Factors affecting preservation of coesite in ultrahigh‐pressure metamorphic rocks: Insights from TEM observations of dislocations within kyanite

To understand the preservation of coesite inclusions in ultrahigh‐pressure (UHP) metamorphic rocks, an integrated petrological, Raman spectroscopic and focussed ion beam (FIB) system–transmission electron microscope (TEM) study was performed on a UHP kyanite eclogite from the Sulu belt in eastern China. Coesite grains have been observed only as rare inclusions in kyanite from the outer segment of garnet and in the matrix. Raman mapping analysis shows that a coesite inclusion in kyanite from the garnet rim records an anisotropic residual stress and retains a maximum residual pressure of ~0.35 GPa. TEM observations show quartz is absent from the coesite inclusion–host kyanite grain boundaries. Numerous dislocations and sub‐grain boundaries are present in the kyanite, but dislocations are not confirmed in the coesite. In particular, dislocations concentrate in the kyanite adjacent to the boundary with the coesite inclusion, and they form a dislocation concentration zone with a dislocation density of ~10⁹ cm^?2. A high‐resolution TEM image and a fast Fourier transform‐filtered image reveal that a tiny dislocation in the dislocation concentration zone is composed of multiple edge dislocations. The estimated dislocation density in most of the kyanite away from the coesite inclusion–host kyanite grain boundaries is ~10⁸ cm^?2, being lower than that in kyanite adjacent to the coesite. In the case of a coesite inclusion in a matrix kyanite, using Raman and TEM analyses, we could not identify any quartz at the grain boundaries. Dislocations are not observed in the coesite, but numerous dislocations and stacking faults are developed in the kyanite. The estimated overall dislocation density in the coesite‐bearing matrix kyanite is ~10⁸ cm^?2, but a high dislocation density region of ~10⁹ cm^?2 is also present near the coesite inclusion–host kyanite grain boundaries. Inclusion and matrix kyanite grains with no coesite have dislocation densities of ≤10⁸ cm^?2. Dislocation density is generally reduced during an annealing process, but our results show that not all dislocations in the kyanite have recovered uniformly during exhumation of the UHP rocks. Hence, one of the key factors acting as a buffer to inhibit the coesite to quartz transformation is the mechanical interaction between the host and the inclusion that lead to the formation of dislocations in the kyanite. The kyanite acts as an excellent pressure container that can preserve coesite during the decompression of rocks from UHP conditions. The search for and study of inclusions in kyanite may be a more suitable approach for tracing the spatial distribution of UHP metamorphic rocks.     

Prograde evolution of Sulu UHP metamorphic rock in Yangzhuang,Junan region,deduced by combined Raman and petrological studies

The prograde metamorphic history of the Sulu ultrahigh‐pressure metamorphic terrane has been revealed using Raman‐based barometry of the SiO₂ phases and other mineral inclusions in garnet porphyroblasts of a coesite eclogite from Yangzhuang, Junan region, eastern China. Garnet porphyroblasts have inner and outer segments with the boundary being marked by discontinuous changes in the grossular content. In the inner segment, the SiO₂ phase inclusions are α‐quartz with no coesite or relict features such as radial cracks. The residual pressures retained by the quartz inclusions systematically increase from the crystal centre to the margin of the inner segment. The metamorphic conditions estimated by calculation from the residual pressure and conventional thermodynamic calculation range from 500 to 630 °C and 1.3 to 2.3 GPa for the stage of the inner segment. Coesite and its pseudomorph occur as inclusions in the outer segment of the garnet and matrix omphacite. This occurrence of coesite is consistent with the pressure and temperature conditions of 660–725 °C and 3.1 GPa estimated by conventional geothermobarometry. Our results suggest that the quartz inclusions in the inner segment were trapped by garnet under α‐quartz‐stable conditions and survived phase transition to coesite at the peak metamorphic stage. The SiO₂ phases and other inclusions in the garnet have retained evidence of the pre‐eclogite prograde stage even during exhumation stage. The combined Raman spectroscopic and petrological approaches used here offers a powerful means for obtaining more robust constraints prograde stages involving garnet growth where different SiO₂ phases are present as inclusions.     

