Oriented Aggregation of Lepidocrocite and Impact on Surface Charge Development

The impact of lepidocrocite (γ-FeOOH) nanoparticle aggregation on mineral surface charge development was resolved in aqueous solutions of NaCl and NaClO4. Synthetic rod-like particles exhibiting charged edge (100) and neutrally/low-charged (010) faces self-aggregated in salt-free solutions. Aggregation was notably imaged by high-resolution transmission electron microscopy, and inferred by decreases in N2(g)-B.E.T. specific surface area from 94 m(2)/g to 77 m(2)/g after 12 months, and to 66 m(2)/g after 33 months storage. Potential determining (H(+), OH(-)) ions loadings in the 4-11 pH range were unchanged only if the particles remained aggregated in NaCl but only if they were disaggregated in NaClO4. These differences, alongside molecular simulations and experimental ion loadings resolved in other studies from our group, point to important controls on background electrolyte ion identity on the aggregation and charge development in lepidocrocite. These results may apply further to other mineral surfaces of comparable surface (hydr)oxo populations.