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.     

Coexisting Amphiboles

Chemical analyses for the following amphibole pairs are presented:anthophyllite—tremolite (or actinolite, or hornblende),cummingtonite (or grunerite)–actinolite (or hornblende),cummingtonite (or grunerite)–anthophyllite (or gedrite),and manganoan cummingtonitemagnesioriebeckite. Nineteen analyses of such pairs are quoted from the literature,and thirty-seven additional pairs have been newly analyzed byelectron probe techniques. Quantitative microprobe determinationsof Si, Al, Fe, Mn, Mg, Ca, and Na were made on polished thin-sections,using naturally occurring, analyzed, homogeneous amphibolesas standards. The literature analyses and the electron probeanalyses for metamorphic, two-amphibole assemblages are givenfor amphiboles in physical contact, which show no textural evidenceof one amphibole being a reaction or alteration product of theother. The chemical data for some of the volcanic, two—amphiboleassemblages were obtained from occurrences that probably donot represent equilibrium pairs. The chemical data are used to determine the extent of the miscibilitygaps between the various amphibole series and the fractionationof the major elements between the two amphiboles of a pair.Anthophyllite and members of the cummingtonite-grunerite seriesgenerally have a larger Fe(total)/Mg ratio than the coexistingcalcic amphibole. The maximum CaO, Al₂O₃and Na₂O contents ofcummingtonite in metamorphic cummingtonite—hornblendepairs are 19 and 32, 02 weight per cent, respectively. Themaximum CaO, A1₂O₃, and Na₂O contents of cummingtonite in metamorphiccummingtonite-hornblende pairs are 19, 32, and 02 weightper cent, respectively. Larger CaO and Al₂O₃ values reportedin the literature were found to be too high because of admixtureof actinolite or hornblende in the analyzed separates. Smallamounts of MnO tend to concentrate preferentially in anthophylliteor cummingtonite of anthophyllite-hornblende and cummingtonite-hornblendepairs. Anthophyllite-cummingtonite pairs may show very similarFe(total)/Mg ratios and differ slightly in Al₂O₃ content only.     

Coarsening kinetics of the exsolution microstructure in alkali feldspar

Actinolite, hornblende and biotite coexisting in greenschist mafic metagreywackes have been analysed with the electron microprobe to obtain information on their chemical relationship during metamorphism. As in some other parts of the world, the two calcic amphiboles coexist in the greenschist facies because of a miscibility gap between them which is observed under conditions of low-pressure regional metamorphism; it is thought that the two amphiboles are in equilibrium, or at least that the actinolite participated in hornblendeforming reactions. Contact metamorphism by granitic intrusives of these metagreywackes has converted them to hornblende hornfelses with the assemblage hornblende, andesine, quartz, biotite±cummingtonite; the hornblendes of the hornfelses are found to have compositions between actinolite and hornblende of the greenschists, and frequently show fine exsolution lamellae of cummingtonite as a result of oversaturation in this component. The distribution of Fe-Mg between hornblende and biotite changes from the greenschist to the hornblende hornfels facies, and the K _D is probably dependent on Al^VI in the hornblende.     

An analytical electron microscopic study of a pyroxene-amphibole intergrowth

Samples of a garnet granulite from the mafic border units of the Lake Chatuge, Georgia alpine peridotite body were found to contain lamellar intergrowths of a pargastic amphibole in augite having the typical appearance of an exsolution feature. Single crystal X-ray diffraction, optical, electron microprobe and conventional and analytical electron microscopic studies have provided data limiting the compositions and structures of the coexisting phases. Individual lamellae of both materials are from 0.5 to 2.0 m in width with the lamellar interface parallel to {0 1 0}. The formulae of the minerals, as determined by a combination of electron microprobe and analytical electron microscopy, are (Na_0.1Ca_1.0Mg_0.6Fe³⁺ _0.3)(Si_1.8Al_0.2)O₆ for the pyroxene and Na_0.7Ca_1.9(Mg_2.1Fe²⁺ _1.4Fe³⁺ _0.5Ti_0.1Cr_0.1Al_0.8)(Si_5.9Al_2.1) O₂₂(OH)₂ for the amphibole. Several other studies have described intergrowths similar to those observed in this work, in general favoring exsolution as the formation mechanism for the intergrowths. In the Lake Chatuge samples however, replacement of pyroxene by amphibole is in part indicated by continuous gradation of amphibole lamellae into amphiboles rimming the clinopyroxenes.Contribution No. 368 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan     