Timing of Himalayan ultrahigh-pressure metamorphism: sinking rate and subduction angle of the Indian continental crust beneath Asia

Coesite relics were discovered as inclusions in clinopyroxene in eclogite and as inclusions in zircon in felsic and pelitic gneisses from Higher Himalayan Crystalline rocks in the upper Kaghan Valley, north‐west Himalaya. The metamorphic peak conditions of the coesite‐bearing eclogites are estimated to be 27–32 kbar and 700–770 °C, using garnet–pyroxene–phengite geobarometry and garnet–pyroxene geothermometry, respectively. Cathodoluminescence (CL) and backscattered electron (BSE) imaging distinguished three different domains in zircon: inner detrital core, widely spaced euhedral oscillatory zones, and thin, broadly zoned outermost rims. Each zircon domain contains a characteristic suite of micrometre‐sized mineral inclusions which were identified by in situ laser Raman microspectroscopy. Core and mantle domains contain quartz, apatite, plagioclase, muscovite and rutile. In contrast, the rim domains contain coesite and minor muscovite. Quartz inclusions were identified in all coesite‐bearing zircon grains, but not coexisting with coesite in the same growth domain (rim domain). ²⁰⁶Pb/²³⁸U zircon ages reveal that the quartz‐bearing mantle domains and the coesite‐bearing rim were formed at c. 50 Ma and 46.2 ± 0.7 Ma, respectively. These facts demonstrate that the continental materials were buried to 100 km within 7–9 Myr after initiation of the India–Asia collision (palaeomagnetic data from the Indian oceanic floor supports an initial India‐Asia contact at 55–53 Ma). Combination of the sinking rate of 1.1–1.4 cm year^?1 with Indian plate velocity of 4.5 cm year^?1 suggests that the Indian continent subducted to about 100 km depth at an average subduction angle of 14–19°.     

High-density nitrogen inclusions in barite from a giant siderite vein: implications for Alpine evolution of the Variscan basement of Western Carpathians, Slovakia

Contrasting compositions and densities of fluid inclusions were revealed in siderite–barite intergrowths of the Dro?diak polymetallic vein hosted in Variscan basement of the Gemeric unit (Central European Carpathians). Primary two‐phase aqueous inclusions in siderite homogenized between 101 and 165 °C, total salinity ranged between 18 and 27 wt%, and CaCl₂/(NaCl + CaCl₂) weight ratios were fixed at 0.1–0.3. By contrast, mono‐ and two‐phase aqueous inclusions in barite exhibited total salinities between 2 and 22 wt%, and the CaCl₂/NaCl ratios ranged from NaCl‐ to CaCl₂‐dominated compositions. The aqueous inclusions in barite were closely associated with very high‐density (0.55–0.745 g cm^?3) nitrogen inclusions, in some cases containing up to 16 mol.% CO₂. Crystallization P–T conditions of siderite (175–210 °C, 1.2–1.7 kbar) constrained by the vertical oxygen isotope gradient along the studied vein, isochores of fluid inclusions and the K/Na exchange thermometer corresponded to minimal palaeodepths between 4.3 and 6.3 km, assuming lithostatic load and average crust density of 2.75 g cm^?3. Maximum fluid pressure during barite crystallization attained 3.6–4.4 kbar at 200–300 °C, and the most dense nitrogen inclusions maintained without decrepitation the residual internal pressure of 2.2 kbar at 25 °C. Contrasting fluid compositions, increasing depths of burial (～4–14 km) and decreasing thermal gradients (～40–15 °C km^?1) during initial mineralization stages of the Dro?diak vein reflect Alpine orogenic processes, rather than an incipient Permian rifting suggested in previous metallogenetic models. Siderite crystallized at rising P–T in a closed, rock‐buffered hydrothermal system developed in the Variscan basement during the north‐vergent Cretaceous thrusting and thickening of the Gemeric crustal wedge. Variable salinities of the barite‐hosted inclusions reflect a fluid mixing in open hydrothermal system, and re‐equilibration textures (lengths of decrepitation cracks proportional to fluid inclusion sizes) correspond to retrograde crystallization trajectory coincidental with transpression or unroofing. Maximum recorded fluid pressures indicate ～12‐km‐thick pile of imbricated nappe units accumulated over the Gemeric basement during the Cretaceous collision.     

