A new formulation of garnet–clinopyroxene geothermometer based on accumulation and statistical analysis of a large experimental data set

Published experimental data including garnet and clinopyroxene as run products were used to develop a new formulation of the garnet–clinopyroxene geothermometer based on 333 garnet–clinopyroxene pairs. Only experiments with graphite capsules were selected because of difficulty in estimating the Fe³⁺ content of clinopyroxene. For the calibration, a published subregular‐solution model was adopted to express the non‐ideality of garnet. The magnitude of the Fe–Mg excess interaction parameter for clinopyroxene (W_FeMg^Cpx), and differences in enthalpy and entropy of the Fe–Mg exchange reaction were regressed from the accumulated experimental data set. As a result, a markedly negative value was obtained for the Fe–Mg excess interaction parameter of clinopyroxene (W_FeMg^Cpx = ? 3843 J mol^?1). The pressure correction is simply treated as linear, and the difference in volume of the Fe–Mg exchange reaction was calculated from a published thermodynamic data set and fixed to be ?120.72 (J kbar^?1 mol^?1). The regressed and obtained thermometer formulation is as follows: where T = temperature, P = pressure (kbar), A = 0.5 X_grs (X_prp ? X_alm ? X_sps), B = 0.5 X_grs (X_prp ? X_alm + X_sps), C = 0.5 (X_grs + X_sps) (X_prp ? X_alm), X_prp = Mg/(Fe²⁺ + Mn + Mg + Ca)^Grt, X_alm = Fe/(Fe²⁺ + Mn + Mg + Ca)^Grt, X_sps = Mn/(Fe²⁺ + Mn + Mg + Ca)^Grt, X_grs = Ca/(Fe²⁺ + Mn + Mg + Ca)^Grt, X_Mg^Cpx = Mg/(Al + Fe^total + Mg)^Cpx, X_Fe^Cpx = Fe²⁺/(Al + Fe^total + Mg)^Cpx, K_D = (Fe²⁺/Mg)^Grt/(Fe²⁺/Mg)^Cpx, Grt = garnet, Cpx = clinopyroxene. A test of this new formulation to the accumulated data gave results that are concordant with the experimental temperatures over the whole range of the experimental temperatures (800–1820 °C), with a standard deviation (1 sigma) of 74 °C. Previous formulations of the thermometer are inconsistent with the accumulated data set; they underestimate temperatures by about 100 °C at >1300 °C and overestimate by 100–200 °C at <1300 °C. In addition, they tend to overestimate temperatures for high‐Ca garnet (X_grs ≈ 0.30–0.50). This new formulation has been tested against previous formulations of the thermometer by application to natural eclogites. This gave temperatures some 20–100 °C lower than previous formulations.     

Metamorphic textures and P–T evolution of high-P granulites from the Lelukuau terrane, NE Grenville Province

High‐pressure (HP) granulites and eclogitized metagabbro are exposed along an orogen‐parallel high‐P belt that was developed at c. 1050–1020 Ma in the NE Grenville Province. Among these rocks, mafic granulites derived from a Labradorian anorthosite suite of the Lelukuau terrane contain garnet, Al‐Na diopside, and, depending on bulk composition, plagioclase and kyanite. Moreover, the distribution of phases is influenced by the original igneous texture. For instance, in high X_MgO leucocratic varieties, garnet porphyroblasts nucleated together with kyanite in An‐rich cores of plagioclase domains whereas in low X_MgO rocks garnet occurs together with clinopyroxene within formerly igneous ferromagnesian domains and kyanite is missing. In contrast, garnet pseudomorphs after igneous plagioclase in melanocratic varieties display evidence of earlier corona development. Metamorphic textures are consistent with a two stage evolution: (a) development of garnet and Al‐Na‐diopside (Cpx₁) under high‐P metamorphic conditions, concomitant with elimination of plagioclase in the mesocratic to melanocratic varieties; and (b) partial loss of Al‐Na from Cpx₁ resulting in production of new andesitic plagioclase, and growth of new clinopyroxene (Cpx₂) after garnet and quartz in leucocratic to mesocratic rocks consistent with decompression. Widespread equilibrium textures between garnet‐Pl₂‐Cpx₂ and/or reset Cpx₁ are consistent with development at the thermal peak. Estimated P–T conditions for the presumed thermal peak fall in the range 1500–1800 MPa and 800–900 °C and are comparable to those recorded by eclogitized gabbros from other parts of the high‐P belt of the NE Grenville province. Low jadeite content of clinopyroxene from the HP granulites is attributed to the low bulk Na₂O/(Na₂O + CaO) of these rocks relative to common basaltic compositions. Scarcity of apparent retrograde textural overprint in both the HP granulites and the eclogites suggests fast subsequent cooling, consistent with extrusion of the high‐P belt towards the foreland shortly after the metamorphic peak.     

