Expansivity and compressibility of wadeite-type K2Si4O9 determined by in situ high T/P experiments, and their implication

Wadeite-type K₂Si₄O₉ was synthesized with a cubic press at 5.4 GPa and 900 °C for 3 h. Its unit-cell parameters were measured by in situ high-T powder X-ray diffraction up to 600 °C at ambient P. The T–V data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (α_T = a ₀ + a ₁ T), yielding a ₀ = 2.47(21) × 10^?5 K^?1 and a ₁ = 1.45(36) × 10^?8 K^?2. Compression experiments at ambient T were conducted up to 10.40 GPa with a diamond-anvil cell combined with synchrotron X-ray radiation. A second-order Birch–Murnaghan equation of state was used to fit the P–V data, yielding K _T = 97(3) GPa and V ₀ = 360.55(9) Å³. These newly determined thermal expansion data and compression data were used to thermodynamically calculate the P–T curves of the following reactions: 2 sanidine (KAlSi₃O₈) = wadeite (K₂Si₄O₉) + kyanite (Al₂SiO₅) + coesite (SiO₂) and wadeite (K₂Si₄O₉) + kyanite (Al₂SiO₅) + coesite/stishovite (SiO₂) = 2 hollandite (KAlSi₃O₈). The calculated phase boundaries are generally consistent with previous experimental determinations.     

Thermal diffusivity and thermal conductivity of single-crystal MgO and Al2O3 and related compounds as a function of temperature

Thermal diffusivity (D) was measured up to ~1,800 K of refractory materials using laser-flash analysis, which lacks radiative transfer gains and contact losses. The focus is on single-crystal MgO and Al₂O₃. These data are needed to benchmark theoretical models and thereby improve understanding of deep mantle processes. Measurements of AlN, Mg(OH)₂, and isostructural BeO show that the power law (D = AT ^?B ) where T is temperature holds for simple structures. Results for more structurally complicated corundum Al₂O₃ with and without impurity atoms are best fit by CT ^d  + ET ^f where d ~ ?1 and f ~ ?4, whereas for isostructural Fe₂O₃, f is near +3 and multiphase ilmenite Fe_1.12Ti_0.88O₃ is fit by the above power law. The positive temperature response for hematite is attributed to diffusive radiative transfer arising from electronic–vibronic coupling. We find good agreement of k and D data on single-crystal and non-porous ceramic Al₂O₃. For the corundum structure, D is nearly independent of T at high T. Although D at 298 K depends strongly on chemical composition, at high temperature, these differences are reduced. Thermal conductivity provided for MgO and Al₂O₃, using LFA data and literature values of density and heat capacity, differs from contact measurements which include systematic errors. The effect of pressure is discussed, along with implications for the deepest mantle.     

A revised model for the density and thermal expansivity of K2O-Na2O-CaO-MgO-Al2O3-SiO2 liquids from 700 to 1900 K: extension to crustal magmatic temperatures

A revised model for the volume and thermal expansivity of K₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂ liquids, which can be applied at crustal magmatic temperatures, has been derived from new low temperature (701–1092 K) density measurements on sixteen supercooled liquids, for which high temperature (1421–1896 K) liquid density data are available. These data were combined with similar measurements previously performed by the present author on eight sodium aluminosilicate samples, for which high temperature density measurements are also available. Compositions (in mol%) range from 37 to 75% SiO₂, 0 to 27% Al₂O₃, 0 to 38% MgO, 0 to 43% CaO, 0 to 33% Na₂O and 0 to 29% K₂O. The strategy employed for the low temperature density measurements is based on the assumption that the volume of a glass is equal to that of the liquid at the limiting fictive temperature, T _f ^′. The volume of the glass and liquid at T _f ^′ was obtained from the glass density at 298 K and the glass thermal expansion coefficient from 298 K to T _f ^′. The low temperature volume data were combined with the existing high temperature measurements to derive a constant thermal expansivity of each liquid over a wide temperature interval (767–1127 degrees) with a fitted 1 error of 0.5 to 5.7%. Calibration of a linear model equation leads to fitted values of Vˉ _i ±1 (cc/mol) at 1373 K for SiO₂ (26.86 ± 0.03), Al₂O₃ (37.42±0.09), MgO (10.71±0.08), CaO (15.41±0.06), Na₂O (26.57±0.06), K₂O (42.45 ± 0.09), and fitted values of dVˉ _i /dT (10⁻³ cc/mol-K) for MgO (3.27±0.17), CaO (3.74±0.12), Na₂O (7.68±0.10) and K₂O (12.08±0.20). The results indicate that neither SiO₂ nor Al₂O₃ contribute to the thermal expansivity of the liquids, and that dV/dT ^liq is independent of temperature between 701 and 1896 K over a wide range of composition. Between 59 and 78% of the thermal expansivity of the experimental liquids is derived from configurational (vs vibrational) contributions. Measured volumes and thermal expansivities can be recovered with this model with a standard deviation of 0.25% and 5.7%, respectively. Received: 2 August 1996 / Accepted: 12 June 1997     

