Metamorphic decarbonation in the Neoproterozoic and its environmental implication

Metamorphic decarbonation reactions and volcanic degassing lead to significant influx of CO₂, a major greenhouse gas, into the ocean-atmosphere system from the solid Earth. Here we present quantitative estimates on CO₂ derived through metamorphic degassing during ultrahigh-temperature (UHT) metamorphism in the Neoproterozoic through the mineralogical and geological analyses of the UHT decarbonation. Our computations show that an extra flux of CO₂ was added to the atmosphere through a Himalayan scale UHT metamorphism to the extent of 6 × 10¹⁶ to 3.0 × 10¹⁸ mol/my, for a duration of 10 my. A calculation of the impact of the extra CO₂ influx to the global mean temperature in the context of carbon cycle and greenhouse effect of CO₂ shows that at the peak influx stage, the steady state temperature would be raised by 4 °C from 15 °C and by 13 °C from 4 °C. Our results have important bearing in evaluating the mechanism of melting and the duration of the Snowball Earth. Our estimate of the maximum degassing rate during UHT metamorphism suggests that the duration of the Marinoan snowball Earth was probably shorter, and the recovery from an ice-covered Earth to ocean-covered Earth was faster than previous estimates.     

Granulite facies metasomatism: zoned calc-silicate boudins from the Rauer Group,East Antarctica

Calc-silicate boudins from the Rauer Group, East Antarctica, were metamorphosed under granulite facies conditions during late Proterozoic (ca. 1,000 Ma) M3 metamorphism. Boudin cores contain low to moderate a_{CO 2} assemblages including wollastonite, grossularandradite (grandite) garnet, clinopyroxene, scapolite, plagioclase, quartz±calcite. Petrological and stable isotopic evidence suggests that these core assemblages resulted from pre-peak M3 infiltration of water-rich fluids; there is no evidence for a pervasive fluid phase under peak M3 conditions. The boudins are separated from the surrounding Fe-rich pelites and semi-pelites by a series of concentric, high-variance reaction zones developed under peak M3 conditions. Variations in mineral assemblage, mineral composition and whole rock composition across these zones suggest that they formed by diffusional masstransfer, controlled principally by a chemical potential gradient in Ca across the original calc-silicate-paragneiss lithological boundary. As a consequence of the nearcomplete decarbonation of the calc-silicatesbefore the M3 peak, development of the diffusion-controlled reaction zones did not liberate significant CO₂ during granulite facies metamorphism. Similar calcite-poor, low a_{CO 2} calc-silicate horizons in other granulite facies terrains are unlikely to have been important local fluid sources during deep crustal metamorphism.     

Newly discovered youngest UHT metamorphism on Earth,Western Sulawesi,Indonesia

Ultrahigh-temperature (UHT) metamorphism represents an extreme crustal thermal event with peak conditions exceeding 900 °C at 7–13 kbar. In the modern-style plate tectonic system, records of the UHT metamorphism are relatively rare due to the secular cooling of Earth. In the Palu region of Western Sulawesi, we newly discovered a series of HT-UHT metamorphic rocks including amphibolite, granulite, eclogites and gneiss. Of them, two granulite samples (18CS14-2, 18CS14-4) with high garnet content (>50 mol%) are chosen for petrographic observation, phase equilibrium modelling, and zircon U-Pb dating. These rocks are characterized by a relic M₁ assemblage of Grt + Ky + Bt + Rt and a M₂ assemblage of Grt + Sil + Pl + Spl + Crd ± Qtz + Ilm + melt. Phase equilibrium modelling based on effective bulk compositions yields UHT conditions of 7.2–8.5 kbar/940–1080 °C (18CS14-2) and 7.0–7.3 kbar/1000–1040 °C (18CS14-4). U-Pb analysis reveals two generations of metamorphic zircon with evolving REE content that is intimately related to garnet growth and decomposition. Zircon age of 36–5.3 Ma is ascribed to syn- to post-M₁ metamorphism, whereas the young zircon age of 5.1–3.8 Ma is linked to syn- and post-M₂ stage. The UHT metamorphism was probably the consequence of the upwelling of asthenospheric mantle triggered by post-collisional delamination of lithosphere in the Miocene-Pliocene (ca. 5 Ma). It could represent the youngest known UHT metamorphism on Earth.     

