High-magnesium Calcite Research Articles

Tuning the Incorporation of Magnesium into Calcite during Its Crystallization from Additive-Free Aqueous Solution

Under ambient conditions, marine organisms are able to synthesize a variety of functional materials, ranging from eye lenses to protective shells through the meticulous control over magnesium incorporation into calcite during its crystallization. The mechanistic understanding of how they achieve such exquisite control, at a constant magnesium-to-calcium ratio and at ambient conditions, is important in the development of bioinspired functional materials. However, the replication of these processes in the laboratory is still challenging. Herein, we present a systematic study on how to tune magnesium incorporation into calcite and polymorph selection in the Ca–Mg–CO3 system through the precise control of the inorganic solutions chemistry at ambient conditions of temperature and pressure, and at a magnesium-to-calcium ratio of 5:1, which is analogous to the ratio found in most seas. By varying the pH, cation-to-anion ratio, and solution concentration, the controlled synthesis of magnesium calcites with 10–45% magnesium was achieved at room temperature. The mechanism of formation is consistent with that observed during biomineralization, during which an intermediate magnesium-rich amorphous calcium carbonate (Mg-ACC) phase forms first and later transforms into high magnesium calcite. Once crystallization occurs, the magnesium calcites that form are stable in solution and exhibit slow growth through Ostwald ripening. Our findings suggest that the precise control of saturation levels is key in driving nucleation and crystallization.

Partitioning and Chemical Environments of Minor Elements in Individual Large Benthic Foraminifera Cultured in Temperature-Controlled Tanks

Because reef-dwelling large benthic foraminifera (LBF) tests, which is composed of high-magnesium calcite, are the common components of modern reef sediments, and ancient reef carbonate rocks, they can provide a continuous record of the paleoenvironment of reef sediments. Evaluation of the responses of the minor element concentrations (Mg, Sr, Na, P, and S) of individual tests to ambient temperature and LBF growth modes was conducted with two cultured species, Calcarina gaudichaudii and Amphisorus kudakajimensis. The elements were assessed as tracers of temperature, salinity, nutrient concentration, and calcification rate. The Mg content of C. gaudichaudii and the Sr content of both species were controlled by temperature. It can be confirmed that the Mg of individual tests of C. gaudichaudii is a useful paleothermometer. There was a large biological modulation of Na, P, and S incorporation. In-situ XANES analysis revealed that both inorganic and organic species contributed to the P and S content of LBF tests. We observed five sulfur components with variable oxidation states.

A review of the nature and origin of limestone microporosity

Abstract 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.

Genetic Mechanism of the Dolomite in Dolomitic Glutenite of the Shahejie Formation—A Case Study of QHD 29-2 Oilfield in Bohai Bay Basin, China

The dolomite in dolomitic glutenite of the shahejie formation in the eastern steep slope of the Shijiutuo bulge in Bohai is a high-quality reservoir, and the content of dolomite is positively correlated with reservoir physical properties. In this paper, by using thin section, core, wall core, geochemical data and analyzing petrology and mineralogy characteristic, we systematically analyzed the paleogeographic environment and genetic mechanism of this kind of dolomite and established the genetic models. The dolomite in the glutenite body has many characteristics of development, which is formed by three kinds of genesis: quasi-synergy dolomitization, buried dolomitization and hydrothermal dolomitization. The dolomite in glutenite is produced in the form of matrix, grain (sandstone, oolith), biological skeleton (conch, ostracod), clastic shell and dolomite cement. The minor elements, carbon and oxygen isotopes, trace minerals and paleontological combinations reveal that the paleogeographic environment was closed continental salt-brackish water bay, the climate was arid and hot, and the evaporation was strong. It provides favorable conditions for the production of the dolomite in dolomitic glutenite. There are three genetic models of dolomite. The first model is penecontemporaneous dolomitization. The climate was arid and hot, the aragonite and high-magnesium calcite deposited with sand and gravel. Due to the effect of evaporation, dolomitization occurred. The second model is buried dolomitization. The water from dehydration of clay minerals causes the Mg2+ in the high-magnesium formation migrating into the rock, leading to the occurrence of dolomitization. The third model is hydrothermal dolomitization. Deep faults can bring geothermal fluids into the overlying reservoir and form the hydrothermal dolomite.

