A thermochemical study of monohydrocalcite

The thermodynamic properties of monohydrocalcite, CaCO₃ · H₂O, have been obtained using a well-characterized natural specimen. Equilibration of the solid with water at 25°C under 0.97 atm CO₂ led to an activity product [Ca²⁺][CO₃^2?] = 10^?7.60±0.03 and a free energy of formation ΔG_f^o = ?325,430 ± 270 calmol^?. The enthalpy of solution of monohydrocalcite in 0.1 N HCl at 25°C led to a standard enthalpy of formation ΔH_f^o = ?358,100 ± 280 cal mol^?1. Estimates of the variation of ΔG_f with temperature and pressure showed monohydrocalcite to be metastable with respect to calcite and aragonite.     

The use of coexisting calcite-ankerite solid solutions as a geothermometer

Limited solid solution of Mg and Fe²⁺ occurs in calcite coexisting with dolomiteankerite. This substitution is strongly temperature-dependent. Experimentally determined calcite compositions co-existing with a dolomite phase are available in the binary system CaCO₃-MgCO₃ between 500° C and 900° C (Harker and Tuttle, 1955). This information is extrapolated to lower temperatures and is combined with three synthetic calcite-ankerite pairs determined at 400° C, 450° C and 500° C (Rosenberg, 1967).The compositions of six naturally occurring calcites coexisting with ankerites from Sofala, N.S.W. are not accurately known, but X-ray determined compositional limits assuming firstly Mg substitution then Fe substitution yield maximum and minimum values for both possibilities. These limits are plotted on the ternary CaCO₃-MgCO₃-FeCO₃ together with the experimentally derived solvus isotherms. Assuming equilibration at constant temperature, actual compositions of these natural calcites plot along the 415° C isotherm.     

Subsolidus and melting relationships for calcite,magnesite and the join CaCO3-MgCO3 36 kb

Subsolidus and melting relations for the CaCO₃-MgCO₃ join at 30 kb have been determined using piston-cylinder apparatus. Data are also presented for the melting curve of CaCO₃ to 30 kb, the decomposition and melting curves of MgCO₃ to 36 kb, and the calcite-aragonite transition at 800°C, 950°C and 1100°C. At 30kb, the melting loop for the CaCO₃-MgCO₃ join extends from 1610°C (CaCO₃) to 1585°C (MgCO₃) through a liquidus minimum at 1290°C (near 42 mole% MgCO₃). The dolomite-magnesite solvus barely intersects the 30 kb melting loop to produce a peritectic reaction at 1385°C. Integration of the new experimental data with other published data permits construction of a complete P-T projection and a sequence of isobars for the CaCO₃-MgCO₃ join for pressures between 5 and 30 kb. The phase relations for this join provide part of the essential framework of the model peridotite system CaO-MgO-SiO₈-CO₂-H₂O, which has particular application to the origin of carbonatitic and kimberlitic magmas. In light of the accumulating evidence for CO₂ in various forms within the upper mantle and of its effect on magmatic processes, analysis of the melting relations in this system is of considerable importance.     

Metamorphic equilibria in the siliceous dolomite system: 6 kbar experimental data and geologic implications

Hydrothermal experiments with H₂O-CO₂ fluids at P_fluid = 6 kbar yielded the following quilibrium conditions for reactions important in metamorphosed siliceous dolomites (T = °C; X = X_co2): (3) dolomite + 2 quartz = diopside + 2 CO₂T = 620 ± 8X = 0.73 ± 0.03 (5) 5 dolomite + 8 quartz + H₂O = tremolite + 3 calcite + 7 CO₂T = 600 ± 5 550 ±5 540±5 500±5X = 0.66 ± 0.03 0.21 ± 0.03 0.21 ± 0.04 0.06 ± 0.02 (7) 3 dolomite + 4 quartz + H₂O = talc + 3 calcite + 3 CO₂T = 550±5 500±5 450 ±5X = 0.25 ± 0.05 0.07 ± 0.02 0.03 ± 0.02 (8) 2 dolomite + talc + 4 quartz = tremolite + 4 CO₂T = 550 ± 5 540 ±5 500 ± 5X = 0.22 ± 0.03 0.21 ± 0.02 0.06 ± 0.02 A thermodynamically self-consistent 6 kbar T-X_CO2, topology results by extrapolating equilibria from experimental brackets using a modified Redlich-Kwong equation for activities in H₂O-CO₂ mixtures. This topology restricts the assemblage talc + calcite to a narrow stability band in T-X_CO2 space at X_CO2 < 0.55 and T < 590°C. Accordingly, the occurrence of talc + calcite in pure siliceous dolomites metamorphosed at P_fluid = 6 kbar implies correspondingly water-rich fluids.     

