Interfacial and Activation Energies of Environmentally Abundant Heterogeneously Nucleated Iron(III) (Hydr)oxide on Quartz

Poorly crystalline iron(III) (hydr)oxide nanoparticles are ubiquitous in environmental systems and play a crucial role in controlling the fate and transport of contaminants. Yet, the thermodynamic and kinetic parameters, e.g., the effective interfacial (alpha') and apparent activation (E-a) energies, of iron(III) (hydr)oxide nucleation on earth-abundant mineral surfaces have not been determined, which hinders an accurate prediction of iron(III) (hydr)oxide formation and its interactions with other toxic or reactive ions. Here, for the first time, we report experimentally obtained a' and Ea for iron(III) (hydr)oxide nucleation on quartz mineral surfaces by employing a flow-through, time-resolved grazing incidence small-angle X-ray scattering (GISAXS). GISAXS enabled the in situ detection of iron(III) (hydr)oxide nucleation rates under different supersaturations (sigma, achieved by varying pH 3.3-3.6) and temperatures (12-35 degrees C). By quantitative analyses based on classical nucleation theory, alpha' was obtained to be 34.6 mJ/m(2) and E-a was quantified as 32.8 kJ/mol. The fundamental thermodynamic and kinetic parameters obtained here will advance our fundamental understanding of the surface chemistry and nucleation behavior of iron(III) (hydr)oxides in subsurface and water treatment systems as well as their effects on the fate and transport of pollutants in natural and engineered water systems. The in situ flow-through GISAXS method can also be adapted to quantify thermodynamic and kinetic parameters at interfaces for many important solid-liquid environmental systems.