Experimental investigation of the mechanism of the reaction: 1 tremolite+11 dolomite ⇌ 8 forsterite+13 calcite+9 CO2+1H2O

Stoichiometric mixtures of tremolite and dolomite were heated to 50° C above equilibrium temperatures to form forsterite and calcite. The pressure of the CO₂-H₂O fluid was 5 Kb and \(X_{{\text{CO}}_{\text{2}} }\) varied from 0.1 to 0.6. The extent of the conversion was determined by the amount of CO₂ produced. The resulting mixtures of unreacted tremolite and dolomite and of newly-formed forsterite and calcite were examined with a scanning electron microscope. All tremolite and dolomite grains showed obvious signs of dissolution. At fluid compositions with \(X_{{\text{CO}}_{\text{2}} }\) less than about 0.4, the forsterite and calcite crystals are randomly distributed throughout the charges, indicating that surfaces of the reactants are not a controlling factor with respect to the sites of nucleation of the products. A change is observed when \(X_{{\text{CO}}_{\text{2}} }\) is greater than about 0.4; the forsterite and calcite crystals now nucleate and grow at the surface of the dolomite grains, thus indicating a change in mechanism at medium CO₂ concentrations. As the reaction progresses, the dolomite grains become more and more surrounded by forsterite and calcite, finally forming armoured relics of dolomite. Under experimental conditions this characteristic texture can only be formed if the CO₂-concentration is greater than about 40 mole %. These findings make it possible to estimate the CO₂-concentration from the texture of the dolomite+tremolite+forsterite+calcite assemblage. The results suggest a dissolution-precipitation mechanism for the reaction investigated. In a simplified form it consists of the following 4 steps:

1. Dissolution of the reactants tremolite and dolomite.
2. Diffusion of the dissolved constituents in the fluid.
3. Heterogeneous nucleation of the product minerals.
4. Growth of forsterite and calcite from the fluid.

Two possible explanations are discussed for the development of the amoured texture at \(X_{{\text{CO}}_{\text{2}} }\) above 0.4. The first is based upon the assumption that dolomite has a lower rate of dissolution than tremolite at high \(X_{{\text{CO}}_{\text{2}} }\) values resulting in preferential calcite and forsterite nucleation and growth on the dolomite surface. An alternative explanation is the formation of a raised CO₂ concentration around the dolomite grains at high \(X_{{\text{CO}}_{\text{2}} }\) values, leading to product precipitation on the dolomite crystals.     

Mechanism and kinetics of the reaction: 1 dolomite + 2 quartz = 1 diopside + 2 CO2: a comparison of rock-sample and of powder experiments

Two experiments using cylindrical samples of a dolomite-quartz rock were carried out in a conventional hydrothermal apparatus for the forward reaction: 1 dolomite + 2 quartz = 1 diopside + 2 CO₂, in order to compare the mechanism and the kinetics with results from experiments using mineral powders of dolomite and quartz at the same P-T-X conditions. Experimental conditions were as follows: total pressure 500 MPa; temperature 680° C (overstepping 65° C); CO₂ content of the fluid phase, consisting of carbon dioxide and water, was nearly 90 mol%; the fluid/rock ratio was 1:37, and the H₂O/rock ratio was about 1:740; run duration was 92 days. Scanning electron microscope (SEM) examination of a polished axial section of the rock cylinders after the run, using back-scattered electrons (BSE), shows that the reaction produced corona textures. The diopside crystals nucleate and grow exclusively on dolomite surfaces adjacent to quartz grains, i.e. in regions where there is intimate contact between the reactants. The dolomite matrix, in contrast, is diopside free. A concept of microsystems is used to compare directly the rock cylinder results with those from runs done with mineral powders. The microsystems, which consist of quartz, dolomite and diopside, are connected by the intergranular space which is filled by the fluid phase. The SEM analysis of the rock cylinders indicates a dissolution-crystallization mechanism operating in the microsystems; this is consistent with the results of experiments using dolomite quartz powders (Lüttge et al. 1989). It can be demonstrated that reaction kinetics in mineral powder runs are interface controlled as long as the newly formed diopside crystals do not cover the dolomite surfaces completely (Lüttge and Metz 1991 c). This result is applicable to each microsystem of the rock cylinder, since the reaction mechanism and the resulting textures are the same in both kinds of experiments. The reaction is much slower outside the microsystems, i.e. in the dolomite matrix but in the close vicinity of the quartz grains. At these places, the reaction is controlled by the transport of Si-species in the CO₂-rich fluid phase filling the intergranular space. The reaction is absent in quartz-free regions of the dolomite matrix. Calculations and measurements of the extent of reaction progress in both kinds of experiments give results of the same order of magnitude: the conversion, and therefore the reaction rate, differs by less than a factor of two. The conclusion is that there are no differences, in principle, concerning mechanisms, rate controls, rates, and resulting textures between rock cylinder experiments, and mineral powder experiments.     

