Synthesis of tourmaline solid solutions in the system Na2O–MgO–Al2O3–SiO2–B2O3–H2O–HCl and the distribution of Na between tourmaline and fluid at 300 to 700 °C and 200 MPa

Tourmaline has been synthesized hydrothermally at 200 MPa between 300 and 700 °C from oxide mixtures with Mg-Al ratios for the end members dravite NaMg₃Al₆(Si₆O₁₈)(BO₃)₃(OH)₃(OH) and Mg-foitite &ding6F;(Mg₂Al)Al₆ (Si₆O₁₈)(BO₃)₃(OH)₃(OH). Six different Na concentrations were investigated to determine the distribution of Na between tourmaline and fluid in the SiO₂-saturated system Na₂O-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl. Synthetic tourmaline ranges from X-site vacant (&ding6F;) tourmaline (Mg-foitite) to nearly ideal dravite with Na=0.95 apfu. There are small, but significant, amounts of proton deficiency and negligible tetrahedral Al. Chemical variation is primarily caused by the substitutions Al&ding6F;Mg_-1Na_-1 and minor AlMg_-1H_-1. Varying amounts of Na and &ding6F; determine the Mg/Al ratios. Besides tourmaline and quartz, additional Mg-Al phases are chlorite and, at 700 °C, cordierite. Albite is also present at high Na concentrations in the bulk composition. The c dimension of the tourmaline crystals increases with Na in tourmaline. The amount of Na in the X-site depends strongly on the bulk concentration of Na in the system as well as on the temperature. These factors in turn control the phase assemblage and the composition of the fluid phase. For the assemblage tourmaline + quartz + chlorite/cordierite + fluid, a linear relationship exists between Na concentration in the fluid (quenched after the run) and tourmaline with temperature: T °C [ᆭ °C]=(Na_fluid/Na_tur)앾.878-14.692 (r²=0.96). For the assemblage tourmaline + albite + quartz + fluid, it is: T °C [ᆣ °C]=(Na_fluid/Na_tur)욝.813-6.231 (r²=0.95), where Na_fluid is the concentration of Na⁺ in the final fluid (mol/l) and Na_tur is the number of Na cations in the X-site of tourmaline. The equations are valid in the temperature range of 500-715 °C. Our experiments demonstrate that the occupancy of the X-site in combination with the changing concentrations of Al and Mg can be used to monitor changes in the fluid composition in equilibrium with a growing tourmaline crystal. Currently, this relation can be applied qualitatively to natural tourmaline to explain zoning in Na- and Al/(Al+Mg).     

An Improved Set of a--X Parameters for Fe--Mg--Ca Garnets and Refinements of the Orthopyroxene-Garnet Thermometer and the Orthopyroxene--Garnet--Plagioclase--Quartz Barometer

An internally consistent set of activity-composition relationsfor Fe-Mg-Ca garnets constrained from calorimetric and phaseequilibrium experiments provides the basis for refining theorthopyroxene-garnet thermometer and the orthopyroxene-garnet-plagioclase-quartzbarometer based on the equilibria FeSiO₃ + 1/3Mg₃Al₂Si₃O₁₂ = MgSiO₃ + 1/3Fe₃Al₂Si₃O₁₂ (A) Mg₂Si₂O₆ + CaAl₂Si₂O₈ = 2/3 Mg₃Al₂Si₃O₁₂ + 1/3 Ca₃Al₂Si₃O₁₂+ SiO₂ (B) Fe₂Si₂O₆ + CaAl₂Si₂O₈ = 2/3 Fe₃Al₂Si₃O₁₂ + 1/3 Ca₃Al₂Si₃O₁₂+ SiO₂. (C) The major modification arises from better constrained valuesof mixing parameters for the pyrope-almandine binary. Thermodynamicanalysis of reversed experimental data on Fe-Mg partioning betweenorthopyroxene and garnet (Kawasaki & Matsui, 1983; Lee &Ganguly, 1988), when combined with the enthalpy of solutiondata for the pyrope-almandine binary (Geiger et al.t 1987),yields and AGIT of the exchange reaction as cal in the temperaturerange 1248–1573 K. The retrieved data, combined with the known thermochemical parametersfor the pyrope-grossular and almandine-grossular binaries andcomplementary phase equilibrium data, have been used to estimatetemperatures from equilibrium (A) and pressures from equilibria(B) and (C). The geothermometer registers temperatures higherby 70–100C than those obtained from Harley's (1984) formulationand 20–40?C lower than those from Lee & Ganguly's(1988) formulation for granulite grade rocks; the scatter inestimated temperatures for all areas is lower when comparedwith the other two formulations. The estimated pressures from(B) and (C) are reasonable for granulite grade rocks in thepressure range 3.0–12.0 kb and agree, in most cases, within? 1000'b. The smaller scatter in the computed temperatures and convergenceof calculated pressure values support the claim that the formulationspresented here represent improved versions of the orthopyroxene-garnetgeothermometer and the orthopyroxene-garnet-plagioclase-quartzgeobarometer.     

