Incipient blueschist metamorphism and metasomatism in the Tavşanli region,Northwest Turkey

Volcano-sedimentary rocks in an imbricate tectonic zone around a peridotite massif have been studied northeast of the town of Tavanli in Northwest Turkey. Basic volcanic rocks, which are the dominant rock type in this zone, show incipient blueschist metamorphism and associated metasomatism. While the igneous textures of the volcanic rocks are retained, augites are partially to completely replaced by sodic pyroxene, and plagioclase is albitised resulting in rocks with 6–8 wt.% Na₂O. The volcanic rocks are cross-cut by numerous veins of calcite, aragonite, quartz, pumpellyite, albite, lawsonite and sodic pyroxene. Pelagic limestones, which are interbedded with the basic volcanic rocks, consist of coarse aragonite grains showing partial replacement by calcite. The occurrence of aragonite, lawsonite and albite indicates conditions of metamorphism for the whole zone in the range of 5–8 kb and 150–200° C. Metasomatism, probably related to high pressure serpentinization, has occurred contemporaneously with the incipient high pressure metamorphism.     

Transformation kinetics of polycrystalline aragonite to calcite: new experimental data,modelling, and implications

Experimental data are used to model the transformation rate of polycrystalline aragonite (grain diameter 80 m) to calcite. Optimized values for nucleation and growth rates were obtained by numerically fitting the overall transformation rates from 280° to 380°C and 0.10 MPa to an expression for a grain-boundary-nucleated and interface-controlled transformation. The nucleation rate is 4–5 orders of magnitude faster than for calcite nucleated within aragonite grains, and the growing in rate is slower below 300°C than for calcite growing in aragonite single crystals. The activation enthalpy for growth in polycrystalline aggregate is 247kJ/mol compared to 163 kJ/mol for growth in single crystals. Permanent deformation of the phases limits the elastic strain energy due to the 7% volume change and reduces the coherency of the calcite/aragonite interace. Theoretical expressions are used to extrapolate the data for nucleation and growth to other temperatures, and data from 0.10 to 400 MPa are used to evaluate the effect of pressure on the grain-boundary nucleation rate. Because of permanent deformation of the phases, the effective strain energy for nucleation is 0.55 kJ/mol, which is less than a quarter of the value for purely elastic deformation. These data are used to predict the percent transformation for various P-T-t paths; without heating during uplift partial preservation of aragonite in dry blueschist facies rocks can occur if the calcite stability field is entered at 235° C, and the kinetic data are also consistent with published P-T-t paths which include heating during uplift. The predicted percent transformation is relatively insensitive to variations in the initial grain size of the aragonite, but strongly dependent on the effective strain energy.     

Comparison of the high-pressure schist belts of New Caledonia and Sanbagawa,Japan

The high-pressure schist terranes of New Caledonia and Sanbagawa were developed along the oceanic sides of sialic forelands by tectonic burial metamorphism. The parent rocks were chemically similar, as volcanic-sedimentary trough or trench sequences, and metamorphic temperatures in both belts were 250° to 600° C. From phase equilibria curves, total pressures were higher for New Caledonia (6–15 kb) than for Sanbagawa (5–11 kb) and the estimated thermal gradients were 7–10° C/km and 15° C/km respectively.PT paths identify the higher pressure in New Caledonia (P differences 2 kb at 300° C and 4 kb at 550° C) with consequent contrast in progressive regional metamorphic zonation for pelites in the two areas: lawsonite-epidote-omphacite (New Caledonia) and chlorite-garnet-biotite (Sanbagawa). In New Caledonia the Na-amphibole is dominantly glaucophane and Na-pyroxenes associated with quartz are Jadeite (Jd_95–100) and omphacite; in Sanbagawa the amphibole is crossite or riebeckite and the pyroxene is omphacite (Jd₅₀). For both areas, garnet rims show increase in pyrope content with advancing grade, but Sanbagawa garnets are richer in almandine. Progressive assemblages within the two belts can be equated by such reactions as:New Caledonia Sanbagawa glaucophane+paragonite+H₂Oalbite+chlorite+quartz glaucophane+epidote+H₂Oalbite+chlorite+actinolite and the lower pressure Japanese associations appear as retrogressive phases in the New Caledonia epidote and omphacite zones.The contrasts inPT gradient, regional zonation and mineralogy are believed due to differences in the tectonic control of metamorphic burial: for New Caledonia, rapid obduction of an upper sialic plate over an inert oceanic plate and sedimentary trough; and for Sanbagawa, slower subduction of trench sediments beneath a relatively immobile upper plate.     

