Magnesian calcite stabilities: A reevaluation

Equilibrium constants at stoichiometric saturation with respect to various magnesian calcite compositions were measured using free-drift dissolution rate data and inverse time plots to estimate equilibrium pH. The equilibrium constants determined for two ultrasonically cleaned and annealed biogenic magnesian calcites (12 and 18 mole % MgCO₃) in CaCl₂ + MgCl₂ media at two Mg:Ca molar ratios (1:5 and 5:1) are about three times smaller than those previously reported by Plummer and Mackenzie (1974). These equilibrium constants are not affected by changes in initial pH value, solid:solution ratio, or solution Mg:Ca molar ratio when the ion activity product is expressed in the fractional exponent form. Other models for expression of the equilibrium ion activity product fail to yield consistent values in solutions of different Mg:Ca molar ratios.Experiments performed using crushed samples not ultrasonically cleaned and annealed yield equilibrium constants which vary with solid:solution ratio. Those performed at high solid:solution ratios yield values which approach those previously reported. Submicron size particles and crystal strain induced by crushing the biogenic carbonates may cause more rapid dissolution rates and, hence, overestimation of the solubility of samples not prepared so as to minimize these effects. Thus, the large range in reported solubilities of magnesium calcites may be a result of differences in sample preparation procedure.The results of these measurements shift the thermodynamic equivalence point of aragonite and magnesian calcite from 7.5 mole % MgCO₃ up to 12 mole % MgCO₃ and prompt a reassessment of models for carbonate diagenetic reactions in natural environments.     

Oxygen isotope fractionation in synthetic magnesian calcite

Mg-bearing calcite was precipitated at 25°C in closed system free-drift experiments from solutions containing NaHCO₃, CaCl₂ and MgCl₂. The chemical and isotope composition of the solution and precipitate were investigated during time course experiments of 24-h duration. Monohydrocalcite and calcite precipitated early in the experiments (<8 h), while Mg-calcite was the predominant precipitate (>95%) thereafter. Solid collected at the end of the experiments displayed compositional zoning from pure calcite in crystal cores to up to 23 mol% MgCO₃ in the rims. Smaller excursions in Mg were superimposed on this chemical record, which is characteristic of oscillatory zoning observed in synthetic and natural solid-solution carbonates of differing solubility. Magnesium also altered the predominant morphology of crystals over time from the {104} to {100} and {110} growth forms.The oxygen isotope fractionation factor for the magnesian-calcite-water system (as 10³lnα_Mg-cl-H2O) displayed a strong dependence on the mol% MgCO₃ in the solid phase, but quantification of the relationship was difficult due to the heterogeneous nature of the precipitate. Considering only the Mg-content and δ¹⁸O values for the bulk solid, 10³lnα_Mg-cl-H2O increased at a rate of 0.17 ± 0.02 per mol% MgCO₃; this value is a factor of three higher than the single previous estimate (Tarutani T., Clayton R.N., and Mayeda T. K. (1969) The effect of polymorphims and magnesium substitution on oxygen isotope fractionation between calcium carbonate and water. Geochim. Cosmochim. Acta 33, 987-996). Nevertheless, extrapolation of our relationship to the pure calcite end member yielded a value of 27.9 ± 0.02, which is similar in magnitude to published values for the calcite-water system. Although no kinetic effect was observed on 10³lnα_Mg-cl-H2O for precipitation rates that ranged from 10^3.21 to 10^4.60 μmol · m⁻² · h⁻¹, it was impossible to disentangle the potential effect(s) of precipitation rate and Mg-content on 10³lnα_Mg-cl-H2O due to the heterogeneous nature of the solid.The results of this study suggest that paleotemperatures inferred from the δ¹⁸O values of high magnesian calcite (>10 mol% MgCO₃) may be significantly underestimated. Also, the results underscore the need for additional experiments to accurately characterize the effect of Mg coprecipitation on the isotope systematics of calcite from a chemically homogeneous precipitate or a heterogeneous material that is analyzed at the scale of chemical and isotopic zonation.     

