Experimentally determined biomediated Sr partition coefficient for dolomite: Significance and implication for natural dolomite

Two strains of moderately halophilic bacteria were grown in aerobic culture experiments containing gel medium to determine the Sr partition coefficient between dolomite and the medium from which it precipitates at 15 to 45 °C. The results demonstrate that Sr incorporation in dolomite does occur not by the substitution of Ca, but rather by Mg. They also suggest that Sr partitioning between the culture medium and the minerals is better described by the Nernst equation (D_Sr^dol = Sr_dol/Sr_bmi), instead of the Henderson and Kracek equation (D_Sr^dol = (Sr/Ca)_dol/(Sr/Ca)_solution. The maximum value for D_Sr^dol occurs at 15 °C in cultures with and without sulfate, while the minimum values occur at 35 °C, where the bacteria exhibit optimal growth. For experiments at 25, 35 and 45 °C, we observed that D_Sr^dol values are greater in cultures with sulfate than in cultures without sulfate, whereas D_Sr^dol values are smaller in cultures with sulfate than in cultures without sulfate at 15 °C.Together, our observations suggest that D_Sr^dol is apparently related to microbial activity, temperature and sulfate concentration, regardless of the convention used to assess the D_Sr^dol. These results have implications for the interpretation of depositional environments of ancient dolomite. The results of our culture experiments show that higher Sr concentrations in ancient dolomite could reflect microbial mediated primary precipitation. In contrast, previous interpretations concluded that high Sr concentrations in ancient dolomites are an indication of secondary replacement of aragonite, which incorporates high Sr concentrations in its crystal lattice, reflecting a diagenetic process.     

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.     

Retrograde fluids in the Archean Shawmere anorthosite, Kapuskasing Structural Zone, Ontario, Canada

The Archean Shawmere anorthosite lies within the granulite facies portion of the Kapuskasing Structural Zone (KSZ), Ontario, and is crosscut by numerous linear alteration veins containing calcite + quartz ± dolomite ± zoisite ± clinozoisite ± margarite ±paragonite ± chlorite. These veins roughly parallel the trend of the Ivanhoe Lake Cataclastic Zone. Equilibria involving clinozoisite + margarite + quartz ± calcite ± plagioclase show that the vein minerals were stable at T < 600 °C, XCO₂ < 0.4 at P ≈ 6 kbar. The stabilities of margarite and paragonite in equilibrium with quartz are also consistent with T < 600 °C and XCO₂ < 0.4 at 6 kbar. Additional assemblages consisting of calcite + clinochlore + quartz + talc + margarite indicate T < 500 °C with XCO₂ > 0.9. Thus, vein formation, while clearly retrograde, spanned a range of temperatures, and fluid compositions evolved from H₂O-rich to CO₂-rich. The calcite in the retrograde veins has δ¹⁸O values that range from 8.4 to 11.2‰ (average = +9.7 ± 0.9‰) and δ¹³C values that range from −3.9 to −1.6‰ (average = −3.1 ± 0.6‰). These values indicate that the fluids from which calcite precipitated underwent extensive exchange with the anorthosite and other crustal lithologies. The fluids may have been initially derived either from devolatilization of metamorphic rocks or crystallization of igneous rocks in the adjacent Abitibi subprovince. Vein quartz contains CO₂-rich fluid inclusions (final melting T = −57.0 to −58.7 °C) that range in size from 5 to 17 μm. Measured homogenization temperatures (T h) range from −44.0 to 14.5 °C, however for most inclusions (46 of S1), T h = −44.0 to −21.1 °C (ρCO₂ ≈ 1.13 to 1.05 g/cm³). At 400 to 600 °C, these densities correspond to pressures of 3.5 to 7 kbar, which is the best estimate of pressures of vein formation. It has been argued that some high density CO₂-rich fluid inclusions found in the KSZ were formed during peak metamorphism and thus document the presence of a CO₂-rich fluid during peak granulite facies metamorphism (Rudnick et al. 1984). The association of high density CO₂-rich fluid inclusions with clearly retrograde veins documents the formation of similar composition and density inclusions after the peak of metamorphism. Thus, the coincidence of entrapment pressures calculated from fluid inclusion density measurements with peak metamorphic pressures alone should not be considered strong evidence for peak metamorphic inclusion entrapment. All fluid inclusion results are consistent with an initially semi-isobaric retrograde P–T path. Received: 2 April 1996 / Accepted: 15 November 1996     

Cation diffusion in aluminosilicate garnets: experimental determination in pyrope-almandine diffusion couples