Uplift-related retrogression history of aragonite marbles in Western Crete (Greece)

In the low-grade, high-pressure (400°C, 10 kbar) metamorphic Phyllite-Quartzite Unit of Western Crete, widespread occurrences of aragonite marbles have been discovered recently. A sedimentary precursor is proved by relic structures (bedding, fossils). Partial or complete transformation of aragonite into calcite is ubiquitous. Compositional and microstructural features reflect the metamorphic history: (1) The high-pressure stage is documented by aragonite that is chemically characterized by incorporation of variable amounts of Sr and the lack of Mg. The most Sr-rich aragonite has about 9 wt% SrO (X _Sr ^arag =0.09). A compositional zoning observed in some aragonite crystals may be due to the prograde divariant calcitearagonite transformation in the system CaCO₃-SrCO₃. Because the parent rocks probably were Sr-poor calcite limestones, one can speculate that strontium has been supplied from an external source under high-pressure conditions. (2) During uplift, calcite replacing aragonite did not equilibrate with unreplaced aragonite. Disequilibrium is indicated by highly variable compositions of calcite crystals that show topotactic relations to the host aragonite. The calcite compositions range from that of the host aragonite (Sr-rich and Mg-free) to Mg-bearing and Sr-poor. (3) Calcite that recrystallized during retrogression is generally Sr-poor (mean value ofX _Sr<0.005), Mg-bearing (X _Mg0.010), and chemically homogeneous. Because practically no Sr remains in the calcite, an interaction with a fluid phase is indicated. In fine-grained calcite marbles rich in solid organic matter, microstructural features indicative of former aragonite may be present. (4) The last stage of retrogression is documented by the appearance of radiating aragonite in veins and nodules. This aragonite, which shows neither deformation nor retrogression, was probably formed metastably in a near-surface environment.     

The calcite-aragonite transition,reinvestigated

The calcite-aragonite equilibrium has been investigated between 200 and 600° C both in a carefully calibrated hydrothermal apparatus and in a piston-cylinder device of high precision. The equilibrium pressure is 5 kb at 180° C, 7 kb at 300° C, 9 kb at 400° C, and 11 kb at 480° C.The calcite-aragonite transition boundary which has been bracketed is continuously curved between 300 and 500° C and is more or less straight above and below this temperature range. It is shown that the calcite I-calcite II reaction is probably a second (and not a first) order transition.The experimental result shows that aragonite may already be formed out of calcite at a depth of 15 km if the temperature is not much higher than 100° C. The calcitearagonite and the albite-jadeite-quartz curves intersect at about 750° C and 20 kb. There is a P-T-field (up to 3.5 kb broad) where aragonite and albite coexist.     

The upper thermal stability of clinochlore,Mg5Al[AlSi3O10](OH)8, at 10–35 kb P_{{\text{H}}_{\text{2}} {\text{O}}}

Clinochlore, which is, within the limits of error, the thermally most stable member of the Mg-chlorites, breaks down at = P _tot to the assemblage enstatite+forsterite+spinel+H₂O along a univariant curve located at 11 kb, 838 ° C; 15kb, 862 ° C; and 18 kb, 880 ° C (±1 kb ±10 ° C). At water pressures above that of an invariant point at 20.3 kb and 894 ° C involving the phases clinochlore, enstatite, forsterite, spinel, pyrope, and hydrous vapor, clinochlore disintegrates to pyrope+forsterite+spinel+H₂O. The resulting univariant curve has a steep, negative dP/dT slope of –930 bar/ °C at least up to 35 kb.Thus, given the proper chemical environment, Mg-chlorites have the potential of appearing as stable phases within the earth's upper mantle to maximum depths between about 60 and 100 km depending on the prevailing undisturbed geotherm, and to still greater depths in subduction zones. However, unequivocal criteria for mantle derived Mg-chlorites are difficult to find in ultrabasic rocks.     