Subsolidus and melting relations for the join CaCO3-MgCO3 at 10 kbar

Mixtures of pure dry CaCO₃ and MgCO₃ were reacted at 10 kbar in a piston-cylinder apparatus. Solidus and liquidus boundaries were delineated by interpretation of quenched textures. X-ray determined compositions of quenched carbonates are not a reliable guide to the phase relations. The binary melting loop for CaCO₃-MgCO₃ extends from CaCO₃ at 1460°C through a liquidus minimum near 30 wt% MgCO₃ and 1075°C, and it is terminated at the incongruent melting reaction for dolomite solid solution at 1125° C (liquid with 32 wt% MgCO₃) Magnesite solid solution dissociates at 1090°C to produce dolomite + periclase + CO₂, truncating the dolomite-magnesite solvus. The 10 kb liquidus minimum at 1075°C and 30 wt% MgCO₃ occurs at lower temperature and higher $\text{Ca}\text{Mg}$ ratio than the 27 kbar liquidus minimum at 1290°C and 38 wt% MgCO₃. This relationship suggests that the first liquid produced by melting of a carbonate-bearing peridotite has increasing $\text{Mg}\text{Ca}$ ratio with increasing pressure. These phase relations provide part of the framework required to trace paths of crystallization of kimberlite and carbonatite magmas.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

The hydrogeochemistry and isotope geochemistry of groundwater from 85 wells in fractured dolomite aquifers of Central Slovenia were investigated. This groundwater represents waters strongly influenced by chemical weathering of dolomite with an average of δ¹³C_CARB value of +2.2 ‰. The major groundwater geochemical composition is HCO₃ ^? > Ca²⁺ > Mg²⁺. Several differences in hydrogeochemical properties among the classes of dolomites were observed when they were divided based on their age and sedimentological properties, with a clear distinction of pure dolomites exhibiting high Mg²⁺/Ca²⁺ ratios and low Na⁺, K⁺ and Si values. Trace element and nutrient concentrations (SO₄ ^2?, NO₃ ^?) were low, implying that karstic and fractured dolomite aquifers are of good quality to be used as tap water. Groundwater was generally slightly oversaturated with respect to calcite and dolomite, and dissolved CO₂ was up to 46 times supersaturated relative to the atmosphere. The isotopic composition of oxygen (δ¹⁸O_H2O), hydrogen (δD_H2O) and tritium ranged from ?10.3 to ?8.4 ‰, from ?68.5 to ?52.7 ‰ and from 3.5 TU to 10.5 TU, respectively. δ¹⁸O and δD values fell between the GMWL (Global Meteoric Water Line) and the MMWL (Mediterranean Meteoric Water Line) and indicate recharge from precipitation with little evaporation. The tritium activity in groundwater suggests that groundwater is generally younger than 50 years. δ¹³C_DIC values ranged from ?14.6 to ?9.3 ‰ and indicated groundwater with a contribution of degraded organic matter/dissolved inorganic carbon in the aquifer. The mass balances for groundwater interacting with carbonate rocks suggested that carbonate dissolution contributes from 43.7 to 65.4 % and degradation of organic matter from 34.6 to 56.3 %.     

Experimentelle Untersuchung der Metamorphose von kieselig dolomitischen Sedimenten

