Abstract

An infrared absorption spectrometer has been constructed to measure the stable isotopic composition of atmospheric methane samples. The spectrometer employs periodically poled lithium niobate to generate 15  μW of tunable difference-frequency radiation from two near-infrared diode lasers that probe the ν3 rotational–vibrational band of methane at 3.4  μm. To enhance the signal, methane is extracted from 25 l of air by use of a cryogenic chromatographic column and is expanded into the multipass cell for analysis. A measurement precision of 12 is demonstrated for both δ13C and δD.

© 2006 Optical Society of America

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  1. V. Ramaswamy, O. Boucher, J. Haigh, D. Hauglustaine, J. Haywood, G. Myhre, T. Nakajima, G. Y. Shi, and S. Solomon, "Radiative forcing of climate change," in Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, J. T. Houghton, Y. Ding, D. J. Griggs, M. Noguer, P. J. van der Linden, X. Dai, K. Maskell, and C. A. Johnson, eds. (Cambridge U. Press, 2001), pp. 349-416.
  2. M. A. K. Khalil and R. A. Rasmussen, "Atmospheric methane: trends over the last 10,000 years," Atmos. Environ. 21, 2445-2452 (1987).
    [CrossRef]
  3. P. Quay, J. Stutsman, D. Wilbur, A. Snover, E. Dlugokencky, and T. Brown, "The isotopic composition of atmospheric methane," Global Biogeochem. Cycles 13, 445-461 (1999).
    [CrossRef]
  4. A. J. Kuhlmann, D. E. J. Worthy, N. B. A. Trivett, and I. Levin, "Methane emissions from a wetland region within the Hudson Bay Lowland: an atmospheric approach," J. Geophys. Res. 103D, 16009-16016 (1998).
    [CrossRef]
  5. A. L. Rice, A. A. Gotoh, H. O. Ajie, and S. C. Tyler, "High-precision continuous-flow measurement of delta C-13 and delta D of atmospheric CH4," Anal. Chem. 73, 4104-4110 (2001).
    [CrossRef]
  6. A. A. Kosterev, R. F. Curl, F. K. Tittel, C. Gmachl, F. Capasso, D. L. Sivco, J. N. Baillargeon, A. L. Hutchinson, and A. Y. Cho, "Methane concentration and isotopic composition measurements with a mid-infrared quantum cascade laser," Opt. Lett. 24, 1762-1764 (1999).
  7. H. Dahnke, D. Kleine, W. Urban, P. Hering, and M. Murtz, "Isotopic ratio measurements of methane in ambient air using mid-infrared cavity leak-out spectroscopy," Appl. Phys. B 72, 121-125 (2001).
  8. K. Yamamoto and N. Yoshida, "High-precision isotopic ratio measurement system for methane (12CH3D/12CH4, 13CH4/12CH4) by using near-infrared diode laser absorption spectroscopy," Spectrochim. Acta Part A 58, 2699-2707 (2002).
    [CrossRef]
  9. P. Bergamaschi, M. Schupp, and G. W. Harris, "High-precision direct measurements of 13CH4/12CH4 and 12CH3D/12CH4 ratios in atmospheric methane sources by means of a long-path tunable diode laser absorption spectrometer," Appl. Opt. 33, 7704-7716 (1994).
  10. P. Bergamaschi, M. Bräunlich, T. Marik, and C. Brenninkmeijer, "Measurements of carbon and hydrogen isotopes of atmospheric methane at Izaña, Tenerife: seasonal cycles and synoptic-scale variations," J. Geophys. Res. 105D, 14531-14546 (2000).
    [CrossRef]
  11. K. P. Petrov, S. Waltman, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Precise measurement of methane in air using diode-pumped 3.4-μm difference-frequency generation in PPLN," Appl. Phys. B 64, 567-572 (1997).
    [CrossRef]
  12. S. Waltman, K. P. Petrov, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Measurement of 13CH4/12CH4 ratios in air using diode-pumped 3.3 μm difference-frequency generation in PPLN," in 1997 Digest of the IEEE/LEOS Summer Topical Meetings (IEEE Press, 1997), pp. 37-38.
  13. T. B. Coplen, "Reporting of stable hydrogen, carbon, and oxygen isotopic abundances (technical report)," Pure Appl. Chem. 66, 273-276 (1994).
  14. D. Guenther, Carbon Cycle Greenhouse Gases Group, Earth System Research Laboratory, National Oceanic and Atmospheric Administration, Boulder, Colo. (personal communication, 2005).

