Phase relations to 3 kbar in the systems edenite + H2O and edenite + excess quartz + H2O

Amphiboles approached edenite (NaCa₂Mg₅Si₇AlO₂₂(OH)₂), richterite (Na₂CaMg₅Si₈O₂₂(OH)₂), tremolite (□Ca₂Mg₅Si₈O₂₂(OH)₂) solid solutions were studied by conventional hydrothermal techniques employing the bulk compositions edenite, and edenite + additional quartz, all with excess H₂O. For the stoichiometric edenite bulk composition + excess H₂O, the equilibrium phase assemblage is diopside + Na-phlogopite + forsterite + fluid at, and just above the amphibole high-temperature limit at 850 ± 5°C, 500 bar, and 880 ± 5°C, 1000 bar. The breakdown temperature of sodic phlogopite is 855 ± 3°C at 500 bar, and 890 ± 5°C at 700 bar, producing nepheline + plagioclase (or melt), additional forsterite and fluid. Diopside and Na-phlogopite solid solution coexist over a broad P_fluid-T region, even within the amphibole field, where they are associated with an edenite-richterite (-tremolite) solid solution of approximate composition Ed₃₅Rc₅₀Tr₁₅.In the system edenite + 4 quartz + excess H₂O, nearly pure tremolite and albite coexist stably between 670° and 830°C at 1000 bar and give way to the possibly metastable assemblage diopside + talc + albite below 670°C. In the presence of albite, tremolite reacts to produce diopside + quartz + enstatite + fluid above 830°C at 1000 bar. For the investigated silica-rich bulk composition, amphibole P_fluid-T stability is divided by the albite melting curve into a tremolite + albite field, and a tremolite + aqueous melt field. Substantial equilibrium solid solution of tremolite towards edenite or richterite was not observed for silica-excess bulk compositions. Metastable edenite-rich amphiboles initially synthesized change to tremolite with increasing run length in the presence of free SiO₂.Edenitic amphibole is stable only over a very limited temperature range in silica-undersaturated environments, thus accounting for its rarity in nature. Na-phlogopite solid solutions are also disfavored by high a_SiO2; even for nepheline-normative lithologies, a hypothesized rapid low-temperature conversion to vermiculite or smectite could partly explain the scarcity of sodic phlogopite in rocks.     

Experimental studies to 10 kb of the bulk composition tremolite50-tschermakite50+excess H2O

Phase relations for the magnesio-hornblende bulk composition, 2 CaO·4 MgO·Al₂O₃·7 SiO₂+ excess H₂O, have been investigated to 10 kb employing hydrothermal and piston-cylinder techniques. The low-temperature limit of amphibole in this system lies at 519° C, 1,000 bars, 541° C, 2,000 bars, and 718° C, 10 kb. The low-T assemblage consists of an+chl+di+tc(+f), and is related to the adjacent high-T equilibrium assemblage, amph+an+chl+f, by the solid-solid reaction (A): 2 di+tc=tr. Small amounts of aluminum, hypothesized to be preferentially dissolved in the cpx (and in the tc) relative to amph, may account for the broad P-T stability range of the di+tc assemblage in the synthetic work relative to systems involving stoichiometric tr, Ca₂Mg₅Si₈O₂₂(OH)₂, such as are common in natural, Al-poor calc-silicate parageneses. Alternatively, the low-temperature assemblage produced in the experiments may be metastable. For the investigated bulk composition, synthetic tremolitic-cummingtonitic amphibole contains relatively modest amounts of ts, Ca₂Mg₃Al₂ ^IVSi₆-Al₂ ^IVO₂₂(OH)₂; at pressures of 1,000–3,000 bars, solid solution extends from near tremolite only to about cu₁₁tr₆₉ts₂₀, analogous to most analyzed natural magnesio-hornblendic specimens. At 10 kb fluid pressure, the solid solution reaches approximately cu₀₆tr₅₃ts₄₁ for the investigated bulk composition, and appears to be virtually independent of temperature. Amphibole and 14 Å chl react within the amphibole stability field, along curve (B), at about 704° C and 2,000 bars, to produce an, en, fo and f (H=40.9 kcal/ mole); at pressures greater than approximately 7kb, due to the incompatibility of an and fo, the higher temperature assemblage consists of amph, an, en, sp and f. Above P _fluid– T curve (B), the amphibole coexists with an+en+fo+f at low pressures; at higher pressures, the amphibole, which is in equilibrium with an+en+sp+f, is relatively more aluminous. The high-T stability limit of aluminous tr+fo lies approximately 20–25° C below the dehydration curve for stoichiometric tremolite on its own bulk composition. Reaction (C), tr+fo=2 di+5 en+f (H = 39.4 kcal/mole), produces an+di+en+f, the highest temperature subsolidus assemblage investigated for the tr₅₀ts₅₀ bulk composition. Hydrous melt is encountered at temperatures at least as low as 900° C at 10 kb, and at that fluid pressure coexists with amphibole over an interval of more than 60° C. Limited solid solution observed between tr and ts in nature (tr_100-70) is accounted for by the restricted range of amphibole compositions produced in the present study. Such amphiboles, moreover, appear to have both high- and low-temperature stability limits, as demonstrated by the experimental results.Institute of Geophysics and Planetary Physics Publication No. 2811     

Stability relations of K2Mg5Si12O30, and end member of the merrihueite-roedderite group of meteoritic minerals

