Phase equilibria involving humite minerals in impure dolomitic limestones

The natural occurrence of critical assemblages among the phases clinohumite, chondrodite, norbergite, tremolite, forsterite, brucite, periclase, diopside, calcite and dolomite, together with experimental and thermochemical data, permits the calculation of phase equilibria governing the stability of the humite group minerals in impure dolomitic limestones. The phase relations are described by 29 divariant (OH-F) continuous reactions, and 11 univariant discontinuous reactions. The equilibrium conditions for these reactions have been calculated and plotted in isobaricT-X(OH-F) andT- phase diagrams. Continuous reactions govern the compositions of (OH-F) solid solutions and the consequent movement of three-phase triangles on the chemographic diagram. Discontinuous reactions result in the appearance or disappearance of a distinct phase assemblage. The pure OH-humite minerals are metastable relative to forsterite+brucite. With increasing fluorine content, clinohumite, followed in turn by chondrodite and norbergite, becomes stable. The stability fields for the individual humite minerals expand to more CO₂-rich fluid compositions with increasing fluorine content and decreasing total pressure. At 1,000 bars, clinohumite can contain a maximum of 58 mole percent fluorine before reacting discontinuously to form chondrodite (X _F=0.61) and forsterite. The stability field for clinohumite+calcite is restricted to fluids with <0.40. At temperatures less than 700°C, the minimum fluorine mole fractions required to stabilize chondrodite and norbergite are 0.31 and 0.62 respectively. At the same conditions, chondrodite can contain a maximum of approximately 85 mole % F. The calculated phase equilibrium boundaries, the range of stable humite compositions and the compositions of coexisting (OH-F) phases are in good overall agreement with natural assemblages. Owing to steepdT/d slopes for several of the humite continuous reactions, the F/(F+OH) ratio of a given humite mineral is a useful indicator of the CO₂/H₂O ratio of the fluid phase.     

Fluid-rock history of granulite facies humite-marbles from Ambasamudram, southern India.

An extensive humite‐bearing marble horizon within a supracrustal sequence at Ambasamudram, southern India, was studied using petrological and stable isotopic techniques to define its metamorphic history and fluid characteristics. At peak metamorphic temperatures of 775±73°C, based on calcite‐graphite carbon isotope thermometry, the mineral assemblages suggest layer‐by‐layer control of fluid compositions. Clinohumite + calcite‐bearing assemblages suggest X_CO2 < 0.4 (at 700°C and 5 kbar), calcite + forsterite + K‐feldspar‐bearing assemblages suggest X_CO2>0.9 (at 790°C); and local wollastonite + scapolite + grossular‐bearing zones formed at X_CO2 of c. 0.3. Retrograde reaction textures such as scapolite + quartz symplectites after feldspar and calcite and replacement of dolomite + diopside or tremolite+dolomite after calcite+forsterite or calcite+clinohumite are indicative of retrogression under high X_CO2 conditions. Calcite preserves late Proterozoic carbon and oxygen isotopic signatures and the marble lacks evidence for extensive retrograde fluid infiltration, while during prograde metamorphism the possible infiltration of aqueous fluids did not produce significant isotopic resetting. Isotopic zonation of calcite and graphite grains was likely produced by localized CO₂ fluid infiltration during retrogression. Contrary to the widespread occurrence of humite‐marbles related to retrograde aqueous fluid infiltration, the Ambasamudram humite‐marbles record a prograde‐to‐peak metamorphic humite formation and retrogression under conditions of low X_H2O.     

Tracing high-pressure metamorphism in marbles: Phase relations in high-grade aluminous calcite–dolomite marbles from the Greek Rhodope massif in the system CaO–MgO–Al2O3–SiO2–CO2 and indications of prior aragonite

Four different types of parageneses of the minerals calcite, dolomite, diopside, forsterite, spinel, amphibole (pargasite), (Ti–)clinohumite and phlogopite were observed in calcite–dolomite marbles collected in the Kimi-Complex of the Rhodope Metamorphic Province (RMP). The presence of former aragonite can be inferred from carbonate inclusions, which, in combination with an analysis of phase relations in the simplified system CaO–MgO–Al₂O₃–SiO₂–CO₂ (CMAS–CO₂) show that the mineral assemblages preserved in these marbles most likely equilibrated at the aragonite–calcite transition, slightly below the coesite stability field, at ca. 720 °C, 25 kbar and a_CO2 ~ 0.01. The thermodynamic model predicts that no matter what activity of CO₂, garnet has to be present in aluminous calcite–dolomite-marble at UHP conditions.     