Diffusion couples made from homogeneous gem quality natural pyrope and almandine garnets were annealed within graphite capsules under anhydrous conditions at 22–40 kbar, 1057–1400 °C in a piston-cylinder apparatus. The concentration profiles that developed in each couple were modeled to retrieve the self diffusion coefficients [D(I)] of the divalent cations Fe, Mg, Mn and Ca. Because of their usually low concentrations and lack of sufficient compositional change across the interface of the diffusion couples, only a few reliable data can be obtained for D(Ca) and D(Mn) from these experiments. However, nine sets of D(Fe) and D(Mg) data were retrieved in the above P-T range, and cast in the form of Arrhenian relation, D=D ₀exp{−[Q(1 bar)+PΔV ⁺]/RT}. The values of the activation energy (Q) and activation volume (ΔV ⁺) depend on whether f _O2 is constrained by graphite in the system C-O or held constant. For the first case, we have for Fe:Q(1 bar)=65,532±10,111 cal/mol, D ₀=3.50 (±2.30)×10⁻⁵ cm²/s, ΔV ⁺=5.6(±2.9) cm³/mol, and for Mg:Q(1 bar)=60,760±8,257 cal/mol, D ₀=4.66 (±2.48)×10⁻⁵ cm²/s, ΔV ⁺=5.3(±3.0) cm³/mol. Here the ΔV ⁺ values have been taken from Chakraborty and Ganguly (1992). For the condition of constant f _O2, the Q values are ∼9 kcal lower and ΔV ⁺ values are ∼4.9 cm³/mol larger than the above values. Lower temperature extrapolation of the Arrhenian relation for D(Mg) is in good agreement with the Mg tracer diffusion data (D ^* _Mg) of Chakraborty and Rubie (1996) and Cygan and Lasaga (1985) at 1 bar, 750–900 °C, when all data are normalized to the same pressure and to f _O2 defined by graphite in the system C-O. The D ^* _Mg data of Schwandt et al. (1995), on the other hand, are lower by more than an order of magnitude than the low temperature extrapolation of the present data, when all data are normalized to the same pressure and to f _O2 defined by the graphite buffer. Comparison of the D(Fe), D(Mg) and D(Mn) data in the pyrope-almandine diffusion couple with those in the spessartine-almandine diffusion couple of Chakraborty and Ganguly (1992) shows that the self diffusion of Fe and Mn are significantly enhanced with the increase in Mn/Mg ratio; the enhancement effect on D(Mg) is, however, relatively small. Proper application of the self diffusion data to calculate interdiffusion coefficient or D matrix elements for the purpose of modeling of diffusion processes in natural garnets must take into account these compositional effects on D(I) along with the effects of thermodynamic nonideality, f _O2, and pressure. Received: 8 May 1997 / Accepted: 2 October 1997     

Structural thermal behavior of paragonite and its dehydroxylate: a high-temperature single-crystal study

 The lattice constants of paragonite-2M₁, NaAl₂(AlSi₃)O₁₀(OH)₂, were determined to 800 °C by the single-crystal diffraction method. Mean thermal expansion coefficients, in the range 25–600 °C, were: α_a = 1.51(8) × 10⁻⁵, α_b = 1.94(6) × 10⁻⁵, α_c = 2.15(7) ×  10⁻⁵ °C⁻¹, and α_V = 5.9(2) × 10⁻⁵ °C⁻¹. At T higher than 600 °C, cell parameters showed a change in expansion rate due to a dehydroxylation process. The structural refinements of natural paragonite, carried out at 25, 210, 450 and 600 °C, before dehydroxylation, showed that the larger thermal expansion along the c parameter was mainly due to interlayer thickness dilatation. In the 25–600 °C range, Si,Al tetrahedra remained quite unchanged, whereas the other polyhedra expanded linearly with expansion rate proportional to their volume. The polyhedron around the interlayer cation Na became more regular with temperature. Tetrahedral rotation angle α changed from 16.2 to 12.9°. The structure of the new phase, nominally NaAl₂ (AlSi₃)O₁₁, obtained as a consequence of dehydroxylation, had a cell volume 4.2% larger than that of paragonite. It was refined at room temperature and its expansion coefficients determined in the range 25–800 °C. The most significant structural difference from paragonite was the presence of Al in fivefold coordination, according to a distorted trigonal bipyramid. Results confirm the structural effects of the dehydration mechanism of micas and dioctahedral 2:1 layer silicates. By combining thermal expansion and compressibility data, the following approximate equation of state in the PTV space was obtained for paragonite: V/V ₀ = 1 + 5.9(2) × 10⁻⁵ T(°C) − 0.00153(4) P(kbar). Received: 12 July 1999 / Revised, accepted: 7 December 1999     