The phase K₂Mg₅Si₁₂O₃₀ was synthesized both hydrothermally and dry under a variety of pressures and temperatures, and its stability relations were determined. Under hydrothermal conditions it exhibits a lower stability limit lying at 595°C, 1 kb, and 650°C, 2 kb, due to its breakdown into the hydrous assemblage quartz+KMg_2.5Si₄O₁₀(OH)₂ (a mica phase). Its upper temperature stability under hydrothermal conditions is given by its incongruent melting to MgSiO₃+liquid. Near 820° C at a fluid pressure of approximately 6.5 kb the two univariant curves for these breakdown reactions intersect thus limiting the stability field to lower fluid pressures. — Under anhydrous conditions K₂Mg₅Si₁₂O₃₀ becomes unstable at pressures between approximately 7 and 32.5 kb due to its incongruent melting to the assemblage MgSiO₃+quartz (or coesite)+liquid; this melting curve has a pronounced negative slope. No subsolidus breakdown assemblage was encountered at 32.5 kb down to temperatures as low as 750°C. This behavior is probably due to the instability of other ternary compounds in the system K₂O-MgO-SiO₂ at high pressures and thus to the existence of very low-temperature eutectics involving only binary and unary solid phases plus liquid.It is likely that these stability relations provide a model for those of the natural minerals merrihueite and roedderite which contain Na and Fe₊₂ partly substituting for K and Mg and which were encountered in several meteorites. Therefore, the cosmic events leading to the formation of these minerals must have taken place at relatively low pressures and high temperatures, especially when water was present. The bulk compositions of these minerals appear to be incompatible with average chondritic matter under equilibrium conditions. Hence merrihueite and roedderite are not likely to be found in equilibrated chondrites which contain feldspars instead.     

Stability and composition relations of calcic amphiboles in ultramafic rocks

Calcic amphiboles are observed in ultramafic rocks that have equilibrated under a broad span of geological conditions and might prove to be good indicators of metamorphic grade if their stabilities could be determined as a function of their compositions. Experiments were performed on the stability of tremolite plus forsterite in the system H₂O-CaO-MgO-SiO₂ from 5 to 20 kbar. A univariant curve was fitted to the experimental brackets using volume, water fugacity, and heat capacity data. The results indicate that the maximum stability of tremolite in the presence of forsterite is about 825° C at 5 kbar. Addition of Al₂O₃ to this system increases the stability of tremolitic amphibole by only 20°–40° C and induces solubility of 5–7 wt.% Al₂O₃ in the amphibole, as determined from quantitative SEM analyses of individual amphibole crystals. Thus substitution of the tschermakite component (Ca₂(Mg₃Al₂) (Si₆Al₂) O₂₂(OH)₂) alone cannot lead to the greatly enhanced Al₂O₃ contents or thermal stability of natural calcic amphiboles. Comparison of the results from this study with experimental results from other studies on synthetic calcic amphiboles indicates that the high thermal stability of natural amphiboles is strongly linked with the substitution of alkalies (Na in particular) in the form of the component Na-Ca₂(Mg₄Al) (Si₆Al₂)O₂₂(OH)₂ (pargasite). Accordingly, experimental data from studies on pargasite have been combined with the appropriate univariant curves to obtain a phase diagram for amphibole-bearing ultramafic rocks modelled by the system H₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂.     

The Origin and Composition of Metasomatic Fluids and Amphiboles beneath Malaita, Solomon Islands

A suite of mantle peridotite xenoliths from the Malaitan alnoitedisplay both trace element enrichment and modal metasomatism.Pargasitic amphibole is present in both garnet- and spinelbearingxenoliths, formed by reaction of a metasomatic fluid (representedby H₂O and Na₂O) with the peridotite assemblage. Two pargasite-formingreactions are postulated, whereby spinel is totally consumed: 6MgAl₂O₄ + 8CaMgSi₂O₆ + 7Mg₂Si₂O₆ + 4H₂O + 2Na₂O = 4NaCa₂Mg₄Al₃Si₆O₁₂(OH)₂+ 6Mg₂SiO₄ or spinel is both a reactant (low Cr) and a product (high Cr): 24MgAlCrO₄ + 16CaMgSi₂O₆ + 14Mg₂Si₂O₆ + 8H₂O + 4Na₂O = 8NaCa₂Mg₄Al₃Si₆O₁₂(OH)₂+ 12MgCr₂O₄ + 12Mg₂SiO₄ Seven garnet—spinel-peridotites display cryptic metasomatismas demonstrated by the LREE enrichment in clinopyroxenes. TheLREE enrichment correlates positively with ¹⁴³ND/¹⁴⁴ND (0?512771–0?513093)which defines a mixing line between a mantle MORB source anda metasomatic fluid. Isotopic evidence (Sr and Nd) from garnet,clinopyroxene, and amphibole demonstrate this fluid has notoriginated in the alnoite sensu stricto. Calculated amphiboleequilibrium liquids show a range in La/Yb and Ce/Yb ratios similarto those calculated for the augite and subcalcic diopside megacrysts.Sr and Nd isotope analyses from amphibole are within error ofthe augite (PHN4074) and subcalcic diopside megacrysts (CRN2I6,PHN4069, and PHN4085). It is concluded that fluids emanatedfrom a proto-alnoite magma throughout megacryst fractionation,and the mixing line was generated during the crystallizationof the subcalcic diopsides. This study demonstrates that metasomatismrepresented in these xenoliths is not a prerequisite for alnoitemagmatism, but is a consequence of it.     