During an experimental investigation of the metamorphism of siliceous dolomites the equilibrium data of the heterogeneous bivariant reaction 1 $$3{\text{ dolomite + 4 quartz + 1 H}}_{\text{2}} O \rightleftharpoons + 3 calcite + 3 CO_2 $$ were determined for the total fluid pressures of 1,000, 3,000 and 5,000 bars. The equilibrium conditions were found by experiments in which dolomite, quartz and water react to form talc, calcite and CO₂, as well as by experiments with reversible reaction direction. Results are shown on the temperature- \(X_{CO_2 } \) -diagram of Fig. 3. The temperature of formation of talc and calcite depends to a considerable extent on the composition of the CO₂-H₂O-gas phase; this can be read straight off the isobaric (P _f =const.) equilibrium curves in Fig. 3. In addition a strong dependence of the equilibrium temperature on the total pressure P _f was established (see Fig. 5). At a total gas pressure of 1,000 bars dolomite and quartz can react, according to the composition of the CO₂-H₂O-gas phase, to talc and calcite over the whole of the temperature range between about 350° and 490° C. This indicates that at low pressures the formation of talc and calcite takes place in the field of the albite-epidote-hornfels facies. At a pressure of 3,000 bars dolomite and quartz are stable up to about 550° C if the fluid phase is rich in carbon dioxide and correspondingly poor in water. Thus, this paragenesis can occur up to the stability field of staurolite [see annotation (5)] if the partial pressure of CO₂ is large. At the higher total gas pressure of 5,000 bars dolomite and quartz react even at medium CO₂-concentrations only at about 580° C to give talc and calcite. Therefore it is expected that in regional metamorphism at about 5,000 bars pressure or more the paragenesis dolomite plus quartz exists up to and within the stability field of staurolite and reacts only here to form talc and calcite after reaction (1) or tremolite and calcite after the following reaction (2)¹: $$5 dolomite + 8 quartz + 1 H_2 O \rightleftharpoons 1 tremolite + 3 calcite + 7 CO_2 $$ . The exact physico-chemical conditions under which dolomite, quartz and water react on the one hand to form talc, calcite and CO₂, and on the other hand to form tremolite, calcite and carbon dioxide, will be discussed later when our experimental investigations on the formation of tremolite are completed. First results were already published in a short note by Metz, Puhan and Winkler (1968).     

Estimation of dolomite formation: Dolomite precipitation and dolomitization

Reactive-transport models are developed here that produce dolomite via two scenarios: primary dolomite (no CaCO₃ dissolution involved) versus secondary dolomite (dolomitization, involving CaCO₃ dissolution). Using the available dolomite precipitation rate kinetics, calculations suggest that tens of meters of thick dolomite deposits cannot form at near room temperature (25-35°C) by inorganic precipitation mechanism, though this mechanism will provide dolomite aggregates that can act as the nuclei for dolomite crystallization during later dolomitization stage. Increase in supersaturation, Mg⁺²/Ca⁺² ratio and CO₃^-2 on the formation of dolomite at near room temperature are subtle except for temperature.This study suggests that microbial mediation is needed for appreciable amount of primary dolomite formation. On the other hand, reactive-transport models depicting dolomitization (temperature range of 40 to 200°C) predicts the formation of two adjacent moving coupled reaction zones (calcite dissolution and dolomite precipitation) with sharp dolomitization front, and generation of >20% of secondary porosity. Due to elevated temperature of formation, dolomitization mechanism is efficient in converting existing calcite into dolomite at a much faster rate compared to primary dolomite formation.     

The effect of bulk composition on the solidus of carbonated eclogite from partial melting experiments at 3 GPa

To explore the effect of bulk composition on the solidus of carbonated eclogite, we determined near-solidus phase relations at 3 GPa for four different nominally anhydrous, carbonated eclogites. Starting materials (SLEC1, SLEC2, SLEC3, and SLEC4) were prepared by adding variable proportions and compositions of carbonate to a natural eclogite xenolith (66039B) from Salt Lake crater, Hawaii. Near-solidus partial melts for all bulk compositions are Fe–Na calcio-dolomitic and coexist with garnet + clinopyroxene + ilmenite ± calcio-dolomitic solid solution. The solidus for SLEC1 (Ca#=100 × molar Ca/(Ca + Mg + Fe_T)=32, 1.63 wt% Na₂O, and 5 wt% CO₂) is bracketed between 1,050°C and 1,075°C (Dasgupta et al. in Earth Planet Sci Lett 227:73–85, 2004), whereas initial melting for SLEC3 (Ca# 41, 1.4 wt% Na₂O, and 4.4 wt% CO₂) is between 1,175°C and 1,200°C. The solidus for SLEC2 (Ca# 33, 1.75 wt% Na₂O, and 15 wt% CO₂) is estimated to be near 1,100°C and the solidus for SLEC3 (Ca# 37, 1.47 wt% Na₂O, and 2.2 wt% CO₂) is between 1,100°C and 1,125°C. Solidus temperatures increase with increasing Ca# of the bulk, owing to the strong influence of the calcite–magnesite binary solidus-minimum on the solidus of carbonate bearing eclogite. Bulk compositions that produce near-solidus crystalline carbonate closer in composition to the minimum along the CaCO₃-MgCO₃ join have lower solidus temperatures. Variations in total CO₂ have significant effect on the solidus if CO₂ is added as CaCO₃, but not if CO₂ is added as a complex mixture that maintains the cationic ratios of the bulk-rock. Thus, as partial melting experiments necessarily have more CO₂ than that likely to be found in natural carbonated eclogites, care must be taken to assure that the compositional shifts associated with excess CO₂ do not unduly influence melting behavior. Near-solidus dolomite and calcite solid solutions have higher Ca/(Ca + Mg) than bulk eclogite compositions, owing to Ca–Mg exchange equilibrium between carbonates and silicates. Carbonates in natural mantle eclogite, which have low bulk CO₂ concentration, will have Ca/Mg buffered by reactions with silicates. Consequently, experiments with high bulk CO₂ may not mimic natural carbonated eclogite phase equilibria unless care is taken to ensure that CO₂ enrichment does not result in inappropriate equilibrium carbonate compositions. Compositions of eclogite-derived carbonate melt span the range of natural carbonatites from oceanic and continental settings. Ca#s of carbonatitic partial melts of eclogite vary significantly and overlap those of partial melts of carbonated lherzolite, however, for a constant Ca-content, Mg# of carbonatites derived from eclogitic sources are likely to be lower than the Mg# of those generated from peridotite.     