Bottom-up effects on biomechanical properties of the skeletal plates of the sea urchin Paracentrotus lividus (Lamarck, 1816) in an acidified ocean scenario

Sea urchins, ecologically important herbivores of shallow subtidal temperate reefs, are considered particularly threatened in a future ocean acidification scenario, since their carbonate structures (skeleton and grazing apparatus) are made up of the very soluble high-magnesium calcite, particularly sensitive to a decrease in pH. The biomechanical properties of their skeletal structures are of great importance for their individual fitness, because the skeleton provides the means for locomotion, grazing and protection from predators. Sea urchin skeleton is composed of discrete calcite plates attached to each other at sutures by organic ligaments. The present study addressed the fate of the sea urchin Paracentrotus lividus (Lamarck, 1816) skeleton in acidified oceans, taking into account the combined effect of reduced pH and macroalgal diet, with potential cascading consequences at the ecosystem level. A breaking test on individual plates of juvenile specimens fed different macroalgal diets has been performed, teasing apart plate strength and stiffness from general robustness. Results showed no direct short-term effect of a decrease in seawater pH nor of the macroalgal diet on single plate mechanical properties. Nevertheless, results from apical plates, the ones presumably formed during the experimental period, provided an indication of a possible diet-mediated response, with sea urchins fed the more calcified macroalga sustaining higher forces before breakage than the one fed the non-calcified algae. This, on the long term, may produce bottom-up effects on sea urchins, leading to potential shifts in the ecosystem equilibrium under an ocean acidified scenario.

Authigenic carbonate formation revealed by lipid biomarker inventory at hydrocarbon seeps: A case study from the Okinawa Trough

Abstract Authigenic carbonates were recovered from the northern Okinawa Trough at 540–700 m water depth. Development of microbial communities and seepage dynamics driving the precipitation of authigenic carbonates remains poorly constrained, even though the source of methane-rich fluids, formation of Fe-rich carbonates, and the potential driving forces were previously reported. Here, petrologic observations, stable carbon and oxygen isotopic compositions, mineralogy, and lipid inventories of authigenic carbonates from the northern Okinawa Trough were analyzed. The carbonate minerals were comprised predominantly of aragonite, high-magnesium calcite, and siderite. The presence of molecular fossils diagnostic for anaerobic methane oxidizing archaea (ANME) and sulfate-reducing bacteria (SRB) with pronounced 13C depletions (as low as −134‰), together with highly negative δ13Ccarb values (as low as −55.8‰), suggest that the carbonates precipitated from anaerobic oxidation of methane (AOM) with microbial methane as the predominant carbon source. The difference between measured and calculated δ18Ocarb values (based on 0‰ of sea water δ18O vs V-SMOW) was higher than +3‰ in one of the carbonates (GGD16), reflecting an origin from gas hydrate dissociation. Most of the carbonates revealed δ18O offsets between measured and calculated values within +3‰, or a lower measured δ18O than calculated value, suggesting a mixture of methane-derived carbonates (low δ13C/high δ18O) and detrital origin carbonates (high δ13C/low δ18O). Biomarker patterns varied significantly among samples. A suite of 13C-depleted biomarkers indicated the predominance of an ANME-1 assemblage for all samples, suggesting carbonates formed at low to medium methane flux. The predominance of ANME-1, abundant detrital minerals, and allochthonous biomarkers, as well as low carbonate contents indicate that most samples formed at greater depth within the sediment column. Only one carbonate sample in this study is interpreted to have precipitated at relatively shallower depth, as indicated by the occurrence of crocetane, dominance of aragonite, and higher overall carbonate content.

Microbialites in Last Glacial Maximum and deglacial reefs of the Great Barrier Reef (IODP Expedition 325, NE Australia)

