Dissolved silica affects the bulk iron redox state and recrystallization of minerals generated by photoferrotrophy in a simulated Archean ocean

Chemical sedimentary deposits called Banded Iron Formations (BIFs) are one of the best surviving records of ancient marine (bio)geochemistry. Many BIF precursor sediments precipitated from ferruginous, silica-rich waters prior to the Great Oxidation Event at ~2.43 Ga. Reconstructing the mineralogy of BIF precursor phases is key to understanding the coevolution of seawater chemistry and early life. Many models of BIF deposition invoke the activity of Fe(II)-oxidizing photoautotrophic bacteria as a mechanism for precipitating mixed-valence Fe(II,III) and/or fully oxidized Fe(III) minerals in the absence of molecular oxygen. Although the identity of phases produced by ancient photoferrotrophs remains debated, laboratory experiments provide a means to explore what their mineral byproducts might have been. Few studies have thoroughly characterized precipitates produced by photoferrotrophs in settings representative of Archean oceans, including investigating how residual Fe(II)_aq can affect the mineralogy of expected solid phases. The concentration of dissolved silica (Si) is also an important variable to consider, as silicate species may influence the identity and reactivity of Fe(III)-bearing phases. To address these uncertainties, we cultured Rhodopseudomonas palustris TIE-1 as a photoferrotroph in synthetic Archean seawater with an initial [Fe(II)_aq] of 1 mM and [Si] spanning 0–1.5 mM. Ferrihydrite was the dominant precipitate across all Si concentrations, even with substantial Fe(II) remaining in solution. Consistent with other studies of microbial iron oxidation, no Fe-silicates were observed across the silica gradient, although Si coprecipitated with ferrihydrite via surface adsorption. More crystalline phases such as lepidocrocite and goethite were only detected at low [Si] and are likely products of Fe(II)-catalyzed ferrihydrite transformation. Finally, we observed a substantial fraction of Fe(II) in precipitates, with the proportion of Fe(II) increasing as a function of [Si]. These experimental results suggest that photoferrotrophy in a Fe(II)-buffered ocean may have exported Fe(II,III)-oxide/silica admixtures to BIF sediments, providing a more chemically diverse substrate than previously hypothesized.