Calcite Mineralogy Research Articles

Multi-proxy assessment of brachiopod shell calcite as a potential archive of seawater temperature and oxygen isotope composition

Abstract. Most of our knowledge of past seawater temperature history is based on δ18O values of calcium carbonate fossil shells. However, the determination of past temperatures using this proxy requires the knowledge of past seawater δ18O values, which is generally poorly constrained. Other paleothermometers using carbonate archives, such as Mg/Ca ratios and clumped isotopes (Δ47), have been developed to allow for paleotemperatures to be estimated independently and to allow past ocean δ18O values to be calculated using various groups of calcifying organisms. Articulated brachiopod shells are some of the most commonly used archives in studies of past oceanic geochemistry and temperature. They are abundant in the fossil record since the Cambrian, and for decades, their low Mg–calcite mineralogy has been considered relatively resistant to diagenetic alteration. Here, we investigate the potential of brachiopod shells as recorders of seawater temperatures and seawater δ18O values using new brachiopod shell geochemical data by testing multiple well-established or suggested paleothermometers applied to carbonate archives. Modern articulated brachiopod shells covering a wide range of temperatures (−1.9 to 25.5 ∘C), depths (5 to 3431 m) and salinities (33.4 to 37.0 PSU) were analysed for their stable isotope compositions (δ13C, δ18O and Δ47) and their elemental ratios (Mg/Ca, Sr/Ca, Na/Ca and Li/Ca). Our data allowed us to propose a revised oxygen isotope fractionation equation between modern-brachiopod shell calcite and seawater: (1) T = - 5.0 ( ± 0.2 ) ( δ 18 O c - δ 18 O sw ) + 19.4 ( ± 0.4 ) , where δ18Oc is in ‰ VPDB, δ18Osw is in ‰ VSMOW, and T is in ∘C. Our results strongly support the use of clumped isotopes as an alternative temperature proxy but confirm significant offsets relative to the canonical relationship established for other biogenic and abiogenic calcium carbonate minerals. Brachiopod shell Mg/Ca ratios show no relationship with seawater temperatures, indicating that this ratio is a poor recorder of past changes in temperatures, an observation at variance with several previous studies. Despite significant correlations with brachiopod living temperature, brachiopod shell Sr/Ca, Na/Ca and Li/Ca values indicate the influence of environmental and biological factors unrelated to temperature, which undermines their potential as alternative temperature proxies. Kinetic effects (growth rates) could explain most of the deviation of brachiopod shell calcite from expected isotopic equilibrium with seawater and part of the distribution of Sr/Ca, Na/Ca and Li/Ca ratios.

U-series and radiocarbon cross dating of speleothems from Nerja Cave (Spain): Evidence of open system behavior. Implication for the Spanish rock art chronology

Two stalagmites from Nerja cave (Andalusia, Spain) were studied. The cave is well known because of its long human occupation from the Upper Palaeolithic to the Chalcolithic and its abundant parietal prehistoric Art. The aims of this study were twofold: i) to compare uranium/thorium (230Th/234U) and Carbon-14 (14C) ages obtained all along the growth axis of the stalagmites in order to understand the consequences of diagenetic processes on the validity of radiometric ages; ii) as one of the stalagmites contains black layers, attributed to combustion soot, to establish when these intense hearths were used and by which culture.230Th/234U and 14C ages were coupled with mineralogical studies using FTIR (Fourier-transform infrared spectroscopy) and thin section observations. The first stalagmite (GN16-9b) displays 230Th/234U ages in stratigraphic order, and compatible with 14C ages corrected for a few percent of dead carbon. Homogeneous composition of aragonitic crystals characterized by their needle-like texture is observed throughout this speleothem. For the second stalagmite (GN16-7), in contrast, 230Th/234U ages display large significant inversions and discordant results on the upper part and at the base of the stalagmite, suggesting a possible open system behavior for this chronometer. Interestingly, 14C ages are in stratigraphic order all along the stalagmite and are compatible with 230Th/234U ages only in its central part. Mineralogical studies display evidence of aragonite to calcite transformation at the top and a complex mineralogical assemblage with interlayered silicates (possibly clays) and calcitic mineralogy for the base of GN16-7. In these parts, discordant 230Th/234U ages were measured. In the middle part of the stalagmite, however, where the fibrous aragonite is well preserved, the 14C and 230Th/234U ages agree. Our data suggest that in the case of aragonite to calcite transformation as shown here, 230Th/234U ages are biased, but 14C ages seem to remain accurate, as already observed in aragonitic marine bio minerals. 14C ages obtained are used for the chronology of the soot layer, determined here between 7900 and 5500 years Cal BP, coherent with previous analysis of charcoals in the same sector of the cave. This study highlights the importance of working with at least two chronometers when stratigraphic age verification is not possible, as is the case of some parietal CaCO3 thin layers used for rock art dating. Recent 230Th/234U ages published for carbonate deposits on Spanish parietal Art are discussed in light of this demonstration.