Late Hercynian U-vein mineralization in the Alps: fluid inclusion and C,O, H isotopic evidence for mixing between two externally derived fluids

Late Hercynian U-bearing carbonate veins within the metamorphic complex of La Lauzière are characterized by two parageneses. The first is dominated by dolomite or ankerite and the second by calcite and pitchblende. Fluids trapped in the dolomites and ankerites at 350–400° C are saline waters (20 to 15 wt % eq. NaCl) with D –34 to –49. In the calcite they are less saline (17 to 8 wt % eq. NaCl) and trapped at 300–350° C with D –50 to –65. All fluids contain trace N₂, CO₂ and probably CH₄. The carbonates have ¹³C –8 to –14. and derived their carbon from organic matter. Evolution of the physico-chemical conditions from dolomite (ankerite) to calcite deposition was progressive.H and O-isotope studies indicate the involvement of two externally derived fluids during vein development. A D-rich ( –35) low fO₂, saline fluid is interpreted to have come from underlying sediments and entered the hotter overlying metamorphic slab and mixed with more oxidizing and less saline U bearing meteoric waters during regional uplift. This evidence for a sedimentary formation water source for the deep fluid implies that the metamorphic complex overthrusted sedimentary formations during the Late-Hercynian.     

The influence of disordered,non-equilibrium dolomites on the Mg-solubility in calcite in the system CaCO3-MgCO3

The influence of different degrees of disorder of dolomites on the solubility of MgCO₃ in calcite has been studied under isothermal and isobaric conditions. At 900° C, 4kb and 1000° C, 5 and 7kb, varied smoothly as function of the particular structural and cationic disorder of coexisting dolomite. Higher degrees of disorder of dolomite, estimated by the d _00.6/d _11.0 values and the peak height ratio I _01.5/I_00.6, lead to greater solubility of MgCO₃ in calcite. The run time for all experiments was 96 h, much longer than in previous work. The influence of disorder of dolomite on appears to be larger than that of temperature, as shown by the large range of (0.12–0.30) in calcite at 900° C 4 kb, found in this study. The state of order of dolomite seems to control the solubility limits in this system, and may explain discrepancies found in previous experimental work.     

The solubility of calcite in water at 6–16 kbar and 500–800 °C

The solubility of calcite in H₂O was measured at 6–16 kbar, 500–800 °C, using a piston-cylinder apparatus. The solubility was determined by the weight loss of a single crystal and by direct analysis of the quench fluid. Calcite dissolves congruently in the pressure (P) and temperature (T) range of this study. At 10 kbar, calcite solubility increases with increasing temperature from 0.016±0.005 molal at 500 °C to 0.057±0.022 molal at 750 °C. The experiments reveal evidence for hydrous melting of calcite between 750 and 800 °C. Solubilities show only a slight increase with increasing P over the range investigated. Comparison with work at low P demonstrates that the P dependence of calcite solubility is large between 1 and 6 kbar, increasing at 500 °C from 1.8×10^–5 molal at 1 kbar to 6.4×10^–3 molal at 6 kbar. The experimental results are described by:

Melting and phase relations in the plane tholeiite-lherzolite-nepheline basanite to 40 kilobars with geological implications