The dolomitization of CaCO3: an experimental study at 252–295°C

The results of experiments on the hydrothermal dolomitization of calcite (between 252 and 295°C) and aragonite (at 252°C) by a 2 M CaCl₂-MgCl₂ aqueous solution are reported and discussed. Dolomitization of calcite proceeds via an intermediate high (ca. 35 mole %) magnesian calcite, whereas that of aragonite is carried out through the conversion of the reactant into a low (5.6 mole %) magnesian calcite which in turn transforms into a high (39.6 mole %) magnesian calcite. Both the intermediate phases and dolomite crystallize through a dissolution-precipitation reaction. The intermediate phases form under local equilibrium within a reaction zone surrounding the dissolving reactant grains. The volume of the reaction zone solution can be estimated from Sr²⁺ and Mg²⁺ partitioning equations. In the case of low magnesian calcite growing at the expense of aragonite at 252°C, the total volume of these zones is in the range of 2 × 10^?5 to 2 × 10^?4 1., out of 5 × 10^?3 1., the volume of the bulk solution.The apparent activation energies for the initial crystallization of high magnesian calcite and dolomite are 48 and 49 kcal/mole, respectively.Calcite transforms completely into dolomite within 100 hr at 252°C. The overall reaction time is reduced to approximately 4 hr at 295°C. The transformation of aragonite to dolomite at 252°C occurs within 24 hr. The nature of the reactant dictates the relative rates of crystallization of the intermediate phases and dolomite. With calcite as reactant, dolomite growth is faster than that of magnesian calcite; this situation is reversed when aragonite is dolomitized.Coprecipitation of Sr²⁺ with dolomite is independent of temperature (within analytical error) between 252 and 295°C. Its partitioning, with respect to calcium, between dolomite and solution results in distribution coefficients in the range of 2.31 × 10^?2 to 2.78 × 10^?2.     

The partitioning of Fe and Mg between olivine and carbonate and the stability of carbonate under mantle conditions

We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K _d (X _Fe ^carb X _Mg ^ol /X _Fe ^ol X _Mg ^carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W _FeMg ^ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO₃ a W _FeMg ^carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K _d substantially enabling us to calculate W _CaMg ^carb -W _CaFe ^carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO₂(CMS)–CO₂ system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO₂. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.     

The dependence of the partitioning of iron and europium between plagioclase and hydrous tonalitic melt on oxygen fugacity

The dependence of iron and europium partitioning between plagioclase and melt on oxygen fugacity was studied in the system SiO₂(Qz)—NaAlSi₃O₈(Ab)—CaAl₂Si₂O₈(An)—H₂O. Experiments were performed at 500 MPa and 850 °C/750 °C under water saturated conditions. The oxygen fugacity was varied in the log f _O2-range from −7.27 to −15.78. To work at the most reducing conditions the classical double-capsule technique was modified. The sample and a C—O—H bearing sensor capsule were placed next to each other within a BN jacket to minimise loss of hydrogen to the vessel atmosphere. By this setup redox conditions slightly more reducing than the FeO—Fe₃O₄ buffer could be maintained even in 96 h runs. Raman spectra showed that the BN was modified by reaction with hydrogen resulting in a low hydrogen permeability. The partition coefficients determined for Eu at 850 °C and 500 MPa vary from 0.095 at conditions of the Cu—Cu₂O buffer to 1.81 at the most reducing conditions (C—O—H sensor). In the same f _O2 interval the partition coefficient for Fe varies from 0.55 at oxidising conditions to 0.08 at the most reducing conditions. The partitioning of Sm, which was added as a reference for a trivalent REE, does not vary with the oxygen fugacity, yielding an average value for D = 0.07. Lowering the temperature to 750 °C for a given f _O2 decreases the partition coefficient of Eu and increases that of Fe. Comparison with published data at 1 atm and at higher temperatures shows that both temperature and composition of the melt have strong effects on the partitioning behaviour. As the change of the partition coefficients in the geologically relevant f _O2 range is quite strong, element partitioning of Eu and Fe might be used to estimate redox conditions for the genesis of igneous rocks. Furthermore, by modelling the partitioning data it is possible to extract information about the redox state of the melt. Resulting ferric-ferrous ratios show significant differences from those predicted by empirical models. Received: 14 October 1998 / Received: 5 March 1999     

Low T heat capacity measurements and new entropy data for titanite (sphene): implications for thermobarometry of high-pressure rocks