238U/235U in calcite is more susceptible to carbonate diagenesis

The uranium isotopic composition (δ238U) of bulk marine calcium carbonates has been extensively explored as a promising paleoredox proxy to track the extent of global oceanic anoxia in deep time. Multiple studies have examined whether primary calcium carbonates can directly capture seawater δ238U and whether bulk measurements of recent and ancient carbonates preserve seawater U isotope signatures. Here we assess the role of diagenesis in altering δ238U signatures in carbonates sediments that have a primary calcitic mineralogy at the Paleocene-Eocene Thermal Maximum (PETM), an interval with rapid global warming and oceanic deoxygenation at ∼56 million years ago.Although primary abiotic and biogenic calcium carbonates (aragonite and calcite) can directly capture seawater δ238U with small offsets (<0.1‰) relative to modern seawater, diagenetic alteration of Bahamian shallow-water platform carbonate sediments that have a predominantly primary aragonitic mineralogy resulted in significantly larger offsets (up to 0.6‰). Since U concentration in primary aragonite is at least one order of magnitude higher than primary calcite (>1 ppm vs. <0.1 ppm), δ238U in calcite should be even more susceptible to diagenesis than that in aragonite.We find strong evidence of this effect in analysis of δ238U in PETM shallow-water carbonate sediments from Drilling Project (ODP) Hole 871C (Limalok Guyot, Pacific Ocean). Our results reveal large fluctuations in bulk carbonate δ238U from −0.69 to +0.71‰ around the PETM boundary but consistently heavier δ238U (between −0.14 and +0.47‰) than modern seawater outside of this interval. The significantly lighter δ238U values than modern seawater were interpreted to result from the operation of a Mn oxide shuttle. The heavier δ238U values are most likely caused by authigenic reductive accumulation of U(IV) in pore waters below the sediment-water interface. We found that carbonate δ238U values higher than modern seawater tend to increase with increasing U/Ca. This relationship is well-explained by an authigenic reductive accumulation model that simply assumes addition to primary calcite during diagenesis of calcitic cements containing isotopically heavier U(IV).Our work confirms expectations that δ238U in primary calcite is more susceptible to the amount of diagenetic cementation compared to primary aragonite, and that variations of δ238U in carbonate sediments with a primary calcitic mineralogy would more dominantly reflect the local redox state of depositional and early diagenetic environments. It is essential to identify the original carbonate mineralogy, the diagenetic history, and constrain the redox state of local deposition environments of sedimentary carbonate rocks when applying bulk carbonate δ238U as a global proxy for oceanic anoxia in deep time.

Microbialite development through the Ediacaran–Cambrian transition in China: Distribution, characteristics, and paleoceanographic implications