Six crystalline mixtures, picrite, olivine-rich tholeiite, nepheline basanite, alkali picrite, olivine-rich basanite, and olivine-rich alkali basalt were recrystallized at pressures to 40 kb, and the phase equilibria and sequences of phases in natural basaltic and peridotitic rocks were investigated.The picrite was recrystallized along the solidus to the assemblages (1) olivine+orthopyroxene+ clinopyroxene +plagioclase+spinel below 13 kb, (2) olivine+orthopyroxene+clinopyroxene+spinel between 13 kb and 18 kb, (3) olivine+orthopyroxene+clinopyroxene+ garnet+spinel between 18 kb and 26 kb, and (4) olivine+clinopyroxene+garnet above 26 kb. The solidus temperature at 1 atm is slightly below 1,100° and rises to 1,320° at 20 kb and 1,570° at 40 kb. Olivine is the primary phase crystallizing from the melt at all pressures to 40 kb.The olivine-rich tholeiite was recrystallized along the solidus into the assemblages (1) olivine+ clinopyroxene+plagioclase+spinel below 13 kb, (2) clinopyroxene+orthopyroxene+ spinel between 13 kb and 18 kb, (3) clinopyroxene+garnet+spinel above 18 kb. The solidus temperature is slightly below 1,100° at 1 atm, 1,370° at 20 kb, and 1,590° at 40 kb. The primary phase is olivine below 20 kb but is orthopyroxene at 40 kb.In the nepheline basanite, olivine is the primary phase below 14 kb, but clinopyroxene is the first phase to appear above 14 kb. In the alkali-picrite the primary phase is olivine to 40 kb. In the olivine-rich basanite, olivine is the primary phase below 35 kb and garnet is the primary phase above 35 kb. In the olivine-rich alkali basalt the primary phase is olivine below 20 kb and is garnet at 40 kb.Mineral assemblages in a granite-basalt-peridotite join are summarized according to reported experimental data on natural rocks. The solidus of mafic rock is approximately given by T=12.5 P _Kb+1,050°. With increasing pressure along the solidus, olivine disappears by reaction with plagioclase at 9 kb in mafic rocks and plagioclase disappears by reaction with olivine at 13 kb in ultramafic rocks. Plagioclase disappears at around 22 kb in mafic rocks, but it persists to higher pressure in acidic rocks. Garnet appears at somewhat above 18 kb in acidic rocks, at 17 kb in mafic rocks, and at 22 kb in ultramafic rocks.The subsolidus equilibrium curves of the reactions are extrapolated according to equilibrium curves of related reactions in simple systems. The pyroxene-hornfels and sanidinite facies is the lowest pressure mineral facies. The pyroxene-granulite facies is an intermediate low pressure mineral facies in which olivine and plagioclase are incompatible and garnet is absent in mafic rocks. The low pressure boundary is at 7.5 kb at 750° C and at 9.5 kb at 1,150° C. The high pressure boundary is 8.0 kb at 750° C and 15.0 kb at 1,150° C. The garnet-granulite facies is an intermediate high pressure facies and is characterized by coexisting garnet and plagioclase in mafic rocks. The upper boundary is at 10.3 kb at 750° C and 18.0 kb at 1,150° C. The eclogite facies is the highest pressure mineral facies, in which jadeite-rich clinopyroxene is stable.Compositions of minerals in natural rocks of the granulite facies and the eclogite facies are considered. Clinopyroxenes in the granulite-facies rocks have smaller jadeite-Tschermak's molecule ratios and higher amounts of Tschermak's molecule than clinopyroxenes in the eclogite-facies rocks. The distribution coefficients of Mg between orthopyroxene and clinopyroxene are normally in the range of 0.5–0.6 in metamorphic rocks in the granulite facies. The distribution coefficients of Mg between garnet and clinopyroxene suggest increasing crystallization temperature of the rocks in the following order: eclogite in glaucophane schist, eclogite and granulite in gneissic terrain, garnet peridotite, and peridotite nodules in kimberlite.Temperatures near the bottom of the crust in orogenic zones characterized by kyanitesillimanite metamorpbism are estimated from the mineral assemblages of metamorphic rocks in Precambrian shields to be about 700° C at 7 kb and 800° C at 9 kb, although heat-flow data suggest that the bottom of Precambrian shield areas is about 400° C and the eclogite facies is stable.The composition of liquid which is in equilibrium with peridotite is estimated to be close to tholeiite basalt at the surface pressure and to be picrite at around 30 kb. The liquid composition becomes poorer in normative olivine with decreasing pressure and temperature.During crystallization at high pressure, olivine and orthopyroxene react with liquid to form clinopyroxene, and a discontinuous reaction series, olivine orthopyroxene clinopyroxene is suggested. By fractional crystallization of pyroxenes the liquid will become poorer in SiO₂. Therefore, if liquid formed by partial melting of peridotite in the mantle slowly rises maintaining equilibrium with the surrounding peridotite, the liquid will become poorer in MgO by crystallization of olivine, and tholeiite basalt magma will arrive at the surface. On the other hand, if the liquid undergoes fractional crystallization in the mantle, the liquid may change in composition to alkali-basalt magma and alkali-basalt volcanism may be seen at a late stage of volcanic activity.Publication No. 681, Institute of Geophysics and Planetary Physics, University of California, Los Angeles.     

