A high-temperature and high-pressure Raman spectroscopic study of CaGeO3 garnet

 High-pressure and high-temperature Raman spectra of CaGeO₃ tetragonal garnet have been collected to 11.5 GPa and 1225 K, respectively, in order to investigate possible intrinsic anharmonic behaviour in this phase. The Raman peak positions were observed to vary linearly with pressure and temperature within the ranges studied, with the higher-energy peaks showing larger P- and T-induced shifts than the low energy modes. The observed T-induced shifts are similar to those reported for grossular and andradite, while the observed P-induced shifts are generally larger than those of aluminosilicate and MgSiO₃ majorite garnets (Gillet et al. 1992; Rauch et al. 1996) due to the larger bulk modulus of CaGeO₃ garnet. The observed mode shifts of CaGeO₃ garnet were used to determine the isothermal and isobaric mode Grüneisen parameters for this phase. These parameters are similar in value to those reported previously for grossular and andradite (Gillet et al. 1992). The calculated intrinsic anharmonic parameters, a _i , for CaGeO₃ garnet were determined to be nonzero, indicating significant anharmonic behaviour for this phase. These values, which range from −3.8 × 10⁻⁵ K⁻¹ to −1.3 × 10⁻⁵ K⁻¹, are also similar to those reported for andradite and grossular, but smaller than those determined for pyrope (Gillet et al. 1992). Hence, we expect MgSiO₃ majorite to show greater anharmonicity than the germanate analogue studied by us. The anharmonic parameters determined for CaGeO₃ tetragonal garnet may now be introduced into quasiharmonic vibrational heat capacity models to account for the observed anharmonic behaviour. Received: 21 April 1999 / Revised, accepted: 11 September 1999     

西藏甲玛铜多金属矿石榴子石矿物学特征及成因意义

甲玛铜多金属矿主要的工业矿体赋存于矽卡岩中,石榴石矽卡岩是主要的矽卡岩类型,因此,研究石榴子石的矿物学特征及其成因具有重要的意义。本文综合前人研究成果,重点对采于甲玛矿区不同钻孔的、不同空间位置的石榴子石进行了矿石学及电子探针分析研究,并系统对比其矿物学特征。对18个石榴子石测点和项目组其它电子探针分析成果表明,甲玛铜多金属矿的石榴子石均为钙质系列,由贫Ti的钙铁榴石和富Ti、Mg、Mn的钙铝榴石组成。受流体氧逸度的制约,矿区中心以钙铁榴石为主,边缘以钙铝榴石为主,从深部至浅部钙铁榴石含量减少,钙铝榴石含量增加。此外,石榴子石"锯齿状"环带成分暗示了其流体过程的多期多阶段性。     

Single crystal Raman spectrum of uvarovite, Ca3Cr2Si3O12

Single-crystal Raman spectra of synthetic end-member uvarovite (Ca₃Cr₂Si₃O₁₂) and of a binary solution (59% uvarovite, 41% andradite) have been measured using single crystal techniques. For each of these garnets, 22 and 21 of the 25 Raman modes were located, respectively. The spectra for uvarovite garnets closely resemble those of the other calcic garnets, grossular, and andradite. The modes for uvarovites do not fit into the same trends as established by the other five anhydrous end-member garnets: the high energy “internal” Si–O modes do not depend on lattice constant in uvarovite. They exceed frequencies for both andradite and grossular. This is likely due to the large crystal field stabilization energy of trivalent chromium. The low energy and midrange modes are at similar frequencies to the other calcic garnets.     

Garnet-bearing granite from the Třebíč pluton, Bohemian Massif (Czech Republic)

Summary Garnet occurs as a significant mineral constituent of felsic garnet-biotite granite in the southern edge of the Třebíč pluton. Two textural groups of garnet were recognized on the basis of their shape and relationship to biotite. Group I garnets are 1.5–2.5 mm, euhedral grains which have no reaction relationship with biotite. They are zoned having high X_Mn at the rims and are considered as magmatic. Group II garnets form grain aggregates up to 2.5 cm in size, with anhedral shape of individual grains. The individual garnet II grains are usually rimmed by biotite and have no compositional zoning. The core of group I garnets and group II garnets contains 67–80 mol% of almandine, 5–19 mol% of pyrope, 7–17 mol% of spessartine and 2–4 mol% of grossular. Biotite occurs in two generations; both are magnesian siderophyllites with Fe/(Fe + Mg) = 0.50–0.69. The matrix biotite in granites (biotite I) has high Ti content (0.09–0.31 apfu) and Fe/(Fe + Mg) ratio between 0.50 and 0.59. Biotite II forms reaction rims around garnet, is poor in Ti (0.00–0.06 apfu) and has a Fe/(Fe + Mg) ratio between 0.61 and 0.69. The textural relationship between biotite and garnet indicates that garnet reacted with granitic melt to form Ti-poor biotite and a new granitic melt, depleted in Ti and Mg and enriched in Fe and Al. In contrast to the host durbachites (hornblende-biotite melagranites), which originated by mixing of crustal melts and upper mantle melts, the origin of garnet-bearing granites is related to partial melting of the aluminium-rich metamorphic series of the Moldanubian Zone.     

