Barium partitioning between alkali feldspar and silicate liquid at high temperature and pressure

Barium partitioning between alkali feldspar and a natural trachyte liquid, enriched with barium, has been determined as a function of pressure and temperature from 10 to 25 kb and 900°–1100° C. Both long duration experiments and a re-equilibration experiment suggest close approach to equilibrium. Partition coefficients (D _Ba) decrease as both temperature and pressure increase (e.g., D _Ba changes from 8.71 at 10 kb, 900° C to 1.48 at 25 kb, 1100° C). Water activity also controls the barium partitioning with a marked decrease in D _Ba ^af/liq for addition of less than 0.8 wt% H₂O, but with no apparent additional effect for higher water contents in the bulk composition (e.g., from 0.8–4.2 wt% H₂O). The composition of alkali feldspar also has a significant effect on D _Ba ^af/liq , but the data obtained do not allow derivation of a complete D-Or relationship. These new data suggest that Henry's Law is obeyed for most of the barium concentrations examined, and the limit of Henry's Law behaviour for barium in alkali feldspar is as high as 6 wt% BaO in alkali feldspar and 1.2 wt% BaO in the melt, similar to the results of Long (1978). The experimental results broadly overlap with natural data for D _Ba, determined from coexisting alkali feldspar phenocrysts and glass (or groundmass).     

Ternary feldspar thermometry in granulites from the Oaxacan Complex,Mexico

Coexisting feldspars from across 2,000 km² of the granulite facies Oaxacan Complex, southern Mexico exhibit variable amounts of solid solution from nearly binary (Ab-An and Ab-Or) to substantially ternary (Ab-An-Or). Reintegrated analyses of 21 coarsely exsolved perthite (AF)-plagioclase (PL) pairs yield AF=Or_30–63 Ab_30–56An_2–15 and PL=Or_1–2Ab_70–84An_11–28. These data have been used to test existing two feldspar geothermometers for this extended composition range.For all compositions, temperature estimates show relatively little spread in value (660° to 795° C, 7 kbar) using the Haselton et al. (1983) calibration (HHHR). These temperatures are in fair agreement with estimates of 750±40° C for feldspar pairs with nearly binary compositions using the Stormer (1975) thermometer (STO). However, STO temperatures increase significantly (to 990° C) with increasing ternary solid solution in AF, suggesting that thermometers derived for binary systems are inaccurate for ternary compositions. Isotherms drawn from HHHR which take into account variable anorthite solution in alkali feldspar show that estimated temperature decreased by 50–100° C for each 5 mole percent anorthite in alkali feldspar.Experimentally determined solvus relations (Seck 1971) require feldspars with significant ternary solid solution to have crystallized or to have equilibrated at higher temperature than feldspars with more binary compositions. However, petrographic and field relations of ternary and binary feldspars in the Oaxacan Complex suggest they were all equilibrated at similar metamorphic pressures and temperatures and do not support a model where ternary feldspars have preserved higher premetamorphic temperatures. The composition of coexisting feldspars from other Precambrian granulite-facies terranes are also inconsistent with Seck's (1971) results. Hence, thermometers which fit Seck's solvus relations may not yield accurate temperatures in high grade metamorphic terranes. Parallel tie-lines for ternary and binary feldspars in the Oaxacan Complex and the consistency of inferred temperatures (HHHR) for many granulite terranes suggest that estimation of temperature using tie-line slopes rather than solvus width may yield more accurate results for these samples.Peak metamorphic conditions in the Oaxacan Complex are inferred to have been 730±50° C, 7±1 kbar. Pressure estimates from four garnet-plagioclase barometers show good agreement. Results of feldspar thermometry are consistent with diopside-forsterite equilibria in marbles which restrict T=720–765° C at P=7 kbar.     