Effect of orthophosphate on the dissolution kinetics of biogenic magnesian calcites

The dissolution behavior of two biogenic Mg-calcites, the echinoid, Tripneustes (12 mol% MgCO₃), and the red alga, Neogoniolithon (18 mol% MgCO₃ plus brucite), was studied using free-drift methods in distilled water and phosphate-spiked solutions at 25°C and P_CO2 = 1 atm. Small concentrations of phosphate strongly inhibit dissolution rates. Inhibition increases with increased phosphate levels and with approach toward saturation. Near saturation, dissolution rates are reduced by 10³ by the presence of 0.6 μmol adsorbed-P/m². The magnitude of phosphate inhibition is similar to that observed for low-Mg calcite, and like calcite, the mechanism of inhibition is probably by adsorption of P at surface kink sites. Phosphate appears to inhibit removal of Mg and Ca equally during Mg-calcite dissolution. Rates of brucite dissolution are unaffected by phosphate.Mg-calcites containing >8.5 mol% MgCO₃ should be thermodynamically unstable relative to aragonite in most natural waters. Recent work, however, shows that in contrast to its effect on the behavior of Mg-calcites. phosphate does not inhibit aragonite dissolution. The presence of phosphate might thus reverse the relative stability of these two minerals during diagenesis of shallow marine carbonate sediments.     

Mineralogical and chemical composition of some carbonate minerals from the Zillerthal Alps,Tyrol (Austria)

Summary 32 carbonate samples from a series of metamorphic rocks of greenschist to almandine-amphibolite facies in the Zillerthal Alps were investigated by optical and chemical methods, X-ray diffractometry, and the scanning electron microscope.The carbonates consist mainly of calcite which contains up to 11 mole % (MgCO₃+FeCO₃). Some of the calcites are characterized by skeleton-like dolomitic exsolutions of rhombohedral shape that are orientated on rhombohedron planes of the calcite matrix.The relations between metamorphic grade and calcite composition will be discussed. The (FeCO₃+MgCO₃)-content of calcite depends on the temperature of formation, CO₂ pressure, and the Fe and Mg concentrations of the carbonate-forming solutions.

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Mineralogische und chemische Zusammensetzung von Karbonaten aus den Zillertaler Alpen, Tirol (Österreich)

Zusammenfassung 32 Karbonatproben aus den Zillertaler Alpen (Tirol, Österreich) wurden mit optischen und röntgendiffraktometrischen Methoden sowie mit dem Elektronenrastermikroskop untersucht.Die Karbonate sind Calcite, die bis zu 11 Mol% (MgCO₃+FeCO₃) enthalten. Die Calcitkristalle zeichnen sich durch skelettartige Dolomitentmischungen aus, die parallel zu Rhomboederflächen des Calcites orientiert sind.Die Karbonate stammen aus einer Serie metamorpher Gesteine der Grünschiefer- bis Almandin-Amphibolitfazies. Es werden die Beziehungen zwischen der Calcitzusammensetzung und dem Metamorphosegrad diskutiert. Der (FeCO₃+MgCO₃)-Gehalt der Calcite hängt von der Bildungstemperatur, vom CO₂-Druck und vom Fe- und Mg-Gehalt der Lösungen ab, aus denen sich die Karbonate gebildet haben.

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With 10 Figures     

Submarine-spring controlled calcification and growth of large Rivularia bioherms, Late Pleistocene (MIS 5e), Gulf of Corinth, Greece

The cyanobacterium Rivularia haematites has calcified to form unusually large (up to 10 m high) bioherms in the Pleistocene Gulf of Corinth. Today R. haematites calcifies only in freshwater environments but these Gulf of Corinth bioherms have a brackish affinity, limited areal extent, and occur within marine deposits. Field relations and preliminary U-series dating suggest a marine isotope stage (MIS) 5e age for the bioherms. This age is compatible with published MIS 5e ages for corals in the marine sediments above the bioherms and is consistent with their current elevation based on average uplift rates. Bioherm growth during MIS 5e constrains their formation during a time of near sea-level highstand when the Gulf of Corinth was marine. Growth cavities in the bioherms are encrusted by brackish tolerant coralline algae. Field mapping of the MIS 5e highstand palaeoshoreline shows the bioherms grew in water <16 m deep. Mg contents of the bioherm calcites, and associated coralline algal skeletons, are both much lower than expected for marine MIS 5e carbonates. They are best explained if the calcites precipitated from brackish fluids with Mg/Ca ratios below 2, implying at least 60% input of freshwater with low Mg/Ca ratio. Sr isotopes confirm a strong input of groundwater that had partially equilibrated with Mesozoic limestones. The limited areal extent of the bioherms and their close association with karstified fault scarps suggest that they formed in shallow sea water where freshwater submarine springs delivered CaCO₃ saturated water that promoted rapid calcification of cyanobacteria. Rapid calcification and strong degassing of CO₂ from the spring water resulted in disequilibrium stable isotope compositions for the calcites.     