Phase Relations on the Actinolite-Pargasite Join

Phase relations along the join Ca₂Mg₄Fe²⁺Si₈O₂₂ (OH)₂ (Actinolite)-NaCa₂Mg_3?2Fe_0?8²⁺AlSi₆Al₂O₂₂(OH)₂ (Pargasite) have been studied at P_H2O = 1 kb andthe oxygen fugacities defined by the iron-wustite(IW) buffer. Actinolite and bornblende are separated by a solvus and thefield of actinolite+hornblende+vapor is present in the regionbetween Ac₈₅Pa₁₅ and Ac₅₅ Pa₄₅ at 680 ?C. Complete miscibilityis achieved at 720 ?C. At temperatures higher than the solvusthere is a continuous solid solution series between the twoend members. The stability field of amphibole solid solutiongradually increases with increasing pargasite content in actinolite.The phase assemblages at temperatures higher than those of asolid solution series between the two end members change withincreasing pargasite content in the bulk composition as follows;Act+Cpx+Qz+V, ActHbl+Cpx+Opx+Qz+V, Hbl+Cpx+Opx+Pl+V and Hbl+Cpx+Pl+Ol+V. In comparison with the Fe-free system, the extent of the miscibilitygap between actinolite and hornblende is reduced by an increasein the Fe²⁺ content. The present study should provide an adequatebasis for the interpretation of actinolite-hornblende pairsin metamorphic rocks.     

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 EMP and TEM--AEM Study of Margarite, Muscovite and Paragonite in Polymetamorphic Metabauxites of Naxos Cyclades, Greece) and the Implications of Fine-scale Mica Interlayering and Multiple Mica Generations

Coexisting white micas and plagioclase were studied by electronmicroprobe (EMP), and transmission and analytical electron microscopy(TEM—AEM) in greenschist- to amphibolite-grade metabauxitesfrom Naxos. The TEM—AEM studies indicate that sub-micronscale (0.01–1.0 µm thick) semicoherent intergrowthsof margarite, paragonite and muscovite are common up to loweramphibolite conditions. If unrecognized, such small-scale micainterlayering can easily lead to incorrect interpretation ofEMP data. Muscovite and paragonite in M₂ greenschist-grade Naxosrocks are mainly relics of an earlier high-pressure metamorphism(M₁). Owing to the medium-pressure M₂ event, margante occursin middle greenschist-grade metabauxites and gradually is replacedby plagioclase + corundum in amphibolite-grade metabauxites.The margarite displays minor ^IVAl_{3 VI}(Fe³⁺, Al) Si_-3 ^VI-_-1 andconsiderable (Na, K) SiCa_-1Al_-1 substitution, resulting in upto 44 mol% paragonite and 6 mol % muscovite in solution. Thecompositional variation of muscovite is mainly described by^VI(Fe²⁺, Mg) Si ^VI Al_-1^VI Al_-1 and _VI(Fe₃₊Al^-1) exchanges, thelatter becoming dominant at amphibolite grade, Muscovite issignificantly richer in Fe than margarite or paragonite. Ca—Na—Kpartitioning data indicate that margarite commonly has a significantlyhigher Na/(Na+ K+Ca) value than coexisting muscovite or plagioclase.Exceptions are found in several greenschist-grade rocks, inwhich M₁-formed mussovite may have failed to equilibrate withM₂ margarite. The sluggishness of K-rich micas to recrystallizeand adjust composidonally to changing P-T conditions is alsoreflected in the results of mus-covite-paragonite solvus thermometry.Chemical data for Ca—Na micas from this study and literaturedata indicate that naturally coexisting margarite—paragonitepairs display considerably less mutual solubility than suggestedby experimental work. The variable and irregular Na partitioningbetween margarite and muscovite as observed in many metamorphicrocks could largely be related to opposing effects of pressureon Na solubility in margarite and paragonite and/or non-equilibriumbetween micas. KEY WORDS: Ca—Na—K mica; margarite; metabauxite; Naxos; sub-micron-scale mica interlayering     

