Distribution of Fe and Mg between coexisting garnet and hornblende in synthetic and natural systems: an empirical calibration of the garnet–hornblende Fe–Mg geothermometer

Multiple regression analysis of a compilation of the Fe²⁺–Mg distribution between garnet and hornblende from experimental runs on basaltic to intermediate compositions (n=22) and coexisting garnet–clinopyroxene–hornblende from natural (intermediate to basaltic) rocks (n=43) has been performed to define ln K_{D(Fe²⁺/Mg)}^Grt–Hbl as a function of temperature and garnet composition. The regression of data covering a large span in pressure (5–16 kbar), temperature (515–1025°C) and composition yields the ln K_{D(Fe²⁺/Mg)}^Grt–Hbl–P–T compositional relationship (r²=0.93):

where

Application of this expression to natural garnet–hornblende pairs in intermediate to basaltic and semipelitic rock types from various settings gives temperatures that are consistent with other methods.     

Micro-XANES determination of ferric iron and its application in thermobarometry

Micro-X-ray absorption near-edge structure (XANES) analysis was employed to determine the content of ferric iron in minerals formed in ultrahigh-pressure (UHP) eclogites. It is observed that omphacite and phengite contain significant amounts of Fe³⁺/Fe_tot (0.2–0.6), whereas only very low contents are present in garnet (Fe³⁺/Fe_tot=0.0–0.03), the latter being consistent with results from stoichiometric charge-balance calculations. Furthermore, considerable variations in the Fe³⁺/Fe_tot ratios of omphacite and phengite are observed depending on the textural sites and local bulk chemistry (eclogite and calc-silicate matrix) within one thin section. The oxidation state of isofacial minerals is thus likely to depend on the local fluid composition, which, in the studied case, is controlled by calcareous and meta-basic mineral compositions. These first in-situ measurements of ferric iron in an eclogite sample from the Dabie Shan, E China, are used to recalculate geothermobarometric data. Calculations demonstrate that the temperature during UHP metamorphism was as high as 780 °C, about 80–100 °C higher than previously estimated. Temperatures based on charge balance calculations often give erroneous results. Pressure estimates are in good agreement with former results and confirm metamorphism in the stability field of diamond (43.7 kbar at 750 °C). These P–T data result in a geothermal gradient of ca. 6 °C/km during UHP metamorphism in the Dabie Shan. However, accounting for ferric iron contents in geothermobarometry creates new difficulties inasmuch as calibrations of geothermometers may not be correctable for Fe³⁺ and the actual effect on Mg–Fe²⁺ partitioning is unknown. The present study further shows that micro-XANES is a promising technique for the in situ determination of ferric iron contents without destroying the textural context of the sample: a clear advantage compared to bulk methods.     

Geothermobarometry in albite-garnet orthogneisses: A case study from the Gran Paradiso nappe (Western Alps)

The aim of this paper is to estimate syntectonic P-T conditions within albite- and garnet-bearing orthogneisses. These rocks are generally characterized by the assemblage quartz + albite + biotite + phengite + CaFe-garnet + epidote + titanite. Garnet contains up to 55 mole per cent of grossular. K-feldspar is a relict magmatic phase.

P-T conditions are estimated using several independent methods. First, it is shown that exchange reactions based on the Fe---Mg partitioning between garnet and biotite or garnet and phengite cannot be used to estimate temperatures in these rocks, due to the high grossular content of garnet. Second, maximum and minimum pressures are constrained, respectively, by the occurrence of albite instead of jadeite + quartz and by the assemblage phengite + biotite + quartz. Third, phase equilibria in albite- and garnet-bearing metagranites are modelled in the system K₂O---CaO---FeO---Al₂O₃---SiO₂---H₂O. Equilibrium curves are calculated for the observed phase compositions. Uncertainties in P-T estimates mainly result from the choice of appropriate non-ideal solution models for the garnet.

An application is developed for granites from the Gran Paradiso nappe (Western Alps). These granites show an heterogeneous deformation of Alpine age expressed by mylonitic shear zones cutting across weakly deformed domains. Estimated P-T conditions for the synkinematic assemblages are 10–16 kbar at 550±50°C.     

