The chemical changes of DOM from black waters to coastal marine waters by HPLC combined with ultrahigh resolution mass spectrometry

How dissolved organic matter (DOM) undergoes chemical changes during its transit from river to ocean remains a challenge due to its complex structure. In this study, DOM along a river transect from black waters to marine waters is characterized using an offline combination of reversed-phase high performance liquid chromatography (RP-HPLC) coupled to electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS), as well as tandem ESI-FTICR-MS. In addition, a water extract from degraded wood that mainly consists of lignins is used for comparison to the DOM from this transect. The HPLC chromatograms of all DOM samples and the wood extract show two major well-separated components; one is hydrophilic and the other is hydrophobic, based on their elution order from the C₁₈ column. From the FTICR-MS analysis of the HPLC fractions, the hydrophilic components mainly contain low molecular weight compounds (less than 400 Da), while the hydrophobic fractions contain the vast majority of compounds of the bulk C₁₈ extracted DOM. The wood extract and the DOM samples from the transect of black waters to coastal marine waters show strikingly similar HPLC chromatograms, and the FTICR-MS analysis further indicates that a large fraction of molecular formulas from these samples are the same, existing as lignin-like compounds. Tandem mass spectrometry experiments show that several representative molecules from the lignin-like compounds have similar functional group losses and fragmentation patterns, consistent with modified lignin structural entities in the wood extract and these DOM samples. Taken together, these data suggest that lignin-derived compounds may survive the transit from the river to the coastal ocean and can accumulate there because of their refractory nature.