2002

K. Yamamoto and N. Yoshida, "High-precision isotopic ratio measurement system for methane (12CH3D/12CH4, 13CH4/12CH4) by using near-infrared diode laser absorption spectroscopy," Spectrochim. Acta Part A 58, 2699-2707 (2002).
[CrossRef]

2001

H. Dahnke, D. Kleine, W. Urban, P. Hering, and M. Murtz, "Isotopic ratio measurements of methane in ambient air using mid-infrared cavity leak-out spectroscopy," Appl. Phys. B 72, 121-125 (2001).

A. L. Rice, A. A. Gotoh, H. O. Ajie, and S. C. Tyler, "High-precision continuous-flow measurement of delta C-13 and delta D of atmospheric CH4," Anal. Chem. 73, 4104-4110 (2001).
[CrossRef]

2000

P. Bergamaschi, M. Bräunlich, T. Marik, and C. Brenninkmeijer, "Measurements of carbon and hydrogen isotopes of atmospheric methane at Izaña, Tenerife: seasonal cycles and synoptic-scale variations," J. Geophys. Res. 105D, 14531-14546 (2000).
[CrossRef]

1999

1998

A. J. Kuhlmann, D. E. J. Worthy, N. B. A. Trivett, and I. Levin, "Methane emissions from a wetland region within the Hudson Bay Lowland: an atmospheric approach," J. Geophys. Res. 103D, 16009-16016 (1998).
[CrossRef]

1997

K. P. Petrov, S. Waltman, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Precise measurement of methane in air using diode-pumped 3.4-μm difference-frequency generation in PPLN," Appl. Phys. B 64, 567-572 (1997).
[CrossRef]

1994

1987

M. A. K. Khalil and R. A. Rasmussen, "Atmospheric methane: trends over the last 10,000 years," Atmos. Environ. 21, 2445-2452 (1987).
[CrossRef]

Ajie, H. O.

A. L. Rice, A. A. Gotoh, H. O. Ajie, and S. C. Tyler, "High-precision continuous-flow measurement of delta C-13 and delta D of atmospheric CH4," Anal. Chem. 73, 4104-4110 (2001).
[CrossRef]

Arbore, M.

K. P. Petrov, S. Waltman, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Precise measurement of methane in air using diode-pumped 3.4-μm difference-frequency generation in PPLN," Appl. Phys. B 64, 567-572 (1997).
[CrossRef]

S. Waltman, K. P. Petrov, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Measurement of 13CH4/12CH4 ratios in air using diode-pumped 3.3 μm difference-frequency generation in PPLN," in 1997 Digest of the IEEE/LEOS Summer Topical Meetings (IEEE Press, 1997), pp. 37-38.

Baillargeon, J. N.

Bergamaschi, P.

P. Bergamaschi, M. Bräunlich, T. Marik, and C. Brenninkmeijer, "Measurements of carbon and hydrogen isotopes of atmospheric methane at Izaña, Tenerife: seasonal cycles and synoptic-scale variations," J. Geophys. Res. 105D, 14531-14546 (2000).
[CrossRef]

P. Bergamaschi, M. Schupp, and G. W. Harris, "High-precision direct measurements of 13CH4/12CH4 and 12CH3D/12CH4 ratios in atmospheric methane sources by means of a long-path tunable diode laser absorption spectrometer," Appl. Opt. 33, 7704-7716 (1994).