Widespread development of microbialites harbors a series of clues about microbial activity, environmental condition, and aquatic chemistry. The Ediacaran-Cambrian transition draws extensive attention on the co-evolution of complex life and Earth's environment but the associated microorganism development has been largely ignored. In this study, we present a high-resolution database with respect to the spatial and temporal distributions of microbialites in China through the terminal Ediacaran to the early Cambrian Period and describe morphological and petrological characteristics of stromatolites and thrombolites in detail to shed light on the evolutionary process of microbial carbonates. Microbialite development experienced two thriving intervals during the Ediacaran-Cambrian transition: latest Ediacaran to early Fortunian, and Cambrian Age 3 to middle Age 4. The columnar and domical stromatolites show no marked morphological changes in the Ediacaran-Cambrian transition, but stratiform stromatolites exhibit a notable decline in Cambrian time, likely caused by increasing bioturbation in the Cambrian shelf environments. Meanwhile, thrombolites evolved to form large and complicated structures in the early Cambrian featured by meter-level mound morphology and columnar-branching microbial forms (fan-like/dendritic structures), likely indicating an improved environmental adaptation (e.g., photosynthesis efficiency and hydrodynamic conditions). Another remarkable change in microbialites is the emergence of large numbers of calcified microbial microfossils preserved within the laminated/clotted mesostructures in Cambrian facies, compared with the Ediacaran forms that lack such unique structural features. For the main control over the Cambrian microbial calcification event, this study stresses again the essential role of seawater chemistry (Mg/Ca molar ratios and Ca 2+ concentrations) in the formation and preservation of calcified microorganisms based on previous insights and elaborate characteristics of their occurrence and microstructures in China. The transition of the Neoproterozoic “aragonite-dolomite sea” to the Cambrian “calcite sea” (likely widely distributed in Age 3) may have promoted to the generation of an original calcite mineralogy in microbial fossils, which has a stronger ability to resist diagenetic dissolution and substitution (e.g., phosphatization and silicification) than that of the aragonite precursor. • We present a high-resolution database with respect to the development of microbialites in China through the E-C transition. • Detailed morphological and petrological characteristics of stromatolites and thrombolites are described. • Microbialite development experienced two thriving intervals in China during the E-C transition. • Thrombolites evolved to form large and complicated structures, likely indicating an improved environmental adaptation. • The primary calcite mineralogical composition is one potential reason for the preservation of the calcified microfossils.

The Impact of Pore Structure on Kerogen Geomechanics

Production stimulation techniques such as the combination of hydraulic fracturing and lateral drilling have made exploiting unconventional formations economically feasible. Advancements in production aspects are not always in lockstep with our ability to predict and model the extent of a fracturing job. Shale is a clastic sedimentary rock composed of a complex mineralogy of clay, quartz, calcite, and fragments of an organic material known as kerogen. The latter, which consists of large chains of aromatic and aliphatic carbons, is highly elastic, a characteristic that impacts the geomechanics of a shale matrix. Following a molecular simulation approach, the objective of this work is to investigate kerogen’s petrophysics on a molecular level and link it to kerogen’s mechanical properties, considering some range of kerogen structures. Nanoporous kerogen structures across a range of densities were formed from single macromolecule units. Eight units were initially placed in a low-density cell. Then, a molecular dynamic protocol was followed to form a final structure with a density of 1.1 g/cc; the range of density values was consistent with what has been reported in the literature. The structures were subjected to petrophysical assessments including a helium porosity analysis and pore size distribution characterization. Mechanical properties such as Young’s modulus, bulk modulus, and Poisson ratio were calculated. The results revealed strong correlations among kerogen’s mechanical properties and petrophysics. The kerogen with the lowest porosity showed the highest degree of elasticity, followed by other structures that exhibited larger pores. The effect temperature and the fluid occupying the pore volume were also investigated. The results signify the impact of kerogen’s microscale intricacies on its mechanical properties and hence on the shale matrix. This work provides a novel methodology for constructing kerogen structures with different microscale properties that will be useful for delineating fundamental characteristics such as mechanical properties. The findings of this work can be used in a larger scale model for a better description of shale’s geomechanics.

Palaeozoic stromatoporoid diagenesis: a synthesis

Palaeozoic stromatoporoids, throughout their 100-million + year history (Middle Ordovician to Late Devonian and rare Carboniferous), are better preserved than originally aragonite molluscs, but less well-preserved than low magnesium-calcite brachiopods, bryozoans, trilobites and corals. However, the original mineralogy of stromatoporoids remains unresolved, and details of their diagenesis are patchy. This study of approximately 2000 stromatoporoids and the literature recognises three diagenetic stages, applicable throughout their geological history. Timing of processes may vary in and between stages; some components are not always present. Stage 1, on or just below sediment surface, comprises the following: micrite filling of upper gallery space after death, then filling of any remaining space by non-ferroan then ferroan calcite in decreasing oxygen of pore-waters; partial lithification of associated sediment from which stromatoporoids may be exhumed and redeposited, evidence of general early lithification of middle Palaeozoic shallow-marine carbonates; microdolomite formation, with the Mg interpreted to have been derived from original high-Mg calcite (HMC) mineralogy (likely overlaps Stage 2). Stage 2, short distance below sediment surface, comprising the following: fabric-retentive recrystallisation (FRR) of stromatoporoid skeletons forming fabric-retentive irregular calcite (FRIC), mostly orientated normal to growth layers, best seen in cross-polarised light. FRIC stops at stromatoporoid margins in contact with sediment and bioclasts. FRIC geometry varies, indicating some taxonomic control. Evidence that FRIC formed early in diagenetic history includes syntaxial continuation of FRIC into some sub-stromatoporoid cavities (Type 1 cement), although others were pre-occupied by early cement fills (Type 2 cement) formed before FRR, preventing syntaxial continuation of FRIC into cavities. Likely contemporaneous with FRIC formation, stromatoporoids in argillaceous micrites drew carbonate from adjacent sediment during reorganisation of argillaceous micrite into limestone–marl rhythms that are also early diagenetic. Stage 3, largely shallow burial, comprises the following: dissolution and silicification, but these may have occurred earlier in stromatoporoid diagenetic histories (more data required); burial pressure dissolution forming stylolites.