Synthesis and upper stability of paragonite

The mineral paragonite, NaAl₂[AlSi₃O₁₀ (OH)]₂, has been synthesized on its own composition starting from a variety of different materials. Indexed powder data and refined cell parameters are given for both the 1M and 2M₁ polymorphs obtained. The upper stability limit of paragonite is marked by its breakdown to albite + corundum + vapour. The univariant equilibria pertaining to this reaction have been established by reversing the reaction at six different pressures, the equilibrium curve running through the following intervals: 1 kb: 530°–550° C 2 kb: 555°–575° C 3 kb: 580°–600° C 5kb: 625°–640° C 6 kb: 620°–650° C 7 kb: 650°–670° C.Comparison with the upper stability limit of muscovite (Velde, 1966) shows that paragonite has a notably lower thermal stability thus explaining the field observation that paragonite is absent in many higher grade metamorphic rocks in which muscovite is still stable.The enthalpy and entropy of the paragonite breakdown reaction have been estimated. Since intermediate albites of varying structural states are in equilibrium with paragonite, corundum and H₂O along the univariant equilibrium curve, two sets of data pertaining to the entropy of paragonite (S ₂₉₈ ⁰ ) as well as the enthalpy ( H _f,298 ⁰ ) and Gibbs free energy ( G _f,298 ⁰ ) of its formation were computed, assuming (1) high albite and (2) low albite as the equilibrium phase. The values are: (1) (2) S ₂₉₈ ⁰ 67.8±3.9 cal deg^–1 gfw^–1 63.7±3.9 cal deg^–1 gfw^–1 H _f,298 ⁰ –1417.9±2.7 kcal gfw^–1 –1420.2±2.6 kcal gfw^–1 G _f,298 ⁰ –1327.4±4.0 kcal gfw^–1 –1328.5±4.0 kcal gfw^–1.Adapted from a part of the author's Habilitationsschrift accepted by the Ruhr University, Bochum (Chatterjee, 1968).     

Calcite solubility and speciation in supercritical NaCl-HCl aqueous fluids

The solubility of calcite in NaCl-H₂O and in HCl-H₂O fluids was measured using an extraction-quench hydrothermal apparatus. Experiments were conducted at 2 kbar, between 400° C and 600° C. Measurements in NaCl-H₂O were conducted in two ways: 1) at constant pressure and NaCl concentration, as a function of temperature; and 2) at constant pressure and temperature, as a function of NaCl concentration. In both the NaCl-H₂O and the HCl-H₂O systems, the solubility of calcite increases with increasing chlorine concentrations. For example, the log calcium molality in equilibrium with calcite increases from –3.75 at 2 kbar and 500° C, in pure H₂O to –3.10 at 2 kbar and 500° C at log NaCl molality=–1.67. At fixed pressure and NaCl molality, the solubility of calcite is almost constant from 400° C to 550° C, but increases somewhat at higher temperatures. The results can be used to determine the dominant calcium species in the experimental solutions as a function of NaCl concentration and to obtain values for the second dissociation constant of CaCl_2(aq). At 2 kbar, 400° C, 500° C, and 600° C, we calculate values for the log of the dissociation constant of CaCl⁺ of –2.1, –3.2, and –4.3, respectively. The 400° C and 500° C values are consistent with those obtained by Frantz and Marshall (1982) using electrical conductance techniques. However, our 600° C value is 0.8 log units higher than that reported by Frantz and Marshall. The calcite solubilities in the NaCl-H₂O and HCl-H₂O systems are inconsistent with the solubilities of calcite in pure H₂O reported by Walther and Long (1986). They are, however, consistent with the measurements of calcite solubilities in pure H₂O presented in this study. These results allow for the calculation of the solubilities of calcium silicates and carbonates in fluids that contain CO₂ and NaCl.     

The upper stability limit of the assemblage paragonite + quartz and its natural occurrences