Hydroxyl defects in garnets from mantle xenoliths in kimberlites of the Siberian platform

A suite of more than 200 garnet single crystals, extracted from 150 xenoliths, covering the whole range of types of garnet parageneses in mantle xenoliths so far known from kimberlites of the Siberian platform and collected from nearly all the kimberlite pipes known in that tectonic unit, as well as some garnets found as inclusions in diamonds and olivine megacrysts from such kimberlites, were studied by means of electron microprobe analysis and single-crystal IR absorption spectroscopy in the v _OH vibrational range in search of the occurrence, energy and intensity of the v _OH bands of hydroxyl defects in such garnets and its potential use in an elucidation of the nature of the fluid phase in the mantle beneath the Siberian platform. The v _OH single-crystal spectra show either one or a combination of two or more of the following major v _OH bands, I 3645–3662 cm⁻¹, II 3561–3583 cm⁻¹, III 3515–3527 cm⁻¹, and minor bands, Ia 3623–3631 cm⁻¹, IIa 3593–3607 cm⁻¹. The type of combination of such bands in the spectrum of a specific garnet depends on the type of the rock series of the host xenolith, Mg, Mg-Ca, Ca, Mg-Fe, or alkremite, on the xenolith type as well as on the chemical composition of the respective garnet. Nearly all garnets contain band systems I and II. Band system III occurs in Ti-rich garnets, with wt% TiO₂ > ca. 0.4, from xenoliths of the Mg-Ca and Mg-Fe series, only. The v _OH spectra do not correspond to those of OH⁻ defects in synthetic pyropes or natural ultra-high pressure garnets from diamondiferous metamorphics. There were no indications of v _OH from inclusions of other minerals within the selected 60 × 60 μm measuring areas in the garnets. The v _OH spectra of pyrope-knorringite- and pyrope-knorringite-uvarovite-rich garnets included in diamonds do not show band systems I to III. Instead, they exhibit one weak, broad band (Δv _OH 200–460 cm⁻¹) near 3570 cm⁻¹, a result that was also obtained on pyrope-knorringite-rich garnets extracted from two olivine megacrysts. The quantitative evaluation, on the basis of relevant existing calibrational data (Bell et al. 1995), of the sum of integral intensities of all v _OH bonds of the garnets studied yielded a wide range of “water” concentrations within the set of the different garnets, between values below the detection limit of our single-crystal IR method, near 2 × 10⁻⁴ wt%, up to 163 × 10⁻⁴ wt%. The “water” contents vary in a complex manner in garnets from different xenolith types, obviously depending on a large number of constraints, inherent in the crystal chemistry as well as the formation conditions of the garnets during the crystallization of their mantle host rocks. Secondary alteration effects during uplift of the kimberlite, play, if any, only a minor role. Despite the very complex pattern of the “water” contents of the garnets, preventing an evaluation of a straightforward correlation between “water” contents of the garnets and the composition of the mantle's fluid phase during garnet formation, at least two general conclusions could be drawn: (1) the wide variation of “water” contents in garnets is not indicative of regional or local differences in the composition of the mantle's fluid phase; (2) garnets formed in the high-pressure/high-temperature diamond-pyrope facies invariably contain significantly lower amounts of “water” than garnets formed under the conditions of the graphite-pyrope facies. This latter result (2) may point to significantly lower f _H2O and f _O2 in the former as compared to the latter facies. Received: 25 November 1997 / Accepted: 9 March 1998     

Local structure of ferric iron-bearing garnets deduced by IR-spectroscopy

Powder IR absorption spectroscopy has been used to characterise cation substitutions in three garnet solid solutions: grossular–andradite, skiagite–andradite and skiagite–almandine. The wavenumber shift of the highest energy mode associated with tetrahedral vibrations depends on the type of cation occupying the adjacent sites in the structure. The wavenumber shifts exhibit positive deviations from linearity that correlate closely with the variations of the Si–O bond distances for all three garnet solid solutions. The autocorrelation function has been used to determine an effective line width (Δcorr) of the absorption bands over a given spectral region. Non-linear behaviour of Δcorr was found for all three solid solutions. An empirical calibration between Δcorr excess and calorimetric enthalpy of mixing data gives an estimate for the symmetric Margules parameters W_spec^H of the three solid solutions. Comparison with the systematics of aluminosilicate garnets in terms of W_spec^H vs. ΔV², where ΔV represents the difference in molar volume between the end members in a binary system, reveals that such a relationship is not generally applicable to garnet solid solutions with an octahedral cation other than Al.     