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.     

Origin and modification of Cambrian dolomites (Red Heart Dolomite and Arthur Creek Formation), Georgina Basin, central Australia

The Early to Middle Cambrian Red Heart Dolomite and lower Arthur Creek Formation of the southern portion of the Georgina Basin, Australia, is an entirely dolomitized succession of shallow-water evaporitic mudflat and deeper-water subtidal lithologies. Three types of dolomite have been identified and are interpreted as: (1) syndepositional dolomite; (2) regional replacement dolomite; and (3) void-filling dolomite (cement). Syndepositional dolomite, derived from saline pore fluids developed in a sabkha environment, is a minor dolomite type with very fine crystal mosaics and has a mottled, non-zoned cathodoluminescence. The widespread regional replacement dolomite ranges from fine- to medium-crystalline forming mainly planar-s and non-planar-a crystal mosaics, and displays blotchy, mottled, non-zoned cathodoluminescence. Void-filling dolomite commonly forms planar-s to planar-e, medium to very coarse crystal mosaics. Rare non-planar-c, very coarsely crystalline saddle dolomite also exists. Void-filling dolomite has a successively zoned cathodoluminescence pattern from non-, to brightly, to dully luminescent. Geochemically, the syndepositional dolomite has δ¹⁸O (PDB) values ranging between ? 5.3 and ? 8.6%_o. Regional replacement dolomites exhibit a wide range of δ¹⁸O values from ? 3.3 to ? 10.9%_o whereas void-filling dolomite has δ¹⁸O values ranging from ? 10.8 to ? 14.3%_o. All three dolomite types have similar δ¹³C (PDB) values, in the range between +1.7 and ?1.7%_o. Three initial dolomitization episodes are interpreted: (1) a sabkha stage, forming the syndepositional dolomite and dolomitizing the evaporitic mudflat lithologies; (2) a brine-reflux stage, replacing the subtidal lithologies; and (3) a burial stage, forming the void-filling dolomite type. Final dolomite stabilization occurred during burial, at elevated temperatures, in the presence of basinal fluids, resulting in progressive recrystallization and stabilization of the earlier-formed syndepositional and replacement dolomites. Both textural and geochemical evolution should be taken into account when studying the origin of dolomites, based on their present geochemical composition. Sulphates are represented by very fine-crystalline syndepositional anhydrite in association with the syndepositional dolomite, and coarse to very coarse anhydrite cement. Evaportic mudflat (sabkha) and burial environments are inferred for the origin of the former and the latter anhydrite types, respectively. Evaporite dissolution breccias, indicative of the former presence of evaporites, are common throughout the succession.     

