Molecular-level insight into the origin-dependent adsorption fractionation of dissolved organic matter on ferrihydrite in aquatic environment: Implications for carbon sink in eutrophic lakes

Molecular fractionation of dissolved organic matter (DOM) induced by adsorption on minerals plays a significant role in carbon biogeochemical cycling in water environment. However, the molecular-level adsorption of algae-derived DOM (ADOM) on minerals in eutrophic lakes remains poorly understood. Herein, we investigated the ferrihydrite-induced adsorptive fractionation of ADOM and humic DOM for comparison by using spectral analysis, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and solid characterization methods. We observed higher adsorption rate but lower adsorption capacity for ADOM than humic DOM. Spectroscopy and FT-ICR-MS indicated compounds with large molecular weight (>350 Da), high unsaturated and oxygen-rich were preferentially adsorbed for both ADOM and humic DOM. Specifically, the adsorption affinity order was aromatics > lignin-like > aliphatic compounds. Furthermore, tannin-like and condensed aromatics were predominantly adsorbed in humic DOM and protein-like formulas in ADOM. The solid characterization of ferrihydrite before and after adsorption further confirmed the dominant adsorption of aromatic and carboxylic-containing species in humic DOM and aliphatic materials in ADOM. Additionally, the contribution variation of oxygen atom to double bond in the molecular formula before and after adsorption identified absorbed oxygen-containing substances were predominantly aromatic carboxylic acids for humic DOM, but few aliphatic hydrocarbons substituted with ethers and alcohols for ADOM. These findings provided new insights into mineral-induced carbon sequestration, that is, increased release of ADOM in eutrophic lakes might influence the amount of organic carbon settled by ferrihydrite, and alter its quality from aromatic to aliphatic compounds transfer from water column to sediment through ferrihydrite adsorption.