Petrology of coesite-bearing eclogite from Habutengsu Valley, western Tianshan, NW China and its tectonometamorphic implication

Coesite inclusions in garnet have been found in eclogite boudins enclosed in coesite‐bearing garnet micaschist in the Habutengsu Valley, Chinese western Tianshan, which are distinguished from their retrograde quartz by means of optical characteristics, CL imaging and Raman spectrum. The coesite‐bearing eclogite is mainly composed of porphyroblastic garnet, omphacite, paragonite, glaucophane and barroisite, minor amounts of rutile and dotted (or banded) graphite. In addition to coesite and quartz, the zoned porphyroblastic garnet contains inclusions of omphacite, Na‐Ca amphibole, calcite, albite, chlorite, rutile, ilmenite and graphite. Multi‐phase inclusions (e.g. Czo + Pg ± Qtz, Grt II + Qtz and Chl + Pg) can be interpreted as breakdown products of former lawsonite and possibly chloritoid. Coesite occurs scattered within a compositionally homogenous but narrow domain of garnet (outer core), indicative of equilibrium at the UHP stage. The estimate by garnet‐clinopyroxene thermometry yields peak temperatures of 420–520 °C at 2.7 GPa. Phase equilibrium calculations further constrain the P–T conditions for the UHP mineral assemblage Grt + Omp + Lws + Gln + Coe to 2.4–2.7 GPa and 470–510 °C. Modelled modal abundances of major minerals along a 5 °C km^?1 geothermal gradient suggests two critical dehydration processes at ～430 and ～510 °C respectively. Computed garnet composition patterns are in good agreement with measured core‐rim profiles. The petrological study of coesite‐bearing eclogite in this paper provides insight into the metamorphic evolution in a cold subduction zone. Together with other reported localities of UHP rocks from the entire orogen of Chinese western Tianshan, it is concluded that the regional extent of UHP‐LT metamorphism in Chinese western Tianshan is extensive and considerably larger than previously thought, although intensive retrogression has erased UHP‐LT assemblages at most localities.     

High Pressure Response of Rutile Polymorphs and Its Significance for Indicating the Subduction Depth of Continental Crust

α-PbO2-type TiO2 （TiO2-Ⅱ） is an important index mineral for ultrahigh-pressure metamorphism. After the discovery of a natural high-pressure phase of titanium oxide with α-PbO2- structure in omphacite from coesite-bearing eclogite at Shima in the Dabie Mountains, China, a nanoscale （〈2 nm） α-PbO2-type TiO2 has been identified through electron diffraction and high-resolution transmission electron microscopy in coesite-bearing jadeite quartzite at Shuanghe in the Dabie Mountains. The crystal structure is orthorhombic with lattice parameters a = 4.58×10-1 nm, b = 5.42×10-1 nm, c = 4.96×10-1 nm and space group Pbcn. The analysis results reveal that ruffle {011}R twin interface is a basic structural unit of α-PbO2-type TiO2. Nucleation of α-PbO2-type TiO2 lamellae is caused by the displacement of one half of the titanium cations within the {011}R twin slab. This displacement reduces the Ti-O-Ti distance and is favored by high pressure. The identification of α- PbO2-type TiO2 in coesite-bearing jadeite quartzite from Shuanghe, Dabie Mountains, provides a new and powerful evidence of ultrahigh-pressure metamorphism at 4--7 GPa, 850℃-900℃, and implies a burial of continental crustal rocks to 130-200 kilometers depth or deeper. The α-PbO2-type TiO2 may be a useful indicator of the pressure and temperature in the diamond stability field.     

TEM investigation of the crystal microstructures in a quartz-coesite assemblage of the western alps

Atransmission electron microscope (TEM) study of quartz-coesite inclusions in garnet in crustal rocks from the Western Alps is presented. Coesite shows a low dislocation density (<10⁷ cm^?2), and quartz a higher density of defects, Brasil twins (10⁴ cm^?1) and dislocations (10⁸ cm^?2). It is concluded that coesite has been not or only slightly plastically deformed and that the yield strength of coesite is higher than that of quartz. The large scale deformation implications are briefly discussed. TEM observations show no systematic topotactic relationship between the two polymorphs and their boundaries have a scalloped morphology which suggests that growth of quartz from coesite was controlled by a diffusion process.     