The breakdown of potassium feldspar at high water pressures

The equilibrium position of the reaction between sanidine and water to form “sanidine hydrate” has been determined by reversal experiments on well characterised synthetic starting materials in a piston cylinder apparatus. The reaction was found to lie between four reversed brackets of 2.35 and 2.50 GPa at 450 °C, 2.40 and 2.59 GPa at 550 °C, 2.67 and 2.74 GPa at 650 °C, and 2.70 and 2.72 GPa at 680 °C. Infrared spectroscopy showed that the dominant water species in sanidine hydrate was structural H₂O. The minimum quantity of this structural H₂O, measured by thermogravimetric analysis, varied between 4.42 and 5.85 wt% over the pressure range of 2.7 to 3.2 GPa and the temperature range of 450 to 680 °C. Systematic variation in water content with pressure and temperature was not clearly established. The maximum value was below 6.07 wt%, the equivalent of 1 molecule of H₂O per formula unit. The water could be removed entirely by heating at atmospheric pressure to produce a metastable, anhydrous, hexagonal KAlSi₃O₈ phase (“hexasanidine”) implying that the structural H₂O content of sanidine hydrate can vary. The unit cell parameters for sanidine hydrate, measured by powder X-ray diffraction, were a = 0.53366 (±0.00022) nm and c = 0.77141 (±0.00052) nm, and those for hexasanidine were a = 0.52893 (±0.00016) nm and c = 0.78185 (±0.00036) nm. The behaviour and properties of sanidine hydrate appear to be analogous to those of the hydrate phase cymrite in the equivalent barium system. The occurrence of sanidine hydrate in the Earth would be limited to high pressure but very low temperature conditions and hence it could be a potential reservoir for water in cold subduction zones. However, sanidine hydrate would probably be constrained to granitic rock compositions at these pressures and temperatures. Received: 6 May 1997 / Accepted: 2 October 1997     

Chemical composition and evolution of the garnets in the Astamal Fe-LREE distal skarn deposit,Qara-Dagh–Sabalan metallogenic belt,Lesser Caucasus,NW Iran

The chemistry of garnet can provide clues to the formation of skarn deposits. The chemical analyses of garnets from the Astamal Fe-LREE distal skarn deposit were completed using an electron probe micro-analyzer. The three types of garnet were identified in the Astamal skarn are: (I) euhedral coarse-grained isotropic garnets (10–30 mm across), which are strongly altered to epidote, calcite and quartz in their rim and core, with intense pervasive retrograde alteration and little variation in the overall composition (Adr_94.3–84.4 Grs_8.5–2.7 Alm_1.9–0.2) (garnet I); (II) anhedral to subhedral brecciated isotropic garnets (5–10 mm across) with minor alteration, a narrow compositional range along the growth lines (Adr_82–65.4 Grs_21.9–11.7 Alm_11.1–2.4) and relatively high Cu (up to 1997 ppm) and Ni (up to 1283 ppm) (garnet II); and (III) subhedral coarser grained garnets (> 30 mm across) with moderate alteration, weak diffusion and irregular zoning of discrete grossular-almandine-rich domains (Adr_84.2–48.8 Grs_32.4–7.6 Alm_19.9–3.5) (garnet III). In the third type, the almandine content increases with increasing grossular/andradite ratio and increasing substitutions of Al for Fe^3 +.Almost all three garnet types have been replaced by fine-grained, dark-brown allanite that is typically disseminated and has the same relief as andradite. The Cu content increases while Ni content decreases slightly towards the rim of garnet II and garnet III. Copper in garnet II is positively correlated with increasing almandine content and decreasing andradite content, indicating that the almandine structure, containing relatively more Fe^2 +, is more suitable than andradite and grossular to host divalent cations such as Cu^2 +. Nickel in garnet II is positively correlated with increasing andradite content, total Fe, and decreasing almandine content. This is because Ni^2 + substitutes for Fe^3 + in the Y (octahedral) position. There are unusual discrete grossular-almandine rich domains within andraditic garnet III, indicating the low diffusivity of Ca compared to Fe at high temperatures.     

Diffusion of dissolved SiO2 in H2O at 1 GPa, with implications for mass transport in the crust and upper mantle