An experimental study of glaucophanic amphiboles in the system Na2O-MgO-Al2O3-SiO2-SiF4 (NMASF): some implications for glaucophane stability in natural and synthetic systems at high temperatures and pressures

The phase relations of glaucophanic amphiboles have been studied at 18–31 kbar/680–950°C in the synthetic system Na₂O–MgO–Al₂O₃–SiO₂–SiF₄ (NMASF) using the bulk composition of fluor-glaucophane, Na₂Mg₃Al₂Si₈O₂₂F₂. Previous experimental studies of glaucophane in the water-bearing system (NMASH) have been hampered by problems of fine grain size (electron microprobe analyses with low oxide totals and contamination by other phases), and consequently good compositional data are lacking. Fluor-amphiboles, on the other hand, generally have much higher thermal stabilities than their hydrous counterparts. By using the fluorine-analogue system NMASF, amphibole crystals sufficiently coarse for electron microprobe analysis have been obtained. Furthermore, NMASH amphibole phase relations are directly analogous to those of the NMASF system because SiF₄ fills the role of H₂O as the fluid species. High-pressure NMASF amphibole parageneses are comparable to those obtained for NMASH amphiboles under similar pressure-temperature conditions, except that the NMASF solidus was not encountered. In the pressure-temperature range of the NMASF experiments, fluor-glaucophane is unstable relative to glaucophanenyböite-Mg-magnesio-katophorite amphiboles. Variations in synthetic fluor-amphibole composition with P and T are discussed in terms of changes in the thermodynamic activities of the principal amphibole end-members, such as glaucophane (a_Gp) and nyböite (a_Ny) using an ideal-mixing-on-sites model. The most glaucophanic amphiboles analysed have a_Gp=0.50–0.60 and coexist with jadeite and coesite at 30 kbar/800°C. Amphiboles become increasingly nyböitic with decreasing pressure through the NaAlSi_-1 exchange, which is the principal variation observed. The most nyböitic amphiboles have a_Ny =0.65–0.70 and coexist with fluor-sodium-phlogopite and quartz at 21–24 kbar/800–850°C. At 800°C amphiboles are essentially glaucophane-nyböite solid solutions. At 850°C there is some minor displacement along MgMgSi_-1, but Mg-magnesio-katophorite activities are very low (<0.06). Activities of the eight other NMASF amphibole end-members are <0.001, except for eckermannite activity which varies from 0.01–0.11. Our results indicate that: (a) synthetic amphiboles mimic the essential stoichiometries observed in blueschist amphiboles; (b) synthetic studies should be relevant to petrologically important high-pressure parageneses and reactions involving glaucophanicamphiboles, sodic pyroxenes, albite and talc; (c) the high-pressure stability limit of fluorglaucophane lies at pressures higher than those reached in this study (31 kbar); (d) in natural systems an approach to glaucophane stoichiometry should be favoured by high water activities as well as high pressures.Abbreviations and formulae used in this paper Glaucophane (Gp) oNa₂(Mg₃Al₂)Si₈O₂₂(OH,F)₂ - Nyböite (Ny) NaNa₂(Mg₃Al₂)Si₇AlO₂₂(OH,F)₂ - Eckermannite (Ek) NaNa₂(Mg₄Al)Si₈O₂₂(OH,F)₂ - Magnesio-cummingtonite (MC) oMg₂(Mg₅)Si₈O₂₂(OH,F)₂ - Sodium-magnesio-cummingtonite (SMC) NaNaMg(Mg₅)Si₈O₂₂(OH,F)₂ - Sodium-anthophyllite (SAn) NaMg₂(Mg₅)Si₇AlO₂₂(OH,F)₂ - Gedrite (Gd) oMg₂(Mg₃Al₂)Si₆Al₂O₂₂(OH,F)₂ - Sodium-gedrite (SGd) NaMg₂(Mg₄Al)Si₆Al₂O₂₂(OH,F)₂ - Mg-magnesio-aluminotaramite (MAT) NaNaMg(Mg₃Al₂)Si₆Al₂O₂₂(OH,F)₂ - Mg-magnesio-katophorite (MKt) NaNaMg(Mg₄Al)Si₇AlO₂₂(OH,F)₂ - Mg-magnesio-barroisite (MBa) oNaMg(Mg₄Al)Si₇AlO₂₂(OH,F)₂ - Jadeite (Jd) NaAlSi₂O₆ - Enstatite (En) Mg₂Si₂O₆ - Forsterite (Fo) Mg₂SiO₄ - Nepheline (Ne) NaAlSiO₄ - Albite (Ab) NaAlSi₃O₈ - Quartz/Coesite (Qz/Co) SiO₂ - Sodium-phlogopite (Sphl) NaMg₃Si₃AlO₁₀(OH,F)₂ - Talc (Tc) oMg₃Si₄O₁₀(OH,F)₂ - o vacant A-site in amphiboles and interlayer site in talc. Octahedral cations in amphiboles are bracketted     

Experimental study of metamorphic reactions and dehydration processes at the blueschist–eclogite transition during warm subduction

