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

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Abstract

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.

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Acknowledgments

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.

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Authors and Affiliations

  1. Institute for Energy Problems of Chemical Physics Russian Academy of Sciences, Leninskij pr. 38 k.2, 119334, Moscow, Russia

    Yury Kostyukevich, Alexey Kononikhin & Eugene Nikolaev

  2. Moscow Institute of Physics and Technology, 141700, Dolgoprudnyi, Moscow Region, Russia

    Yury Kostyukevich, Alexey Kononikhin & Igor Popov

  3. Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1-3, 119991, Moscow, Russia

    Alexander Zherebker & Irina Perminova

  4. Emanuel Institute for Biochemical Physics Russian Academy of Sciences, Kosygina st. 4, 119334, Moscow, Russia

    Igor Popov & Eugene Nikolaev

  5. Skolkovo Institute of Science and Technology, Novaya St., 100, 143025, Skolkovo, Russian Federation

    Yury Kostyukevich & Eugene Nikolaev

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  1. Yury Kostyukevich
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  2. Alexey Kononikhin
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  3. Alexander Zherebker
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Correspondence to Eugene Nikolaev.

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Kostyukevich, Y., Kononikhin, A., Zherebker, A. et al. Enumeration of non-labile oxygen atoms in dissolved organic matter by use of 16O/18O exchange and Fourier transform ion-cyclotron resonance mass spectrometry. Anal Bioanal Chem 406, 6655–6664 (2014). https://doi.org/10.1007/s00216-014-8097-9

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