Exploring the secondary mineral products generated by microbial iron respiration in Archean ocean simulations

Marine chemical sedimentary deposits known as Banded Iron Formations (BIFs) archive Archean ocean chemistry and, potentially, signs of ancient microbial life. BIFs contain a diversity of iron- and silica-rich minerals in disequilibrium, and thus many interpretations of these phases suggest they formed secondarily during early diagenetic processes. One such hypothesis posits that the early diagenetic microbial respiration of primary iron(III) oxides in BIFs resulted in the formation of other iron phases, including the iron-rich silicates, carbonates, and magnetite common in BIF assemblages. Here, we simulated this proposed pathway in laboratory incubations combining a model dissimilatory iron-reducing (DIR) bacterium, Shewanella putrefaciens CN32, and the ferric oxyhydroxide mineral ferrihydrite under conditions mimicking the predicted Archean seawater geochemistry. We assessed the impact of dissolved silica, calcium, and magnesium on the bioreduced precipitates. After harvesting the solid products from these experiments, we analyzed the reduced mineral phases using Raman spectroscopy, electron microscopy, powder x-ray diffraction, and spectrophotometric techniques to identify mineral precipitates and track the bulk distributions of Fe(II) and Fe(III). These techniques detected a diverse range of calcium carbonate morphologies and polymorphism in incubations with calcium, as well as secondary ferric oxide phases like goethite in silica-free experiments. We also identified aggregates of curling, iron- and silica-rich amorphous precipitates in all incubations amended with silica. Although ferric oxides persist even in our electron acceptor-limited incubations, our observations indicate that microbial iron reduction of ferrihydrite is a viable pathway for the formation of early iron silicate phases. This finding allows us to draw parallels between our experimental proto-silicates and the recently characterized iron silicate nanoinclusions in BIF chert deposits, suggesting that early iron silicates could possibly be signatures of iron-reducing metabolisms on early Earth.