Origin of peraluminous minerals (corundum,spinel, and sapphirine) in a highly calcic anorthosite from the Sittampundi Layered Complex,Tamil Nadu,India

The highly calcic anorthosite (An_>95) from the Sittampundi Layered Complex (SLC) develops corundum, spinel and sapphirine that are hitherto not reported from any anorthositic rocks in the world. Petrological observations indicate the following sequence of mineral growth: plagioclase_matrix → corundum; clinopyroxene → amphibole; corundum + amphibole → plagioclase_corona + spinel; and spinel + corundum → coronitic sapphirine. Phase relations in the CaO–Na₂O–Al₂O₃–SiO₂–H₂O (CNASH) system suggest that corundum was presumably developed through vapour present incongruent melting of the highly calcic plagioclase during ultra-high temperature (UHT) metamorphism (T ≥ 1000 °C, P ≥ 9 kbar). Topological constraints in parts of the Na₂O–CaO–MgO–Al₂O₃–SiO₂–H₂O (NCMASH) system suggest that subsequent to the UHT metamorphism, aqueous fluid(s) permeated the rock and the assemblage corundum + amphibole + anorthite + clinozoisite was stabilized during high-pressure (HP) metamorphism (11 ± 2 kbar, 750 ± 50 °C). Constraints of the NCMASH topology and thermodynamic and textural modeling study suggest that coronitic plagioclase and spinel formed at the expense of corundum + amphibole during a steeply decompressive retrograde P–T path (7–8 kbar and 700–800 °C) in an open system. Textural modeling studies combined with chemical potential diagrams (μSiO₂–μMgO) in the MASH system support the view that sapphirine also formed from due to silica and Mg metasomatism of the precursor spinel ± corundum, on the steeply decompressive retrograde P–T path, prior to onset of significant cooling of the SLC. Extremely channelized fluid flow and large positive solid volume change of the stoichiometrically balanced sapphirine forming reaction explains the localized growth of sapphirine.     

Synthesis of cordierite using industrial waste fly ash

Fly ash is a product arising from coal combustion in thermal power plants. It represents a major source of environmental pollution. It is well known by its chemical composition rich of SiO₂ and Al₂O₃. With the aim of preserving the environment against this contamination, fly ash was used along with the starting materials for producing glass cordierite (2MgO, 2Al₂O₃, 5SiO₂). Four formulations were developed by mixing the silica gel, magnesium chloride (MgCl₂.6H₂O) and fly ash in the percentages enclosing the stoichiometry of cordierite (2MgO, 2Al₂O₃, 5SiO₂). Different experimental techniques (DTA/TGA, X-ray diffraction, FTIR and SEM) were used to characterise the prepared formulations. The results shown that for all formulations, a cordierite phase was obtained at 1200 °C along with several secondary phases such as mullite, cristobalite, silicon oxide, enstatite and spinel. At 1300 °C, pure indialite (α-cordierite) was obtained along with a small amount of spinel. The four formulations sintered at 1200 °C exhibit a homogenous morphology and high porosity. The acicular-shaped indialite grains were observed in both formulations with excess of alumina and excess of magnesia.     

Metastable staurolite–cordierite assemblage of the Bossòst dome: Late Variscan decompression and polyphase metamorphism in the Axial Zone of the central Pyrenees

A kilometre-scale shear zone is recognized in the Cambro–Ordovician schist of the Bossòst dome, a Variscan metamorphic and structural dome in the Axial Zone of the central Pyrenees. Non-coaxial deformation is recorded by rotated garnet and staurolite porphyroblasts following regional metamorphism M₁, while coaxial conditions prevailed during later contact metamorphic M₂ growth of andalusite and cordierite. Mineral compositions and bulk rock analyses show that garnet–staurolite–andalusite–cordierite assemblages are significantly enriched in Mg and Mn over the garnet–staurolite assemblage, which lacks sufficient Mg for cordierite to form. The garnet–staurolite assemblage preserves conditions during M₁, estimated by AFM diagrams and P–T pseudosections to be 5.5 kbar and 580 °C, respectively. Pseudosections also indicate that staurolite is not a stable phase in cordierite–andalusite assemblages of M₂, suggesting polyphase metamorphism and decompression along a clockwise P–T path for the staurolite–cordierite–andalusite assemblages. This concurs with proposed extensional tectonics along the regional shear zone. To cite this article: J.E. Mezger et al., C. R. Geoscience 336 (2004).     