Metamorphism of Calcareous Rocks in Three Roof Pendants in the Sierra Nevada, California

Two roof pendants in the Hope Valley area, Alpine County, containabundant calc-silicate assemblages which can be related to univariantor invariant equilibria in the CaO-Al₃O₃-SiO₂-H₂O-CO₂ system.Such assemblages are considered to represent components of reactionsthat buffered the chemistry of the pore fluid. Through dataobtained from microprobe analysis it is concluded that solidsolution in plagioclase, garnet, and clinozoisite are importantvariables such that on a TXco₂ projection each sample had aunique path during metamorphism. Differences in the plagioclasecomposition of nearby samples with assemblages related by thereaction: grossularite_(s.s)+quartz = anorthite_(s.s.)+wollastonite, suggest unique equilibration temperatures for assemblages inlocal domains. In the Twin Lakes pendant in Fresno County, thereaction: clinohumite+calcite+CO₂= 4forsterite+dolomite+H₂O, is importantin magnesian marbles. Contrasting parageneses, which are relatedby this equilibrium, are considered to reflect variations influid composition. Constrasting assemblages in calc-silicaterocks, which are linked by the reactions: calcite+quartz= wollastonite+CO₂, tremolite+calcite= dolomite+diopside+CO₂+H₂O, exist down to the scale of a thin section. Variation in Ti contentof idocrase may be an important factor in assemblages linkedby reactions involving this phase. This study suggests that during contact metamorphism of calcareousrocks in the Sierra Nevada, H₂O and CO₂ behaved as ‘initialvalue components’ (Zen, 1963) whose activities were controlledby reactions withion local systems.     

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.     

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.     

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.     

Fluid compositions and local fluid buffering during the retrograde metamorphism of Al-bearing dolomitic calc-silicate granulites in the Limpopo Central Zone,southern Africa

Calc-silicate granulites were examined to evaluate the fluid composition and retrograde metamorphic conditions in the Central Zone of the Limpopo Belt, southern Africa. Quartz deficient assemblages are characterized by minerals such as diopside, forsterite, spinel and/or magnesiohornblende and tremolite in the presence of calcite and dolomite. Although the granulites are Al-poor (Al₂O₃ is less than or equal to 1.0 wt.%) and dolomitic in composition, they include Al-bearing phases. Phase analyses for the assemblages in the two model systems CaO–MgO–SiO₂–H₂O–CO₂ and CaO–MgO–SiO₂–Al₂O₃–H₂O–CO₂ provide constraints on fluid compositions in the granulite facies and retrograde metamorphisms in the Limpopo Central Zone. In the presence of amphiboles, isobaric T–X(CO₂) phase relations suggest that high X(CO₂) conditions were established in the calc-silicate rocks of present study. The phase relations with tschermakitic amphiboles at 0.35 GPa restrict diopside-spinel occurrences in the presence of calcite, dolomite and forsterite within very-high X(CO₂) with low a(H₂O). The fluid compositions, X(CO₂), were effectively buffered by the mineral assemblages during granulite facies metamorphism to subsequent decompression and cooling stages. The presence or absence of retrograde magnesiohornblende and tremolite appeared to be controlled not only by infiltration of H₂O-rich fluid during retrograde metamorphism but also Al content in the local bulk rock compositions. The presence of the two-amphibole phases shows that the fluid compositions were locally buffered in the Al-bearing dolomitic granulites. Comparing the calculated X(CO₂) values in the present study area and in the Alldays area, a difference of retrograde hydration effects is observed.     

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.     

The reaction chlorite+dolomite=spinel+forsterite+calcite+carbon dioxide+water

The reaction chlorite+dolomite=spinel+ forsterite+calcite+CO₂+H₂O has been studied with hydrothermal equipment technique in a C-O-H fluid at P _fluid=1,000, 2,000 and 3,000 bars and fo₂ controlled by NB or QFM buffer. The equilibrium conditions for the reaction has been determined as log K=–57,119/T+95.77+0.9860(P-1)/T(bar,°K). The mineral mixtures had an excess of dolomite. The composition of the chlorite among the reaction products has been analysed and found to have a higher Al/Si ratio than clinochlore.     

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.     