The assemblage paragonite + quartz is encountered frequently in low- to medium-grade metamorphic rocks. With rising grade of metamorphism they react mutually to yield the condensed assemblage albite + Al₂SiO₅.The univariant curve pertaining to the equilibrium paragonite + quartz=albite + andalusite + H₂O has been located experimentally. The reversed P _{H 2 O}-T data are: 1 kb: 470–490° C 2 kb: 510–530° C 3 kb: 540–560° C 4 kb: 560–580° C 5 kb: 590–600° C The univariant curve pertaining to the equilibrium paragonite + quartz=albite + kyanite + H₂O runs through the following P _{H 2 O}-T-intervals: 5 kb: 570–625° C 6 kb: 600–630° C 7 kb: 620–640° C Thermodynamic calculations of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of the phase paragonite from the experimental data presented above and those obtained from the equilibria of the reaction paragonite=albite + corundum + H₂O (Chatterjee, 1970), agree within the limits of uncertainty. This prompts the idea that Zen's (1969) suggestion of a possible error of approximately 7 kcal in G _f,298 ⁰ of the Al₂SiO₅ polymorphs may in fact be due to an error of similar magnitude in G _f,298 ⁰ of corundum.A best estimate of S ₂₉₈ ⁰ , H _f,298 ⁰ and G _f,298 ⁰ of paragonite based on these considerations yield: S ₂₉₈ ⁰ : 67.61±3.9 cal deg^–1 gfw^–1 H _f,298 ⁰ : –1411.4±2.7 kcal gfw^–1 G _f,298 ⁰ : –1320.9±4.0 kcal gfw^–1 These numbers will be subject to change when better thermochemical data on corundum and albite are available.In medium-grade metamorphic rocks the assemblage paragonite + quartz is commonly found in stable coexistence with such other phases as muscovite, staurolite, andalusite, kyanite, but not with cordierite or sillimanite. However, the assemblage paragonite-sillimanite has been reported to be stable in the absence of quartz. All these petrologic observations can be explained on the basis of the stability data of the phases and phase assemblages concerned.     

Contact metamorphism and metasomatism at a dolerite-limestone contact in the Gebel Yelleq area, Northern Sinai, Egypt

Summary At the northeastern flank of Gebel Yelleq, northern Sinai, pure limestones of Upper Cretaceous age were subjected to a thermal overprint, caused by a c. 80m thick Tertiary olivine dolerite sill. Metasomatic supply of Si, Al, Fe, Mg and Ti was greater to the c. 7m wide upper than to the c. 25m wide lower thermal aureole. The greater width of the lower aureole is possibly due to a longer duration of the thermal overprint at this contact. Mineral assemblages in both aureoles are (from the contact outward):(i) clinopyroxene + garnet ± wollastonite + calcite(ii) garnet ± wollastonite + calcite;(iii) wollastonite + calcite.In places, late stage xenoblasts of apophyllite and witherite overgrow these assemblages. Garnets are grandites to melanites with Grs_56–86Adr_14–42Sch_0–2Sps_0–0.2Prp₀ in the lower, and Grs_29–94Adr_5–64Sch_0–12Sps_0–0.2Prp_0–1.7 in the upper aureole. Close to the upper contact, clinopyroxene is virtually pure diopside with X _Mg = Mg/(Mg + Fe²⁺) = 0.97–1.0, whereas clinopyroxenes farther away from the upper contact and in the lower aureole have X _Mg-values of 0.49 and 0.53, respectively.The minimum temperatures reached during contact metamorphism in the upper and lower aureole are defined by the lower stability limit of wollastonite. The temperatures are inferred with a calculated T-X(CO₂) projection in the system CMASCH and are estimated at c. 290 °C and 380 °C for X(CO₂) values of 0.05 and 0.25, respectively. A pressure of roughly 100 bar is estimated for the lower dolerite-limestone contact. As indicated by one-dimensional thermal modelling, a maximum temperature of 695 °C was attained at this contact, assuming a magma temperature of 1150 °C. Further modelling results indicate (i) wollastonite, which occurs first 13 m away from the lower contact, formed at a maximum temperature of c. 575 °C, (ii) there, wollastonite formation lasted for approximately 170 years and, (iii) at the outer rim of the lower aureole, the maximum temperature reached was 480 °C, and temperatures sufficient for wollastonite formation lasted for about 140 years.     

