Unravelling molecular fractionation of dissolved organic matter on ferrihydrite-phosphate complexes

Association of dissolved organic matter (DOM) with iron (Fe) oxyhydroxides leading to significant molecular fractionation, plays a significant role in biogeochemical cycling of carbon in soils. However, the molecular effects of coexisting phosphate, a widely distributed oxyanion in agricultural soils that has a strong affinity with Fe oxyhydroxides on such a process remain poorly understood. Here, using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) with a superiority in deciphering DOM characteristics at the molecular level, this study reveals the DOM molecular fractionation characteristics on ferrihydrite-phosphate (Fh-P) complexes. Results show that the adsorption of DOM on Fh-P complexes can be significantly inhibited by similar to 50% compared to that on ferrihydrite. Optical spectroscopy and FT-ICR-MS further indicate that phosphate can greatly change the molecular fractionation of DOM on Fh-P complexes. Phosphate preferentially inhibits the highly aromatic, hydrophobic, and high molecular weight compounds (> 400 Da) of DOM on Fh-P complexes, such as condensed hydrocarbon and tannin; more CHONS compounds preferentially adsorb on the Fh-P complexes than thoseon ferrihydrite. Phosphate inhibits the adsorption of DOM with the characteristics of high oxygen atoms number, aromaticity index (AI), and double bond equivalents (DBE) on ferrihydrite. Our study demonstrates that the inhibitory effects of phosphate on the adsorption of the DOM can significantly influence the fractionation and adsorption of DOM by ferrihydrite. The findings of this work deepen our understanding of biogeochemical cycling of DOM in soil and aquifer environments.