Bio-mineral needle fiber calcite (NFC) in Tunisian Pleistocene calcretes (topology and crystallization)

The microfacies of Pleistocene calcareous crust in Tunisia revealed the presence of diverse aspects of acicular crystallizations in a porous system. These crystallizations are in the shape of branched filaments, mono or polycrystalline rods which are either smooth or serrated (calcite), and serrated edge needle (calcium oxalate). The genesis of these acicular structures seems to be directly or indirectly linked to the organic activity. In fact, the facies are tied to the biological activity or biochemical interactions, which occur between living organisms and the mineral (calcite), triggering a succession of precipitation and dissolution reactions. These reactions, which are characteristic of vadose environments, have actively contributed to the endurance of calcareous crusts due to premature or delayed diagenesis. The acicular calcite, found in the Tunisian Pleistocene calcretes, reflects regional climates that influence the form and mineralogy of needle fiber calcite.

RETRACTED: Sedimentary characteristics and origin of dolomitic ooids of the terminal Ediacaran Dengying Formation at Yulin (Chongqing, South China)

Abstract The Ediacaran was a crucial transition period in the evolutionary history of the Earth. Ediacaran ooids in the Dengying Formation from the Yulin section in southwestern China are important archives of paleoenvironmental information. Although these ooids have been totally dolomitized, the cortical fabric characteristics are locally preserved well, indicating that these ooids were mimetically replaced. The common occurrence of concentric–radial fabrics and low level of Sr concentrations (60.3 ± 8.8 ppm) in the studied ooid cortex is more likely suggestive of a primary low-Mg calcite mineralogy and that a calcite sea might exist during deposition of the second member of the Dengying Formation. In situ geochemical data for the ooid cortices obtained by laser ablation inductively coupled plasma mass spectrometry show that these ooids have middle rare earth element enrichment (PrN/SmN = 0.7 ± 0.1 and SmN/YbN = 1.5 ± 0.4) and high Fe contents (8200 ± 1800 ppm). This suggests ferruginous pore waters, which were related to the selective or preferential absorption and release of REEs by Fe-Mn oxyhydroxides.

Quantifying susceptibility of marine invertebrate biocomposites to dissolution in reduced pH.

Ocean acidification threatens many ecologically and economically important marine calcifiers. The increase in shell dissolution under the resulting reduced pH is an important and increasingly recognized threat. The biocomposites that make up calcified hardparts have a range of taxon-specific compositions and microstructures, and it is evident that these may influence susceptibilities to dissolution. Here, we show how dissolution (thickness loss), under both ambient and predicted end-century pH (approx. 7.6), varies between seven different bivalve molluscs and one crustacean biocomposite and investigate how this relates to details of their microstructure and composition. Over 100 days, the dissolution of all microstructures was greater under the lower pH in the end-century conditions. Dissolution of lobster cuticle was greater than that of any bivalve microstructure, despite its calcite mineralogy, showing the importance of other microstructural characteristics besides carbonate polymorph. Organic content had the strongest positive correlation with dissolution when all microstructures were considered, and together with Mg/Ca ratio, explained 80–90% of the variance in dissolution. Organic content, Mg/Ca ratio, crystal density and mineralogy were all required to explain the maximum variance in dissolution within only bivalve microstructures, but still only explained 50–60% of the variation in dissolution.