Phase relations of a simplified Marly rock system with application to the Western Hohe Tauern (Austria)

The regional distribution of metamorphic mineral assemblages in Mesozoic carbonate rocks of the Western Hohe Tauern allows the mapping of isograds based on the appearance of biotite+calcite and biotite+zoisite+calcite. The latter isograd corresponds approximately to the thermal maximum of the alpidic metamorphism in the central part of this area. An estimate of P, T, X _fluid conditions can be obtained from phase relations among muscovite, biotite, chlorite, margarite, tremolite, zoisite, anorthite, quartz, calcite, and dolomite in the system K₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O-CO₂ which approximates the composition of marls. Calculations based on various experimental and thermodynamic data have been made with emphasis on phase relations pertinent to a group of carbonate rocks with very low Fe and Na contents in non-opaque minerals. Significant and opposite deviations from the phase relations for stochiometric end member mineral compositions are due to the substitutions F-OH and Mg+Si-2Al. Consistency of observed and calculated phase relations is favoured by high F-contents. For the majority of carbonate rocks in the high metamorphic zone, maximum temperatures around 550° C, minimum pressures of 4–6 kb, and relatively low XCO₂ values within the stability field of zoisite and of biotite+calcite+quartz are indicated.     

Petrogenetic grids for metacarbonate rocks: pressure-temperature phase-diagram projection for mixed-volatile systems

Isothermal or isobaric phase diagram sections as a function of fluid composition (X ^F) are widely used for interpreting the genetic history of metacarbonate rocks. This approach has the disadvantages that: (1) the influence of a key metamorphic variable, either pressure (P) or temperature (T), is obscured; (2) the diagrams are inappropriate for systems that are not fluid-saturated. These problems are avoided by constructing phase-diagram projections in which the volatile composition of the system is projected onto a P-T coordinate frame, i.e., a petrogenetic grid. The univariant curves of such P-T projections trace the conditions of the invariant points of isothermal or isobaric phase-diagram sections, thereby defining the absolute stability of high-variance mineral assemblages, with and without a coexistent fluid phase. Petrogenetic grids for metacarbonate rocks are most useful for the study of regional metamorphism and for systems in which fluid composition has not been externally controlled. A calculated example of a P-T projection for the system CaO−MgO−SiO₂−H₂O−CO₂ suggests that many assemblages (e.g., calcite +tale, enstatite+fluid, magnesite+tremolite, antigorite+diopside+dolomite, and calcite+forsterite+tremolite) in mixed-volatile systems have stability fields that make them useful as P-T indicators. Consideration of the principles governing projection topology demonstrates that the univariant curves around a fluid present invariant point cannot be oriented independently with respect to the direction of compositional variation in the fluid phase. This has the interesting predictive implication that if the direction of compositional variation along one univariant curve around an invariant point is known, then the direction of compositional variation along the remaining curves can be determined solely from topologic constraints. The same constraints can be applied to systems containing simple mineral solutions or melts in order to predict compositional variations.     

Humite- and scapolite-bearing assemblages in marbles and calcsilicates of Dronning Maud Land, Antarctica: new data for Gondwana reconstructions

This study investigates marbles and calcsilicates in Central Dronning Maud Land (CDML), East Antarctica. The paleogeographic positioning of CDML as part of Gondwana is still unclear; however, rock types, mineral assemblages, textures and P–T conditions observed in this study are remarkably similar to the Kerala Khondalite Belt in India. The CDML marbles and calcsilicates experienced a Pan-African granulite facies metamorphism at c. 570 Ma and an amphibolite facies retrogression at c. 520 Ma. The highest grade assemblage in marbles is forsterite+spinel+calcite+dolomite, in calcsilicates the assemblages are diopside+spinel, diopside+garnet, scapolite+wollastonite+clinopyroxene±quartz, scapolite±anorthite±calcite+clinopyroxene+wollastonite. These assemblages constrain the peak metamorphic conditions to 830±20 °C, 6.8±0.5 kbar and X _CO2>0.46. During retrogression, highly fluoric humite-group minerals (humite, clinohumite, chondrodite) replaced forsterite, and garnet rims formed at the expense of scapolite during reactions with wollastonite, calcite or clinopyroxene but without involvement of anorthite. Metamorphic conditions were about 650 °C, 4.5±0.7 kbar, 0.2< X _CO2^fluid<0.36, and the co-existence of garnet, clinopyroxene, wollastonite and quartz constrains f_O2 to FMQ-1.5 log units. Mineral textures indicate a very limited influx of H₂O-rich fluid during amphibolite facies retrogression and point to significant variations of fluid composition in mm-sized areas of the rock. Gypsum was observed in two samples; it probably replaced metamorphic anhydrite which appears to have formed under amphibolite facies conditions. The observed extensive anorogenic magmatism (anorthosites, A-type granitoids) and the character of metamorphism between 610 and 510 Ma suggest that the crustal thermal structure was characterized by a long-lived (50–100 Ma) rise of the crustal geotherm probably caused by magmatic underplating.     

