Eclogites from the south Tianshan, NW China: petrological characteristic and calculated mineral equilibria in the Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O system

Eclogites from the south Tianshan, NW China are grouped into two types: glaucophane and hornblende eclogites, composed, respectively, of garnet + omphacite + glaucophane + paragonite + epidote + quartz and garnet + omphacite + hornblende (sensu lato) + paragonite + epidote + quartz, plus accessory rutile and ilmenite. These eclogites are diverse both in mineral composition and texture not only between the two types but also among the different selected samples within the glaucophane eclogite. Using thermocalc 3.1 and recent models of activity–composition relation for minerals, a P–T projection and a series of P–T pseudosections for specific samples of eclogite have been calculated in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCFMASH) with quartz and water taken to be in excess. On the basis of these phase diagrams, the phase relations and P–T conditions are well delineated. The three selected samples of glaucophane eclogite AK05, AK11 and AK17 are estimated to have peak P–T conditions, respectively, of 540–550 °C at c. 16 kbar, c. 560 °C at 15–17 kbar and c. 580 °C at 15–19 kbar, and two samples of hornblende eclogite AK10 and AK30 of 610–630 °C and 17–18 kbar. Together with H₂O‐content contours in the related P–T pseudosections and textural relations, both types of eclogite are inferred to show clockwise P–T paths, with the hornblende eclogite being transformed from the glaucophane eclogite assemblage dominantly through increasing temperature.     

The stability of sapphirine-quartz and hypersthene-sillimanite-quartz assemblages: an experimental investigation in the system FeO−MgO−Al2O3−SiO2 under H2O and CO2 conditions

Phase relations and mineral chemistry involving the phases garnet (Gt), spinel (Sp), hypersthene (Hy), sapphirine (Sa), cordierite (Cd), sillimanite (Sil) and quartz (Qz) have been experimentally determined in the system FMAS (FeO−MgO−Al₂O₂−SiO₂) under low fO₂ and for various H₂O/CO₂ conditions. Several compositions were studied with 100 (Mg/Mg+Fe) ratio ranging from 64 to 87 with excess quartz and sillimanite. Our data do not show any differences in Gt−Cd stability and composition as a function of H₂O, CO₂ and H₂O−CO₂ (±CH₄) content, in good agreement with a previous experimental study at lower temperature (Aranovich and Podlesskii 1983). At 1,000° C and 11 kbar, under CO₂-saturated conditions, cordierite grew from a crystalline mix unseeded with cordierite. Thus, under water-absent conditions, cordierite will have a high-P stability field in the presence of CO₂. If water has a pressure stabilizing effect on cordierite, then our results would indicate that the effects of H₂O and CO₂ are of the same magnitude at high temperature. Our data support the theoretical P-T grid proposed by Hensen (1986) for high-T metapelites and are largely consistent with the high-temperature experimental data of Hensen and Green (1973). The univariant boundary Gt+Cd=Hy+Sil+Qz, which marks the disappearance of Hy−Sil−Qz assemblages, has a negative dP/dT slope above 1,000° C and a positive one below this temperature. Extrapolation of our data to iron-free systems shows that the high-P breakdown limit of Mg-cordierite has a negative slope in the range 1,025–1,300° C and probably positive below 1,000° C. This indicates a maximum of stability for Mg-cordierite at around 1,000° C and 13 kbar. Because of the curvature of the univariant reactions En+Sil=Py+Qz, Mg−Cd=En+Sil+Qz and Gt+Cd=Hy+Sil+Qz, the iron-free invariant point involving the phases Py, En, Cd, Sil and Qz probably does not exist. Sapphirine—Qz-bearing assemblages are stable only at temperatures above 1,050° C. At 1,075° C, the joint Gt−Sa is stable up to 11 kbar. At higher pressure, garnet, sapphirine and quartz react according to the reaction Gt+Sa+Qz=Hy+Sil. Reequilibrated sapphirines are more aluminous than the theoretical endmember Mg₂Al₄SiO₁₀ due to AlAl=MgSi substitutions [100(Al₂O₃/Al₂O₃+FeO+MgO) in experimental sapphirines ranges from 50.5 to 52.2]. Sapphirine in the assemblage Sa−Cd−Sil−Qz shows a decrease in Al content with decreasing temperature and pressure, such that the alumina isopleths for sapphirine have a slight negative dP/dT slope. A similar decrease in Al content of sapphirine with temperature is also observed in Sa−Sil−Qz assemblages.     