Metastable melting in the granite system Qz-Or-Ab-An-H2O

Time studies were performed in the quinary system Qz-Or-Ab-An-H₂O at kbars and T=665 ° and 660 ° C. Starting material was a mixture of quartz, alkali feldspar Or₈₀ and plagioclase An₃₁. The compositions of plagioclases of run products were determined and compared with the plagioclase of stable solidus conditions.The solidus of the granite system was fixed at P _HäO=5 kbars using various plagioclase — and appropriate alkali feldspar — compositions besides quartz in the starting mixture (Fig. 1).The results of time studies (Table 3 and Fig. 3) reveal metastable melting in the granite system Qz-Or-Ab-An-H₂O. Plagioclase melts almost stoichiometrically. The new plagioclase compositions formed during melting of cotectic compositions approach the theoretically expected stable plagioclase compositions only extremely slowly. An extrapolation of the data achieved in run times of 5–1,500 h indicates attainment of equilibrium after 10¹⁴ years. Metastable melting of granitic compositions is not only considered as an experimental problem but also as a rock forming process in nature.     

Origin and evolution of a peraluminous silicic ignimbrite suite: The Violet Town Volcanics

The Violet Town Volcanics are a 373 Ma old, comagmatic, S-type volcanic sequence mainly comprising crystal-rich intracaldera ignimbrites. Rock types vary from rhyolites to rhyodacites, all containing magmatic cordierite and garnet phenocrysts. Variation in the suite is primarily due to fractionation of early-crystallized quartz, plagioclase and biotite (plus minor accessory phases) in a high-level magma chamber prior to eruption. Early magmatic crystallization occurred at around 4 kb and 850° C with melt water contents between 2.8 and 4 wt.%. This high-temperature, markedly water-undersaturated, restite-poor, granitic magma was generated by partial melting reactions involving biotite breakdown in a dominantly quartzofeldspathic source terrain, leaving a granulite facies residue.Table of Less Common Abbreviations Used Pkb pressure in kilobars - T° C temperature in degrees Celsius - mole fraction of water in the fluid - aH₂O activity of water - Bi biotite - Cd cordierite - Gt garnet - Py pyrope - Gr grossular - Alm almandine - Sp spessartine - He hercynite - Ilm ilmenite - Kfs potassium feldspar - Opx orthopyroxene - Pl plagioclase - An anorthite - Q quartz - Sill sillimanite - Ap apatite     

Ternary feldspars: Kinetics and possible equilibria at 800° C

The ternary feldspar system KAlSi₃O₈ - NaAlSi₃O₈ - CaAl₂Si₂O₈ was reinvestigated at 650 ° C and 800 ° C (P _H2O = 1 kb) using mixtures of crystalline plagioclases and alkali feldspars as starting materials. The compositions of plagioclases and alkali feldspars of the run products were determined by X-ray means. The Or-content of the feldspar phases was determined by measuring the position of the (201) X-ray peak of the unexchanged feldspars, whereas the An-content was determined by measuring the same X-ray peak of the K-exchanged feldspars. The reaction rate of a reaction leading to a more An-rich plagioclase (type II reaction) is much faster than a reaction producing a more Ab-rich plagioclase (type I). In a type II reaction run times of approximately 20 days are needed to reach new constant plagioclase and alkali feldspar compositions at 650 ° C, and 10 days are needed to reach constant compositions at 800 ° C. In a reaction of type I only the outer zone of the plagioclases reacts to more Abrich compositions. A diffuse zone with a wide range of compositions was observed in 650 ° C runs. Equilibrium could not be reached in these experiments within 45 days. At 800 ° C a new zone having a specific composition develops in 42 days. This new zone is believed to be in equilibrium with the coexisting alkali feldspar. The depth of reaction is calculated as 0.03 μm after 42 days (800 ° C, P _f= 1 kb). The reaction between the two feldspar phases could be reversed at 800 ° C. The following compositions are considered to represent equilibrium data at 800 ° C and P _t = 1 kb:

An 43 Ab 51 Or 6 coexisting with Or 79 Ab 20 An 1, and

An 40 Ab 54 Or 6 coexisting with Or 75 Ab 24 An 1.

Recent data obtained with gels of ternary feldspar composition as starting materials do not agree with the results presented in this paper. Gels obviously crystallize spontaneously forming coexisting feldspars of non - equilibrium composition - alkali feldspars too rich in Ab and plagioclases too rich in An.     

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.     