Cation diffusion rates at 690 ± 30 °C have been calculated by inverse modelling of observed manganese (Mn) zonation profiles in 40 garnets from two kyanite-bearing metapelite samples from the High Himalayan Crystalline Series, Zanskar, northwest India. Knowledge of the initial growth profile of Mn in garnet is a pre-requisite for this technique. Following previous workers we model Mn partitioning into growing garnet in terms of a Rayleigh fractionation process, and demonstrate that the Mn_{garnet:whole rock} partition coefficient is 60–100. Three-dimensional zonation profiles were obtained by successively grinding and polishing ∼1 cm slabs of each sample at 0.1–0.2 mm intervals and analysing the garnets at each stage, thus ensuring that core sections were measured. The diffusion model assumes that garnet has a spherical geometry and behaves as a closed system, and simulates diffusive modification of the hypothetical Mn Rayleigh growth profile for each garnet. The derived measure of the time-integrated diffusion history for each garnet is then combined with radiometric and field-relation constraints for the duration of the Himalayan metamorphic event to calculate cation diffusion rates. The average cation interdiffusion rate calculated for garnets in the two samples examined is (6 ± 3.2) × 10⁻²³ m²s⁻¹. This interdiffusion rate pertains to a temperature of 690 ± 30 °C, which is 0.97 × T _PEAK, the peak temperature conditions experienced by the samples estimated using standard thermobarometric techniques. Garnet compositions are P_y2–17Alm_65–77Gro_6–16Sp_1–17. These new diffusion data are consistent with, and more precise than, existing high-temperature (>1000 °C) experimentally determined diffusion data, although some uncertainties remain difficult to constrain. Qualitative comparison between diffusively modified Mn growth profiles in garnets from the Scottish Dalradian and the Himalayan garnets suggests that the duration of metamorphism affecting the Dalradian garnets was 10–20 times longer than that endured by the Himalayan garnets. Received: 5 June 1996 / Accepted: 29 January 1997     

Compositional evolution of grossular garnet from leucotonalitic pegmatite at Ruda nad Moravou, Czech Republic; a complex EMPA, LA-ICP-MS, IR and CL study

Five distinct paragenetic, morphological and compositional types of grossular garnet (G1, G2, G3, G4, G5) were distinguished within the individual (sub)units of the zoned leucotonalitic pegmatite cutting serpentinized lherzolite with rodingite dikes at ??ár near Ruda nad Moravou, Staré Město Unit, Northern Moravia. Detailed study using Electron Microprobe Analysis, Laser Ablation Inductively Coupled Plasma Mass Spectrometry, Cathodoluminiscence and Infrared Spectroscopy revealed distinct compositional trends in major, minor and trace elements. The contents of Fe³⁺, Mn, Mg and Ti increase from early garnet (G1) in the outermost grossular subunit through the interstitial garnet (G2) in the leucocratic subunit to graphic intergrowths of quartz+garnet (G3) in the coarse-grained unit. Then these constituents decrease in inclusions of garnet (G4) from the blocky unit and large crystals of garnet (G5) from the quartz core. Some trace elements (V, Ni, Y) exhibit the same trends, only Be evidently increases in garnet from border zone to the centre. Fluorine has negative correlation with Fe³⁺ as well as some trace elements (Ta, Pb). Concentrations of H₂O in garnets, up to 0.22 wt.% H₂O, are comparable with spessartine-almandine garnets from the Rutherford No. 2 pegmatite, Virginia, and grossular garnets from high-temperature calc-silicate rocks (skarns). Water contents correlate positively with Fe³⁺, but inversely with F. The use of water contents in garnet to elucidate the fluctuations of activity of H₂O during the pegmatite formation is only limited; the incorporation of hydrous defects seems to be controlled instead by crystal-structural constraints. However, the sum of all volatile components (H₂O + F) increases about twice from the outermost subunit to the centre of the pegmatite body.     

Pressure–volume–temperature equation of state of andradite and grossular, by high-pressure and -temperature powder diffraction

 The thermoelastic parameters of natural andradite and grossular have been investigated by high-pressure and -temperature synchrotron X-ray powder diffraction, at ESRF, on the ID30 beamline. The P–V–T data have been fitted by Birch-Murnaghan-like EOSs, using both the approximated and the general form. We have obtained for andradite K ₀=158.0(±1.5) GPa, (dK/dT )₀=−0.020(3) GPa K⁻¹ and α₀=31.6(2) 10⁻⁶ K⁻¹, and for grossular K ₀=168.2(±1.7) GPa, (dK/dT)₀=−0.016(3) GPa K⁻¹ and α₀=27.8(2) 10⁻⁶ K⁻¹. Comparisons between the present issues and thermoelastic properties of garnets earlier determined are carried out. Received: 7 July 2000 / Accepted: 20 October 2000     

Hydrogen in some natural garnets studied by nuclear reaction analysis and vibrational spectroscopy