Calculated phase equilibria in K2O-FeO-MgO-Al2O3-SiO2-H2O for silica-undersaturated sapphirine-bearing mineral assemblages

Silica‐undersaturated, sapphirine‐bearing granulites occur in a large number of localities worldwide. Such rocks have historically been under‐utilized for estimating P–T evolution histories because of limited experimental work, and a consequent poor understanding of the topology and P–T location of silica‐undersaturated mineral equilibria. Here, a calculated P–T projection for sapphirine‐bearing, silica‐undersaturated metapelitic rock compositions is constructed using THERMOCALC for the FeO‐MgO‐Al₂O₃‐SiO₂ (FMAS) and KFMASH (+K₂O + H₂O) chemical systems, allowing quantitative analysis of silica‐undersaturated mineral assemblages. This study builds on that for KFMASH sapphirine + quartz equilibria [Kelsey et al. (2004) Journal of Metamorphic Geology, vol. 22, pp. 559–578]. FMAS equilibria are significantly displaced in P–T space from silicate melt‐bearing KFMASH equilibria. The large number of univariant silica‐undersaturated KFMASH equilibria result in a P–T projection that is topologically more complex than could be established on the basis of experiments and/or natural assemblages. Coexisting sapphirine and silicate melt (with or without corundum) occur down to c. 900 °C in KFMASH, some 100 °C lower than in silica‐saturated compositions, and from pressures of c.≤1 to ≥12 kbar. Mineral compositions and composition ranges for the calculated phases are consistent with natural examples. Bulk silica has a significant effect on the stability of sapphirine‐bearing assemblages at a given P–T, resulting in a wide variety of possible granulite facies assemblages in silica‐undersaturated metapelites. Calculated pseudosections are able to reproduce many naturally occurring silica‐undersaturated assemblages, either within a single assemblage field or as the product of a P–T trajectory crossing several fields. With an understanding of the importance of bulk composition on sapphirine stability and textural development, silica‐undersaturated assemblages may be utilized in a quantitative manner in the detailed metamorphic investigation of high‐grade terranes.     

Experimental study of phase relations involving osumilite in the system K2O-FeO-MgO-Al2O3-SiO2-H2O at high pressure and temperature

Abstract Phase relations and mineral chemistry for garnet (Grt), orthopyroxene (Opx), sapphirine (Spr), water-undersaturated cordierite (Crd), osumilite (Osu), sillimanite (Sil), K-feldspar (Kfs), quartz (Qtz) and a water-undersaturated liquid (Liq) have been determined experimentally in the system KFMASH (K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O) under low P_H2O and f_O2 conditions. Four compositions have been studied with 100 [Mg/(Mg + Fe)] ranging from 65.6 to 89.7. Based on our experimental data, a P-T grid is derived for the KFMASH system in the presence of quartz, orthopyroxene and liquid. Osumilite has been found in various mineral assemblages from 950 to 1100°C and 7.5 to 11 kbar. In the temperature range 1000-1100°C, the pair Os-Grt is stable over a pressure range of about 3kbar. The divariant reaction Os + Opx = Grt + Kfs + Qtz runs to the right with increasing pressure. Because osumilite is the most magnesian phase it is restricted to Mg-rich compositions at high pressure. The reaction defining the upper pressure stability limit of Os-Grt is located around 11 kbar with a nearly flat dP/dT slope over the temperature range 950–100°C. Over the entire temperature range investigated osumilite is not stable beyond 12 kbar. The data imply a restricted pressure range between 11 and 12 kbar for the stability of the assemblage Os-Opx-Sil-Kfs-Qtz. At 1050°C and above, osumilite occurs in various mineral assemblages together with the high-T pair Spr-Qtz. When coexisting with garnet, orthopyroxene or sapphirine, osumilite is always the most magnesian phase. At 1050 and 1100°C, liquid is invariably the most Fe-rich phase in the run product. Our data support a theoretical P-T grid for the KFMAS system in which osumilite is stable outside the field of the high-T assemblage Spr-Qtz. Moreover, our grid indicates that Os-Opx-Sil-Kfs-Qtz has a more restricted pressure and compositional stability domain than Os-Grt, in agreement with natural occurrences. Osumilite is stable over a large pressure range, such that in Mg-rich rocks, and at high temperature, it can occur at any depth in normal thickness continental crust.     

Sapphirine-bearing orthopyroxene-kyanite/sillimanite granulites from South Harris, NW Scotland: evidence for Proterozoic UHT metamorphism in the Lewisian

Sapphirine-bearing orthopyroxene-kyanite (Opx-Ky) and -sillimanite (Opx-Sil) granulites have been found in the Lewisian complex of South Harris in northwest Scotland. In the Opx-Ky granulites, orthopyroxene and kyanite are intergrown in a stable mineral assemblage, which indicates metamorphic condition at 800–900 °C >12 kbar. Sillimanite inclusions within orthopyroxene suggest that sillimanite formed earlier; conditions are estimated at 950 ± 30 °C at 10 kbar from orthopyroxene isopleths for aluminous orthopyroxene (<9.7 wt%). In the Opx-Sil granulite, the orthopyroxene + sillimanite + garnet + sapphirine assemblage is stable at the peak metamorphic stages, indicating P-T condition of 930–950 °C, >8 kbar according to the FMAS petrogenetic grid, and similar conditions were obtained by using orthopyroxene-garnet geothermobarometers. The two types of orthopyroxene-aluminosilicate granulites indicate that the peak metamorphic conditions were over 900 °C, compatible with ultra-high temperature metamorphism. As accessory sapphirine occurs in several assemblages and with different compositions; it is interpreted to be formed at different stages of the metamorphism. These granulites were formed during Early Proterozoic high-grade metamorphism due to the emplacement of the South Harris Igneous Complex at c. 2170–1870 Ma, and are not related to the major metamorphic episode of the Badcallian/Inverian metamorphism at c. 2700–2500 Ma in the mainland Lewisian. Received: 17 July 1998 / Accepted 8 March 1999     