Microbialites are volumetrically abundant components in Last Glacial Maximum and deglacial reefs in the Australian Great Barrier Reef sampled by IODP Expedition 325 in 34 holes from 17 sites (M0030–M0058), along four transects on the shelf edge. Detailed radiometric datings show that four distinct reef phases developed between 28and 10 ka, displaying offlapping and then backstepping patterns. The reef boundstone facies include coralgal, coralgal-microbialite and microbialite boundstone. The microbialite consists of combinations of micrite/microspar, bioclasts, siliciclastic grains (up to 14.5%), fenestrae and encrusting epibionts. The micrite/microspar is high-magnesian calcite commonly irregularly clotted, fenestral and peloidal. Mesoscale microbialite fabrics include laminated, structureless, digitate, intraskeletal and boring-filling, and coatings on debris. Intraskeletal and boring-filling is the first fabric to develop in skeletal voids and borings. It is usually followed by structureless and laminated microbialite, locally overlain by digitate fabric. Microbialite-coated debris can occur at any stage in this succession, including in bioclastic accumulations where the scarce in situ framework builders are mainly encrusting corals. Lipid biomarkers of intermediate to high specificity for sulfate-reducing bacteria, together with δ13C values of these lipids, indicate that microbialite formation was favored by sulfate-reducing bacteria in anoxic microenvironments, probably under high nutrient levels. The microbialite in fore-reef deposits accumulated in the photic zone in water depths of a few to several tens of meters, within small spaces generated by large bioclasts and encrusting corals in the topmost centimeters of the sediment. These crusts that formed on the illuminated surface constitute a previously unrecognized style of microbialite formation in Quaternary reefs. As with the cryptic crusts described from other reef locations, its greatest development occurred during the Last Glacial Maximum and early deglaciation. Microbial carbonate formation during this interval may reflect elevated seawater carbonate saturation corresponding with relatively low levels of atmospheric CO2.

Diagenesis of Holocene Beachrock in Northeastern Brazil: Petrology, Isotopic Evidence and Age

This work aims to understand beachrock formation during Holocene through petrology, geochemistry and dating of a core located 5,43m deep in relation to present-day sea-level in the Piedade Beach in Jaboatao dos Guararapes- PE. The core is located 143 meters distant from the coast line towards mainland. Four lithofacies have been identified, taking into account differences in texture and sedimentary structures. The framework grain size ranges from medium to very coarse sand, indicating variations in depositional energy. Petrographic data indicate that the beachrocks have values of 64.23% to 70.69% of framework composed of quartz grains. Carbonate cement (represents 13.5%) consisting of high magnesium calcite surrounding grains as isopachous fringe (4.15% to 11.95%), micritic cement (0.60% to 6.42%) and equant cement (0.26% to 7.01%), indicates marine environment precipitation. The results of the isotopic composition of carbon and oxygen present valuesof 3.09‰ to 3.89‰, with an average of 3.63‰ to δ 13 C PDB and of -0.91‰ to 0.96‰, with an average of 0.54‰ to δ 18 O PDB, suggesting that the cement is formed in a shallow marine environment with freshwater influence. The values obtained in paleotemperature vary from 21oC to 30oC, with an average of 23oC, with little variation indicating precipitation in a shallow water environment. In the study area, the beachrocks are indicators of sea level and the results suggest that between 7.509 years B.P. and 5982 years B.P. there was a marine transgression process, with sea level 9.18 m lower than the current sea level.

Calibration between temperature and Mg/Ca and oxygen isotope ratios in high-magnesium calcite tests of asexually reproduced juveniles of large benthic foraminifers

Abstract Mg/Ca ratios and oxygen isotope ratios (δ18O) in biogenic high‑magnesium calcite tests precipitated by reef-dwelling large benthic foraminifers can be used as paleotemperature proxies because they correlated well with the temperature of seawater. However, it is still unclear whether there is an interspecies difference in temperature correlation among several perforate and imperforate species. We used four species of large benthic foraminifer s to perform culture experiments at controlled temperatures (21–31 °C). Neorotalia calcar, Baculogypsina sphaerulata, and Calcarina gaudichaudii were selected as the perforate species, whereas Amphisorus kudakajimensis was chosen as the imperforate species. The data obtained by analyses suggest linear relations between Mg/Ca and temperature except at 31 °C, and also in the case of A. kudakajimensis except at 29 °C, which is likely caused by thermal stress resulting in metabolic anomaly in the foraminifers. Furthermore, A. kudakajimensis (imperforate species) had a different Mg/Ca–temperature equation form those of perforate species. The combined Mg/Ca–temperature and δ18O–temperature equations are yielded using the least square method as follows: Mg/Ca = 2.73 T + 74.7 for three perforate species, which is applicable to a temperature range between 21 °C to 30 °C. The temperature relation of δ18O is different even among perforate species. We observed that the δ18O values were closer to the equilibrium of pure calcite than those of high‑magnesium calcite. The δ18O–temperature (T) equations are yielded using the least square method as follows: T = 15.1–6.17 (δ18Oc − δ18Osw) for C. gaudichaudii, T = 17.7–5.14 (δ18Oc − δ18Osw) for N. calcar, and T = 16.1–5.10 (δ18Oc – δ18Osw) for B. sphaerulata. A species-specific calibration is necessary for the relation between δ18O and temperature. As long as the optimum temperature range is the same, foraminifers belonging to the Calcarinidae show the same Mg/Ca–temperature relationship.