Raman microprobe (RMP) determinations of natural and synthetic coesite

Raman microprobe (RMP) spectra of synthetic coesiste and three natural coesites from eclogite — facies rocks are provided and evaluated for characterisation purposes. The main coesite line lies at 521 cm^?1 and the other characteristic lines attributed to coesite occur at 117, 177 and 271 cm^?1. Two petrologically useful applications were (a) the confirmation of the coesite structure in very small natural crystals deduced to be coesite from petrographic observations only, and (b) the recognition of sub-microscopic crystallites of quartz in incipiently — transformed coesite in all the natural samples.     

Quartz paramorphs after former stishovite in UHP eclogite from the South Altyn Tagh,Western China and its Significance

The long prism/needle‐shaped polycrystalline quartz aggregates and square/parallelogram‐shaped singlephase quartz inclusions in omphacite and garnet of ultrahigh pressure eclogite were first discovered from the Jiangalesayi area, South Altyn UHP belt. Based on their morphology, these quartz inclusions are quartz paramorphs after stishovite. The minimum peak pressure of the eclogite is estimated to be >8–9 GPa at 800– 1000 °C based on the stability field of stishovite. This new evidence, together with previous stishovite exsolution microstructure in the gneiss from the same region, suggests an ultra‐deep subduction and exhumation of the South Altyn continental rocks to/from mantle depths in stishovite stability field. Evidence of ultra‐deep subduction of continental materials might be more common and diverse than previous thought. Exhumation of subducted continental rocks from≥300 km has been considered impossible because they are denser than mantle at these depths. How did the stishovite bearing continental rocks of the South Altyn exhumated? As we all know, the densities of stishovite (4.3 g/cm³) are much higher than coesite (2.9 g/cm³), and stishovite transforms into coesite with temperature increases. Density calculations were performed for subducted continental rocks along phase transition of stishovite to coesite, using the third‐order Birch‐Murnaghan equation of state based on mineral fractions obtained from experiments and Perple_X. The results show that the density of Siliceous rocks decrease remarkably, lower than the surrounding mantle in coesite stability field, whereas the density of Oligosiliceous and Silicon unsaturated rocks is higher than surrounding mantle. Thus, we propose that the thermal induced transformation could provide an initial driven force for the exhumation of ultra‐deep subducted silica‐enriched felsic continental rocks. Temperature increase could be derived from an increased geothermal gradient from convective mantle or mantle plume. Mafic to ultra‐mafic rocks and silica‐deficient rocks may be captured by the upwelling subducted continental rocks and exhumated together.     

Quartz‐in‐garnet and Ti‐in‐quartz thermobarometry: Methodology and first application to a quartzofeldspathic gneiss from eastern Papua New Guinea

Mineral inclusions are ubiquitous in metamorphic rocks and elastic models for host‐inclusion pairs have become frequently used tools for investigating pressure–temperature (P–T) conditions of mineral entrapment. Inclusions can retain remnant pressures () that are relatable to their entrapment P–T conditions using an isotropic elastic model and P–T–V equations of state for host and inclusion minerals. Elastic models are used to constrain P–T curves, known as isomekes, which represent the possible inclusion entrapment conditions. However, isomekes require a temperature estimate for use as a thermobarometer. Previous studies obtained temperature estimates from thermometric methods external of the host‐inclusion system. In this study, we present the first P–T estimates of quartz inclusion entrapment by integrating the quartz‐in‐garnet elastic model with titanium concentration measurements of inclusions and a Ti‐in‐quartz solubility model (QuiG‐TiQ). QuiG‐TiQ was used to determine entrapment P–T conditions of quartz inclusions in garnet from a quartzofeldspathic gneiss from Goodenough Island, part of the (ultra)high‐pressure terrane of Papua New Guinea. Raman spectroscopic measurements of the 128, 206, and 464 cm^?1 bands of quartz were used to calculate inclusion pressures using hydrostatic pressure calibrations (), a volume strain calculation (), and elastic tensor calculation (), that account for deviatoric stress. values calculated from the 128, 206, and 464 cm^?1 bands’ hydrostatic calibrations are significantly different from one another with values of 1.8 ± 0.1, 2.0 ± 0.1, and 2.5 ± 0.1 kbar, respectively. We quantified elastic anisotropy using the 128, 206 and 464 cm^?1 Raman band frequencies of quartz inclusions and stRAinMAN software (Angel, Murri, Mihailova, & Alvaro, 2019,  234 :129–140). The amount of elastic anisotropy in quartz inclusions varied by ~230%. A subset of inclusions with nearly isotropic strains gives an average and of 2.5 ± 0.2 and 2.6 ± 0.2 kbar, respectively. Depending on the sign and magnitude, inclusions with large anisotropic strains respectively overestimate or underestimate inclusion pressures and are significantly different (<3.8 kbar) from the inclusions that have nearly isotropic strains. Titanium concentrations were measured in quartz inclusions exposed at the surface of the garnet. The average Ti‐in‐quartz isopleth (19 ± 1 ppm [2σ]) intersects the average QuiG isomeke at 10.2 ± 0.3 kbar and 601 ± 6°C, which are interpreted as the P–T conditions of quartzofeldspathic gneiss garnet growth and entrapment of quartz inclusions. The P–T intersection point of QuiG and Ti‐in‐quartz univariant curves represents mechanical and chemical equilibrium during crystallization of garnet, quartz, and rutile. These three minerals are common in many bulk rock compositions that crystallize over a wide range of P–T conditions thus permitting application of QuiG‐TiQ to many metamorphic rocks.     

