Pressure effect on magnesian calcite coating calcite and synthetic magnesian calcite seeds added to seawater in a closed system

When pure crystalline calcite seeds are added to supersaturated seawater, precipitation results in a coating which with time equilibrates at atmospheric pressure with seawater and corresponds to a calcite containing probably only 2 or 3% of MgCO₃ (mole fraction).If synthetic crystalline magnesian calcite is added, the surface layer equilibrates not only with respect to seawater but also in relation with the crystalline sites initiating precipitation. Adding Mg_0.03Ca_0.97CO₃ results in a coating with a solubility close to that of calcite. This confirms that the surface coating on pure calcite seeds contains about 2 or 3% MgCO₃ (K'_sp = 10?6.30).The surface layer precipitated on a synthetic Mg_0.08Ca_0.92CO₃ equilibrates finally with a carbonate more soluble than calcite (K'_sp = 10?5.94) corresponding to the seeds composition.Experiments at 1000 kg cm t-2 imply that when magnesian calcites are precipitated at the surface of calcite or magnesian calcite seeds, the precipitate must be hydrated, otherwise pressure accelerated recrystallization or rearrangement with loss of Mg would thermodynamically be impossible.By changing the pressure of a seawater sample originally saturated with a solid carbonate phase, changes in pH result from the effect of pressure on the dissociation constants of carbonic acid and boric acid causing either undersaturation or supersaturation with respect to the solid. By changing pressure we can show whether precipitation, dissolution and recrystallization are reversible processes if pH is taken as criteria of reversibility.     

Strain determination using cathodoluminescence of calcite overgrowths

Cathodoluminescence is used in a new application to study extensional strains recorded by calcite overgrowths on detrital calcite grains. The geometry of the overgrowths yields an extension of +0.39 that is parallel to a pressure solution cleavage. A volume change of −0.21 was calculated from this geometry and an independently determined strain ratio.     

The influence of temperature and seawater composition on calcite crystal growth mechanisms and kinetics: Implications for Mg incorporation in calcite lattice

The composition of carbonate minerals formed in past and present oceans is assumed to be significantly controlled by temperature and seawater composition. To determine if and how temperature is kinetically responsible for the amount of Mg incorporated in calcite, we quantified the influence of temperature and specific dissolved components on the complex mechanism of calcite precipitation in seawater. A kinetic study was carried out in artificial seawater and NaCl-CaCl₂ solutions, each having a total ionic strength of 0.7 M. The constant addition technique was used to maintain [Ca²⁺] at 10.5 mmol kg⁻¹ while [] was varied to isolate the role of this variable on the precipitation rate of calcite.Our results show that the overall reaction of calcite precipitation in both seawater and NaCl-CaCl₂ solutions is dominated by the following reaction:

     

Relict magnesian calcite oolite and subsidence of the Amazon shelf

Oolitic sediments occur over large portions of the outer continental shelf off northernmost Brazil and southern French Guiana. Carbon-14 dates, stable isotope values and analogies with similar deposits from other areas in the world indicate that the ooids were formed in shallow water (possibly protected hypersaline environments) during low stands of sea level. In contrast to both modern ooids and other relict ooids, however, the Amazon shelf ooids are composed entirely of magnesian calcite (12 mol % MgCO₃) and possess radial crystal microstructures. A comparison of water depths and ages of the Amazon ooids with the generally accepted eustatic sea level curve indicates that the Amazon shelf subsided more than 100 m 16-21 thousand years ago. Prior to and subsequent to the subsidence, however, the outer shelf remained relatively stable.     

Microtexture of dolomite within exsolved magnesian calcite — examples from the Damara orogen (Namibia)

Exsolved magnesian calcite grains containing rods of dolomite were etched to remove the calcite matrix and investigated with a scanning electron microscope. The rods were found to be composed of small rhombohedral dolomite crystals. The single rhombohedrons are stacked with the threefold axis subparallel in all rods of the exsolved host crystal. The curvature of exsolution rods in the host is due to a step by step displacement of the single rhombohedrons.     

The chemistry of orthophosphate uptake from seawater on to calcite and aragonite

The chemistry of orthophosphate uptake from synthetic seawater onto the surfaces of synthetic calcite, aragonite and low-magnesium biogenic calcite has been studied, in order to elucidate the kinetics of the process (generally believed to be the major control of dissolved reactive phosphate in carbonate-rich marine sediments). Our results differ from those obtained by others, who have studied orthophosphate uptake in low ionic strength solutions and at much higher supersaturations relative to apatite.In both ‘free drift’ and chemostat experiments, Mg and F have only a minor effect on the reaction rate. Even at constant solution composition the rate of orthophosphate uptake was found to decrease by 10⁶ over a two week period. The data from the ‘free drift’ experiments can be fitted to the Elovich equation. This indicates that the kinetics observed for this reaction can be explained by an exponential decrease in available surface reaction sites and/or a linear increase in the activation energy associated with chemisorption as the reaction proceeds.     

