Interfacial Molecular Fractionation on Ferrihydrite Reduces the Photochemical Reactivity of Dissolved Organic Matter.

The selective sorption of dissolved organic matter (DOM) on minerals is a widespread geochemical process in the natural environment. Recent studies have explored the influence of this process on the molecular fractionation of DOM at water-mineral interfaces. However, it remains unclear how molecular fractionation affects the photochemistry of DOM. Here, we demonstrate that the adsorptive fractionation of DOM on ferrihydrite greatly reduces its photoproduction of reactive oxygen species (ROS) including 1O2, O2•-, and •OH normalized to organic carbon (ROSOC). The ROSOC for 1O2, O2•-, and •OH were positively correlated with the abundances of polyphenols and oxygenated polycyclic aromatics, which were also observed using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis to be preferentially sequestered by ferrihydrite. The molecules that preferentially remained in the solution after adsorption displayed low levels of ROSOC. The molecular fractionation of DOM induced by adsorption on ferrihydrite therefore influenced the molecular components and also significantly reduced the photoreactive fractions of DOM in waters. These results are very important in promoting our understanding of the effects of molecular fractionation on the biogeochemical features, behaviors, and implications of DOM in the environment.