson, A. T. and Long, A.: New approaches to CO$_2 $ analysis in polar ice cores, J. Geophys. Res., 102, 26601–26606, 1997.

Zhang, J., Quay, P. D., and Wilbur, D. O.: Carbon isotope fractionation during gas-water exchange and dissolution of CO2, Geochim. Cosmochim. Ac., 59, 107–114, 1995.

Zumbrunn, R., Neftel, A., and Oeschger, H.: CO2 measurements on 1-cm3 ice samples with IR laserspectrometer (IRLS) combined with a new dry extraction device, Earth Planet. Sc. Lett., 60, 318–324, 1982.