Stability of sapphirine + quartz in the oxidized rocks of the Wilson Lake terrane,Labrador: calculated equilibria in NCKFMASHTO

The equilibrium coexistence of sapphirine + quartz is inferred to record temperatures in excess of 980 °C, based on the stability of this assemblage in the simplified chemical system FeO–MgO–Al₂O₃–SiO₂ (FMAS) system. However, the potential for sapphirine to contain significant Fe³⁺ suggests that the stability of sapphirine + quartz could extend to lower temperatures than those constrained in this ideal system. The Wilson Lake terrane in the Grenville Province of central Labrador preserves sapphirine + quartz‐bearing assemblages in highly oxidized bulk compositions, and provides an opportunity to explore the stability of sapphirine + quartz in such rock compositions within the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) chemical system. Starting with the phase equilibria in FeO–MgO–Al₂O₃–SiO₂–TiO₂–O (FMASTO), expansion into K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (KFMASHTO) allows the effect of the stability of the additional phases, biotite, K‐feldspar and melt, on the stability of sapphirine + quartz to be assessed. These phase relations are evaluated generally using P–T projections, and the ultimate extension into NCKFMASHTO is done with pseudosections. Conditions of peak metamorphism in the Wilson Lake terrane are constrained using P–T pseudosections, and the appropriate H₂O and O contents to use in the modelled compositions are investigated using T–M_H2O and T–M_O pseudosections. The peak P–T estimates from a sapphirine + quartz‐bearing sample are ～960 to 935 °C at ～10 to 8.6 kbar, similar to estimates from orthopyroxene + sillimanite + quartz ± garnet‐bearing samples. Whereas the sapphirine + quartz‐bearing sample is more Fe‐rich than the orthopyroxene + sillimanite‐bearing sample on an all‐Fe‐as‐FeO basis, once the oxidation state is taken into account, the former is effectively more magnesian than the latter, accounting for the sapphirine occurrence.     

Calculated phase equilibria in K2O-FeO-MgO-Al2O3-SiO2-H2O for sapphirine-quartz-bearing mineral assemblages

Sapphirine, coexisting with quartz, is an indicator mineral for ultrahigh‐temperature metamorphism in aluminous rock compositions. Here a new activity‐composition model for sapphirine is combined with the internally consistent thermodynamic dataset used by THERMOCALC, for calculations primarily in K₂O‐FeO‐MgO‐Al₂O₃‐SiO₂‐H₂O (KFMASH). A discrepancy between published experimentally derived FMAS grids and our calculations is understood with reference to H₂O. Published FMAS grids effectively represent constant a_H2O sections, thereby limiting their detailed use for the interpretation of mineral reaction textures in compositions with differing H₂O. For the calculated KFMASH univariant reaction grid, sapphirine + quartz assemblages occur at P–T in excess of 6–7 kbar and 1005 °C. Sapphirine compositions and composition ranges are consistent with natural examples. However, as many univariant equilibria are typically not ‘seen’ by a specific bulk composition, the univariant reaction grid may reveal little about the detailed topology of multi‐variant equilibria, and therefore is of limited use for interpreting the P–T evolution of mineral assemblages and reaction sequences. Calculated pseudosections, which quantify bulk composition and multi‐variant equilibria, predict experimentally determined KFMASH mineral assemblages with consistent topology, and also indicate that sapphirine stabilizes at increasingly higher pressure and temperature as X_Mg increases. Although coexisting sapphirine and quartz can occur in relatively iron‐rich rocks if the bulk chemistry is sufficiently aluminous, the P–T window of stability shrinks with decreasing X_Mg. An array of mineral assemblages and mineral reaction sequences from natural sapphirine + quartz and other rocks from Enderby Land, Antarctica, are reproducible with calculated pseudosections. That consistent phase diagram calculations involving sapphirine can be performed allows for a more thorough assessment of the metamorphic evolution of high‐temperature granulite facies terranes than was previously possible. The establishment of a a‐x model for sapphirine provides the basis for expansion to larger, more geologically realistic chemical systems (e.g. involving Fe³⁺).     