The accepted standard state entropy of titanite (sphene) has been questioned in several recent studies, which suggested a revision from the literature value 129.3 ± 0.8 J/mol K to values in the range of 110–120 J/mol K. The heat capacity of titanite was therefore re-measured with a PPMS in the range 5 to 300 K and the standard entropy of titanite was calculated as 127.2 ± 0.2 J/mol K, much closer to the original data than the suggested revisions. Volume parameters for a modified Murgnahan equation of state: V _P,T  = V ₂₉₈° × [1 + a°(T − 298) − 20a°(T − 298)] × [1 – 4P/(K ₂₉₈ × (1 – 1.5 × 10⁻⁴ [T − 298]) + 4P)]^1/4 were fit to recent unit cell determinations at elevated pressures and temperatures, yielding the constants V ₂₉₈° = 5.568 J/bar, a° = 3.1 × 10⁻⁵ K⁻¹, and K = 1,100 kbar. The standard Gibbs free energy of formation of titanite, −2456.2 kJ/mol (∆H°_f = −2598.4 kJ/mol) was calculated from the new entropy and volume data combined with data from experimental reversals on the reaction, titanite + kyanite = anorthite + rutile. This value is 4–11 kJ/mol less negative than that obtained from experimental determinations of the enthalpy of formation, and it is slightly more negative than values given in internally consistent databases. The displacement of most calculated phase equilibria involving titanite is not large except for reactions with small ∆S. Re-calculated baric estimates for several metamorphic suites yield pressure differences on the order of 2 kbar in eclogites and 10 kbar for ultra-high pressure titanite-bearing assemblages.     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln=Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1,100 K) and SmCaAl[Al₂O₇] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶ K⁻¹+3.6(7)×10⁻⁹ΔT K⁻² and α₃=15.0(1)×10⁻⁶ K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶ K⁻¹+2.0(2)×10⁻⁹ΔT K⁻² and α₃=8.5(2)×10⁻⁶ K⁻¹+2.0(3)×10⁻⁹ΔT K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)× 10⁻⁶ K⁻¹+1.7(2)×10⁻⁹ΔT K⁻² and α₃=9.344(5)×10⁻⁶ K⁻¹. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)-(Ln ³⁺+Al³⁺) in the melilite-type structure. Electronic Supplementary Material Supplementary material is available for this article at     

Trends in phosphatase activity along a successional gradient of tidal freshwater marshes on the Cooper River South Carolina

Phosphatase activity was measured in sediments from tidal freshwater habitats adjacent to the Cooper River in South Carolina representing different stages of ecological succession. It was found that sediment (0–5 cm) acid phosphatase activity, alkaline phosphatase activity and phosphodiesterase activity increased with increasing successional stage and phytomass. Acid phosphatase activity in creased from 7.5±1.2 (±1 SD) in subtidal sediment from a shallow open water habitat without vegetation to 61.2±4.9 μmol g⁻¹ hr⁻¹ (μmol of p-nitrophenol released per gram of dry sediment per hour) in intertidal sediments colonized by emergent macrophytes, while alkaline phosphatase activity increased from 2.1±0.1 to 19.01±1.5 μmol g⁻¹ hr⁻¹. Phosphodiesterase activity increased from 1.8±0.1 to 20.2±2.0 μmol g⁻¹ hr⁻¹ along the same gradient. Acid phosphatase activity was highly correlated (R²=0.92, P<0.001) with the organic matter content of the sediment. A study of phosphatase kinetics showed that V_max of all phosphatases also increased along the successional gradient. Trends in phosphatase activity and V_max correlated positively with plant biomass and negatively with concentrations of soluble reactive phosphorus in porewater, sediment extractable phosphorus, and total phosphourus. The porewater N∶P atom ratio decreased along the succession gradient from 25.3 in an early stage, open water community to 13.0 in a community dominated by emergent vegetation. The data also show that the distribution of the forms of phosphorus changed with successional stage. The change in distribution and the increased biological demand for phosphorus that paralleled succession were mediated by the activity of phosphatase enzymes.     