Experimental constraints on the storage conditions of phonolites from the Kerguelen Archipelago

Phase relations of a phonolite (K1) and a tephri-phonolite (K2) from the Upper Miocene lavas in the Southeast Province of the Kerguelen Archipelago have been investigated in the P/T range 100–500 MPa and 700–900 °C at two fO₂ conditions (~ NNO and ~ NNO+2.3) to clarify the differentiation and pre-eruptive conditions of these magmas. Crystallization experiments were performed in cold seal pressure vessels (CSPV) and internally heated pressure vessels (IHPV) at various X_H2O, under reducing (log fO₂ ~ NNO) and oxidizing conditions (log fO₂ ~ NNO+2.3). Under reducing conditions, the resulting phase assemblage for K1 was: titanomagnetite, nepheline, alkali feldspar, clinopyroxene and biotite; under oxidizing conditions, the assemblage was: magnetite, plagioclase, alkali feldspar, nepheline, titanite (minerals given in the order of appearance with decreasing T at 200 MPa for 4 wt% water in the melt). It is emphasized that an effect of fO₂ on the phase stability of feldspars and feldspathoides was observed. Comparison of the natural and experimental phase assemblages shows that the pre-eruptive conditions for K1 must have been in the log fO₂ range NNO+1–NNO+2, at pressures above 200–250 MPa. Assuming a temperature of 800 °C, the water content of the melt is constrained to be between 4 and 6 wt% H₂O. The pre-eruptive fO₂ conditions for the less evolved sample K2 are more oxidizing with log fO₂ close to NNO+2.3. The experimental results show that the enrichment of alkalis in residual melts during differentiation of tephri-phonolites is enhanced at high fO₂.Editorial responsibility: J. Hoefs     

Activity/composition relations in the ternary feldspars

Activity/composition relations are presented for high-structural state feldspars whose bulk compositions lie within the ternary system NaAlSi₃O₈ CaAl₂Si₂O₈-KAlSi₃O₈. The expressions are parameterized from the data for coexisting feldspars of Seck (1971a) using an asymmetric regular solution approximation for the excess Gibbs free energy of mixing and an Al-avoidance model for the configurational entropy of solution. The solution properties of the plagioclase and alkali-feldspar binaries have been made to conform to the recent work of Thompson and Hovis (1979) and Newton et al. (1980). Using the proposed model the ternary feldspar solvus is extrapolated in temperature (up to 1,500° C) and pressure (up to 5kbars). A new two-feldspar geothermometer is presented which provides somewhat more reasonable estimates of crystallization temperatures than the equations and graphs of Stornier (1975), Powell and Powell (1977), Brown and Parsons (1981) and Haselton et al. (1983). In conjunction, some criteria are suggested for establishing the existence of equilibrium tie-lines between coexisting ternary feldspars in rhyolites and trachytes. Calculated values of the activity of KAlSi₃O₈ in plagioclase are examined in some detail. These compare favorably with independent estimates obtained from experimentally grown plagioclases precipitating at liquidus temperatures from igneous rocks of widely varying alkali contents.     

Feldspar geothermometry of the Hell Canyon Pluton,Boulder Batholith,Montana

The bulk compositions of the groundmass alkali feldspar from the Hell Canyon Pluton is 0.146mole% albite. The composition of the outermost zone of the oscillatory zoned plagioclase is 0.686 mole% albite, whereas the most calcic cores have a composition of 0.43 mole% albite. The structural state of the alkali feldspar is near orthoclase. Both composition of coexisting feldspars and structural state of the alkali feldspar are nearly constant throughout the pluton.Exsolved albite in the alkali feldspar have a composition of 0.965 mole% albite and the orthoclase host has a composition of 0.032 mole%. Singe crystal X-ray studies indicate that the albite intergrowths are coherent with the host.Equilibrium temperatures derived from the coexisting feldspar average 554 ° C; about 150 ° C, too low for the minimum solidus temperatures for reasonable emplacement pressures (2 kb). If this minimum solidus temperature is assumed, then the alkali feldspar has lost about 0.15 mole% albite. This loss was most likely caused by hydrothermal solutions associated with the crystallizing magma and equilibrated at about 550 ° C. However, based on the coherent albite intergrowths and the orthoclase structure state it can be inferred that the system was relatively free of volatiles below 500 ° C. Final equilibirium between orthoclase host and albite intergrowths occurred at about 311 ° C.     