Petrology of the Blue Mountain Complex, Marlborough, New Zealand

Blue Mountain is a central-type alkali ultrabasic-gabbro ringcomplex (lxl7middot;5 km) introducing Upper Jurassic sediments,Marlborough, New Zealand. The ultrabasic-gabbroic rocks containlenses of kaersutite pegmatite and sodic syenite pegmatite andare intruded by ring dykes of titanaugite-ilmenite gabbro andlamprophyre. The margin of the intrusion is defined by a ringdyke of alkali gabbro. The plutonic rocks are cut by a swarmof hornblendebiotite-rich lamprophyre dykes. Thermal metamorphismhas converted the sediments to a hornfels ranging in grade fromthe albite-epidote hornfels facies to the upper limit of thehornblende hornfels facies. The rocks are nepheline normative and consist of olivine (Fo_82–74),endiopside (Ca₄₅Mg₄₈Fe₇–Ca₃₆Mg₅₅Fe₉), titanaugite (Ca₄₀Mg₅₀Fe₁₀–Ca₄₄Mg₃₉Fe₁₇),plagioclase (An_73–18), and ilmenitetitaniferous magnetite,with various amounts of titaniferous hornblende and titanbiotite.There is a complete gradation between endiopside and titanaugitewith the coupled substitution R_y⁺²+Si;;(Ti⁺⁴+Fe⁺³+Al⁺³ and asympathetic increase in CaAl₂SiO₆ (0·2–10·2percent) and CaTiAl₂O₆ (2·1–8·1 per cent)with fractionation. Endiopside shows a small, progressive Mgenrichment along a trend subparallel to the CaMgSi₂O₆–Mg₂Si₂O₆boundary, and titanaugite is enriched in Ca and Fe⁺²+Fe⁺³ withdifferentiation. Oscillatory zoning between endiopside and titanaugiteis common. Exsolved ilmenite needles occur in the most Fe-richtitanaugites. The amphiboles show the trend: titaniferous hornblende(1·0–57middot;7 per cent TiO₂) kaersutite (6·4per cent TiO2) Fe-rich hastingsite (18·0–19·1per cent FeO as total Fe). Biotite is high in TiO₂ (6·6–7·8per cent). Ilmenite and titaniferous magnetite (3·5–10·6per cent TiO₂) are typically homogeneous grains; their compositioncan be expressed in terms of R⁺²RO₃:R⁺²O:R₂⁺³O₄. The intrusion of igneous rocks was probably controlled by subterraneanring fracturing. Subsidence of the country rock within the ringfracture provided space for periodic injections of magma froma lower reservoir up the initial ring fracture to form the BlueMountain rocks at a higher level. Downward movement of the floorof the intrusion during crystallization caused inward slumpingof the cumulates which affected the textural, mineralogical,and chemical evolution of the rocks in different parts of theintrusion. The order of mineral fractionation is reflected by the chemicalvariation in the in situ ultrabasic-gabbroic rocks and the successiveintrusions of titanaugite-ilmenite gabbro and lamprophyre ringdykes, marginal alkali gabbro and lamprophyre dyke swarm. Aninitial decrease, then increase in SiO2; a steady decrease inMgO, CaO, Ni, and Cr: an initial increase, then decrease inFeO+Fe₂O₃, TiO₂, MnO, and V; almost linear increase in A1₂O₃and late stage increase in alkalis and P₂O₃, implies fractionationof olivine and endiopside, followed by titanaugite and Fe-Tioxides, followed by plagioclase, hornblende, biotite, and apatite.Reversals in the composition of cumulus olivine and endiopsideand Solidification Index, indicate that the ultrabasic-gabbroicsequence is composed of four main injections of magma. The ultrabasic rocks crystallized under conditions of high P_H2Oand fairly high, constant     