Uranium isotope variations in a dolomitized Jurassic carbonate platform (Tithonian; Franconian Alb, Southern Germany)

The uranium (U) isotopic composition (δ238U) of limestones is increasingly used to quantitatively track changes in paleoredox conditions of the global ocean. However, many limestones have undergone significant dolomitization during diagenesis. To assess the potential impact of diagenetic changes on the U isotope composition of dolomitized rocks, we examined the uranium isotopic composition of a Jurassic carbonate platform of the Franconian Alb in Southern Germany. This platform underwent dolomitization during shallow burial due to the supply of magnesium-rich fluids in the form of slightly modified seawater. This type of dolomitization is common in the geologic record. The carbonate platform of the Franconian Alb can therefore serve as an example for many dolomitized carbonate platforms.A positive correlation between the concentrations of redox sensitive elements (e.g., Re and V) and δ238U confirms that the authigenic uptake of U under reducing conditions preferentially incorporates U enriched in 238U. This positive correlation between redox sensitive elements and δ238U does not change within the dolomitized interval, suggesting that the δ238U is not altered during shallow burial dolomitization of limestones. Therefore, our results indicate that dolostones can retain information about secular variations in seawater δ238U.The diagenetic uptake of U shifts δ238U of bulk carbonate sediments to values heavier than contemporaneous seawater. The magnitude of this offset correlates with the level of authigenic enrichment of redox sensitive elements in our sample set. Samples with high Re and V concentrations and high Re/Mo ratios are the most enriched in 238U. This positive correlation could be used to constrain the amount of diagenetic offset of bulk δ238U values from seawater. This is particularly important in carbonate systems that had a primary calcitic mineralogy. Primary calcite precipitates have low U concentrations and so small amounts of 238U uptake during diagenesis can have a significant impact on the bulk composition.The samples with the most depleted δ238U values have high Mo concentrations and low Re/Mo ratios. As carbonate sediments are generally Mo poor, the high Mo concentrations suggests that the depleted δ238U values might be linked to a manganese cycle that operated across the sediment-water interface during the deposition of this Jurassic carbonate platform.

Evaluating modes I, II, and mixed mode I-II fracture toughnesses of crystalline rocks using discrete element method

ABSTRACTSeveral cracked chevron-notched Brazilian disk (CCNBD) and hollow center cracked disk (HCCD) samples of crystalline building stones naming Maroon, Baghat, and Neiriz in Iran, bearing the same calcite mineralogy and different grain size distributions were numerically modeled using three-dimensional particle flow code, with the respective microscopic mechanical properties measured through calibration technique. The simulation of CCNBD and HCCD samples highlights higher toughness compared to laboratory measurements. The values regarding HCCD samples are in a better agreement with experimental results than those regarding the CCNBD samples. The principal objective was to evaluate the reliability of numerical simulations in estimating fracture toughness and to recognize the mechanism and the mode of failure, of which laboratory tests are incapable. At microscales, failures occurring due to tensile or shear loadings may not be subsumed within any category as such at macroscales with failure modes I and II. Experimental and numerical results show that the KIC values determined from both CCNBD and HCCD samples have a negative correlation with the grain size distributions of the marbles. However, no specific trend as such was identified for KIIC.

New constraints on the last aragonite–calcite sea transition from early Jurassic ooids

Calcite and aragonite seas are commonly distinguished based on the prevailing primary mineralogy of ooids and carbonate cements over time. Secular oscillations of these seas are usually attributed to changes in ocean chemistry and paleoclimate. While the veracity of such oscillations has been verified by independent data and modeling approaches, the timing of the transition from one ocean state to the other remains poorly resolved. Here, the timing of the last aragonite–calcite sea transition is estimated by assessing the preservation of Early Jurassic ooids from the Trento Platform in northern Italy. Point counting of ooid-bearing limestones from four distinct stratigraphic levels provides a contrasting pattern: Hettangian and Sinemurian ooids are all poorly preserved and were probably predominantly originally aragonitic, whereas Pliensbachian and Toarcian ooids are excellently preserved, suggesting a primary calcitic mineralogy. Although calcitic ooids may have already been common in the Late Triassic, it is proposed that the last aragonite–calcite sea transition occurred in the Early Jurassic between the Sinemurian and Pliensbachian, at least in this subtropical region. Therefore, the selective extinction of aragonite-secreting organisms at the end-Triassic mass extinction cannot be attributed to secular changes in ocean chemistry.