Biotite and garnet compositional variation and mineral equilibria in Grenville gneisses of the Otter Lake area, Quebec

Garnet-biotite gneisses, some of which contain sillimanite or hornblende, are widespread within the Otter Lake terrain, a portion of the Grenville Province of the Canadian Shield. The metamorphic grade is upper amphibolite to, locally, lower granulite facies. The atomic ratio Fe²⁺/(Fe²⁺+ Fe³⁺) in biotite ranges from 0.79 to 0.89 (ferrous iron determinations in 10 highly pure separates), with a mean of 0.86. Mg and Fe²⁺ atoms occupy 67–78% of the octahedral sites, the remainder are occupied by Fe³⁺, Ti, and Al, and some are vacant. Mg/(Mg + Fe²⁺), denoted X, in the analysed samples ranges from 0.32 to 0.65. Garnet contains 1–24% grossular, 1–12% spessartine and X ranges from 0.07 to 0.34. Compositional variation in biotite and garnet is examined in relation to three mineral equilibria: (I) biotite + sillimanite + quartz = garnet + K-feldspar + H₂O; (II) pyrope + annite = almandine + phlogopite; (III) anorthite = grossular + sillimanite + quartz. Measurements of X (biotite) and X (garnet) are used to construct an illustrative model for equilibrium (I) which relates the observed variation in X to a temperature range of 70°C or a range in H₂O activity of 0.6; the latter interpretation is preferred. In sillimanite-free gneisses, the distribution of Mg and Fe²⁺ between garnet (low in Ca and Mn) and biotite is adequately described by a distribution coefficient (KD) of 4.1 (equilibrium II). The observed increase in the distribution coefficient with increasing Ca in garnet is ln K_D= 1.3 + 2.5 × 10^?2 [Ca] where [Ca] = 100 Ca/(Mg + Fe²⁺+ Mn + Ca). The distribution coefficient is apparently unaffected by the presence of up to 12% spessartine in garnet. In several specimens of garnet-sillimanite-plagioclase gneiss, the Ca contents of garnet and of plagioclase increase in unison, as required by equilibrium (III). The mean pressure calculated from these data (n= 17) is 5.9 kbar, and the 95% confidence limits are ±0.5 kbar.     

Constraining the P–T path of a MORB-type eclogite using pseudosections, garnet zoning and garnet-clinopyroxene thermometry: an example from the Bohemian Massif

A mid‐ocean ridge basalt (MORB)‐type eclogite from the Moldanubian domain in the Bohemian Massif retains evidence of its prograde path in the form of inclusions of hornblende, plagioclase, clinopyroxene, titanite, ilmenite and rutile preserved in zoned garnet. Prograde zoning involves a flat grossular core followed by a grossular spike and decrease at the rim, whereas Fe/(Fe + Mg) is also flat in the core and then decreases at the rim. In a pseudosection for H₂O‐saturated conditions, garnet with such a zoning grows along an isothermal burial path at c. 750 °C from 10 kbar in the assemblage plagioclase‐hornblende‐diopsidic clinopyroxene‐quartz, then in hornblende‐diopsidic clinopyroxene‐quartz, and ends its growth at 17–18 kbar. From this point, there is no pseudosection‐based information on further increase in pressure or temperature. Then, with garnet‐clinopyroxene thermometry, the focus is on the dependence on, and the uncertainties stemming from the unknown Fe³⁺ content in clinopyroxene. Assuming no Fe³⁺ in the clinopyroxene gives a serious and unwarranted upward bias to calculated temperatures. A Fe³⁺‐contributed uncertainty of ±40 °C combined with a calibration and other uncertainties gives a peak temperature of 760 ± 90 °C at 18 kbar, consistent with no further heating following burial to eclogite facies conditions. Further pseudosection modelling suggests that decompression to c. 12 kbar occurred essentially isothermally from the metamorphic peak under H₂O‐undersaturated conditions (c. 1.3 mol.% H₂O) that allowed the preservation of the majority of garnet with symplectitic as well as relict clinopyroxene. The modelling also shows that a MORB‐type eclogite decompressed to c. 8 kbar ends as an amphibolite if it is H₂O saturated, but if it is H₂O‐undersaturated it contains assemblages with orthopyroxene. Increasing H₂O undersaturation causes an earlier transition to SiO₂ undersaturation on decompression, leading to the appearance of spinel‐bearing assemblages. Granulite facies‐looking overprints of eclogites may develop at amphibolite facies conditions.     