Pro- and retrograde P–T evolution of granulites of the Beit Bridge Complex (Limpopo Belt, South Africa): constraints from quantitative phase diagrams and geotectonic implications

Interpretations based on quantitative phase diagrams in the system CaO–Na₂O–K₂O–TiO₂–MnO–FeO–MgO–Al₂O₃–SiO₂–H₂O indicate that mineral assemblages, zonations and microstructures observed in migmatitic rocks from the Beit Bridge Complex (Messina area, Limpopo Belt) formed along a clockwise P–T path. That path displays a prograde P–T increase from 600 °C/7.0 kbar to 780 °C/9–10 kbar (pressure peak) and 820 °C/8 kbar (thermal peak), followed by a P–T decrease to 600 °C/4 kbar. The data used to construct the P–T path were derived from three samples of migmatitic gneiss from a restricted area, each of which has a distinct bulk composition: (1) a K, Al‐rich garnet–biotite–cordierite–sillimanite–K‐feldspar–plagioclase–quartz–graphite gneiss (2) a K‐poor, Al‐rich garnet–biotite–staurolite–cordierite–kyanite–sillimanite–plagioclase–quartz–rutile gneiss, and (3) a K, Al‐poor, Fe‐rich garnet–orthopyroxene–biotite–chlorite–plagioclase–quartz–rutile–ilmenite gneiss. Preservation of continuous prograde garnet growth zonation demonstrates that the pro‐ and retrograde P–T evolution of the gneisses must have been rapid, occurring during a single orogenic cycle. These petrological findings in combination with existing geochronological and structural data show that granulite facies metamorphism of the Beit Bridge metasedimentary rocks resulted from an orogenic event during the Palaeoproterozoic (c. 2.0 Ga), caused by oblique collision between the Kaapvaal and Zimbabwe Cratons. Abbreviations follow Kretz (1983 ).     

Storage conditions of Bezymianny Volcano parental magmas: results of phase equilibria experiments at 100 and 700 MPa

The crystallization sequence of a basaltic andesite from Bezymianny Volcano, Kamchatka, Russia, was simulated experimentally at 100 and 700 MPa at various water activities (aH₂O) to investigate the compositional evolution of residual liquids. The temperature (T) range of the experiments was 950–1,150 °C, aH₂O varied between 0.1 and 1, and the log of oxygen fugacity (fO₂) varied between quartz–fayalite–magnetite (QFM) and QFM + 4.1. The comparison of the experimentally produced liquids and natural samples was used to constrain the pressure (P)–T–aH₂O–fO₂ conditions of the Bezymianny parental magma in the intra-crustal magma plumbing system. The phase equilibria constraints suggest that parental basaltic andesite magmas should contain ~2–2.5 wt% H₂O; they can be stored in upper crustal levels at a depth of ~15 km, and at this depth they start to crystallize at ~1,110 °C. The subsequent chemical evolution of this parental magma most probably proceeded as decompressional crystallization occurred during magma ascent. The final depths at which crystallization products accumulated prior to eruption are not well constrained experimentally but should not be shallower than 3–4 km because amphibole is present in natural magmas (>150 MPa). Thus, the major volume of Bezymianny andesites was produced in a mid-crustal magma chamber as a result of decompressional crystallization of parental basaltic andesites, accompanied by mixing with silicic products from the earlier stages of magma fractionation. In addition, these processes are complicated by the release of volatiles due to magma degassing, which occurs at various stages during magma ascent.     

Granulite formation in a Gondwana fragment: petrology and mineral equilibrium modeling of incipient charnockite from Mavadi, southern India

We report a new occurrence of incipient charnockite from Mavadi in the Trivandrum Granulite Block (TGB), southern India, and discuss the petrogenesis of granulite formation in an arrested stage on the basis of petrography, geothermobarometry, and mineral equilibrium modeling. In Mavadi, patches and lenses of charnockite (Kfs?+?Qtz?+?Pl?+?Bt?+?Grt?+?Opx?+?Ilm?+?Mag) of about 30 to 220 cm in length occur within Opx-free Grt-Bt gneiss (Kfs?+?Qtz?+?Pl?+?Bt?+?Grt?+?Ilm). The application of mineral equilibrium modeling on the charnockite assemblage in the NCKFMASHTO system to constrain the conditions of charnockitization defines a P–T range of 800 °C at 4.5 kbar to 850 °C at 8.5 kbar, which is broadly consistent with the results from the conventional geothermobarometry (810–880 °C at 7.7–8.0 kbar) on these rocks. The P–T conditions are lower than the peak metamorphic conditions reported for the ultrahigh-temperature granulites from this area (T?>?900 °C). The heterogeneity in peak P–T conditions within the same crustal block might be related to local buffering of metamorphic temperatures by the Opx-Bt-Kfs-Qtz assemblage. The result of T versus mole H₂O (M(H₂O)) modeling demonstrated that the Opx-free assemblage in the Grt-Bt gneiss is stable at M(H₂O)?=?0.3 to 1.5 mol%, and orthopyroxene occurs as a stable mineral at M(H₂O) <0.3 mol%, which is consistent with the petrogenetic model of incipient charnockite related to the lowering of the water activity and stabilization of orthopyroxene through the breakdown of biotite by dehydration caused by the infiltration of CO₂-rich fluid from external sources. We also propose a possible alternative mechanism to form charnockite from Grt-Bt gneiss through slight variations in bulk-rock chemistry (particularly for the K- and Fe-rich portion of Grt-Bt gneiss) that can enhance the stability of orthopyroxene rather than that of biotite, with K-metasomatism playing a possible role.     