'Forbidden zone' subduction of sediments to 150 km depth— the reaction of dolomite to magnesite + aragonite in the UHPM metapelites from western Tianshan, China

The solid‐state reaction magnesite (MgCO₃) + calcite (aragonite) (CaCO₃) = dolomite (CaMg(CO₃)₂) has been identified in metapelites from western Tianshan, China. Petrological studies show that two metamorphic stages are recorded in the metapelites: (1) the peak mineral assemblage of magnesite and calcite pseudomorphs after aragonite which is only preserved as inclusions within dolomite; and (2) the retrograde glaucophane‐chloritoid facies mineral assemblage of glaucophane, chloritoid, dolomite, garnet, paragonite, chlorite and quartz. The peak metamorphic temperatures and pressures are calculated to be 560–600 °C, 4.95–5.07 GPa based on the calcite–dolomite geothermometer and the equilibrium calculation of the reaction dolomite = magnesite + aragonite, respectively. These give direct evidence in UHP metamorphic rocks from Tianshan, China, that carbonate sediments were subducted to greater than 150 km depth. This UHP metamorphism represents a geotherm lower than any previously estimated for subduction metamorphism (< 3.7 °C km^?1) and is within what was previously considered a ‘forbidden’ condition within Earth. In terms of the carbon cycle, this demonstrates that carbonate sediments can be subducted to at least 150 km depth without releasing significant CO₂ to the overlying mantle wedge.     

Active ankerite cementation in the subsurface Eocene of southwest Texas

In subsurface samples of Wilcox (Eocene) sandstones, calcite cements occur above 2315 m depths, whereas ankerites occur at depths from 2560 m (temperatures 125 ° C) to at least 4650 m (temperatures 210 ° C). Microprobe analyses indicate that some shallow ankerites have appreciable excess calcium, analogous to protodomites. Ankerites at depths greater than 3200 m have compositions of about CaMg_0.5Fe_0.5(CO₃)₂.Oxygen isotope data suggests that the ankerites are similar to low temperature hydrothermal dolomites and that they have probably formed in pore fluids with higher O₁₈/O₁₆ ratios than sea water. The isotopic data also suggest that the ankerites have formed over a more limited temperature interval than they occur today.The ankerite is believed to have formed from calcite by the reaction 4CaCO₃+Fe²⁺+Mg²⁺=2CaMg_0.5Fe_0.5(CO₃)₂ +2Ca²⁺. Iron and magnesium for this reaction was apparently released by the breakdown of smectite to illite in mixed-layer clays. Bulk chemical analyses suggest that some iron was transferred from shales into sandstones. Mass balance and chemical considerations are compatible with this model.     

Calciocarbonatite and magnesiocarbonatite rocks and magmas represented in the system CaO-MgO-CO2-H2O at 0.2 GPa

Summary ?The low-pressure eutectic for the coprecipitation of calcite, portlandite, and periclase/brucite (with H₂O-rich vapor) has served as a model for the existence and crystallization of carbonatite magmas. Attempts to determine conditions for the appearance of dolomite at this eutectic have been unsuccessful. We have discovered a second low-temperature eutectic for more magnesian liquids which excludes portlandite and includes dolomite (all results are vapor-saturated). Addition of Ca(OH)₂-Mg(OH)₂ to CaCO₃-MgCO₃ at 0.2 GPa depresses the liquidus to temperatures below the crest of the calcite-dolomite solvus; the vapor-saturated liquidus surface falls steeply, and the field boundary for liquids coexisting with calcite and periclase reaches a peritectic at 880 °C, where a narrow field for liquidus dolomite begins, extending down to the eutectic at 659 °C for the coprecipitation of calcite, dolomite and periclase (brucite should replace periclase at slightly higher pressures). The calcite liquidus is very large. The field boundary for coexistence of calcite and dolomite extends approximately in the direction from CaMg(CO₃)₂ towards Mg(OH)₂. The results illustrate conditions for the formation of mineral-specific cumulates from variable magma compositions. Hydrous (or sodic) carbonate-rich liquids with compositions from CaCO₃ to CaMg(CO₃)₂ will precipitate calcite-carbonatites first, followed by calcite-dolomite-carbonatites, with the prospect of precipitating dolomite-carbonatite alone through a limited temperature interval, and with periclase joining the assemblage in the closing stages. Periclase in the Fe-free system may represent the ubiquitous occurrence of magnetite in natural carbonatites. The restricted range for the precipitation of dolomite-carbonatites adds credibility to the evidence for primary magnesiocarbonatite (near-dolomite composition) magmas. Magnesiocarbonatite magmas can precipitate much calcite-carbonatite rock.