Oriented inclusions of pyroxene,amphibole and rutile in garnet from the Lüliangshan garnet peridotite massif,North Qaidam UHPM belt,NW China: an electron backscatter diffraction study

Oriented inclusions of clinopyroxene, orthopyroxene, sodic amphibole and rutile have been identified in garnet from the Lüliangshan garnet peridotite massif in the North Qaidam ultrahigh‐pressure metamorphic (UHPM) belt, northern Tibetan Plateau, NW China. Electron backscatter diffraction (EBSD) analyses demonstrate that nearly half of the measured intracrystalline clinopyroxene (8 out of 17) have topotactic crystallographic relationships with host garnet, that is, (100)_Cpx//{112}_Grt, (010)_Cpx//{110}_Grt and [001]_Cpx//<111>_Grt. One‐fifth of the oriented sodic amphibole (23 out of 110) inclusions of have topotactic crystallographic relationships with host garnet, that is, (010)_Amp//{112}_Grt, (100)_Amp//{110}_Grt and [001]_Amp//<111>_Grt. Over a third of rutile (36 out of 99) inclusions also show a close crystallographic orientation relationship with host garnet in that one <103>_Rt and one <110>_Rt parallel to two <111>_Grt while the axes of [001]_Rt exhibit small girdles centred the axes of <111>_Grt. But, no ‘well‐fit’ crystallographic relationship was observed between orthopyroxene inclusions and host garnet. Considering a very long and complex history for the Lüliangshan garnet peridotite, we suggest that the low fit rates for these oriented minerals may result from several possible assumptions including different generations or multi‐stage formation mechanisms, heterogeneous nucleation and growth under non‐equilibrium conditions, and partial changes of initial crystallographic orientations of some inclusions. However, the residual quantitative ‘well‐fit’ crystallographic information is sufficient to indicate that the nucleation and growth of many pyroxene, amphibole and rutile are controlled by the lattice of the host garnet. The revealed close topotactic relationships accompanied by clear shape orientations provide quantitative microstructural evidence demonstrating a most likely exsolution/precipitate origin for at least some of the oriented phases of pyroxene, sodic amphibole and rutile from former majoritic garnet and support an ultra‐deep (>180 km depth) origin of the Lüliangshan garnet massif.     

密云杂岩西段等压冷却P－T－t轨迹确定及地球动力学成因

非平衡结构代表的变质反应性质和多种矿物地质温压计的研究表明,北京太古宙密云杂岩西段第二期区域变质作用的退变质P-T轨迹具等压冷却特点。Sm-Nd同位素定年显示,区内广泛发育的石榴石冠状体形成于(1717±34)Ma.初步分析认为,P-T-t轨迹的地球动力学成因可与吕梁运动期间华北地台裂谷作用和同构造壳下岩浆增生的演化背景相联系。     

Assessment of the Garnet-Clinopyroxene Thermometer

A thermometer based on the MgFe_?1 exchange equilibrium between garnet and clinopyroxene is formulated by using new experimental data measured at 600° to 950°C, 0.8 to 3.0 GPa, and f(O₂) defined by the fayalite-quartz-magnetite buffer in the basalt-H₂O system. The new formulation is T = 3820 / 1.828 + lnK_D (1 + a(2.2 ? p)), where T is temperature (K), P is pressure (GPa), KD is the Fe-Mg partition coefficient between garnet and clino-pyroxene, defined as KD = (Fe²+/Mg)garnet/(Fe²+/Mg) clinopyroxene, and a = 132/T. Application of the thermometer to rocks in amphibolite, granulite, and eclogite terranes yields temperatures that are in reasonable agreement with other well-calibrated thermometers and the experimental calibrations by Ellis and Green (1979) and Pattison and Newton (1989).     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part II: δ13C Matrix Effects

This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe²⁺ substitution on SIMS δ¹⁸O bias measured from the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂], whereas this complementary work explores the compositional dependence of SIMS δ¹³C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ¹³C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).     

Constraining peak P–T conditions in UHP eclogites: calculated phase equilibria in kyanite‐ and phengite‐bearing eclogite of the Tromsø Nappe,Norway

Kyanite‐ and phengite‐bearing eclogites have better potential to constrain the peak metamorphic P–T conditions from phase equilibria between garnet + omphacite + kyanite + phengite + quartz/coesite than common, mostly bimineralic (garnet + omphacite) eclogites, as exemplified by this study. Textural relationships, conventional geothermobarometry and thermodynamic modelling have been used to constrain the metamorphic evolution of the Tromsdalstind eclogite from the Tromsø Nappe, one of the biggest exposures of eclogite in the Scandinavian Caledonides. The phase relationships demonstrate that the rock progressively dehydrated, resulting in breakdown of amphibole and zoisite at increasing pressure. The peak‐pressure mineral assemblage was garnet + omphacite + kyanite + phengite + coesite, inferred from polycrystalline quartz included in radially fractured omphacite. This omphacite, with up to 37 mol.% of jadeite and 3% of the Ca‐Eskola component, contains oriented rods of silica composition. Garnet shows higher grossular (X_Grs = 0.25–0.29), but lower pyrope‐content (X_Prp = 0. 37–0.39) in the core than the rim, while phengite contains up to 3.5 Si pfu. The compositional isopleths for garnet core, phengite and omphacite constrain the P–T conditions to 3.2–3.5 GPa and 720–800 °C, in good agreement with the results obtained from conventional geothermobarometry (3.2–3.5 GPa & 730–780 °C). Peak‐pressure assemblage is variably overprinted by symplectites of diopside + plagioclase after omphacite, biotite and plagioclase after phengite, and sapphirine + spinel + corundum + plagioclase after kyanite. Exhumation from ultrahigh‐pressure (UHP) conditions to 1.3–1.5 GPa at 740–770 °C is constrained by the garnet rim (X_Ca^Grt = 0.18–0.21) and symplectite clinopyroxene (X_Na^Cpx = 0.13–0.21), and to 0.5–0.7 GPa at 700–800 °C by sapphirine (X_Mg = 0.86–0.87) and spinel (X_Mg = 0.60–0.62) compositional isopleths. UHP metamorphism in the Tromsø Nappe is more widespread than previously known. Available data suggest that UHP eclogites were uplifted to lower crustal levels rapidly, within a short time interval (452–449 Ma) prior to the Scandian collision between Laurentia and Baltica. The Tromsø Nappe as the highest tectonic unit of the North Norwegian Caledonides is considered to be of Laurentian origin and UHP metamorphism could have resulted from subduction along the Laurentian continental margin. An alternative is that the Tromsø Nappe belonged to a continental margin of Baltica, which had already been subducted before the terminal Scandian collision, and was emplaced as an out‐of‐sequence thrust during the Scandian lateral transport of nappes.     