Quick, Easy, and Economic Mineralogical Studies of Flooded Chalk for EOR Experiments Using Raman Spectroscopy

Understanding the chalk-fluid interactions and the associated mineralogical and mechanical alterations on a sub-micron scale are major goals in Enhanced Oil Recovery. Mechanical strength, porosity, and permeability of chalk are linked to mineral dissolution that occurs during brine injections, and affect the reservoir potential. This paper presents a novel “single grain” methodology to recognize the varieties of carbonates in rocks and loose sediments: Raman spectroscopy is a non-destructive, quick, and user-friendly technique representing a powerful tool to identify minerals down to 1 µm. An innovative working technique for oil exploration is proposed, as the mineralogy of micron-sized crystals grown in two flooded chalk samples (Liége, Belgium) was successfully investigated by Raman spectroscopy. The drilled chalk cores were flooded with MgCl2 for ca. 1.5 (Long Term Test) and 3 years (Ultra Long Term Test) under North Sea reservoir conditions (Long Term Test: 130 °C, 1 PV/day, 9.3 MPa effective stress; Ultra Long Term Test: 130 °C, varying between 1–3 PV/day, 10.4 MPa effective stress). Raman spectroscopy was able to identify the presence of recrystallized magnesite along the core of the Long Term Test up to 4 cm from the injection surface, down to the crystal size of 1–2 µm. In the Ultra Long Term Test core, the growth of MgCO3 affected nearly the entire core (7 cm). In both samples, no dolomite or high-magnesium calcite secondary growth could be detected when analysing 557 and 90 Raman spectra on the Long and Ultra Long Term Test, respectively. This study can offer Raman spectroscopy as a breakthrough tool in petroleum exploration of unconventional reservoirs, due to its quickness, spatial resolution, and non-destructive acquisition of data. These characteristics would encourage its use coupled with electron microscopes and energy dispersive systems or even electron microprobe studies.

The unique biomineralization transcriptome and proteome of Lytechinus variegatus teeth

ABSTRACTBackground: Matrix-regulated biomineralization involves the specific nucleation and growth of mineral phases within or upon preformed structured organic matrices. We hypothesized that there might be a general mechanism whereby anionic, phosphorylated mineral ion-binding proteins assist in specifically locating the mineral ions with respect to the mineralizing structural organic matrix. Here we extended these studies to invertebrate mineralization in Lytechinus variegatus (Lv) teeth. Materials and Methods: The tooth proteins were extracted and the phosphoproteins occluded in the mineral were enriched by passage through a ProQ Diamond phosphoprotein enrichment column, and subjected to MS/MS analysis. A Lv RNA-seq derived transcriptome database was generated. The MS/MS data found 25 proteins previously classified as “Predicted uncharacterized proteins” and many of the spicule matrix proteins. As these 25 proteins were also identified with the transcriptome analysis, and were thus no longer “hypothetical” but real proteins in the Lv tooth. Each protein was analyzed for the presence of a signal peptide, an acidic pI≤4, and the ability to be phosphorylated. Results: Four new Lv tooth specific Pro-Ala-rich proteins were found, representing a new class of proteins. Conclusion: The tooth is different from the spicules and other urchin skeletal elements in that only the tooth contains both “high” and “very high” magnesium calcite, [Ca(1–X) Mg(X) CO3], where X is the mole fraction of Mg. We speculate that our newly discovered proline-alanine rich proteins, also containing sequences of acidic amino acids, may be involved in the formation of high magnesium and very high magnesium calcite.