Die obere Stabilitätsgrenze von Tremolit bei der Metamorphose von kieseligen Karbonaten

During the metamorphism of siliceous carbonates, decomposition of tremolite yields diopside, enstatite, quartz and H₂O according to the following reaction: 1 tremolite 2 diopside + 3 enstatite + 1 quartz + 1 H₂O.For the application to natural processes, it is of special interest to evaluate the equilibrium temperature of this reaction, as a function of the CO₂-content of the H₂O-CO₂ fluid phase for several total pressures. These values were calculated for the total pressures of 1000 and 2000 bars, usingBoyd's experimentally determined univariant equilibrium data [Fig. 1 (Boyd, 1954 and 1959)]. Curves (a) and (b) of Fig. 3 give the results in a temperature-X _{CO 2}-diagram.The decomposition curves of tremolite intersect the equilibrium curves of other reactions which also take place during metamorphism of siliceous carbonates. If the total pressure can be estimated, these points of intersection together with the appropriate field observations will give information on the temperature and composition of the fluid phase during metamorphism.     

Experimentelle Untersuchung der Metamorphose von kieselig dolomitischen Sedimenten

The equilibrium conditions of the following diospide forming reactions have been determined: 1 tremolite+3 calcite+2 quartz 5 diopside+3 CO₂+1 H₂O (6) 1 Ca₂Mg₅[(OH)₂Si₈O₂₂]+3 CaCO₃+2 SiO₂ 5 CaMg[Si₂O₆]+3 CO₂+1 H₂O 1 tremolite+3 calcite 4 diopside+1 dolomite+1 CO₂+1 H₂O (7) 1 Ca₂Mg₅[(OH)₂Si₈O₂₂]+3 CaCO₃ 4 CaMg[Si₂O₆]+1 CaMg(CO₃)₂+1 CO₂+1 H₂O 1 dolomite+2 quartz 1 diopside+2 CO₂ (8) 1 CaMg(CO₃)₂+2 SiO₂ 1 CaMg[Si₂O₆]+2 CO₂ The experimentally determined equilibrium data of the heterogeneous bivariant reaction (6) are shown in the temperature- -diagram of Fig. 6. For the total fluid pressures of 500 and 1,000 bars the equilibrium temperatures valid for -values >0.75 were calculated using equilibrium constants derived from experimental equilibrium data at smaller values of , and fugacities of CO₂ and H₂O (see Fig. 7). The equilibrium data of reaction (6) were also calculated thermodynamically for the total fluid pressure of 500 and 1,000 bars (see Fig. 3). The results found by this method agree well with those of the experimental investigation (see Figs. 8 and 9). The equilibrium data of the heterogeneous univariant reaction (8) were calculated thermodynamically only (see Fig. 10), because an experimental determination has not been successful so far. The calculated decrease of the equilibrium temperature of reaction (8) caused by a decrease of the CO₂-concentration and a corresponding increase of the H₂O-concentration is shown in Fig. 11. Combining this curve and the equilibrium curve of reaction (6) determined at a fluid pressure of 1,000 bars, an isobaric invariant point of intersection results [see Fig. 12 and also point (II) in Fig. 2 of Metz and Trommsdorff (1968)]. From this point of intersection two further equilibrium curves radiate, i.e. the isobaric univariant equilibrium curves of the reaction (4) (not investigated in this paper) and (7) (see Fig. 14); this follows from phase theory. The equilibrium data of the heterogeneous bivariant reaction (7) were calculated thermodynamically for the total fluid pressure of 1,000 bars. The calculated -curve, since precisely meeting the isobaric invariant point (II), is very well consistent with the equilibrium data of reactions (6) and (8).During metamorphism of siliceous dolomites diopside is formed almost exclusively by reaction (6). In Fig. 15 the equilibrium data of this reaction are shown in a P _f -temperature-diagram (P _f is the total fluid pressure). In this diagram the maximum temperatures at which diopside is formed correspond to the temperature-maxima of the -equilibrium curves of Fig. 6. The temperature range shown in Fig. 15 covers all equilibrium temperatures for -values from 0.1 to approx. 1.0; the extremely low temperatures of diopside formation valid for <0.1 are not included. Generally, however, such low CO₂ concentrations are not to be expected in the process of diopside formation during the progressive metamorphism of siliceous dolomites, because the formation of tremolite consuming H₂O and liberating CO₂ is the preceeding reaction at lower temperatures. Apart from the conditions of diopside formation, Fig. 15 includes the pressure-temperature data of staurolite formation (Hoschek, 1965–1969; Richardson, 1968; Ganguly and Newton, 1968). The equilibrium data of both reactions show that the formation of staurolite in FeO-rich pelitic sediments coincides with diopside formation in siliceous dolomites only at pressures below approx. 1 kb. This is realized during shallow contact metamorphism; while at higher pressures the formation of diopside takes place at higher temperatures than the formation of staurolite. These statements which are results of equilibrium data determined experimentally very well agree with petrographic observations, e.g. in the contact aureole of Bergell granite, and in the regional metamorphism of the Lepontine Alps (E. Niggli, 1960; E. Niggli and C. E. Niggli, 1965; Trommsdorff, 1966).     

