Petrochemistry, oxygen isotopes and U-Pb SHRIMP geochronology of mafic–ultramafic bodies from the Sulu UHP terrane, China

Two Rongcheng eclogite‐bearing peridotite bodies (Chijiadian and Macaokuang) occur as lenses within the country rock gneiss of the northern Sulu terrane. The Chijiadian ultramafic body consists of garnet lherzolite, whereas the Macaokuang body is mainly meta‐dunite. Both ultramafics are characterized by high MgO contents, low fertile element concentrations and total REE contents, which suggests that they were derived from depleted, residual mantle. High FeO contents, an LREE‐enriched pattern and trace‐element contents indicate that the bulk‐rock compositions of these ultramafic rocks were modified by metasomatism. Oxygen‐isotope compositions of analysed garnet, olivine, clinopyroxene and orthopyroxene from these two ultramafic bodies are between +5.2‰ and +6.2‰ (δ¹⁸O), in the range of typical mantle values (+5.1 to +6.6‰). The eclogite enclosed within the Chijiadian lherzolite shows an LREE‐enriched pattern and was formed by melts derived from variable degrees (0.005–0.05) of partial melting of peridotite. It has higher δ¹⁸O values (+7.6‰ for garnet and +7.7‰ for omphacite) than those of lherzolite. Small O‐isotope fractionations (ΔCpx‐Ol: 0.4‰, ΔCpx‐Grt: 0.1‰, ΔGrt‐Ol: 0.3–0.4‰) in both eclogite and ultramafic rocks suggest isotopic equilibrium at high temperature. The P–T estimates suggest that these rocks experienced subduction‐zone ultrahigh‐pressure (UHP) metamorphism at ～700–800 °C, 5 GPa, with a low geothermal gradient. Zircon from the Macaokuang eclogite contains inclusions of garnet and diopside. The 225 ± 2 Ma U/Pb age obtained from these zircon may date either the prograde conditions just before peak metamorphism or the UHP metamorphic event, and therefore constrains the timing of subduction‐related UHP metamorphism for the Rongcheng mafic–ultramafic bodies.     

Humite- and scapolite-bearing assemblages in marbles and calcsilicates of Dronning Maud Land, Antarctica: new data for Gondwana reconstructions

This study investigates marbles and calcsilicates in Central Dronning Maud Land (CDML), East Antarctica. The paleogeographic positioning of CDML as part of Gondwana is still unclear; however, rock types, mineral assemblages, textures and P–T conditions observed in this study are remarkably similar to the Kerala Khondalite Belt in India. The CDML marbles and calcsilicates experienced a Pan-African granulite facies metamorphism at c. 570 Ma and an amphibolite facies retrogression at c. 520 Ma. The highest grade assemblage in marbles is forsterite+spinel+calcite+dolomite, in calcsilicates the assemblages are diopside+spinel, diopside+garnet, scapolite+wollastonite+clinopyroxene±quartz, scapolite±anorthite±calcite+clinopyroxene+wollastonite. These assemblages constrain the peak metamorphic conditions to 830±20 °C, 6.8±0.5 kbar and X _CO2>0.46. During retrogression, highly fluoric humite-group minerals (humite, clinohumite, chondrodite) replaced forsterite, and garnet rims formed at the expense of scapolite during reactions with wollastonite, calcite or clinopyroxene but without involvement of anorthite. Metamorphic conditions were about 650 °C, 4.5±0.7 kbar, 0.2< X _CO2^fluid<0.36, and the co-existence of garnet, clinopyroxene, wollastonite and quartz constrains f_O2 to FMQ-1.5 log units. Mineral textures indicate a very limited influx of H₂O-rich fluid during amphibolite facies retrogression and point to significant variations of fluid composition in mm-sized areas of the rock. Gypsum was observed in two samples; it probably replaced metamorphic anhydrite which appears to have formed under amphibolite facies conditions. The observed extensive anorogenic magmatism (anorthosites, A-type granitoids) and the character of metamorphism between 610 and 510 Ma suggest that the crustal thermal structure was characterized by a long-lived (50–100 Ma) rise of the crustal geotherm probably caused by magmatic underplating.     