The transition between blueschist and eclogite plays an important role in subduction zones via dehydration and densification processes in descending oceanic slabs. There are a number of previous petrological studies describing potential mineral reactions taking place at the transition. An experimental determination of such reactions could help constrain the pressure–temperature conditions of the transition as well as the processes of dehydration. However, previous experimental contributions have focused on the stability of spontaneously formed hydrous minerals in basaltic compositions rather than on reactions among already formed blueschist facies minerals. Therefore, this study conducted three groups of experiments to explore the metamorphic reactions among blueschist facies minerals at conditions corresponding to warm subduction, where faster reaction rates are possible on the time scale of laboratory experiments. The first group of experiments was to establish experimental reversals of the reaction glaucophane+paragonite to jadeite+pyrope+quartz+H₂O over the range of 2.2–3.5 GPa and 650–820°C. This reaction has long been treated as key to the blueschist–eclogite transition. However, only the growth of glaucophane+paragonite was observed at the intersectional stability field of both paragonite and jadeite+quartz, confirming thermodynamic calculations that the reaction is not stable in the system Na₂O–MgO–Al₂O₃–SiO₂–H₂O. The second set of experiments involved unreversed experiments using glaucophane+zoisite ±quartz in low‐Fe and Ca‐rich systems and were run at 1.8–2.4 GPa and 600–780°C. These produced omphacite+paragonite/kyanite+H₂O accompanied by compositional shifts in the sodium amphibole, glaucophane, towards sodium–calcium amphiboles such as winchite (?(CaNa)(Mg₄Al)Si₈O₂₂(OH)₂) and barroisite (?(CaNa)(Mg₃Al₂)(AlSi₇)O₂₂(OH)₂). This suggests that a two‐step dehydration occurs, first involving the breakdown of glaucophane+zoisite towards a paragonite‐bearing assemblage, then the breakdown of paragonite to release H₂O. It also indicates that sodium–calcium amphibole can coexist with eclogite phases, thereby extending the thermal stability of amphibole to greater subduction zone depths. The third set of experiments was an experimental investigation at 2.0–2.4 GPa and 630–850°C involving a high‐Fe (Fe#=Fe_total/(Fe_total+Mg)≈0.36) natural glaucophane, synthetic paragonite and their eclogite‐forming reaction products. The results indicated that garnet and omphacite grew over most of these pressure–temperature conditions, which demonstrates the importance of Fe‐rich glaucophane in forming the key eclogite assemblage of garnet+omphacite, even under warm subduction zone conditions. Based on the experiments of this study, reaction between glaucophane+zoisite is instrumental in controlling dehydration processes at the blueschist–eclogite transition during warm subduction.     

Amphibole-plagioclase equilibria: An empirical model for the relation albite+tremolite=edenite+4 quartz

Equilibria between plagioclase, calcic amphibole and quartz can be described, in part, by the relation among mineral components: NaAlSi₃O₈+Ca₂Mg₅Si₈O₂₂(OH)₂ = NaCa₂Mg₅AlSi₇O₂₂(OH)₂+4SiO₂; this relation governs the partitioning of Na between plagioclase and the A-site of coexisting amphibole. Data from natural amphibolites reveal that this partitioning is systematic and sensitive to metamorphic grade. The ideal portion of the equilibrium constant (K _id = X _{Na, A}/X_{, A} · X _Ab) derived from natural samples is sensitive to bulk composition, inasmuch as both plagioclase and amphibole are highly non-ideal. Samples from a single outcrop have values ranging from 0.5 (X _Ab=0.74) to 4.1 (X _Ab=0.10). The continuous reaction, NaAlSi₃O₈+Ca₂Mg₅Si₈O₂₂(OH)₂ = NaCa₂Mg₅AlSi₇O₂₂(OH)₂+4SiO₂, proceeds to the right with increasing grade of metamorphism and for a given bulk composition, K _id increases with increasing temperature. Two related discontinuous reactions, actinolite+albite=hornblende+oligoclase+quartz and actinolite+oligoclase=hornblende+anorthite+quartz, also proceed to the right with increasing metamorphic grade and result in changes in the topology of a phase diagram that describes the partitioning of Na between plagioclase and amphibole A-site. A Schreinemakers' net is presented that is consistent with natural occurrences. The results of this study should aid in the delineation of metamorphic facies within amphibolites.     

Compositional limits and analogs of monoclinic triple-chain silicates

Growing recognition of triple-chain silicates in nature has prompted experimental research into the conditions under which they can form and the extent of solid solution that is feasible for some key chemical substitutions. Experiments were done primarily in the range of 0.1–0.5 GPa and 200–850 °C for durations of 18–1,034 h. A wide range of bulk compositions were explored in this study that can be classified broadly into two groups: those that are Na free and involve various possible chemical substitutions into jimthompsonite (Mg₁₀Si₁₂O₃₂(OH)₄), and those that are Na bearing and involve chemical substitutions into the ideal end-member Na₄Mg₈Si₁₂O₃₂(OH)₄. Numerous attempts to synthesize jimthompsonite or clinojimthompsonite were unsuccessful despite the type of starting material used (reagent oxides, magnesite + SiO₂, talc + enstatite, or anthophyllite). Similarly, the chemical substitutions of F⁻ for OH⁻, Mn²⁺, Ca²⁺, or Fe²⁺ for Mg²⁺, and 2Li⁺ for Mg²⁺ and a vacancy were unsuccessful at nucleating triple-chain silicates. Conversely, nearly pure yields of monoclinic triple-chain silicate could be made at temperatures of 440–630 °C and 0.2 GPa from the composition Na₄Mg₈Si₁₂O₃₂(OH)₄, as found in previous studies, though its composition is most likely depleted in Na as evidenced by electron microprobe and FTIR analysis. Pure yields of triple-chain silicate were also obtained for the F-analog composition Na₄Mg₈Si₁₂O₃₂F₄ at 550–750 °C and 0.2–0.5 GPa if a flux consisting of Na-halide salt and water in a 2:1 ratio by weight was used. In addition, limited chemical substitution could be documented for the substitutions of 2 Na⁺ for Na⁺ + H⁺ and of Mg²⁺ + vacancy for 2Na⁺. For the former, the Na content appears to be limited to 2.5 cations giving the ideal composition of Na_2.5Mg₈Si₁₂O_30.5(OH)_5.5, while for the latter substitution the Na content may go as low as 1.1 cations giving the composition Na_1.1Mg_9.4Si₁₂O_31.9(OH)_4.1 based on a fixed number of Si cations. Further investigation involving Mg for Na cation exchange may provide a pathway for the synthesis of Na-free clinojimthompsonite. Fairly extensive solid solution was also observed for triple-chain silicates made along the compositional join Na₄Mg₈Si₁₂O₃₂(OH)₄–Ca₂Mg₈Si₁₂O₃₂(OH)₄ where the limit of Ca substitution at 450 °C and 0.2 GPa corresponds to Na_0.7Ca_1.8Mg_7.8Si₁₂O_31.9(OH)_4.1 (with the OH content adjusted to achieve charge balance). Aside from the Na content, this composition is similar to that observed as wide-chain lamellae in host actinolite. The relative ease with which Na-rich triple chains can be made experimentally suggests that these phases might exist in nature; this study provides additional insights into the range of compositions and formation conditions at which they might occur.     