Sapphirine parageneses from the Caraiba complex, Bahia, Brazil: the influence of Fe2+–Fe3+ distribution on the stability of sapphirine in natural assemblages

Abstract Sapphirine-bearing rocks occur in three conformable, metre-size lenses in intrusive quartzo-feldspathic orthogneisses in the Curaçà valley of the Archaean Caraiba complex of Brazil. In the lenses there are six different sapphirine-bearing rock types, which have the following phases (each containing phlogopite in addition): A: Sapphirine, orthopyroxene; B: Sapphirine, cordierite, orthopyroxene, spinel; C: Sapphirine, cordierite; D: Sapphirine, cordierite, orthopyroxene, quartz; E: Sapphirine, cordierite, orthopyroxene, sillimanite, quartz; F: Sapphirine, cordierite, K-feldspar, quartz. Neither sapphirine and quartz nor orthopyroxene and sillimanite have been found in contact, however. During mylonitization, introduction of silica into the three quartz-free rocks (which represent relict protolith material) gave rise to the three cordierite and quartz-bearing rocks. Stable parageneses in the more magnesian rocks were sapphirine–orthopyroxene and sapphirine–cordierite. In more iron-rich rocks, sapphirine–cordierite, sapphirine-cordierite–sillimanite, cordierite–sillimanite, sapphirine–cordierite–spinel–magnetite and quartz–cordierite–orthopyroxene were stable. The iron oxide content in sapphirine of the six rocks increases from an average of 2.0 to 10.5 wt % (total Fe as FeO) in the order: C,F–A,D–B,E. With increase in Fe there is an increase in recalculated Fe₂O₃ in sapphirine. The four rock types associated with the sapphirine-bearing lenses are: I: Orthopyroxene, cordierite, biotite, quartz, feldspar tonalitic to grandioritic gneiss; II: Biotite, quartz, feldspar gneiss; III: Orthopyroxene, clinopyroxene, hornblende, plagioclase meta-norite; IV: Biotite, orthopyroxene, quartz, feldspar, garnet, cordierite, sillimanite granulite gneiss. The stable parageneses in type IV are orthopyroxene–cordierite–quartz, garnet–sillimanite–quartz and garnet–cordierite–sillimanite. Geothermobarometry suggests that the associated host rocks equilibrated at 720–750°C and 5.5–6.5 kbar. Petrogenetic grids for the FMASH and FMAFSH (FeO–MgO–Al₂O₃–Fe₂O₃–SiO₂–H₂O) model systems indicate that sapphirine-bearing assemblages without garnet were stabilized by a high Fe³⁺ content and a high X_Mg= (Mg/ (Mg+Fe²⁺)) under these P–T conditions.     

Distribution of cations at two tetrahedral sites in Ca2MgSi2O7-Ca2Fe3+AlSiO7 series synthetic melilite and its relation to incommensurate structure

Synthetic melilites on the join Ca₂MgSi₂O₇ (åkermanite: Ak)-Ca₂Fe³⁺AlSiO₇ (ferrialuminium gehlenite: FAGeh) were studied using X-ray powder diffraction and ⁵⁷Fe Mössbauer spectroscopic methods to determine the distribution of Fe³⁺ between two different tetrahedral sites (T1 and T2), and the relationship between ionic substitution and incommensurate (IC) structure. Melilites were synthesized from starting materials with compositions of Ak₁₀₀, Ak₈₀FAGeh₂₀, Ak₇₀FAGeh₃₀ and Ak₅₀FAGeh₅₀ by sintering at 1,170–1,350 °C and 1 atm. The average chemical compositions and end-member components, Ak, FAGeh and Geh (Ca₂Al₂SiO₇), of the synthetic melilites were Ca_2.015Mg_1.023Si_1.981O₇ (Ak₁₀₀), Ca_2.017Mg_0.788Fe _0.187 ³⁺ Al_0.221Si_1.791O₇ (Ak₇₈FAGeh₁₉Geh₃), Ca_1.995Mg_0.695Fe _0.258 ³⁺ Al_0.318Si_1.723O₇ (Ak₆₉FAGeh₂₅Geh₆) and Ca_1.982Mg_0.495Fe _0.449 ³⁺ Al_0.519Si_1.535O₇ (Ak₄₉FAGeh₄₄Geh₇), respectively. Rietveld refinements using X-ray powder diffraction data measured using CuK _α -radiation at room temperature converged successfully with goodness-of-fits of 1.15–1.26. The refined Fe occupancies at the T1 and T2 sites and the Mg and Si contents determined by electron microprobe analysis gave the site populations of [0.788Mg + 0.082Fe³⁺ + 0.130Al]_T1[0.104Fe³⁺ + 0.104Al + 1.792Si]_T2 for Ak₇₈FAGeh₁₉Geh₃, [0.695Mg + 0.127Fe³⁺ + 0.178Al]_T1[0.132Fe³⁺ + 0.144Al + 1.724Si]_T2 for Ak₆₉FAGeh₂₅Geh₆ and [0.495Mg + 0.202Fe³⁺ + 0.303Al]_T1[0.248Fe³⁺ + 0.216Al + 1.536Si]_T2 for Ak₄₉FAGeh₄₄Geh₇ (apfu: atoms per formula unit), respectively. The results indicate that Fe³⁺ is distributed at both the T1 and the T2 sites. The mean T1–O distance decreases with the substitution of Fe³⁺ + Al³⁺ for Mg²⁺ at the T1 site, whereas the mean T2–O distance increases with substitution of Fe³⁺ + Al³⁺ for Si⁴⁺ at the T2 site, causing decrease in the a dimension and increase in the c dimension. However, in spite of the successful Rietveld refinements for the X-ray powder diffraction data measured using CuK _α-radiation at room temperature, each Bragg reflection measured using CuK _α1-radiation at room temperature showed weak shoulders, which were not observed in those measured at 200 °C. The Mössbauer spectra of the melilites measured at room temperature consist of two doublets assigned to Fe³⁺ at the T1 site and two or three doublets to Fe³⁺ at the T2 site, implying the existence of multiple T1 and T2 sites with different site distortions. These facts can be interpreted in terms of the IC structure in all synthetic melilites at room temperature, respectively. The results of Mössbauer analysis indicate that the IC structure in melilite is caused by not only known multiple T1 site, but also multiple T2 site at room temperature.     