Decoding the complex internal chemical structure of garnet porphyroblasts from the Zermatt area,Western Alps

Garnet is a prototypical mineral in metamorphic rocks because it commonly preserves chemical and textural features that can be used for untangling its metamorphic development. Large garnet porphyroblasts may show extremely complex internal structures as a result of a polycyclic growth history, deformation, and modification of growth structures by intra‐ and intercrystalline diffusion. The complex internal structure of garnet porphyroblasts from garnet–phengite schists (GPS) of the Zermatt area (Western Alps) has been successfully decoded. The centimetre‐sized garnet porphyroblasts are composed of granulite facies garnet fragments overgrown by a younger generation of grossular‐rich eclogite facies garnet. The early granulite facies garnet (G‐Grt) formed from low‐P, high‐T metamorphism during a pre‐Alpine orogenic event. The late garnet (E‐Grt) is typical of high‐pressure, low‐temperature (HPLT) metamorphism and can be related to Alpine subduction of the schists. Thus, the garnet of the GPS are polycyclic (polymetamorphic). G‐Grt formation occurred at ~670 MPa and 780°C, E‐Grt formed at ~1.7 GPa and 530°C. The G‐Grt is relatively rich in Prp and poor in Grs, while E‐Grt is rich in Grs and poor in Prp. The Alm content (mol.%) of G‐Grt is 68 of E‐Grt 55. After formation of E‐Grt between and around fragmented G‐Grt at 530°C, the GPS have been further subducted and reached a maximum temperature of 580°C before exhumation started. Garnet composition profiles indicate that the initially very sharp contacts between the granulite facies fragments of G‐Grt and fracture seals of HPLT garnet (E‐Grt) have been modified by cation diffusion. The profiles suggest that Ca did not exchange at the scale of 1 µm, whereas Fe and Mg did efficiently diffuse at the derived maximum temperature of 580°C for the GPS at the scale of 7–8 µm. The Grt–Grt diffusion profiles resulted from spending c. 10 Ma at 530–580°C along the P–T–t path. The measured Grt composition profiles are consistent with diffusivities of log D_MgFe = ?25.8 m²/s from modelled diffusion profiles. Mg loss by diffusion from G‐Grt is compensated by Fe gain by diffusion from E‐Grt to maintain charge balance. This leads to a distinctive Fe concentration profile typical of uphill diffusion.     

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.     

Oscillatory zoning in garnet from the Willsboro Wollastonite Skarn, Adirondack Mts, New York: a record of shallow hydrothermal processes preserved in a granulite facies terrane

Oscillatory zoning in low δ¹⁸O skarn garnet from the Willsboro wollastonite deposit, NE Adirondack Mts, NY, USA, preserves a record of the temporal evolution of mixing hydrothermal fluids from different sources. Garnet with oscillatory zoning are large (1–3 cm diameter) euhedral crystals that grew in formerly fluid filled cavities. They contain millimetre‐scale oscillatory zoning of varying grossular–andradite composition (X_Adr = 0.13–0.36). The δ¹⁸O values of the garnet zones vary from 0.80 to 6.26‰ VSMOW and correlate with X_Adr. The shape, pattern and number of garnet zones varies from crystal to crystal, as does the magnitude of the correlated chemistry changes, suggesting fluid system variability, temporal and/or spatial, over the time of garnet growth. The zones of correlated Fe content and δ¹⁸O indicate that a high Fe³⁺/Al, high δ¹⁸O fluid mixed with a lower Fe³⁺/Al and δ¹⁸O fluid. The high δ¹⁸O, Fe enriched fluids were likely magmatic fluids expelled from crystallizing anorthosite. The low δ¹⁸O fluids were meteoric in origin. These are the first skarn garnet with oscillatory zoning reported from granulite facies rocks. Geochronologic, stable isotope, petrologic and field evidence indicates that the Adirondacks are a polymetamorphic terrane, where localized contact metamorphism around shallowly intruded anorthosite was followed by a regional granulite facies overprint. The growth of these garnet in equilibrium with meteoric and magmatic fluids indicates an origin in the shallow contact aureole of the anorthosite prior to regional metamorphism. The zoning was preserved due to the slow diffusion of oxygen and cations in the large garnet and protection from deformation and recrystallization in zones of low strain in thick, rigid, garnetite layers. The garnet provide new information about the hydrothermal system adjacent to the shallowly intruded massif anorthosite that predates regional metamorphism in this geologically complex, polymetamorphic terrane.     