Antigorite-ophicarbonates: Phase relations in a portion of the system CaO-MgO-SiO2-H2O-CO2

The occurrence of critical assemblages among antigorite, diopside, tremolite, forsterite, talc, calcite, dolomite and magnesite in progressively metamorphosed ophicarbonate rocks, together with experimental data, permits the construction of phase diagrams in terms of the variables P, T, and composition of a binary CO₂-H₂O fluid. Equilibrium constants are given for the 30 equilibria that describe all relations among the above phases. Ophicalcite, ophidolomite, and ophimagnesite assemblages occupy partially overlapping fields in the diagram. The upper temperature limit of ophicalcite rocks lies below that of ophidolomite and ophimagnesite. The fluid phase in ophicarbonate rocks has 0.8$$ " align="middle" border="0"> , and there are indications that during their progressive metamorphism is approximately equal to P _total.     

Phase relations and metamorphic history of a clinohumite-chlorite-serpentine-marble from the Western Tauern Area (Austria)

Several different metamorphic events — an early or prevariscian regional, a variscian contact and the alpine regional — on marbles from the Schlegeistal (Western Tauern Area, Tyrol, Austria) have resulted in a great variety of mineral assemblages. These assemblages include calcite, dolomite, tremolite, diopside, forsterite, clinohumite-titanianclinohumite-chondrodite, chlorite-serpentine, brucite, and boron minerals karlite and ludwigite.Microprobe analysis fo the minerals indicate that three different generations of chlorite minerals exist (clinochlor, penninite, Al-serpentine). The occurence of these chlorites is explained by formation of serpentine component during the last (alpine) regional metamorphism from the breakdown of forsterite, humite-minerals and diopside. The phase relations are described in the system CaO-MgO-SiO₂-H₂O-CO₂-HF and a petrogenetic grid for the low low X _F ^mineral region is given. The reactions are typical for ophicarbonate rocks, but include clinohumite and chlorite, due to the presence of F and minor amounts of Al₂O₃.     

Mechanism and kinetics of pseudomorphic mineral replacement reactions: A case study of the replacement of pentlandite by violarite