Magnesium calcite in Muschelkalk limestones of the Polish part of the Germanic Basin

Magnesium calcite, which is usually observed in many natural low-temperature environments, was identified in Triassic limestones of the Polish part of the Germanic Basin. The occurrence of unstable magnesium calcite in Triassic limestones is remarkable. High-Mg calcite was identified in all beds of the Muschelkalk Karchowice Formation: Lower Crinoidea Beds, Lower Biohermal Beds, Upper Crinoidea Beds and Upper Biohermal Beds. The general chemical formulas of magnesium calcite of mentioned unites are: (Ca0.87–0.80,Mg0.13–0.20)CO3, (Ca0.83–0.75,Mg0.17–0.25)CO3, (Ca0.81,Mg0.19)CO3, (Ca0.78–0.77,Mg0.22–0.23)CO3 respectively. This mineral originated probably during the early stage of diagenesis, during compaction of limestones deposited in a warm, shallow marine environment. Some amounts of magnesium come from high-Mg skeletons of marine organisms (such as echinoderms). Diagnenetic processes and the conditions in seawater, especially higher salinity, influence the preservation of high magnesium calcite in the Muschelkalk limestone of the Polish part of the Germanic Basin.

Inter and intraspecific comparisons of the skeletal Mg/Ca ratios of high latitude Antarctic echinoderms

AbstractEchinoderms are vulnerable to ocean acidification because of their high magnesium calcite skeletons. Here, skeletal Mg/Ca ratios were examined within and between individuals of 20 Antarctic echinoderms representative of the asteroids, ophiuroids and echinoids. The highest mean Mg/Ca ratios occurred in the discs and arms (0.111 and 0.110, respectively) of brittle-stars and the lowest in the spines (0.010) of cidaroid sea urchins. Many taxa (11 of 14 species) from the collection sites showed no intraspecific differences in Mg/Ca ratios between given skeletal components. Exceptions were the spines of two regular sea urchins and the skeletal ossicles of the combined arms and disc of a brittle-star. The relationship between skeletal magnesium content and latitude was further evaluated and an inverse correlation was found between Antarctic echinoderm taxa skeletal magnesium content and latitude across 62° to 76°, indicating that the relationship occurs over relatively narrow latitudes. Upon examination of an even narrower range (70–76° latitude), a region where the mineralogy of echinoderm skeletons has not been investigated, the predicted inverse relationship between Mg/Ca ratio and latitude was still observed in sea-stars, but not in brittle-stars or sea urchins.

Methane-derived stromatolitic carbonate crust from an active fluid seepage in the western basin of the Sea of Marmara: Mineralogical, isotopic and molecular geochemical characterization

Cold seeps along the North Anatolian fault in the Sea of Marmara (Turkey) were explored during submersible dives of the Marsite cruise in November 2014 when sediments, pore waters and carbonate crusts were sampled at active fluid seeping sites. In this study, we investigate the mineralogy, carbon and oxygen isotopic compositions and the lipid biomarkers of a carbonate crust from the western Tekirdağ basin of the Sea of Marmara. This crust exhibits a laminated domal structure that resembles stromatolite. The mineralogy of authigenic seep-carbonate is mostly represented by aragonite associated with minor amounts of high-magnesian calcite. The abundance of pyrite associated with the authigenic seep-carbonate points to very intense bacterial sulfate reduction. The carbon (−42.6‰ to −34.4‰) and oxygen (−1.5‰ to +1.1‰) isotopic compositions of the authigenic seep-carbonate crust indicate that carbonate precipitation was related to anaerobic oxidation of methane and occurred in mixtures of bottom seawater with brackish water expelled from the underlying sediments. Abundant microbial lipid biomarkers with negative δ13C values (−121‰ to −96‰), confirm that anaerobic oxidation of methane (AOM) coupled with sulfate reduction, was mediated by methanotrophic archaea (ANME) and sulfate reducing bacteria (SRB). Diagnostic lipid fingerprints indicate that ANME-2 archaea and associated SRB were the prevalent AOM-mediating consortia, which characterize moderate to high methane flow at this site. Moreover, changes in microbial lipid distribution within the carbonate crust suggest a variation in the intensity of methane emission.

