Precipitation of protodolomite facilitated by sulfate-reducing bacteria: The role of capsule extracellular polymeric substances

The origin of dolomite has long puzzled geologists. It has recently been documented that sulfate-reducing bacteria (SRB) are capable of catalyzing the formation of protodolomite, a previously proposed precursor of ordered sedimentary dolomite. However, the catalytic mechanism of SRB remains incompletely understood. This experimental study is aimed at probing the effect of capsule extracellular polymeric substances (capsule EPS) from SRB on the crystallization of protodolomite in vivo. The capsule EPS tested herein was isolated from a protodolomite-mediating SRB, Desulfotomaculum ruminis, and added into a solution wherein the degree of oversaturation was close to the growth medium of D. ruminis at stationary phase. The solid products were characterized with X-ray diffraction (XRD), Raman spectroscopy and, scanning and transmission electron microscopy (SEM and TEM). Our results indicated that aragonite emerged in the reactors without capsule EPS, while Ca-Mg carbonates (Mg-calcite and protodolomite) were produced in the systems amended with capsule EPS. The incorporation amount of Mg2+ in Ca-Mg carbonates was enhanced with the increasing concentration of capsule EPS. The predominant occurrence of protodolomite was found in the reactor with 140 mg/L capsule EPS. These resulting protodolomites were spherical in shape, and composed of numerous nano-particles. The catalytic influence of capsule EPS on the precipitation of protodolomite might be attributed to their strong Mg2+ binding capacity, potentially diminishing Mg-hydration, which is a potent inhibitor of protodolomite crystallization. The results of Fourier transformation infrared (FT-IR) spectra showed that Mg2+ was bonded with carboxyl and hydroxyl groups on capsule EPS. This inferred adsorption capacity of capsule EPS was also supported by new calculations of complexation chemistry between Mg-H2O complex and organic compounds present in capsule EPS.