Origin of the Rubian carbonate-hosted magnesite deposit, Galicia, NW Spain: mineralogical, REE, fluid inclusion and isotope evidence

The Rubian magnesite deposit (West Asturian—Leonese Zone, Iberian Variscan belt) is hosted by a 100-m-thick folded and metamorphosed Lower Cambrian carbonate/siliciclastic metasedimentary sequence—the Cándana Limestone Formation. It comprises upper (20-m thickness) and lower (17-m thickness) lens-shaped ore bodies separated by 55 m of slates and micaceous schists. The main (lower) magnesite ore body comprises a package of magnesite beds with dolomite-rich intercalations, sandwiched between slates and micaceous schists. In the upper ore body, the magnesite beds are thinner (centimetre scale mainly) and occur between slate beds. Mafic dolerite dykes intrude the mineralisation. The mineralisation passes eastwards into sequence of bedded dolostone (Buxan) and laminated to banded calcitic marble (Mao). These show significant Variscan extensional shearing or fold-related deformation, whereas neither Rubian dolomite nor magnesite show evidence of tectonic disturbance. This suggests that the dolomitisation and magnesite formation postdate the main Variscan deformation. In addition, the morphology of magnesite crystals and primary fluid inclusions indicate that magnesite is a neoformed hydrothermal mineral. Magnesite contains irregularly distributed dolomite inclusions (<50 μm) and these are interpreted as relics of a metasomatically replaced dolostone precursor. The total rare earth element (REE) contents of magnesite are very similar to those of Buxan dolostone but are depleted in light rare earth elements (LREE); heavy rare earth element concentrations are comparable. However, magnesite REE chondrite normalised profiles lack any characteristic anomaly indicative of marine environment. Compared with Mao calcite, magnesite is distinct in terms of both REE concentrations and patterns. Fluid inclusion studies show that the mineralising fluids were MgCl₂–NaCl–CaCl₂–H₂O aqueous brines exhibiting highly variable salinities (3.3 to 29.5 wt.% salts). This may be the result of a combination of fluid mixing, migration of pulses of variable-salinity brines and/or local dissolution and replacement processes of the host dolostone. Fluid inclusion data and comparison with other N Iberian dolostone-hosted metasomatic deposits suggest that Rubian magnesite probably formed at temperatures between 160 and 200°C. This corresponds, at hydrostatic pressure (500 bar), to a depth of formation of ~~5 km. Mineralisation-related Rubian dolomite yields δ ¹⁸O values (δ ¹⁸O: 12.0–15.4‰, mean: 14.4±1.1‰) depleted by around 5‰ compared with barren Buxan dolomite (δ ¹⁸O: 17.1–20.2‰, mean: 19.4±1.0‰). This was interpreted to reflect an influx of ¹⁸O-depleted waters accompanied by a temperature increase in a fluid-dominated system. Overlapping calculated δ ¹⁸O_fluid values (~+5‰ at 200°C) for fluids in equilibrium with Rubian dolomite and magnesite show that they were formed by the same hydrothermal system at different temperatures. In terms of δ ¹³C values, Rubian dolomite (δ ¹³C: −1.4 to 1.9‰, mean: 0.4±1.3‰) and magnesite (δ ¹³C: −2.3 to 2.4‰, mean: 0.60±1.0‰) generally exhibit more negative δ ¹³C values compared with Buxan dolomite (δ ¹³C: −0.2 to 1.9‰, mean: 0.8±0.6‰) and Mao calcite (δ ¹³C: −0.3 to 1.5‰, mean: 0.6±0.6‰), indicating progressive modification to lower δ ¹³C values through interaction with hydrothermal fluids. ⁸⁷Sr/⁸⁶Sr ratios, calculated at 290 Ma, vary from 0.70849 to 0.70976 for the Mao calcite and from 0.70538 to 0.70880 for the Buxan dolostone. The ⁸⁷Sr/⁸⁶Sr ratios in Rubian magnesite are more radiogenic and range from 0.71123 to 0.71494. The combined δ ¹⁸O–δ ¹³C and ⁸⁷Sr/⁸⁶Sr data indicate that the magnesite-related fluids were modified basinal brines that have reacted and equilibrated with intercalated siliciclastic rocks. Magnesite formation is genetically linked to regional hydrothermal dolomitisation associated with lithospheric delamination, late-Variscan high heat flow and extensional tectonics in the NW Iberian Belt. A comparison with genetic models for the Puebla de Lillo talc deposits suggests that the formation of hydrothermal replacive magnesite at Rubian resulted from a metasomatic column with magnesite forming at higher fluid/rock ratios than dolomite. In this study, magnesite generation took place via the local reaction of hydrothermal dolostone with the same hydrothermal fluids in very high permeability zones at high fluid/rock ratios (e.g. faults). It was also possibly aided by additional heat from intrusive dykes or sub-cropping igneous bodies. This would locally raise isotherms enabling a transition from the dolomite stability field to that of magnesite.Editorial handling: F. Tornos     

Volume and grain boundary diffusion of calcium in natural and hot-pressed calcite aggregates