Petrology of the Blue Mountain Complex, Marlborough, New Zealand

Blue Mountain is a central-type alkali ultrabasic-gabbro ringcomplex (1?1?5 km) introducing Upper Jurassic sediments, Marlborough,New Zealand. The ultrabasic-gabbroic rocks contain lenses ofkaersutite pegmatite and sodic syenite pegmatite and are intrudedby ring dykes of titanaugite-ilmenite gabbro and lamprophyre.The margin of the intrusion is defined by a ring dyke of alkaligabbro. The plutonic rocks are cut by a swarm of hornblende-biotite-richlamprophyre dykes. Thermal metamorphism has converted the sedimentsto a hornfels ranging in grade from the albite-epidote hornfelsfacies to the upper limit of the hornblende hornfels facies. The rocks are nepheline normative and consist of olivine (Fo_82-74),endiopside (Ca₄₅Mg₄₈Fe₇-Ca₃₆Mg₅₅Fe₉), titanaugite (Ca₄₀Mg₅₀Fe₁₀-Ca₄₄Mg₃₉Fe₁₇),plagioclase (An_73-18), and ilmenitetitaniferous magnetite, withvarious amounts of titaniferous hornblende and titanbiotite.There is a complete gradation between end-iopside and titanaugitewith the coupled substitution R_y^+z+Si(Ti⁺⁴+Fe⁺³)+Al⁺³ and asympathetic increase in CaAl₂SiO₆ (0?2-10?2 percent) and CaTiAl₂O₆(2?1-8?1 per cent) with fractionation. Endiopside shows a small,progressive Mg enrichment along a trend subparallel to the CaMgSi₂O₆-Mg₂Si₂O₆boundary, and titanaugite is enriched in Ca and Fe⁺²+Fe⁺³ withdifferentiation. Oscillatory zoning between endiopside and titanaugiteis common. Exsolved ilmenite needles occur in the most Fe-richtitanaugites. The amphiboles show the trend: titaniferous hornblende(1?0–5?7 per cent TiO₂)kaersutite (6?4 per cent TiO₂)Fe-richhastingsite (18?0–19?1 per cent FeO as total Fe). Biotiteis high in TiO₂ (6?6–7?8 per cent). Ilmenite and titaniferousmagnetite (3?5–10?6 per cent TiO₂) are typically homogeneousgrains; their composition can be expressed in terms of R⁺²RO₃:R⁺²O:R₂⁺³O₄. The intrusion of igneous rocks was probably controlled by subterraneanring fracturing. Subsidence of the country rock within the ringfracture provided space for periodic injections of magma froma lower reservoir up the initial ring fracture to form the BlueMountain rocks at a higher level. Downward movement of the floorof the intrusion during crystallization caused inward slumpingof the cumulates which affected the textural, mineralogical,and chemical evolution of the rocks in different parts of theintrusion. The order of mineral fractionation is reflected by the chemicalvariation in the in situ ultrabasic-gabbroic rocks and the successiveintrusions of titanaugite-ilmenite gabbro and lamprophyre ringdykes, marginal alkali gabbro and lamprophyre dyke swarm. Aninitial decrease, then increase in SiO₂; a steady decrease inMgO, CaO, Ni, and Cr: an initial increase, then decrease inFeO+Fe₂O₃, TiO₂, MnO, and V; almost linear increase in Al₂O₃and late stage increase in alkalis and P₂O₃, implies fractionationof olivine and endiopside, followed by titanaugite and Fe-Tioxides, followed by plagioclase, hornblende, biotite, and apatite.Reversals in the composition of cumulus olivine and endiopsideand Solidification Index, indicate that the ultrabasic-gabbroicsequence is composed of four main injections of magma. The ultrabasic rocks crystallized under conditions of high PH₂Oand fairly high, constant P_O2; P_H2 and P_O2 increased duringthe formation of the gabbroic rocks until fracturing of thechamber roof occurred. The abundance of euhedral amphibole inthe latter injection phases suggests that amphibole accumulatedfrom a hydrous SiO₂ undersaturated magma when an increase inP_O2, stabilized its crystallization. Plutonic complexes similar to Blue Mountain are found withinand beneath the volcanic piles of many oceanic islands, e.g.Canaries, Reunion, and Tahiti, and those intruding thick sedimentarysequences, as at Blue Mountain, e.g. the pipe-like intrusionsof the Monteregian Hills, Quebec.     