What determines sclerobiont colonization on marine mollusk shells?

Empty mollusk shells may act as colonization surfaces for sclerobionts depending on the physical, chemical, and biological attributes of the shells. However, the main factors that can affect the establishment of an organism on hard substrates and the colonization patterns on modern and time-averaged shells remain unclear. Using experimental and field approaches, we compared sclerobiont (i.e., bacteria and invertebrate) colonization patterns on the exposed shells (internal and external sides) of three bivalve species (Anadara brasiliana, Mactra isabelleana, and Amarilladesma mactroides) with different external shell textures. In addition, we evaluated the influence of the host characteristics (mode of life, body size, color alteration, external and internal ornamentation and mineralogy) of sclerobionts on dead mollusk shells (bivalve and gastropod) collected from the Southern Brazilian coast. Finally, we compared field observations with experiments to evaluate how the biological signs of the present-day invertebrate settlements are preserved in molluscan death assemblages (incipient fossil record) in a subtropical shallow coastal setting. The results enhance our understanding of sclerobiont colonization over modern and paleoecology perspectives. The data suggest that sclerobiont settlement is enhanced by (i) high(er) biofilm bacteria density, which is more attracted to surfaces with high ornamentation; (ii) heterogeneous internal and external shell surface; (iii) shallow infaunal or attached epifaunal life modes; (iv) colorful or post-mortem oxidized shell surfaces; (v) shell size (<50 mm2 or >1,351 mm2); and (vi) calcitic mineralogy. Although the biofilm bacteria density, shell size, and texture are considered the most important factors, the effects of other covarying attributes should also be considered. We observed a similar pattern of sclerobiont colonization frequency over modern and paleoecology perspectives, with an increase of invertebrates occurring on textured bivalve shells. This study demonstrates how bacterial biofilms may influence sclerobiont colonization on biological hosts (mollusks), and shows how ecological relationships in marine organisms may be relevant for interpreting the fossil record of sclerobionts.

Aragonitic scleractinian corals in the Cretaceous calcitic sea

Abstract Changes in seawater chemistry have affected the evolution of calcifying marine organisms, including their skeletal polymorph (calcite versus aragonite), which is believed to have been strongly influenced by the Mg/Ca ratio at the time these animals first emerged. However, we show that micrabaciids, a scleractinian coral clade that first appeared in the fossil record of the Cretaceous, when the ocean Mg/Ca ratio was near the lowest in the Phanerozoic (thus a priori favoring calcitic mineralogy), formed skeletons composed exclusively of aragonite. Exceptionally preserved aragonitic coralla of Micrabacia from the Late Cretaceous Ripley Formation (southeastern USA) have skeletal microstructures identical to their modern representatives. In addition, skeletons of Micrabacia from Cretaceous chalk deposits of eastern Poland are clearly diagenetically altered in a manner consistent with originally aragonitic mineralogy. These deposits have also preserved fossils of the scleractinian Coelosmilia, the skeleton of which is interpreted as originally calcitic. These findings show that if changes in seawater Mg/Ca ratio influenced the mineralogy of scleractinian corals, the outcome was taxon specific. The aragonitic mineralogy, unique skeletal microstructures and ultrastructures, and low Mg/Ca ratios in both fossil and living micrabaciids indicate that their biomineralization process is strongly controlled and has withstood major fluctuations in seawater chemistry during the past 70 m.y.

Experimental Investigation of CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;-Water-Rock Interactions during CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; Flooding in Carbonate Reservoir

Injecting CO2 into underground reservoir to displace oil is a viable means of reducing greenhouse gas emission to the atmosphere and enhancing oil recovery. To evaluate the effect of CO2-water-rock interactions on the characteristics of carbonate reservoir at high pressure, the mineralogy of calcite, the ion concentration in the reacted solution, the surface texture of calcite, the permeability of calcite after reacted with injected CO2 and deionized water was investigated by X-ray diffraction (XRD), inductive coupled plasma-atomic emission spectrometry (ICP-AES), scanning electronic microscope (SEM), and sand-packed model at pressure of 5.0 MPa. The results show that the mineral dissolution of calcite would occur when interacting with injected CO2 and water. The mineral dissolution of calcite caused the change of surface texture of calcite and increase in Ca2+, HCO-3 ion concentration in the solution. With the increase of CO2 pressure, the surface dissolution of calcite appeared more obvious. With the increase of reaction temperature, the surface dissolution of calcite also appeared more obvious and Ca2+, HCO-3 ion concentration in the solution increased first, then decreased. The mineral dissolution of calcite caused the improvement in water permeability of calcite/quartzsand-packed model.