The upper thermal stability of chlorite + quartz: an experimental study in the system MgO-Al2O3-SiO2-H2O

Experiments up to water pressures of 21 kbar have been undertaken to bracket the reactions chlorite + quartz = talc + kyanite + H₂O, chlorite + quartz = talc + cordierite + H₂O, and talc + kyanite + quartz = cordierite ± H₂O by reversed runs in the system MgO-Al₂O₃-SiO₂-H₂O (MASH). These reaction curves intersect at an invariant point (IP1) at PH₂O = 6.4 ± 0.2 kbar and a temperature of 624 ± 4°C. The curve of the chlorite + quartz breakdown to talc + kyanite + H₂O at water pressures above 6.4 kbar shows a negative dP/dT, with the slope decreasing with rising pressure, whereas the slope of the breakdown curve to talc + cordierite + H₂O at water pressures is clearly positive. The composition of the chlorite solid solution reacting with quartz has been estimated to be approximately Mg_4.85Al_1.15[Al_1.15Si_2.85O₁₀](OH)₈ over the entire pressure range investigated. The composition of the talc solid solution forming by the breakdown of chlorite + quartz appears to be Mg_2.94Al_0.06[Al_0.06Si_3.94O₁₀](OH)₂ at PH₂O = 2kbar. With increasing pressure, the Al content of talc decreases, reaching a value of about 0.06 atoms per formula unit at P,H₂O = 21 kbar. As a consequence of the new experimental data, the existing phase topologies of the MASH-system and K₂O-MASH-system have been revised. For example, the invariant point IP1 and the univariant reaction curve kyanite + talc + H₂O = chlorite + cordierite are stable. For this reason, the development of medium- to high-temperature metamorphic rocks compositionally approximating the MASH-system must be reconsidered. The whiteschists from Sar e Sang, Afghanistan, are treated as an example. The application of the present experimental data to metamorphic rocks of more normal composition requires the examination of the influence of further components. This leads to the conclusion that the introduction of Fe²⁺ into magnesian chlorite extends its stability field in the presence of quartz by 10°-15°C in comparison with pure Mg-chlorite.     

Franciscan eclogite revisited: Reevaluation of the P–T evolution of tectonic blocks from Tiburon Peninsula, California, U.S.A.

Summary High-grade blocks in the Franciscan complex at Tiburon, California, record relatively low temperature eclogite-facies metamorphism and blueschist-facies overprinting. The eclogite-facies mineral assemblage contains prograde-zoned garnet + omphacite + epidote ± hornblende (katophoritic and barroisitic Ca–Na amphibole) ± glaucophane + phengite (∼3.5 Si p.f.u.) ± paragonite + rutile + quartz. The blueschist-facies mineral assemblage contains chlorite + titanite + glaucophane + epidote ± albite ± phengite (∼3.3 Si p.f.u.). Albite is not stable in the eclogite stage. New calculations based on garnet-omphacite-phengite thermobarometry and THERMOCALC average-P–T calculations yield peak eclogite-facies P–T conditions of P = 2.2–2.5 GPa and T = 550–620 °C; porphyroclastic omphacite with inclusions of garnet and paragonite yields an average-P–T of 1.8 ± 0.2 GPa at 490 ± 70 °C for the pre-peak stage. The inferred counterclockwise hairpin P–T trajectory suggests prograde eclogitization of a relatively “cold” subducting slab, and subsequent exhumation and blueschist-facies recrystallization by a decreasing geotherm. Although an epidote-garnet amphibolitic assemblage is ubiquitous in some blocks, P–T pseudosection analyses imply that the epidote-garnet amphibolitic assemblage is stable during prograde eclogite-facies metamorphism. Available geochronologic data combined with our new insight for the maximum pressure suggest an average exhumation rate of ∼5 km/Ma, as rapid as those of some ultrahigh pressure metamorphic terranes.     

Al zoning in orthopyroxene in a sapphirine quartzite: evidence for >1120 °C UHT metamorphism in the Napier Complex, Antarctica, and implications for the entropy of sapphirine

A unique sapphirine + orthopyroxene + quartz granulite from Mt. Riiser-Larsen in the Tula Mountains of Enderby Land, East Antarctica, preserves two generations of coarse and texturally equilibrated orthopyroxene and sapphirine coexisting with quartz. Initial subhedral orthopyroxene porphyroblasts retain core compositions enriched in Al₂O₃ (12.2 ± 0.5 wt%) compared with their rims and finer orthopyroxene (9.6 ± 0.5 wt% Al₂O₃) that forms granoblastic textures with sapphirine. Sapphirine and quartz also form symplectites on and along cleavage planes within orthopyroxene. These compositional and textural features are consistent with the reaction [2MgAl₂SiO₆=Mg₂Al₄ SiO₁₀ + SiO₂] leading to the formation of sapphirine + quartz at the expense of aluminous orthopyroxene. Calculations in the MAS and FMAS systems and theoretical considerations involving the phases enstatite, sapphirine, sillimanite, quartz and cordierite indicate that the reaction above progresses from left to right with decreasing temperature in the orthopyroxene + sapphirine + quartz field, at pressures of ca. 8–10 kbar. The temperature difference required to account for the ca. 2.5–3 wt% decrease in Al₂O₃ in orthopyroxene is at least 60–80 °C, and implies peak temperatures for the initial assemblage of at least 1120 °C if the second granoblastic assemblage equilibrated at 1040 °C, the P–T conditions required by the sapphirine + quartz association and other P–T-sensitive assemblage indicators in the Napier Complex. It is not possible to distinguish whether the two assemblages are simply related by cooling and re-equilibration or reflect a polyphase evolution involving the superposition of a second UHT event on an earlier, even higher temperature, UHT metamorphism. Preliminary thermodynamic modelling of the reaction above incorporating the observed range in orthopyroxene Al₂O₃ zoning indicates that present estimates for the entropy of high-temperature sapphirine are potentially too high by 15–18% compared with sapphirine entropy estimates that are consistent with MAS system experiments. The Mt. Riiser-Larsen sapphirine–quartz rocks preserve the first definitive record of regional metamorphic temperatures in excess of 1120 °C in the Napier Complex, or indeed any UHT granulite terrain worldwide. Similarly high peak temperatures may be retrieved from detailed studies of sapphirine–quartz granulites from other regions, further expanding the thermal realm of crustal metamorphism, but progress will critically depend on the experimental acquisition of new entropy data for sapphirine. Received: 3 September 1998 / Accepted: 8 November 1999     