Pressure-temperature path of Sanbagawa prograde metamorphism deduced from grossular zoning of garnet

The zonal structure of prograde garnet in pelitic schists from the medium-grade garnet zone and the higher-grade albite-biotite zone was examined to investigate the evolution of prograde P–T paths of the Sanbagawa metamorphism. The garnet studied shows a bell-shaped chemical zoning of the spessartine component, which decreases in abundance from the core towards the rim. Almandine and pyrope contents and X_Mg [=Mg/(Mg+Fe²⁺)] increase monotonously outwards. The general scheme of the zonal structure for grossular content [X_Grs=Ca/(Fe²⁺+Mn+Mg+Ca)] can be summarized as: (1) X_Grs increases outwards (inner segment) and reaches a maximum at an intermediate position between the crystal core and the rim, then decreases towards the outermost rim (outer segment) (2) the inner segment of garnet in the garnet zone samples tends to have a higher X_Grs/X_Sps values for a given X_Sps than those in the albite–biotite zone samples (3) average X_Sps at the maximum X_Grs position in the albite–biotite zone samples ranges from 0.02 to 0.12 and is lower than that in the garnet zone samples (0.13–0.32) (4) the maximum X_Grs in the albite–biotite zone samples (0.34–0.39 on average) tends to be higher than that in the garnet zone samples (0.26–0.36), and (5) differences of X_Grs between the maximum and rim in the albite–biotite zone samples are between 0.10 and 0.14 and higher than those in the garnet zone samples (< 0.11). These facts imply that albite–biotite zone materials (a) were recrystallized under lower dP/dT conditions at an early stage of the prograde metamorphism (b) began their exhumation under higher P–T conditions and (c) have been continuously heated during exhumation for a longer duration than the garnet zone materials. The systematic changes of prograde P–T paths can be interpreted as documenting the evolution of the Sanbagawa subduction zone.     

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.     

The influence of Fe<Superscript>3+</Superscript> on garnet–orthopyroxene and garnet–olivine geothermometers

Applying Fe²⁺–Mg exchange geothermometers to natural samples may lead to incorrect temperature estimates if significant Fe³⁺ is present. In order to quantify this effect, high-pressure experiments were carried out in a belt apparatus in a natural system close to CFMAS at 5 GPa and 1,100–1,400 °C. The oxygen fugacity in the experiments was at or below the Re–ReO₂ buffer. This is at significantly more oxidized conditions than in previous experiments, and, as consequence, higher Fe³⁺/Fe²⁺ ratios were generated. The Fe³⁺ content of garnet in the experiments was quantified by electron microprobe using the flank method. Making the usual assumption that Fe_total = Fe²⁺, the two-pyroxene thermometer of Brey and Köhler (J Pet 31:1353–1378, 1990) reproduced the experimental temperature to ±35 °C and the garnet–clinopyroxene Fe²⁺–Mg exchange thermometer of Krogh (Contrib Miner Pet 99:44–48, 1988) overestimated the temperatures on average by only 25 °C. On the other hand, application of the garnet–olivine (O’Neill and Wood in Contrib Miner Pet 70:59–70, 1979) and garnet–orthopyroxene (Harley in Contrib Miner Pet 86:359–373, 1984) exchange geothermometers yielded an underestimation in calculated temperatures of >200 °C. However, making explicit accounting for Fe³⁺ in garnet (i.e. using only measured Fe²⁺) leads to a vast improvement in the agreement between calculated and experimental temperatures, generally to within ±70 °C for the garnet–orthopyroxene geothermometer as well as noticeable improvement of calculated temperatures for the garnet–olivine geothermometer. Our results demonstrate that the two-pyroxene and garnet–clinopyroxene thermometers are rather insensitive to the presence of Fe³⁺ whilst direct accounting of Fe³⁺ in garnet is essential when applying the garnet–olivine and garnet–orthopyroxene thermometers.     