Comprehensive chemical analyses of natural cordierites: implications for exchange mechanisms

Cordierite samples from pegmatites and metamorphic rocks have been analysed for major [electron microprobe analysis (EMPA)] and trace elements [inductively coupled plasma mass spectrometry (ICP-MS), secondary ion mass spectrometry analyses (SIMS)] as well as for H₂O and CO₂ (coulometric titration), and the results evaluated in conjunction with published data in order to determine which exchange mechanisms are significant. Apart from the homovalent substitutions FeMg₋₁ and MnMg₋₁ on the octahedral site, some minor KNa₋₁ on the Ch0 channel site, and Fe³⁺Al₋₁ on the T₁1 tetrahedral site, the three most important substitution mechanisms are those for the incorporation of Li on the octahedral sites (NaLi□₋₁Mg₋₁), and of Be and other divalent cations on the tetrahedral T₁1 site (NaBe□₋₁Al₋₁ and Na(Mg,Fe²⁺)□₋₁Al₋₁). The dominant role of the last vector is clearly demonstrated. We propose a new generalized formula for cordierite: ^Ch(Na,K)_0–1 ^VI(Mg,Fe²⁺,Mn,Li)₂ ^IVSi₅ ^IVAl₃ ^IV(Al, Be, Mg, Fe²⁺, Fe³⁺)O₁₈ *x^Ch(H₂O, CO₂…). Our results show that the population of (Mg, Fe²⁺) on the T₁1-site is limited to about 0.08 a.p.f.u. Other exchange mechanisms that were encountered in experiments operate only under P–T conditions or in bulk compositions that are rarely realized in nature. Routine analyses by electron microprobe in which Li and Be are not determined can be plotted as (Mg+Fe+Mn) versus (Si+Al) to assess whether significant amounts of Li and Be could be present. These amounts can be calculated as Li (a.p.f.u.)=Al+Na–4 and Be (a.p.f.u.)=10–2Al–M²⁺–Na.     

Recalibration of mutually consistent garnet–biotite and garnet–cordierite geothermometers

Garnet–biotite and garnet–cordierite geothermometers have been consistently calibrated, using the results of Fe²⁺–Mg cation exchange experiments and utilizing recently evaluated nonideal mixing properties of garnet. Nonideal mixing parameters of biotite (including Fe, Mg, Al^VI, and Ti) and of cordierite (involving Fe and Mg) are evaluated in terms of iterative multiple least-square regressions of the experimental results. Assuming the presence of ferric Fe in biotite in relation to the coexisting Fe-oxide phases (Case A), and assuming the absence of ferric Fe in biotite (Case B), two formulae of garnet–biotite thermometer have been derived. The garnet–cordierite geothermometer was constructed using Margules parameters of garnet adopted in the garnet–biotite geothermometers. The newly calibrated garnet–biotite and garnet–cordierite thermometers clearly show improved conformity in the calculated temperatures. The thermometers give temperatures that are consistent with each other using natural garnet–biotite–cordierite assemblages within ±50 °C. The effects of ferric Fe in biotite on garnet–biotite thermometry have been evaluated comparing the two calibrations of the thermometer. The effects are significant; it is clarified that taking ferric Fe content in biotite into account leads to less dispersion of thermometric results.     

The effect of Fe-oxidizing bacteria on Fe-silicate mineral dissolution

Acidithiobacillus ferrooxidans are commonly present in acid mine drainage (AMD). A. ferrooxidans derive metabolic energy from oxidation of Fe²⁺ present in natural acid solutions and also may be able to utilize Fe²⁺ released by dissolution of silicate minerals during acid neutralization reactions. Natural and synthetic fayalites were reacted in solutions with initial pH values of 2.0, 3.0 and 4.0 in the presence of A. ferrooxidans and in abiotic solutions in order to determine whether these chemolithotrophic bacteria can be sustained by acid-promoted fayalite dissolution and to measure the impact of their metabolism on acid neutralization rates. The production of almost the maximum Fe³⁺ from the available Fe in solution in microbial experiments (compared to no production of Fe³⁺ in abiotic controls) confirms A. ferrooxidans metabolism. Furthermore, cell division was detected and the total cell numbers increased over the duration of experiments. Thus, over the pH range 2–4, fayalite dissolution can sustain growth of A. ferrooxidans. However, ferric iron released by A. ferrooxidans metabolism dramatically inhibited dissolution rates by 50–98% compared to the abiotic controls.

