Fractionation and characterization of dissolved organic matter using solid‐phase extraction followed by Fourier transform ion cyclotron resonance mass spectrometry with electrospray, atmospheric pressure photoionization, and laser desorption ionization

Rationale Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR MS) combined with different ionization techniques provides a powerful means to characterize dissolved organic matter (DOM) at the molecular level. Solid‐phase extraction (SPE) is currently the most widely utilized method for extracting the DOM, but one‐step elution using methanol does not provide a comprehensive picture of DOM. The development of efficient extraction and enrichment methods as well as characterization techniques from water samples remains a priority for DOM research, which is investigated in this study. Methods The DOM was extracted from lake water by SPE using one‐step elution (methanol or dichloromethane) and multistep elution (water, methanol, acetone, and dichloromethane). A combination of electrospray ionization (ESI), atmospheric pressure photoionization (APPI), and matrix‐free laser desorption ionization (LDI) was utilized for FT‐ICR MS analysis in both positive (+) and negative (−) ion modes. Results The total recovery of the multistep elution was 23.5% higher as compared to the investigated one‐step elution procedure (85% vs. 61.6%); however, a comparison of the observed molecular species and the range of diversity under different ionization techniques along with the statistical analyses showed that proper selection of solvent and ionization method was required to explore specific compounds from the sample. Conclusions For DOM species containing different heteroatoms, a combination of ESI, APPI, and LDI can offer a comprehensive profile of DOM in aquatic ecosystems. The specific molecular formulae of each ionization technique are characterized as follows: ESI— mode exhibited strong selectivity for lignin‐like and tannins‐like species with high oxygen content, as well as organosulfates. ESI+ favored lipid species and peptide/protein compounds. Unsaturated and condensed aromatic hydrocarbons with low oxygen were preferably ionized by both APPI and LDI.