Analytical and Bioanalytical Chemistry

, Volume 378, Issue 2, pp 256–269 | Cite as

Mass spectrometric method for the absolute calibration of the intramolecular nitrogen isotope distribution in nitrous oxide

  • Jan Kaiser
  • Sunyoung Park
  • Kristie A. Boering
  • Carl A. M. Brenninkmeijer
  • Andreas Hilkert
  • Thomas Röckmann
Original Paper


A mass spectrometric method to determine the absolute intramolecular (position-dependent) nitrogen isotope ratios of nitrous oxide (N2O) has been developed. It is based on the addition of different amounts of doubly labeled 15N2O to an N2O sample of the isotope ratio mass spectrometer reference gas, and subsequent measurement of the relative ion current ratios of species with mass 30, 31, 44, 45, and 46. All relevant quantities are measured by isotope ratio mass spectrometers, which means that the machines’ inherent high precision of the order of 10−5 can be fully exploited. External determination of dilution factors with generally lower precision is avoided. The method itself can be implemented within a day, but a calibration of the oxygen and average nitrogen isotope ratios relative to a primary isotopic reference material of known absolute isotopic composition has to be performed separately. The underlying theoretical framework is explored in depth. The effect of interferences due to 14N15N16O and 15N14N16O in the 15N2O sample and due to 15N 2 + formation are fully accounted for in the calculation of the final position-dependent nitrogen isotope ratios. Considering all known statistical uncertainties of measured quantities and absolute isotope ratios of primary isotopic reference materials, we achieve an overall uncertainty of 0.9‰ (1σ). Using tropospheric N2O as common reference point for intercomparison purposes, we find a substantially higher relative enrichment of 15N at the central nitrogen atom over 15N at the terminal nitrogen atom than measured previously for tropospheric N2O based on a chemical conversion method: 46.3±1.4‰ as opposed to 18.7±2.2‰. However, our method depends critically on the absolute isotope ratios of the primary isotopic reference materials air–N2 and VSMOW. If they are systematically wrong, our estimates will also necessarily be incorrect.


Nitrous oxide Isotopic composition Absolute position-dependent calibration Intramolecular nitrogen isotope ratios Isotope ratio mass spectrometry 



We would like to acknowledge Claus Koeppel and Tae Siek Rhee for help with the mass spectrometric measurements as well as Hairigh Avak and Jens Radke for assistance with the MAT 253 mass spectrometer in the Application Laboratory of Thermo Finnigan MAT, Bremen. Willi Brand is thanked for useful discussions on isotope ratio mass spectrometric finesses. John Crowley helped with the FTIR measurements. The work at UC Berkeley was supported by the US National Science Foundation Atmospheric Chemistry Program (ATM-9901463), the NASA Upper Atmospheric Research Program (NAG2–1483), the David and Lucile Packard Foundation, and the Earth Science Division, Lawrence Berkeley National Laboratory.


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Copyright information

© Springer-Verlag 2004

Authors and Affiliations

  • Jan Kaiser
    • 1
    • 2
    • 6
  • Sunyoung Park
    • 3
  • Kristie A. Boering
    • 3
    • 4
  • Carl A. M. Brenninkmeijer
    • 1
  • Andreas Hilkert
    • 5
  • Thomas Röckmann
    • 2
  1. 1.Department of Atmospheric ChemistryMax Planck Institute for ChemistryMainzGermany
  2. 2.Atmospheric Physics DivisionMax Planck Institute for Nuclear PhysicsHeidelbergGermany
  3. 3.Department of Earth and Planetary ScienceUniversity of CaliforniaBerkeleyUSA
  4. 4.Department of Chemistry, University of California, Berkeley and Earth Science DivisionLawrence Berkeley National LaboratoryBerkeleyUSA
  5. 5.Thermo Finnigan MATBremenGermany
  6. 6.Department of GeosciencesPrinceton UniversityPrincetonUSA

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