Linking the molecular composition of autochthonous dissolved organic matter to source identification for freshwater lake ecosystems by combination of optical spectroscopy and FT-ICR-MS analysis

[Display omitted] •Autochthonous end-members were characterized by optical spectroscopy and FT-ICR-MS.•Autochthonous DOM was more aliphatic and less oxidized than allochthonous DOM.•Molecular DOM composition was directly associated with their optical properties.•Multivariate analysis with FT-ICR-MS was useful for source analysis of freshwaters. Autochthonous dissolved organic matter (DOM) is increasingly released in lakes due to eutrophication, and thus affects the composition and environmental behaviors of DOM in eutrophic lakes. However, there are only limited studies on the molecular characteristics of autochthonous DOM and its influencing mechanisms. Herein, end-member DOM samples of macrophytes, algae, sediments and freshwater DOM samples in eutrophic lakes (Ch:Taihu and Dianchi) were collected and characterized by optical spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The results revealed the chemical structures of autochthonous DOM were more aliphatic and less oxidized, which was marked by increases in lipid compounds and decreases in the lignin components as compared to the allochthonous DOM-dominated freshwaters. More specially, algae-derived DOM contains more lipid compounds, while macrophyte-derived DOM was dominated by lignin and tannin compounds according to Van Krevelen plots. Sediment-derived DOM contained more N-containing compounds. The traditional optical indices indicated the relative aromaticity covaried with polyphenolic and polycyclic aromatics, whereas those reflecting autochthonous DOM covaried with more aliphatic compounds. Multivariate analysis of FT-ICR-MS data of end-members and freshwaters revealed the predominant terrestrial input to Lake Taihu and greater contribution of algae released DOM to Dianchi. This study provides critical information about the characteristics of autochthonous DOM at a molecular level and confirmed autochthonous DOM was compositionally distinct from allochthonous DOM. Overall autochthonous DOM should be gained more attention in the eutrophic lakes.