Although pseudomorphic mineral replacement reactions are common in all geological environments, and have long been considered important to many geological processes such as metamorphism, metasomatism, diagenesis, and chemical weathering, their mechanisms are still not well known. We present a combined textural and kinetic study of the replacement of pentlandite, (Fe,Ni)₉S₈, by violarite (NiFe)₃S₄, and describe the mechanisms and kinetic behavior of this reaction by considering the role of the fluid phase, the causes of coupling between pentlandite dissolution and violarite precipitation, the rate-limiting steps controlling the kinetic behavior, and the origin of the length scale of the features preserved during pseudomorphism.The experiments were conducted under mild hydrothermal conditions (80-210 °C, vapor saturated pressures). Reaction kinetics shows a complex behavior depending on various physical and chemical parameters including temperature, pH, concentrations of various reaction species, solid-weight-to-fluid-volume-ratio and specific surface area. The rate of replacement (i) increases with temperature from 80 to 125 °C, then decreases as temperature further increases to 210 °C, (ii) first increases then decreases with decreasing pH from pH 6 to 1, (iii) increases with increasing concentration of oxidants such as O_2(aq), H₂O₂, and KMnO₄, but decreases with increasing concentration of Ni²⁺ and Fe³⁺, and with increasing solid-weight-to-fluid-volume ratio, (iv) increases linearly with the specific surface area. This kinetic behavior as well as the resulting textures revealed a coupled dissolution-reprecipitation reaction mechanism.Nanometer-scale pseudomorphic replacement, through which the crystallographic orientation of pentlandite is inherited by violarite, occurs only between 1 < pH < 6, and spatial coupling between dissolution and reprecipitation is controlled by the local solution chemistry as well as by epitaxial nucleation mediated by the pentlandite substrate. The kinetic results show that pentlandite dissolution is rate-limiting under mild acidic to neutral conditions (1 < pH < 6), while violarite precipitation is rate-limiting under strong acidic conditions (pH 1). The difference in rate-limiting steps influences the coupling mechanism and causes the different degrees of preservation (length scale of pseudomorphism) and different morphologies observed at high and low pHs: pentlandite dissolution being rate-limiting results in nanoscale coupling between dissolution and precipitation and thus nanoscale pseudomorphism (length scale <20 nm), in which the replacement precisely preserves the morphology and internal details, resembling remarkably the natural pentlandite/violarite assemblages. In contrast, violarite precipitation being rate-limiting results in microscale pseudomorphism (length scale ∼10 μm): the morphology of the pentlandite grains is only roughly preserved and internal details are not preserved.This case study illustrates some general principles of replacement reactions proceeding via the coupled dissolution-reprecipitation mechanism: (i) primary mineral dissolution needs to be rate-limiting compared to the secondary mineral precipitation in order to achieve a high degree pseudomorphic replacement; (ii) the effects of solution composition on reaction kinetics can be qualitatively rationalized by considering the rate-limiting step reaction.     

Prograde and retrograde fluid flow during contact metamorphism of siliceous carbonate rocks from the Ballachulish aureole,Scotland

 Siliceous dolomites and limestones contain abundant retrograde minerals produced by hydration-carbonation reactions as the aureole cooled. Marbles that contained periclase at the peak of metamorphism bear secondary brucite, dolomite, and serpentine; forsterite-dolomite marbles have retrograde tremolite and serpentine; wollastonite limestones contain secondary calcite and quartz; and wollastonite-free limestones have retrograde tremolite. Secondary tremolite never appears in marbles where brucite has replaced periclase or in wollastonite-bearing limestones. A model for infiltration of siliceous carbonates by CO₂-H₂O fluid that assumes (a) vertical upwardly-directed flow, (b) fluid flux proportional to cooling rate, and (c) flow and reaction under conditions of local equilibrium between peak temperatures and ≈400 °C, reproduces the modes of altered carbonate rocks, observed reaction textures, and the incompatibility between tremolite and brucite and between tremolite and wollastonite. Except for samples from a dolomite xenolith, retrograde time-integrated flux recorded by reaction progress is on the order of 1000 mol fluid/cm² rock. Local focusing of flow near the contact is indicated by samples from the xenolith that record values an order of magnitude greater. Formation of periclase, forsterite, and wollastonite at the peak of metamorphism also required infiltration with prograde time-integrated flux approximately 100–1000 mol/cm². The comparatively small values of prograde and retrograde time-integrated flux are consistent with lack of stable isotope alteration of the carbonates and with the success of conductive thermal models in reproducing peak metamorphic temperatures recorded by mineral equilibria. Although isobaric univariant assemblages are ubiquitous in the carbonates, most formed during retrograde metamorphism. Isobaric univariant assemblages observed in metacarbonates from contact aureoles may not record physical conditions at the peak of metamorphism as is commonly assumed. Received: 19 September 1995 / Accepted: 14 March 1996     

Mechanism of pyroxene and amphibole weathering—I. Experimental studies of iron-free minerals

The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca²⁺, Mg²⁺, and Si(OH)₄ and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M₂ structural sites. Loss mainly from M₂ sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca²⁺ and/or Mg²⁺ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on a_H⁺ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.     