A suite of 11 gem-quality, optically completely clear garnet crystals with a broad variety of compositions in the space of the end members pyrope–almandine–spessartine–grossular–andradite–goldmanite were analyzed for trace amounts of “water” by nuclear reaction analysis, NRA, based on the reaction ¹H(¹⁵N, αγ)¹²C, and by single-crystal absorption spectroscopy in the ν_OH vibrational range using microscope-FTIR-spectroscopic methods. The aim was to establish a calibration of the highly sensitive IR method with high areal resolution for “water” determination in garnets, by studying garnets of a wide compositional range, and to check for compositional dependencies of the integral molar absorptivities of the “water” component, ?_int[1mol_H2O^?1cm^?2], in the nominally “water”-free garnets. The results of NRA show a broad variation of water contents in the range (14 ± 3) to (950 ± 80) wt ppm_H2O, the values being low and very high for the garnet solid solutions (PyrAlm)_SS and close-to-end-member Gross_SS, respectively. There were no indications of inhomogeneities in the OH distribution, except possibly for one of the garnets (grossular, variety hessonite, from Tanzania). The quantitative evaluation of the complex ν_OH spectra, which showed similar shape only for members of the (PyrAlm)_SS, yielded integral absorption coefficients, α_int (cm^?2), which allowed the calculation of integral molar absorptivities, ?_int, using the “water” values of NRA. The ?_int values obtained varied in a wide range but with no obvious correlation with the composition of the garnet except for the extremely high values, in the 10⁴ range, of the two specimen with compositions close to end-member grossular. In all other garnets, ?_int was in the 10³ range with an average of ?_int=3630±1580[1mol_H2O^?1cm^?2]. Therefore, this value is proposed for the use in routine “water” determinations of compositionally different garnets by the micro-IR method, except for garnets near to end-member grossular.     

Enstatite–sapphirine crack-related assemblages in ultrahigh-pressure pyrope megablasts, Dora-Maira massif, western Alps

Throughout the ultrahigh-pressure (UHP) metamorphic unit of the Dora-Maira massif, western Alps, pyrope megablasts contain the typical assemblage clinochlore–kyanite–talc–rutile ± phlogopite ± ellenbergerite as prograde inclusions. In the upper part of the UHP unit in Val Gilba, some megablasts (XMg=0.89–0.98) contain in addition polymineralic inclusions consisting of various combinations of enstatite, gedrite, sapphirine, clinochlore, talc, magnesiostaurolite and rare corundum or spinel. We present evidence that these assemblages developed from cracks running across the megablasts, and are therefore of late origin, post-dating the highest-pressure stage. Enstatite (XMg=0.94–0.99) contains 0.7 to, typically, 3 wt% Al₂O₃, but up to 8.4 wt% in the presence of sapphirine. Sapphirine (XMg=0.96–0.998, Be-free) shows the largest compositional variations, with Si contents ranging from 1.7 to at least 2.1 atoms pfu, thereby clearly exceeding the 2:2:1 stoichiometry. The late-stage talc contains up to 4 wt% Al₂O₃, 0.35 wt% Na₂O and 0.6 wt% F; gedrite 1.1–2.9 wt% Na₂O and up to 0.36 wt% F. The successive development within pyrope of alternative hydrous assemblages involving first enstatite plus an Al-rich phase (kyanite, sapphirine, magnesiostaurolite) ± clinochlore, then a gedrite compositionally close to pyrope, then talc plus an Al-rich phase (sapphirine, corundum), is a clear record of decompression. However, the temperature conditions implied under the assumption of high H₂O activity are 100 to 150 °C higher than, and so inconsistent with existing constraints on the decompression path. These constraints are in particular the stability of talc + phengite in the matrix assemblage during decompression, and the absence of regional evidence for a granulite-facies event. This inconsistency can only be alleviated if H₂O activity inside the garnet megablast was (or became) considerably reduced with respect to that in the matrix. Fluid influx into an opening fracture in garnet, sealing of the fracture by breakdown products of pyrope and continued evolution under closed-system conditions may have led to increasing solute concentration and such low H₂O activity within the garnet megablast, driving the microsystem toward fluid-absent conditions. Micrometre-size inclusions of Ca-sulfate and crandallite-type compounds in minerals of these reactive areas may be evidence for such residual brines and suggest that these were phosphate- and sulfate- rather than halide-dominated. This finding is additional evidence for the very local control that fluid composition and H₂O activity may have on the occurrence of granulite-facies assemblages, regardless of temperature. It highlights the role of deformation (here fracturing) in triggering reactions in otherwise unreactive systems. It also shows how carefully inclusion- to-host relationships have to be considered, post-growth reaction within the host being more common than hitherto reported. Received: 4 February 1999 / Accepted: 24 August 2000     