Experimental study of aluminum speciation in fluoride-rich supercritical fluids

The solubility of the albite-paragonite-quartz mineral assemblage was measured as a function of NaCl and fluorine concentration at 400°C, 500 bars and at 450°C, 500 and 1000 bars. Decreasing Al concentrations with increasing NaCl molality in F-free fluids of low salinity (mNaCl < 0.01) demonstrates that Al(OH)₄⁻ dominates Al speciation and is formed according to the reaction 0.5 NaAl₃Si₃O₁₂H_2(cr)+2 H₂O = 0.5 NaAlSi₃O_8(cr)+Al(OH)₄⁻+H⁺. Log K results for this reaction are −11.28 ± 0.10 and −10.59 ± 0.10 at 400°C, 500 bars and 450°C, 1000 bars, respectively. Upon further salinity increase, Al concentration becomes constant (at 400°C, 500 bars) or even rises (at 450°C, 1000 bars). The observed Al behavior can be explained by the formation of NaAl(OH)₄⁰_(aq) or NaAl(OH)₃Cl_(aq)⁰. The calculated constant for the reaction Al(OH)₄⁻+Na⁺=NaAl(OH)₄⁰_(aq) expressed in log units is equal to 2.46 and 2.04 at 400°C, 500 bars and 450°C, 1000 bars, respectively. These values are in good agreement with the predictions given in Diakonov et al. (1996). Addition of fluoride at m(NaCl) = const = 0.5 caused a sharp increase in Al concentration in equilibrium with the albite-paragonite-quartz mineral assemblage. As fluid pH was also constant, this solubility increase indicates strong aluminum-fluoride complexation with the formation of NaAl(OH)₃F_(aq)⁰ and NaAl(OH)₂F₂⁰_(aq), according to 0.5 NaAl₃Si₃O₁₂H_2(cr)+Na⁺+HF_(aq)⁰+H₂O = 0.5 NaAlSi₃O_8(cr)+ NaAl(OH)₃F_(aq)⁰+H⁺, log K = −5.17 and −5.23 at 400°C and 450°C, 500 bars, respectively, and 0.5 NaAl₃Si₃O₁₂H_2(cr)+Na⁺+2 HF_(aq)⁰ = 0.5 NaAlSi₃O_8(cr)+NaAl(OH)₂F₂⁰_(aq)+H⁺, log K = −2.19 and −1.64 at the same P-T conditions. It was found that temperature increase and pressure decrease promote the formation of Na-Al-OH-F species. Stability of NaAl(OH)₂F₂⁰_(aq) in low-density fluids also increases relative to NaAl(OH)₃F_(aq)⁰. These complexes, together with Al(OH)₂F_(aq)⁰ and AlOHF₂⁰_(aq), whose stability constants were calculated from the corundum solubility measured by Soboleva and Zaraisky (1990) and Zaraisky (1994), are likely to dominate Al speciation in metamorphic fluids containing several ppm of fluorine.     

The timescale and mechanism of granulite formation at Kurunegala,Sri Lanka

Incipient charnockite formation at Kurunegala in Sri Lanka is characterized by the growth of orthopyroxene at the expense of amphibole and biotite in an originally homogeneous gneiss. Mineral equilibria in the charnockite assemblage record pressure-temperature (P-T) conditions of 738±60° C and 6.9±1.2 kbar at-17.0±1.2 log fO₂ and aH₂O=0.18±0.16. Wholerock trace-element and isotopic measurements show that charnockite formation was accompanied by a systematic depletion of Sm>Rb>Pb>U>Sr>Nd, with a fractionation of Rb/Sr, Sm/Nd and Th/U ratios, and crystallization of the charnockite assemblage at 535±5 Ma. Major element (Fe–Mg–Ca) and Sm–Nd equilibration between minerals occurred at 524±9 Ma, whereas, Pb and Rb–Sr underwent continued exchange to 501±5 Ma and 486±1 Ma, respectively. Trace-element data for both amphibolite and charnockite minerals show that depletion on a whole-rock scale can be accounted for either by changes in mineral modes or trace-element abundances, within the immediate area of dehydration. The fractionation of Sm/Nd on a whole-rock scale is controlled by the breakdown of amphibole, without the growth of a major new host-phase for Sm in the charnockite. Rubidium and Sr are dependent on the relative behaviour of biotite, plagioclase and alkali-feldspar. Modelling of dehydration-melting involving the breakdown of amphibole, biotite, and alkali-feldspar reproduces the observed Sm/Nd and Rb/Sr fractionation, and indicates the loss of small melt fractions, on a cm scale, from the charnockite. These observations suggest that partial melting is the most plausible means of effecting both the dehydration and depletion that accompanies charnockite formation.     