Synthesis and stability of deerite,Fe 12 2+ Fe 6 3+ [Si12O40](OH)10, and Fe3+⇋Al3+ substitutions at 15–28 kb

Deerite, Fe ₁₂ ²⁺ Fe ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀, thus far known from ten localities in glaucophane schist terranes, was synthesized at water pressures of 20–25 kb and temperatures of 550–600 °C under the of the Ni/NiO buffer. The X-ray powder diagram, lattice constants and infrared spectrum of the synthetic phase are closely similar to those of the natural mineral. A solid solution series extends from this ferri-deerite end member to some 20 mole % of a hypothetical alumino-deerite, Fe ₁₂ ²⁺ Al ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀. The upper temperature breakdown of ferri-deerite to the assemblage ferrosilite +magnetite+quartz+water occurs at about 490 °C at 15 kb, and 610 °C at 25 kb fluid pressure for the of the Ni/NiO buffer. Extrapolation of these data to lower water pressures indicates that deerite can be a stable mineral only in very low-temperature, high-pressure environments.     

Antigorite-ophicarbonates: Contact metamorphism in Valmalenco,Italy

Outside the Bergell tonalite contact aureole, ophicarbonate rocks consist of blocks of antigorite schist embedded in veins of calcite ± tremolite. An antigorite schistosity predates some of these calcite veins. Mono- and bimineralic assemblages occur in reaction zones associated with the veins. Within the aureole, the ophicarbonate veining becomes less distinct and polymineralic assemblages become more frequent. A regular sequence of isobaric univariant assemblages is found, separated by isograds corresponding to isobaric invariant assemblages. In order of increasing grade the invariant assemblages are: antigorite+diopside+olivine+tremolite+calcite antigorite+dolomite+olivine+tremolite+calcite antigorite+olivine+talc+magnesite antigorite+dolomite+olivine+tremolite+talc These assemblages match a previously derived topology in P-T-X_CO2 space for the system CaO-MgO-SiO₂-H₂O-CO₂; the field sequence can be used to adjust the relative locations of calculated invariant points with respect to temperature. Isobaric univariant and invariant assemblages are plotted along a profile map to permit direct comparison with the phase diagram.It is inferred that, during the formation of the ophicarbonate veins, calcite precipitated from fluid introduced into the serpentinite. During contact metamorphism, however, the compositions of pore fluids evolved by reaction in the ophicarbonate rocks were largely buffered by the solid phases. This control occurred on a small scale, because there are local variations in the buffering solid assemblages within a centimeter range.     

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.     

Carbonate-hosted talc deposits in the contact aureole of an igneous intrusion (Hwanggangri mineralized zone,South Korea): geochemistry,phase relationships,and stable isotope studies

Many talc deposits occur in the Hwanggangri Mineralized Zone (HMZ) in dolomitic marbles of the Cambro-Ordovician Samtaesan Formation within 1 km of the contact with the Cretaceous Muamsa Granite. Talc commonly forms fine-grained, fibrous aggregates, or pseudomorphs after tremolite; abundant tremolite is included as impurities in the talc ore. Talc generally was derived from tremolite in calc-silicate rock within the dolomitic marble. Calc-silicate rock, consisting mainly of tremolite and diopside, was generated from silicic metasomatism during the prograde stage, which promoted decarbonation reactions until dolomite was exhausted locally. Hydrothermal alteration of calc-silicate rock to talc is marked by the addition of Mg and Si, and the leaching of Ca; Cr, Co, and Ni were relatively immobile during the retrograde stage. Contact metamorphism related to the granite intrusion generated the successive appearance of tremolite, diopside, and forsterite, or wollastonite-bearing assemblages in the marble, depending on the bulk rock composition. The X_CO2 content of the metamorphic fluids rose initially above X_CO2=0.6, and decreased steadily toward a water-rich composition with increasing temperature above 600 °C in the calcitic marble, while buffered reaction of the dolomitic marble occurred at higher X_CO2 conditions above 600 °C. Talc mineralization developed under metastable conditions with infiltration of large amounts of igneous fluids along a fault-shattered zone during the retrograde stage and is characterized by the loss of Ca²⁺ with the addition of Mg²⁺. Oxygen and carbon isotopic variations of carbonate and calc-silicate minerals are in agreement with theoretical relationships determined for decarbonation products of contact metamorphism. Talc formation temperatures obtained from oxygen isotope fractionation, T–X_CO2 relationships, and activity diagrams range from 380 to 400 °C.     