Reactions Leading to the Disappearance of Pumpellyite in Low-grade Metamorphic Rocks of the Sanbagawa Metamorphic Belt in Central Shikoku, Japan

The major mineral assemblages of the metabasites of the Omoiji-Nagasawaarea in central Shikoku are hematite+epidote+chlorite+actinolite,riebeckitic actinolite+epidote+chlorite, epidote+chlorite+actinolite,and pumpellyite+epidote+chlorite+actinolite. The constituentminerals are often heterogeneous and assemblages in the fieldof a thin section sometimes do not obey the phase rule, butif grains apparently in non-equilibrium with others are excludedand domains of chemical equilibrium are appropriately chosenthe assemblages approximately obey the phase rule. The stability of hematite, pumpellyite, and epidote associatedwith chlorite and actinolite can be dealt with in terms of aternary system with appropriate excess phases. By fixing theFe²⁺/(Fe²⁺ +Mg) ratio of chlorite, it is dealt with in termsof stability relations in the system Ca₂Al₃Si₃O₁₂(OH)–Ca₂AlFe₂Si₃O₁₂(OH)with excess chlorite, actinolite, quartz, and controlled P_H2O.The maximum and minimum Fe³⁺ contents of epidote in this modelsystem are determined by hematite+epidote+chlorite+actinoliteand pumpellyite+epidote+chlorite+actinolite assemblages. Themaximum Fe³⁺ of the three phase assemblage epidote+chlorite+actinoliteis insensitive to temperature, but the minimum Fe³⁺ contentof epidote is sensitive to temperature and can be used to definethe metamorphic grade by a continuous quantity related to temperature.The phase relations expected for the model system are in goodagreement with the parageneses of the Sanbagawa terrain in centralShikoku and offer an explanation to the rule of Miyashiro &Seki (1958a) that the compositional range of epidote enlargeswith increasing temperature. The model also makes it possibleto estimate semi-quantitatively the temperature range in whichthe assemblage pumpellyite+epidote+chlorite+actinolite is stable.The possible maximum range is about 120 ?C, but the assemblageis stable in metabasite only for about 90 ?C. The higher temperaturelimit of the pumpellyite-actinolite facies defined by the disappearanceof pumpellyite in metabasite corresponds to the temperatureat which epidote with Fe³⁺/(Fe³⁺ +Al) = 0.10 0.15 coexistswith pumpellyite, actinolite, and chlorite. The compositions of epidotes in the metabasites of the Omoiji-Nagasawaarea cluster around Fe³⁺/(Fe³⁺ +Al) = 0.33. The grade of thisarea is close to the lower temperature stability limit of thepumpellyite+epidote+chlorite+actinolite assemblage.     

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.     