Boucher, O.

V. Ramaswamy, O. Boucher, J. Haigh, D. Hauglustaine, J. Haywood, G. Myhre, T. Nakajima, G. Y. Shi, and S. Solomon, "Radiative forcing of climate change," in Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, J. T. Houghton, Y. Ding, D. J. Griggs, M. Noguer, P. J. van der Linden, X. Dai, K. Maskell, and C. A. Johnson, eds. (Cambridge U. Press, 2001), pp. 349-416.

Bräunlich, M.

P. Bergamaschi, M. Bräunlich, T. Marik, and C. Brenninkmeijer, "Measurements of carbon and hydrogen isotopes of atmospheric methane at Izaña, Tenerife: seasonal cycles and synoptic-scale variations," J. Geophys. Res. 105D, 14531-14546 (2000).
[CrossRef]

Brenninkmeijer, C.

P. Bergamaschi, M. Bräunlich, T. Marik, and C. Brenninkmeijer, "Measurements of carbon and hydrogen isotopes of atmospheric methane at Izaña, Tenerife: seasonal cycles and synoptic-scale variations," J. Geophys. Res. 105D, 14531-14546 (2000).
[CrossRef]

Brown, T.

P. Quay, J. Stutsman, D. Wilbur, A. Snover, E. Dlugokencky, and T. Brown, "The isotopic composition of atmospheric methane," Global Biogeochem. Cycles 13, 445-461 (1999).
[CrossRef]

Cho, A. Y.

Coplen, T. B.

T. B. Coplen, "Reporting of stable hydrogen, carbon, and oxygen isotopic abundances (technical report)," Pure Appl. Chem. 66, 273-276 (1994).

Curl, R. F.

Dahnke, H.

H. Dahnke, D. Kleine, W. Urban, P. Hering, and M. Murtz, "Isotopic ratio measurements of methane in ambient air using mid-infrared cavity leak-out spectroscopy," Appl. Phys. B 72, 121-125 (2001).

Dlugokencky, E.

P. Quay, J. Stutsman, D. Wilbur, A. Snover, E. Dlugokencky, and T. Brown, "The isotopic composition of atmospheric methane," Global Biogeochem. Cycles 13, 445-461 (1999).
[CrossRef]

Dlugokencky, E. J.

K. P. Petrov, S. Waltman, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Precise measurement of methane in air using diode-pumped 3.4-μm difference-frequency generation in PPLN," Appl. Phys. B 64, 567-572 (1997).
[CrossRef]

S. Waltman, K. P. Petrov, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Measurement of 13CH4/12CH4 ratios in air using diode-pumped 3.3 μm difference-frequency generation in PPLN," in 1997 Digest of the IEEE/LEOS Summer Topical Meetings (IEEE Press, 1997), pp. 37-38.

Fejer, M. M.

K. P. Petrov, S. Waltman, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Precise measurement of methane in air using diode-pumped 3.4-μm difference-frequency generation in PPLN," Appl. Phys. B 64, 567-572 (1997).
[CrossRef]

S. Waltman, K. P. Petrov, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Measurement of 13CH4/12CH4 ratios in air using diode-pumped 3.3 μm difference-frequency generation in PPLN," in 1997 Digest of the IEEE/LEOS Summer Topical Meetings (IEEE Press, 1997), pp. 37-38.

Gmachl, C.

Gotoh, A. A.

A. L. Rice, A. A. Gotoh, H. O. Ajie, and S. C. Tyler, "High-precision continuous-flow measurement of delta C-13 and delta D of atmospheric CH4," Anal. Chem. 73, 4104-4110 (2001).
[CrossRef]

Guenther, D.

D. Guenther, Carbon Cycle Greenhouse Gases Group, Earth System Research Laboratory, National Oceanic and Atmospheric Administration, Boulder, Colo. (personal communication, 2005).

Haigh, J.