Two sets of abiotic experiments were conducted to determine why microbial iron oxidation suppressed fayalite dissolution. Firstly, fayalite was dissolved at pH 2 in fully oxygenated and anoxic solutions. No significant difference was observed between rates in these experiments, as expected, due to extremely slow inorganic ferrous iron oxidation rates at pH 2. Experiments were also carried out to determine the effects of the concentrations of Fe²⁺, Mg²⁺ and Fe³⁺ on fayalite dissolution. Neither Fe²⁺ nor Mg²⁺ had an effect on the dissolution reaction. However, Fe³⁺, in the solution, inhibited both silica and iron release in the control, very similar to the biologically mediated fayalite dissolution reaction. Because ferric iron produced in microbial experiments was partitioned into nanocrystalline goethite (with very low Si) that was loosely associated with fayalite surfaces or coated the A. ferrooxidans cells, the decreased rates of accumulation of Fe and Si in solution cannot be attributed to diffusion inhibition by goethite or to precipitation of Fe–Si-rich minerals. The magnitude of the effect of Fe³⁺ addition (or enzymatic iron oxidation) on fayalite dissolution rates, especially at low extents of fayalite reaction, is most consistent with suppression of dissolution by interaction between Fe³⁺ and surface sites. These results suggest that microorganisms can significantly reduce the rate at which silicate hydrolysis reactions can neutralize acidic solutions in the environment.     

Experimental synthesis and phase relations of phengitic muscovite from 6.5 to 11 GPa in a calcareous metapelite from the Dabie Mountains, China

The stability and phase relations of phengitic muscovite in a metapelitic bulk composition containing a mixed H₂O+CO₂ fluid were investigated at 6.5–11 GPa, 750–1050°C in synthesis experiments performed in a multianvil apparatus. Starting material consisted of a natural calcareous metapelite from the coesite zone of the Dabie Mountains, China, ultrahigh-pressure metamorphic complex that had experienced peak metamorphic pressures greater than 3 GPa. The sample contains a total of 2.1 wt.% H₂O and 6.3 wt.% CO₂ bound in hydrous and carbonate minerals. No additional fluid was added to the starting material. Phengite is stable in this bulk composition from 6.5 to 9 GPa at 900°C and coexists with an eclogitic phase assemblage consisting of garnet, omphacite, coesite, rutile, and fluid. Phengite dehydrates to produce K-hollandite between 8 and 11 GPa, 750–900°C. Phengite melting/dissolution occurs between 900°C and 975°C at 6.5–8 GPa and is associated with the appearance of kyanite in the phase assemblage. The formation of K-hollandite is accompanied by the appearance of magnesite and topaz-OH in the phase assemblage as well as by significant increases in the grossular content of garnet (average X_grs=0.52, X_py=0.19) and the jadeite content of omphacite (X_jd=0.92). Mass balance indicates that the volatile content of the fluid phase changes markedly at the phengite/K-hollandite phase boundary. At P≤8 GPa, fluid coexisting with phengite appears to be relatively CO₂-rich (XCO₂/XH₂O=2.2), whereas fluid coexisting with K-hollandite and magnesite at 11 GPa is rich in H₂O (XCO₂/XH₂O=0.2). Analysis of quench material and mass balance calculations indicate that fluids at all pressures and temperatures examined contain an abundance of dissolved solutes (approximately 40 mol% at 8 GPa, 60 mol% at 11 GPa) that act to dilute the volatile content of the fluid phase. The average phengite content of muscovite is positively correlated with pressure and ranges from 3.62 Si per formula unit (pfu) at 6.5 GPa to 3.80 Si pfu at 9 GPa. The extent of the phengite substitution in muscovite in this bulk composition appears to be limited to a maximum of 3.80–3.85 Si pfu at P=9 GPa. These experiments show that phengite should be stable in metasediments in mature subduction zones to depths of up to 300 km even under conditions in which aH₂O1. Other high-pressure hydrous phases such as lawsonite, MgMgAl-pumpellyite, and topaz-OH that may form in subducted sediments do not occur within the phengite stability field in this system, and may require more H₂O-rich fluid compositions in order to form. The wide range of conditions under which phengite occurs and its participation in mixed volatile reactions that may buffer the composition of the fluid phase suggest that phengite may significantly influence the nature of metasomatic fluids released from deeply subducted sediments at depths of up to 300 km at convergent plate boundaries.     