P–T evolution and episodic zircon growth in barroisite eclogites of the Lanterman Range,northern Victoria Land,Antarctica

Prograde P–T–t paths of eclogites are often ambiguous owing to high variance of mineral assemblages, large uncertainty in isotopic age determinations and/or variable degree of retrograde equilibration. We investigated these issues using the barroisite eclogites from the Lanterman Range, northern Victoria Land, Antarctica, which are relatively uncommon but free of retrogression. These eclogites revealed three stages of prograde metamorphism, defining two distinctive P–T trajectories, M_1–2 and M₃. Inclusion minerals in garnet porphyroblasts suggest that initial prograde assemblages (M₁) consist of garnet+omphacite+barroisite/Mg‐pargasite+epidote+phengite+paragonite+rutile/titanite+quartz, and subsequent M₂ assemblages of garnet+omphacite+barroisite+phengite+rutile±quartz. The inclusion‐rich inner part of garnet porphyroblasts preserves a bell‐shaped Mn profile of the M₁, whereas the inclusion‐poor outer part (M₂) is typified by the outward decrease in Ca/Mg and X_Fe (=Fe²⁺/(Fe²⁺+Mg)) values. A pseudosection modelling employing fractionated bulk‐rock composition suggests that the eclogites have initially evolved from ~15 to 20 kbar and 520–570°C (M₁) to ~22–25 kbar and 630–650°C (M₂). The latter is in accordance with P–T conditions estimated from two independent geothermobarometers: the garnet–clinopyroxene–phengite (~25 ± 3 kbar and 660 ± 100°C) and Zr‐in‐rutile (~650–700°C at 22–27 kbar). The second segment (M_3A–B) of prograde P–T path is recorded in the grossular‐rich overgrowth rim of garnet. Apart from disequilibrium growth of the M_3A garnet, ubiquitous overgrowth of the M_3B garnet permits us to estimate the P–T conditions at ~26 ± 3 kbar and 720 ± 80°C. The cathodoluminescence (CL) imaging of zircon grains separated from a barroisite eclogite revealed three distinct zones with bright rim, dark mantle and moderately dark core. Eclogitic phases such as garnet, omphacite, epidote and rutile are present as fine‐grained inclusions in the mantle and rim of zircon, in contrast to their absence in the core. The sensitive high‐resolution ion microprobe U–Pb dating on metamorphic mantle domains and neoblasts yielded a weighted mean ²⁰⁶Pb/²³⁸U age of 515 ± 4 Ma (tσ), representing the time of the M₂ stage. On the other hand, overgrowth rims as well as bright‐CL neoblasts of zircon were dated at 498 ± 11 Ma (tσ), corresponding to the M₃. Average burial rates estimated from the M₂ and M₃ ages are too low (<2 mm/year) for cold subduction regime (~5–10°C/km), suggesting that an exhumation stage intervened between two prograde segments of P–T path. Thus, the P–T–t evolution of barroisite eclogites is typified by two discrete episodes with an c. 15 Ma gap during the middle Cambrian subduction of the Antarctic Ross Orogeny.     

Internally consistent geothermometers for garnet peridotites and pyroxenites

Mutual relationships among temperatures estimated with the most widely used geothermometers for garnet peridotites and pyroxenites demonstrate that the methods are not internally consistent and may diverge by over 200°C even in well-equilibrated mantle xenoliths. The Taylor (N Jb Min Abh 172:381–408, 1998) two-pyroxene (TA98) and the Nimis and Taylor (Contrib Mineral Petrol 139:541–554, 2000) single-clinopyroxene thermometers are shown to provide the most reliable estimates, as they reproduce the temperatures of experiments in a variety of simple and natural peridotitic systems. Discrepancies between these two thermometers are negligible in applications to a wide variety of natural samples (≤30°C). The Brey and Köhler (J Petrol 31:1353–1378, 1990) Ca-in-Opx thermometer shows good agreement with TA98 in the range 1,000–1,400°C and a positive bias at lower T (up to +90°C, on average, at T _TA98 = 700°C). The popular Brey and Köhler (J Petrol 31:1353–1378, 1990) two-pyroxene thermometer performs well on clinopyroxene with Na contents of ~0.05 atoms per 6-oxygen formula, but shows a systematic positive bias with increasing Na_Cpx (+150°C at Na_Cpx = 0.25). Among Fe–Mg exchange thermometers, the Harley (Contrib Mineral Petrol 86:359–373, 1984) orthopyroxene–garnet and the recent Wu and Zhao (J Metamorphic Geol 25:497–505, 2007) olivine–garnet formulations show the highest precision, but systematically diverge (up to ca. 150°C, on average) from TA98 estimates at T far from 1,100°C and at T < 1,200°C, respectively; these systematic errors are also evident by comparison with experimental data for natural peridotite systems. The older O’Neill and Wood (Contrib Mineral Petrol 70:59–70, 1979) version of the olivine–garnet Fe–Mg thermometer and all popular versions of the clinopyroxene–garnet Fe–Mg thermometer show unacceptably low precision, with discrepancies exceeding 200°C when compared to TA98 results for well-equilibrated xenoliths. Empirical correction to the Brey and Köhler (J Petrol 31:1353–1378, 1990) Ca-in-Opx thermometer and recalibration of the orthopyroxene–garnet thermometer, using well-equilibrated mantle xenoliths and TA98 temperatures as calibrants, are provided in this study to ensure consistency with TA98 estimates in the range 700–1,400°C. Observed discrepancies between the new orthopyroxene–garnet thermometer and TA98 for some localities can be interpreted in the light of orthopyroxene–garnet Fe³⁺ partitioning systematics and suggest localized and lateral variations in mantle redox conditions, in broad agreement with existing oxybarometric data. Kinetic decoupling of Ca–Mg and Fe–Mg exchange equilibria caused by transient heating appears to be common, but not ubiquitous, near the base of the lithosphere.     