V. Ramaswamy, O. Boucher, J. Haigh, D. Hauglustaine, J. Haywood, G. Myhre, T. Nakajima, G. Y. Shi, and S. Solomon, "Radiative forcing of climate change," in Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, J. T. Houghton, Y. Ding, D. J. Griggs, M. Noguer, P. J. van der Linden, X. Dai, K. Maskell, and C. A. Johnson, eds. (Cambridge U. Press, 2001), pp. 349-416.

Harris, G. W.

Hauglustaine, D.

V. Ramaswamy, O. Boucher, J. Haigh, D. Hauglustaine, J. Haywood, G. Myhre, T. Nakajima, G. Y. Shi, and S. Solomon, "Radiative forcing of climate change," in Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, J. T. Houghton, Y. Ding, D. J. Griggs, M. Noguer, P. J. van der Linden, X. Dai, K. Maskell, and C. A. Johnson, eds. (Cambridge U. Press, 2001), pp. 349-416.

Haywood, J.

V. Ramaswamy, O. Boucher, J. Haigh, D. Hauglustaine, J. Haywood, G. Myhre, T. Nakajima, G. Y. Shi, and S. Solomon, "Radiative forcing of climate change," in Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, J. T. Houghton, Y. Ding, D. J. Griggs, M. Noguer, P. J. van der Linden, X. Dai, K. Maskell, and C. A. Johnson, eds. (Cambridge U. Press, 2001), pp. 349-416.

Hering, P.

H. Dahnke, D. Kleine, W. Urban, P. Hering, and M. Murtz, "Isotopic ratio measurements of methane in ambient air using mid-infrared cavity leak-out spectroscopy," Appl. Phys. B 72, 121-125 (2001).

Hollberg, L. W.

K. P. Petrov, S. Waltman, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Precise measurement of methane in air using diode-pumped 3.4-μm difference-frequency generation in PPLN," Appl. Phys. B 64, 567-572 (1997).
[CrossRef]

S. Waltman, K. P. Petrov, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Measurement of 13CH4/12CH4 ratios in air using diode-pumped 3.3 μm difference-frequency generation in PPLN," in 1997 Digest of the IEEE/LEOS Summer Topical Meetings (IEEE Press, 1997), pp. 37-38.

Hutchinson, A. L.

Khalil, M. A. K.

M. A. K. Khalil and R. A. Rasmussen, "Atmospheric methane: trends over the last 10,000 years," Atmos. Environ. 21, 2445-2452 (1987).
[CrossRef]

Kleine, D.

H. Dahnke, D. Kleine, W. Urban, P. Hering, and M. Murtz, "Isotopic ratio measurements of methane in ambient air using mid-infrared cavity leak-out spectroscopy," Appl. Phys. B 72, 121-125 (2001).

Kosterev, A. A.

Kuhlmann, A. J.

A. J. Kuhlmann, D. E. J. Worthy, N. B. A. Trivett, and I. Levin, "Methane emissions from a wetland region within the Hudson Bay Lowland: an atmospheric approach," J. Geophys. Res. 103D, 16009-16016 (1998).
[CrossRef]

Levin, I.

A. J. Kuhlmann, D. E. J. Worthy, N. B. A. Trivett, and I. Levin, "Methane emissions from a wetland region within the Hudson Bay Lowland: an atmospheric approach," J. Geophys. Res. 103D, 16009-16016 (1998).
[CrossRef]

Marik, T.

P. Bergamaschi, M. Bräunlich, T. Marik, and C. Brenninkmeijer, "Measurements of carbon and hydrogen isotopes of atmospheric methane at Izaña, Tenerife: seasonal cycles and synoptic-scale variations," J. Geophys. Res. 105D, 14531-14546 (2000).
[CrossRef]

Murtz, M.

H. Dahnke, D. Kleine, W. Urban, P. Hering, and M. Murtz, "Isotopic ratio measurements of methane in ambient air using mid-infrared cavity leak-out spectroscopy," Appl. Phys. B 72, 121-125 (2001).

