Organomineralization of dolomite in hypersaline microbial mats from Qatar sabkhas visualized by TEM & STXM

Abstract

Deep insight into the low-temperature mineralization mechanism of dolomite in sediments has remained elusive. This issue is popularly termed “The Dolomite Problem” due to its multifactorial nature. Dolomite has been observed to mineralize in the exopolymeric substances produced by microbial mat communities (Bontognali et al. 2013), where productivity is high. One working hypothesis suggests that degrading organic matter in hypersaline environments releases the necessary component ions, increasing saturation with respect to dolomite (DiLoreto et al. 2019, Dupraz et al. 2009, Petrash et al. 2017). Other models suggest a dissolution-reprecipitation reaction of calcite to dolomite (Rivers 2023). High-resolution micro-spectroscopy techniques (such as transmission electron microscopy, TEM; and scanning transmission X-ray microscopy, STXM) can be used to determine chemical changes in crystals nucleating in a matrix, however to date very little studies have focused on observing dolomite mineralization at the nano-scale. The present study investigates microbial mats collected from hypersaline salt flats in the Persian gulf at micro- to nano-meter scales using high-spatial and -energy resolution TEM (Thermo Scientific Talos 200X at the Canadian Centre for Electron Microscopy) and STXM (PolLux Beamline at the Swiss Light Source at Paul Scherrer Institut), specifically to see changes in carbonate mineralization due to interactions with organic matter. C, Ca and O elemental maps of carbonate crystals were obtained with EDXS (energy-dispersive X-ray spectroscopy) in TEM. These crystals were also indexed by SAED (selected area electron diffraction in TEM). Fine spectral signatures (near-edge X-ray absorption fine structures, or NEXAFS) at the C K-edge (280-290 eV) and Ca L2,3-edge (344-356 eV) in STXM were used to determine the chemical identity of carbonate minerals and surrounding organic matter of the microbial mats. The results of the study show that dolomite nucleates in close association with the organic matter of the mats, where degradation is highest (defined in our adjacent study as the increase in C:N ratio). In TEM, polycrystalline dolomite is seen mineralizing in the matrix of the microbial mat organic material (Fig. 1). In STXM, the identity of the carbonate mineral changes from calcite on the outside to dolomite on the inside of the microbial mat particle (Fig. 2). In addition, our microsensor observations of elevated H2S concentrations, surface oxygenation from oxygenic phototrophy, high reduction potential, high organic carbon, high Mg:Ca ratio and high organic matter degradation (by C:N ratio) in each of the studied microbial mats confirms that the ideal dolomite mineralization conditions according to models of the dolomite problem are present in each case.