Experimental silicate mineral/melt partition coefficients for beryllium and the crustal Be cycle from migmatite to pegmatite

Partition coefficients (D_Be^mineral/melt) for beryllium between hydrous granitic melt and alkali feldspars, plagioclase feldspars, quartz, dark mica, and white mica were determined by experiment at 200 MPa H₂O as a function of temperature (650-900°C), activity of Be in melt (trace levels to beryl saturation), bulk composition, and thermal run direction. At trace levels, Be is compatible in plagioclase of An₃₁ (1.84 at 700°C) and muscovite (1.35 at 700°C) but incompatible in biotite (0.39-0.54 from 650-800°C), alkali feldspar (0.38-0.19 from 680-850°C), quartz (0.24 at 800°C), and albite (0.10 at 750°C). The partition coefficients are different at saturation of the melt in beryl: lower in the case of plagioclase of An₃₁ (0.89 at 700°C), muscovite (0.87 at 700°C), biotite (0.18-0.08 from 675-800°C), alkali feldspar (0.18-0.14 from 680-700°C), and quartz (0.17-0.08 from 750-800°C), but higher in the case of albite (0.37 at 750°C).With other data sources, these new partition coefficients were utilized to track, first, the distribution of Be between aluminous quartzofeldspathic source rocks and their anatectic melts, and second, the dispersion or concentration of Be in melt through igneous crystal fractionation of different magma types (e.g., S-type, I-type) up to beryl-saturated granitic pegmatites and, finally, into their hydrothermal aureoles. Among the rock-forming minerals, cordierite, calcic oligoclase, and muscovite (in this order) control the fate of Be because of the compatibility of Be in these phases. In general, beryl-bearing pegmatites can arise only after extended crystal fractionation of large magma batches (to F, fraction of melt remaining, ≤0.05); granitic magmas that originate from cordierite-bearing protoliths or that contain large modal quantities of calcic oligoclase will not achieve beryl saturation at any point in their evolution.     

The stability of CaCO3·6H2O (ikaite)

Experimental runs were made in cold-seal pressure vessels using synthetic CaCO₈·6H₂O, calcite and aragonite as starting materials. The reaction CaCO₃·6H₂O (ikaite) ? CaCO₃ (calcite I) + 6H₂O was reversed across its metastable extension into the aragonite stability field and the phase boundary is defined by brackets at 4.14kb, 14.3°C and 2.96 kb, ?3.0°C. An invariant point for CaCO₃·6H₂O, calcite I, aragonite and water thus occurs at about 3.02 kb and ?2.0°C. No other reaction could be reversed. Calculations based on the equilibrium phase boundary between calcite and ikaite and the available thermochemical data for calcite and water yield the stadard free energy of formation, standard enthalpy of formation and third law entropy of CaCO₃·6H₂O at 25°C and 1 bar total pressure; ?607.3 kcal/mole, ?705.8 kcal/mole, and 88.4 cal/deg mole, respectively.     

Origin of mantle (rapakivi) feldspars: experimental evidence of a dissolution- and diffusion-controlled mechanism

Experiments designed to simulate the dissolution of alkali feldspar during magma mixing produced plagioclase mantles that are texturally and compositionally similar to those in some hybrid volcanic rocks. In hydrous dacite melt (69% SiO₂) at 0.8 GPa, 850°C, orthoclase (Or₉₃) and sanidine (Or₃₀) partially dissolved and were mantled by sodic plagioclase (An_25–30). Although plagioclase nucleated epitaxially as a thin shell on the alkali feldspar surface near the time of initial resorption, plagioclase subsequently grew inward —mostly in the form of parallel blades — toaard the receding dissolution surface. Orthoclase dissolved at a rate approximately proportional to the square root of run duration, indicating diffusional control. Plagioclase grew inward within a static boundary zone of melt that formed between the original crystal-dacite interface and the dissolution surface. During orthoclase dissolution, this boundary zone rapidly and simultancously gained Na (by diffusion from dacite) and lost K (by diffusion into dacite); Ca diffused more slowly into this zone, from which non-feldspar species were mostly excluded. Plagioclase was stable where sufficient Ca had diffused in that the boundary zone melt intersected the plagioclase-saturation liquidus. Plagioclase subsequently grew toward the receding dissolution surface as the Ca compositional gradient (and hence the site of plagioclase saturation) stepped inward. Crystallization of plagioclase in the form of parallel blades allowed continued diffusive exchange of melt components between the dissolution surface and the host melt. Bladed growth also served to maintain (at blade tips) proximity of plagioclase to the dissolution surface, thereby apparently preserving (locally) a thin zone of low-variance melt. In natural systems, mantling of alkali feldspar by plagioclase will occur in a similar manner when (a) P, T, or X are changed to induce alkali feldspar dissolution, (b) sufficient Ca is available in the host melt to drive (by diffusion) boundary zone melt compositions to plagioclase saturation, and (c) temperatures are low enough to stabilize sodic plagioclase and to maintain a coherent boundary zone. These reqjirements are satisfied in volcanic systems when alkali feldspar is juxtaposed during mixing with hybrid melts of dacitic composition. Mantled feldspars in some intrusive systems (i.e., rapakivi granites) may form by a similar dissolution- and diffusion-controlled mechanism. Textural evidence of a similar origin may be obscurred in intrusive rocks, however, by products of late-stage magmatic and subsolidus processes.     