Myhre, G.

V. Ramaswamy, O. Boucher, J. Haigh, D. Hauglustaine, J. Haywood, G. Myhre, T. Nakajima, G. Y. Shi, and S. Solomon, "Radiative forcing of climate change," in Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, J. T. Houghton, Y. Ding, D. J. Griggs, M. Noguer, P. J. van der Linden, X. Dai, K. Maskell, and C. A. Johnson, eds. (Cambridge U. Press, 2001), pp. 349-416.

Nakajima, T.

V. Ramaswamy, O. Boucher, J. Haigh, D. Hauglustaine, J. Haywood, G. Myhre, T. Nakajima, G. Y. Shi, and S. Solomon, "Radiative forcing of climate change," in Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, J. T. Houghton, Y. Ding, D. J. Griggs, M. Noguer, P. J. van der Linden, X. Dai, K. Maskell, and C. A. Johnson, eds. (Cambridge U. Press, 2001), pp. 349-416.

Petrov, K. P.

K. P. Petrov, S. Waltman, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Precise measurement of methane in air using diode-pumped 3.4-μm difference-frequency generation in PPLN," Appl. Phys. B 64, 567-572 (1997).
[CrossRef]

S. Waltman, K. P. Petrov, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Measurement of 13CH4/12CH4 ratios in air using diode-pumped 3.3 μm difference-frequency generation in PPLN," in 1997 Digest of the IEEE/LEOS Summer Topical Meetings (IEEE Press, 1997), pp. 37-38.

Quay, P.

P. Quay, J. Stutsman, D. Wilbur, A. Snover, E. Dlugokencky, and T. Brown, "The isotopic composition of atmospheric methane," Global Biogeochem. Cycles 13, 445-461 (1999).
[CrossRef]

Ramaswamy, V.

V. Ramaswamy, O. Boucher, J. Haigh, D. Hauglustaine, J. Haywood, G. Myhre, T. Nakajima, G. Y. Shi, and S. Solomon, "Radiative forcing of climate change," in Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, J. T. Houghton, Y. Ding, D. J. Griggs, M. Noguer, P. J. van der Linden, X. Dai, K. Maskell, and C. A. Johnson, eds. (Cambridge U. Press, 2001), pp. 349-416.

Rasmussen, R. A.

M. A. K. Khalil and R. A. Rasmussen, "Atmospheric methane: trends over the last 10,000 years," Atmos. Environ. 21, 2445-2452 (1987).
[CrossRef]

Rice, A. L.

A. L. Rice, A. A. Gotoh, H. O. Ajie, and S. C. Tyler, "High-precision continuous-flow measurement of delta C-13 and delta D of atmospheric CH4," Anal. Chem. 73, 4104-4110 (2001).
[CrossRef]

Schupp, M.

Shi, G. Y.

V. Ramaswamy, O. Boucher, J. Haigh, D. Hauglustaine, J. Haywood, G. Myhre, T. Nakajima, G. Y. Shi, and S. Solomon, "Radiative forcing of climate change," in Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, J. T. Houghton, Y. Ding, D. J. Griggs, M. Noguer, P. J. van der Linden, X. Dai, K. Maskell, and C. A. Johnson, eds. (Cambridge U. Press, 2001), pp. 349-416.

Sivco, D. L.

Snover, A.

P. Quay, J. Stutsman, D. Wilbur, A. Snover, E. Dlugokencky, and T. Brown, "The isotopic composition of atmospheric methane," Global Biogeochem. Cycles 13, 445-461 (1999).
[CrossRef]

Solomon, S.

V. Ramaswamy, O. Boucher, J. Haigh, D. Hauglustaine, J. Haywood, G. Myhre, T. Nakajima, G. Y. Shi, and S. Solomon, "Radiative forcing of climate change," in Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, J. T. Houghton, Y. Ding, D. J. Griggs, M. Noguer, P. J. van der Linden, X. Dai, K. Maskell, and C. A. Johnson, eds. (Cambridge U. Press, 2001), pp. 349-416.