Oxygen isotope exchange and disequilibrium between calcite and tremolite in the absence and presence of an experimental C–O–H fluid

Oxygen isotope exchange between minerals during metamorphism can occur in either the presence or the absence of aqueous fluids. Oxygen isotope partitioning among minerals and fluid is governed by both chemical and isotopic equilibria during these processes, which progress by intragranular and intergranular diffusion as well as by surface reactions. We have carried out isotope exchange experiments in two- and three-phase systems, respectively, between calcite and tremolite at high temperatures and pressures. The two-phase system experiments were conducted without fluid either at 1 GPa and 680 °C for 7 days or at 500 MPa and 560 °C for 20 days. Extrapolated equilibrium fractionations between calcite and tremolite are significantly lower than existing empirical estimates and experimental determinations in the presence of small amounts of fluid, but closely match calculated fractionations by means of the increment method for framework oxygen in tremolite. The small fractionations measured in the direct calcite–tremolite exchange experiments are interpreted by different rates of oxygen isotope exchange between hydroxyl oxygen, framework oxygen and calcite during the solid–solid reactions where significant recrystallization occurs. The three-phase system experiments were accomplished in the presence of a large amount of fluid (CO₂+H₂O) at 500 MPa and 560 °C under conditions of phase equilibrium for 5, 10, 20, 40, 80, 120, 160, and 200 days. The results show that oxygen isotope exchange between minerals and fluid proceeds in two stages: first, through a mechanism of dissolution-recrystallization and very rapidly; second, through a mechanism of diffusion and very slowly. Synthetic calcite shows a greater rate of isotopic exchange with fluid than natural calcite in the first stage. The rate of oxygen diffusion in calcite is approximately equal to or slightly greater than that in tremolite in the second stage. A calculation using available diffusion coefficients for calcite suggests that grain boundary diffusion, rather than volume diffusion, has been the dominant mechanism of oxygen transport between the fluid and the mineral grains in the later stage.Editorial responsibility: T.L. Grove     

Metamorphism at the northwest contact of the Stanhope Pluton,Quebec Appalachians: Mineral equilibria in interbedded pelite and calc-schist

The interbedding of pelite and calc-schist in part of the contact aureole of a Devonian (biotite K-Ar age 346±4 Ma) granite pluton that straddles the Quebec-Vermont border offers an opportunity to compare metamorphic conditions prevailing in both rock types, and to test for internal consistency among several different geothermometers and geobarometers.Microprobe analyses and recent thermodynamic data are used with simple activity-composition models to estimate P-T-X _fluid conditions near the sillimanite zone. Calculations yield the following results: P=2 to 3 kb, and T =400° to 600° C in the inner one kilometre of the aureole; was around 0.8. Estimates are based on the calc-silicate isobaric invariant assemblages tremolite-K-feldspar-plagioclase-clinozoisite-phlogopite-calcite-quartz and diopside-tremolite-plagiolase-clinozoisite-calcite-quartz, and the paragonite-andalusite-sillimanite-albite-quartz equilibrium. The solid-solid reaction phlogopite+2 diopside + 4 quartz=tremolite+K-feldspar in the calc-schist (combined with the andalusite-sillimanite equilibrium), and phase relations in the granite yield apparently inconsistent results.The implied 6 to 10 km of cover at the time of intrusion may have been provided by subsequently eroded thrust sheets.     

Die Reaktion Phlogopit + Calcit + Quarz = Tremolit + Kalifeldspat + H2O + C2O

Hydrothermal experiments with mixtures of synthetic minerals have shown the reversibility of the reaction 5 phlogopite + 6 calcite + 24 quartz = 3 tremolite + 5 K-feldspar + 2 H₂O + 6 CO₂. In an isobaric T – diagram the equilibrium curve reaches a maximum at = 0,75. The P, T-values for this maximum are: 2 kb-523°; 4 kb-585°; 6 kb-625°; P±5%, T±10° C. These results give a first approximation of the P, T conditions responsible for a similar mineral reaction which has been recorded from natural metamorphic assemblages.

