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1. A review of the nature and origin of limestone microporosity

   https://doi.org/10.1016/j.marpetgeo.2019.03.037  

   Hashim, Mohammed S. Kaczmarek ( April 2019 , Marine and petroleum geology)

   Limestone microporosity is ubiquitous and extensively developed in most Phanerozoic limestones. From an economic perspective, microporosity is important because it contributes substantially to the carbonate pore system, which can host significant volumes of water and hydrocarbons. Therefore, determining the presence and distribution of limestone micropores is necessary for accurate hydrocarbon estimations, reservoir characterization, and fluid flow simulations. From an academic standpoint, microporosity is important because its genesis is intimately linked with the mineralogical stabilization of metastable sediments, a fundamental process in carbonate diagenesis. Many types of micropores contribute to what has been referred to as microporosity, but the vast majority is hosted among low-magnesium calcite (LMC) microcrystals that are present in limestone matrix and allochems. Geochemical, textural, and mineralogical data from natural settings and laboratory experiments indicate that LMC microcrystals are diagenetic in origin. More specifically, these data support a diagenetic model of mineralogical stabilization that involves dissolution of precursor sediments dominated by aragonite and high-magnesium calcite (HMC) minerals, and precipitation of LMC microcrystal cements. The stabilization process is inferred to take place in the meteoric, marine, and burial diagenetic realms. Although it has not been directly observed, carbon and oxygen isotopes, as well as trace element data suggest that LMC microcrystals form during burial diagenesis in marine-like fluids. Evidence suggests that porosity is not generated during this dissolution-precipitation process, but rather inherited from the precursor sediments. The final arrangement of the micropores in a limestone, however, depends on the precise diagenetic pathway. LMC microcrystals exhibit a range of microcrystalline textures that are classified on the basis of crystal morphology and size. The three main textural classes - granular (framework), fitted (mosaic), and clustered - have been recognized across a wide range of ages, depositional settings, burial depths, and precursor types, and are characterized by distinct petrophysical properties, such as porosity, permeability, and pore-throat size. Observations from modern sediments also support the hypothesis that LMC microcrystals develop from aragonite and HMC dominated lime mud. The origin of lime mud has been extensively studied but still highly debated. Of particular interest to the discussion of microporosity are proposed secular variations in the dominant mineralogy of carbonate sediments through the Phanerozoic. Microporous limestones comprised of LMC microcrystals are equally abundant during times of aragonite seas and calcite seas, which suggests that no special mineral precursor is required. Microporous textures are also observed in deep marine chalks where micropores are hosted between chalk constituents. Unlike shallow marine limestones, deep marine sediments start out as mostly LMC therefore mineralogical stabilization is not a significant process in chalk diagenesis. 

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2. Rhombic calcite microcrystals as a textural proxy for meteoric diagenesis

   https://doi.org/10.1038/s41598-021-04219-2  

   Hashim, Mohammed S. ; Kaczmarek, Stephen E. ( January 2022 , Scientific Reports)

   Numerous Phanerozoic limestones are comprised of diagenetic calcite microcrystals formed during mineralogical stabilization of metastable carbonate sediments. Previous laboratory experiments show that calcite microcrystals crystallizing under conditions similar to those that characterize meteoric diagenetic settings (impurity-free, low degree of supersaturation, high fluid:solid ratio) exhibit the rhombic form/morphology, whereas calcite microcrystals crystallizing under conditions similar to those that prevail in marine and marine burial diagenetic settings (impurity-rich, high degree of supersaturation, low fluid:solid ratio) exhibit non-rhombic forms. Based on these experimental observations, it is proposed here that rhombic calcite microcrystals form exclusively in meteoric environments. This hypothesis is tested using new and previously published textural and geochemical data from the rock record. These data show that the vast majority of Phanerozoic limestones characterized by rhombic microcrystals also exhibit petrographic and/or geochemical evidence (depleted δ¹³C, δ¹⁸O, and trace elements) indicative of meteoric diagenesis whereas non-rhombic forms are associated with marine burial conditions. By linking calcite microcrystal textures to specific diagenetic environments, our observations bring clarity to the conditions under which the various microcrystal textures form. Furthermore, the hypothesis that rhombic calcite microcrystals form exclusively in meteoric environments implies that this crystal form may be a useful textural proxy for meteoric diagenesis.

    

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3. The Transformation of Aragonite to Calcite in the Presence of Magnesium: Implications for Marine Diagenesis

   Hashim, M. ; Kaczmarek, S.E. ( September 2021 , Earth and planetary science letters)

   null (Ed.)

   Magnesium (Mg) in natural waters plays a critical role in governing carbonate mineral formation, dissolution, and diagenesis. Previous laboratory experiments show that Mg can strongly inhibit direct calcite precipitation as well as aragonite to calcite diagenetic transformation. Data from natural settings, however, suggest that diagenetic calcite in most Phanerozoic limestones has formed in the shallow marine burial realm in the presence of ample Mg. Thus, the diagenetic conditions under which aragonite-rich sediments convert to calcite-rich limestones are poorly understood. Here, we present data from laboratory experiments whereby aragonite is converted to calcite at 70◦C in Mg-bearing solutions to investigate the effects of fluid:solid ratio (F:S), which varies greatly across diagenetic environments, on Mg inhibition and incorporation in calcite. Our data show that not only can the transformation of aragonite to calcite occur in solutions with higher [Mg] than previously shown possible in laboratory experiments, but that progressively lower F:S increase the rate at which aragonite stabilizes to calcite. For example, in experiments with an F:S of 0.3 mL/g, which corresponds to sediments in a closed system with 50% porosity, aragonite stabilizes to calcite in solution with [Mg]=30 mM (Mg/Ca=5.14) when an initial high degree of undersaturation with respect to aragonite is used and in a solution with [Mg]=20 (Mg/Ca=5.14) when a low degree of undersaturation is used. In contrast, aragonite does not stabilize to calcite after nearly 3000 h in experiments with an F:S of 100 mL/g, which is more typical of an open system, even in a solution with [Mg]=5 mM (Mg/Ca=5.14) regardless of the degree of undersaturation. Our results also show that the amount of Mg incorporated into calcite products increases linearly with the increase of F:S. Collectively, these observations further point to F:S as an important factor in carbonate diagenesis with broad implications. First, the observations that transformation of aragonite to calcite is inhibited at high [Mg] and F:S imply that calcite precipitation is unlikely to occur in marine diagenetic environments that are in direct hydrologic contact with seawater. This leaves aragonite dissolution as the dominant diagenetic process in these environments, which may represent an underrated source of alkalinity to the open ocean. Second, transformation from aragonite-rich sediments to the calcite-rich limestones that dominate the rock record is likely promoted by a decrease in the F:S and the development of a closed system during progressive burial. 