Stutsman, J.

P. Quay, J. Stutsman, D. Wilbur, A. Snover, E. Dlugokencky, and T. Brown, "The isotopic composition of atmospheric methane," Global Biogeochem. Cycles 13, 445-461 (1999).
[CrossRef]

Tittel, F. K.

A. A. Kosterev, R. F. Curl, F. K. Tittel, C. Gmachl, F. Capasso, D. L. Sivco, J. N. Baillargeon, A. L. Hutchinson, and A. Y. Cho, "Methane concentration and isotopic composition measurements with a mid-infrared quantum cascade laser," Opt. Lett. 24, 1762-1764 (1999).

K. P. Petrov, S. Waltman, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Precise measurement of methane in air using diode-pumped 3.4-μm difference-frequency generation in PPLN," Appl. Phys. B 64, 567-572 (1997).
[CrossRef]

S. Waltman, K. P. Petrov, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Measurement of 13CH4/12CH4 ratios in air using diode-pumped 3.3 μm difference-frequency generation in PPLN," in 1997 Digest of the IEEE/LEOS Summer Topical Meetings (IEEE Press, 1997), pp. 37-38.

Trivett, N. B. A.

A. J. Kuhlmann, D. E. J. Worthy, N. B. A. Trivett, and I. Levin, "Methane emissions from a wetland region within the Hudson Bay Lowland: an atmospheric approach," J. Geophys. Res. 103D, 16009-16016 (1998).
[CrossRef]

Tyler, S. C.

A. L. Rice, A. A. Gotoh, H. O. Ajie, and S. C. Tyler, "High-precision continuous-flow measurement of delta C-13 and delta D of atmospheric CH4," Anal. Chem. 73, 4104-4110 (2001).
[CrossRef]

Urban, W.

H. Dahnke, D. Kleine, W. Urban, P. Hering, and M. Murtz, "Isotopic ratio measurements of methane in ambient air using mid-infrared cavity leak-out spectroscopy," Appl. Phys. B 72, 121-125 (2001).

Waltman, S.

K. P. Petrov, S. Waltman, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Precise measurement of methane in air using diode-pumped 3.4-μm difference-frequency generation in PPLN," Appl. Phys. B 64, 567-572 (1997).
[CrossRef]

S. Waltman, K. P. Petrov, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Measurement of 13CH4/12CH4 ratios in air using diode-pumped 3.3 μm difference-frequency generation in PPLN," in 1997 Digest of the IEEE/LEOS Summer Topical Meetings (IEEE Press, 1997), pp. 37-38.

Wilbur, D.

P. Quay, J. Stutsman, D. Wilbur, A. Snover, E. Dlugokencky, and T. Brown, "The isotopic composition of atmospheric methane," Global Biogeochem. Cycles 13, 445-461 (1999).
[CrossRef]

Worthy, D. E. J.

A. J. Kuhlmann, D. E. J. Worthy, N. B. A. Trivett, and I. Levin, "Methane emissions from a wetland region within the Hudson Bay Lowland: an atmospheric approach," J. Geophys. Res. 103D, 16009-16016 (1998).
[CrossRef]

Yamamoto, K.

K. Yamamoto and N. Yoshida, "High-precision isotopic ratio measurement system for methane (12CH3D/12CH4, 13CH4/12CH4) by using near-infrared diode laser absorption spectroscopy," Spectrochim. Acta Part A 58, 2699-2707 (2002).
[CrossRef]

Yoshida, N.

K. Yamamoto and N. Yoshida, "High-precision isotopic ratio measurement system for methane (12CH3D/12CH4, 13CH4/12CH4) by using near-infrared diode laser absorption spectroscopy," Spectrochim. Acta Part A 58, 2699-2707 (2002).
[CrossRef]

Anal. Chem.