The solubility of calcite in seawater solutions of various magnesium concentration, It = 0.697 m at 25 °C and one atmosphere total pressure

Stoichiometric solubility constants of calcite in initially supersaturated solutions of various magnesium to calcium concentration ratios but identical ionic strength were determined at 25°C and one atmosphere total pressure.The thermodynamic solubility constant of calcite is used with ion pairing equations to interpret the data reported in this study. Results indicate that even though magnesian calcites, rather than pure calcite, precipitate from seawater solutions containing magnesium ions, the incorporation of MgCO₃ in the calcite crystal lattice does not extensively alter the equilibrium calcium carbonate activity product.The equilibrium activity of the ionic species in solution and the composition of magnesian calcite overgrowths precipitated from solutions of similar composition are used to calculate the solubility of magnesian calcites. The values for magnesian calcite solubilities obtained by this approach are lower than those obtained from the dissolution kinetics of biogenic carbonates.     

Temperature Dependence of Mineral Precipitation Rates Along the CaCO3–MgCO3 Join

The large variation in precipitation rate and abundance of mineralscomprising the CaCO₃–MgCO₃ binary join can be understood in terms of their large differences in activation energy. Following the treatment of Lippmann (1973), activation energy isextrapolated along the join as a linear function of mole percentmagnesium. For the dolomite-type carbonates, the predicted activationenergy is compatible with recent measurements of calcian protodolomitekinetics; cation ordering in ideal dolomite can thus be seen as anadditional contribution to activation energy. Although no activationenergies are available for magnesian calcites, treatment of rate datafor these phases using the formalism of stoichiometric saturationsuggests a possible change in mechanism or rate-limiting step astemperature is decreased from 25 to 5 °C.     

Grain growth kinetics of dolomite,magnesite and calcite: a comparative study

The rates of grain growth of stoichiometric dolomite [CaMg(CO₃)₂] and magnesite (MgCO₃) have been measured at temperatures T of 700–800°C at a confining pressure P _c of 300 MPa, and compared with growth rates of calcite (CaCO₃). Dry, fine-grained aggregates of the three carbonates were synthesized from high purity powders by hot isostatic pressing (HIP); initial mean grain sizes of HIP-synthesized carbonates were 1.4, 1.1, and 17 μm, respectively, for CaMg(CO₃)₂, MgCO₃, and CaCO₃, with porosities of 2, 28, and 0.04% by volume. Grain sizes of all carbonates coarsened during subsequent isostatic annealing, with mean values reaching 3.9, 5.1, and 27 μm for CaMg(CO₃)₂, MgCO₃, and CaCO₃, respectively, in 1 week. Grain growth of dolomite is much slower than the growth rates of magnesite or calcite; assuming normal grain growth and n = 3 for all three carbonates, the rate constant K for dolomite (≃5 × 10⁻⁵ μm³/s) at T = 800°C is less than that for magnesite by a factor of ~30 and less than that for calcite by three orders of magnitude. Variations in carbonate grain growth may be affected by differences in cation composition and densities of pores at grain boundaries that decrease grain boundary mobility. However, rates of coarsening correlate best with the extent of solid solution; K is the largest for calcite with extensive Mg substitution for Ca, while K is the smallest for dolomite with negligible solid solution. Secondary phases may nucleate at advancing dolomite grain boundaries, with implications for deformation processes, rheology, and reaction kinetics of carbonates.     