---

Zusammenfassung ?Calciokarbonatitische und magnesiokarbonatitische Gesteine und Magmen im System CaO-MgO-CO ₂ -H ₂ O bei 0.2 GPa Das Niedrigdruck-Eutektikum der gemeinsamen Ausscheidung von Calcit, Portlandit und Periklas/Brucit (mit H₂O-reicher Fluidphase) diente als Modell um die Existenz und Kristallisation karbonatitischer Magmen zu erkl?ren. Versuche die Bedingungen des Auftretens von Dolomit an diesem Eutektikum zu bestimmen blieben bisher ergebnislos. Wir entdeckten ein zweites Niedrigtemperatur-Eutektikum für magnesiumreichere Schmelzen, das Portlandit ausschlie?t, aber Dolomit inkludiert (alle Ergebnisse bei Fluids?ttigung). Die Zugabe von Ca(OH)₂-Mg(OH)₂ zu CaCO₃-MgCO₃ bei 0.2 GPa senkt den Liquidus auf Temperaturen unter die Solvus-Schwelle von Calcit-Dolomit. Die fluidges?ttigte Liquidusfl?che verl?uft steil und die Grenzfl?che von Schmelze, die mit Calcit und Periklas koexistiert erreicht ein Peritektikum bei 880 °C. Dort ?ffnet sich ein schmales Feld für Liquidus-Dolomit, das bis zum Eutektikum bei 659 °C reicht, an dem Calcit, Dolomit und Periklas (Brucit sollte Periklas bei geringfügig h?heren Drucken ersetzen) gemeinsam ausgeschieden werden. Der Calcit- Liquidus ist sehr gro?. Die Linie an der Calcit und Dolomit koexistieren erstreckt sich ungef?hr von CaMg(CO₃)₂ zu Mg(OH)₂. Die Ergebnisse zeigen die Bildungsbedingungen für die Bildung mineralspezifischer Kumulate aus unterschiedlichen Magmenzusammensetzungen. Aus w?ssrigen (oder Na-reichen) karbonatreichen Schmelzen mit Zusammensetzungen zwischen CaCO₃ und CaMg(CO₃)₂ werden sich zuerst Calcitkarbonatite und dann Calcit-Dolomitkarbonatite ausscheiden, mit der M?glichkeit Dolomitkarbonatite über ein sehr eingeschr?nktes Temperaturintervall zu bilden und mit Periklas, der zu dieser Vergesellschaftung im Endstadium hinzukommt. Periklas im Fe-freien System k?nnte das weitverbreitete Analog zu Magnetit in natürlichen Karbonatiten sein. Der enge Bereich für die Ausscheidung von Dolomitkarbonatiten untermauert die Existenz prim?rer magnesiokarbonatitischer Magmen (nahe der Zusammensetzung von Dolomit). Magnesiokarbonatitische Magmen k?nnen daher entsprechende Mengen an calcitkarbonatitischen Gesteinen ausscheiden.

---

---

Received July 20, 1998;/revised version accepted August 18, 1999     

Phase relations of talc and tremolite in metamorphic calcite-dolomite sediments in the southern portion of the Damara Belt (South West Africa)

The occurrence of talc and tremolite in a temperature gradient was investigated in siliceous calcite-dolomite sediments exposed along a strip in the southeastern part of the Damara Orogen. Five bivariant reactions may lead to the formation of talc and tremolite:

1. 3 dolomite+4 quartz+1 H₂O ? 1 talc+3 calcite+3 CO₂
2. 5 talc+6 calcite+4 quartz ? 1 tremolite+6 CO₂+2 H₂O
3. 2 talc+3 calcite ? 1 tremolite+1 dolomite+1 CO₂+1 H₂O
4. 5 dolomite+8 quartz+1 H₂O ? 1 tremolite+3 calcite+7 CO₂
5. 2 dolomite+1 talc+4 quartz ? 1 tremolite+4 CO₂.

The common paragenesis of four mineral assemblages tc+cc+dol+qtz¹ and tre+tc+ cc+qtz with increasing temperature over an extended area show that the reactions must have taken place along the equilibrium curve or when fluid pressure is not constant along the equilibrium plane of reactions (1) or (2). The described occurrence of the five mineral assemblage tre+tc+cc+dol+qtz can be stable only on the isobaric intersection point, or when P _f is variable on the univariant intersection curve of the equilibrium planes of all five reactions. The genetic relations of the described parageneses are illustrated with the help of a phase diagram. Minimum P-T conditions which prevailed during metamorphism in this part of the Damara Orogen have been estimated to be about 590° C and 5 kb.     