Composition of carbonate overgrowths produced on Iceland spar calcite crystals buried in bahamian carbonate-rich sediments

High-magnesium calcite overgrowths were precipitated on Iceland spar calcite crystals buried in Bahamian sediments. Their composition was within the range of carbonate cements in this area. The precipitation rate of the overgrowths was slower and the magnesium content higher than predicted from laboratory experiments, possibly due to adsorption of organic compounds.     

Genesis and composition of lazurite in magnesian skarns

The genesis and composition of lazurite was considered in the metasomatic rocks and deposits of the Baikal area, Pamirs, Hindu Kush, and other regions. It was shown that formation of lazurite is related to the prograde bimetasomatic or contact-metasomatic magnesian skarn processes developing in dolomites. The skarnized sedimentary or metamorphic rocks should be salt-bearing, contain sulfur-bearing minerals, and be affected by Cl-bearing hydrothermal solutions. Both abyssal and hypabyssal skarn bodies show distinct zoning. Depending on the PT parameters, their metasomatic columns can vary, with the preservation of the Mg/Ca ratio from the carbonate precursor. The formation of contact-metasomatic lazurite mineralization is promoted by high-alkali magmatic solutions, which cause the replacement of dolomites by skarn. Lazurite can also be formed during the postmagmatic stage, owing to a change in the mineral composition of the adjacent aluminosilicate and magnesian-skarn rocks at abyssal and hypabyssal deposits around the world. The occurrence of authigenic lazurite emphasizes its polygenetic formation. Original Russian Text ? S.M. Aleksandrov, V.G. Senin, 2006, published in Geokhimiya, 2006, No. 10, pp. 1053–1067.     

Precipitation and lithification of magnesian calcite in the deep-sea sediments of the eastern Mediterranean Sea*

Magnesian calcite is an important sedimentary component in the deep-sea sediments of the eastern Mediterranean Sea, comprising an average of 20–50% of the carbonate fraction in most areas. The lack of any obvious biogenic source, plus similarities with magnesian-rich lutites from the Red Sea and deep-sea cements from other areas suggest that this magnesian calcite was precipitated inorganically. Although the exact mode of precipitation is not understood at present, it probably occurred at the water-sediment interface under elevated salinity and temperature conditions, such as those present in the modern eastern Mediterranean. Precipitation did not occur during periods of lower temperatures and/or salinities such as during the stagnant conditions caused by the influx of fresh waters from melting Pleistocene glaciers. The eastern Mediterranean magnesium-rich sediments appear to represent an intermediate stage between normal deep-sea sediments and those from the warm hpyersaline Red Sea. Normal deep-sea carbonates are composed almost entirely of biogenic calcite, whereas the Red Sea magnesian calcite alternates with layers of aragonite that were precipitated under elevated salinity and temperature conditions brought about by lowered stands of sea level.     

Compositional and morphological features of aragonite precipitated experimentally from seawater and biogenically by corals

The morphology and composition of abiogenic (synthetic) aragonites precipitated experimentally from seawater and the aragonite accreted by scleractinian corals were characterized at the micron and nano scale. The synthetic aragonites precipitated from supersaturated seawater solutions as spherulites, typically 20-100 μm in diameter, with aggregates of sub-micron granular materials occupying their centers and elongate (fibrous) needles radiating out to the edge. Using Sr isotope spikes, the formation of the central granular material was shown to be associated with high fluid pH and saturation state whereas needle growth occurred at lower pH and saturation state. The granular aggregates have significantly higher Mg/Ca and Ba/Ca ratios than the surrounding fibers.Two types of crystals are identified in the coral skeleton: aggregates of sub-micron granular material and bundles of elongate (fibrous) crystals that radiate out from the aggregates. The granular materials are found in “centers of calcification” and in fine bands that transect the fiber bundles. They have significantly higher Mg/Ca and Ba/Ca ratios than the surrounding fibers.The observed relationship between seawater saturation state and crystal morphology and composition in the synthetic aragonites was used as a framework to interpret observations of the coral skeleton. We propose that coral skeletal growth can be viewed as a cyclical process driven by changes in the saturation state of the coral’s calcifying fluids. When saturation state is high, granular crystals precipitate at the tips of the existing skeletal elements forming the centers of calcification. As the saturation state decreases, aragonitic fibres grow in bundles that radiate out from the centers of calcification.     

Identification and composition of secondary meniscus calcite in fossil coral and the effect on predicted sea surface temperature

This study uses electron backscatter diffraction (EBSD) and atomic force microscopy (AFM) to identify secondary calcite in coral skeletons. Secondary calcite appears to have nucleated on the original aragonite dissepiments, producing horizontal structures that mimic the morphology of the original coral aragonite, forming dissepiment-like meniscus structures. The Sr/Ca and δ¹⁸O of the pristine aragonite and secondary calcite were analysed by secondary ion mass spectrometry (SIMS). The effect of calcite inclusion on the mean geochemistry of the coral carbonate and subsequent sea surface temperature (SST) calculations were determined for both Sr/Ca and δ¹⁸O. Inclusion of as little as 1% secondary calcite within the primary coral aragonite elevates the Sr/Ca-derived SST by 1.2 °C and could markedly offset estimates of past tropical climate. Conversely, inclusion of 10% secondary calcite has little effect on the SST estimated from δ¹⁸O (+ 0.6 °C) indicating that this proxy is relatively robust to even large amounts of calcite. The different extents to which the two proxies would be influenced by inadvertent inclusion of such meniscus calcite demonstrate the importance of a multi-proxy approach.     