The role of magnesium in the crystal growth of calcite and aragonite from sea water

The seeded precipitation (crystal growth) of aragonite and calcite from sea water, magnesium-depleted sea water, and magnesium-free sea water has been studied by means of the steady-state disequilibrium initial rate method. Dissolved magnesium at sea water levels appears to have no effect on the rate of crystal growth of aragonite, but a strong retarding effect on that of calcite. By contrast, at levels less than about 5 per cent of the sea water level, Mg has little or no effect on calcite growth. Extended crystal growth on pure calcite seeds in sea water of normal Mg content resulted in the crystallization of magnesium calcite overgrowths, containing 7–10 mole % MgCO₃ in solid solution. This suggests that the rate inhibition by Mg is due to its incorporation within the calcite crystal structure during growth, which causes the resulting magnesian calcite to be considerably more soluble than pure calcite. The standard free energy of formation of 8.5 mole% Mg calcite calculated on this assumption is in good agreement with independent estimates of magnesian calcite stability.From the work of Katz (Geochim. Cosmochim. Acta37, 1563–1586, 1973), Plummer and Mackenzie (Amer. J. Sci. 273, 515–522, 1974), and the present paper, it can be predicted that the most stable calcite in Ca-Mg exchange equilibrium with sea water contains between 2 and 7 mole%MgCO₃ in solid solution. Likewise, calcites containing more than 8.5 mole% MgCO₃ are less stable, and those containing less than 8.5 mole% MgCO₃ are more stable than aragonite plus Ca and Mg in sea water.     

Petrographic and geochemical features of the dolostones at the Gölboğazı Formation (Upper Devonian), Southwest Konya,Turkey

This paper describes the occurrence of dolostone and the mechanism of dolomitization of the Upper Devonian Gölbo?az? Formation in the allochthonous Taurus Mountains Alada? unit in Turkey. The Upper Devonian Gölbo?az? Formation carbonates, with dominant ostracod-bearing mudstone and wackestone, formed tidal and subtidal environments, and some of these rocks were dolomitized from shallow to deep burial. On the basis of the field, the petrographic and geochemical features, four different replaceable and cement dolostone phases have been recognized. The replacive dolostones contain (1) very fine to fine crystalline planar-s dolostone (df1), (2) medium to coarse crystalline planar-s to planar-e dolostone (df2), (3) coarse to very coarse crystalline non-planar-a dolostone (df3), and (4) coarse to very coarse crystalline planar dolostone cement (df4). The replacive dolostones are disordered to moderate the ordered and calcium-rich. They are non-stoichiometric and have 46–59 mol% CaCO₃ and 41–54 mol% MgCO₃ total contents. The df1 dolostones have MgCO₃ contents of 41–54 mol%, the df2 dolostones have 41–53 mol%, the df3 dolostones have 49 mol%, and the df4 dolostones have 49–50 mol%, respectively. The Gölbo?az? dolostones have δ¹⁸O values of ?9.44 to ?2.20‰ Vienna Pee Dee Belemnite (VPDB) and δ¹³C values of ?1.58 to +2.52 VPDB. Sr, Na, Mn, and Fe concentrations of replacive dolostones are 74–184, 148–593, below detection level (bdl)–619, and 1049–9233 ppm, respectively. The petrographic and geochemical data demonstrate that the replacive dolostones occurred prior to the chemical compaction at shallow to intermediate burial depths from Late Devonian seawater and/or seawater lightly modified by water–rock interaction process and later recrystallized by basinal brines at increasing burial depths and temperature. The North American Shale Composite-normalized rare earth element values of both limestone and dolostone show very similar rare earth element patterns characterized by slightly or considerably negative cerium (Ce) anomalies and a clear depletion in all rare earth element species. The dedolomitization observed in the Gölbo?az? Formation is thought to occur by the oxidizing effect of the meteoric water in the shallow burial environment during the telodiagenesis.     