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Herrn Prof. H. G. F. Winkler danke ich für anregende Diskussionen, desgleichen Herrn Dr. D. Puhan für wichtige Hinweise und Mitteilung seiner exp. Daten. Herrn Prof. V. Trommsdorff und Herrn P. H. Thompson bin ich für petrographische Angaben zu Dank verpflichtet. Der Aufbau der Hydrothermalanlage und die Finanzierung der laufenden Untersuchungen wurde aus den Mitteln des Fonds zur Förderung der wissenschaftlichen Forschung ermöglicht. Für diese Unterstützung gilt daher mein besonderer Dank.     

Relationship between fluid-bearing and fluid-absent invariant points and a petrogenetic grid for a greenschist facies assemblage in the system CaO-MgO-Al2O3-SiO2-CO2-H2O

In the 6 component system CaO-MgO-Al₂O₃-SiO₂-CO₂-H₂ with 9 solid phases (quartz, plagioclase, epidote, tremolite, talc, chlorite, magnesite, calcite, dolomite) and a fluid phase, all 17 possible fluid-absent reactions have been set up and balanced. Using molar entropy and volume data for the solid phases, these reactions are arranged in P-T space about the 8 possible fluid-absent invariant points after the method of Schreinemakers. Field observations in Ordovician greenschist facies basic volcanics at Sofala N.S.W., indicate that neither talc+epidote nor magnesite+calcite are stable under the conditions of metamorphism. Assuming these conditions to apply to the theoretical study here, the fluid-absent invariant points are arranged in a relative fashion with fluid-absent reactions subdividing P-T space into smaller areas.A scheme which permits a fluid of composition (i.e. a fluid containing CO₂ and H₂O together with other components), is modeled by treating H₂O as a mobile component independent of CO₂, and by allowing values that lie off the locus of binary H₂O-CO₂. Taking into account that neither talc+epidote nor magnesite +calcite is to be permitted, the fluid scheme is used to set up and balance all 39 possible fluid-bearing reactions. These are then arranged about 20 valid fluid-bearing invariant points in space after the method of Korzhinskii and Sehreinemakers.A characteristic solid phase assemblage is defined for each P-T area using chemographic relations inherent from the fluid-absent boundary reactions. The fluid-bearing invariant points that have a solid assemblage compatible with the characteristic assemblage in a particular P-T area are stable within the P-T regime of that area. When these stable fluidbearing invariant points are arranged in a relative fashion in space, they outline a fluid grid which can be used to study the possible effects of local variation in X _fluid over the particular P-T regime.Symbols Used U chemical potential - S entropy - V molar volume - n coefficient of a phase in a reaction - X mole fraction - T temperature - P pressure - F number of degrees of freedom - C number of components - p number of phases - s solid - slope of reaction - 1 quartz - 2 plagioclase - 3 epidote - 4 tremolite - 5 talc - 6 chlorite - 7 dolomite - 8 magnesite - 9 calcite     

Metamorphism and Fluid Infiltration of the Calc-silicate Aureole of the Beinn an Dubhaich Granite, Skye

The Tertiary Beinn an Dubhaich granite intruded at 75OC and05 kb into siliceous dolostones and limestones of the UpperDurness Group in Strath, Skye, with the consequent developmentof talc, tremolite, diopside, olivine, and periclase in thebulk of the aureole, and abundant fluoro-borosilicate skarnsimmediately adjacent to the pluton. With increasing grade thelimestones develop the mineral sequence talc, tremolite, diopside,and olivine, whereas the dolostones develop the sequence talc,tremolite, olivine, and periclase. The abundant chert nodulesin the dolostones take either of the two reaction paths, dependenton their size. Those below 2–7 mm in dimension followthe dolostone reaction path, whereas larger nodules follow thelimestone reaction path. The presence of monticellite in thehighest-grade rocks points to the flushing of the contact byvolumes of water-rich fluid, derived presumably from the granite.Consideration of low-grade olivine-bearing veins and fracturesin the dolostones also points to the presence of extremely water-richfluid in the more distal parts of the aureole. Using simplebox models with constant porosity, it is shown that the observedreaction progress in oli vine-grade and talc-grade rocks canonly be accounted for if the rocks were infiltrated by substantialvolumes of water-bearing fluid. Minimum estimates for volumesof infiltrated fluid show that rocks nearest the pluton wereprobably infiltrated by greater amounts of fluid than thosefurther away. Low-grade rocks which suffered greatest amountsof infiltration are the brecciated dolostones nearest the Thrust.     