The incorporation of Mg2+ and Sr2+ into calcite overgrowths: influences of growth rate and solution composition

The concentrations of Mg²⁺ and Sr²⁺ incorporated within calcite overgrowths precipitated from seawater and related solutions, determined at 25°C, were independent of the precipitation rate over approximately an order of magnitude. The saturation states used to produce this range of precipitation rates varied from 3 to 17 depending on the composition of the solution.The amount of Mg²⁺ incorporated in the overgrowths was not directly proportional to $\text{Mg}{}^{\mathrm{2+}}\text{Ca}{}^{\mathrm{2+}}$ in solution over the entire range (1–20) of ratios studied. Below a ratio of 7.5, the overgrowth was enriched in MgCO₃ relative to what is predicted by the constant distribution coefficient measured above a ratio of 7.5. This increased MgCO₃ correlates with the relative enrichment of adsorbed Mg²⁺. Above a ratio of 7.5 the concentration of MgCO₃ in the calcite overgrowths followed a classical thermodynamic behavior characterized by a constant distribution coefficient of 0.0123 (±0.008 std dev).The concentration of SrCO₃ incorporated in the overgrowths was linearly related to the MgCO₃ content of the overgrowths, and is attributed to increased solubility of SrCO₃ in calcite due to the incorporation of the smaller Mg²⁺ ions.The kinetic data indicate that the growth mechanism involves the adsorption of the cations on the surface of the calcite prior to dehydration and final incorporation. It is suggested that dehydration of cations at the surface is the rate controlling step.     

Effects of seed material and solution composition on calcite precipitation

We studied the effects of seed material and solution composition on calcite crystal precipitation using a pH-stat system. The seed materials investigated included quartz, dolomite, two calcites with different particle size and specific surface area, and two dried precipitates from precipitative softening water treatment plants. Our results indicated that, of the seed materials examined, only calcite had the ability to initiate calcite precipitation in a solution with a degree of supersaturation of 5.3 over a period of two hours, and that the precipitation rate was proportional to the available surface area of the seed. For different solution compositions with the same degree of supersaturation, the calcite precipitation rate increased with increasing carbonate/calcium ratio, which contradicts the generally accepted empirical rate expression that the degree of supersaturation is the sole factor controlling precipitation kinetics. By applying a surface complexation model, the surface concentrations of two species, >CO₃⁻ and >CaCO₃⁻, appear to be responsible for catalyzing calcite precipitation.     

Temperature effects on the calcite skeletal composition of deep-water gorgonians (Isididae)

We test for and calibrate a proxy for ocean temperature based on the skeletal composition of the widely distributed, deep-sea gorgonians in the family Isididae (bamboo corals), through use of three complementary methods: a short-term comparison of element/Ca ratios to a four-year temperature record, a long-term comparison with oceanographic records spanning forty years, and a geographic comparison of Isidids collected at sites ranging from the tropics to Antarctica. The assays consistently support a temperature-dependency for Mg/Ca ratios and suggest S/Ca is indirectly affected by temperature, but indicate little or no effect of temperature on P/Ca and Sr/Ca. The consensus relationship between Mg/Ca and temperature for Isidid calcite from the comparisons with the temperature time-series is T = −0.505 + 0.048 Mg/Ca, where T is in °C, Mg/Ca is in mmol/mol, and the applicable range is 3-6 °C. The results of the geographic assay, though imprecise, suggest the applicable range extends to temperatures below freezing. The scatter of data points around the regression of temperature and Mg/Ca is wide in all assays. This could reflect the effect of factors other than temperature on Mg/Ca ratios, but is also likely to reflect limitations of the field data, the effects of assumed constant growth rates in the corals and instrumental analytical error. The combined effects of micro-scale variability in growth rates and wide confidence intervals for each data point suggests that environmental reconstruction from Isidid internode calcite from sparse data or at time scales less than decades be done with caution. Comparisons within and among colonies do not indicate strong vital effects on ontogenetic variability in the corals, other than possibly close to the central pore of the coral. However, similar Mg/Ca ratios for Isidids from Antarctic and more temperate regions suggest adaptation to local conditions and hence a role for physiology at higher taxonomic levels, at least. Taxonomically higher level vital effects are also suggested by large differences between gorgonian families in their regressions between Mg/Ca and temperature, by Mg/Ca ratios that overlap over a wide temperature and habitat range, and for a non-linear relationship between temperature and the slope of the Mg/Ca-temperature relationship across the order.