Geochemistry of meteoric calcite cements in some Pleistocene limestones

In this study, the stable isotope and trace element geochemistries of meteoric cements in Pleistocene limestones from Enewetak Atoll (western Pacific Ocean), Cat Island (Bahamas), and Yucatan were characterized to help interpret similar cements in ancient rocks. Meteoric calcite cements have a narrow range of δ¹⁸O values and a broad range of δ¹³C values in each geographical province. These Pleistocene cements were precipitated from water with stable oxygen isotopic compositions similar to modern rainwater in each location. Enewetak calcite cements have a mean δ¹⁸O composition of ?6.5%₀ (PDB) and δ¹³C values ranging from ?9.6 to +0.4%0 (PDB). Sparry calcite cements from Cat Island have a mean δ¹⁸O composition of ?4.1%₀ and δ¹³C values ranging from ?6.3 to + 1.1%₀. Sparry cements from Yucatan have a mean δ¹⁸O composition of ?5.7%₀ and δ¹³C values of ?8.0 to ?2.7%₀. The mean δ¹⁸O values of these Pleistocene meteoric calcite cements vary by 2.4%₀ due to climatic variations not related directly to latitude. The δ¹³C compositions of meteoric cements are distinctly lower than those of the depositional sediments. Variations in δ¹³C are not simply a function of distance below an exposure surface. Meteoric phreatic cements often have δ¹³C compositions of less than —4.0%₀, which suggests that soil-derived CO₂ and organic material were washed into the water table penecontemporaneous with precipitation of phreatic cements. Concentrations of strontium and magnesium are quite variable within and between the three geographical provinces. Mean strontium concentrations for sparry calcite cements are, for Enewetak Atoll, 620 ppm (σ= 510 ppm); for Cat Island, 1200 ppm (σ= 980 ppm); and for Yucatan, 700 ppm (σ= 390 ppm). Equant cements, intraskeletal cements, and Bahamian cements have higher mean strontium concentrations than other cements. Equant and intraskeletal cements probably precipitated in more closed or stagnant aqueous environments. Bahamian depositional sediments had higher strontium concentrations which probably caused high strontium concentrations in their cements. Magnesium concentrations in Pleistocene meteoric cements are similar in samples from Enewetak Atoll (mean =1.00 mol% MgCO₃; σ= 0.60 mol% MgCO₃) and Cat Island (mean = 0.84 mol% MgCO₃; σ= 0.52mol% MgCO₃) but Yucatan samples have higher magnesium concentrations (mean = 2.20 mol% MgCO₃: σ= 0.84mol% MgCO₃). Higher magnesium concentrations in some Yucatan cements probably reflect precipitation in environments where sea water mixed with fresh water.     

Change in carbonate budget and composition during subduction below metal saturation boundary

It is generally accepted that carbonates can be subducted to the mantle depths, where they are reduced with iron metal to produce a diamond. In this work, we found that this is not always the case. The mantle carbonates from inclusions in diamonds show a wide range of cation compositions (Mg, Fe, Ca, Na, and K). Here we studied the reaction kinetics of these carbonates with iron metal at 6–6.5 GPa and 1000–1500 °C. We found that the reduction of carbonate with Fe produces C-bearing species (Fe, Fe-C melt, Fe₃C, Fe₇C₃, C) and wüstite containing Na₂O, CaO, and MgO. The reaction rate constants (k = Δx²/2t) are log-linear relative to 1/T and their temperature dependences are determined to bek_MgCO3 (m²/s) = 4.37 × 10^?3 exp [?251 (kJ/mol)/RT]k_CaMg(CO3)2 (m²/s) = 1.48 × 10^?3 exp [?264 (kJ/mol)/RT]k_CaCO3 (m²/s) = 3.06 × 10^?5 exp [?245 (kJ/mol)/RT] andk_Na2CO3 (m²/s) = 1.88 × 10^?10 exp [?155 (kJ/mol)/RT].According to obtained results at least, 45–70 vol% of carbonates preserve during subduction down to the 660-km discontinuity if no melting occurs. The slab stagnation and warming, subsequent carbonate melting, and infiltration into the mantle saturated with iron metal are accompanied by a reduction of carbonate melt with Fe. The established sequence of reactivity of carbonates: FeCO₃ ≥ MgCO₃ > CaMg(CO₃)₂ > CaCO₃ ? Na₂CO₃, where K₂CO₃ does not react at all with iron metal, implies that during reduction carbonate melt with Fe evolves toward alkali-rich. The above conclusions are consistent with the findings of carbonates in inclusions in diamonds from the lower mantle and high concentrations of alkalis, particularly K, in mantle carbonatite melts entrapped by diamonds from kimberlites and placers worldwide.     