Garnet-cordierite-biotite equilibria in the Steinach aureole,Bavaria

Three garnet-biotite pairs and eleven garnet-cordierite-biotite triplets from the Steinach aureole (Oberpfalz, North-East Bavaria) were analyzed using an electron probe microanalyzer.The regional metamorphic muscovite-biotite schists contain garnets strongly zoned with Mn-Ca-rich centers and Fe-rich edges, the average composition being almandine 67 — spessartine 4 — pyrope 4 — grossular (+andradite) 25.The first contact garnet that is formed in mica schists of the outermost part of the aureole is small, virtually unzoned, and has an average composition of almandine 52 — spessartine 37 — pyrope 8 — grossular (+andradite) 3. With increasing metamorphic grade, there is a consistent trend to form garnets richer in Fe ending up with a composition almandine 84.5 — spessartine 5.5 — pyrope 7.5 — grossular (+andradite) 2.5. This trend is accompanied by a general increase in grain size and modal amount of garnet. Associated cordierites and biotites also become richer in Fe with increasing grade. While the garnets in the highest grade sillimanite hornfelses are poorly zoned, the transitional andalusite-sillimanite hornfelses contain garnets with distinct but variable zonation profiles.These facts can possibly be explained by the time-temperature relationships in the thermal aureole. In a phase diagram such as the Al-Fe-Mg-Mn tetrahedron, the limiting mineral compositions of a four-phase volume or a three-phase triangle are fixed by T and P (the latter remaining effectively constant within a thermal aureole). Thus, in garnet-cordierite-biotite assemblages, garnet zonation should be controlled by temperature variation rather than by a non-equilibrium depletion process. Taking into account the experimental data of Dahl (1968), a zoned garnet from a transitional andalusite-sillimanite hornfels would reflect a temperature increase of about 40° C during its growth. A hypothetical P-X diagram is proposed to show semi-quantitatively the compositional variation of garnet-cordierite pairs with varying pressures (T constant).     

Ca–Mn exchange between grossular and MnCl2 solutions at 2 kbar and 600°°C: reaction mechanism and evidence for non-ideal mixing in spessartine-grossular garnets

 The hydrothermal reaction between grossular and 1 molar manganese chloride solution was studied at 2 kbar and 600 °C at various bulk Ca/(Ca+Mn) compositions: Ca₃Al₂Si₃O₁₂+3Mn²⁺(aq) ⇔ Mn₃Al₂Si₃O₁₂+3Ca²⁺(aq) The reaction products are garnets of the spessartine-grossular solid-solution series which discontinuously armour the dissolving grossular grains. The first garnet to crystallize is spessartine rich (X ^gt _Mn≥0.95), reflecting the high Mn content of the solution, but as the reaction proceeds more calcium-rich garnets progressively overgrow the initial products. The armouring product layer is detached from the dissolving grossular, which allows the progressive overgrowth to occur on both its external and internal surfaces and results in the development of a two directional Ca/(Ca+Mn) zoning pattern in the product grains. The compositional changes in the run products are consistent with attainment of heterogeneous equilibrium between the external rims of the spessartine-grossular garnets and the bulk solutions in runs of duration ≥24 hours. Plots of ln K_D versus X ^gt _Ca maxima show linear variations that are not consistent with the ideal mixing that has been proposed for spessartine-grossular garnets at temperatures of 900 to 1200 °C. The data rather fit a regular solution model with the parameters ΔG° (600 °C, 2 kbar)=−8.0±0.8 kJ/mol and w ^gt _CaMn=2.6±2.0 kJ/mol. Existing solubility measurements and thermodynamic data from other Ca and Mn silicates support the calculated data. Grossular activities calculated using the w ^gt _CaMn parameter indicate that even in manganese-rich metapelites pressure estimates calculated using the garnet-plagioclase-Al₂SiO₅-quartz barometer will not be increased by more than 0.2 kbar. Received: 18 January 1995/Accepted: 4 June 1996     

Diamond precipitation and mantle metasomatism – evidence from the trace element chemistry of silicate inclusions in diamonds from Akwatia, Ghana

Trace element concentrations in the four principal peridotitic silicate phases (garnet, olivine, orthopyroxene, clinopyroxene) included in diamonds from Akwatia (Birim Field, Ghana) were determined using SIMS. Incompatible trace elements are hosted in garnet and clinopyroxene except for Sr which is equally distributed between orthopyroxene and garnet in harzburgitic paragenesis diamonds. The separation between lherzolitic and harzburgitic inclusion parageneses, which is commonly made using compositional fields for garnets in a CaO versus Cr₂O₃ diagram, is also apparent from the Ti and Sr contents in both olivine and garnet. Titanium is much higher in the lherzolitic and Sr in the harzburgitic inclusions. Chondrite normalised REE patterns of lherzolitic garnets are enriched (10–20 times chondrite) in HREE (La_N/Yb_N = 0.02–0.06) while harzburgitic garnets have sinusoidal REE_N patterns, with the highest concentrations for Ce and Nd (2–8 times chondritic) and a minimum at Ho (0.2–0.7 times chondritic). Clinopyroxene inclusions show negative slopes with La enrichment 10–100 times chondritic and low Lu (0.1–1 times chondritic). Both a lherzolitic and a harzburgitic garnet with very high knorringite contents (14 and 21 wt% Cr₂O₃ respectively) could be readily distinguished from other garnets of their parageneses by much higher levels of LREE enrichment. The REE patterns for calculated melt compositions from lherzolitic garnet inclusions fall into the compositional field for kimberlitic-lamproitic and carbonatitic melts. Much more strongly fractionated REE patterns calculated from harzburgitic garnets, and low concentrations in Ti, Y, Zr, and Hf, differ significantly from known alkaline and carbonatitic melts and require a different agent. Equilibration temperatures for harzburgitic inclusions are generally below the C-H-O solidus of their paragenesis, those of lherzolitic inclusions are above. Crystallisation of harzburgitic diamonds from CO₂-bearing melts or fluids may thus be excluded. Diamond inclusion chemistry and mineralogy also is inconsistent with known examples of metasomatism by H₂O-rich melts. We therefore favour diamond precipitation by oxidation of CH₄-rich fluids with highly fractionated trace element patterns which are possibly due to “chromatographic” fractionation processes. Received: 27 January 1996 / Accepted: 5 May 1997     

