The Formation and Stability of HA–Fe/Mn Colloids in Saturated Porous Media

Abstract

Fe/Mn (hydr)oxides are metallic compounds that exhibit significant redox activity in environmental media and play a pivotal role in geochemical processes, thereby influencing the fate of metals in porous media. The morphology of Fe/Mn (hydr)oxides in natural environments and their interactions with trace metals are significantly influenced by the presence of natural organic matter (NOM). However, there is limited understanding regarding the formation, transport, and stability of Fe/Mn (hydr)oxides in the environment. The present study employed humic acid (HA) as a representative NOM material to investigate the positive influence of HA on the formation of Fe/Mn colloids. However, there remains limited comprehension regarding the formation, transport, and stability of Fe/Mn (hydr)oxides in the natural environment. In this study, we investigated the positive effect of natural organic matter (NOM) on the formation of Fe/Mn colloids using humic acid (HA) as a representative NOM material. We comprehensively characterized the chemical and physical properties of HA–Fe/Mn colloids formed under various environmentally relevant conditions and quantitatively analyzed their subsequent aggregation and stability behaviors. The findings suggest that the molar ratios of C to Fe/Mn (hydr)oxide play a pivotal role in influencing the properties of HA–Fe/Mn colloids. The formation and stability of HA–Fe/Mn colloids exhibit an upward trend with increasing initial molar ratios of C to Fe/Mn. Redox and metal–carboxylic acid complexation reactions between HA and hydrated iron/manganese oxides play a pivotal role in forming colloidal HA–Fe/Mn complexes. Subsequent investigations simulating porous media environments have demonstrated that the colloidal structure resulting from the interaction between HA and Fe/Mn facilitates their migration within surrounding porous media while also enhancing their retention in the surface layers of these media. This study offers novel insights into the formation and stabilization mechanisms of HA–Fe/Mn colloids, which are pivotal for comprehending the behavior of Fe/Mn colloids and the involvement of Fe/Mn (hydr)oxides in geochemical cycling processes within porous media.