Work

Surface Charge and Size Evolution of Silica–Iron Colloidal Particles in Simulated Late-Archaean Seawater

Year: 2025

Type: article

Abstract: Late-Archean seawater functioned as a vast, redox-tuned colloidal system for which its kinetics were largely governed by the surface chemistry of silica–iron nanoparticles. By reproducing Archean seawater (≈0.7 M ionic strength, 25 °C) in laboratory anoxic-to-mildly oxic reactors, the ζ potential (zeta-potential(ζ)) of silica–iron nanoparticles was investigated, and we tracked how transient O2 pulses (≤9 mg L−1) regulated it. The zeta (ζ) potential was applied as the key diagnostic parameter to quantify both the sign of the ζ potential and the colloidal stability of simulated silica–iron particles in dispersion. Under strictly anoxic conditions, silica colloids (SiO2(aq)) exhibit a persistently negative ζ potential (ζ ≈ −25 mV) in the simulated seawater (pH 6.5), arising from deprotonated silanol groups (≡Si–O−). Upon the addition of Fe2+, the inner-sphere complexation of ferrous ions on SiO2 colloids partially replaces ≡Si–O− with ≡Si–O–Fe+/≡Si–O–Fe–OH sites; the net negative charge density at the outer Stern plane nevertheless increases, and the ζ potential shifts from −25 mV to −30 mV. As the simulated seawater was oxygenated, the dissolved and surface-bound Fe2+ ions were oxidized to Fe3+, causing the ζ potential to exceed −30 mV. This study demonstrates that Fe2+–silica interactions generate electrostatic destabilization, suspending micron-scale aggregates and thus modulating the solubility and speciation of SiO2 in early oceans. Also, transient micro-oxic pulses are shown to shift silica–iron colloids between metastable aggregation and dispersion by modulating their ζ potential. Subsequently, AFM and TEM were used to characterize the morphological changes in the colloidal particles from the liquid state to the dry state. Furthermore, infrared and XPS analyses were conducted on the colloidal samples. These findings provide certain reference significance for reconstructing the chemical evolution process of seawater in the Late-Archean period and for understanding the factors influencing the silicon–iron cycle of seawater in the Late-Archean era.

Source: Minerals

DOI: 10.3390/min15111123