High‐resolution geochemical record of fluid–rock interaction in a mid‐crustal shear zone: a comparative study of major element and oxygen isotope transport in garnet

Garnet grains from an intensely metasomatized mid‐crustal shear zone in the Reynolds Range, central Australia, exhibit a diverse assortment of textural and compositional characteristics that provide important insights into the geochemical effects of fluid–rock interaction. Electron microprobe X‐ray maps and major element profiles, in situ secondary ion mass spectrometry oxygen isotope analyses, and U–Pb and Sm–Nd geochronology are used to reconstruct their thermal, temporal and fluid evolution. These techniques reveal a detailed sequence of garnet growth, re‐equilibration and dissolution during intracontinental reworking associated with the Ordovician–Carboniferous (450–300 Ma) Alice Springs Orogeny. A euhedral garnet porphyroblast displays bell‐shaped major element profiles diagnostic of prograde growth zoning during shear zone burial. Coexisting granulitic garnet porphyroclasts inherited from precursor wall rocks show extensive cation re‐equilibration assisted by fracturing and fragmentation. Oxygen isotope variations in the former are inversely correlated with the molar proportion of grossular, suggesting that isotopic fractionation is linked to Ca substitution. The latter generally show close correspondence to the isotopic composition of their precursor, indicating slow intergranular diffusion of O relative to Fe²⁺, Mg and Mn. Peak metamorphism associated with shearing (～550 °C; 5.0–6.5 kbar) occurred at c. 360 Ma, followed by rapid exhumation and cooling. Progressive Mn enrichment in rim domains indicates that the retrograde evolution caused partial garnet dissolution. Accompanying intra‐mineral porosity production then stimulated limited oxygen isotope exchange between relict granulitic garnet grains and adjacent metasomatic biotite, resulting in increased garnet δ¹⁸O values over length scales <200 μm. Spatially restricted oxygen interdiffusion was thus facilitated by increased fluid access to reaction interfaces. The concentration of Ca in channelled fracture networks suggests that its mobility was enhanced by a similar mechanism. In contrast, the intergranular diffusion of Fe²⁺, Mg and Mn was rock‐wide under the same P–T regime, as demonstrated by a lack of local spatial variations in the re‐equilibration of these components. The extraction of detailed reaction histories from garnet must therefore take into account the variable length‐ and time‐scales of elemental and isotopic exchange, particularly where the involvement of a fluid phase enhances the possibility of measureable resetting profiles being generated for slowly diffusing components such as Ca and O, even at low ambient temperatures and relatively fast cooling rates.     

Effects of cation substitutions in garnet and pyroxene on equilibrium oxygen isotope fractionations