Ternary Ca–Fe–Mg carbonates: subsolidus phase relations at 3.5 GPa and a thermodynamic solid solution model including order/disorder

Subduction carries atmospheric and crustal carbon hosted in the altered oceanic crystalline basement and in pelagic sediments back into the mantle. Reactions involving complex carbonate solid solutions(s) lead to the transfer of carbon into the mantle, where it may be stored as graphite/diamond, in fluids or melts, or in carbonates. To constrain the thermodynamics and thus reactions of the ternary Ca–Mg–Fe carbonate solid solution, piston cylinder experiments have been performed in the system CaCO₃–MgCO₃–FeCO₃ at a pressure of 3.5 GPa and temperatures of 900–1,100°C. At 900°C, the system has two miscibility gaps: the solvus dolomite–calcite, which closes at X _MgCO3 ~0.7, and the solvus dolomite–magnesite, which ranges from the Mg to the Fe side of the ternary. With increasing temperature, the two miscibility gaps become narrower until complete solid solutions between CaCO₃–Ca_0.5Mg_0.5CO₃ is reached at 1,100°C and between CaCO₃–FeCO₃ at 1,000°C. The solvi are characterized by strong compositional asymmetry and by an order–disorder mechanism. To deal with these features, a solid solution model based on the van Laar macroscopic formalism has been calculated for ternary carbonates. This thermodynamic solid solution model is able to reproduce the experimentally constrained phase relations in the system CaCO₃–MgCO₃–FeCO₃ in a broad P–T range. To test our model, calculated phase equilibria were compared with experiments performed in carbonated mafic protolithes, demonstrating the reliability of our solid solution model at pressures up to 6 GPa in complex systems.     

Geochemistry of early precambrian carbonate rocks from the Brazilian Shield: Implications for archean carbonate sedimentation

Petrological and geochemical studies were carried out on early Precambrian carbonate rocks metamorphosed under granulite facies conditions from three areas of Bahia State (Brazil). Older rocks attributable to the Archean or lower Proterozoic consist of carbonates (mainly dolomite) and abundant, partially-serpentinized forsterite. Chemical data confirm their strong magnesian character and the almost complete absence of elements like Al, Ti, Na, K, Zr etc., which are normally found in the non-carbonate detrital part of impure carbonate rocks. Comparison with other carbonate rocks of similar silica content further emphasizes the scarcity of these elements. Samples of probably more recent origin belonging to migmatized complex of Central Bahia are more calcic in character and have a higher Sr and Ba content. The MgCO₃ solvus thermometer in calcites coexisting with dolomite was determined both by chemical and X-ray procedures. Temperature values for carbonates under granulite facies range between 472 and 640° C. These temperatures seem to represent quench or recrystallization temperatures. The general geochemistry of carbonate rocks suggests two main hypotheses for their formation: a) chemical precipitation of pure carbonates during the Archean and later silica enrichment by metasomatic reactions; b) chemical co-precipitation in the Archean or early Proterozoic of carbonates and silica from silica-rich sea water. In this case precipitation would have occurred locally owing to increasing CO₂ pressure (due, for example, to exhalative volcanism) or in limited evaporitic basins in areas of temporary stability bordering the continents.     

Methane-derived authigenic carbonates from the northern Gulf of Mexico — MD02 Cruise

Authigenic carbonates were sampled in piston cores collected from both the Tunica Mound and the Mississippi Canyon area on the continental slope of the northern Gulf of Mexico during a Marion Dufresne cruise in July 2002. The carbonates are present as hardgrounds, porous crusts, concretions or nodules and shell fragments with or without carbonate cements. Carbonates occurred at gas venting sites which are likely to overlie gas hydrates bearing sediments. Electron microprobe, X-ray diffraction (XRD) and thinsection investigations show that these carbonates are high-Mg calcite (6–21 mol% MgCO₃), with significant presence of framboidal pyrite. All carbonates are depleted in ¹³C (δ¹³C = − 61.9 to − 31.5‰ PDB) indicating that the carbon is derived mainly from anaerobic methane oxidation (AMO). Age estimates based on ¹⁴C dating of shell fragments and on regional sedimentation rates indicate that these authigenic carbonates formed within the last 1000 yr in the Mississippi Canyon and within 5500 yr at the Tunica Mound. The oxygen isotopic composition of carbonates ranges from + 3.4 to + 5.9‰ PDB. Oxygen isotopic compositions and Mg²⁺ contents of carbonates, and present in-situ temperatures of bottom seawater/sediments, show that some of these carbonates, especially from a core associated with underlying massive gas hydrates precipitated in or near equilibrium with bottom-water. On the other hand, those carbonates more enriched in ¹⁸O are interpreted to have precipitated from ¹⁸O-rich fluids which are thought to have been derived from the dissociation of gas hydrates. The dissociation of gas hydrates in the northern Gulf of Mexico within the last 5500 yr may be caused by nearby salt movement and related brines.     