Impact of diagenetic alteration on brachiopod shell magnesium isotope (δ26Mg) signatures: Experimental versus field data

Due to their thermodynamically stable low-Mg calcite mineralogy, the shells of brachiopods are often counted among the most reliable archives of the physicochemical conditions that occurred during the Phanerozoic in marine waters. Consequently, traditional and non-traditional isotope and elemental proxy data from brachiopod valves have been analyzed in numerous studies and results obtained have been placed in context with ancient seawater properties. This paper tests the sensitivity of brachiopod shell magnesium isotope (δ26Mg) data to diagenetic alteration. We apply a dual approach by: (i) performing hydrothermal alteration experiments using meteoric, marine, and burial reactive fluids; and (ii) comparing these data to naturally altered, ancient brachiopod shells. The degree of alteration of individual shells is assessed by a combination of fluorescence and cathodoluminescence microscopy. The absence of luminescence might indicate both well-preserved shell material, but also the secondary enrichment of quenching elements such as iron along diagenetic pathways. Complementary oxygen isotope data provide insight into the question of open versus closed system behavior of brachiopod shells. Brachiopod shell magnesium isotope values respond to differential fluid temperature, chemistry, and experiment durations. The patterns observed are complicated by the interplay of kinetic and thermodynamic patterns and the presence of variable amounts of water soluble and water insoluble organic matter within these biominerals. Generally, the range in bulk δ26Mg from experimentally altered (1.52‰) and that of bulk samples from ancient, diagenetically altered brachiopod valves (1.53‰) exceed the geochemical variability of δ26Mgbrachiopod bulk values of most recent specimens (1.26‰) in the lower and upper range. More 26Mg enriched (0.8‰) and more 26Mg depleted (0.7‰) values, respectively, are found in altered shells in comparison to unaltered ones. The data shown here are considered significant for those aiming to reconstruct palaeoenvironmental parameters based on brachiopod archives. Consequently, we propose tentative guidelines for magnesium isotope research applied to ancient carbonates.

Hydrogeochemical and geomorphological investigation of travertine deposition in the Garab Spring region, NE Iran

In this research, the hydrogeochemical and geomorphological evidences of travertine deposition were investigated to detect the Garab Spring region as a unique travertine zone of northeastern Iran. Some of the hydrological and geochemical properties of the water and rocks were analyzed. According to the concentration of major components, the chemical property of the Garab Spring water was identified as Na–Cl and Ca–HCO3–SO4. Based on the geochemical results of XRF, the most important compositions of the rock samples were demonstrated as CaO, Fe2O3 and MgO with 59.24, 8.78 and 7.14 %, respectively. The petrography analysis indicated calcite mineralogy. Furthermore, the geomorphological shapes of the rocks were categorized into both robust travertine and fragile tufa.

Middle–late Pleistocene and Holocene chronostratigraphy and climate history of the Tamala Limestone, Cooloongup and Safety Bay Sands, Nambung National Park, southwestern Western Australia

The Pleistocene Tamala Limestone outcrops for ~1000 km along the southwestern Australian coast. Detailed mapping of excellent exposures at Nambung National Park and surrounding areas, together with mineralogical analyses and dating, identified five members: White Desert, Nambung, Stockyard Gully, Pinnacles Desert and Grey members (in stratigraphic order). The two youngest members can be easily recognised because they partly retain the original aragonite and high-Mg calcite mineralogy of the bioclasts (the youngest Grey Member to the greatest extent). Each member consists of an eolian calcarenite/calcrete-microbialite/paleosol cycle. The eolianites were deposited during interglacial highstands (MIS 5, 7, 9, 11 and possibly 13), under the influence of strong south to southwesterly winds that blew the sand well inland and up to over 100 m above sea-level. This scenario continued during the Holocene transgression, showing that dune activity in this region was a characteristic of the relatively humid interglacial climates rather than the drier glacial periods. Towards the end of most interglacial episodes, the rainfall was sufficiently high that the dunes were stabilised by vegetation, and there was significant subsoil dissolution of the eolianite, forming a karst surface. In the following glacial climates, laminated microbialites were deposited in the karst voids within some members; in others a calcrete layer is present, probably reflecting a semiarid climate. The paleosols capping each member contain an eolian input of silt and some clay owing to the increased wind activity associated with the glacial climates when they were deposited. The laterally extensive quartzose Cooloongup Sand was deposited on top of the Tamala Limestone during the glacial climate of MIS 2–4, reflecting the low rainfall and strong winds. The quartz sand was derived from dissolution of the eolianites during preceding periods of karstification.