 Calcium self-diffusion rates in natural calcite single crystals were experimentally determined at 700 to 900° C and 0.1 MPa in a stream of CO₂. Diffusion coefficients (D) were determined from ⁴²Ca concentration profiles measured with an ion microprobe. The Arrhenius parameters yield an activation energy (Q)=382±37 kJ/mol and pre-exponential factor (D₀)=0.13 m²/s, and there is no measurable anisotropy. Calcium grain boundary diffusion rates were experimentally determined in natural (Solnhofen) limestone and hot-pressed calcite aggregates at 650° to 850° C and 0.1 to 100 MPa pressure. The Solnhofen limestone was first pre-annealed for 24 h at 700° C and 100 MPa confining pressure under anhydrous conditions to produce an equilibrium microstructure for the diffusion experiments. Values for the product of the grain boundary diffusion coefficient (D′) and the effective grain boundary diffusion width (δ) were determined from ⁴²Ca concentration profiles measured with an ion microprobe. The results show that there is no measurable difference between D′δ values obtained for pre-annealed Solnhofen samples at 0.1 and 100 MPa or between hot-pressed calcite aggregates and pre-annealed Solnhofen samples. The temperature dependence for calcium grain boundary diffusion in Solnhofen samples annealed at 0.1 MPa is described by the Arrhenius parameters D^′ ₀δ=1.5×10⁻⁹ m³/s and Q=267±47 kJ/mol. Comparison of the results of this study with previously published data show that calcium is the slowest volume diffusing species in calcite. The calcium diffusivities measured in this study place constraints on several geological processes that involve diffusive mass transfer including diffusion-accommodated mechanisms in the deformation of calcite rocks. Received: 19 December 1994/Accepted: 30 June 1995     

Origin of ultramafic-hosted magnesite on Margarita Island,Venezuela

Ultramafic-hosted deposits of magnesite (MgCO₃) have been studied on Margarita Island, Venezuela, to elucidate the source of carbon and conditions of formation for this type of ore. Petrographic, mineralogic, and δ¹⁸O data indicate that magnesite precipitated on Margarita in near-surface environments at low P and T. δ¹³C ranges from −9 to −16‰ PDB within the magnesite and −8 to −10‰ PDB within some calcite and dolomite elsewhere on the island. The isotopically light dolomite fills karst and the calcite occurs as stock-work veins which resemble the magnesite deposits. These carbon isotopic ratios are consistent with a deep-seated source rather than an overlying source from a zone of surficial weathering. However, there is not much enrichment of precious metals and no enrichment of heavy rare-earth elements, as would be expected if the carbon had migrated upward as aqueous carbonate ions. The carbon probably has risen as a gaseous mixture of CO₂ and CH₄ which partially dissolved in near-surface water before leaching cations and precipitating as magnesite and other carbonates. The process probably is ongoing, given regional exhalation of carbonaceous gases.     

Cr and Al diffusion in chromite spinel: experimental determination and its implication for diffusion creep

Diffusion coefficients of Cr and Al in chromite spinel have been determined at pressures ranging from 3 to 7 GPa and temperatures ranging from 1,400 to 1,700°C by using the diffusion couple of natural single crystals of MgAl₂O₄ spinel and chromite. The interdiffusion coefficient of Cr–Al as a function of Cr# (=Cr/(Cr + Al)) was determined as D _Cr–Al = D ₀ exp {−(Q′ + PV*)/RT}, where D ₀ = exp{(10.3 ± 0.08) × Cr#^0.54±0.02} + (1170 ± 31.2) cm²/s, Q′ = 520 ± 81 kJ/mol at 3 GPa, and V* = 1.36 ± 0.25 cm³/mol at 1,600°C, which is applicable up to Cr# = 0.8. The estimation of the self-diffusion coefficients of Cr and Al from Cr–Al interdiffusion shows that the diffusivity of Cr is more than one order of magnitude smaller than that of Al. These results are in agreement with patterns of multipolar Cr–Al zoning observed in natural chromite spinel samples deformed by diffusion creep.     