The compositional variation of synthetic sodic amphiboles at high and ultra-high pressures

Sodic amphiboles in high pressure and ultra-high pressure (UHP) metamorphic rocks are complex solid solutions in the system Na₂O–MgO–Al₂O₃–SiO₂–H₂O (NMASH) whose compositions vary with pressure and temperature. We conducted piston-cylinder experiments at 20–30?kbar and 700–800?°C to investigate the stability and compositional variations of sodic amphiboles, based on the reaction glaucophane=2jadeite+talc, by using the starting assemblage of natural glaucophane, talc and quartz, with synthetic jadeite. A close approach to equilibrium was achieved by performing compositional reversals, by evaluating compositional changes with time, and by suppressing the formation of Na-phyllosilicates. STEM observations show that the abundance of wide-chain structures in the synthetic amphiboles is low. An important feature of sodic amphibole in the NMASH system is that the assemblage jadeite–talc?±?quartz does not fix its composition at glaucophane. This is because other amphibole species such as cummingtonite (Cm), nyböite (Nyb), Al–Na-cummingtonite (Al–Na-Cm) and sodium anthophyllite (Na-Anth) are also buffered via the model reactions: 3cummingtonite?+?4quartz?+?4H₂O=7talc, nyböite?+?3quartz=3jadeite?+?talc, 3Al–Na-cummingtonite + 11quartz + 2H₂O=6jadeite + 5talc, and 3 sodium anthophyllite?+?13quartz?+?4H₂O=3 jadeite + 7talc. We observed that at all pressures and temperatures investigated, the compositions of newly grown amphiboles deviate significantly from stoichiometric glaucophane due to varying substitutions of Al^IV for Si, Mg on the M(4) site, and Na on the A-site. The deviation can be described chiefly by two compositional vectors: [Na^AAl^IV]<=>[□^ASi] (edenite) toward nyböite, and [Na^(M4)Al^VI]<=>[Mg^(M4)Mg^VI] toward cummingtonite. The extent of nyböite and cummingtonite substitution increases with temperature and decreases with pressure in the experiments. Similar compositional variations occur in sodic amphiboles from UHP rocks. The experimentally calibrated compositional changes therefore may prove useful for thermobarometric applications.     

High-<Emphasis Type="Italic">T</Emphasis> behaviour of gedrite: thermoelasticity,cation ordering and dehydrogenation

The thermoelastic behaviour of a natural gedrite having the crystal-chemical formula ^ANa_0.47 ^B(Na_0.03 Mg_1.05 Fe_0.86²⁺ Mn_0.02 Ca_0.04) ^C(Mg_3.44 Fe_0.36²⁺ Al_1.15 Ti_0.05⁴⁺) ^T(Si_6.31 Al_1.69)O₂₂ ^W(OH)₂ has been studied by single-crystal X-ray diffraction to 973 K (Stage 1). After data collection at 973 K, the crystal was heated to 1,173 K to induce dehydrogenation, which was registered by significant changes in unit-cell parameters, M1–O3 and M3–O3 bond lengths and refined site-scattering values of M1 and M4 sites. These changes and the crystal-chemical formula calculated from structure refinement show that all Fe²⁺ originally at M4 migrates into the ribbon of octahedrally coordinated sites, where most of it oxidises to Fe³⁺, and there is a corresponding exchange of Mg from the ribbon into M4. The resulting composition is that of an oxo-gedrite with an inferred crystal-chemical formula ^ANa_0.47 ^B(Na_0.03 Mg_1.93 Ca_0.04) ^C(Mg_2.56 Mn_0.02²⁺ Fe_0.10²⁺ Fe_1.22³⁺ Al_1.15 Ti_0.05⁴⁺) ^T(Si_6.31 Al_1.69) O₂₂ ^W[O_1.12²⁻ (OH)_0.88]. This marked redistribution of Mg and Fe is interpreted as being driven by rapid dehydrogenation at the H3A and H3B sites, such that all available Fe in the structure orders at M1 and M3 sites and is oxidised to Fe³⁺. Thermoelastic data are reported for gedrite and oxo-gedrite; the latter was measured during cooling from 1,173 to 298 K (Stage 2) and checked after further heating to 1,273 K (Stage 3). The thermoelastic properties of gedrite and oxo-gedrite are compared with each other and those of anthophyllite.     