Petrogenesis of the garnet peridotite and garnet-free peridotite of the Zhimafang ultramafic body in the Sulu ultrahigh-pressure metamorphic belt, eastern China

The CCSD‐PP1 drillhole penetrated a 110‐m‐thick sequence of the Zhimafang ultramafic body in the Sulu ultrahigh‐pressure (UHP) metamorphic belt, east China. The sequence consists of interlayered garnet‐bearing (Grt) and garnet‐free (GF) peridotite. Eleven layers of Grt‐peridotite, ranging from 1.2 to 9.5 m in thickness, have an aggregate thickness of 54.49 m, whereas eight layers of GF‐peridotite, ranging from 2.2 to 14.2 m in thickness, have a total thickness of 57.53 m. The boundaries between the two rock types are gradational. The Grt‐peridotites have slightly higher contents of Al₂O₃, CaO and SiO₂, and lower Mg^#s (0.90–0.92) than the GF‐peridotites (Mg^#s 0.91–0.93). Both contain low TiO₂ (<0.05 wt%) and have higher modal abundances of enstatite (average 10 vol.%) than diopside (1–5 vol.%), typical of depleted‐type upper mantle. The diopside in these rocks has high and relatively uniform Mg^# members (0.93–0.95), but highly variable Al₂O₃ (0.2–2.3 wt%), Na₂O (0.5–2.5 wt%) and Cr₂O₃ (0.38–2.09 wt%). Enstatite (En_92?93) contains very low Al₂O₃ (0–0.3 wt%). Both porphyroblastic and equigranular garnet are present. The equigranular varieties are zoned, from core to rim in Cr₂O₃ (3.4–4.2 wt%), MgO (18.4–17.5 wt%) and Al₂O₃ (21.1–20.1 wt%). Titania is very low in all the garnet, mostly <0.05 wt%. Chromite or chromium (Cr)‐spinel occur both in the Grt‐ and GF‐peridotite, and are characterized by high contents of Cr₂O₃ (49–58 wt%) and FeO (24–43 wt%), similar to that in iron‐rich Alpine‐type peridotites. Based on the bulk‐rock MgO–FeO compositions, the Zhimafang Grt‐peridotite probably underwent 20–30% partial melting, whereas the GF‐peridotite may have undergone as much as 35–40% partial melting, suggesting that the two rock types owe their differences to different degrees of partial melting rather than to pressure differences during metamorphism.     

High-temperature and high-pressure equation of state for the hexagonal phase in the system NaAlSiO4 – MgAl2O4