Fluid infiltration during contact metamorphism of interbedded marble and calc-silicate hornfels, Twin Lakes area, central Sierra Nevada, California

Abstract In the Twin Lakes area, central Sierra Nevada, California, most contact metamorphosed marbles contain calcite + dolomite + forsterite ± diopside ± phlogopite ± tremolite, and most calc-silicate hornfelses contain calcite + diopside + wollastonite + quartz ± anorthite ± K-feldspar ± grossular ± titanite. Mineral-fluid equilibria involving calcite + dolomite + tremolite + diopside + forsterite in two marble samples and wollastonite + anorthite + quartz + grossular in three hornfels samples record P± 3 kbar and T± 630° C. Various isobaric univariant assemblages record CO₂-H₂O fluid compositions of χCO₂= 0.61–0.74 in the marbles and χCO₂= 0.11 in the hornfelses. Assuming a siliceous dolomitic limestone protolith consisting of dolomite + quartz ° Calcite ± K-feldspar ± muscovite ± rutile, all plausible prograde reaction pathways were deduced for marble and hornfels on isobaric T-XCO₂ diagrams in the model system K₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O-CO₂. Progress of the prograde reactions was estimated from measured modes and mass-balance calculations. Time-integrated fluxes of reactive fluid which infiltrated samples were computed for a temperature gradient of 150 °C/km along the fluid flow path, calculated fluid compositions, and estimated reaction progress using the mass-continuity equation. Marbles and hornfelses record values in the range 0.1–3.6 × 10⁴ cm³/cm² and 4.8–12.9 × 10⁴ cm³/cm², respectively. For an estimated duration of metamorphism of 10⁵ years, average in situ metamorphic rock permeabilities, calculated from Darcy's Law, are 0.1–8 × 10^?6 D in the marbles and 10–27 × 10^?6 D in the hornfelses. Reactive metamorphic fluids flowed up-temperature, and were preferentially channellized in hornfelses relative to the marbles. These results appear to give a general characterization of hydrothermal activity during contact metamorphism of small pendants and screens (dimensions ± 1 km or less) associated with emplacement of the Sierra Nevada batholith.     

Double carbonate breakdown reactions at high pressures: an experimental study in the system CaO–MgO–FeO–MnO–CO2

The pressure–temperature conditions of the reactions of the double carbonates CaM(CO₃)₂, where M = Mg (dolomite), Fe (ankerite) and Mn (kutnohorite), to MCO₃ plus CaCO₃ (aragonite) have been investigated at 5–8 GPa, 600–1,100°C, using multi-anvil apparatus. The reaction dolomite = magnesite + aragonite is in good agreement with the results of Sato and Katsura (Earth Planet Sci 184:529–534, 2001), but in poor agreement with the results of Luth (Contrib Mineral Petrol 141:222–232, 2001). The dolomite is partially disordered at 620°C, and fully disordered at 1,100°C. All ankerite and kutnohorite samples, including the synthetic starting materials, are disordered. The P–T slopes of the three reactions increase in the order M = Mg, Fe, Mn. The shallower slope for the reaction involving magnesite is due partly to its having a higher compressibility than expected from unit-cell volume considerations. At low pressures there is a preference for partitioning into the double carbonate of Mg > Fe > Mn. At high pressures the partitioning preference is reversed. Using the measured reaction positions, the P–T conditions at which dolomite solid solutions will break down on increasing P and T in subduction zones can be estimated.     

Behavior of epidote at high pressure and high temperature: a powder diffraction study up to 10 GPa and 1,200 K

The thermo-elastic behavior of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH)] has been investigated up to 1,200 K (at 0.0001 GPa) and 10 GPa (at 298 K) by means of in situ synchrotron powder diffraction. No phase transition has been observed within the temperature and pressure range investigated. P–V data fitted with a third-order Birch–Murnaghan equation of state (BM-EoS) give V ₀ = 458.8(1)ų, K _T0 = 111(3) GPa, and K′ = 7.6(7). The confidence ellipse from the variance–covariance matrix of K _T0 and K′ from the least-square procedure is strongly elongated with negative slope. The evolution of the “Eulerian finite strain” vs “normalized stress” yields Fe(0) = 114(1) GPa as intercept values, and the slope of the regression line gives K′ = 7.0(4). The evolution of the lattice parameters with pressure is slightly anisotropic. The elastic parameters calculated with a linearized BM-EoS are: a ₀ = 8.8877(7) Å, K _T0(a) = 117(2) GPa, and K′(a) = 3.7(4) for the a-axis; b ₀ = 5.6271(7) Å, K _T0(b) = 126(3) GPa, and K′(b) = 12(1) for the b-axis; and c ₀ = 10.1527(7) Å, K _T0(c) = 90(1) GPa, and K’(c) = 8.1(4) for the c-axis [K _T0(a):K _T0(b):K _T0(c) = 1.30:1.40:1]. The β angle decreases with pressure, β_P(°) = β_P0 −0.0286(9)P +0.00134(9)P ² (P in GPa). The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α₀ + α₁ T ^−1/2. The refined parameters for epidote are: α₀ = 5.1(2) × 10⁻⁵ K⁻¹ and α₁ = −5.1(6) × 10⁻⁴ K^1/2 for the unit-cell volume, α₀(a) = 1.21(7) × 10⁻⁵ K⁻¹ and α₁(a) = −1.2(2) × 10⁻⁴ K^1/2 for the a-axis, α₀(b) = 1.88(7) × 10⁻⁵ K⁻¹ and α₁(b) = −1.7(2) × 10⁻⁴ K^1/2 for the b-axis, and α₀(c) = 2.14(9) × 10⁻⁵ K⁻¹ and α₁(c) = −2.0(2) × 10⁻⁴ K^1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α₀(a): α₀(b): α₀(c) = 1 : 1.55 : 1.77. The β angle increases continuously with T, with β_T(°) = β_T0 + 2.5(1) × 10⁻⁴ T + 1.3(7) × 10⁻⁸ T ². A comparison between the thermo-elastic parameters of epidote and clinozoisite is carried out.     