Synthetic and natural tremolite in equilibrium with forsterite,enstatite, diopside and fluid

The following equilibrium among tremolite forsterite, diopside, and orthorhombic enstatite has been investigated using either synthetic tremolite or natural amphibole in the starting materials: Ca₂Mg₅Si₈O₂₂(OH)₂+Mg₂SiO₄ =2 CaMgSi₂O₆+5MgSiO₃+H₂O A significant increase in the stability of the reactants was observed with natural rather than synthetic tremolite. For example, in nearly pure H₂O with the H₂ content of the fluid buffered by nickel-bunsenite at one kilobar (10⁸ pascals), the breakdown of the assemblage with synthetic amphibole occurs at 708±20° C. The breakdown of the assemblage with natural amphibole, Ca_2.16Mg_4.94Fe_0.03Si_7.92 Al_0.01O₂₂(OH)₂F_0.03 occurs at 841±47° C. The shift in the breakdown curve is attributed to variation in the properties of the amphiboles since all other factors were common in the experiments. The reactions have also been investigated with hydrogen fugacity defined by the methane buffer and the NB, OH (XG, COH) buffer. Analysis of the experimental data by linear programming indicates that the enthalpy of reaction is tightly constrained when the calorimetrically determined entropy of 160.92 joules/degree is used. The resulting enthalpy of reaction is 113.96±1.82 kilojoules with the natural amphibole and 104.83±0.12 kilojoules with synthetic tremolite. Deviation of the natural amphibole from the ideal tremolite formula as well as a greater number of defects and dislocations in the synthetic amphibole may have contributed to the change in stability.     

Petrology and geochemistry of prograde deserpentinized peridotites from Happo-O’ne, Japan: Evidence of element mobility during deserpentinization

The prograde deserpentinized peridotites from the talc zone in the Happo-O’ne complex, central Japan, show differences in their field relation and mineral assemblage with the high-P retrograde peridotites of the other part of the complex. They show a mineral assemblage, olivine + talc + antigorite ± prograde tremolite ± chlorite, formed by thermal metamorphism around the granitic intrusion at T, 500-650 °C and P < 7 kbar. The olivine has numerous opaque inclusions and high Fo (91.5-96.5) relative to the retrograde olivine, reflecting its formation by deserpentinization. The prograde tremolite, which is low in Al₂O₃ (<1.0 wt.%), Cr₂O₃ (<0.35 wt.%), and Na₂O (<0.6 wt.%) but high in Mg# (up to 0.98) and SiO₂ (up to 59.9 wt.%), is different in size, shape and chemistry from the retrograde tremolite. The prograde peridotites display a U-shaped REE pattern (0.02-0.5 times PM), similar to diopside-zone retrograde metaperidotites, possible protoliths. They are enriched in LILE (e.g., Cs, Pb, Sr, Rb) relative to HFSE (e.g., Ta, Hf, Zr, Nb), like their protoliths, because of their local re-equilibration with the fluid released during dehydration of the protoliths. They have high contents of REE and some trace elements (e.g., Cs, Th, U, Ta) relative to their protoliths because of an external-element addition from the granitic magma. In-situ analyses of peridotitic silicates confirmed that the prograde tremolite and talc display a spoon-shaped primitive mantle (PM)-normalized REE pattern (0.1-3 times PM) in which LREE are higher than HREE contents. The prograde tremolite is depleted in Al, Na, Cr, Sc, V, Ti, B, HREE and Li, but is enriched in Si, Cs, U, Th, HFSE (Hf, Zr, Nb, Ta), Rb and Ba relative to the retrograde tremolite; the immobile-element depletion in this tremolite is inherited from its source (antigorite + secondary diopside), whereas the depletion of mobile elements (e.g., Li, B, Na, Al) is ascribed to their mobility during the deserpentinization and/or the depleted character of the source of tremolite. The enrichment of HFSE and LILE in the prograde tremolite is related to an external addition of these elements from fluid/melt of the surrounding granitic magma and/or in situ equilibrium with LILE-bearing fluid released during dehydration of serpentinized retrograde metaperidotites and olivine-bearing serpentinites (protoliths). The prograde olivine is higher in REE and most trace-element contents than the retrograde one due to the external addition of these elements; it is enriched in B, Co and Ni, but depleted in Li that was liberated during deserpentinization by prograde metamorphism.