A garnet–hornblende geothermometer: calibration, testing, and application to the Pelona Schist, Southern California

Abstract A garnet–hornblende Fe–Mg exchange geothermometer has been calibrated against the garnet–clinopyroxene geothermometer of Ellis & Green (1979) using data on coexisting garnet + hornblende + clinopyroxene in amphibolite and granulite facies metamorphic assemblages. Data for the Fe–Mg exchange reaction between garnet and hornblende have been fitted to the equation. In K_D=Δ (X_Ca,g) where K_D is the Fe–Mg distribution coefficient, using a robust regression approach, giving a thermometer of the form: with very satisfactory agreement between garnet–hornblende and garnet–clinopyroxene temperatures. The thermometer is applicable below about 850°C to rocks with Mn-poor garnet and common hornblende of widely varying chemistry metamorphosed at low a_O2. Application of the garnet–hornblende geothermometer to Dalradian garnet amphibolites gives temperatures in good agreement with those predicted by pelite petrogenetic grids, ranging from 520°C for the lower garnet zone to 565–610°C for the staurolite to kyanite zones. These results suggest that systematic errors introduced by closure temperature problems in the application of the garnet–clinopyroxene geothermometer to the ‘calibration’data set are not serious. Application to ‘eclogitic’garnet amphibolites suggests that garnet and hornblende seldom attain Fe–Mg exchange equilibrium in these rocks. Quartzo-feldspathic and mafic schists of the Pelona Schist on Sierra Pelona, Southern California, were metamorphosed under high pressure greenschist, epidote–amphibolite and (oligoclase) amphibolite facies beneath the Vincent Thrust at pressures deduced to be 10±1 kbar using the phengite geobarometer, and 8–9kbar using the jadeite content of clinopyroxene in equilibrium with oligoclase and quartz. Application of the garnet–hornblende thermometer gives temperatures ranging from about 480°C at the garnet isograd through 570°C at the oligoclase isograd to a maximum of 620–650°C near the thrust. Inverted thermal gradients beneath the Vincent Thrust were in the range 170 to 250°C per km close to the thrust.     

Metamorphic evolution, mineral chemistry and thermobarometry of schists and orthogneisses hosting ultra-high pressure eclogites in the Dabieshan of central China

As is typical of ultra-high pressure (UHP) terrains, the regional extent of the UHP terrain in the Dabieshan of central China is highly speculative, since the volume of eclogites and paragneisses preserving unequivocal evidence of coesite and/or diamond stability is very small. By contrast, the common garnet (X_Mn=0.18–0.45)–phengite (Si=3.2–3.35)–zoned epidote (Ps_38–97)–biotite–titanite–two feldspars–quartz assemblages in the more extensive orthogneisses have been previously thought to have formed under low P–T conditions of ca. 400±50°C at 4 kbar. However, certain orthogneiss samples preserve garnets with X_Ca up to 0.50, rutile inclusions within titanite or epidote and relict phengite inclusions within epidote with Si contents p.f.u. of up to 3.49 — overlapping with the highest values (3.49–3.62) recorded for phengites in samples of undoubted UHP schists. These and other mineral composition features (such as A-site deficiencies in the highest Si phengites, Na in garnets linked to Y+Yb substitution and Al F Ti₋₁ O₋₁ substitution in titanites) are taken to be pointers towards the orthogneisses having experienced a similar metamorphic evolution to the associated UHP schists and eclogites. Re-evaluated garnet–phengite and garnet–biotite Fe/Mg exchange thermometry and calculated 5 rutile+3 grossular+2SiO₂+H₂O=5 titanite+2 zoisite equilibria indicate that the orthogneisses may indeed have followed a common subduction-related clockwise P–T path with the UHP paragneisses and eclogites through conditions of P_max at ca. 690°C–715°C and 36 kbar to T_max at ca. 710°C–755°C and 18 kbar, prior to extensive re-crystallisation and re-equilibration of these ductile orthogneisses at ca. 400°C–450°C and 6 kbar. The consequential conclusion, that it is no longer necessary to resort to models of tectonic juxtapositioning to explain the spatial association of these Dabieshan orthogneisses with undoubted UHP lithologies, has far-reaching implications for the interpretation of controversial gneiss–eclogite relationships in other UHP metamorphic terrains.     