A. L. Rice, A. A. Gotoh, H. O. Ajie, and S. C. Tyler, "High-precision continuous-flow measurement of delta C-13 and delta D of atmospheric CH4," Anal. Chem. 73, 4104-4110 (2001).
[CrossRef]

Appl. Opt.

Appl. Phys. B

H. Dahnke, D. Kleine, W. Urban, P. Hering, and M. Murtz, "Isotopic ratio measurements of methane in ambient air using mid-infrared cavity leak-out spectroscopy," Appl. Phys. B 72, 121-125 (2001).

K. P. Petrov, S. Waltman, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Precise measurement of methane in air using diode-pumped 3.4-μm difference-frequency generation in PPLN," Appl. Phys. B 64, 567-572 (1997).
[CrossRef]

Atmos. Environ.

M. A. K. Khalil and R. A. Rasmussen, "Atmospheric methane: trends over the last 10,000 years," Atmos. Environ. 21, 2445-2452 (1987).
[CrossRef]

Global Biogeochem. Cycles

P. Quay, J. Stutsman, D. Wilbur, A. Snover, E. Dlugokencky, and T. Brown, "The isotopic composition of atmospheric methane," Global Biogeochem. Cycles 13, 445-461 (1999).
[CrossRef]

J. Geophys. Res.

A. J. Kuhlmann, D. E. J. Worthy, N. B. A. Trivett, and I. Levin, "Methane emissions from a wetland region within the Hudson Bay Lowland: an atmospheric approach," J. Geophys. Res. 103D, 16009-16016 (1998).
[CrossRef]

P. Bergamaschi, M. Bräunlich, T. Marik, and C. Brenninkmeijer, "Measurements of carbon and hydrogen isotopes of atmospheric methane at Izaña, Tenerife: seasonal cycles and synoptic-scale variations," J. Geophys. Res. 105D, 14531-14546 (2000).
[CrossRef]

Opt. Lett.

Pure Appl. Chem.

T. B. Coplen, "Reporting of stable hydrogen, carbon, and oxygen isotopic abundances (technical report)," Pure Appl. Chem. 66, 273-276 (1994).

Spectrochim. Acta Part A

K. Yamamoto and N. Yoshida, "High-precision isotopic ratio measurement system for methane (12CH3D/12CH4, 13CH4/12CH4) by using near-infrared diode laser absorption spectroscopy," Spectrochim. Acta Part A 58, 2699-2707 (2002).
[CrossRef]

Other

V. Ramaswamy, O. Boucher, J. Haigh, D. Hauglustaine, J. Haywood, G. Myhre, T. Nakajima, G. Y. Shi, and S. Solomon, "Radiative forcing of climate change," in Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, J. T. Houghton, Y. Ding, D. J. Griggs, M. Noguer, P. J. van der Linden, X. Dai, K. Maskell, and C. A. Johnson, eds. (Cambridge U. Press, 2001), pp. 349-416.

D. Guenther, Carbon Cycle Greenhouse Gases Group, Earth System Research Laboratory, National Oceanic and Atmospheric Administration, Boulder, Colo. (personal communication, 2005).

S. Waltman, K. P. Petrov, E. J. Dlugokencky, M. Arbore, M. M. Fejer, F. K. Tittel, and L. W. Hollberg, "Measurement of 13CH4/12CH4 ratios in air using diode-pumped 3.3 μm difference-frequency generation in PPLN," in 1997 Digest of the IEEE/LEOS Summer Topical Meetings (IEEE Press, 1997), pp. 37-38.

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Figures (4)

Fig. 1
Fig. 1

Optical design of the laser spectrometer shown with a typical spectrum.

Fig. 2
Fig. 2

Cryogenic methane trap diagram.

Fig. 3
Fig. 3

Second-harmonic signal of methane in the D∕H spectral region. The sample gas spectrum is shown as the solid curve, overplotted with the spectral average of all sample gas scans (dashed curve) used as the reference spectrum. The deuterium absorption is labeled as peak A and hydrogen as peak B.