Thermal equation of state of an Al-rich phase with Na_1.13Mg_1.51Al_4.47Si_1.62O₁₂ composition has been derived from in situ X-ray diffraction experiments using synchrotron radiation and a multianvil apparatus at pressures up to 24 GPa and temperatures up to 1,900 K. The Al-rich phase exhibited a hexagonal symmetry throughout the present pressure–temperature conditions and the refined unit-cell parameters at ambient condition were: a=8.729(1) Å, c=2.7695(5) Å, V ₀=182.77(6) Å³ (Z=1; formula weight=420.78 g/mol), yielding the zero-pressure density ρ₀=3.823(1) g/cm³ . A least-square fitting of the pressure-volume-temperature data based on Anderson’s pressure scale of gold (Anderson et al. in J Appl Phys 65:1534–543, 1989) to high-temperature Birch-Murnaghan equation of state yielded the isothermal bulk modulus K ₀=176(2) GPa, its pressure derivative K ₀ ^′ =4.9(3), temperature derivative (?K _T /?T) _P =?0.030(3) GPa K^?1 and thermal expansivity α(T)=3.36(6)×10^?5+7.2(1.9)×10^?9 T, while those values of K ₀=181.7(4) GPa, (?K _T /?T) _P =?0.020(2) GPa K^?1 and α(T)=3.28(7)×10^?5+3.0(9)×10^?9 T were obtained when K ₀ ^′ was assumed to be 4.0. The estimated bulk density of subducting MORB becomes denser with increasing depth as compared with earlier estimates (Ono et al. in Phys Chem Miner 29:527–531 2002; Vanpeteghem et al. in Phys Earth Planet Inter 138:223–230 2003; Guignot and Andrault in Phys Earth Planet Inter 143–44:107–128 2004), although the difference is insignificant (<0.6%) when the proportions of the hexagonal phase in the MORB compositions (～20%) are taken into account.     

Origin of zoned spinel by coupled dissolution–precipitation and inter-crystalline diffusion: evidence from serpentinized wehrlite, Bangriposi, Eastern India

Textural and mineral–chemical characteristics in the Bangriposi wehrlites (Eastern India) provide insight into metamorphic processes that morphologically and chemically modified magmatic spinel during serpentinization of wehrlite. Aluminous chromite included in unaltered magmatic olivine is chemically homogenous. In sub-cm to 10s-of-micron-wide veins, magnetite associated with antigorite and clinochlore comprising the serpentine matrix is near-stoichiometric. But Al–Cr–Fe³⁺ spinels in the chlorite–magnetite veins are invariably zoned, e.g., chemically homogenous Al-rich chromite interior successively mantled by ferritchromite/Cr-rich magnetite zone and magnetite continuous with vein magnetite in the serpentine matrix. In aluminous chromite, ferritchromite/Cr-rich magnetite zones are symmetrically disposed adjacent to fracture-controlled magnetite veins that are physically continuous with magnetite rim. The morphology of ferritchromite–Cr-rich magnetite mimics the morphology of aluminous chromite interior but is incongruous with the exterior margin of magnetite mantle. Micropores are abundant in magnetite veins, but are fewer in and do not appear to be integral to the adjacent ferritchromite–Cr-rich magnetite zones. Sandwiched between chemically homogenous aluminous chromite interior and magnetite mantle, ferritchromite–Cr-rich magnetite zones show rim-ward decrease in Cr₂O₃, Al₂O₃ and MgO and complementary increase in Fe₂O₃ at constant FeO. In diffusion profiles, Fe₂O₃–Cr₂O₃ crossover coincides with Al₂O₃ decrease to values <0.5 wt% in ferritchromite zone, with Cr₂O₃ continuing to decrease within magnetite mantle. Following fluid-mediated (hydrous) dissolution of magmatic olivine and olivine + Al–chromite aggregates, antigorite + magnetite and chlorite + magnetite were transported in 10s-of-microns to sub-cm-wide veins and precipitated along porosity networks during serpentinization (T: 550–600 °C, f(O₂): ?19 to ?22 log units). These veins acted as conduits for precipitation of magnetite as mantles and veins apophytic in chemically/morphologically modified magmatic Al-rich chromite. Inter-crystalline diffusion induced by chemical gradient at interfaces separating aluminous chromite interiors and magnetite mantles/veins led to the growth of ferritchromite/Cr-rich magnetite zones, mimicking the morphology of chemically modified Al–Cr–Fe–Mg spinel interiors. Inter-crystalline diffusion outlasted fluid-mediated aluminous chromite dissolution, mass transfer and magnetite precipitation.     

Polymetamorphic history of a relict Permian hornfels from the central Gran Paradiso Massif (Western Alps,Italy): a microstructural and thermodynamic modelling study

A petrological and thermobarometric study of the Lago Teleccio hornfelses was undertaken to reconstruct the polymetamorphic evolution and constrain the P–T conditions of Permian contact metamorphism. The Lago Teleccio metasedimentary rocks record a Variscan regional metamorphism characterized by amphibolite facies mineral assemblages including quartz, plagioclase, K‐feldspar (Kfs 1), biotite, garnet (Grt 1) and staurolite; this was followed by a late‐Variscan mylonitization event. Metamorphism of the Variscan metamorphic rocks at the contact with a Permian granitic intrusion produced static recrystallization and/or new growth of quartz, garnet (Grt 2), plagioclase, K‐feldspar (Kfs 2), cordierite, green spinel, biotite and prismatic sillimanite (Contact 1). This thermal event, which occurred at a peak pressure of 0.23–0.35 GPa, temperature of 670–700 °C and a_H2O of 0.75–1, was followed either during post‐contact metamorphism cooling or, more likely, during the early‐Alpine metamorphism by the breakdown of cordierite into an anhydrous kyanite + orthopyroxene + quartz assemblage. The poorly developed early‐Alpine eclogite facies metamorphism (Alpine 1) was characterized by relatively anhydrous mineral associations and low strain, which locally produced coronitic and pseudomorphous microstructures in metasedimentary rocks, with scanty formation of jadeite, zoisite and a new high‐pressure garnet (Grt 3). Greenschist facies retrogression (Alpine 2) was characterized by the local development of a chlorite‐ and muscovite‐bearing mineral association, suggestive of aqueous fluid incursion. In the hornfelses, the limited extent of metamorphic overprinting is suggested by the fine grain size of the Alpine mineral associations, which formed at the expense of the Permian contact metamorphic associations, and was favoured by the anhydrous mineralogy of the hornfelses.     