High-grade metamorphic rocks were used to explore oxygen isotope fractionations between pyroxene and garnet, and to investigate the effects on fractionation factors of the cation substitutions Fe³⁺Al_?1 and Ca(Fe,Mg)_?1. Recrystallized, granulite facies (725 °C) wollastonite ores from the northern Adirondack highlands contain essentially only the minerals clinopyroxene (a Di–Hd solid solution)+garnet (a Grs–Adr solid solution)±wollastonite, and exhibit a systematic dependence of measured fractionations on the Fe³⁺ content of calcic garnet: Δ(Cpx–CaGrt)=(0.14±0.12)+(0.78±0.20)X_Adr and Δ(Wo–CaGrt)=(0.15±0.22)+(0.57±0.33)X_Adr. In eclogites formed at T ≤650 °C, measured compositions of Ca-poor garnet and omphacite combined with experimental data indicate that Ca-poor, Fe-rich garnet is enriched in ¹⁸O compared to both diopside and grossular: extrapolating to 1000 K, Δ(Alm–Di)≈c. 0.2 and Δ(Alm–Grs)≈c. 0.5. Orthopyroxene and clinopyroxene from Gore Mountain, New York, show a constant fractionation that is independent of rock type, as expected if they have the same closure temperature. These data imply Δ(Opx-Cpx)≈c. 0.7 at 1000 K. Measured fractionations among Ca-poor garnet, orthopyroxene, clinopyroxene and hornblende in the Gore Mountain rocks further indicate an ¹⁸O enrichment in Ca-poor garnet over Grs (≈c. 0.5 at 1000 K). The new measurements are indistinguishable from expected equilibrium values based on experiments for the minerals enstatite, diopside, grossular, wollastonite and feldspar, but consistently indicate a significant isotope effect for the simple octahedral cation substitutions Fe³⁺Al_?1 (Grs vs. Adr) and Ca(Fe,Mg)_?1 (Ca-poor garnet vs. Grs; Opx vs. Cpx). Neither cation substitution has been directly investigated for its effect on ¹⁸O/¹⁶O fractionation with experiments in silicates. Chemical characterization of minerals is required prior to petrological interpretation of oxygen isotope trends.     

An experimental study of the effect of Ca upon garnet-clinopyroxene Fe-Mg exchange equilibria

A series of basaltic compositions and compositions within the simple system CaO-MgO-FeO-Al₂O₃-SiO₂ have been crystallized to garnetclinopyroxene bearing mineral assemblages in the range 24–30 kb pressure, 750°–1,300° C temperature. Microprobe analyses of coexisting garnet and clinopyroxene show that K _D(Fe²⁺/Mg^G+/Fe²⁺/Mg^Cpx) for the Fe-Mg exchange reaction between coexisting garnet and clinopyroxene is obviously dependent upon the Ca-content and apparently independent of the Mg/(Mg+Fe) content of the clinopyroxene and garnet. The Ca-effect is believed to be due to a combination of non-ideal Ca-Mg substitutions in the garnet and clinopyroxene. Our data and interpretation reconciles previous inconsistencies in the temperature dependence of K _D ^? values determined in experimental studies of simple systems, complex basalt, grospydite and garnet peridotite compositions. Previous differences between the effect of pressure upon K _Das predicted from simple system theory (Banno, 1970), and that observed in experiments on multicomponent natural rock compositions (Råheim and Green, 1974a) can now be resolved. We have determined K _Das a function of P, T, and X _Gt ^Ca (grossular) and derived the empirical relation $$T\left( {^\circ {\text{K}}} \right) = \frac{{3104X_{{\text{Ca}}}^{{\text{Gt}}} + 3030 + 10.86P\left( {{\text{kb}}} \right)}}{{\ln K_{\text{D}} + 1.9034}}$$ . This empirical relationship has been applied to garnet-clinopyroxene bearing rocks from a wide range of geological environments. The geothermometer yields similar estimates for garnet-clinopyroxene equilibration for neighbouring rocks of different composition and different K _Dvalues. In addition, temperature estimates using the above relationship are more consistent with independent temperature estimates based on other geothermometers than previous estimates which did not correct for the Ca-effect. An alternative approach to the above empirical geothermometer was attempted using regular solution models to derive Margules parameters for various solid solutions in garnets and clinopyroxenes. The derived Margules parameters are broadly consistent with those determined from binary solution studies, but caution must be exercised in interpreting them in terms of actual thermodynamic properties of the relevant crystalline solid solutions because of the assumptions which necessarily have to be made in this approach.     

Matrix Corrections and Error Analysis in High‐Precision SIMS 18O/16O Measurements of Ca–Mg–Fe Garnet

We report technical and data treatment methods for making accurate, high‐precision measurements of ¹⁸O/¹⁶O in Ca–Mg–Fe garnet utilising the Cameca IMS 1280 multi‐collector ion microprobe. Matrix effects were similar to those shown by previous work, whereby Ca abundance is correlated with instrumental mass fractionation (IMF). After correction for this effect, there appeared to be no significant secondary effect associated with Mg/Fe²⁺ for routine operational conditions. In contrast, investigation of the IMF associated with Mn‐ or Cr‐rich garnet showed that these substitutions are significant and require a more complex calibration scheme. The Ca‐related calibration applied to low‐Cr, low‐Mn garnet was reproducible across different sample mounts and under a range of instrument settings and therefore should be applicable to similar instruments of this type. The repeatability of the measurements was often better than ± 0.2‰ (2s), a precision that is similar to the repeatability of bulk techniques. At this precision, the uncertainties due to spot‐to‐spot repeatability were at the same magnitude as those associated with matrix corrections (± 0.1–0.3‰) and the uncertainties in reference materials (± 0.1–0.2‰). Therefore, it is necessary to accurately estimate and propagate uncertainties associated with these parameters – in some cases, uncertainties in reference materials or matrix corrections dominate the uncertainty budget.     