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).     

Liquidas phase relationships in the system CaAl2Si2O8-NaAlSi3O8-KAlSi3O8-NaAlSiO4-KAlSiO4 atP(H2O)=5 kb

Liquidus phase equilibria have been determined in the system CaAl₂Si₂O₈-NaAlSi₃O₈-KAlSi₃O₈-NaAlSiO₄-KAlSiO₄ (An-Ab-Or-Ne-Ks) at a pressure of water of 5 kb, for low anorthite contents. The main effects of increasing anorthite content on phase relationships in the system Ab-Or-Ne-Ks include the expansion of the plagioclase stability field towards the potassium-rich part of the system, and an accompanying contraction of the alkali feldspar, leucite, nepheline and kalsilite stability fields; and an increase in liquidus temperatures throughout most of the compositional range. Two quaternary invariant points have been identified in the system, one a reaction point between the fields of alkali feldspar, plagioclase, nepheline and kalsilite at approximately An₄, and the other probably a quaternary eutectic between the fields of alkali feldspar, plagioclase, leucite and kalsilite at approximately An₆. A shallow minimum trough in liquidus temperatures occurs on the two-feldspar surface, and this would be expected to control the paths of liquids cooling under equilibrium conditions. Phase relationships in this quaternary system have been applied to the interpretation of the histories of the potassium-rich rocks of the Roman Volcanic Region, Italy. Differentiation of the phonolitic series in this region may have occurred by two-feldspar fractionation.     

An experimental study of Fe-Mg partitioning between garnet and olivine and its calibration as a geothermometer

The partitioning of Fe and Mg between coexisting garnet and olivine has been studied at 30 kb pressure and temperatures of 900 ° to 1,400 °C. The results of both synthesis and reversal experiments demonstrate that K _D (= (Fe/Mg)_gt/(Fe/Mg)_OI) is strongly dependent on Fe/Mg ratio and on the calcium content of the garnet. For example, at 1,000 °C/30 kb, K _D varies from about 1.2 in very iron-rich compositions to 1.9 at the magnesium end of the series. Increasing the mole fraction of calcium in the garnet from 0 to 0.3 at 1,000 ° C increases K _D in magnesian compositions from 1.9 to about 2.5.The observed temperature and composition dependence of K _D has been formulated into an equation suitable for geothermometry by considering the solid solution properties of the olivine and garnet phases. It was found that, within experimental error, the simplest kind of nonideal solution model (Regular Solution) fits the experimental data adequately. The use of more complex models did not markedly improve the fit to the data, so the model with the least number of variables was adopted.Multiple linear regression of the experimental data (72 points) yielded, for the exchange reaction: 3Fe₂SiO₄+2Mg₃Al₂Si₃O₁₂ olivine garnet 2Fe₂Al₂Si₃O₁₂+3Mg₂SiO₄ garnet olivine H ° (30kb) of –10,750 cal and S ° of –4.26 cal deg^–1 mol^–1. Absolute magnitudes of interaction parameters (W _ij ) derived from the regression are subject to considerable uncertainty. The partition coefficient is, however, strongly dependent on the following differences between solution parameters and these differences are fairly well constrained: W _FeMg ^ol -W _FeMg ^gt 800 cal W _CaMg ^gt -W _CaFe ^gt 2,670 cal.The geothermometer is most sensitive in the temperature and composition regions where K _D is substantially greater than 1. Thus, for example, peridotitic compositions at temperatures less than about 1,300 ° C should yield calculated temperatures within 60 °C of the true value. Iron rich compositions (at any temperature) and magnesian compositions at temperatures well above 1,300 °C could not be expected to yield accurate calculated temperatures.For a fixed K _D the influence of pressure is to raise the calculated temperature by between 3 and 6 °C per kbar.     