Synthesis and stability of micas in the system K2O-MgO-SiO2-H2O and their relations to phlogopite

A series of alumina-free micas was synthesized hydrothermally in the potassium-poor portion of the system K₂O-MgO-SiO₂-H₂O. One end member of this series has the composition KMg_2.5[Si₄O₁₀](OH)₂, which, because of its octahedral occupancy, is intermediate between the dioctahedral and trioctahedral micas.From this end member a series of mica solid solutions extends towards more Mg-rich compositions. Single phase micas were obtained along the substitution line 2Mg for Si which appears to involve incorporation of part of the Mg in tetrahedral sites. It leads to a theoretical end member with a structural formula KMg₃[Si_3.5Mg_0.5O₁₀](OH)₂. Solid solutions containing up to 75 mole % of this theoretical end member could be synthesized. The observed densities, water contents, and a one-dimensional Fourier synthesis are consistent with the assumed substitution.At 1 kb fluid pressure and 620° C the Si-rich end member KMg_2.5[Si₄O₁₀](OH)₂ decomposes to a more Mg-rich mica, the roedderite phase K₂Mg₅Si₁₂O₃₀, liquid, and H₂O-rich vapor. With increasing Mg-content the thermal stability of the mica solid solutions increases up to 860°C at a composition of about K₂O·6.2MgO·7.4SiO₂·2H₂O, i.e. KMg_2.8[Si_3.7Mg_0.3O₁₀](OH)₂. This mica disintegrates directly into forsterite + liquid + H₂O-rich vapor. The mica phase richest in Mg with a composition of about K₂O·6.5MgO·7.25SiO₂·2H₂O, i.e. KMg_2.875 [Si_3.625Mg_0.375O₁₀](OH)₂, breaks down at 765° C into forsterite, a more Si-rich mica, liquid, and H₂O-rich vapor.This binary series of alumina-free micas forms a complete series of ternary solid solutions with normal phlogopite, KMg₃[Si₃AlO₁₀](OH)₂. Analyses of some natural phlogopites showing Si in excess of 3.0 (up to 3.18) per formula unit can be explained through this ternary miscibility range.     

Stability range and decomposition of potassic richterite and phlogopite end members at 5–15 GPa

Summary The phase relations of K-richterite, KNaCaMg₅Si₈O₂₂(OH)₂, and phlogopite, K₃Mg₆ Al₂Si₆O₂₀(OH)₂, have been investigated at pressures of 5–15 GPa and temperatures of 1000–1500 °C. K-richterite is stable to about 1450 °C at 9–10 GPa, where the dp/dT-slope of the decomposition curve changes from positive to negative. At 1000 °C the alkali-rich, low-Al amphibole is stable to more than 14 GPa. Phlogopite has a more limited stability range with a maximum thermal stability limit of 1350 °C at 4–5 GPa and a pressure stability limit of 9–10 GPa at 1000 °C. The high-pressure decomposition reactions for both of the phases produce relatively small amounts of highly alkaline water-dominated fluids, in combination with mineral assemblages that are relatively close to the decomposing hydrous phase in bulk composition. In contrast, the incongruent melting of K-richterite and phlogopite in the 1–3 GPa range involves a larger proportion of hydrous silicate melts. The K-richterite breakdown produces high-Ca pyroxene and orthoenstatite or clinoenstatite at all pressures above 4 GPa. At higher pressures additional phases are: wadeite-structured K₂Si^VISi^IV ₃O₉ at 10 GPa and 1500 °C, wadeite-structured K₂Si^VISi^IV ₃O₉ and phase X at 15 GPa and 1500 °C, and stishovite at 15 GPa and 1100 °C. The solid breakdown phases of phlogopite are dominated by pyrope and forsterite. At 9–10 GPa and 1100–1400 °C phase X is an additional phase, partly accompanied by clinoenstatite close to the decomposition curve. Phase X has variable composition. In the KCMSH-system (K₂CaMg₅Si₈O₂₂(OH)₂) investigated by Inoue et al. (1998) and in the KMASH-system investigated in this report the compositions are approximately K₄Mg₈Si₈O₂₅(OH)₂ and K_3.7Mg_7.4Al_0.6Si_8.0O₂₅(OH)₂, respectively. Observations from natural compositions and from the phlogopite-diopside system indicate that phlogopite-clinopyroxene assemblages are stable along common geothermal gradients (including subduction zones) to 8–9 GPa and are replaced by K-richterite at higher pressures. The stability relations of the pure end member phases of K-richterite and phlogopite are consistent with these observations, suggesting that K-richterite may be stable into the mantle transition zone, at least along colder slab geotherms. The breakdown of moderate proportions of K-richterite in peridotite in the upper part of the transition zone may be accompanied by the formation of the potassic and hydrous phase X. Additional hydrogen released by this breakdown may dissolve in wadsleyite. Therefore, very small amounts of hydrous fluids may be released during such a decomposition. Received April 10, 2000; revised version accepted November 6, 2000     

Characterization of polysomatism in biopyriboles: Double-/triple-chain lamellar intergrowths

As a first step towards accurate quantification of the polysomatic states of biopyriboles, we have studied the polysomatic transformation between amphibole and hydrous triple-chain silicate (TCS) in the synthetic system Na₂O-MgO-SiO₂-H₂O (NMSH). The reaction is: 4Na₂Mg₄Si₆O₁₆(OH)₂ TCS 3Na_2.67Mg_5.33Si₈O_21.33(OH)_2.67. Amphibole We have characterised a polysomatic intergrowth of amphibole and TCS (synthesized at 2 kbar/(653° C) by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), infrared spectroscopy and ²⁹Si magic-angle-spinning (MAS) NMR spectroscopy. The sample is a fine-scale lamellar intergrowth of double- and triple-chain structures; lamellae are 27 Å to hundreds of Ångströms wide. The ²⁹Si MAS NMR spectrum of the intergrowth is explicitly a superposition of the individual amphibole and TCS spectra. By ensuring that the recycle delay time used considers the longest spin-lattice relaxation time (ca. 900 s), the relative amounts of double- and triple-chain structures can be quantified by simple deconvolution of the spectrum. The relative amounts of double- and triple-chain structures are 42 ± 5 and 58 ± 5 mol%, respectively. With regard to quantifying populations of chain multiplicities in biopyriboles, we believe that ²⁹Si NMR is more accurate than the conventional HRTEM fringe-counting method (Maresch and Czank 1983, 1988), and is far superior to XRD and infrared spectroscopy, which suffer from high sensitivity to particle size and calibration problems. ²⁹Si MAS NMR can provide an accurate means of monitoring the progress of polysomatic reactions in biopyriboles. It is likely to be most effective for samples containing only a few different chain multiplicities (e.g. m = 1, 2, 3 and perhaps 4), such as occur in natural pyroxenes and amphiboles.     

