Analytical and Bioanalytical Chemistry

, Volume 406, Issue 26, pp 6655–6664 | Cite as

Enumeration of non-labile oxygen atoms in dissolved organic matter by use of 16O/18O exchange and Fourier transform ion-cyclotron resonance mass spectrometry

  • Yury Kostyukevich
  • Alexey Kononikhin
  • Alexander Zherebker
  • Igor Popov
  • Irina Perminova
  • Eugene Nikolaev
Research Paper


We report a simple approach for enumeration of non-labile oxygen atoms in individual molecules of dissolved organic matter (DOM), using acid-catalyzed 16O/18O exchange and ultrahigh-resolution Fourier-transform ion-cyclotron-resonance mass spectrometry (FTICR-MS). We found that by dissolving DOM in H2 18O at 95 °C for 20 days it is possible to replace all oxygen atoms of DOM molecules (excluding oxygen from ether groups) with 18O. The number of exchanges in each molecule can be determined using high-resolution FTICR. Using the proposed method we identified the number of non-labile oxygen atoms in 231 molecules composing DOM. Also, using a previously developed hydrogen–deuterium (H/D)-exchange approach we identified the number of labile hydrogen atoms in 450 individual molecular formulas. In addition, we observed that several backbone hydrogen atoms can be exchanged for deuterium under acidic conditions. The method can be used for structural and chemical characterization of individual DOM molecules, comparing different DOM samples, and investigation of biological pathways of DOM in the environment.


Isotope exchange Dissolved organic matter FTICR ESI 



This work was supported by Russian Foundation for Basic Research (grants 13- 04-40110-n-komfi, 13-08-01445-a, 14-08-31652–mol-a).

Competing financial interest

The authors declare no competing financial interests.

Supplementary material

216_2014_8097_MOESM1_ESM.pdf (2 mb)
ESM 1 (PDF 2056 kb)


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Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Yury Kostyukevich
    • 1
    • 2
    • 5
  • Alexey Kononikhin
    • 1
    • 2
  • Alexander Zherebker
    • 3
  • Igor Popov
    • 2
    • 4
  • Irina Perminova
    • 3
  • Eugene Nikolaev
    • 1
    • 4
    • 5
  1. 1.Institute for Energy Problems of Chemical Physics Russian Academy of SciencesMoscowRussia
  2. 2.Moscow Institute of Physics and TechnologyDolgoprudnyiRussia
  3. 3.Department of ChemistryLomonosov Moscow State UniversityMoscowRussia
  4. 4.Emanuel Institute for Biochemical Physics Russian Academy of SciencesMoscowRussia
  5. 5.Skolkovo Institute of Science and TechnologySkolkovoRussian Federation

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