Ca-Mg inter-diffusion in synthetic polycrystalline dolomite-calcite aggregate at elevated temperatures and pressure

This study measures the reaction rate of dolomite and aragonite (calcite) into Mg-calcite at 800, 850, and 900°C and 1.6 GPa. The dry synthetic dolomite-aragonite aggregate transformed very rapidly into dolomite-calcite polycrystalline aggregate while Mg-calcites formed at a relatively slow rate, becoming progressively richer in Mg with run time. We modeled the reaction progress semi-empirically by the first-order rate law. The temperature dependence of the overall transport rate of MgCO₃ into calcite can be described by the kinetic parameters (E?=?231.7 kJ/mol and A _o ?=?22.69 h^?1). Extrapolation using the Arrhenius equation to the conditions during exhumation of UHPM rocks indicates that the reaction of dolomite with aragonite into Mg-saturated calcite can be completed as the P-T path enters the Mg-calcite stability field in a geologically short time period (<1 Ky). On the other hand, the extrapolation of the rate to prograde metamorphic conditions reveals that the Mg-calcite formed from dolomitic marble in the absence of metamorphic fluid may not reach Mg-saturation until temperatures corresponding to high-grade metamorphism (e.g., >340°C and >10 My). SEM-EDS analysis of individual calcite grains shows compositional gradients of Mg in the calcite grains. The Mg-Ca inter-diffusion coefficient at 850°C is around 1.68?×?10^?14 m²/sec if diffusion is the major control of the reaction. The calculated closure temperatures for Ca-Mg inter-diffusion as a function of cooling rate and grain size reveal that Ca/Mg resetting in calcite in a dry polycrystalline carbonate aggregate (with grain size around 1 mm) may not occur at temperatures below 480°C at a geological cooling rate around 10°C/My, unless other processes, such as short-circuit interdiffusion along grain boundaries and dislocations, are involved.     

Epithermal mineralization and ore controls of the Shasta Au-Ag deposit, Toodoggone District, British Columbia, Canada

The Shasta gold-silver deposit, British Columbia, Canada, is an adularia-sericite-type epithermal deposit in which deposition of precious metals coincided with the transition of quartz- to calcite-dominant gangue. Mineralization is associated with stockwork-breccia zones in potassically altered dacitic lapilli tuffs and flows, and consists of pyrite, sphalerite, chalcopyrite, galena, acanthite, electrum and native silver. Pre- and post-ore veins consist solely of quartz and calcite, respectively. Fluid inclusion microthermometry indicates that ore minerals were deposited between 280 ° and 225 °C, from a relatively dilute hydrothermal fluid (˜1.5 wt.% NaCl equivalent). Abundant vapor-rich inclusions in ore-stage calcite are consistent with boiling. Oxygen and hydrogen isotopic data (δ¹⁸O_fluid = −1.5 to −4.1‰; δD_fluid = −148 to −171‰) suggest that the fluid had a meteoric origin, but was ¹⁸O-enriched by interaction with volcanic wallrocks. Initial (˜280 °C) fluid pH and log f O₂ conditions are estimated at 5.3 to 6.0, and −32.5 to −33 bar, respectively; during ore deposition, the fluid became more alkaline and oxidizing. Ore deposition at Shasta is attributed to localization of meteoric hydrothermal fluids by extensional faults; mineralization was controlled by boiling in response to hydraulic brecciation. Calcite and base metal sulfides precipitated due to the increase in pH that accompanied boiling, and the associated decrease in H₂S concentration led to precipitation of gold and silver. Received: 23 February 1995 / Accepted: 16 April 1996