A multi-analytical study of the crystal structure of unusual Ti–Zr–Cr-rich Andradite from the Maronia skarn, Rhodope massif, western Thrace, Greece

Unusual Ti–Cr–Zr-rich garnet crystals from high-temperature melilitic skarn of the Maronia area, western Thrace, Greece, were investigated by electron-microprobe analysis, powder and single-crystal X-ray diffraction, IR, Raman and Mössbauer spectroscopy. Chemical data showed that the garnets contain up to 8 wt.% TiO₂, 8 wt.% Cr₂O₃ and 4 wt.% ZrO₂, representing a solid solution of andradite (Ca₃Fe³⁺ ₂Si₃O₁₂ ≈46 mol%), uvarovite (Ca₃Cr₂Si₃O₁₂ ≈23 mol%), grossular (Ca₃Al₂Si₃O₁₂ ≈10 mol%), schorlomite (Ca₃Ti₂[Si,(Fe³⁺,Al³⁺)₂]O₁₂ ≈15 mol%), and kimzeyite (Ca₃Zr₂[Si,Al₂]₃O₁₂ ≈6 mol%). The Mössbauer analysis showed that the total Fe is ferric, preferentially located at the octahedral site and to a smaller extent at the tetrahedral site. Single-crystal XRD analysis, Raman and IR spectroscopy verified substitution of Si mainly by Al³⁺, Fe³⁺ and Ti⁴⁺. Cr³⁺ and Zr⁴⁺ are found at the octahedral site along with Fe³⁺, Al³⁺ and Ti⁴⁺. The measured H₂O content is 0.20 wt.%. The analytical data suggest that the structural formula of the Maronia garnet can be given as: (Ca_2.99Mg_0.03)_Σ=3.02(Fe³⁺ _0.67Cr_0.54Al_0.33Ti_0.29Zr_0.15)_Σ=1.98(Si_2.42Ti_0.24Fe_0.18Al_0.14)_Σ=2.98O₁₂OH_0.11. Ti-rich garnets are not common and their crystal chemistry is still under investigation. The present work presents new evidence that will enable the elucidation of the structural chemistry of Ti- and Cr-rich garnets.     

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.     

Comparative compressibilities of majorite-type garnets

Relative compressibilities of five silicate garnets were determined by single-crystal x-ray diffraction on crystals grouped in the same high-pressure mount. The specimens include a natural pyrope [(Mg_2.84Fe_0.10Ca_0,06) Al₂Si₃O₁₂], and four synthetic specimens with octahedrally-coordinated silicon: majorite [Mg₃(MgSi)Si₃O₁₂], calcium-bearing majorite [(Ca_0.49Mg_2.51)(MgSi)Si₃0₁₂], sodium majorite [(Na_1.88Mgp_0.12)(Mg_0.06Si_1.94)Si₃O₁₂], and an intermediate composition [(Na_0.37Mg_2.48)(Mg_0.13Al_1.07 Si₀₈₀) Si₃O₁₂]. Small differences in the compressibilities of these crystals are revealed because they are subjected simultaneously to the same pressure. Bulk-moduli of the garnets range from 164.8 ± 2.3 GPa for calcium majorite to 191.5 ± 2.5 GPa for sodium majorite, assuming K′=4. Two factors, molar volume and octahedral cation valence, appear to control garnet compression.     

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.     

The Mineralogy and Geochemistry of the Metamorphosed Basic and Ultrabasic Rocks of the Jijal Complex, Kohistan, NW Pakistan