A new pair of coexisting amphiboles : the grünerite and ferropargasite pair

A new coexisting amphibole pair was recently found in the Jianshan iron deposit, Loufan of Shanxi Province, China. Electron microprobe analysis shows that the coexisting pair is composed of grünerite K_0.001 (Na_0.027 Ca_0.073 Mn_0.031 Fe _1.801 ²⁺ )_1.932 (Fe _2.948 ²⁺ Mg_1.964 Ti_0.002 Al_0.087)₅Si_8.069 O_22.10(OH)₂ and ferropargasite (K_0.135 Na_0.461)_0.596 (Na_0.088 Ca_1.853 Mn_0.005 Fe _0.072 ²⁺ )₂(Mn_0.005Fe _2.789 ²⁺ Mg_0.875Ti_0.021Fe _0.499 ³⁺ Al_0.812)₅(Si_6.103Al_1.897)₈O_22.00(OH)₂. The two kinds of amphiboles occur in amphibole schist not only as separate phenocrysts, but also are combined to form “single-crystal” phenocrysts in the form of topotactic intergrowths with the common c- and b-axes. The boundary between topotactic grünerite and ferropargasite is optically and chemically sharp. In comparison with the coexisting ferromagnesian amphibole and calcic amphibole pair discovered by predecessors, the newly discovered pair has lower Mg/Fe ratios and wider miscibility gaps.     

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     

Occurrence of wide-chain Ca-pyriboles as primary crystals in the Salton Sea Geothermal Field,California, USA

Amphiboles and pyroxenes occurring in the Salton Sea Geothermal Field were found to contain coherent intergrowths of chain silicates with other than double and single chain widths by using transmission and analytical electron microscopy. Both occur in the biotite zone at the temperature (depth) interval of 310° C (1,060 m) to 330° C (1,547m) which approximately corresponds to temperatures of the greenschist facies. The amphiboles occur as euhedral fibrous crystals occupying void space and are composed primarily of irregularly alternating (010) slabs of double or triple chains, with rare quadruple and quintuple chains. Primary crystallization from solution results in euhedral crystals. Clinopyroxenes formed mainly as a porefilling cement and subordinately as prismatic crystals coexisting with fibrous amphiboles. Fine lamellae of double and triple chains are irregularly intercalated with pyroxene. AEM analyses yield formulae (Ca_1.8Mg_2.9Fe_1.9Mn_0.1) Si₈O_21.8(OH)_1.8 (310° C) and (Ca_2.0Fe_2.5Mg_2.3) Si₈O_21.8 (OH)_2.0 (330° C) for amphiboles and (Ca_1.1Fe_0.6Mg_0.3) Si₂O₆ for clinopyroxene. Thermodynamic calculations at P_fluid=100 bar of equilibrium reactions of (1) 3 chlorite +10 calcite + 21 quartz = 3 actinolite + 2 clinozoisite + 8 H₂O + 10 CO₂ and (2) actinolite+ 3 calcite+ 2 quartz = 5 clinopyroxene + H₂O + 3 CO₂ using Mg-end member phases indicate that formation of amphibole and pyroxene require very water-rich conditions at temperatures below 330° C.Contribution No. 420 from the Mineralogical Laboratory, Department of Geological Sciences, University of Michigan, Ann Arbor, Michigan     

A crystal chemical study of protoanthophyllite: orthoamphiboles with the protoamphibole structure