Subduction metamorphism of serpentinite‐hosted carbonates beyond antigorite‐serpentinite dehydration (Nevado‐Filábride Complex,Spain)

At sub‐arc depths, the release of carbon from subducting slab lithologies is mostly controlled by fluid released by devolatilization reactions such as dehydration of antigorite (Atg‐) serpentinite to prograde peridotite. Here we investigate carbonate–silicate rocks hosted in Atg‐serpentinite and prograde chlorite (Chl‐) harzburgite in the Milagrosa and Almirez ultramafic massifs of the palaeo‐subducted Nevado‐Filábride Complex (NFC, Betic Cordillera, S. Spain). These massifs provide a unique opportunity to study the stability of carbonate during subduction metamorphism at P–T conditions before and after the dehydration of Atg‐serpentinite in a warm subduction setting. In the Milagrosa massif, carbonate–silicate rocks occur as lenses of Ti‐clinohumite–diopside–calcite marbles, diopside–dolomite marbles and antigorite–diopside–dolomite rocks hosted in clinopyroxene‐bearing Atg‐serpentinite. In Almirez, carbonate–silicate rocks are hosted in Chl‐harzburgite and show a high‐grade assemblage composed of olivine, Ti‐clinohumite, diopside, chlorite, dolomite, calcite, Cr‐bearing magnetite, pentlandite and rare aragonite inclusions. These NFC carbonate–silicate rocks have variable CaO and CO₂ contents at nearly constant Mg/Si ratio and high Ni and Cr contents, indicating that their protoliths were variable mixtures of serpentine and Ca‐carbonate (i.e., ophicarbonates). Thermodynamic modelling shows that the carbonate–silicate rocks attained peak metamorphic conditions similar to those of their host serpentinite (Milagrosa massif; 550–600°C and 1.0–1.4 GPa) and Chl‐harzburgite (Almirez massif; 1.7–1.9 GPa and 680°C). Microstructures, mineral chemistry and phase relations indicate that the hybrid carbonate–silicate bulk rock compositions formed before prograde metamorphism, likely during seawater hydrothermal alteration, and subsequently underwent subduction metamorphism. In the CaO–MgO–SiO₂ ternary, these processes resulted in a compositional variability of NFC serpentinite‐hosted carbonate–silicate rocks along the serpentine‐calcite mixing trend, similar to that observed in serpentinite‐hosted carbonate‐rocks in other palaeo‐subducted metamorphic terranes. Thermodynamic modelling using classical models of binary H₂O–CO₂ fluids shows that the compositional variability along this binary determines the temperature of the main devolatilization reactions, the fluid composition and the mineral assemblages of reaction products during prograde subduction metamorphism. Thermodynamic modelling considering electrolytic fluids reveals that H₂O and molecular CO₂ are the main fluid species and charged carbon‐bearing species occur only in minor amounts in equilibrium with carbonate–silicate rocks in warm subduction settings. Consequently, accounting for electrolytic fluids at these conditions slightly increases the solubility of carbon in the fluids compared with predictions by classical binary H₂O–CO₂ fluids, but does not affect the topology of phase relations in serpentinite‐hosted carbonate‐rocks. Phase relations, mineral composition and assemblages of Milagrosa and Almirez (meta)‐serpentinite‐hosted carbonate–silicate rocks are consistent with local equilibrium between an infiltrating fluid and the bulk rock composition and indicate a limited role of infiltration‐driven decarbonation. Our study shows natural evidence for the preservation of carbonates in serpentinite‐hosted carbonate–silicate rocks beyond the Atg‐serpentinite breakdown at sub‐arc depths, demonstrating that carbon can be recycled into the deep mantle.     

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).     