The Jijal complex, covering more than 150 sq. km in the extremenorth of Pakistan, is a tectonic wedge of garnet granulitesintruded in the south by a 10 x 4 km slab of ultramafic rocks.The granulites are divisible into plagioclase-bearing (basicto intermediate) and plagioclase-free (ultrabasic to basic)types, the two types reflecting differences in bulk chemistry.Garnet + plagioclase + clinopyroxene + quartz + rutile ±hornblende ± epidote is the most common assemblage. Theplagioclase-free rocks are composed mainly of two or three ofthe minerals garnet, amphibole, clinopyroxene and epidote. Orthopyroxeneoccurs in websteritic rocks devoid of epidote. Much of the amphiboleand some epidote appear to be prograde products. Although variationdiagrams do not reveal a genetic link between the two typesof granulite, it is considered that they are comagmatic ratherthan the products of two or more unrelated magmas. The compositions of garnet (Py_28–46 Alm _27–43Gro_16–28),clinopyroxene (Mg_44–34Fe_5–17Ca_51–49, Al₂O₃3·0–9·9 per cent), orthopyroxene (with upto 5·5 per cent Al₂O₃), amphibole (with up to 16·3per cent Al₂O₃ and high Al^vi/Al^iv), and the abundance of garnetsuggest a high-pressure origin for the granulites. The rocksappear to have differentiated from a tholeiitic magma of oceanicaffinity or they may be genetically related to the pyroxenegranulites of Swat considered to have originally crystallizedfrom a calc-alkaline magma of island arc or continental marginaffinity. They probably crystallized in the ancient Tethyancrust/upper mantle (or less likely in a continental margin),later to be metamorphosed to granulites (670–790 °C,12–14 kb) during the collision of the Indian-Asian landmasses,and carried upwards during later Himalayan orogenic episodes. The ultramafic rocks are alpine-type in nature and devoid ofgarnet. They are dominated by diopsidites; dunites, peridotites,and harzburgites together form <50 per cent of the area ofoutcrop. The chemistry of the rocks, and their olivines (Fo_92–89)and clinopyroxenes (Mg_49.5–48Fe_2.8–5.2Ca_47.4–46.8)are similar to those of alpine complexes of the harzburgitesubtype. It is not clear whether they represent a faulted slabof suboceanic crust/upper mantle, mantle diapirs in deep orogenicroots, or dismembered ultramafic rocks differentiated from abasaltic magma. They seem to have a complex history; their presentmineralogy is suggestive of high grade metamorphism (800–850°C, 8–12 kb). They are magmatically unrelated to thegarnet granulites and were probably intruded into the latteras plastic crystalline material after both had been independentlymetamorphosed, but before the entire complex was carried tectonicallyinto its present surroundings. The abundances of the diopsiditesis in marked contrast to other alpine-type complexes and thepossibility of Ca and Si metasomatism during or before theirmetamorphism should not be totally ruled out.     

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, epidote-diopside-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+spinelto much lower pressures than the three kilobars found in thepure 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: Mg₂Si₃(Na,K)(Al^VI)₂(Al^IV)₃.     

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.     

Ferric iron partitioning between plagioclase and silicate liquid: thermodynamics and petrological applications

A series of Fe and Mg partition experiments between plagioclase and silicate liquid were performed in the system SiO₂-Al₂O₃-Fe₂O₃-FeO-MgO-CaO-Na₂O under oxygen fugacities from below the IW buffer up to that of air. A thermodynamic model of plagioclase solid solution for the (CaAl,NaSi,KSi)(Fe³⁺,Al³⁺)Si₂O₈-Ca(Fe²⁺,Mg)Si₃O₈ system is proposed and is calibrated by regression analysis based on new and previously reported experimental data of Fe and Mg partitioning between plagioclase and silicate liquid, and reported thermodynamic properties of end members, ternary feldspar and silicate liquid. Using the derived thermodynamic model, FeO^t, MgO content and Mg/(Fe^t+Mg) in plagioclase can be predicted from liquid composition with standard deviations of ǂ.34 wt% (relative error =9%) and ǂ.08 wt% (14%) and ǂ.7 (8%) respectively. Calculated Fe³⁺-Al exchange chemical potentials of plagioclase, m_{Fe^{3 +} ( Al )- 1} ^Pl{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Pl}} agree with those calculated using reported thermodynamic models for multicomponent spinel, m_{Fe^{3 +} ( Al )- 1} ^Sp{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Sp}} and clinopyroxene, m_{Fe^{3 +} ( Al )- 1} ^Cpx{\rm \mu }_{{\rm Fe}^{{\rm 3 + }} \left( {{\rm Al}} \right)_{{\rm - 1}} }^{{\rm Cpx}} . The FeO^t content of plagioclase coexisting with spinel or clinopyroxene is affected by Fe³⁺/(Fe³⁺+Al) and Mg/(Fe+Mg) of spinel or clinopyroxene and temperature, while it is independent of the anorthite content of plagioclase. Three oxygen barometers based on the proposed model are investigated. Although the oxygen fugacities predicted by the plagioclase-liquid oxygen barometer are scattered, this study found that plagioclase-spinel-clinopyroxene-oxygen and plagioclase-olivine-oxygen equilibria can be used as practical oxygen barometers. As a petrological application, prediction of plagioclase composition and f_O2 are carried out for the Upper Zone of the Skaergaard intrusion. The estimated oxygen fugacities are well below QFM buffer and consistent with the estimation of oxidization states in previous studies.     