A petrogenetic grid for aluminous granulite facies metapelites in the KFMASH system

Due to the retrograde cation exchange problems experienced by conventional geothermobarometers above their closure temperatures, petrogenetic grids are a potentially powerful alternative to unravelling the P–T evolution of ultrahigh‐T granulite terranes. A new qualitative KFMASH (K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O) petrogenetic grid for Mg–Al rich metapelites containing K‐feldspar, sillimanite and quartzofeldspathic melt that successfully accounts for the majority of assemblages composed of variations of sapphirine, spinel, garnet, orthopyroxene, cordierite, biotite and quartz is developed. Univariant reactions are predicted utilizing a newly derived ‘melt projection’ and these reactions are entirely consistent with algebraically calculated reaction coefficients obtained using a set of standard phase compositions. Based upon observations of commonly associated mineral assemblages in natural lithologies the [Spr, Spl], [Qtz, Spl], [Bt, Spl], [Opx, Spr], [Opx, Qtz] and [Bt, Opx] invariant points are assumed to be stable, whilst the [Grt, Spr], [Grt, Qtz], [Spr, Qtz] and [Crd, Qtz] are assumed to be metastable. Biotite‐bearing assemblages are confined to the lowest temperatures, and sapphirine + quartz to the highest temperatures. Orthopyroxene + sillimanite ± quartz assemblages are confined to the highest pressures, whilst spinel‐bearing assemblages are stabilized by lower pressures. The alternative choice of invariant point stability leads to significant differences between this grid and previously proposed topologies. Spinel cannot be stable along with the orthopyroxene and sillimanite assemblage as previously proposed. Further, more subtle differences in topology result from the treatment of H₂O in the chemographic projection used to deduce univariant reactions, and projecting from a water‐bearing quartzofeldspathic melt does not yield the same reaction coefficients as projection from H₂O. The new grid allows reinterpretation of previously proposed evolutionary P–T paths for Mg–Al rich granulites from the Napier Complex and Rauer Group, East Antarctica, and In Ouzzal, Algeria.     

The thermodynamic properties of H2O in magnesium and iron cordierite

 The equilibrium water content of cordierite has been measured for 31 samples synthesized at pressures of 1000 and 2000 bars and temperatures from 600 to 750° C using the cold-seal hydrothermal technique. Ten data points are presented for pure magnesian cordierite, 11 data points for intermediate iron/magnesium ratios from 0.25 to 0.65 and 10 data points for pure iron cordierite. By representing the contribution of H₂O to the heat capacity of cordierite as steam at the same temperature and pressure, it is possible to calculate a standard enthalpy and entropy of reaction at 298.18° K and 1 bar for, (Mg,Fe)₂Al₄Si₅O₁₈+H₂O ⇄ (Fe,Mg)₂Al₄Si₅O₁₈.H₂O Combining the 31 new data points with 89 previously published experimental measurements gives: ΔH ^° _r =–37141±3520 J and ΔS ^° _r =–99.2±4 J/degree. This enthalpy of reaction is within experimental uncertainty of calorimetric data. The enthalpy and entropy of hydration derived separately for magnesian cordierite (–34400±3016 J, –96.5±3.4 J/degree) and iron cordierite (–39613±2475, –99.5±2.5 J/degree) cannot be distinguished within the present experimental uncertainty. The water content as a function of temperature, T(K), and water fugacity, f(bars), is given by n _H2O=1/[1+1/(K ⋅ f _H2O)] where the equilibrium constant for the hydration reaction as written above is, ln K=4466.4/T–11.906 with the standard state for H₂O as the gas at 1 bar and T, and for cordierite components, the hydrous and anhydrous endmembers at P and T. Received: 2 August 1994/Accepted: 7 February 1996     