The geotherm of the lithosphere beneath Qilin, SE China: a re-appraisal and implications for P–T estimation of Fe-rich pyroxenites

The Qilin geotherm established by Xu et al. [Xu, X.S., O'Reilly, S.Y., Zhou, X.M. and Griffin, W.L., 1996. A xenolith-derived geotherm and the crust-mantle boundary at Qilin, southeastern China. Lithos, 38: 41–62.] using the Ellis and Green [Ellis D.J. and Green D.H., 1979. An experimental study of the effect of Ca upon garnet-clinopyroxene Fe-Mg exchange equilibria. Contrib. Mineral. Petrol., 71: 13–22]/Wood [Wood B.J., 1974. Solubility of alumina in orthopyroxene coexisting with garnet. Contrib. Mineral. Petrol. 46: 1-15] combination is in need of revision on the basis of re-evaluation of geothermobarometers, comparison of calculated pressures and temperatures with experimentally determined phase relationships and geological/geophysical data. The invalid assumption that all iron is present as Fe²⁺ in minerals, and the thermal destruction of equilibrium Fe–Mg exchange between clinopyroxene and garnet that may have resulted from heating of the Qilin xenoliths by the host magma resulted in unrealistically high temperatures estimated by the Ellis and Green's thermometer. An important implication arising from this study is that care must be taken when applying thermobarometers to Fe-rich pyroxenites for the purpose of geotherm construction and a comprehensive analysis is often required.     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

Melting relations and major element partitioning in an oxidized bulk Earth model composition at 15–26 GPa

Melting experiments were performed on an FeO-rich bulk Earth model composition in the CMFAS system in order to investigate the partitioning of major elements between coexisting minerals and melts. The starting material (34.2% SiO₂, 3.86% Al₂O₃, 35.2% FeO, 25.0% MgO and 1.88% CaO), contained in Re-capsules, was a mixture of crystalline forsterite and fayalite, and a glass containing SiO₂, Al₂O₃, and CaO. Olivine is the first liquidus phase at 10 GPa but is replaced by majoritic garnet (ga) in the 15–26 GPa range. Magnesiowüstite (mw) crystallizes close to the liquidus and is joined by perovskite (pv) at 26 GPa.

The quenched melt compositions are homogeneous throughout the melt region of the charges and are only slightly enriched in Si, Ca and Fe, and depleted in Mg, relative to the starting composition. The Fe/Mg and Ca/Al ratios in all of the minerals increase rapidly below the liquidus to become compatible with the bulk composition at the solidus. At 26 GPa, a relative density sequence of mw>pv>melt>ga is observed. This indicates that majorite floating, combined with the sinking of magnesiowüstite and perovskite can be expected during the solidification of a Hadean magma ocean and in hot mantle plumes early in the Earth's history. The mineral–melt partitioning relations indicate that fractional crystallization or partial melting in the transition zone and the upper part of the lower mantle would increase the Fe/Mg and Ca/Al ratios of the melt, even if magnesiowüstite was predominant in the solid fraction. A significant contribution of accumulated mw to the segregation of the protocore is therefore unlikely. The suggested process of perovskite fractionation to the lower mantle is not capable of increasing the Mg/Si ratio in the residual melt, and the combined fractionation of perovskite and magnesiowüstite produces a melt with elevated ratios of Si/Mg, Ca/Al and Fe/Mg.     