Fluid infiltration during contact metamorphism of interbedded marble and calc-silicate hornfels, Twin Lakes area, central Sierra Nevada, California

Abstract In the Twin Lakes area, central Sierra Nevada, California, most contact metamorphosed marbles contain calcite + dolomite + forsterite ± diopside ± phlogopite ± tremolite, and most calc-silicate hornfelses contain calcite + diopside + wollastonite + quartz ± anorthite ± K-feldspar ± grossular ± titanite. Mineral-fluid equilibria involving calcite + dolomite + tremolite + diopside + forsterite in two marble samples and wollastonite + anorthite + quartz + grossular in three hornfels samples record P± 3 kbar and T± 630° C. Various isobaric univariant assemblages record CO₂-H₂O fluid compositions of χCO₂= 0.61–0.74 in the marbles and χCO₂= 0.11 in the hornfelses. Assuming a siliceous dolomitic limestone protolith consisting of dolomite + quartz ° Calcite ± K-feldspar ± muscovite ± rutile, all plausible prograde reaction pathways were deduced for marble and hornfels on isobaric T-XCO₂ diagrams in the model system K₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O-CO₂. Progress of the prograde reactions was estimated from measured modes and mass-balance calculations. Time-integrated fluxes of reactive fluid which infiltrated samples were computed for a temperature gradient of 150 °C/km along the fluid flow path, calculated fluid compositions, and estimated reaction progress using the mass-continuity equation. Marbles and hornfelses record values in the range 0.1–3.6 × 10⁴ cm³/cm² and 4.8–12.9 × 10⁴ cm³/cm², respectively. For an estimated duration of metamorphism of 10⁵ years, average in situ metamorphic rock permeabilities, calculated from Darcy's Law, are 0.1–8 × 10^?6 D in the marbles and 10–27 × 10^?6 D in the hornfelses. Reactive metamorphic fluids flowed up-temperature, and were preferentially channellized in hornfelses relative to the marbles. These results appear to give a general characterization of hydrothermal activity during contact metamorphism of small pendants and screens (dimensions ± 1 km or less) associated with emplacement of the Sierra Nevada batholith.     

Metamorphic evolution of diamond-bearing and associated rocks from the Kokchetav Massif, northern Kazakhstan

Representative diamond-bearing gneisses and dolomitic marble, eclogite and Ti-clinohumite-bearing garnet peridotite from Unit I at Kumdy Kol and whiteschist from Unit II at Kulet, eastern Kokchetav Massif, northern Kazakhstan, were studied. Diamond-bearing gneisses contain variable assemblages, including Grt+Bt+Qtz±Pl±Kfs±Zo±Chl±Tur±Cal and minor Ap, Rt and Zrn; abundant inclusions of diamond, graphite+chlorite (or calcite), phengite, clinopyroxene, K-feldspar, biotite, rutile, titanite, calcite and zircon occur in garnet. Diamond-bearing dolomitic marbles consist of Dol+Di±Grt+Phl; inclusions of diamond, dolomite±graphite, biotite, and clinopyroxene were identified in garnet. Whiteschists carry the assemblage Ky+Tlc+Grt+Rt; garnet shows compositional zoning, and contains abundant inclusions of talc, kyanite and rutile with minor phlogopite, chlorite, margarite and zoisite. Inclusions and zoning patterns of garnet delineate the prograde P–T path. Inclusions of quartz pseudomorphs after coesite were identified in garnet from both eclogite and gneiss. Other ultrahigh-pressure (UHP) indicators include Na-bearing garnet (up to 0.14 wt% Na₂O) with omphacitic Cpx in eclogite, occurrence of high-K diopside (up to 1.56 wt% K₂O) and phlogopite in diamond-bearing dolomitic marble, and Cr-bearing kyanite in whiteschist. These UHP rocks exhibit at least three stages of metamorphic recrystallization. The Fe-Mg partitioning between clinopyroxene and garnet yields a peak temperature of 800–1000 °C at P >40 kbar for diamond-bearing rocks, and about 740–780 °C at >28–35 kbar for eclogite, whiteschist and Ti-bearing garnet peridotite. The formation of symplectitic plagioclase+amphibole after clinopyroxene, and replacement of garnet by biotite, amphibole, or plagioclase mark retrograde amphibolite facies recrystallization at 650–680 °C and pressure less than about 10 kbar. The exsolution of calcite from dolomite, and development of matrix chlorite and actinolite imply an even lower grade greenschist facies overprint at c. 420 °C and 2–3 kbar. A clockwise P–T path suggests that supracrustal sediments together with basaltic and ultramafic lenses apparently were subjected to UHP subduction-zone metamorphism within the diamond stability field. Tectonic mixing may have occurred prior to UHP metamorphism at mantle depths. During subsequent exhumation and juxtaposition of many other tectonic units, intense deformation chaotically mixed and mylonitized these lithotectonic assemblages.     