The timing of stabilisation and the exhumation rate for ultra-high pressure rocks in the Western Gneiss Region of Norway

New petrographic evidence and a review of the latest radiometric age data are taken to indicate that formation of the ultra‐high pressure (UHP) eclogites within the Western Gneiss Region of Norway probably occurred within the 400–410 Ma time frame. Thus, this event took place significantly later than the previous, widely accepted age of c. 425 Ma for the timing of the high pressure metamorphism in this part of the Scandinavian Caledonides. Garnet growth under UHP (coesite‐stable) conditions is recognised as a discrete, younger event following on from earlier garnet formed under firstly amphibolite facies then quartz‐stable, eclogite facies conditions. Currently, the best constrained and most precise age, specifically for UHP mineral growth, is the 402 ± 2 Ma U–Pb age for metamorphic zircon (some of which retain coesite inclusions) from the Hareidland eclogite. Exhumation must have followed shortly thereafter and, based on synoptic pressure–temperature and depth–time curves, must have been very fast. Our data and those of others indicate an initial fast exhumation to about 35 km depth by about 395 Ma at a mean rate of about 10 mm a^?1. This rapid exhumation rate may have been driven by the appreciable residual buoyancy of the deeply subducted continental crustal slab due to incomplete eclogitization of the dominant Proterozoic orthogneisses during the short‐lived UHP event. Subsequent exhumation to 8–10 km depth by about 375 Ma occurred at a much slower mean rate of about 1.3 mm a^?1 with the late‐stage extensional collapse of the Caledonian orogen playing an increasingly important role, especially in the final unroofing of the Western Gneiss Region with some remarkably preserved UHP rocks.     

Discovery of diamond in the Tromsø Nappe,Scandinavian Caledonides (N. Norway)

We report the first finding of diamond in crustal rocks from the Tromsø Nappe of the North Norwegian Caledonides. Diamond occurs in situ as inclusions in garnet from gneiss at Tønsvika near Tromsø. The rock is composed essentially of garnet, biotite, white mica, quartz and plagioclase, minor constituents include kyanite, zoisite, rutile, tourmaline, amphibole, zircon, apatite and carbonates (magnesite, dolomite, calcite). The microdiamond, identified by micro‐Raman spectroscopy, is cuboidal to octahedral in shape and ranges from 5 to 50 μm in diameter. The diamond occurs as single grains and as composite diamond + carbonate inclusions. Diamond vibration bands show a downshift from 1 332 to 1 325 cm^?1, the majority of Raman peaks are centred between 1 332 and 1 330 cm^?1 and all peaks exhibit a full width at half maximum between 3 and 5 cm^?1. Several spectra show Raman bands typical for disordered and ordered graphite (sp²‐bonded carbon) indicating partial transformation of diamond to graphite. The calculated peak P–T conditions for the diamond‐bearing sample are 3.5 ± 0.5 GPa and 770 ± 50 °C. Metamorphic diamond found in situ in crustal rocks of the Tromsø Nappe thus provides unequivocal evidence for ultrahigh pressure metamorphism in this allochthonous unit of the Scandinavian Caledonides. Deep continental subduction, most probably in the Late Ordovician and shortly before or during the initial collision between Baltica and Laurentia, was required to stabilize the diamond at UHP conditions.     