Prograde and retrograde history of the Junction School eclogite,California, and an evaluation of garnet–phengite–clinopyroxene thermobarometry

Quantitative thermobarometry of inclusions in zoned garnet from a Franciscan eclogite block record a counter-clockwise P–T path from blueschist to eclogite and back. Garnet retains prograde zoning from inclusion-rich Alm₅₂Grs₃₀Pyp₆Sps₁₂ cores to inclusion-poor Alm₆₂Grs₂₅Pyp₁₂Sps₁ mantles, with overgrowths of highly variable composition. Barometry using the Waters–Martin version of the garnet–phengite–omphacite thermobarometer yields conditions of 7–15 kbar, 400–500°C (garnet cores), 18–22 kbar, ∼550°C (mantles), and 10–14 kbar, 350–450°C (overgrowths), in agreement with clinozoisite–sphene–rutile–garnet–quartz barometry. These pressures are ∼10–15 kbar less than those obtained using more recent, fully thermodynamic calibrations of the phengite–omphacite–garnet thermobarometer. Low early temperatures suggest that the block was subducted in a thermally mature subduction zone and not at the inception of subduction when prograde temperature is expected to be higher. Franciscan high-grade blocks likely represent crust subducted throughout the history of this convergent margin, rather than only at the inception of the subduction zone.     

A multi-stage pressure—temperature record in the Chilka Lake granulites: the epitome of the metamorphic evolution of Eastern Ghats,India?

Abstract Metapelitic and charnockitic granulites exposed around Chilka Lake in the northern sector of the Eastern Ghats, India, preserve a multi-stage P—T record. A high-T decompression from above 10 kbar to 8 kbar around 1100°C has been determined from Mg-rich metapelites (X_Mg>0.60) with quartz-cordierite-orthopyroxene-sillimanite and cordierite—orthopyroxene—sapphirine—spinel assemblages. Between this and a second decompression to 6.0 kbar, isobaric cooling from 830 to 670°C at 8 kbar is evident. These changes are registered by the rim compositions of orthopyroxene and garnet in charnockites and metapelites with an orthopyroxene—quartz—garnet—plagioclase—cordierite assemblage, and are further supported by the garnet + quartz ± orthopyroxene + cordierite and biotite-producing reactions in sapphirine-bearing metapelites. Another indication of isobaric cooling from 800 to 650°C at 6.0 kbar is evident from rim compositions of orthopyroxene and garnet in patchy charnockites. Two sets of P—T values are obtained from metapelites with a quartz—plagioclase—garnet—sillimanite—cordierite assemblage: garnet and plagioclase cores yield 6.2 kbar, 700°C and the rims 5 kbar, 650°C, suggesting a third decompression. The earliest deformation (F1) structures are preserved in the larger charnockite bodies and the metapelites which retain the high P—T record. The effects of post-crystalline F2 deformation are observed in garnet megacrysts formed during or prior to F1 in some metapelites. Fold styles indicate a compressional regime during F1 and an extensional regime during F2. These lines of evidence and two phases of cooling at different pressures point to a discontinuity after the first cooling, and imply reworking. Two segments of the present P—T path replicate parts of the P—T paths suggested for four other granulite terranes in the Eastern Ghats, and the sense of all the paths is the same. This, plus the signature of three phases of deformation identified in the Eastern Ghats, suggests that the Chilka Lake granulites could epitomize the metamorphic evolution of the Eastern Ghats.     

The stability of sapphirine + quartz: calculated phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O

The presence in rocks of coexisting sapphirine + quartz has been widely used to diagnose conditions of ultra‐high‐temperature (UHT) metamorphism (>900 °C), an inference based on the restriction of this assemblage to temperatures >980 °C in the conventionally considered FeO–MgO–Al₂O₃–SiO₂ (FMAS) chemical system. With a new thermodynamic model for sapphirine that includes Fe₂O₃, phase equilibra modelling using thermocalc software has been undertaken in the FeO–MgO–Al₂O₃–SiO₂–O (FMASO) and FeO–MgO–Al₂O₃–SiO₂– TiO₂–O (FMASTO) chemical systems. Using a variety of calculated phase diagrams for quartz‐saturated systems, the effects of Fe₂O₃ and TiO₂ on FMAS phase relations are shown to be considerable. Importantly, the stability field of sapphirine + quartz assemblages extends down temperature to 850 °C in oxidized systems and thus out of the UHT range.     