New Reference Materials and Assessment of Matrix Effects for SIMS Measurements of Oxygen Isotopes in Garnet

Accurate ion microprobe analysis of oxygen isotope ratios in garnet requires appropriate reference materials to correct for instrumental mass fractionation that partly depends on the garnet chemistry (matrix effect). The matrix effect correlated with grossular, spessartine and andradite components was characterised for the Cameca IMS 1280HR at the SwissSIMS laboratory based on sixteen reference garnet samples. The correlations fit a second‐degree polynomial with maximum bias of ca. 4‰, 2‰ and 8‰, respectively. While the grossular composition range 0–25% is adequately covered by available reference materials, there is a paucity of them for intermediate compositions. We characterise three new garnet reference materials GRS2, GRS‐JH2 and CAP02 with a grossular content of 88.3 ± 1.2% (2s), 83.3 ± 0.8% and 32.5 ± 3.0%, respectively. Their micro scale homogeneity in oxygen isotope composition was evaluated by multiple SIMS sessions. The reference δ¹⁸O value was determined by CO₂ laser fluorination (δ¹⁸O_LF). GRS2 has δ¹⁸O_LF = 8.01 ± 0.10‰ (2s) and repeatability within each SIMS session of 0.30–0.60‰ (2s), GRS‐JH2 has δ¹⁸O_LF = 18.70 ± 0.08‰ and repeatability of 0.24–0.42‰ and CAP02 has δ¹⁸O_LF = 4.64 ± 0.16‰ and repeatability of 0.40–0.46‰.     

Trace-element partitioning between garnet,clinopyroxene and Fe-rich picritic melts at 3 to 7 GPa

We have determined mineral-melt partition coefficients (D values) for 20 trace elements in garnet-pyroxenite run products, generated in 3 to 7 GPa, 1,425–1,750°C experiments on a high-Fe mantle melt (97SB68) from the Paraná-Etendeka continental-flood-basalt (CFB) province. D values for both garnet (∼Py₆₃Al₂₅Gr₁₂) and clinopyroxene (∼Ca_0.2Mg_0.6Fe_0.2Si₂O₆) show a large variation with temperature but are less dependent on pressure. At 3 GPa, D ^cpx/liq values for pyroxenes in garnet-pyroxenite run products are generally lower than those reported from Ca-rich pyroxenes generated in melting experiments on eclogites and basalts (∼Ca_0.3–0.5Mg_0.3–0.6Fe_0.07–0.2Si₂O₆) but higher than those for Ca-poor pyroxenes from peridotites (∼Ca_0.2Mg_0.7Fe_0.1Si₂O₆). D ^grt/liq values for light and heavy rare-earth elements are ≤0.07 and >0.8, respectively, and are similar to those for peridotitic garnets that have comparable grossular but higher pyrope contents (Py_70–88Al_l7–20Gr_8–14). 97SB68 D _LREE^grt/liq values are higher and D _HREE^grt/liq values lower than those for eclogitic garnets which generally have higher grossular contents but lower pyrope contents (Py_20–70Al_10–50Gr_10–55). D values agree with those predicted by lattice strain modelling and suggest that equilibrium was closely approached for all of our experimental runs. Correlations of D values with lattice-strain parameters and major-element contents suggest that the wollastonite component and pyrope:grossular ratio exert major controls on 97SB68 clinopyroxene and garnet partitioning, respectively. These are controlled by the prevailing pressure and temperature conditions for a given bulk-composition. The composition of co-existing melt was found to have a relatively minor effect on 97SB68 D values. The variations in D values displayed by different mantle lithologies are subtle and our study confirms previous investigations which have suggested that the modal proportions of garnet and clinopyroxene are by far the most influential factor in determining incompatible trace-element concentrations in mantle melts. The trace-element partition coefficients we have determined may be used to place high-pressure constraints on garnet-pyroxenite melting models.     