Fig. 4
Fig. 4

Second-harmonic signal of methane in the 13C∕12C spectral region. The sample cell spectrum is shown as the solid curve and the corresponding reference spectrum as the dashed curve. 13C absorption is labeled as peak C and 12C as peak D.

Tables (2)

Tables Icon

Table 1 Estimated Line Intensity Contributions of Methane Isotopes (HITRAN) to the Observed Absorption Profiles a

Tables Icon

Table 2 Measurement Uncertainty Summary

Equations (165)

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15   μW
3.4   μm
12
δ 13 C
20 %
1745
C 13
H 2
CH 4
CO 2
H 2 O
H 2 O
H 2
C 13 H 4
C 12 H 3 D
0.003   amu
CH 4
H 2
ν 4
8.1   μm
δ 13 C
± 11
3   μm
1.7   μm
± 0.7
± 0.027
δ 13 C
δD
± 0.5
± 1.0
C 12 H 3 D / C 12 H 4
3.3   μm
< 1   ppb
C 13 H 4 / C 12 H 4
± 44
C 13 / C 12
3.32 3.41   μm
( 3020 2930 cm 1 )
2950.8508 / 2951.3057 cm 1
( C 12 H 3 D / C 12 H 4 )
3005.3149 / 3005.7333 cm 1
( C 13 H 4 / C 12 H 4 )
100   mW
809   nm
500   mW
1066   nm
LiNO 3
22.2   μm
0.4   mW
W 2 cm 1
60 %
3.3   μm
15   μW
3005
cm 1
300 cm 3
36   m
500 cm 3
( 1.0   m
0.1810 %
N 2
O 2
2950 cm 1
17 %
2 × 10 12
W Hz - 1 / 2
1.0 cm 1
10   Hz
2950 cm 1
3523   m
1763   ppb
0.78   Hz
InSb sam
16
2950.8508 cm 1
C 13 / C 12
3 / 8
80 / 100
150   W
300 ° C
30 ml / min
180 ° C
200 ml / min
25 ° C
1   atm
155 ° C
1 ° C / min
300 ° C
1.0   g
4   h .
0.448 %
( 4.48   mmol   mol 1 )
27   Torr
0.102 %
( 1.02   mmol   mol 1 )
95   Torr
O 2
N 2
CO 2
7
± 0.4 %
3005.3149 / 3005.7333 cm 1
3005.44 cm 1
C 13 H 4 / C 12 H 4
C 12 H 3 D / C 12 H 4
5.1 / K
0.02 cm 1
2950.8508 / 2951.3057 cm 1
ν 3
C 12 H 3 D
2950.8508 cm 1
C 12 H 4
2950.8627 cm 1
5.0 %
C 12 H 4
2951.3057 cm 1
C 12 H 4
2951.3816 cm 1
1.5 %
C 12 H 3 D
2951.3598 cm 1
3005.3149 / 3005.7333 cm 1
ν 3
C 13 / C 12
C 13 H 4
3005.3149 cm 1
C 13 H 4
3005.3305 cm 1
C 12 H 4
3005.
3011 cm 1
C 12 H 4
0.6 %
C 12 H 4
3005.
7333 cm 1
3005.7266 cm 1
2950 cm 1
C 13 H 4
C 12 H 4
δ ( C 13   or   D ) = ( R sam / R ref 1 ) × 1000.
D / H ( [ A ] / [ B ] )
C 13 / C 12 ( [ C ] / [ D ] )
C 13
H 2
R ave,sam
( R ref )
C 13 / C 12
δD
± 12
± 69
δ 13 C
δ 13 C
± 10
± 13
( 3005.3149 / 2950.8508 cm 1
δ 13 C
δ 13 C
δD
δ 13 C
3000 cm 1
C 13 / C 12
D / H
C 13
H 2

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