Multiple-step recrystallization within massive ancient dolomite units: an example from the Dinantian of Belgium

South of the Caledonian Brabant-Wales Massif a more than 200 m thick Tournaisian to Lower Visean replacive dolomite unit can be followed for several hundred kilometres from the Boulonnais (France) to Aachen (Germany). Field observations, of features such as karst cavities occurring at the top of the Lower Visean dolomite which are filled by Lower Visean crinoidal limestone, indicate that dolomitization and karstification took place during the Early Visean. This early development of the dolomite is in agreement with the presence of stylolites cutting the dolomite fabric. The minor element composition of the majority of the dolomites remains almost uniform throughout the entire studied area. Values for Fe, Mn, Na and Sr are normally in the range 700–4700 ppm, 15–400 ppm, 80–300 ppm and 50–200 ppm, respectively. The δ¹³C values (range-0.72 to +5.31%_o) mainly reflect the carbon isotopic composition of the precursor limestones. The δ¹⁸O values, in contrast, are highly variable: ranging from-19.15 to +0.85%_o. This rather large range of δ¹⁸O values is explained by multiple-step re-equilibration/recrystallization during progressive burial and subsequent uplift of the dolomites. These processes are also responsible for the high ⁸⁷Sr/⁸⁶Sr values of the dolomites which range from about 0.7088 to 0.7098. They are distinctly more radiogenic than Lower Visean marine carbonates (0.7076–0.7078). Correlation, however, of δ¹⁸O values or ⁸⁷Sr/⁸⁶Sr ratios with dolomite and/or cathodoluminescenec (CL) textures has not been very successful. This suggests that recrystallization may remain unrecognized if only petrographic techniques are used. Nevertheless, certain CL textures can be related to specific interactions with the ambient recrystallizing fluids.     

The kinetics of calcite precipitation from a high salinity water

Calcium carbonate is one of the most common and important scale-forming minerals in oilfield produced water, but the kinetics of CaCO₃ precipitation has been ignored in most scale prediction models because of the lack of reliable precipitation rate model. There are none in the open literature for oilfield conditions (temperature > 100°C, pressure > 200 bar and salinity > 0.5 mol kg− 1). In this work the kinetics of calcite (CaCO₃) precipitation from high salinity waters (up to 2 mol kg⁻¹) have been studied by a pH-free-drift method in a closed water system. This method. is much easier to operate than the often used steady-state method. The experimental results indicate that the calcite precipitation rate is not only affected by the solution CaCO₃ saturation level, but also by the solution pH, ionic strength and the concentration ratios of Ca to HCO₃₋ ions (C_Ca²⁺/C_HCO3⁻). When the concentration ratios of Ca to HCO₃⁻ ions are close to their chemical stoichiometric ratio of 0.5, the calcite growth from a supersaturated solution is believed to be surface reaction controlled. However, at higher C_Ca²⁺C_HCO3⁻ ratios, the transportation of the lattice ions to calcite crystal surface has to be considered.     

Interaction between dissolved silica and calcium carbonate: 1. Spontaneous precipitation of calcium carbonate in the presence of dissolved silica

The kinetics of spontaneous precipitation of CaCO₃ from aqueous solution in the presence of dissolved silica was investigated by recording pH as a function of time. The presence of dissolved silica, at concentrations below saturation with respect to the amorphous phase, decreases induction time for CaCO₃ nucleation, but does not affect CaCO₃ polymorphism. For a “pure” system without silica, the surface free energy, σ, determined from classical nucleation theory is 42 mJ m⁻². This agrees well with values reported in the literature for vaterite and indicates some degree of heterogeneous nucleation, which can occur because of the relatively low degree of supersaturation used for the experiments. In the presence of 1 and 2 mM silica, σ is 37 and 34 mJ m⁻², indicating an increasing degree of heterogeneous nucleation as the amount of polymeric silica increases. The ratio of Ca²⁺ to CO₃²⁻ activity was a governing parameter for determining which CaCO₃ polymorph precipitated. At high Ca²⁺ to CO₃²⁻ activity ratios, almost all initial solid was vaterite, whereas at low ratios, a mixture of vaterite and calcite was observed. In solutions with low Ca²⁺ to CO₃²⁻ activity ratios, the presence of silica at concentrations above saturation with respect to amorphous silica led to formation of only calcite and strongly influenced the crystalline structure and morphology of the precipitates. At high Ca²⁺ to CO₃²⁻ ratios, system behaviour did not differ from that without silica.