Chemical composition and species attribution of tourmalines from a rare-metal pegmatite vein with scapolite, Sangilen Upland, Tuva

A detailed study of the chemical composition and substitutions in calcium tourmalines from a scapolite-bearing rare-metal pegmatite vein from the Sol’bel’der River basin has shown that their species attribution is determined by occupancy of octahedral site Y. The composition of the yellow tourmaline most abundant in the central part of the pegmatite bodyis rather constant and characterized by the ideal formula Ca(Mg₂Li)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃F. Variations in the chemical composition of zonal tourmaline crystals from the contact part of the pegmatite are controlled by abrupt change in the chemical medium during their formation. The yellow cores of these crystals are close in composition to tourmaline from the central part of the pegmatite vein. The Mg content abruptly decreases toward the crystal margin: Mg²⁺ → Fe²⁺, 2Mg²⁺ → Li⁺ + Al³⁺, and Mg²⁺ + OH → Al³⁺ + O²⁻. The composition of dark green marginal zones in tourmaline is characterized by the ideal formula Ca(Al_1.5Li_1.5)Al₆(Si₆O₁₈)(BO₃)₃ (OH₂O)(F). The results indicate specific formation conditions of pegmatite. The crystallochemical formulas of the studied tourmalines allow us to regard them as new mineral species in the tourmaline group.     

Sillimanite and Ilmenite from High-grade Metamorphic Rocks of Antarctica and Other Areas

Sillimanite from a variety of high-grade metamorphic rocks containsfrom 0.13 to 1.82 weight per cent Fe₂O₃ and less than 0.1 weightper cent TiO₂. The iron is trivalent and substitutes for Alonly. Ilmenite associated with the sillimanite contains no morethan 0.4 weight per cent Al₂O₃, SiO₂, CaO, and MnO; and MgOdoes not exceed 1.6 weight per cent. It ranges in compositionfrom Ilm₉₉Hem₁ to Ilm₈₅Hem₁₅. A least squares fit of precision unit cell data on 10 analyzedsillimanites gives the following cell dimensions for iron-freesillimanite: a = 7.4830 Á, b = 7.6708 Á, c = 5.7694Á and V = 331.15 Á³. The projected increase incell volume with substitution of 10 mole per cent Fe₂SiO₃ is1.66 per cent. A regular increase in the Fe₂O₃ content of sillimanite withincreasing Fe₂O₃ content of associated ilmenite in 15 of 21samples analyzed suggests that sillimanite and ilmenite crystallizedin equilibrium in the 15 samples. The compositions of the tensillimanite-ilmenite pairs analyzed by the author fit the followingempirical curve (sol;(X_Fe2O3)Il = 1.110 x 10^–3. This regularincrease in Fe₂O₃ contents fits a model of Fe³⁺ substitutionfor Al on two independent sites in sillimanite and a coupledsubstitution of for Fe²⁺ Ti on two sites in ilmenite. Sillimaniteand ilmenite are behaving as ideal solutions over the compositionalrange 0 < X_Fe2SIO3 < 0.013 in sillimanite and 0 < X_Fe2O3< 0.15 in ilmenite. Equations have been derived for expressing the variation inFe₂O₃ content of sillimanite associated with quartz and ilmeniteor hematite as a function of pressure, temperature, and Fe₂O₃content of the oxide minerals. For example, the Fe₂O₃ contentof a sillimanite with 1.5 mole per cent Fe₂SiO₃ coexisting withTi-free hematite is calculated to decrease 11 per cent witha 5 kb increase in pressure. The rate of increase with temperatureof the Fe₂O₃ content of sillimanite is greater in hematite-bearingassemblages than in ilmenite-bearing assemblages.