Decarbonation reaction of magnesite in subducting slabs at the lower mantle

High-pressure and temperature experiments (28–62 GPa, and 1,490–2,000 K, corresponding to approximately 770–1,500 km depth in the mantle) have been conducted on a MgCO₃ + SiO₂ mixture using a laser-heated diamond anvil cell combined with analytical transmission electron microscope observation of the product phases to constrain the fate of carbonates carried on the subducting basalt into the lower mantle. At these conditions, the decarbonation reaction MgCO₃ (magnesite) + SiO₂ (stishovite) → MgSiO₃ (perovskite) + CO₂ (solid) has been recognized. This indicates that above reaction takes place as a candidate for decarbonation of the carbonated subducting mid ocean ridge basalts in the Earth’s lower mantle.     

火成碳酸岩的实验岩石学研究及对地球深部碳循环的意义

火成碳酸岩是地表出露较少的幔源岩石之一。实验岩石学研究表明碳酸盐化的橄榄岩和循环的地壳物质(如碳酸盐化榴辉岩或泥质岩)的低程度(<1%)部分熔融均可以产生碳酸岩质的熔体,其中碳酸盐化泥质岩具有最低的熔融温度且更加富碱质、CO2和不相容元素;富CO2的霞石质等硅酸盐岩浆也可以通过不混溶或分离结晶作用产生碳酸岩,用于解释碳酸岩在空间中常与碱性硅酸岩的共生关系。由于碳酸岩熔体具有极低的粘度和高的活性,形成后在上升过程中会将二辉橄榄岩转变为异剥橄榄岩,是引起地幔交代作用和地幔地球化学不均一性的重要介质之一。实验表明在俯冲作用过程中,大多数的碳酸盐在位于岛弧之下的含水熔融并不分解而是被带入到深部地幔并且稳定存在,含碳地幔的熔融又会形成碳酸岩质的熔体,这说明俯冲循环物质可能对碳酸岩的成因也起着重要的作用。然而,对于碳酸岩的初始熔体成分、岩浆演化、地幔交代作用、成矿特征以及碳从地球深部返回到地表的途径和过程等都存在着很大的争议。我国火成碳酸岩出露相对较多,分布广泛,因此,加强我国碳酸岩以及伴生硅酸岩的成因研究,同时开展与碳酸岩相关的实验岩石学工作,不仅可以检验现有的成因理论,而且有助于提高我国对火成碳酸岩的研究水平;由于其特殊的成因背景,还可为许多存在很大争议的重大地质事件提供新的科学依据。     

Refining the P–T records of UHT crustal metamorphism

Ultra‐high‐temperature (UHT) metamorphism occurs when the continental crust is subjected to temperatures of greater than 900 °C at depths of 20–40 km. UHT metamorphism provides evidence that major tectonic processes may operate under thermal conditions more extreme than those generally produced in numerical models of orogenesis. Evidence for UHT metamorphism is recorded in mineral assemblages formed in magnesian pelites, supported by high‐temperature indicators including mesoperthitic feldspar, aluminous orthopyroxene and high Zr contents in rutile. Recent theoretical, experimental and thermodynamic data set constraints on metamorphic phase equilibria in FMAS, KFMASH and more complex chemical systems have greatly improved quantification of the P–T conditions and paths of UHT metamorphic belts. However, despite these advances key issues that remain to be addressed include improving experimental constraints on the thermodynamic properties of sapphirine, quantifying the effects of oxidation state on sapphirine, orthopyroxene and spinel stabilities and quantifying the effects of H₂O–CO₂ in cordierite on phase equilibria and reaction texture analysis. These areas of uncertainty mean that UHT mineral assemblages must still be examined using theoretical and semi‐quantitative approaches, such as P(–T)–μ sections, and conventional thermobarometry in concert with calculated phase equilibrium methods. In the cases of UHT terranes that preserve microtextural and mineral assemblage evidence for steep or ‘near‐isothermal’ decompression P–T paths, the presence of H₂O and CO₂ in cordierite is critical to estimates of the P–T path slopes, the pressures at which reaction textures have formed and the impact of fluid infiltration. Many UHT terranes have evolved from peak P–T conditions of 8–11 kbar and 900–1030 °C to lower pressure conditions of 8 to 6 kbar whilst still at temperature in the range of 950 to 800 °C. These decompressional P–T paths, with characteristic dP/dT gradients of ～25 ± 10 bar °C^?1, are similar in broad shape to those generated in deep‐crustal channel flow models for the later stages of orogenic collapse, but lie at significantly higher temperatures for any specified pressure. This thermal gap presents a key challenge in the tectonic modelling of UHT metamorphism, with implications for the evolution of the crust, sub‐crustal lithosphere and asthenospheric mantle during the development of hot orogens.     