A Giant Underwater, Encrusted Stalactite from the Blue Hole, Lighthouse Reef, Belize, Revisited: a Complex History of Biologically Induced Carbonate Accretion Under Changing Meteoric and Marine Conditions

A late Pleistocene to Holocene submerged and encrusted speleothem exhibits a complex history including a meteoric phase and two marine phases. A combined study using petrography, mineralogy, and inorganic and organic geochemistry, as well as geochronology has shown that phototrophic and heterotrophic biological activity impacted carbonate precipitation during all phases of carbonate accretion. The stalactite formed ca. 30 m below modern sea level at a marginal overhang in the Blue Hole of Lighthouse Reef Atoll. Unlike purely meteoric speleothems, the Belize example consists of a meteoric core, a marine aragonite crust, and a serpulid-micrite-rich outer crust as a result of postglacial flooding of the karst cave. The core of the stalactite has a tufaceous texture, containing algal or microbial remains, and consists entirely of low-magnesium calcite, formed 19.55-10.68 kyr BP. The texture suggests that the stalactite formed at the cave entrance, and, hence, the former cave ceiling had apparently collapsed earlier during the Pleistocene. Oxygen (δ18O) and carbon (δ13C) isotopes across the core suggest a trend towards drier conditions and reduced soil and plant cover after the last glacial maximum. The marine aragonite crust consists of stacked botryoids in which individual crystals up to 700 lm have dark terminations enriched in high-magnesium calcite. This crust accreted from 10.82 to 9.95 kyr BP in warm shallow water during the early Holocene thermal optimum. Carbonate accretion rates were considerable and averaged 125 μm/yr. The crust has a dense, laminated texture on one side and a porous, shrubby texture on the other. The presence of n-C16:1ω5, n-C17:1ω6, and 10Me-C16 fatty acids in the laminated crust suggests that sulfate-reducing bacteria contributed to aragonite formation in an environment that was less open than the formation environment of the porous crust, where these biomarkers are lacking (n-C16:1ω5,n-C17:1ω6) or are less abundant (10Me-C16). Enrichment of 34S and 18O in carbonate-associated sulfate (CAS) relative to seawater sulfate also suggests sulfate reduction during carbonate formation. The greater contribution of heterotrophic processes to aragonite precipitation in the laminated crust is also reflected in δ13C values as low as -1.3%, whereas no such depletion is observed in the aragonite of the porous crust (δ13C values as low as 0.0%). A pronounced isotopic variability and excursions to positive δ13C values as high as +3.5%0 in the inner half of the laminated crust indicate an episodic, local impact of photosynthesis on aragonite precipitation, whereas the lack of such excursions in the porous crust (δ13C values as high as +1.5%0) is again best explained by a more open environment of formation. After a ca. 5 kyr hiatus, from 4.39 kyr BP, a biogenic crust of abundant serpulids and finely crystalline, microbial and detrital carbonate, consisting of high-magnesium calcite and aragonite, accreted on the outer surface of the stalactite. Outermost crust accretion was probably influenced by the inundation of the Lighthouse Reef lagoon that started to shed abundant fine-grained carbonate sediment into the Blue Hole. The stalactite broke off the cave ceiling either before or after the formation of the outermost crust, likely due to seismic movements along the nearby plate boundary. The study demonstrates that like speleothems from the terrestrial realm, submerged stalactites may have had complex histories with great potential as paleoenvironmental archives.

High-Magnesium Calcite Mesocrystals: Formation in Aqueous Solution under Ambient Conditions.

Mesocrystals of high-magnesian calcites are commonly found in biogenic calcites. Under ambient conditions, it remains challenging to prepare mesocrystals of high-magnesian calcite in aqueous solution. We report that mesocrystals of calcite with magnesium content of about 20 mol % can be obtained from the phase transformation of magnesian amorphous calcium carbonate (Mg-ACC) in lipid solution. The limited water content on the Mg-ACC surface would reduce the extent of the dissolution-reprecipitation process and bias the phase transformation pathway toward solid-state reaction. We infer from the selected area electron diffraction patterns and the dark-field transmission electron microscopic images that the formation of Mg-calcite mesocrystals occurs through solid-state secondary nucleation, for which the phase transformation is initiated near the mineral surface and the crystalline phase propagates gradually toward the interior part of the microspheres of Mg-ACC.