SHRIMP U–Pb ages of ultrahigh-pressure and retrograde metamorphism of gneisses, south-western Sulu terrane, eastern China

Laser Raman spectroscopy and cathodoluminescence (CL) images reveal that most zircon separated from paragneiss and orthogneiss in drillhole CCSD‐PP2 at Donghai, south‐western Sulu terrane, retain low‐P mineral‐bearing inherited cores, ultrahigh‐pressure (UHP) mineral‐bearing mantles and low‐P mineral‐bearing (e.g. quartz) rims. SHRIMP U–Pb analyses of these zoned zircon identify three discrete and meaningful age groups: Proterozoic protolith ages (> 680 Ma) are recorded in the inherited cores, the UHP metamorphic event in the coesite‐bearing mantles occurred at 231 ± 4 Ma, and the late amphibolite facies retrogressive overprint in the quartz‐bearing rims was at 211 ± 4 Ma. Thus, Neoproterozoic supracrustal protoliths of the Sulu UHP rocks were subducted to mantle depths in the Middle Triassic, and exhumed to mid‐crustal levels in the Late Triassic. The exhumation rate deduced from the SHRIMP data and metamorphic P–T conditions is 5.0 km Ma^?1. Exhumation of the Sulu UHP terrane may have resulted from buoyancy forces after slab break‐off at mantle depths.     

Determining the amount of overstepping required to nucleate garnet during Barrovian regional metamorphism,Connecticut Valley Synclinorium

The novel method of inclusion barometry coupled with the calculation of the required affinity for garnet nucleation is applied to three samples from the previously well‐characterized Connecticut Valley Synclinorium in central Vermont. Raman shifts for quartz inclusions record a range of maximum peak shifts of the quartz 464 cm^?1 peak from 2.4 to 3.0 cm^?1. Temperature of garnet nucleation was constrained by calculating mineral assemblage diagrams in the MnNCKFMASHT system and plotting the intersection of quartz inclusion in garnet barometry (QuiG, quartz‐in‐garnet) with Zr‐in‐rutile thermometry. Utilizing the intersection of Zr‐in‐rutile thermometry with QuiG barometry, garnet nucleation is inferred to have occurred within a P–T range of ~8.6–9.5 kbar and ~560–575°C. These P–T conditions for garnet nucleation are significantly higher than calculated equilibrium garnet‐in isograds for the three samples. Affinities for garnet nucleation were calculated as the difference between the free energy of a fictive garnet composition based on the matrix assemblage and the free energy of the nucleated garnet. The calculated nucleation affinity varied from 300 to 600 kJ/mol O for St–Ky grade samples. These results suggest that the assumption that metamorphism proceeds as a sequence of near‐equilibrium conditions cannot, in general, be made for regional metamorphic terranes. This body of work agrees with numerous recent studies showing that garnet‐producing reactions must be overstepped in order to for garnet to nucleate.     

Experimental study of quartz inclusions in garnet at pressures up to 3.0 GPa: evaluating validity of the quartz-in-garnet inclusion elastic thermobarometer

Garnet crystals with quartz inclusions were hydrothermally crystallized from oxide starting materials in piston–cylinder apparatuses at pressures from 0.5 to 3 GPa and temperatures ranging from 700 to 800 °C to study how entrapment conditions affect remnant pressures of quartz inclusions used for quartz-in-garnet (QuiG) elastic thermobarometry. Systematic changes of the 128, 206 and 464 cm^?1 Raman band frequencies of quartz were used to determine pressures of quartz inclusions in garnet using Raman spectroscopy calibrations that describe the P–T dependencies of Raman band shifts for quartz under hydrostatic pressure. Within analytical uncertainties, inclusion pressures calculated for each of the three Raman band frequencies are equivalent, which suggests that non-hydrostatic stress effects caused by elastic anisotropy in quartz are smaller than measurement errors. The experimental quartz inclusions have pressures ranging from ??0.351 to 1.247 GPa that span the range of values observed for quartz inclusions in garnets from natural rocks. Quartz inclusion pressures were used to model P–T conditions at which the inclusions could have been trapped. The accuracy of QuiG thermobarometry was evaluated by considering the differences between pressures measured during experiments and pressures calculated using published equation of state parameters for quartz and garnet. Our experimental results demonstrate that Raman measurements performed at room temperature can be used without corrections to estimate garnet crystallization pressures. Calculated entrapment pressures for quartz inclusions in garnet are less than ~?10% different from pressures measured during the experiments. Because the method is simple to apply with reasonable accuracy, we expect widespread usage of QuiG thermobarometry to estimate crystallization conditions for garnet-bearing silicic rocks.     