Origin of the Matauri Bay halloysite deposit, Northland, New Zealand

At the Matauri Bay halloysite deposit, economically valuable halloysite-rich clays are hosted by a sanidine rhyolite dome (Ar–Ar dated at 10.1?±?0.03?Ma). The rhyolite dome intrudes an older basalt and is overlain by alluvial sediments and a younger basalt (4.0?±?0.7?Ma). A blanket-like, halloysite-rich zone is restricted to depths of 10–30?m from the present day erosion surface. Primary sanidine and plagioclase phenocrysts in rhyolite are completely leached out in the halloysite-rich zone but are only partially leached out at greater depth. Halloysite was formed by hydrolysis and cation leaching of sanidine and plagioclase phenocrysts and groundmass glass in the rhyolite, resulting in loss of K, Ca, Na and Si and enrichment in OH (LOI 6–10%) and Al₂O₃ (20–30%) relative to least-altered rhyolite with 1.8% LOI and 14.5% Al₂O₃. Oxygen and hydrogen isotope data indicate the halloysite is supergene rather than hydrothermal in origin, which is consistent with the absence of pyrite, alunite and other acid-sulphate type hydrothermal minerals, and with the blanket-like alteration profile. The dominance of halloysite over kaolinite was favoured by water-saturated weathering conditions during the late Miocene-Pliocene subtropical weathering regime in Northland.     

Phase relations in high-pressure metapelites in the system KFMASH (K2O–FeO–MgO–Al2O3–SiO2–H2O) with application to natural rocks

Using a previously published, internally consistent thermodynamic dataset and updated models of activity–composition relations for solid solutions, petrogenetic grids in the model system KFMASH (K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O) and the subsystems KMASH and KFASH have been calculated with the software THERMOCALC 3.1 in the P–T range 5–36 kbar and 400–810 °C, involving garnet, chloritoid, biotite, carpholite, talc, chlorite, staurolite and kyanite/sillimanite with phengite, quartz/coesite and H₂O in excess. These grids, together with calculated AFM compatibility diagrams and pseudosections, are shown to be powerful tools for delineating the phase equilibria and P–T conditions of pelitic high-P assemblages for a variety of bulk compositions. The calculated equilibria and mineral compositions are in good agreement with petrological observation. The calculation indicates that the typical whiteschist assemblage kyanite–talc is restricted to the rocks with extremely high X_Mg values, decreasing X_Mg in a bulk composition favoring the stability of chloritoid and garnet. Also, the chloritoid–talc paragenesis is stable over 19–20 kbar in a temperature range of ca. 520–620 °C, being more petrologically important than the previously highlighted assemblage talc–phengite. Moreover, contours of the calculated Si isopleths in phengite in P–T and P–X pseudosections for different bulk compositions extend the experimentally derived phengite geobarometers to various KFMASH assemblages.     

Effects of temperature on the crystal structure of epidote: a neutron single-crystal diffraction study at 293 and 1,070 K

The effects of temperature on the crystal structure of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH), a = 8.890(6), b = 5.630(4), c = 10.150(6) Å and β = 115.36(5)°, Sp. Gr. P2₁ /m] have been investigated by means of neutron single-crystal diffraction at 293 and 1,070 K. At room conditions, the structural refinement confirms the presence of Fe³⁺ at the M₃ site [%Fe(M3) = 73.1(8)%] and all attempts to refine the amount of Fe at the M(1) site were unsuccessful. Only one independent proton site was located. Two possible hydrogen bonds, with O(2) and O(4) as acceptors [i.e. O(10)–H(1)···O(2) and O(10)–H(1)···O(4)], occur. However, the topological configuration of the bonds suggests that the O(10)–H(1)···O(4) is energetically more favourable, as H(1)···O(4) = 1.9731(28) Å, O(10)···O(4) = 2.9318(22) Å and O(10)–H(1)···O4 = 166.7(2)°, whereas H(1)···O(2) = 2.5921(23) Å, O(10)···O(2) = 2.8221(17) Å and O(10)–H(1)···O2 = 93.3(1)°. The O(10)–H(1) bond distance corrected for “riding motion” is 0.9943 Å. The diffraction data at 1,070 K show that epidote is stable within the T-range investigated, and that its crystallinity is maintained. A positive thermal expansion is observed along all the three crystallographic axes. At 1,070 K the structural refinement again shows that Fe³⁺ share the M(3) site along with Al³⁺ [%Fe(M3)_1,070K = 74(2)%]. The refined amount of Fe³⁺ at the M(1) is not significant [%Fe(M1)_1,070K = 1(2)%]. The tetrahedral and octahedral bond distances and angles show a slight distortion of the polyhedra at high-T, but a significant increase of the bond distances compared to those at room temperature is observed, especially for bond distances corrected for “rigid body motions”. The high-T conditions also affect the inter-polyhedral configurations: the bridging angle Si(2)–O(9)–Si(1) of the Si₂O₇ group increases significantly with T. The high-T structure refinement shows that no dehydration effect occurs at least within the T-range investigated. The configuration of the H-bonding is basically maintained with temperature. However, the hydrogen bond strength changes at 1,070 K, as the O(10)···O(4) and H(1)···O(4) distances are slightly longer than those at 293 K. The anisotropic displacement parameters of the proton site are significantly larger than those at room condition. Reasons for the thermal stability of epidote up to 1,070 K observed in this study, the absence of dehydration and/or non-convergent ordering of Al and Fe³⁺ between different octahedral sites and/or convergent ordering on M(3) are discussed.