Two new protoamphibole-type amphiboles with space group type Pnmn, have been found in nature: protoferro-anthophyllite (Fe_0.80Mn_0.20)₂ (Fe_0.98Mg_0.02)₅ (Si₄O₁₁)₂(OH)₂, and protomangano-ferro-anthophyllite, (Mn_0.70Fe_0.30)₂ (Fe_0.82Mg_0.18)₅ (Si₄O₁₁)₂(OH)₂. Protoferro-anthophyllite (PFA) occurs in pegmatites at both Gifu Prefecture, Japan and at Cheyenne Mountain, El Paso County, Colorado, USA. Protomangano-ferro-anthophyllite, (PMFA) occurs in pegmatites at Fukushima Prefecture and in a Mn mine at Tochigi Prefecture, Japan. Structure determinations of the two amphiboles show that both are isostructural with the synthetic fluorian-amphibole, protoamphibole (= protofluorian-lithian-anthophyllite). A calculation of the procrystal electron density distributions, the bond paths and the bond critical point properties of PFA, PMFA, grunerite and protoamphibole indicates that the M4 cation in these amphiboles is 4-coordinated. A calculation of the electron density distributions at the Becke3LYP/6-311G(2d,p) level for model silicate tetrahedra for these amphiboles and anthophyllite reveals that the value of the electron density at the bond critical points, ρ(r _c ), for the SiO(nbr) bonds is larger, on average (0.93 e/ų), than that for the SiO(br) bonds (0.90 e/ų). The observed SiO bond lengths decrease linearly with increasing ρ(r _c ) while the magnitudes of the curvatures of ρ(r _c ) both perpendicular and parallel to the bonds and the Laplacian of ρ(r _c ) each increases. These trends are associated with an increase in the electronegativity of the Si cation, a possible increase in the covalent character of the SiO bond and a tendency for SiO(nbr) bonds to be involved in wider OSiO angles than SiO(br) bonds. It is possible, if not likely, that protoanthophyllite has often been misidentified as anthophyllite.     

Phase Equilibria of Amphibolites from the Post Pond Volcanics, Mt. Cube Quadrangle, Vermont

Amphibolites of the Post Pond Volcanics, south-west corner ofthe Mt. Cube Quadrangle, Vermont, are characterized by a greatdiversity of bulk rock types that give rise to a wide varietyof low-variance mineral assemblges. Original rock types arebelieved to have been intrusive and extrusive volcanics, hydrothermallyaltered volcanics and volcanogenic sediments with or withoutadmixtures of sedimentary detritus. Metamorphism was of staurolite-kyanitegrade. Geothermometry yields a temperature of 535 ± 20°C at pressures of 5–6 kb. Partitioning of Fe and Mg between coexisting phases is systematic,indicating a close approach to chemical equilibrium was attained.Relative enrichment of Fe/Mg is garnet > staurolite >gedrite > anthophyllite cummingtonite hornblende > biotite> chlorite > wonesite > cordierite dolomite > talc;relative enrichment in Mn/Mg is garnet > dolomite > gedrite> staurolite cummingtonite > hornblende > anthophyllite> cordierite > biotite > wonesite > chlorite >talc. between coexisting amphiboles varies as a function ofbulk Fe/Mg, which is inconsistent with an ideal molecular solutionmodel for amphiboles. Mineral assemblages are conveniently divided into carbonate+ hornblende-bearing, hornblende-bearing (carbonate-absent)and hornblende-absent. The carbonate-bearing assemblages allcontain hornblende + dolomite+ calcite + plagioclase (andesineand/or anorthite) + quartz with the additional phases garnetand epidote (in Fe-rich rocks) and chlorite ± cummingtonite(in magnesian rocks). Carbonate-bearing assemblages are restrictedto the most calcic bulk compositions. Hornblende-bearing (carbonate absent) assemblages occur in rocksof lower CaO content than the carbonate-bearing assemblages.All of these assemblages contain hornblende + andesine ±quartz + Fe-Ti oxide (rutile in magnesian rocks and ilmenitein Fe-rich rocks). In rocks of low Al content, cummingtoniteand two orthoamphiboles (gedrite and anthophyllite) are common.In addition, garnet is found in Fe-rich rocks and chlorite isfound in Mg-rich rocks. Several samples were found that containhornblende + cummingtonite + gedrite + anthophyllite ±garnet +chlorite + andesine + quartz + Fe-Ti oxide ±biotite. Aluminous assemblages contain hornblende + staurolite+ garnet ± anorthite/bytownite (coexisting with andesine)± gedrite ± biotite ± chlorite ±andesine ± quartz ± ilmenite. Hornblende-absentassemblages are restricted to Mg-rich, Ca-poor bulk compositions.These rocks contain chlorite ± cordierite ± staurolite± talc ± gedrite ± anthophyllite ±cummingtonite ± garnet ± biotite ± rutile± quartz ± andesine. The actual assemblage observeddepends strongly on Fe/Mg, Ca/Na and Al/Al + Fe + Mg. The chemistry of these rocks can be represented, to a firstapproximation, by the model system SiO₂–Al₂O₃–MgO–FeO–CaO–Na₂O–H₂O–CO₂;graphical representation is thus achieved by projection fromquartz, andesine, H₂O and CO₂ into the tetrahedron Fe–Ca–Mg–Al.The volumes defined by compositions of coexisting phases filla large portion of this tetrahedron. In general, the distributionof these phase volumes is quite regular, although in detailthere are a large number of phase volumes that overlap otherphase volumes, especially with respect to Fe/Mg ratios. Algebraicand graphical analysis of numerous different assemblages indicatethat every one of the phase volumes should shift to more magnesiancompositions with decreasing µ_H2O. It is therefore suggestedthat the overlapping phase volumes are the result of differentassemblages having crystallized in equilibrium with differentvalues of µ_H2O or µ_CO2 and that the different valuesmay have been inherited from the original H₂O and CO₂ contentof the volcanic prototype. If true, this implies that eithera fluid phase was not present during metamorphism, or that fluidflow between rocks was very restricted.     