Recrystallization of dolomite: evidence from the Monterey Formation (Miocene), California

Dolomites from the upper calcareous-siliceous member of the Miocene Monterey Formation exposed west of Santa Barbara, California, were analysed for geochemical, isotopic and crystallographic variation. The data clearly document the progressive recrystallization of dolomite during burial diagenesis in marine pore fluids. Recrystallization is recognized by the following compositional and crystallographic variations. Dolomites have decreasing δ¹⁸O and δ¹³C compositions, decreasing Sr contents and increasing Mg contents with increasing burial depths and temperatures from east to west in the study area. δ¹⁸O values vary from 5·3‰ in the east to − 5·5‰ PDB in the west and are interpreted to reflect the greater extent and higher temperature of dolomite recrystallization in the west. δ¹³C values correlate with δ¹⁸O and decrease from 13·6‰ in the east to − 8·7‰ PDB in the west. Sr concentrations correlate positively with δ¹⁸O values and decrease from a mean of 750 ppm in the east to a mean of 250 ppm in the west. Mol% MgCO₃ values inversely correlate with δ¹⁸O values and increase from a minimum of 41·0 in the east to a maximum of 51·4 in the west. Rietveld refinements of powder X-ray diffraction data indicate that the more recrystallized dolomites have more contracted unit cells and increased cation ordering. The fraction of the Ca sites in the dolomites that are occupied by Ca atoms increases slightly with the approach to stoichiometry. The fraction of the Mg sites occupied by Mg atoms strongly correlates with mol% MgCO₃. Even in early diagenetic, non-stoichiometric dolomites, there is little substitution of Mg in Ca sites. During recrystallization, the amount of Mg substituting for Ca in Ca sites decreases even further. Most of the disorder in the least recrystallized, non-stoichiometric dolomites is related to substitution of excess Ca on Mg sites.     

Decarbonation reaction of magnesite in subducting slabs at the lower mantle

High-pressure and temperature experiments (28–62 GPa, and 1,490–2,000 K, corresponding to approximately 770–1,500 km depth in the mantle) have been conducted on a MgCO₃ + SiO₂ mixture using a laser-heated diamond anvil cell combined with analytical transmission electron microscope observation of the product phases to constrain the fate of carbonates carried on the subducting basalt into the lower mantle. At these conditions, the decarbonation reaction MgCO₃ (magnesite) + SiO₂ (stishovite) → MgSiO₃ (perovskite) + CO₂ (solid) has been recognized. This indicates that above reaction takes place as a candidate for decarbonation of the carbonated subducting mid ocean ridge basalts in the Earth’s lower mantle.     

The dissolution kinetics of shallow marine carbonates in seawater: A laboratory study

The dissolution kinetics of shallow water marine carbonates (low-Mg calcite, aragonite and Mg-calcites) were investigated in seawater (S = 35) at 25°C and a P_CO2 of 10^?2.5 atm. using the pH-stat method. Carbonate dissoluton rates (μmoles g^?1 hr^?1) fit the empirical kinetic expression, R = k(1 - Ω)ⁿ, where R = dissolution rate, k = rate constant, Ω = saturation state, and n = order of reaction. Reaction orders were near 2.9 for low-Mg calcites, 2.5 for aragonites and 3.4 for Mg-calcites.The rate constant, k, expressed as μmoles g^?1 hr^?1, varied by nearly a factor of ten for the different samples, reflecting differences in amount of reactive surface area. Reactive surface area of the biogenic phases ranged from 0.3% to 66% of the total surface area determined by the BET gas adsorption method. The discrepancy between reactive and total surface area was greatest for samples with high BET surface areas (> 1 m² g^?1) and delicate microstructures.Relative dissolution rates of the various biogenic carbonates as a function of seawater calcium carbonate ion molal product (IMP) were related to both mineral stability and grain microstructure. In seawater undersaturated with respect to aragonite, finely crystalline aragonites dissolved more rapidly than thermodynamically less stable high Mg-calcites (15–18 mole% MgCO₃) with lower reactive surface areas. Therefore, under certain conditions, differences in grain microstructural complexity can override thermodynamic constraints and lead to selective dissolution of a thermodynamically more stable mineral phase.     