Inorganic control on original carbonate mineralogy and creation of gas reservoir of the Upper Jurassic carbonates in the Kopet-Dagh Basin, NE, Iran

The Upper Jurassic Mozduran Formation (Oxfordian–Tithonian) is the main petroleum reservoir in the Kopet-Dagh Basin, northeast Iran, which consists predominantly of carbonate rocks with subordinate evaporites and siliciclastics deposited in platform to deep marine settings of a subtropical sea. Detailed field surveys, petrographic investigations, facies and wire line log analyses were carried out at eight surface sections and four wells in the Kopet-Dagh Basin. Integration of petrographic and isotopic data suggests primary low-Mg calcite mineralogy of Oxfordian and Tithonian ooids. On the other hand, in the wells, Kimmeridgian ooids and cements are dominantly aragonitic and high-Mg calcite mineralogy (HMC). Marine cements with isopachous, fibrous and isopachous bladed fabrics indicate original aragonite and HMC mineralogy, respectively. The domination of aragonite mineralogy could be related to increased hypersalinity, evaporite precipitation and consequently an increase in Mg/Ca ratio, which resulted in formation of aragonite in preference to calcite. Preserved ooids with radial and concentric cortices in shallow-water settings that are nearby siliciclastic source, together with aragonitic and HMC ooids accompanied by evaporites in the drilled fields, suggest original mineralogy was probably controlled inorganically following local salinity variations. This study suggests that Kimmeridgian pay zones are mainly controlled by depositional facies, aragonitic and HMC mineralogy, and diagenetic processes such as dolomitization and dissolution.

First description of Phanerozoic radiaxial fibrous dolomite

The petrographic analysis and crystallographic analysis of concretionary carbonate cements (“coal balls”) from Carboniferous paralic swamp deposits reveal the presence of (length fast) radiaxial fibrous dolomite (RFD), a fabric not previously reported from the Phanerozoic. This finding is of significance as earlier reports of Phanerozoic radiaxial fibrous carbonates are exclusively of calcite mineralogy. Dolomite concretions described here formed beneath marine transgressive intervals within palustrine coal seams. This is of significance as seawater was arguably the main source of Mg2+ ions for dolomite formation. Here, data from optical microscopy, cathodoluminescence, electron backscattered diffraction, X-ray diffraction and geochemical analyses are presented to characterize three paragenetic dolomite phases and one calcite phase in these concretions. The main focus is on the earliest diagenetic, non-stoichiometric (degree of order: 0.41–0.46) phase I, characterized by botryoidal dolomite constructed of fibres up to 110μm wide with a systematic undulatory extinction and converging crystal axes. Petrographic and crystallographic evidence clearly qualifies phase I dolomite as radiaxial fibrous. Conversely, fascicular optical fabrics were not found. Carbon-isotope ratios (δ13C) are depleted (between −11.8 and −22.1‰) as expected for carbonate precipitation from marine pore-fluids in organic-matter-rich, paralic sediment. Oxygen isotope (δ18O) ratios range between −1.3 and −6.0‰. The earliest diagenetic nature of these cements is documented by the presence of ubiquitous, non-compacted fossil plant remains encased in phase I dolomite as well as by the complex zoned luminescence patterns in the crystals and is supported by crystallographic and thermodynamic considerations. It is argued that organic matter, and specifically carboxyl groups, reduced thermodynamic barriers for dolomite formation and facilitated Mg/CaCO3 precipitation. The data shown here reveal a hitherto unknown level of complexity with respect to radiaxial fibrous carbonates and are of importance for those concerned with dolomite and carbonate petrography in general.