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.     

Dehydration melting of tonalites. Part I. Beginning of melting

 The beginning of dehydration melting in the tonalite system (biotite-plagioclase-quartz) is investigated in the pressure range of 2–12 kbar. A special method consisting of surrounding a crystal of natural plagioclase (An₄₅) with a biotite-quartz mixture, and observing reactions at the plagioclase margin was employed for precise determination of the solidus for dehydration melting. The beginning of dehydration melting was worked out at 5 kbar for a range of compositions of biotite varying from iron-free phlogopite to iron-rich Ann₇₀, with and without titanium, fluorine and extra aluminium in the biotite. The dehydration melting of phlogopite + plagioclase (An₄₅) + quartz begins between 750 and 770°C at pressures of 2 and 5 kbar, at approximately 740°C at 8 kbar and between 700 and 730°C at 10 kbar. At 12 kbar, the first melts are observed at temperatures as low as 700°C. The data indicate an almost vertical dehydration melting solidus curve at low pressures which bends backward to lower temperatures at higher pressures (> 5 kbar). The new phases observed at pressures ≤ 10 kbar are melt + enstatite + clinopyroxene + potassium feldspar ± amphibole. In addition to these, zoisite was also observed at 12 kbar. With increasing temperature, phlogopite becomes enriched in aluminium and deficient in potassium. Substitution of octahedral magnesium by aluminium and titanium in the phlogopite, as well as substitution of hydroxyl by fluorine, have little effect on the beginning of dehydration melting temperatures in this system. The dehydration melting of biotite (Ann₅₀) + plagioclase (An₄₅) + quartz begins 50°C below that of phlogopite bearing starting composition. Solid reaction products are orthopyroxene + clinopyroxene + potassium feldspar ± amphibole. Epidote was also observed above 8 kbar, and garnet at 12 kbar (750°C). The experiments on the iron-bearing system performed at ≤ 5 kbar were buffered with NiNiO. The f _{O 2} in high pressure runs lies close to CoCoO. With the substitution of octahedral magnesium and iron by aluminium and titanium, and replacement of hydroxyl by fluorine in biotite, the beginning of dehydration melting temperatures in this system increase up to 780°C at 5 kbar, which is 70°C above the beginning of dehydration melting of the assemblage containing biotite (Ann₅₀) of ideal composition. The dehydration melting at 5 kbar in the more iron-rich Ann₇₀-bearing starting composition begins at 730°C, and in the Ann₂₅-bearing assemblage at 710°C. This indicates that quartz-biotite-plagioclase assemblages with intermediate compositions of biotite (Ann₂₅ and Ann₅₀) melt at lower temperatures as compared to those containing Fe-richer or Mg-richer biotites. This study shows that the dehydration melting of tonalites may begin at considerably lower temperatures than previously thought, especially at high pressures (>5 kbar). Received: 27 December 1995 / Accepted: 7 May 1996     

P–T–t evolution of spinel–cordierite–garnet gneisses from the Sauwald Zone (Southern Bohemian Massif, Upper Austria): is there evidence for two independent late-Variscan low-P/high-T events in the Moldanubian Unit?

The Sauwald Zone, located at the southern rim of the Bohemian Massif in Upper Austria, belongs to the Moldanubian Unit. It exposes uniform biotite + plagioclase ± cordierite paragneisses that formed during the post-collisional high-T/low-P stage of the Variscan orogeny. Rare metapelitic inlayers contain the mineral assemblage garnet + cordierite + green spinel + sillimanite + K-feldspar + plagioclase + biotite + quartz. Mineral chemical and textural data indicate four stages of mineral growth: (1) peak assemblage as inclusions in garnet (stage 1): garnet core + cordierite + green spinel + sillimanite + plagioclase (An_35–65); (2) post-peak assemblages in the matrix (stages 2, 3): cordierite + spinel (brown-green and brown) ± sillimanite ± garnet rim + plagioclase (An_10–45); and (3) late-stage growth of fibrolite, muscovite and albite (An_0–15) during stage 4. Calculation of the P–T conditions of the peak assemblage (stage 1) yields 750–840°C, 0.29–0.53 GPa and for the stage 2 matrix assemblage garnet + cordierite + green spinel + sillimanite + plagioclase 620–730°C, 0.27–0.36 GPa. The observed phase relations indicate a clockwise P–T path, which terminates below 0.38 GPa. The P–T evolution of the Sauwald Zone and the Monotonous Unit are very similar, however, monazite ages of the former are younger (321 ± 9 Ma vs. 334 ± 1 Ma). This indicates that high-T/low-P metamorphism in the Sauwald Zone was either of longer duration or there were two independent phases of late-Variscan low-P/high-T metamorphism in the Moldanubian Unit.     