Titanian clinohumite–garnet–pyroxene rock from the Su-Lu UHP metamorphic terrane, China: chemical evolution and tectonic implications

A garnet–pyroxene rock containing abundant Ti-clinohumite (ca. 40 vol.%) occurs along with eclogites as small blocks in quartzo-feldsparthic gneiss in the southern end of the Chinese Su-Lu ultrahigh-pressure (UHP) metamorphic terrane. It consists of three aggregates: (1) Ti-clinohumite-dominated aggregate with interstitial garnet and pyroxene, (2) garnet+pyroxene aggregate with Ti-clinohumite inclusions, and (3) Ti-clinohumite-free aggregate dominated by garnet. Apatite, phlogopite, zircon, hematite, pentlandite, and an unknown Ni-Fe-volatile-Si (NFVS) mineral, which is replaced by Ni-greenalite, occur as accessories. Serpentine is the major secondary mineral. Garnet (Prp_63.9–64.6Alm_25.8–26.9Grs_1.4–7.9Uva_0.5–7.6Sps_1.0) in all three aggregates is pyrope-rich with very low grossular component, with that in the aggregate (2) most enriched in Cr (Cr₂O₃=2.55 wt.%). Orthopyroxene is depleted in Al (Al₂O₃=0.16 wt.% in the cores) and Ca (CaO=0.06–0.09 wt.% in the cores), with X_Mg (Mg/(Mg+Fe)) values at ca. 0.900. Clinopyroxene is chromian diopside with Fe³⁺≥Fe²⁺. Matrix clinopyroxene has a lower X_Mg (0.862) than that (0.887) included in Ti-clinohumite. The rock contains modest amount of heavy rare earth elements (HREE) (10 to 12×C1 chondrite), with significant enrichment in Cr, Co, Ni, V, Sr, and light rare earth elements (LREE) (22 to 33×C1 chondrite). The clinopyroxene is very enriched in Cr (Cr₂O₃ is up to 2.09 wt.% in the cores) and Sr (ca. 350 ppm) and LREE (Ce_N/Yb_N=157.7). Ti-clinohumite is enriched in Ni (1981 ppm), Co (123 ppm), and Nb (85 ppm).

While it is possible to enrich ultramafites in incompatible elements in a subducted slab, the high Al, Fe, Ti, and low Si, Ca, and Na contents in the Ti-clinohumite rock are difficult to account for by crustal metasomatism of an ultramafite. On the other hand, the similarity in major and trace element compositions and their systematic variations between the Ti-clinohumite-garnet-pyroxene rock of this study and those of Mg-metasomatised Fe–Ti gabbros reported in the literature suggest that crustal metasomatism occurred in a gabbroic protolith, which resulted in addition of Cr, Co, Ni, and Mg and removal of Si, Ca, Na, Al, and Fe. This implies that the rock was in contact with an ultramafite at low pressure. During subsequent subduction, the metagabbro was thrust into the country gneiss, where gneiss-derived hydrous fluids caused enrichment of Sr and LREE in recrystallised clinopyroxene. P–T estimates for the high-pressure assemblage are ca. 4.2 GPa and ca. 760 °C, compatible with those for the eclogites and gneisses in this terrane. It is possible that the Ti-clinohumite-garnet-pyroxene rock and associated eclogites represent remnants of former oceanic crust that was subducted to a great depth.     

A review and analysis of silicate mineral dissolution experiments in natural silicate melts

We present a database and a graphical analysis of published experimental results for dissolution rates of olivine, quartz plagioclase, clinopyroxene, orthopyroxene, spinel, and garnet in basaltic and andesitic melts covering a range of experimental temperatures (1100–1500°C) and pressures (10⁵ Pa-3.0 GPa). The published datasets of Donaldson (1985, 1990) and Brearly and Scarfe (1986) are the most complete. Experimental dissolution rates from all datasets are recalculated and normalized to a constant oxygen basis to allow for direct comparison of dissolution rates between different minerals. Dissolution rates (ν) range from 5·10⁻¹⁰ oxygen equivalent moles (o.e.m.) cm⁻² s⁻¹ for olivine in a basaltic melt to 1.3·10⁻⁵ o.e.m. cm⁻² s⁻¹ for garnet in a basaltic melt. Values of ln ν are Arthenian for the experiments examined and activation energies range from 118 to 1800 kJ/o.e.m. for quartz and clinopyroxene, respectively.

The relationship between calculated A/RT for the dissolution reactions, where A is the thermodynamic potential affinity, and values of ν is linear for olivine, plagioclase, and quartz. We interpret this as strong evidence in support of using calculated A as a predictor of ν for, at least, superliquidus melt conditions.     