Greenschist amphiboles from Haast river,New Zealand

A section across the Haast Schist Group in the Southern Alps of New Zealand shows a sequence of metamorphosed eugeosynclinal sediments. Meta-basic rocks (greenschists) have been studied to determine the nature of the actinolite-hornblende transition and to investigate the change in amphibole composition through the Metamorphic Facies Series.Electron microprobe analyses of 21 representative amphiboles, including 3 amphibole pairs can be shown to support theories of a miscibility break in the calciferous amphibole solid solution series. The existence of a miscibility break is further supported by the widespread appearance, even at low metamorphic grades, of exsolution lamellae in actinolite and hornblende amphiboles.Amphibolite facies amphiboles differ from greenschist facies amphiboles in that (a) there are increased amounts of Ti entering the lattice and (b) that there is an increased occupancy of the A site at higher metamorphic grades.     

A new thermodynamic model for clino- and orthoamphiboles in the system Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–O

A recent thermodynamic model for the Na–Ca clinoamphiboles in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–O (NCFMASHO), is improved, and extended to include cummingtonite–grunerite and the orthoamphiboles, anthophyllite and gedrite. The clinoamphibole model in NCMASH is adopted, but the extension into the FeO- and Fe₂O₃-bearing systems is revised to provide thermodynamic consistency and better agreement with natural assemblage data. The new model involves order–disorder of Fe–Mg between the M2, M13 and M4 sites in the amphibole structure, calibrated using the experimental data on site distributions in cummingtonite–grunerite. In the independent set of end-members used to represent the thermodynamics, grunerite (rather than ferroactinolite) is used for FeO, with two ordered Fe–Mg end-members, and magnesioriebeckite (rather than ferritschermakite) is used for Fe₂O₃. Natural assemblage data for coexisting clinoamphiboles are used to constrain the interaction energies between the various amphibole end-members. For orthamphibole, the assumption is made that the site distributions and the non-ideal formulation is the same as for clinoamphibole. The data set end-members anthophyllite, ferroanthophyllite and gedrite, are used; for the others, they are based on the clinoamphibole end-members, with the necessary adjustments to their enthalpies constrained by natural assemblage data for coexisting clino- and orthoamphiboles. The efficacy of the models is illustrated with P – T grids and various pseudosections, with a particular emphasis on the prediction of mineral assemblages in ferric-bearing systems.     