Dehydration melting of tonalites. Part II. Composition of melts and solids

 Dehydration melting of tonalitic compositions (phlogopite or biotite-plagioclase-quartz assemblages) is investigated within a temperature range of 700–1000°C and pressure range of 2–15 kbar. The solid reaction products in the case of the phlogopite-plagioclase(An₄₅)-quartz starting material are enstatite, clinopyroxene and potassium feldspar, with amphiboles occurring occasionally. At 12 kbar, zoisite is observed below 800°C, and garnet at 900°C. The reaction products of dehydration melting of the biotite (Ann₅₀)-plagioclase (An₄₅)-quartz assemblage are melt, orthopyroxene, clinopyroxene, amphibole and potassium feldspar. At pressures > 8 kbar and temperatures below 800°C, epidote is also formed. Almandine-rich garnet appears above 10 kbar at temperatures ≥ 750°C. The composition of melts is granitic to granodioritic, hence showing the importance of dehydration melting of tonalites for the formation of granitic melts and granulitic restites at pressure-temperature conditions within the continental crust. The melt compositions plot close to the cotectic line dividing the liquidus surfaces between quartz and potassium feldspar in the haplogranite system at 5 kbar and a _{H 2O} = 1. The composition of the melts changes with the composition of the starting material, temperature and pressure. With increasing temperature, the melt becomes enriched in Al₂O₃ and FeO+MgO. Potash in the melt is highest just when biotite disappears. The amount of CaO decreases up to 900°C at 5 kbar whereas at higher temperatures it increases as amphibole, clinopyroxene and more An-component dissolve in the melt. The Na₂O content of the melt increases slightly with increase in temperature. The composition of the melt at temperatures > 900°C approaches that of the starting assemblage. The melt fraction varies with composition and proportion of hydrous phases in the starting composition as well as temperature and pressure. With increasing modal biotite from 20 to 30 wt%, the melt proportion increases from 19.8 to 22.3 vol.% (850°C and 5 kbar). With increasing temperature from 800 to 950°C (at 5 kbar), the increase in melt fraction is from 11 to 25.8 vol.%. The effect of pressure on the melt fraction is observed to be relatively small and the melt proportion in the same assemblage decreases at 850°C from 19.8 vol.% at 5 kbar to 15.3 vol.% at 15 kbar. Selected experiments were reversed at 2 and 5 kbar to demonstrate that near equilibrium compositions were obtained in runs of longer duration. Received: 27 December 1995 / Accepted: 7 May 1996     

Beginning of melting in the granite system Qz-Or-Ab-An-H2O

The beginning of melting in the system Qz-Or-Ab-An-H₂ O was experimentally reversed in the pressure range kbar using starting materials made up of mixtures of quartz and synthetic feldspars. With increasing pressure the melting temperature decreases from 690° C at 2 kbar to 630° C at 17 kbar in the An-free alkalifeldspar granite system Qz-Or-Ab-H₂O. In the granite system Qz-Or-Ab-An-H₂O the increase of the solidus temperature with increasing An-content is only very small. In comparison to the alkalifeldspar granite system the solidus temperature increases by 3° C (7° C) if albite is replaced by plagioclase An 20 (An 40). The difference between the solidus temperatures of the alkalifeldspar granite system and of quartz — anorthite — sanidine assemblages (system Qz-Or-An-H₂O) is approximately 50° C. With increasing water pressures plagioclase and plagioclase-alkalifeldspar assemblages become unstable and are replaced by zoisite+kyanite+quartz and zoisite+muscovite-paragonite_ss +quartz, respectively. The pressure stability limits of these assemblages are found to lie between 6 and 16 kbar at 600° C. At high water pressures (10–18 kbar) zoisite — muscovite — quartz assemblages are stable up to 700 and 720° C. The solidus curve of this assemblage is 10–20° C above the beginning of melting of sanidine — zoisite — muscovite — quartz mixtures. The amount of water necessary to produce sufficient amounts of melt to change a metamorphic rock into a magmatic looking one is only small. In case of layered migmatites it is shown that 1 % of water (or even less) is sufficient to transform portions of a gneiss into (magmatic looking) leucosomes. High grade metamorphic rocks were probably relatively dry, and anatectic magmas of granitic or granodioritic composition are usually not saturated with water.     

Kornerupine parageneses in whiteschists and other magnesian rocks: is kornerupine + talc a high-pressure assemblage equivalent to tourmaline + orthoamphibole?