Petrogenesis of kyanite‐ and corundum‐bearing mafic granulite in a meta‐ophiolite,SE Turkey

Although ophiolitic rocks are abundant in Anatolia (Turkey), only in rare cases have they experienced high‐grade metamorphism. Even more uncommon, in Anatolia and elsewhere are high‐grade meta‐ophiolites that retain an oceanic lithosphere stratigraphy from upper crustal mafic volcanic rocks through lower crustal gabbro to mantle peridotite. The Berit meta‐ophiolite of SE Turkey exhibits both features: from structurally higher to lower levels, it consists of garnet amphibolite (metabasalt), granulite facies metagabbro (as lenses in amphibolite inferred to be retrogressed granulite) and metaperidotite (locally with metapyroxenite layers). Whole‐rock major and trace‐element data indicate a tholeiitic protolith that formed in a suprasubduction setting. This paper presents new results for the metamorphic P–T conditions and path of oceanic lower crustal rocks in the Berit meta‐ophiolite, and an evaluation of the tectonic processes that may drive granulite facies metamorphism of ophiolite gabbro. In the Do?an?ehir (Malatya, Turkey) region, granulite facies gabbroic rocks contain garnet (Grt)+clinopyroxene (Cpx)+plagioclase (Pl)+corundum (Crn)±orthopyroxene (Opx)±kyanite (Ky)±sapphirine (Spr)±rutile. Some exhibit symplectites consisting of Crn+Cpx, Ky+Cpx and/or coronas of garnet (outer shell) around a polygonal aggregate of clinopyroxene that in some cases surrounds a polygonal aggregate of orthopyroxene. Coronitic and non‐coronitic textures occur in proximity in mm‐ to cm‐scale layers; corona structures typically occur in plagioclase‐rich layers. Their formation is therefore related primarily to protolith type (troctolite v. gabbro) rather than P–T path. Phase diagrams calculated for a kyanite‐rich granulite, a plagioclase‐rich non‐coronitic granulite, and a plagioclase‐rich coronitic granulite (taking into account changes in effective bulk composition during texture development) predict peak conditions of ~800°C, 1.1–1.5 GPa; these conditions do not require invoking an unusually high geothermal gradient. In the coronitic metagabbro, reaction textures formed along the prograde path: Crn–Cpx symplectites grew at the expense of garnet, sapphirine and plagioclase. Peak conditions were followed by isobaric cooling of ~150°C. Hornblende–plagioclase thermometry results for host amphibolite (Hbl+Pl±Crn±Grt±relict Cpx) indicate retrograde conditions of 620–675°C and 0.5–0.8 GPa accompanied by infiltration of H₂O‐rich fluid. This anticlockwise P–T path differs from an isothermal decompression path previously proposed for these rocks based on the presence of symplectite. Metamorphism of the ophiolitic rocks was driven by closing of the southern Neotethys Ocean, as oceanic lithosphere was obducted (most SE Anatolian ophiolites) or underthrust (Berit meta‐ophiolite). This was followed by subduction of a continental margin, driving cooling of the Berit granulite after the thermal peak at depths of ~40 km.     

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

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

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.     

Garnet–clinopyroxene intermediate granulites in the St. Leonhard massif of the Bohemian Massif: ultrahigh‐temperature metamorphism at high pressure or not?