Model for the formation of fluorine-bearing rocks in the Carboniferous deposits of the Moscow artesian basin

The paper presents the results of the statistical and thermodynamic analysis of hydrogeochemical information on the genesis of F-bearing waters in the Carboniferous deposits of the Moscow artesian basin. The F concentration is demonstrated to increase with increasing salinity of the aqueous solution. As follows from the analysis of mineral equilibria, the saturation concentrations of the aqueous phase with respect to fluorite in association with calcite and gypsum is less than 2–3 mg of F/l. At the saturation of the aqueous phase with respect to fluorite in association with dolomite, the equilibrium concentration of F increases with increasing Mg concentration and decreasing equilibrium partial CO₂ pressure and can reach 8–10 mg of F/l. The main reason for this enrichment of the aqueous phase in F is certain features of mineral equilibria in the system of aqueous solution with Ca and Mg carbonates. An increase in the Mg²⁺ concentration in the aqueous phase decreases the Ca²⁺ concentration in the solubility equilibrium of dolomite, and this, in turn, decreases the F^? concentration in the solubility equilibrium of fluorite.     

REE-bearing minerals in a Ti-rich vein from the Adamello contact aureole (Italy)

Zirconolite, aeschynite-(Ce), titanite and apatite have been found as minor or accessory minerals in a Ti-rich (TiO₂=2.1–4.5 wt.%) hydrothermal vein occurring in dolomite marbles at the contact with a tonalite intrusion of the Tertiary Adamello batholith (northern Italy). The vein consists of four distinct mineral zones, comprising from margin to center: (1) forsterite+calcite, (2) pargasite+calcite+titanite+sulfides, (3) phlogopite +calcite+titanite+sulfides, and (4) titanian clinohumite +spinel+calcite+sulfides. Zirconolite occurs in two vein zones only: in the phlogopite zone it is invariably anhedral, often corroded, and exhibits complex chemical zonation patterns. In the titanian clinohumite zone zirconolite is idiomorphic and characterized by a pronounced discontinous chemical zoning, but shows no evidence of corrosion. The considerable compositional variation observed for zirconolite (in wt.%: (REE₂O₃)=0.74–16.8, UO₂=0.59–24.0, ThO₂=0.67–17.1) is due to the zoning, and may be attributed to four major substitutions described by the exchange vectors:

Constraints on phase diagram topology for the system CaO−MgO−SiO2−CO2−H2O

Published phase diagrams for the siliceous carbonate system CaO–MgO–SiO₂–CO₂–H₂O are contradictory because of different estimates of the relative stability of magnesite. Experimental data on magnesite are too ambiguous to determine the validity of these estimates. Therefore, field evidence is used to select the correct phase diagram topology for siliceous carbonate and carbonate ultramafic rocks at pressures of about 2–5 kbar. The primary selection criterion is provided by the existence of the stable assemblage talc+dolomite+forsterite+tremolite+antigorite, which occurs in the Bergell contact aureole and Swiss Central Alps. Field evidence also is used to argue that the reaction magnesite+quartz=enstatite must occur at lower temperature than the reaction dolomite+quartz=diopside. T-X _{CO 2} and P _{CO 2}-T phase diagrams consistent with these observations are calculated from experimental and thermo-dynamic data. For antigorite ophicarbonate rocks, remarkable agreement is obtained between the spatial distribution of low variance mineral assemblages and the calculated diagrams.     

Titanian clinohumite and geikielite in marbles from the Bergell contact aureole

The assemblage titanian clinohumite+forsterite +spinel+calcite is widespread in marbles from the eastern Bergell contact aureole (Switzerland/Italy). The Bergell titanian clinohumites vary considerably in composition (TiO₂: 0.19 to 2.05 wt%, F: 2.2 to 3.4 wt%). Electron microprobe analyses show that the titanian clinohumites contain less than detectable amounts of Co, Cu, Ni, Zn, Al, Cr and Cl. No trace of ferric iron could be detected by Moessbauer spectroscopy. Moreover, the Moessbauer spectra indicate that Fe²⁺ occurs only in one of the five octahedral positions in the crystal structure of the studied titanian clinohumite. Under the conditions of the contact metamorphism (600–650° C, 3 kb total pressure) the compositional variation along the exchange vector TiO₂M_–1 (OH,F)_–2 takes place at constantx _OH which is fixed by the pore fluid. Titanian clinohumite sometimes contains geikielite inclusions which strongly fractionate Fe and Mn relative to titanian clinohumite. The geikielites from the Bergell marbles are poor in Cr₂O₃, Fe₂O₃ and MnO, and thus different from those found in carbonatites, kimberlites and serpentinized ultramafic rocks.