Thermal effects of massive CO2 emissions associated with subduction volcanism

Large volumes of CO₂ are emitted during volcanic activity at convergent plate boundaries, not only from volcanic centres. Their C isotopic signature indicates that this CO₂ is mainly derived from the decarbonation of subducted limestones or carbonated metabasalts, not as often admitted from magma degassing. On the example of Milos (Aegean Sea) it is argued that these fluids originate from intermediate depth in the mantle and carry sufficient heat to account for the generation of subduction-related magmas, as well as for the geothermal manifestations at the surface. The heat that is required for the decarbonation reactions is drawn by conduction from a wide zone surrounding the subducting slab and then rapidly transported upward by convection of the mixed CO₂–H₂O fluids that originate from the sediments in the slab. The transport takes place in a focused way through ‘chimneys’ in the upper mantle, where magmas are generated by the introduced heat and water. In the crust, the hot fluids cause thermal-dome-type metamorphism. In volcanic areas, magmas are commonly held responsible for the major part of heat transfer from the mantle to the surface. Here it is argued that most of the heat transfer is by hot gases. To cite this article: R.D. Schuiling, C. R. Geoscience 336 (2004).     

Fluid characteristics of retrogressed eclogites and mafic granulites from the Cambrian Gondwana suture zone in southern India

Eclogite-facies rocks and high-pressure granulites provide windows to the deeper parts of subduction zones and the root of mountain chains, carrying potential records of fluids associated with subduction-accretion-collision tectonics. Here, we report petrological and fluid inclusion data on retrogressed eclogite and high-pressure granulite samples from Sittampundi, Kanji Malai and Perundarai in southern India. These rocks occur within the trace of the Cambrian collisional suture which marks the final phase of amalgamation of the Gondwana supercontinent. The garnet–clinopyroxene assemblage in the eclogites preserves relict omphacite, whereas the high-pressure granulites are characterized by an assemblage of garnet and clinopyroxene in the absence of omphacite and with minor plagioclase, orthopyroxene, and quartz. Phase relations computed for the eclogite assemblage yield peak P–T conditions of 19 kbar and 1,010°C. The mafic granulites also preserve the memory of high to ultrahigh-temperature metamorphism followed by an isothermal decompression. Systematic fluid inclusion optical, microthermometric and laser Raman spectroscopic studies were conducted in garnet and plagioclase from the eclogite–high pressure granulite suite. The results suggest that the early fluids were a mixture of CO₂, CH₄ and N₂ probably derived from decarbonation and devolatilization reactions in a subduction setting during the prograde stage. The later generation inclusions, which constitute the dominant category in all the samples studied, are characterized by a near-pure CO₂ composition with moderate to high densities (up to 1.154 g/cm³). The highest density fluid inclusions recorded in this study occur within the mafic granulites from Sittampundi (0.968–1.154 g/cm³) and Kanji Malai (1.092–1.116 g/cm³). In some cases, carbonate minerals such as dolomite and calcite are associated with the CO₂-rich fluid inclusions. The composition and densities of the later generation fluids closely match with those of the CO₂-bearing fluid inclusions reported from ultrahigh-temperature granulites occurring proximal to the eclogite–high pressure granulite suite within this suture zone, and suggest a common tectonic link for the fluid regime. We evaluate the fluid characteristics associated with convergent plate margin processes and propose that the early aqueous fluids probably associated with the eclogites were consumed during the formation of the retrograde hydrous mineral assemblages, whereas the fluid regime of the high-pressure and ultrahigh-temperature granulites was mostly CO₂-dominated. The tectonic setting of the rocks along a collisional suture marking the trace along which crustal blocks were welded through subduction–collision process is in favor of a model involving the derivation of CO₂ from sub-lithospheric sources such as a carbonated tectosphere invaded by hot asthenosphere, or underplated mafic magmas.     