Garnet–clinopyroxene intermediate granulites occur as thin layers within garnet–kyanite–K–feldspar felsic granulites of the St. Leonhard granulite body in the Bohemian Massif. They consist of several domains. One domain consists of coarser‐grained coexisting ternary feldspar, clinopyroxene, garnet, quartz and accessory rutile and zircon. The garnet has 16–20% grossular, and the clinopyroxene has 9% jadeite and contains orthopyroxene exsolution lamellae. Reintegrated ternary feldspar and the Zr‐in‐rutile thermometer give temperatures higher than 950 °C. Mineral equilibria modelling suggests crystallization at 14 kbar. The occurrence and preservation of this mineral assemblage is consistent with crystallization from hot dry melt. Between these domains is a finer‐grained deformed matrix made up of diopsidic clinopyroxene, orthopyroxene, plagioclase and K‐feldspar, apparently produced by reworking of the coarser‐grained domains. Embedded in this matrix, and pre‐dating the reworking deformation, are garnet porphyroblasts that contain clinopyroxene, feldspar, quartz, rutile and zircon inclusions. In contrast with the garnet in the coarser‐grained domains, the garnet generally has >30% grossular, the included clinopyroxene has 7–27% jadeite and the Zr content of rutile indicates much lower temperatures. Some of these high‐grossular garnet show zoning in Fe/(Fe + Mg), decreasing from 0.7 in the core to 0.6 and then increasing to 0.7 at the rim. These garnet are enigmatic, but with reference to appropriate pseudosections are consistent with localized new mineral growth from 650 to 850 °C and 10 to 17 kbar, or with equilibration at 20 kbar and 770 °C, modified by two‐stage diffusional re‐equilibration of rims, at 10–15 and 8 kbar. The strong pervasive deformation has obscured relationships that might have aided the interpretation of the origin of these porphyroblasts. The evolution of these rocks is consistent with formation by igneous crystallization and subsequent metamorphism to high‐T and high‐P, rather than an origin by ultrahigh‐T metamorphism. Regarding the petrographic complexity, combination of the high grossular garnet with the ternary feldspar to infer ultrahigh‐T metamorphism at high pressure is not justified.     

Genesis of wollastonite- and grandite-rich skarns in a suite of marble-calc-silicate rocks from Sittampundi, Tamil Nadu: constraints on the P–T–fluid regime in parts of the Pan-African mobile belt of South India

The Pan-African tectonothermal activities in areas near Sittampundi, south India, are characterized by metamorphic changes in an interlayered sequence of migmatitic metapelites, marble and calc-silicate rocks. This rock sequence underwent multiple episodes of folding, and was intruded by granite batholiths during and subsequent to these folding events. The marble and the calc-silicate rocks develop a variety of skarns, which on the basis of mineralogy; can be divided into the following types: Type I: wollastonite?+?clinopyroxene (mg#?=?71–73)?+?grandite (16–21 mol% Adr)?+?quartz?±?calcite, Type II: grandite (25–29 mol% Adr )?+?clinopyroxene (mg#?=?70)?+?calcite?+?quartz, and Type III: grandite (36–38 mol% Adr)?+?clinopyroxene (mg#?=?55–65)?+?epidote?+?scapolite?+?calcite?+?quartz. Type I skarn is 2–10 cm thick, and is dominated by wollastonite (>70 vol%) and commonly occurs as boudinaged layers parallel to the regional foliation Sn₁ related to the Fn₁ folds. Locally, thin discontinuous lenses and stringers of this skarn develop along the axial planes of Fn₂ folds. The Type II skarn, on the other hand, is devoid of wollastonite, rich in grandite garnet (40–70 vol%) and developed preferentially at the interface of clinopyroxene-rich calc-silicates layers and host marble during the later folding event. Reaction textures and the phase compositional data suggest the following reactions in the skarns: 1. calcite?+?SiO₂?→?wollastonite?+?V, 2. calcite?+?clinopyroxene?+?O₂?→?grandite?+?SiO₂?+?V, 3. scapolite?+?calcite?+?quartz?+?clinopyroxene?+?O₂?→?grandite?+?V and 4. epidote?+?calcite?+?quartz?+?clinopyroxene?+?O₂?→?grandite?+?V Textural relations and composition of phases demonstrate that (a) silica metasomatism of the host marble by infiltration of aqueous fluids (X_CO2?<?0.15) led to production of large volumes of wollastonite in the wollastonite-rich skarn whereas mobility of FeO, SiO₂ and CaO across the interface of marble and calc-silicate and infiltration of aqueous fluids (X_CO2?<?0.35) were instrumental for the formation of grandite skarns. Composition of minerals in type II skarn indicates that Al₂O₃ was introduced in the host marble by the infiltrating fluid. Interpretation of mineral assemblages observed in the interlayered metapelites and the calcareous rocks in pseudosections, isothermal P-X_CO2 and isobaric T-X_CO2 diagrams tightly bracket the “peak” metamorphic conditions at c.9?±?1 kbar and 750°?±?30°C. Subsequent to ‘peak’ metamorphic conditions, the rocks were exhumed on a steeply decompressive P–T path. The estimated ‘peak’ P–T estimates are inconsistent with the “extreme” metamorphic conditions (>11 kbar and >950°C) inferred for the Pan-African tectonothermal events from the neighboring areas. Field and petrological attributes of these skarn rocks are consistent with the infiltration of aqueous fluid predominantly during the Fn₁ folding event at or close to the ‘peak’ metamorphic conditions. Petrological features indicate that the buffering capacity of the rocks was lost during the formation of type I and II skarns. However, the host rock could buffer the composition of the permeated fluids during the formation of type III skarn. Aqueous fluids derived from prograde metamorphism of the metapelites seem to be the likely source for the metasomatic fluids that led to the formation of the skarn rocks.     

