Nano scale visualization of enhanced adsorption and distribution of humic acid on hematite: Effect of Pb(II) ions

The interactions between soil organic matter (SOM) and minerals are key processes controlling the organic carbon (OC) stability in the environment, but the underlying mechanisms responsible for OC distribution on minerals are still not clear. In this study, a common crystalline iron oxide, hematite, and a typical SOM component, humic acid (HA), were chosen to explore, at the nano and even sub-nano scales, HA adsorption and distribution on hematite under the impact of Pb(II) ions. Adsorption experiments and spherical aberration corrected scanning transmission electron microscopy (Cs-STEM) coupled with energy dispersive X-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS) demonstrated that Pb(II) enhanced the adsorption of HA on hematite, but the nano scale distributions of HA varied between experimental conditions. The Cs-STEM, EDS, and the EELS analyses clearly unveiled that, with the presence of Pb(II), the hematite aggregates became more dispersed, and HA was not only adsorbed on the edges hematite nanoparticles, but also was localized in the extended areas away from the hematite particles/aggregates, which resulted in a heterogeneous distribution of OC in hematite-HA systems. Our imaging methods provided direct visualization of the mineral-SOM-metal interactions at nano scales, which shed lights on the underlying mechanisms for OC stabilization in natural environments and can enable more robust constraints in the models of organic matter-mineral interactions.