Aragonite crystallization from strained calcite at reduced pressures and its bearing on aragonite in low-grade metamorphism

Aragonite, the dense form of CaCO₃, grew hydrothermally at 100–300° C and dry at 300–400° C at very low pressures from calcite strained by grinding. Nearly complete inversion to aragonite occurred in some runs with Ca-Mg chloride solutions at 0–2.4 kb and 100–200° C on strained calcite having a (10¯14) reflection with a half-width of 0.48° 2 Cu K. A little aragonite grew dry at one atm. from the ground calcite at 300–400° C in a few hrs. Simultaneous shear during recrystallization of calcite in a rotating squeezer resulted in significant aragonite at 300–400° C several kb. below the stability field. No inversion occurred in any ground calcite when previously annealed in CO₂ at 500° C for a few hrs. Thermochemical data show that at least 200 cal/mole of strain energy can be produced in calcite by mild deformation. This much stored energy would lower the pressure requirements of aragonite, relative to the strained calcite by more than 3 kb, and our observation that aragonite growth was faster than strain recovery of calcite indicates that aragonite can grow in nature at reduced pressures from strained calcite.Some experiments were also carried out on highly magnesian calcites with the thought that aragonite might also form at the expense of this metastable material. No aragonite was produced, but the possibility that this mechanism could be operative in nature cannot be discounted.The microtexture of aragonitic deformed marbles from NW Washington (prehnite-pumpellyite facies rocks, courtesy of J. A. Vance) as well as electron probe microanalysis of these rocks indicates that aragonite selectively replaced highly strained calcite. The calcite-aragonite transition is thus a questionable indicator of high-pressure in certain metamorphic rocks.     

Melting of plagioclase-quartz assemblages at 2 kbar water pressure

The melting of plagioclase and quartz has been investigated at P _H2O =2kb. A single crystal of plagioclase was surrounded by quartz powder and water. A reaction rim consisting of glass and of An-rich plagioclase developed around unchanged starting plagioclase. Microprobe determinations of melt and coexisting plagioclase compositions reveal a strong fractionation of plagioclase components between melt and new plagioclase. For example at 850° C the approximate X _An of melt is 0.3 and that of plagioclase is 0.8. The temperature interval between beginning of melting and complete melting of cotectic compositions is 100° C or more for quartz-plagioclase mixtures with plagioclases between An 40 and An 75. In comparison to the system Ab-An-H₂O the plagioclase melting loop is somewhat wider in the investigated system Qz-Ab-An-H₂O but the temperature interval is much smaller (100° C) than in the system Ab-An-H₂O (200° C). The solidus data indicated by the new plagioclase compositions are practically identical with those observed in beginning of melting experiments. The results show that fractionation of plagioclase components between partial melts and restite plagioclase can be more pronounced in multi-component rocks than in the pure plagioclase system. This finding is important for the development of albite rich rocks from more basic compositions.     

Mineral Equilibria in the System Nepheline-Alkali Feldspar-Plagioclase and their Petrological Significance

The purpose of this work is a theoretical consideration of equilibriumconditions in the system nepheline-alkali feldspar-plagioclase-alkalichloride aqueous solution based on the thermodynamic treatmentof experimental data (Orville, 1963; Iiyama et al., 1963; Debronet al., 1961) for particular systems. The excess thermodynamicfunctions (Z^E, S^E, H^E, V^E) of solid solutions were calculatedfor it. These data enable us to derive the diagrams of isothermsfor the distribution of sodium components between nephelineand alkali feldspar; between plagioclase and alkali feldspar;and among plagioclase, nepheline, and alkali feldspar for thetemperature range 400–1000 C. In order to check the calculated diagrams we analysed the mineralsfrom the binary and ternary assemblages of the systems nepheline$alkalifeldspar$plagioclase from various igneous massifs of nephelinesyenites of the world. Temperatures obtained from differentgeothermometers were found to coincide satisfactorily.     