P–T-deformation-Fe3+/Fe2+ mapping at the thin section scale and comparison with XANES mapping: application to a garnet-bearing metapelite from the Sambagawa metamorphic belt (Japan)

Quantitative X‐ray maps of composition from a chlorite, K‐white mica, albite, quartz and garnet bearing thin section from a Sambagawa blueschist facies metapelite were combined with a multi‐equilibrium calculation method to calculate a P–T‐Fe³⁺/Fe²⁺‐deformation map at the millimetre scale. The studied sample was chosen because elongated chlorite crystallization tails (pressure shadows) rimmed by phengite are present, which is an appropriate assemblage for the quantification of the P–T evolution. Chlorite temperature and Fe³⁺ content maps were calculated by successive iterations for each pixel analysis of Fe³⁺ until convergence of the four chlorite‐quartz‐H₂O equilibria that can be written using the Fe‐ and Mg‐amesite, clinchlore, daphnite and sudoite chlorite end‐members. The calculated map of Fe²⁺/Fe³⁺ in chlorite is in good qualitative agreement with the in situ mapping of this ratio using XANES (X‐ray absorption near edge structure) techniques. The temperature map indicates that high temperature chlorite zones with low Fe³⁺ contents alternate with lower temperature zones and higher Fe³⁺ contents in the crystallization tail. Late fractures perpendicular to the elongation axis of the tail are filled by very low temperature chlorite (<250 °C) showing Fe³⁺/Fe_total up to 0.4. Groups of chlorite and mica pixels were then identified based on compositional and structural criteria, and a P–T‐deformation map was calculated using representative analyses of these groups. The calculated P–T‐deformation map suggests that in contrast to chlorite, the composition of most mica did not change significantly during exhumation. Mica reequilibrated in late EW shear bands only. EW shearing was already active at 0.1 GPa, 500 °C, which corresponds to the peak temperature (and probably pressure) conditions, at reduced redox conditions. The intensity of deformation probably decreased with decrease in temperature to ～350–400 °C. At this temperature, a second main deformation event corresponding to a further EW stretching occurred and was still active below 250 °C and more oxidizing conditions. These results indicate that the scale at which P–T data can be obtained is now close to the scale of observation of structural geologists. A close link between deformation and mineral reaction is therefore possible at the microscopic scale, which provides information about the relationship between deformation and mineral reactivity, the modalities of deformation with time and the P–T conditions at which it occurred.     

Metamorphic evolution of low-T eclogite from the North Qilian orogen, NW China: evidence from petrology and calculated phase equilibria in the system NCKFMASHO

Low‐T eclogites in the North Qilian orogen, NW China share a common assemblage of garnet, omphacite, glaucophane, epidote, phengite, quartz and rutile with or without paragonite. Phase relations for the low‐T eclogites can be modelled well in the system NCKFMASHO with the updated solid‐solution models for amphibole and clinopyroxene. Garnet in the eclogite typically exhibits growth zonations in which pyrope increases while grossular somewhat decreases from core to rim, which is modelled as having formed mainly in the P–T conditions of lawsonite‐eclogite facies at the pre‐peak stage. Omphacite shows an increase in jadeite component as aegirine and also total FeO decrease in going from the inclusions in garnet to grains in the matrix, and from core to rim of zoned crystals, reflecting an increase in metamorphic P–T conditions. Glaucophane exhibits a compositional variation in X(gl) (= Fe²⁺/(Fe²⁺ + Mg)) and F(gl) (= Fe³⁺/(Fe³⁺ + Al) in M2 site), which decrease from the inclusions in garnet to crystals in the matrix, consistent with an increase in P–T conditions. However, for zoned matrix crystals, the X(gl) and F(gl) increase from core to rim, is interpreted to reflect a late‐stage decompression. Using composition isopleths for garnet rim and phengite in P–T pseudosections, peak P–T conditions for three samples Q5–45, Q5–01 and Q7–28 were estimated as 530–540 °C at 2.10–2.25 GPa, 580–590 °C at 2.30–2.45 GPa and 575–590 °C at 2.50–2.65 GPa, respectively, for the same assemblage garnet + omphacite + glaucophane + lawsonite (+ phengite + quartz + rutile) at the peak stage. The eclogites suggest similar P–T ranges to their surrounding felsic–pelitic schists. During post‐peak decompression of the eclogites, the most distinctive change involves the transformation of lawsonite to epidote, releasing large amount of water in the rock. The released fluid promoted further growth of glaucophane at the expense of omphacite and, in appropriate bulk‐rock compositions, paragonite formed. The decompression of eclogite did not lead to pronounced changes in garnet and phengite compositions. Peak P–T conditions of the North Qilian eclogite are well constrained using both the average P–T and pseudosection approaches in Thermocalc. Generally, the conventional garnet–clinopyroxene geothermometer is too sensitive to be used for constraining the temperature of low‐T eclogite because of the uncertainty in Fe³⁺ determination in omphacite and slight variations in mineral compositions because of incomplete equilibration.