Growth mechanisms,structural defects and composition of synthetic tremolite: what are the effects on macroscopic properties?

Amorphous gels and oxides corresponding to Ca₂Mg₅Si₈O₂₃ in bulk composition have been reacted to phase assemblages containing tremolitic amphibole using routine hydrothermal methods in the pressure/temperature range from 1–22 kbar and 600–875° C. The products have been characterized by X-ray diffraction, optical microscopy and high-resolution electron microscopy. The nature of the amphibole microstructure and the types of intergrown biopyriboles vary markedly as a function of synthesis temperature and pressure, reflecting different amphibole growth mechanisms. At P(H₂O)<10 kbar, within or very near the stability field of fale, amphibole forms by topotactic reaction from this metastably crystallized, intermediate phase; chain multiplicity faults (CMFs) with m3 are numerous; the bulk compositional shift in the disordered amphibole crystals is compensated in the run product by coexisting diopside. At P(H₂O)10 kbar, but still in the talc stability field, amphibole grows topotactically from and also nucleates preferentially on metastable diopside by a dissolution/regrowth process; the two phases form fine ( 100 Å) lamellar intergrowths with almost no CMFs with m3, and the compositional shift induced by armoured diopside relics is compensated by discrete talc. The same lamellar amphibole/diopside microstructure is observed at temperatures above the talc stability field and at all pressures investigated, but the compositional shift is compensated by enstatite+quartz. Varying the experimental parameters (run duration; H₂O content) does not significantly affect the above observations. For the wide range of pressures and temperatures investigated, the synthetic amphiboles of the present study appear to correspond very closely to end-member tremolite. The observed product assemblages and apparent compositional shifts of the amphibole, equivalent in Ca/Mg ratio to as much as 11 mol% magnesiocummingtonite component, can be explained by the incorporation of CMFs in this phase. We argue that CMF-induced shifts in Ca/Mg ratios also play a significant role for the 10 mol% magnesiocummingtonite component commonly assumed in analogous experiments in the present literature. The genuine magnesiocummingtonite solid-solution component may be much less than 10 mol%. Empirical high-resolution transmission electron microscopy observations of preferential corrosion structures at crystal terminations suggest that, to a first approximation, structurally disordered tremolites exhibit the reaction behaviour of mechanical mixtures down to the unit-cell scale. The thermodynamic properties of synthetic tremolite, even in small intergrown lamellae within disordered crystals, should therefore closely approach those of discrete, ideal tremolite single crystals, in accord with the converging agreement shown by recent comparative experimental studies on the phase relationships of natural and synthetic tremolite.     

Contact Metamorphism of Serpentinite, Chloritic Blackwall and Rodingite at Paddy-Go-Easy Pass, Central Cascades, Washington

The 2 km wide contact aureole produced from serpentinite bythe intrusion of the Mount Stuart Batholith into the IngallsComplex at Paddy-Go-Easy Pass contains the following ultramaficassemblages, in order of increasing grade: serpentine-forsterite-diopside,serpentine-forsterite-tremolite, forsterite-talc, forsterite-anthophyllite,forsterite-enstatite-anthophyllite, forsterite-enstatite-chlorite,forsterite-enstatite-spinel. Associated metarodingites displayfive metamorphic zones, the diagnostic assemblages of whichare, in increasing grade: grossular-idocrase-chlorite, grossular-diopside-chlorite,epidote-diopside-chlorite, epidotediopside-spinel, plagioclase-grossular-diopside.Mafic hornfels in the aureole contains no orthopyroxene, indicatingthat the conditions of pyroxene hornfels facies were not reached. The breakdown of chlorite is best displayed in aluminous blackwallreaction zones around mafic inclusions in the peridotite. Attemperatures above those of the anthophyllite-out isograd, butwithin the field of forsterite+tremolite, these chlorite-richrocks react to form the assemblage: forsterite-enstatite-spinel.Calculations show that cordierite did not form as a result ofchlorite breakdown in the natural system because impurities,such as iron and chromium, displaced the equilibrium: forsterite+cordierite= enstatite+spinel to much lower pressures than the three kilobarsfound in the pure system. The primary chromite of the peridotite has been altered to chrome-magnetitein the serpentinite. This alteration seems to be isochemicalover the whole rock, as true chromite, formed by metamorphism,occurs at grades above that of the forsterite-enstatite-anthophylliteassemblage. Calcic amphibole in high-grade metaperidotite is tremolite,even in the presence of aluminous chromite, whereas that inmetamorphosed blackwall rock grades from tremolite into hornblende.The pattern of substitution appears to be: Mg₂Si₃rlhar2;(Na,K)(Al^VI)₂(Al^IV)₃.     