Kornerupine, (□,Fe,Mg)(Mg,Fe,Al)₉(Si,Al,B)₅ (O,OH,F)₂₂, has been reported with talc in rocks from six localities worldwide, but only at Chilapila Hill in the Lufilian Arc, Zambia do textural relationships imply that kornerupine (Krn) equilibrated with talc (Tlc) during a prograde metamorphic event at T≈ 640 °C, P≈ 13 kbar; a prograde Krn + Tlc assemblage has also been reported from Mautia Hill, Tanzania (P ≤ 13 kbar). In order to estimate possible constraints on the stability range for the kornerupine + talc paragenesis in nature, we constructed a P-T diagram in the model system MgO-Al₂O₃-SiO₂-H₂O (MASH) for seven phases quartz (Qtz), B-free kornerupine sensu stricto, anthophyllite (Ath), chlorite (Chl), cordierite (Crd), kyanite (Ky), and talc. The minimum pressure for Krn + Tlc + Ky stability in MASH is close to that for Ky + Tlc stability, i.e., 6–8 kbar, at T≤ 780 °C. However, in the natural system, B₂O₃ and Na₂O are major constituents in Krn and orthoamphibole (Oam), respectively, and dravitic tourmaline (Tur) is widespread. The critical assemblage alternative to Krn + Tlc in nature is Tur + Oam. The upper pressure limit of Tur + Ath is determined by the upper pressure for anthophyllite: 7.7–10.5 kbar at 682–794 °C in the MgO-SiO₂-H₂O system (Chernosky et al. 1985, Am Mineral 70:223–236), and is undoubtedly higher in the presence of Na₂O, CaO, and Al₂O₃. At three of the six localities, talc is a retrograde phase; nonetheless, it possibly equilibrated with kornerupine on the retrograde path or during a later metamorphic event at P-T conditions appropriate for Ky + Tlc. At the sixth locality (Mulvoj, southwestern Pamir Mountains, Tajikistan), Krn is found in the same thin section as talc and kyanite and all three minerals formed during a prograde metamorphic event at T≥ 650 °C, P near 7 kbar. However, Krn is restricted to a lens 4 to 6 mm thick of phlogopite + anthophyllite + Tur and it does not touch either talc or kyanite. A reaction relating the Mulvoj and Chilapila Hill (Krn + Tlc + Ky + Qtz + Tur) parageneses is calculated from compositions in the Mulvoj rock to be 0.40Tur + 2.55Ath + 1.33H₂O + 0.27F = Krn + 2.16Tlc + 0.36B₂O₃ + 0.02Rutile + 0.19Na₂O + 0.17CaO. Given the difference in metamorphic pressures estimated for Mulvoj and Chilapila Hill, Krn + Tlc is inferred to be favored by increasing pressure as well as by low Na₂O and CaO contents. Some FeO, F, Fe₂O₃, and BeO are present in measurable amounts in at least one of the phases in the Mulvoj and Chilapila Hill whiteschists (e.g., Krn contains 0.24–0.67 wt% BeO), but the effect of these constituents is subordinate to that of Na₂O, CaO and B₂O₃. The Krn + Tlc could be a more important assemblage in B-bearing whiteschists than has been reported to date, particularly at pressures where orthoamphibole is no longer stable. Received: 21 April 1997 / Accepted: 13 October 1997     

Geothermobarometry of a stilpnomelane–garnet-bearing metapegmatite: P–T constraints on the Eo-Alpine metamorphic overprint of the Austroalpine nappes north of the Tauern Window

The Ordovician Kellerjochgneiss (Schwaz Augengneiss) is a polymetamorphic orthogneiss-bearing unit and is part of the Austroalpine basement nappes north of the Tauern Window. Within the Kellerjochgneiss a small, strongly deformed metapegmatite dike occurs. The pegmatite crosscuts the gneiss discordantly and contains the mineral assemblage muscovite 1,2+plagioclase+K-feldspar+chlorite+quartz+garnet 1 (Alm_67–76Andr_0.9–2Sps_17–28Prp_0.4–5)+garnet 2 (Grs_36–46Alm_24–32Andr_8–21Sps_15–17Prp_0–1)±stilpnomelane±biotite±clinozoisite. The magmatic protolith assemblage is comprised of relict K-feldspar, quartz and garnet 1. Textural observations indicate that biotite and muscovite cores (muscovite 1) are either part of the magmatic- or an earlier (Variscan?) metamorphic assemblage. Geothermobarometry of the metapegmatite was done on the latest-stage (Eo-Alpine) mineral assemblage garnet 2+muscovite 2+chlorite+stilpnomelane+plagioclase+quartz. Calculations of H₂O-absent intersections in the system [KCNFMAS] with the multi-equilibrium program THERMOCALC v.3.1 yielded P–T estimates of 4.4 to 6.7 kbar and 321°C to 376°C. Calculations of the P–T conditions by using the assemblage muscovite 2+chlorite+stilpnomelane+quartz yielded slightly higher pressures of 6.4 to 7.2 kbar at temperatures of 310–325°C. Correlating these P–T data with geochronological data from the neighbouring lithologies (Kellerjochgneiss, Innsbruck Quartzphyllite, Wildschönau Schists) and with structural investigations from these units indicate that the P–T estimates obtained in this investigation represent the Eo-Alpine metamorphic overprint. Hence, these unusual rocks provide important information on the Eo-Alpine P–T conditions since most samples studied from the investigated Austroalpine basement nappes north of the Tauern Window rarely contain mineral assemblages suitable for geothermobarometry.