Direct Evidence for Temporal Molecular Fractionation of Dissolved Organic Matter at the Iron Oxyhydroxide Interface.

While the importance of organic matter adsorption onto reactive iron-bearing mineral surfaces to carbon stabilization in soils and sediments has been well-established, fundamental understanding of how compounds assemble at the mineral interface remains elusive. Organic matter is thought to layer sequentially onto the mineral surface, forming molecular architecture stratified by bond strength and compound polarity. However, prominent complexation models lack experimental backing, despite the role of such architecture in fractionated, compound-dependent persistence of organic matter and modulating future perturbations in mineral stabilization capacity. Here, we use kinetic assays and ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry under high temporal frequency to directly detect the molecular partitioning of organic matter onto an iron oxyhydroxide during adsorption. We observed three sequential intervals of discrete molecular composition throughout the adsorption reaction, in which rapid primary adsorption of aromatic compounds was followed by secondary lignin-like and tertiary aliphatic compounds. These findings, paired with observed differential fractionation along formulas nitrogen and oxygen content and decreasing selective sorption with reaction time, support "zonal" assembly models. This work presents direct detection of sequential molecular assembly of organic matter at the mineral interface, an important yet abstruse regulator of carbon stabilization and composition across temporal and spatial scales.