西藏知不拉铜多金属矿床地质、石榴子石分带特征及其地质意义

西藏知不拉铜多金属床是冈底斯成矿带东段典型的矽卡岩矿床,石榴子石是矿区最主要的矽卡岩矿物,其颗粒间的空隙是金属矿物的主要赋存部位。本文通过详细的钻孔编录,结合岩矿鉴定及电子探针分析,划分出两种不同类型的石榴子环带,并在垂向上具有明显的分带:产于顶板凝灰岩中的石榴子石以钙铁榴石为主,环带中心颜色深,向外逐渐变浅,由纯钙铁榴石过渡到钙铝榴石;而位于底板大理岩附近石榴子石多以钙铝榴石为主,从环带核部向外颜色变深,化学组成由钙铝榴石向钙铁榴石变化,其它化学成分变化不大。反映该区上下两套不同性质围岩在石榴子石形成过程中所起的作用不同,其中上部凝灰岩主要提供了Fe,底部大理岩则是Ca的来源,热液流体贡献Si、Al及部分Fe,并随着环境和物质成分改变导致环带外侧具有不同于核部的变化趋势。这很好地解释了石榴子石矽卡岩在空间上具有上部为钙铁榴石、向下逐渐过渡到钙铝榴石的空间分带。石榴子石特征及分带显示了其属热液接触交代成因,这为矿床类型的确定提供了依据,也为在该区域内寻找类似矿床指明了方向。     

Phase relations and formation of sodium-rich majoritic garnet in the system Mg3Al2Si3O12–Na2MgSi5O12 at 7.0 and 8.5 GPa

The pseudo-binary system Mg₃Al₂Si₃O₁₂–Na₂MgSi₅O₁₂ modelling the sodium-bearing garnet solid solutions has been studied at 7 and 8.5 GPa and 1,500–1,950°C. The Na-bearing garnet is a liquidus phase of the system up to 60 mol% Na₂MgSi₅O₁₂ (NaGrt). At higher content of NaGrt in the system, enstatite (up to ∼80 mol%) and then coesite are observed as liquidus phases. Our experiments provided evidence for a stable sodium incorporation in garnet (0.3–0.6 wt% Na₂O) and its control by temperature and pressure. The highest sodium contents were obtained in experiments at P = 8.5 GPa. Near the liquidus (T = 1,840°C), the equilibrium concentration of Na₂O in garnet is 0.7–0.8 wt% (∼6 mol% Na₂MgSi₅O₁₂). With the temperature decrease, Na concentration in Grt increases, and the maximal Na₂MgSi₅O₁₂ content of ∼12 mol% (1.52 wt% Na₂O) is gained at the solidus of the system (T = 1,760°С). The data obtained show that most of natural diamonds, with inclusions of Na-bearing garnets usually containing <0.4 wt% Na₂O, could be formed from sodium-rich melts at pressures lower than 7 GPa. Majoritic garnets with higher sodium concentrations (>1 wt% Na₂O) may crystallize at a pressure range of 7.0–8.5 GPa. However the upper pressure limit for the formation of naturally occurring Na-bearing garnets is restricted by the eclogite/garnetite bulk composition.     

Igneous garnet and amphibole fractionation in the roots of island arcs: experimental constraints on andesitic liquids