Counteractive effects of increased temperature and pCO2 on the thickness and chemistry of the carapace of juvenile blue crab, Callinectes sapidus, from the Patuxent River, Chesapeake Bay

Exoskeletons are central to the physiology and survival of marine invertebrates, but future increases in the temperature and pCO2 of the marine environment may alter the biomineralization processes involved in their formation. Thus, it is important to consider the impacts of a changing climate on the functionality of invertebrate exoskeletons. In this study, juvenile blue crab, Callinectes sapidus, from the Chesapeake Bay were exposed to increased temperature and pCO2 in a 2×2 factorial design for a period of two molts (approximately 30days). Treatment levels were chosen to represent current (26°C and 800μatm CO2) and predicted future conditions in the year 2100 (32°C and 8000μatm CO2) in the Chesapeake Bay. Thickness was determined by light microscopy and carapace calcium (Ca) and magnesium (Mg) content were determined by Inductively Coupled Plasma – Atomic Emission Spectrometry. All Ca and Mg in the carapace were assumed to be present in the form of high‑magnesium calcite (HMC). Increased temperature decreased the thickness of juvenile blue crab carapaces by 8.5% and significantly reduced weight percent HMC by 2.0% (P<0.05). Increased pCO2 significantly increased weight percent HMC by 2.0% but a significant increase in Mg content was also found. The observed counteractive effects of temperature and pCO2 on weight percent HMC underscore the importance of assessing such interactions in studies that quantify the impacts of multiple environmental stressors. Combined with new data regarding the influence of increased temperature and pCO2 on blue crab growth, the results of this study indicate tradeoffs between carapace thickness and chemistry with growth in juvenile blue crab exposed to future warming.

The role of organominerals in the lithification of calcareous lumps within the intertidal sediments of Bubiyan Island, Kuwait, Arabian Gulf

Calcareous lumps of varying sizes and shapes are scattered on the landward part of the muddy intertidal flat along the southern coast of Bubiyan Island, northeast Kuwait. Two main lithotypes are recognized, namely, hard sandy crust fragments which are mostly formed of porous calcareous grainstone (bio-oosparite) and lithified muddy lumps that consist of calcareous wackestone (bio-micrite). They were originally eroded from the soft tidal flat sediments then lithified. Petrographic, mineralogical, and SEM/EDS examinations revealed that lithification of these calcareous lumps is attributed to cementation by biologically influenced organominerals, mainly high magnesium calcite and aragonite. The conditions responsible for the precipitation of these organominerals as well as variation in their mineralogy within each type of these calcareous lumps were discussed.

The oldest Cambrian skeletal fossils of Spain (Cadenas Ibéricas, Aragón)

AbstractDiverse skeletal assemblage has been discovered in the Ediacaran/Cambrian strata of the Codos locality in NE Spain (Aragón, Cadenas Ibéricas). This assemblage includes at least seven genera, only three of which can be ascribed to known taxa. All the fossils are preserved in phosphate but their original microstructures are traceable by both elementary composition and microstructural features that are indicative for primary aragonite and high-magnesium calcite biomineralogies. Already these early skeletal fossils show sophisticated microstructures represented by heterogeneous multilayered composites to satisfy the requirements for better protection against both chemical dissolution and mechanical predator deterioration. The most common and best-preserved fossil, which is tubicolous Codositubulus grioensis gen. et sp. nov., is described here. The composition of the fossil assemblage and its stratigraphic position are indicative for the lowermost Terreneuvian (lower Cambrian) or even pre-Terreneuvian age of this fauna.

Interactive effects of temperature, food and skeletal mineralogy mediate biological responses to ocean acidification in a widely distributed bryozoan.

Marine invertebrates with skeletons made of high-magnesium calcite may be especially susceptible to ocean acidification (OA) due to the elevated solubility of this form of calcium carbonate. However, skeletal composition can vary plastically within some species, and it is largely unknown how concurrent changes in multiple oceanographic parameters will interact to affect skeletal mineralogy, growth and vulnerability to future OA. We explored these interactive effects by culturing genetic clones of the bryozoan Jellyella tuberculata (formerly Membranipora tuberculata) under factorial combinations of dissolved carbon dioxide (CO2), temperature and food concentrations. High CO2 and cold temperature induced degeneration of zooids in colonies. However, colonies still maintained high growth efficiencies under these adverse conditions, indicating a compensatory trade-off whereby colonies degenerate more zooids under stress, redirecting energy to the growth and maintenance of new zooids. Low-food concentration and elevated temperatures also had interactive effects on skeletal mineralogy, resulting in skeletal calcite with higher concentrations of magnesium, which readily dissolved under high CO2 For taxa that weakly regulate skeletal magnesium concentration, skeletal dissolution may be a more widespread phenomenon than is currently documented and is a growing concern as oceans continue to warm and acidify.