Thermochemical study Mg–Fe amphiboles

The paper presents data on the thermochemical study (high-temperature melt calorimetry in a Tian–Calvet microcalorometer) of two natural Mg–Fe amphiboles: anthophyllite Mg_2.0(Mg_4.8Fe_0.2 ²⁺)[Si_8.0O₂₂](OH)₂ from Kukh-i-Lal, southwestern Pamirs, Tajikistan, and gedrite Na_0.4Mg_2.0(Mg_1.7Fe_0.2 ²⁺Al_1.3)[Si_6.3Al_1.7O₂₂](OH)₂ from the Kola Peninsula, Russia. The enthalpy of formation from elements is obtained as–12021 ± 20 kJ/mol for anthophyllite and as–11545 ± 12 kJ/mol for gedrite. The standard entropy, enthalpy, and Gibbs energy of formation are evaluated for Mg–Fe amphiboles of theoretical composition.     

Thermodynamic study of calcic amphiboles

The paper reports original thermochemical data on six natural amphibole samples of different composition. The data were obtained by high-temperature melt solution calorimetry in a Tian–Calvet microcalorometer and include the enthalpies of formation from elements for actinolite Ca_1.95(Mg_4.4Fe _0.5 ²⁺ Al₀₁)[Si_8.0O₂₂](OH)₂(–12024 ± 13 kJ/mol) and Ca_2.0(Mg_2.9Fe _1.9 ²⁺ Fe _0.2 ³⁺ )[Si_7.8Al_0.2O₂₂](OH)₂, (–11462 ± 18 kJ/mol), and Na_0.1Ca_2.0(Mg_3.2Fe _1.6 ²⁺ Fe _0.2 ³⁺ )[Si_7.7Al_0.3O₂₂](OH)₂ (–11588 ± 14 kJ/mol); for pargasite Na_0.5K_0.5Ca_2.0-(Mg_3.4Fe _1.8 ²⁺ Al_0.8)[Si_6.2Al_1.8O₂₂](OH)₂ (–12316 ± 10 kJ/mol) and Na_0.8K_0.2Ca_2.0(Mg_2.8Fe _1.3 ³⁺ Al_0.9) [Si_6.1Al_1.9O₂₂](OH)₂ (–12 223 ± 9 kJ/mol); and for hastingsite Na_0.3K_0.2Ca_2.0(Mg_0.4Fe _1.3 ²⁺ Fe _0.9 ³⁺ Al_0.2) [Si_6.4Al_1.6O₂₂](OH)₂ (?10909 ± 11 kJ/mol). The standard entropy, enthalpy, and Gibbs free energy of formation are estimated for amphiboles of theoretical composition: end members and intermediate members of the isomorphic series tremolite–ferroactinolite, edenite–ferroedenite, pargasite–ferropargasite, and hastingsite.     

Synthesis,lattice constants and OH-valence vibrations of an orthorhombic amphibole with excess OH in the system Li2O-MgO-SiO2-H2O

Orthorhombic amphiboles with excess OH, which can be schematically deduced from anthophyllite by the combined substitutions Mg²⁺ + O^2–Li⁺+OH^– and Mg²⁺2 Li⁺, were synthesized at 750–875° C/1 kbar in the system Li₂O-MgO-SiO₂-H₂O. Their phase relations are presented for 800° C/1 kbar . An amphibole with the analytical composition 2.70 wt% Li₂O, 31.1 wt% MgO, 63.0 wt% SiO₂, and 3.29 wt% H₂O has lattice constants a ₀ 18.588 (11), b ₀ 17.966 (10), c ₀ 5.262 (3) Å, V ₀ 1,757.2 (1.5) ų (referred to Space Group Pnma). The OH-valence vibrational spectrum of this amphibole showed v _OH bands at 3,667, 3,708, and 3,725 (shoulder) cm^–1, which are ascribed to OH in the configurations (MgMgMg)-OH, (MgMgMg)-OH-Li (Li in the A-site) of the pseudotrigonal (M1M1M3)-OH arrangement in the amphibole structure, and to Si-OH, respectively. No explanation can at present be offered for an additional shoulder at 3,695 cm^–1. The proposed structural formula is (Li_{0.27 0.73})(Li_1.11 Mg_0.89)· (Mg₅)(Si_8.01O_21.20(OH)_0.80)(OH)_2.00.     

Thermochemical study of natural montmorillonite

The paper reports results of an experimental thermochemical study (in a heat-flux Tian-Calvet microcalorimeter) of montmorillonite from (I) the Taganskoe and (II) Askanskoe deposits and (III) from the caldera of Uzon volcano, Kamchatka. The enthalpy of formation Δ _f H _el ⁰ (298.15 K) of dehydrated hydroxyl-bearing montmorillonite was determined by melt solution calorimetry: ?5677.6 ± 7.6 kJ/mol for Na_0.3Ca_0.1(Mg_0.4Al_1.6)[Si_3.9Al_0.1O₁₀](OH)₂ (I), ?5614.3 ± 7.0 kJ/mol for Na_0.4K_0.1(Ca_0.1Mg_0.3Al_1.5Fe _0.1 ³⁺ )[Si_3.9Al_0.1O₁₀](OH)₂ (II), ?5719 ± 11 kJ/mol for K_0.1Ca_0.2Mg_0.2(Mg_0.6Al_1.3Fe _0.1 ³⁺ ) [Si_3.7Al_0.3O10](OH)₂ (III), and ?6454 ± 11 kJ/mol for water-bearing montmorillonite (I) Na_0.3Ca_0.1(Mg_0.4Al_1.6)[Si_3.9Al_0.1O₁₀](OH)₂ · 2.6H₂O. The paper reports estimated enthalpy of formation for the smectite end members of the theoretical composition of K-, Na-, Mg-, and Ca-montmorillonite and experimental data on the enthalpy of dehydration (14 ± 2 kJ per mole of H₂O) and dehydroxylation (166 ± 10 kJ per mole of H₂O) for Na-montmorillonite.