Stromatolites are domes, columns, or nearly flat crusts of laminated sedimentary rocks, usually consisting of Ca-Mg carbonates. Stromatolites result from lithification of microbial mats, which are benthic microbial ecosystems where microorganisms arrange themselves in layers according to their physiology. Despite a century of research, the hypothesis of stromatolite genesis by lithification of microbial mats remains controversial, and a convincing explanation for how stromatolites arise from microbial mats is still lacking. In this work, we analyze in detail a stromatolite from Lagoa Vermelha, a coastal hypersaline lagoon in Rio de Janeiro State, Brazil. The stromatolite presents a laminated core and thrombolitic regions at the periphery. Both thrombolitic and laminated facies consist of fine-grained authigenic minerals with minor contributions of bioclasts and quartz grains. X-ray diffraction shows aragonite, high-magnesium calcite (HMC) containing about 17% MgCO3, a very-high-Mg calcite (VHMC) containing 29–46% MgCO3, and small amounts of quartz and pyrite. Scanning electron microscopy of polished samples coupled to energy-dispersive X-ray analysis (EDS) showed that each lamina was composed of 1–4 distinct mineral phases embedded within each other, indicating sequential steps of precipitation of Ca-Mg carbonates under distinct biogeochemical conditions. The coexistence of different phases in a single lamina suggests that several processes contribute to mineral deposition as the incipient stromatolite laminae are left behind by microorganisms from the lower layers of the microbial mat when they grow and/or move upwards.
Quantitative phase analyses of carbonate rocks containing Mg-rich calcite and non-stoichiometric dolomite by the Rietveld method yielded improved results when the substitutions are refined for either minerals. The refinement is constrained by the c-axis of the lattice for both minerals using the formula c = −1.8603 nMg + 17.061 for calcite, where nMg is the molar fraction of Mg replacing Ca, and c = 16.0032 + 0.8632∆n Ca for dolomite, with ∆n Ca being the excess Ca in its B site. The one-step procedure was implemented into the Topas software and tested on twenty-two carbonate rock samples from diverse geological settings, considered analogues to petroleum system lithotypes of the pre-evaporite deposits of Southeastern Brazil. The case study spans over a wide range of calcite and dolomite compositions: up to 0.287 apfu Mg in magnesian calcite, and Ca in excess of up to 0.25 apfu in non-stoichiometric dolomite, which are maximum substitutions the formulas support. The method overcomes the limitations for the quantification of minerals by stoichiometry based on whole-rock chemical analysis for complex mineralogy and can be employed for multiple generations of either carbonate. It returns the mineral quantification with unprecedented detailing of the carbonates' composition, which compares very well to spot analysis (both SEM-EDS and EMPA) if those cover the full range of compositions. The conciliation of the quantification results based on the XRD is also excellent against chemical analysis, thermogravimetry, and carbon elemental analysis.
Because of their extreme heterogeneity at multiple scales, carbonate rocks present a great challenge for studying and managing oil reservoirs. Depositional processes and diagenetic alterations of carbonates may have produced very complex pore structures and, consequently, variable fluid storage and flow properties of hydrocarbon reservoirs. To understand the impact of mineralogy on the pore system, we analyzed four carbonate rock samples (coquinas) from the Morro do Chaves Formation in Brazil. For this study, we used thin sections and XRD for their mineralogical characterization, together with routine core analysis, NMR, MICP and microCT for the petrophysical characterizations. The samples revealed very similar porosity values but considerably different permeabilities. Samples with a relatively high quartz content (terrigenous material) generally had lower permeabilities, mostly caused by more mineral fragmentation. Samples with little or no quartz in turn exhibited high permeabilities due to less fragmentation and more diagenetic actions (e.g., dissolution of shells). Results confirm that carbonate minerals are very susceptible to diagenesis, leading to modifications in their pore body and pore throat sizes, and creating pores classified as moldic and vug pores, or even clogging them. For one of the samples, we acquired detailed pore skeleton information based on microCT images to obtain a more complete understanding of its structural characteristics.
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