Microtextures and crystal chemistry in P21/c pigeonites

Summary ?A single-crystal X-ray investigation was performed on crystals of P2₁/c natural pigeonite with varying Ca and Fe^* ( = Fe²⁺ + Mn²⁺) contents, in order to verify the effect of microtextural disorder on structure refinements and to constrain the crystal chemistry of pigeonite. Antiphase domains and exsolution lamellae affect differently the refinement results. In a crystal free of exsolution the structure obtained after refinement with all reflections is an average of that of the antiphase domains and of their boundaries, whereas in an exsolved crystal it represents only the structure of the prevailing pigeonite lamellae. The refinement using only h + k odd reflections seems to give the structure of the Ca-free pigeonite characteristic of the antiphase domains rather than that of Ca-rich domain walls. The ratio of the scale factors in refinements with all reflections and with only h + k odd reflections allows the ratios of the exsolved augite and pigeonite phases to be estimated. The crystal chemistry of the investigated samples follows the trends outlined by data on Ca-free and Fe-free synthetic samples. In particular, it is shown that Ca and Fe^* substitution for Mg induce similar changes in the average structure, i.e. both induce an expansion in the M1 polyhedron and decrease the difference between the M2–O3 distances. Received October 18, 2001; revised version accepted February 15, 2002     

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.     

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

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

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.     

Stability and chemical equilibrium of amphibole in calc-alkaline magmas: an overview, new thermobarometric formulations and application to subduction-related volcanoes

This work focuses on a rigorous analysis of the physical–chemical, compositional and textural relationships of amphibole stability and the development of new thermobarometric formulations for amphibole-bearing calc-alkaline products of subduction-related systems. Literature experimental results (550–1,120°C, <1,200 MPa, −1 ≤ ΔNNO ≤ +5), H₂O–CO₂ solubility models, a multitude of amphibole-bearing calc-alkaline products (whole-rocks and glasses, representing 38 volcanoes worldwide), crustal and high-P (1–3 GPa) mantle amphibole compositions have been used. Calcic amphiboles of basalt-rhyolite volcanic products display tschermakitic pargasite (37%), magnesiohastingsite (32%) and magnesiohornblende (31%) compositions with aluminium number (i.e. Al# = ^[6]Al/Al_T) ≤ 0.21. A few volcanic amphiboles (~1%) show high Al# (>0.21) and are inferred to represent xenocrysts of crustal or mantle materials. Most experimental results on calc-alkaline suites have been found to be unsuitable for using in thermobarometric calibrations due to the high Al# (>0.21) of amphiboles and high Al₂O₃/SiO₂ ratios of the coexisting melts. The pre-eruptive crystallization of consistent amphiboles is confined to relatively narrow physical–chemical ranges, next to their dehydration curves. The widespread occurrence of amphiboles with dehydration (breakdown) rims made of anhydrous phases and/or glass, related to sub-volcanic processes such as magma mixing and/or slow ascent during extrusion, confirms that crystal destabilization occurs with relatively low T–P shifts. At the stability curves, the variance of the system decreases so that amphibole composition and physical–chemical conditions are strictly linked to each other. This allowed us to retrieve some empirical thermobarometric formulations which work independently with different compositional components (i.e. Si^*, Al_T, Mg^*, ^[6]Al^*) of a single phase (amphibole), and are therefore easily applicable to all types of calc-alkaline volcanic products (including hybrid andesites). The Si^*-sensitive thermometer and the fO₂–Mg^* equation account for accuracies of ±22°C (σ_est) and 0.4 log units (maximum error), respectively. The uncertainties of the Al_T-sensitive barometer increase with pressure and decrease with temperature. Near the P–T stability curve, the error is <11% whereas for crystal-rich (porphyritic index i.e. PI > 35%) and lower-T magmas, the uncertainty increases up to 24%, consistent with depth uncertainties of 0.4 km, at 90 MPa (~3.4 km), and 7.9 km, at 800 MPa (~30 km), respectively. For magnesiohornblendes, the ^[6]Al^*-sensitive hygrometer has an accuracy of 0.4 wt% (σ_est) whereas for magnesiohastingsite and tschermakitic pargasite species, H₂O_melt uncertainties can be as high as 15% relative. The thermobarometric results obtained with the application of these equations to calc-alkaline amphibole-bearing products were finally, and successfully, crosschecked on several subduction-related volcanoes, through complementary methodologies such as pre-eruptive seismicity (volcano-tectonic earthquake locations and frequency), seismic tomography, Fe–Ti oxides, amphibole–plagioclase, plagioclase–liquid equilibria thermobarometry and melt inclusion studies. A user-friendly spreadsheet (i.e. AMP-TB.xls) to calculate the physical–chemical conditions of amphibole crystallization is also provided.     