To evaluate the role of garnet and amphibole fractionation at conditions relevant for the crystallization of magmas in the roots of island arcs, a series of experiments were performed on a synthetic andesite at conditions ranging from 0.8 to 1.2 GPa, 800–1,000°C and variable H₂O contents. At water undersaturated conditions and fO₂ established around QFM, garnet has a wide stability field. At 1.2 GPa garnet + amphibole are the high-temperature liquidus phases followed by plagioclase at lower temperature. Clinopyroxene reaches its maximal stability at H₂O-contents ≤9 wt% at 950°C and is replaced by amphibole at lower temperature. The slopes of the plagioclase-in boundaries are moderately negative in space. At 0.8 GPa, garnet is stable at magmatic H₂O contents exceeding 8 wt% and is replaced by spinel at decreasing dissolved H₂O. The liquids formed by crystallization evolve through continuous silica increase from andesite to dacite and rhyolite for the 1.2 GPa series, but show substantial enrichment in FeO/MgO for the 0.8 GPa series related to the contrasting roles of garnet and amphibole in fractionating Fe–Mg in derivative liquids. Our experiments indicate that the stability of igneous garnet increases with increasing dissolved H₂O in silicate liquids and is thus likely to affect trace element compositions of H₂O-rich derivative arc volcanic rocks by fractionation. Garnet-controlled trace element ratios cannot be used as a proxy for ‘slab melting’, or dehydration melting in the deep arc. Garnet fractionation, either in the deep crust via formation of garnet gabbros, or in the upper mantle via formation of garnet pyroxenites remains an important alternative, despite the rare occurrence of magmatic garnet in volcanic rocks.     

滇西红牛矽卡岩型铜矿床石榴子石特征

红牛矽卡岩型铜矿床是义敦岛弧南段格咱火山-岩浆弧新探明的铜矿床之一,目前探明铜金属资源量已达大型规模。与由侵入岩和大理岩直接接触形成的典型矽卡岩矿床不同,红牛铜矿床是隐伏岩体远程矽卡岩化的产物,其矽卡岩矿体与地层产状基本一致,通常相间排列,且距离岩体较远,大理岩中可见粗粒石榴子石和硅灰石,矽卡岩中常见大理岩捕掳体。根据矽卡岩矿物组合可将该矿床矽卡岩类型划分为石榴子石矽卡岩、石榴子石透辉石(或透辉石石榴子石)矽卡岩、透辉石矽卡岩、符山石-石榴子石矽卡岩、硅灰石-石榴子石矽卡岩、绿帘石-石榴子石矽卡岩、阳起石-绿帘石矽卡岩、硅灰石矽卡岩和绿帘石矽卡岩,其中以石榴子石矽卡岩、透辉石矽卡岩和硅灰石矽卡岩为主。石榴子石是最重要的矽卡岩矿物,分布广泛、颜色变化大,且石榴子石矽卡岩中黄铜矿、黄铁矿、磁黄铁矿化最好。本文通过对0ZK10、3ZK11和7ZK16钻孔岩芯的地质编录,查明石榴子石在红牛铜矿床的空间分布和矿化特征,采集该矿区新鲜的石榴子石矽卡岩、矽卡岩化大理岩和角岩磨制成光薄片,开展详细的显微镜下鉴定工作,观察石榴子石的颜色、粒度、结构、光性等岩相学特征,并通过电子探针分析其化学成分。红牛铜矿床石榴子石集中产出于矽卡岩中,少量产出于矽卡岩化大理岩和角岩中,具有明显的两期。早期石榴子石分布广泛,多呈褐色-红褐色,非均质性,异常干涉色,粒径一般在0.2~4mm之间,半自形-自形中细粒结构,韵律环带发育。SiO2含量变化范围为35.18%~37.69%、CaO为33.34%~36.35%、Al2O3为3.64%~13.69%、FeO为11.90%~24.18%、MgO为0.00%~0.08%,FeO和Al2O3含量变化呈负相关,SiO2和CaO含量变化整体呈正相关。石榴子石端员组分总体以钙铁榴石(36.88%~82.36%)为主,其次为钙铝榴石(16.59%~60.75%),还有少量的镁铝榴石、铁铝榴石和锰铝榴石,属于钙铁榴石-钙铝榴石系列(And37-82Gro17-61Spe+Pyr+Alm0.33-3.71)。晚期石榴子石呈浅褐色-浅红色,多发育于矽卡岩化角岩和大理岩中,少量发育于矽卡岩中,半自形-他形粒状结构,均质性,全消光,常具有溶蚀结构。SiO2含量变化范围为35.06%~36.27%、CaO为33.07%~33.77%、Al2O3为0.04%~1.05%、FeO为27.38%~28.18%、MgO为0.00%~0.04%,属于钙铁榴石(94.42%~98.46%)。早期石榴子石韵律环带发育,其主量元素含量变化显示出一定的规律性,由核部向边缘,SiO2和CaO基本保持不变,FeO含量增加,Al2O3含量减少,钙铁榴石含量增加,钙铝榴石含量减少,反映在石榴子石形成早期,成岩环境为低氧逸度、酸性还原环境;形成过程中氧逸度增加,成矿溶液由酸性向弱碱性演化。黄铜矿、磁黄铁矿、辉钼矿等金属硫化物多呈他形充填于石榴子石颗粒之间,或在石榴子石的裂隙中形成细脉,或沿石榴子石生长环带面交代,表明石榴子石形成于矽卡岩早期、早于铜矿化,并为金属硫化物的沉淀富集提供了空间。