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4. Mg zonation and heterogeneity in low-Mg calcite microcrystals of a depositional chalk

   https://doi.org/10.2110/jsr.2020.173  

   Rinderknecht, Chanse J. ; Hasiuk, Franek J. ; Oborny, Stephan C. ( August 2021 , Journal of Sedimentary Research)

   null (Ed.)

   ABSTRACT Diagenetic low-magnesium calcite (LMC) microcrystals constitute the framework that hosts most micropores in limestone reservoirs and therefore create the storage capacity for hydrocarbons, water, and anthropogenic CO2. Limestones dominated by LMC microcrystals are also commonly used for paleoclimate reconstructions and chemostratigraphic correlations. LMC microcrystals are well known to exhibit a range of textures (e.g., granular, fitted, clustered), but there exists uncertainty with regard to how these textures form. One hypothesis is that during crystal growth, Mg is incorporated into diagenetic overgrowths (cement), where the chemical zonation and microtexture may reflect diagenetic processes. To evaluate small-scale geochemical zonation in LMC microcrystals, this study uses scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) to measure the Mg/Ca ratio across the interiors of LMC granular microcrystals from a Late Cretaceous marine chalk from the Tor Fm. (Norwegian North Sea). Mg/Ca zonation was identified in all LMC microcrystals with a diameter > 5 μm. Generally, the cores of large crystals have lower Mg/Ca (≈ 5.9 mmol/mol) and the rims have elevated Mg/Ca (≈ 13 mmol/mol). Smaller microcrystals (< 5 μm) show no resolvable zonation, but do exhibit a wide range in Mg/Ca content from 2.9 to 32.2 mmol/mol. Measured Mg/Ca values are arbitrarily divided into three populations: low Mg (average ≈ 5.9 mmol/mol), intermediate Mg (average ≈ 13.3 mmol/mol), and high Mg (average ≈ 20 mmol/mol). The observed zonation and Mg enrichment within LMC microcrystals is interpreted to reflect depositional as well as multiple diagenetic signals, such as constructive precipitation through recrystallization and pore-filling cementation. Although chalk from the Tor Fm. is dominated by granular euhedral LMC microcrystals, using SEM-EDS to find Mg/Ca heterogeneity in other LMC microcrystal textures may provide insight into the diagenetic processes that create textural variations in micropore-dominated limestones. The Mg data also more broadly suggest that there is useful, measurable diagenetic information in material that is otherwise considered homogeneous. Distinguishing between possible primary compositions and secondary cementation has implications for studies that rely on the primary chemistry of fine-grained carbonate deposits (e.g., micrite), such as paleoclimatology, Mg paleothermometry, and chemostratigraphy. 

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5. Characteristics and Consequences of Red Bed Bleaching by Hydrocarbon Migration: A Natural Example From the Entrada Sandstone, Southern Utah

   https://doi.org/10.1029/2022GC010465  

   Bailey, Lydia R. ; Drake, Henrik ; Whitehouse, Martin J. ; Reiners, Peter W. ( August 2022 , Geochemistry, Geophysics, Geosystems)

   Extensive regions of yellow and white (“bleached”) sandstones within the terrestrial Jurassic red bed deposits of the Colorado Plateau reflect widespread interaction with subsurface reduced fluids which resulted in the dissolution of iron‐oxide grain coatings. Reduced fluids such as hydrocarbons, CO₂, and organic acids have been proposed as bleaching agents. In this study, we characterize an altered section of the Slick Rock member of the Jurassic Entrada Sandstone that exposes bleached sandstone with bitumen‐saturated pore spaces. We observe differences in texture, porosity, mineralogy, and geochemistry between red, pink, yellow, and gray facies. In the bleached yellow facies we observe quartz overgrowths, partially dissolved K‐feldspar, calcite cement, fine‐grained illite, TiO₂‐minerals, and pyrite concretions. Clay mineral content is highest at the margins of the bleached section. Fe₂O₃concentrations are reduced up to 3× from the red to gray facies but enriched up to 50× in iron‐oxide concretions. Metals such as Zn, Pb, and rare‐earth elements are significantly enriched in the concretions. Supported by a batch geochemical model, we conclude the interaction of red sandstones with reduced hydrocarbon‐bearing fluids caused iron‐oxide and K‐feldspar dissolution, and precipitation of quartz, calcite, clay, and pyrite. Localized redistribution of iron into concretions can account for most of the iron removed during bleaching. Pyrite and carbonate stable isotopic data suggest the hydrocarbons were sourced from the Pennsylvanian Paradox Formation. Bitumen in pore spaces and pyrite precipitation formed a reductant trap required to produce Cu, U, and V enrichment in all altered facies by younger, oxidized saline brines.

    

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