Exsolution textures of orthopyroxene and clinopyroxene in high-grade BIF of the Voronezh Crystalline Massif: evidence of ultrahigh-temperature metamorphism

Archaean banded iron formation (BIF) of the Voronezh Crystalline Massif (VCM) contains coexisting clino‐ and orthopyroxenes with exsolution textures. The pyroxene in the VCM BIF is found in two generations, with only the first generation containing such textures. Clinopyroxene contains large (up to 5–10 μm) (0 0 1) orthopyroxene (Opx1L) lamellae in a host clinopyroxene (Cpx1H). This host Cpx, in turn, exsolves into thin (～1 μm) (1 0 0) lamellae of orthopyroxene (Opx2L) and clinopyroxene (Cpx2H). Orthopyroxene exhibits similar exsolution textures with large (up to 50 μm) (0 0 1) clinopyroxene (Cpx1L) lamellae developed in a host orthopyroxene (Opx1H). This clinopyroxene Cpx1L shows further exsolution of thin (1 0 0) Opx2LL lamellae and clinopyroxene (Cpx2LH). Point microprobe analysis, raster‐mode microprobe analysis, and microprobe element mapping of mineral grains with a large number of point analysis were used to determine the composition of the exsolution products and the primary chemistry of the coexisting clinopyroxene (CaO = 14.86–17.26 wt%) and pigeonite (CaO = 4.45–6.23 wt%). These pyroxenes crystallized during the peak of metamorphism, and application of the Lindsley geothermometer suggested that they formed at extremely high temperatures of about 1000 °C. Primary very dense CO₂‐rich fluid inclusions (ρ = 1.152 g cm^?3, T_h = ?49.2 °C) were discovered for the first time in these BIF. With these data, the metamorphic pressure was estimated as 10–11 kbar (depth 36–40 km). Such ultrahigh temperature–high pressure (UHT–HP) conditions for the regional metamorphism of the Precambrian BIF have previously been reported only for Archaean meta‐ironstone from the Napier Complex (Enderby Land, Antarctica). They give an insight into the peak metamorphic conditions of the BIF of the VCM, their burial under thickened continental crust during this period of Earth evolution and suggest a more complicated multistage metamorphic and tectono‐thermal history for the region than has previously been postulated.     

Macroscopically‐Zoned Grandite from the Garnetite Skarn of Meka Presedla (Kopaonik Mountain,Serbia)

The macroscopically-zoned grandite from the garnetite skarn of Meka Presedla (Kopaonik Mountain, Serbia) was studied with optical microscopy, electron microprobe analysis (EMPA), Fourier transform infra-red (FT–IR), and Raman methods. The EMPA results indicate that the main core–rim compositional variations (Ca2.93–2.97Mn0.05–0.06Mg0.00–0.01Al1.14–1.26Fe3+0.72–0.83Ti0.00–0.02Si2.97–3.02O12) slightly differ along the zones, showing evidence for a quasi-cyclic alternation of the oscillatory zoning nature. Among this, considerable variation is observed only by the Al–Fe3+ substitutions in the octahedral site. The EMPA also indicate that the grandite zones compositionally vary, mostly within ±1 and ±2 mol% of the homogeneity level range, that is, Grs64±1Adr36±1Sps2 (A), Grs62±1Adr38±1Sps2 (B), Grs59±2Adr40±2Sps2 (C), Grs58±2Adr41±2Sps2 (D), and Grs58±1Adr41±1Sps2 (E). Therefore, the investigated garnet can be considered as relatively highly homogeneous. The majority of compositions lie within the narrow miscibility region of 0.58±2相似文献   