Fluid inclusion constraints on the uplift history of the metamorphosed massive sulphide deposits at Ducktown, Tennessee

Abstract Standard petrographic, microthermometric and Raman spectroscopic analyses of fluid inclusions from the metamorphosed massive sulphide deposits at Ducktown, Tennessee, indicate that fluids with a wide range of compositions in the C–O–H–N–S–salt system were involved in the syn- to post-metamorphic history of these deposits. Primary fluid inclusions from peak metamorphic clinopyroxene contain low-salinity, H₂O–CH₄ fluids and calcite, quartz and pyrrhotite daughter crystals. Many of these inclusions exhibit morphologies resembling those produced in laboratory experiments in which confining pressures significantly exceed the internal pressures of the inclusions. Secondary inclusions in metamorphic quartz from veins, pods, and host matrix record a complex uplift history involving a variety of fluids in the C–O–H–N–salt system. Early fluids were generated by local devolatilization reactions while later fluids were derived externally. Isochores calculated for secondary inclusions in addition to the chronology of trapping and morphological features of primary and secondary fluid inclusions suggest an uplift path which was concave toward the temperature axis over the P–T range 6–3 kbar and 550–225° C. Immiscible H₂O–CH₄–N₂–NaCl fluids were trapped under lithostatic to hydrostatic pressure conditions at 3–0.5 kbar and 215 ± 20° C. Entrapment occurred during Alleghanian thrusting, and the fluids may have been derived by tectonically driven expulsion of pore fluids and thermal maturation of organic material in lower-plate sedimentary rocks which are thought to underlie the deposits. Episodic fracturing and concomitant pressure decreases in upper-plate rocks, which host the ore bodies, would have allowed these fluids to move upward and become immiscible. Post-Alleghanian uplift appears to have been temperature-convex. Uplift rates of 0.10–0.05 mm year^?1 from middle Ordovician to middle Silurian – late Devonian, and 0.07–0.12 mm year^?1 from middle Silurian – late Devonian to late Permian are suggested by our uplift path and available geochronological data.     

Raman spectroscopy of natural silica in Chicxulub impactite,MexicoSpectroscopie Raman de silices naturelles dans l'impactite de Chicxulub,Mexique

A series of natural silica impactite samples from Chicxulub (Mexico) was investigated by Raman microprobe (RMP) analysis. The data yield evidence for high-pressure shock metamorphism in the rock. The impactite contains three polymorphs of silica: the original α-quartz, and two high-pressure varieties – coesite and disordered quartz representing various degrees of crystallinity. We found systematic changes in frequencies and half-widths of the Raman bands, caused by increasing irregularities of bond-lengths and bond-angles and a general breaking-up of the structure as a result of impact events. Therefore, RMP is an adequate tool for measuring the crystallinity of disordered quartz. The half-width Γ and the frequency ω of the symmetric SiOSi stretching vibrational band (A₁ mode) of the SiO₄ tetrahedra are the most amenable parameters for estimating the degree of crystallinity. In well-crystallized quartz, Γ=5 cm^?1 and ω=464 cm^?1, while in highly disordered quartz this line shifts up to ω=455 cm^?1 and broadens up to Γ=30 cm^?1. The Raman lineshapes appear to depend strongly on the degree of lattice disorder subsequent to impact events. To cite this article: M. Ostroumov et al., C. R. Geoscience 334 (2002) 21–26     

CO_2 Density-Raman Shift Relation Derived from Synthetic Inclusions in Fused Silica Capillaries and Its Application

Abstract: The densities of CO2 inclusions in minerals are commonly used to determine the crystallizing conditions of the host minerals. However, conventional microthermometry is difficult to apply for inclusions of small size (< 5–10 μm) or low density. Raman analysis is an alternative method for determining CO2 density, provided that the CO2 density–Raman shift relation is known. This study aims to establish this CO2 density–Raman shift relation by using CO2 inclusions synthesized in fused silica capillaries. By using this newly-developed synthetic technique, we formed pure CO2 inclusions, and their densities were determined by microthermometry. The Raman analysis showed that the relation between CO2 density (D in g/cm3) and the separations (Δ in cm?1) between the two main bands (i.e. Fermi diad bands) in CO2 Raman spectra can be represented by a cubic equation: D (g/cm3)=0.74203(?0.019Δ3+5.90332Δ2?610.79472Δ+21050.30165)?3.54278 (r2=0.99920). Our calculated D value for a given Δ is between those obtained from two previously-reported equations, which were derived from different experimental methods. An example was given in this study to demonstrate that the densities of natural CO2 inclusions that could not be derived from microthermometry could be determined by using our method.     

