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High precision and continuous field measurements of δ 13C and δ 18O in carbon dioxide with a cryogen-free QCLAS

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Abstract

The present paper describes a compact and cryogen-free, quantum cascade laser based absorption spectrometer (QCLAS) designed for in situ, continuous and high precision isotope ratio measurements of atmospheric CO2. The mobile instrument incorporates several new features including a novel astigmatic multi-pass cell assembly, a quasi-room temperature quantum cascade laser, thermoelectrically cooled detectors as well as a new retrieval approach. The combination of these features now makes it possible to measure isotope ratios of ambient CO2 with a precision of 0.03 and 0.05‰ for δ13C and δ18O, respectively, using a 100 s integration time. A robust and optimized calibration procedure was developed to bring the retrieved isotope ratios on an absolute scale. This assures an accuracy better than 0.1‰ under laboratory conditions. The instrument performance was also assessed in a field campaign in which the spectrometer operated autonomously and provided mixing ratio values for the main three CO2 isotopologues at one second time resolution. An accuracy of 0.2‰ was routinely obtained for both isotope ratios during the entire period. The results were in excellent agreement with the standard laboratory-based isotope ratio mass spectrometer measurements made on field-collected flask samples. A few illustrative examples are used to depict the potential of this optical method in atmosphere–biosphere research.

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References

  1. S. Solomon, D. Qin, M. Manning, Z. Chen, M. Marquis, K.B. Averyt, M. Tignor, H.L. Miller (Eds.), IPCC, 2007: Climate Change 2007: The Physical Science Basis (Cambridge University Press, Cambridge, 2007)

  2. P.P. Tans, I.Y. Fung, T. Takahashi, Science 247, 1431 (1990)

    Article  ADS  Google Scholar 

  3. M. Trolier, J.W.C. White, P.P. Tans, K.A. Masarie, P.A. Gemery, J. Geophys. Res. 101, 25897 (1996)

    Article  ADS  Google Scholar 

  4. T.J. Conway, P.P. Tans, L.S. Waterman, K.W. Thoning, D.R. Kitzis, K.A. Masarie, N. Zhang, J. Geophys. Res. 99, 22831 (1994)

    Article  ADS  Google Scholar 

  5. C.D. Keeling, J.F.S. Chin, T.P. Whorf, Nature 382, 146 (1996)

    Article  ADS  Google Scholar 

  6. C.D. Keeling, Geochim. Cosmochim. Acta 13, 322 (1958)

    Article  ADS  Google Scholar 

  7. G.D. Farquhar, J. Lloyd, J.A. Taylor, L.B. Flanagan, J.P. Syvertsen, K.T. Hubick, S.C. Wong, J.R. Ehleringer, Nature 363, 439 (1993)

    Article  ADS  Google Scholar 

  8. P. Ciais, P.P. Tans, M. Trolier, J.W.C. White, R.J. Francey, Science 269, 1098 (1995)

    Article  ADS  Google Scholar 

  9. D. Nelson, J.B. McManus, S.C. Herndon, M.S. Zahniser, B. Tuzson, L. Emmenegger, Appl. Phys. B 90, 301 (2008)

    Article  ADS  Google Scholar 

  10. P. Bergamaschi, M. Schupp, G.W. Harris, Appl. Opt. 33, 7704 (1994)

    ADS  Google Scholar 

  11. G. Gagliardi, R. Restieri, G. Casa, L. Gianfrani, Opt. Lasers Eng. 37, 131 (2002)

    Article  Google Scholar 

  12. J. Zhang, T.J. Griffis, J.M. Baker, Plant Cell Environ. 29, 483 (2006)

    Google Scholar 

  13. T.J. Griffis, J.M. Baker, S.D. Sargent, B.D. Tanner, J. Zhang, Agric. For. Meteorol. 124, 15 (2004)

    Article  Google Scholar 

  14. D.R. Bowling, S.D. Sargent, B.D. Tanner, J.R. Ehleringer, Agric. For. Meteorol. 118, 1 (2003)

    Article  Google Scholar 

  15. H. Waechter, M.W. Sigrist, Appl. Phys. B 87, 539 (2007)

    Article  ADS  Google Scholar 

  16. M. Erdelyi, D. Richter, F.K. Tittel, Appl. Phys. B 75, 289 (2002)

    Article  ADS  Google Scholar 

  17. P. Bergamaschi, M. Schupp, G.W. Harris, Appl. Opt. 33, 7704 (1994)

    Article  ADS  Google Scholar 

  18. J.B. McManus, M.S. Zahniser, D.D. Nelson, L.R. Williams, C.E. Kolb, Spectrochim. Acta A 58, 2465 (2002)

    Article  Google Scholar 

  19. K. Uehara, K. Yamamoto, T. Kikugawa, N. Yoshida, Spectrochim. Acta A 59, 957 (2003)

    Article  Google Scholar 

  20. C. Janssen, B. Tuzson, Appl. Phys. B 82, 487 (2006)

    Article  ADS  Google Scholar 

  21. E.R.T. Kerstel, R. van Trigt, N. Dam, J. Reuss, H.A.J. Meijer, Anal. Chem. 71, 5297 (1999)

    Article  Google Scholar 

  22. E.D. Murnick, J.O. Okil, Isotope Environ. Health Stud. 41, 363 (2005)

    Google Scholar 

  23. J.B. McManus, D.D. Nelson, J.H. Shorter, R. Jimenez, S. Herndon, S.R. Saleska, M.S. Zahniser, J. Mod. Opt. 52, 2309 (2005)