Synthetic gedrite: a stable phase in the system MgO-Al2O3-SiO2-H2O (MASH) at 800 °C and 10 kbar water pressure, and the influence of FeNaCa impurities

Seeded, solid-media piston-cylinder runs of unusually long duration up to 31 days indicate growth or persistence of synthetic gedrite of the composition □Mg₆Al[AlSi₇O₂₂](OH)₂(=6:1:7), prepared from the purest chemicals available, at 10 kbar water pressure and 800 °C. Conversely, breakdown was observed at 11 kbar and 850 °C to aluminous enstatite, Al₂SiO₅, and a melt of the composition MgO·Al₂O₃·8SiO₂. Thus, pure gedrite free of iron, sodium, and calcium is likely to have only a small PT stability field in the MASH system, estimated as 10 ± 1 kbar, 800 ± 20 °C, even though metastable growth of gedrite can be observed over a larger PT range. A second starting material with the anhydrous composition 5MgO · 2Al₂O₃ · 6SiO₂ also yielded gedrite of the composition 6:1:7, together with more aluminous phases such as kyanite, corundum or sapphirine, thus suggesting that the end-member gedrite defined as □Mg₅Al₂[Al₂Si₆O₂₂](OH)₂(=5:2:6) by the IMA Commission on New Minerals and Mineral Names probably does not exist. With the use of this second starting material, which contains FeNaCa impurities, growth of 6:1:7-gedrite was observed over a still wider PT-range. Seeded runs indicate that the true stability field of such slightly impure 6:1:7-gedrites may also be larger than that of the pure MASH phase and extend at least to 15 kbar, 800 °C. There is, thus, a remarkable stabilization effect on the orthoamphibole structure by impurities amounting only to a total of less than one weight percent of oxides in the starting material. The gedrites synthesized are structurally well ordered amphiboles nearly free of chain multiplicity faults, as revealed by HRTEM. The X-ray diffraction work on the gedrites synthesized yielded the smallest cell volume yet reported for this phase. The small stability field of the pure MASH gedrite is intersected by the upper pressure stability limit of hydrous cordierite for excess-H₂O conditions, thus leading to complicated phase relations for both gedrite and cordierite involving the additional phases aluminous enstatite, talc, quartz, Al₂SiO₅, melt and perhaps boron-free kornerupine. Received: 29 July 1998 / Accepted: 7 January 1999     

Low temperature spectral studies of Mn3+-bearing andalusite and epidote type minerals in the range 30000–5000 cm−1

Polarized absorption spectra of natural piemontite (Ca_1.802Mn ²⁺_0.178 Mg_0.025) (Mn ³⁺_0.829 Fe ³⁺_0.346 Al_1.825) [(Si_2.992Al_0.008) O₁₂OH], viridine (Al_1.945Mn ³⁺_0.033 Fe ³⁺_0.063 Mg_0.003) [O|Si_0.970 O₄], and kanonaite (Al_1.291Mn ³⁺_0.682 Fe ³⁺_0.019 ) [O|Si_1.006 O₄] were measured at 295 and ca. 100 K. For piemontite, lowering the temperature resulted in a sharpening of broad bands in the 10 000–25 000 cm⁻¹ region supporting their assignment to single ion Mn³⁺ in M3 non-centrosymmetric sites.

Alternatively, in kanonaite, temperature behaviour pointed to a slightly stronger influence of vibronic coupling on strong bands near 16 000 and 22 000 cm⁻¹, which supported an interpretation of Mn³⁺ in nearly centrosymmetric M1 sites. Measurements at ca. 100 K show pronounced fine structure in the viridine spectra which is attributed to Fe³⁺. The ɛ values for Mn³⁺ spin-allowed bands in the three minerals lie in the range 18 to 227 [1·g-atom⁻¹·cm⁻¹].

For the same band and polarisation, ɛ values in Mn³⁺-bearing andalusite-type minerals viridine and kanonaite are the same, which indicates an absence of strong magnetic coupling effects between Mn³⁺ ions in the andalusite type structure down to ca. 100 K.

In silicates, the high ɛ values for Mn³⁺ spin-allowed bands, in comparison to those obtained for Fe²⁺ spin-allowed bands from sites of “similar distortion”, is attributed to a higher degree of covalency in the Mn³⁺-O bonds compared to the Fe²⁺-O bonds, as a result of the higher valence state of manganese.