Synthesis and stability relations of wairakite,CaAl2 Si4 O12·2H2O

Hydrothermal investigation of the bulk composition CaO·Al₂O₃·4SiO₂ + excess H₂O has been conducted using conventional techniques over the temperature range 200–500° C and 500–5,000 bars P _fluid. The fully ordered wairakite was synthesized unequivocally in the laboratory, probably for the first time.The gradual, sluggish and continuous transformation from disordered to ordered wairakite evidently accounts for failure by previous investigators to synthesize ordered wairakite in runs of week-long duration. The dehydration of metastable disordered wairakite to metastable hexagonal anorthite, quartz and H₂O has been determined; this reaction takes place at temperatures exceeding 400° C, even at fluid pressures of 500 bars or less. The upper P _fluid-T boundary of the disordered phase is equivalent to the maximum temperature curve of synthetic wairakite presented by previous investigators. The hydrothermal breakdown of natural wairakite above its stability limit appears to be a very slow process.The equilibrium dehydration of wairakite to anorthite, quartz and H₂O occurs at 330±5° C at 500 bars, 348±5° C at 1,000 bars, 372±5° C at 2,000 bars and 385±5° C at 3,000 bars. Where fluid pressure equals total pressure, the thermal stability range of wairakite is about 100° C wide. At lower temperatures wairakite reacts with H₂O to form laumontite. Reconnaissance experiments dealing with the effect of CO₂ on stabilities of calcium zeolites suggest that wairakite or laumontite may be replaced by the assemblage calcite + montmorillonite in the presence of a CO₂-bearing fluid phase.The determined P _fluid -T field of wairakite is compatible with field observations in some metamorphic terrains where it is related to the shallow emplacement of granitic magma and with direct pressure-temperature measurements in certain active geothermal areas. Under inferred conditions of higher _CO2/_H2O ratios, essentially unmetamorphosed rocks grade directly into those characteristic of the greenschist facies; moderately high values of _CO2 in carbonate-bearing rocks result in the downgrade extension of the greenschist facies at the expense of zeolite-bearing assemblages.     

Petrogenesis of Franciscan glaucophane schists and associated metamorphic rocks,California

Rocks of the glaucophane-schist facies are widely though irregularly developed in the Franciscan formation of California. Minerals critical of the facies are lawsonite, aragonite, jadeite and omphacitic pyroxenes associated with quartz; amphiboles of the glaucophane-crossite series are almost ubiquitous. The most widely distributed rock, occurring over areas of many square kilometers, is jadeite-lawsonite metagraywacke, commonly veined with aragonite. More spectacular, but occurring mainly in isolated blocks are coarse-grained glaucophane-lawsonite Schists of many kinds. Commonly, but by no means invariably, they are closely associated with bodies of serpentinite. Also common in the vicinity of serpentinite masses are blocks of amphibolite and eclogite.All the metamorphic rocks are considered to be Franciscan sediments and basic volcanics metamorphosed and metasomatized in the deep levels of a folded geosynclinal prism. Experimental data on the stability fields of jadeite-quartz, aragonite, and lawsonite show that the glaucophane-schist facies represents metamorphism at pressures of between 5 and 10 kb and temperatures of 150–300° C. Such conditions could develop at depths greater than 15 km provided a very low geothermal gradient (10°/km) were maintained. The metagray-wackes are considered to represent a regional response to such conditions.The role of serpentinites in glaucophane-schist metamorphism is discussed in terms of a tentatively proposed model: — In very deep levels — perhaps at depths as great as 30 km, bodies of hot ultramafic magma develop restricted aureoles' in which temperatures of 400–600° C are maintained fer perhaps 100–1000 years. The products of metamorphism, which also involves desilication under the influence of the ultramafic magma, are eclogite and amphibolite. Later, and perhaps at higher levels serpentinization of the now solid ultramafic masses (near 400° C), causes renewed metamorphism at lower grades. Marginal development of glaucophane Schists and prehnite and hydrogarnet rocks, and retrogressive alteration of eclogite and amphibolite to glaucophane-schist assemblages is attributed to this period.     

Cordierite gneisses and associated lithologies of the Guri area,Northwest Guayana Shield,Venezuela

Gneisses in the Guri area of the Venezuelan Guayana Shield contain mineral assemblages with cordierite, garnet, sillimanite, hypersthene, biotite and Fe-Ti oxide intergrowths.Analysis of mineral assemblages and compositional relationships in the light of experimental data indicate metamorphic conditions of 725–800° C, 5–6 kb P _T , <P _T for the highest grade rocks and 650–700° C, 5–7 kb P _T , approximating P _T for the lowest grade rocks. Oxygen fugacities in different lithologies ranged between those of the MH and QFM buffers.The distribution coefficient K _D (Mg-Fe) (gar-bio), decreases by 0.006 per atom percent increase in (Mn/Mn+Mg+Fe)gar, falls in the range of K _D typical of the sillimanite-K feldspar zone and granulite facies, and is systematically lower in lower grade rocks-all in accord with observation in other localities. K _D (Mg-Fe) (cord-bio) ranges from 3.0 in the highest grade rocks to 10.0 in the lowest grade rocks, appears independent of FeO/MgO of cordierite or biotite, and varies systematically with grade. In contrast with conclusions based on observation in other localities, data from the Guri area suggest -K_D(cord-bio) may be a sensitive index of grade.A number of mineralogic and geologic observations are difficultly reconciled with existing experimental data.     