    Article  ADS  Google Scholar 

  24. D. Weidmann, C.B. Roller, C. Oppenheimer, A. Fried, F.K. Tittel, Isotope Environ. Health Stud. 41, 293 (2005)

    Google Scholar 

  25. A.A. Kosterev, R.F. Curl, F.K. Tittel, C. Gmachl, F. Capasso, D.L. Sivco, J.N. Baillargeon, A.L. Hutchinson, A.Y. Cho, Opt. Lett. 24, 1762 (1999)

    Article  ADS  Google Scholar 

  26. J.B. McManus, D.D. Nelson, S.C. Herndon, J.H. Shorter, M.S. Zahniser, S. Blaser, L. Hvozdara, A. Muller, M. Giovannini, J. Faist, Appl. Phys. B 85, 235 (2006)

    Article  ADS  Google Scholar 

  27. D.D. Nelson, J.H. Shorter, J.B. McManus, M.S. Zahniser, Appl. Phys. B 75, 343 (2002)

    Article  ADS  Google Scholar 

  28. B. Tuzson, M.J. Zeeman, M.S. Zahniser, L. Emmenegger, Infrared Phys. Technol. 51, 198 (2008)

    Article  ADS  Google Scholar 

  29. P. Werle, R. Mucke, F. Slemr, Appl. Phys. B 57, 131 (1993)

    Article  ADS  Google Scholar 

  30. L.S. Rothman, D. Jacquemart, A. Barbe, D.C. Benner, M. Birk, L.R. Brown, M.R. Carleer, C. Chackerian, K. Chance, L.H. Coudert, V. Dana, V.M. Devi, J.-M. Flaud, R.R. Gamache, A. Goldman, J.-M. Hartmann, K.W. Jucks, A.G. Maki, J.-Y. Mandin, S.T. Massie, J. Orphal, A. Perrin, C.P. Rinsland, M.A.H. Smith, J. Tennyson, R.N. Tolchenov, R.A. Toth, J. Vander Auwera, P. Varanasi, G. Wagner, J. Quantum Spectrosc. Radiat. Transf. 96, 139 (2005)

  31. J. Mohn, R.A. Werner, B. Buchmann, L. Emmenegger, J. Mol. Struct. 834–836, 95 (2007)

    Google Scholar 

  32. R.A. Werner, W.A. Brand, Rapid Commun. Mass. Spectrom. 15, 501 (2001)

    Google Scholar 

  33. D.E. Theis, M. Saurer, H. Blum, E. Frossard, R.T.W. Siegwolf, Rapid Commun. Mass. Spectrom. 18, 2106 (2004)

    Google Scholar 

  34. R.A. Werner, M. Rothe, W.A. Brand, Rapid Commun. Mass. Spectrom. 15, 2152 (2001)

    Google Scholar 

  35. P. Ghosh, M. Patecki, M. Rothe, W.A. Brand, Rapid Commun. Mass. Spectrom. 19, 1097 (2005)

    Google Scholar 

  36. G.D. Farquhar, J.R. Ehleringer, K.T. Hubick, Ann. Rev. Plant. Physiol. Plant Mol. Biol. 40, 503 (1989)

    Google Scholar 

  37. D. Yakir, X.F. Wang, Nature 380, 515 (1996)

    Article  ADS  Google Scholar 

  38. D.E. Pataki, J.R. Ehleringer, L.B. Flanagan, D. Yakir, D.R. Bowling, C.J. Still, N. Buchmann, J.O. Kaplan, J.A. Berry, Global Biogeochem. Cycl. 17, 1022 (2003)

    Article  ADS  Google Scholar 

  39. L.B. Flanagan, J.R. Brooks, G.T. Varney, J.R. Ehleringer, Global Biogeochem. Cycl. 11, 83 (1997)

    Article  ADS  Google Scholar 

  40. N. Buchmann, J.R. Ehleringer, Agric. For. Meteorol. 89, 45 (1998)

    Article  Google Scholar 

  41. L.B. Flanagan, G.T. Varney, Oecologia 101, 37 (1995)

  42. P.A. Gemery, M. Trolier, J.W.C. White, J. Geophys. Res. 101, 14415 (1996)

    Google Scholar 

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Authors and Affiliations

  1. Empa, Swiss Federal Laboratories for Materials Testing and Research, Laboratory for Air Pollution and Environmental Technology, Überlandstr. 129, 8600, Dübendorf, Switzerland

    B. Tuzson, J. Mohn & L. Emmenegger

  2. Institute of Plant Sciences, Grassland Science Group, ETH Zurich, Universitätsstr. 2, 8092, Zürich, Switzerland

    M.J. Zeeman, R.A. Werner & W. Eugster

  3. Aerodyne Research Inc., 45 Manning Road, Billerica, MA, 01821, USA

    M.S. Zahniser, D.D. Nelson & J.B. McManus

Authors
  1. B. Tuzson
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  2. J. Mohn
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  3. M.J. Zeeman
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  4. R.A. Werner
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  5. W. Eugster
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  6. M.S. Zahniser
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  7. D.D. Nelson
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  8. J.B. McManus
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  9. L. Emmenegger
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Correspondence to B. Tuzson.

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PACS

07.57.Ty; 42.62.Fi; 92.60.Kc

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Tuzson, B., Mohn, J., Zeeman, M. et al. High precision and continuous field measurements of δ 13C and δ 18O in carbon dioxide with a cryogen-free QCLAS. Appl. Phys. B 92, 451–458 (2008). https://doi.org/10.1007/s00340-008-3085-4

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  • DOI: https://doi.org/10.1007/s00340-008-3085-4

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