Marcasite precipitation from hydrothermal solutions

Pyrite and marcasite were precipitated by both slow addition of aqueous Fe²⁺ and SiO₃²⁻ to an H₂S solution and by mixing aqueous Fe²⁺ and Na₂S₄ solutions at 75°C. H₂S₂ or HS₂⁻ and H₂S₄ or HS₄⁻ were formed in the S₂O₃²⁻ and Na₂S₄ experiments, respectively. Marcasite formed at pH < pK₁ of the polysulfide species present (for H₂S₂, pK₁ = 5.0; for H₂S₄, pK₁ = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H₂S₂ and HS₂ are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H₂S₂ and HS₂ are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS₂ and S₂²⁻ are strongly attracted to the positive pyrite growth sites. Masking of 1π_g^* electrons in the S₂ group by the protons makes HS₂ and H₂S₂ isoelectronic with AsS²⁻ and As₂²⁻, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H₂S₂ was formed near the site of deposition by either partial oxidation of aqueous H₂S by O₂ or by the reaction of higher oxidation state sulfur species that are reactive with H₂S at the conditions of formation e.g., S₂O₃²⁻ but not SO₄²⁻. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).     

The effect of garnet cell volume on the distribution of Mg and Fe in garnet exchange equilibria

The distribution of Mg in garnet exchange equilibria has been examined in three regional metamorphic and four eclogitic parageneses. Garnet cell volume has been found to have a significant effect on the distribution of Mg between garnet and coexisting ferromagnesian minerals. When the activity of Mg is corrected for the variation in cell volume, the range in variation of the distribution coefficients is strongly reduced within each group. Also the relative positions of the different groups in the distribution diagrams are in better accordance with geological evidence of crystallization temperatures. It is proposed that the effect of the garnet cell volume on the Mg distribution may be used as a geobarometer. The distribution of Ca between garnet and plagioclase is also discussed and it is found that the Ca partitioning is not suitable for geobarometry, as this partioning is dependent on the Mg/Fe ratio of the garnet.     

Diffusion-controlled corona reaction and overstepping of equilibrium in a garnet granulite, Yenisey Ridge, Siberia

Diffusion modelling is applied to layered garnet–pyroxene–quartz coronas, formed by a pressure-induced reaction between plagioclase and primary pyroxene in a metabasic granulite. The reconstructed reaction involves some change in composition of reactant minerals. The distribution of minerals between layers is satisfactorily explained by diffusion-controlled reaction with local equilibrium, in which the diffusion coefficient for Al was smaller than those for Fe, Mg and Ca by a factor of approximately four. Diffusion of Mg towards plagioclase implies a chemical-potential gradient for MgO component in a direction opposite to the changing Mg content of garnet; this is explained by the influence of Al₂O₃ on the chemical potential of the pyrope end-member. Grain-boundary diffusion is suggested to have operated, possibly with composition gradients different from those in the bulk minerals. Chemical-potential differences across the corona are estimated from the variation in garnet composition, enabling affinity (the free energy change driving the reaction) to be estimated as 6.9±1.8  kJ per 24-oxygen mole of garnet produced. This implies that the pressure for equilibrium among the minerals was overstepped by 1.4±0.4  kbar. The probable P–T conditions of reaction were in the range 650–790  °C, 8–10  kbar. Assuming a timescale of reaction between 10⁶ and 10⁸ years, estimated diffusion coefficients for Fe, Mg and Ca are in the range 9×10⁻²³ to 5×10⁻²⁰ m² s⁻¹. These are consistent with experimental values in the literature for solid-state diffusion, including grain-boundary diffusion.     

