Fe(III) nucleation in the presence of bivalent cations and oxyanions leads to subnanoscale 7 Å polymers.
Highly disordered Fe(III) phases formed in the presence of bivalent cations and oxyanions represent important components of the global Fe cycle due to their potential for rapid turnover and their critical roles in controlling the speciation of major and trace elements. However, a poor understanding of the formation pathway and structure of these Fe phases has prevented assessments of their thermodynamic properties and biogeochemical reactivity. In this work, we derive structural models for the Fe(III)-As(V)-Ca and Fe(III)-P-Ca polymers formed from Fe(II) oxidation and Fe(III) polymerization in the presence of As(V)/P and Ca. The polymer phase consists of a less than 7 Å coherent network of As(V)/P coordinated to Fe(III) polyhedra, with varying amounts of Ca bound directly and indirectly to the oxyanion. This phase forms at the onset of Fe(II) oxidation and, because of its large oxyanion:Fe solids ratio, depletes the oxyanion concentration with only small amounts of Fe. Our results demonstrate that when a steady supply of Fe(III) is provided from an Fe(II) source, these Fe(III) polymers, which dominate oxyanion uptake, form with little dependence on the initial oxyanion concentration. The formation mechanisms and structures of the oxyanion-rich Fe(III) polymers determined in this study enable future thermodynamic investigations of these phases, which are required to model the interrelated biogeochemical cycles of Fe, As(V)/P, and Ca.