Integrating X‐ray mapping and microtomography of garnet with thermobarometry to define the P–T evolution of the (near) UHP Międzygórze eclogite,Sudetes, SW Poland

Detailed X‐ray compositional mapping and microtomography have revealed the complex zoning and growth history of garnet in a kyanite‐bearing eclogite. The garnet occurs as clusters of coalesced grains with cores revealing slightly higher Ca and lower Mg than the rims forming the coalescence zones between the grains. Core regions of the garnet host inclusions of omphacite with the highest jadeite, and phengite with the highest Si, similar to values in the cores of omphacite and phengite located in the matrix. Therefore, the core compositions of garnet, omphacite, and phengite have been chosen for the peak pressure estimate. Coupled conventional thermobarometry, average P–T, and phase equilibrium modelling in the NCKFMMnASHT system yields P–T conditions of 26–30 kbar at 800–930°C. Although coesite is not preserved, these P–T conditions partially overlap the coesite stability field, suggesting near ultra‐high–pressure (UHP) conditions during the formation of this eclogite. Therefore, the peak pressure assemblage is suggested to have been garnet–omphacite–kyanite–phengite–coesite/quartz–rutile. Additional lines of evidence for the possible UHP origin of the Mi?dzygórze eclogite are the presence of rod‐shaped inclusions of quartz parallel to the c‐axis in omphacite as well as relatively high values of Ca‐Tschermak and Ca‐Eskola components. Late zoisite, rare diopside–plagioclase symplectites rimming omphacite, and minor phlogopite–plagioclase symplectites replacing phengite formed during retrogression together with later amphibole. These retrograde assemblages lack minerals typical of granulite facies, which suggests simultaneous decompression and cooling during exhumation before the crustal‐scale folding that was responsible for final exhumation of the eclogite.     

Partial melting of metapelites at ultrahigh-pressure conditions, Greenland Caledonides

Eclogite, orthogneiss and, by association, metapelite from an island at 78°N in North‐East Greenland experienced ultrahigh‐pressure (UHP) metamorphism at approximately 970 °C and 3.6 GPa, at the end of the Caledonian collision, 360–350 Ma. Hydrous metapelites contain abundant leucocratic layers and lenses composed of medium‐grained, anhedral, equigranular quartz, antiperthitic plagioclase and K‐feldspar with minor small garnet and kyanite crystals. Leucosomes are generally parallel to the matrix foliation, are interlayered with residual quartz bands, anastomose around residual garnet and commonly cross‐cut micaceous segregations. Textures suggest that the leucosomes crystallized from a syntectonic melt, but crystallized at the end of local high‐grade deformation. The metapelite outcrop is < 1.5 km from kyanite eclogites with confirmed coesite, but the metapelites lack coesite and palisade textures diagnostic of coesite pseudomorphs. They do contain highly fractured garnet megacrysts with polycrystalline quartz inclusions (some surrounded by radial fractures) and Ti‐rich phengite inclusions that suggest the former presence of coesite. Polyphase inclusions in garnet contain reactants and products of the inferred dehydration melting reaction: Phe + Qtz = Ky + Kfs + Rt + melt. The reactants are thought to have been early inclusions of hydrous phases within garnet that melted and then crystallized new phases. Garnet surrounding these inclusions has patchy zoning with elevated Ca, consistent with experiments that produced similar patchy microstructures in garnet around inclusions with an unequivocal melt origin. The peak UHP metamorphic assemblage in these rocks is inferred to have been phengite, coesite, garnet, kyanite, rutile, fluid ± omphacite ± epidote. Phase diagrams indicate that dehydration melting of phengite in this assemblage would have occurred after decompression from peak pressure, but still above the coesite to quartz transition. Unusual crown‐ and moat‐like textures in garnet around some polycrystalline quartz inclusions are also consistent with the inference that melting took place at UHP conditions.