Origin of rutile needles in star garnet and implications for interpretation of inclusion textures in ultrahigh‐pressure metamorphic rocks

The asterism effect of star garnet has been attributed to the oriented distribution of needle‐like rutile inclusions. Rutile needles occur in garnet from a wide range of metamorphic settings and rock bulk compositions, and their origin has been ascribed to different mechanisms, such as exsolution, and used to interpret petrological and tectonic processes. Results from an optical and transmission electron microscopy of Idaho star garnet indicate a co‐precipitation origin. It was found that rutile needles are predominantly oriented along the <103>_rt//<111>_grt and <001>_rt//<001>_grt directions following multiple crystallographic orientation relationships (CORs); i.e. COR‐1, 2, 2′, 3, 4 and 5 in 6‐ray star garnet, and are oriented solely along the <103>_rt//<111>_grt directions following exclusively COR‐2 in 4‐ray star garnet. The sole presence of COR‐2 <111>_grt needles in the common 4‐ray star garnet, in contrast to the presence of both <111>_grt and <001>_grt needles with multiple CORs in the rare 6‐ray star garnet, suggests that the COR‐2 <111>_grt needle probably is the energetically most favoured variant, as is also supported by the coincidence site lattice considerations. The unique crystallography‐controlled microstructures of 4‐ray star garnet, including the cloudy domains behind the {111}_grt or {100}_grt fronts with abundant inclusions of rutile needle, rutile compound needle and multiple‐phase‐inclusion, as well as the clear domains behind the {110}_grt fronts with only a few above inclusions concentrated exclusively within the linear, <110>_grt‐oriented, continuous tube‐like domains, further suggest that the COR‐2 <111>_grt needles in 4‐ray star garnet most likely have a growth‐in origin, co‐precipitating with garnet at its growth fronts close to thermodynamic equilibrium conditions. The 6‐ray star garnet, on the other hand, most likely formed under far‐from equilibrium conditions, thereby yielding a maximum of 99 crystallographic variants of rutile needles with multiple CORs in a single crystal. In the light of these findings, along with the common occurrences of the sole COR in many inclusion‐host systems owing to the requirement to minimize the energy barrier in an exsolution process, the presence of both <103>_rt//<111>_grt and <001>_rt//<001>_grt needles with multiple CORs in garnet of Sulu eclogite and Erzegebirge quartzofeldspathic rock would therefore cast doubt on the assertion of an exsolution origin of rutile needles in garnet from these ultrahigh‐pressure rocks.     

Influence of natural organic acids on the Mg/Ca ratio in the bottom sediments of highly mineralized lakes

Thermodynamic modeling of equilibria in the system water–rock–organic acids was used to study the influence of organic acids on Ca and Mg redistribution between a solution and a solid phase in connection with the use of calcites of variable composition Ca_xMg_1–xCO₃ as indicators of paleoclimatic environments. In the thermodynamic model, high-molecular humic substances (fulvic + humic acids) were represented by a set of independent metal-binding centers. Therefore, their number was preset based on the given density of proton- or metal-binding sites. The numerical implementation of several geochemical situations involving the dissolution/deposition of calcites with different Mg contents showed that the main effect of fulvic and humic acids is the acidification of solutions and the reduction of carbonate stability. Although humic substances can play an important role in fixing Ca and Mg and removing them from solution, their actual concentrations in natural media (<<1 g/L) do not cause significant changes in the composition of Ca_xMg_1–xCO₃ phases. On the other hand, there is quantitative evidence that variations in the Mg/Ca ratio in a solution and a solid phase are significantly influenced by the evaporative concentration of Mg-oversaturated solutions, alkalization/acidification during their evolution, or CO₂ content variations owing to changes in climate and lake activity.