Petrogenetic significance of orthopyroxene-free garnet + clinopyroxene + plagioclase ± quartz-bearing metabasites with respect to the amphibolite and granulite facies

Orthopyroxene‐free garnet + clinopyroxene + plagioclase ± quartz‐bearing mineral assemblages represent the paragenetic link between plagioclase‐free eclogite facies metabasites and orthopyroxene‐bearing granulite facies metabasites. Although these assemblages are most commonly developed under P–T conditions consistent with high pressure granulite facies, they sometimes occur at lower grade in the amphibolite facies. Thus, these assemblages are characteristic but not definitive of high pressure granulite facies. Compositional factors favouring their development at amphibolite grade include Fe‐rich mineral compositions, Ca‐rich garnet and plagioclase, and Ti‐poor hornblende. The generalized reaction that accounts for the prograde development of garnet + clinopyroxene + plagioclase ± quartz from a hornblende + plagioclase + quartz‐bearing (amphibolite) precursor is Hbl + Pl + Qtz=Grt + Cpx + liquid or vapour, depending on whether the reaction occurs above or below the solidus. There are significant discrepancies between experimental and natural constraints on the P–T conditions of orthopyroxene‐free garnet + clinopyroxene + plagioclase ± quartz‐bearing mineral assemblages and therefore on the P–T position of this reaction. Semi‐quantitative thermodynamic modelling of this reaction is hampered by the lack of a melt model and gives results that are only moderately successful in rationalizing the natural and experimental data.     

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

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

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

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

Oriented growth of garnet by topotactic reactions and epitaxy in high‐pressure,mafic garnet granulite formed by dehydration melting of metastable hornblende‐gabbronorite (Jijal Complex,Kohistan Complex,north Pakistan)

Garnet growth in high‐pressure, mafic garnet granulites formed by dehydration melting of hornblende‐gabbronorite protoliths in the Jijal complex (Kohistan palaeo‐island arc complex, north Pakistan) was investigated through a microstructural EBSD‐SEM and HRTEM study. Composite samples preserve a sharp transition in which the low‐pressure precursor is replaced by garnet through a millimetre‐sized reaction front. A magmatic foliation in the gabbronorite is defined by mafic‐rich layering, with an associated magmatic lineation defined by the shape‐preferred orientation (SPO) of mafic clusters composed of orthopyroxene (Opx), clinopyroxene (Cpx), amphibole (Amp) and oxides. The shape of the reaction front is convoluted and oblique to the magmatic layering. Opx, Amp and, to a lesser extent, Cpx show a strong lattice‐preferred orientation (LPO) characterized by an alignment of [001] axes parallel to the magmatic lineation in the precursor hornblende‐gabbronorite. Product garnet (Grt) also displays a strong LPO. Two of the four 〈111〉 axes are within the magmatic foliation plane and the density maximum is subparallel to the precursor magmatic lineation. The crystallographic relationship 〈111〉_Grt // [001]_Opx,Cpx,Amp deduced from the LPO was confirmed by TEM observations. The sharp and discontinuous modal and compositional variations observed at the reaction front attest to the kinetic inhibition of prograde solid‐state reactions predicted by equilibrium‐phase diagrams. The P–T field for the equilibration of Jijal garnet granulites shows that the reaction affinities are 5–10 kJ mol.^?1 for the Grt‐in reaction and 0–5 kJ mol.^?1 for the Opx‐out reaction. Petrographic and textural observations indicate that garnet first nucleated on amphibole at the rims of mafic clusters; this topotactic replacement resulted in a strong LPO of garnet. Once the amphibole was consumed in the reaction, the parallelism of [001] axes of the mafic‐phase reactants favoured the growth of garnet crystals with similar orientations over a pyroxene substrate. These aggregates eventually sintered into single‐crystal garnet. In the absence of deformation, the orientation of mafic precursor phases conditioned the nucleation site and the crystallographic orientation of garnet because of topotaxial transformation reactions and homoepitaxial growth of garnet during the formation of high‐pressure, mafic garnet‐granulite after low‐pressure mafic protoliths.