Stable isotope variations in the Quaternary epithermal calcite-fluorite deposit at Monte delle Fate near Cerveteri (Latium,central Italy)

Carbon, oxygen and hydrogen isotope variations have been measured in samples from the epithermal fluorite vein deposit at Monte delle Fate, Latium. The ranges in ¹³C and ¹⁸O of calcite are –1.3 to 3.4 and 9.5 to 17.3, respectively. D values of water extracted from fluid inclusions are –49 to –39 for calcite and –41 to –34 for fluorite. Fluid inclusion filling temperatures (225°–240°C) and salinites (3.75) are nearly the same for both fluorite and sparry calcite. An elongated form of calcite, of minor abundance, precipitated at lower temperatures. The data indicate that (1) the CO₂ involved in the mineralization was provided by the local marine limestones, (2) the waters were meteoric in origin and underwent an ¹⁸O shift of 10 permil by exchange with marine country rocks, and (3) all geochemical features can be explained by the action of two hydrothermal fluids. Hot brines recently discovered in the Cesano geothermal area, 30 km to the east, have temperatures and some chemical characteristics similar to the hydrothermal fluids at Monte delle Fate.     

Enstatite-jadeite join and its role in the Earth's mantle

Phase relations on the enstatite-jadeite join were experimentally determined at solidus temperatures and 90–152 kb, and at 1400–2050°C/175–219 kb, with a split-sphere anvil apparatus (USSA-2000). New findings include immiscibility in garnet and determination of the stability of NaAlSiO₄ (calcium ferrite structure) with stishovite. A thermodynamic model for the enstatite-jadeite join was developed to calculate a complete phase diagram for the join at 500–2500°C and 0–270 kb. The results indicate that the two major discontinuities in the Earth's mantle at 400 and 670 km depths could correspond respectively to the formation and the breakdown of garnet with a pyroxene composition. A model for a chondritic upper mantle is proposed in which large-scale chemical and mineral layering was produced by fractionation of liquidus phases in a magma ocean. Solidification was completed at 400 km depth by crystallization of sodium-enriched residual melts, which produced a pyroxene layer at 300–400 km depths.     

Carbon isotopic study on coexisting calcite and graphite in the Ryoke metamorphic rocks,northern Kiso district,central Japan

Carbon isotope fractionation between coexisting calcite and grpahite ( ¹³C_cc-gr) has been determined in metamorphosed limestones and calc-silicate rocks from the Ryoke metamorphic belt in the northern Kiso district. In this district, the Ryoke metamorphic rocks, ranging from the lower greenschist facies to the upper amphibolite facies, are widely distributed. The fractionation of ¹³C/¹²C between calcite and graphite decreases regularly with increasing metamorphic grade and is independent of absolute ¹³C values of calcite. This evidence suggests that carbon isotopic exchange equilibrium has been attained during metamorphism even in the greenschist facies and isotopic modification, possibly caused by retrogressive metamorphism, is not distinguished. For T=270–650° C, the fractionation is expressed by the following equation: ¹³C_cc-gr=8.9×10⁶T^–2–7.1 (T in °K).This equation has a slope steeper than the current results on the ¹³C_cc-gr versus 10⁶T^–2 diagram. It can be used as a potential geothermometer for almost the entire temperature range of metamorphism. ¹³C values of carbonaceous matter in unmetamorphosed limestones in this district are approximately –22, due to its biogenic origin. Graphite from metamorphosed limestones is also considered to be of biogenic origin but shows enrichment of ¹³C due to isotopic exchange with calcite. ¹³C values of graphite as well as ¹³C_cc-gr confirm that zone II represents the lowest grade zone of Ryoke metamorphism. The maximum equilibrium fractionation of ¹³C between calcite and graphite is considered to be approximately 23%, which corresponds to 270° C. Below this temperature, it seems that carbon isotopic exchange between the minerals does not occur.Calcite in marble from the higher grade zones has relatively lower ¹³C and ¹⁸O values. The depletion of heavy isotopes is considered to be caused by the loss of ¹³C and ¹⁸O enriched carbon dioxide during decarbonation reactions. For oxygen, it is considered that isotopic exchange with metamorphic fluids plays an important role in lowering the ¹⁸O value of calcite in some higher grade marbles.