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 output: Contribution to journalArticlepeer-review

46 Scopus citations

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 H218O 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.

Original languageEnglish
Pages (from-to)6655-6664
Number of pages10
JournalAnalytical and Bioanalytical Chemistry
Volume406
Issue number26
DOIs
StatePublished - 1 Jan 2014
Externally publishedYes

Keywords

  • Dissolved organic matter
  • ESI
  • FTICR
  • Isotope exchange

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry

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