Rhyolites contaminated with metapelite and gabbro,Lipari, Aeolian Islands,Italy: products of lower crustal fusion or of assimilation plus fractional crystallization?

Pleistocene lavas from Monte S. Angelo and Chiesa Vecchia volcanoes on Lipari contain two suites of inclusions. A metapelitic suite consists of gneisses and granulites with combinations of cordierite, garnet, corundum, hercynite, andalusite, sillimanite, orthopyroxene, ilmenite, magnetite, biotite, plagioclase, and quartz. A gabbroic suite has cumulus texture and contains plagioclase, orthopyroxene, clinopyroxene, and magnetite. All megacryst phases in the lavas appear to be derived from rock fragments, with the exception of euhedral strongly zoned calcic plagioclase, and none has grown by homogeneous nucleation from liquid represented by the groundmass, which is peraluminous rhyolite (>70 wt% SiO₂, >6 wt% K₂O). Ground-mass microcrysts were nearly all derived from disaggregated metapelites; overgrowths of alkali feldspar on plagioclase and of orthopyroxene on clinopyroxene, and quartz intergrown with alkali feldspar, are the only phases that grew from the rhyolitic liquid. Euhedral cordierite, hercynite, and plagioclase at the margins of some rock fragments grew by reaction of metapelite with liquid.For grains in contact within metapelite inclusions, geothermometers and geobarometers yield estimates of equilibration conditions in the range of 800±100° C and 5±1 kbar. Compositions of phases in the same thin section, but not in the same inclusion, yield broadly erratic P and T estimates indicating disequilibrium among metapelite inclusions. Pyroxene thermometry in the gabbro suite indicates a crystallization temperature of 1020±50° C and a lack of subsequent thermal equilibration with the rhyolitic liquid.The metapelite suite may partly be restite, but much is xenolithic, derived from a vertical interval of perhaps several kilometers, and may have undergone a much earlier episode of melting. The gabbro fragments are accidental xenoliths incorporated as the magma rose. Contaminants (metapelite and gabbro) account for 50 vol.% of the lavas, and cause them to be classified as high-K andesite according to whole-rock major element analysis.The rhyolitic liquid may have originated by partial fusion of metapelites in the lower crust, or by fractional crystallization of mafic mantle-derived magma combined with assimilation of metapelite; the bulk of the evidence favors assimilation-fractional crystallization. Miocene and younger metapelite-contaminated rhyolites also occur in Tuscany, SE Spain, E Morocco, and NW Tunisia, and are associated in each region with mafic silica-undersaturated lavas, implying crustal underplating around the western Mediterranean before, during, and after formation of the Tyrrhenian basin.     

Stability of titanian clinohumite: Experiments and thermodynamic analysis

Reversed hydrothermal experiments on a natural titanoclinohumite [Ti-Cl; approximate formula Mg_7.5FeTi_0.5O₁₆(OH)] show that it breaks down at 475°±11° C (3.5 kbar), 620°±11° C (14 kbar) and 675°±8° C (21 kbar) to the assemblage olivine +ilmenite+vapor. An internal-consistency analysis of the data yields _r G _s ^/0 (298 K, 1 bar)=36,760±3,326 cal (mole Ti-Cl)^–1. _r S _s ^/0 (298 K, 1 bar)=34.14±5.91 cal deg^–1(mole Ti-Cl)^–1. Linear correlation coefficient r _G–S 1.0. A solution model that accounts for TiO₂-M(OH)₂ and F-OH substitution shows that the results for our nearly F-free Ti-Cl are in reasonable agreement with the unreversed breakdown experiments of Mer-rill et al. (1972) on a F-bearing Ti-Cl.Because fluorine is necessary to stabilize Ti-Cl under mantle conditions, we suggest that Ti-Cl is much more likely to be a storage device for fluorine than for water in the mantle.