上天、入地、下海:极端条件下矿物学研究

上天、入地、下海,进行极端条件下的矿物学研究,研究微矿物,发现新矿物。主要利用金刚石压机,结合使用国内外同步辐射X-光源、中子源,以及其他多种物理的、化学的、光学的测试手段(如岩石矿物化学分析,光薄片测定,电子探针,离子探针,扫描电镜,透射电镜,红外、紫外、拉曼光谱,激光加热等),对来自天外的陨石、陨石坑样品、地球深处地幔源矿物以及海底甲烷水合物进行了一些研究。模拟不同温度和压力下各种不同成分的矿物材料的晶体结构、物理和化学性质。文章着重研究从地球内核到地壳海底的各种不同组分在不同温度、压力极端环境下形成的各种各样的典型矿物:从金属固体内核和金属液体外核中的ε-Fe到核幔边界(CMB)地球D″层的后钙钛矿(Post-Perovskite)结构(ppv)镁铁硅酸盐(Mg,Fe)SiO₃,从下地幔中的铁磁性钙钛矿(Perovskite)结构(pv)镁铁硅酸盐布里奇曼石(Bridgmanite)(Mg,Fe)SiO₃、镁铁氧化物(Fe,Mg)O和后尖晶石(Post-Spinel)结构的含Fe³⁺毛河光矿(Maohokite)(HP-Mg$Fe^{3+}_{2}O_{4}$)到过渡带、上地幔和地壳中的镁铁硅酸盐、硅氧化物、铬铁氧化物和金刚石及其内含物以及甲烷水合物(CH₄·H₂O)等。进行高温高压极端条件下的矿物学研究,为探索地球结构性质、形成动力和发展历史提供了新的窗口。     

Phase relations of pumpellyite-actinolite facies metabasites in the Sanbagawa metamorphic belt in central Shikoku, Japan

Sanbagawa metabasites metamorphosed at conditions near the upper limit of the pumpellytic-actinolite facies were examined in terms of phase equilibria in the five component system Al₂O₃---Fe₂O₃---CaO---MgO---FeO. The Fe³⁺ content of epidote measured as X^Ep_Fe (=Fe/(Fe + Al) of epidote) in the assemblage epidote-chlorite-actinolite-pumpellyite decreases gradually towards the higher-grade, pumpellyite-free areas. The progressive change in X_Fe^Ep can be detected within one metabasite bed 200 meters thick near the upper limit of the pumpellyite-actinolite facies. The Mg---Fe²⁺ substitution, as expressed by variation of Fe/(Fe + Mg) in chlorite (0.40–0.55) has little effect on the Fe³⁺ + Al) ratios of epidote and pumpellyite in the above-mentioned assemblage. The lowet X_Fe^Ep in the pumpellite-bearing assemblage is 0.15 and hence the upper limit of the pumpellyite-actinolite facies is defined by the appearance of an epidote-chlorite-actinolite assemblage with X^Ep_Fc = C.15     

Geothermobarometry of UHP and HP eclogites and schists – an evaluation of equilibria among garnet–clinopyroxene–kyanite–phengite–coesite/quartz

Geothermometry of eclogites and other high pressure (HP)/ultrahigh‐pressure (UHP) rocks has been a challenge, due to severe problems related to the reliability of the garnet–clinopyroxene Fe–Mg exchange thermometer to omphacite‐bearing assemblages. Likewise, reliable geobarometers for eclogites and related HP/UHP rocks are scarce. In this paper, a set of internally consistent geothermobarometric expressions have been formulated for reactions between the UHP assemblage garnet–clinopyroxene–kyanite–phengite–coesite, and the corresponding HP assemblage garnet–clinopyroxene–kyanite–phengite–quartz. In the system KCMASH, the end members grossular (Grs) and pyrope (Prp) in garnet, diopside (Di) in clinopyroxene, muscovite (Ms) and celadonite (Cel) in phengite together with kyanite and coesite or quartz define invariant points in the coesite and quartz stability field, respectively, depending on which SiO₂ polymorph is stable. Thus, a set of net transfer reactions including these end members will uniquely define equilibrium temperatures and pressures for phengite–kyanite–SiO₂‐bearing eclogites. Application to relevant eclogites from various localities worldwide show good consistency with petrographic evidence. Eclogites containing either coesite or polycrystalline quartz after coesite all plot within the coesite stability field, while typical quartz‐bearing eclogites with no evidence of former coesite fall within the quartz stability field. Diamondiferous coesite–kyanite eclogite and grospydite xenoliths in kimberlites all fall into the diamond stability field. The present method also yields consistent values as compared with the garnet–clinopyroxene Fe–Mg geothermometer for these kinds of rocks, but also indicates some unsystematic scatter of the latter thermometer. The net transfer geothermobarometric method presented in this paper is suggested to be less affected by later thermal re‐equilibration than common cation exchange thermometers.