俯冲带碳酸盐化对深部碳循环的启示:以中国西南天山碳酸盐化云母片岩为例

俯冲带可将地球表层碳输送至深部地幔,同时也记录着俯冲板片来源碳质流体的迁移沉淀机制,对地球深部碳循环具有重大影响。近年来,俯冲带脱碳机制的研究表明流体溶解脱碳作用是冷的大洋俯冲板片释放COH流体的重要方式,而上覆板块(尤其地幔楔)则被认为是缓冲这些COH流体的重要场所,甚至是俯冲带CO_2的唯一"归宿"。事实上,俯冲带岩石本身的固碳能力却受到了忽视,而对俯冲带岩石捕获和固存CO_2(carbon capture and storage,CCS)能力的评估对全球碳通量的估算尤为重要。本文以中国西南天山高压-超高压变质带中碳酸盐化云母片岩为例,探讨俯冲带岩石的碳酸盐化对深部碳循环的影响。西南天山长阿吾子一带的碳酸盐化云母片岩记录了俯冲板片起源的碳质流体对俯冲带云母片岩的交代作用,地球化学特征表明蛇纹岩释放的富水流体溶解俯冲洋壳中的碳酸盐可能是产生COH流体的重要机制。基于碳质流体对多硅白云母(Si(a.p.f.u.)=3.58～3.73)的交代及相对高压的碳酸盐矿物(主要为白云石和菱镁矿)与金红石的共生,结合区域上碳酸盐化云母片岩与高压碳酸盐化蛇纹岩(HP-ophidolomite)的伴生,我们认为云母片岩的碳酸盐化作用可能发生在俯冲板片峰期稍后的高压折返阶段。俯冲带云母片岩的固碳作用表明除了上覆板块,俯冲带岩石本身对于碳质流体也具有很好的吸收能力。初步估算表明俯冲带云母片岩的碳酸盐化每年可固存至少2.46～6.68Mt/yr,约占俯冲板片每年进碳量的4%～17%。     

Carbonation and melting reactions in the system CaO–MgO–SiO2–CO2 at mantle pressures with geophysical and petrological applications

Bowen's petrogenetic grid was based initially on a series of decarbonation reactions in the system CaO-MgO-SiO₂-CO₂ with starting assemblages including calcite, dolomite, magnesite and quartz, and products including enstatite, forsterite, diopside and wollastonite. We review the positions of 14 decarbonation reactions, experimentally determined or estimated, extending the grid to mantle pressures to evaluate the effect of CO₂ on model mantle peridotite composed of forsterite(Fo)+orthopyroxene(Opx)+clinopyroxene(Cpx). Each reaction terminates at an invariant point involving a liquid, CO₂, carbonates, and silicates. The fusion curves for the mantle mineral assemblages in the presence of excess CO₂ also terminate at these invariant points. The points are connected by a series of reactions involving liquidus relationships among the carbonates and mantle silicates, at temperatures lower (1,100–1,300° C) than the silicate-CO₂ melting reactions (1,400–1,600° C). Review of experimental data in the bounding ternary systems together with preliminary data for the system CaO-MgO-SiO₂-CO₂ permits construction of a partly schematic framework for decarbonation and melting reactions at upper mantle pressures. The key to several problems in the peridotite-CO₂ subsystem is the intersection of a subsolidus carbonation reaction with a melting reaction at an invariant point near 24 kb and 1,200°C. There is an intricate series of reactions between 25 kb and 35 kb involving changes in silicate and carbonate phase fields on the CO₂-saturated liquidus surfaces. Conclusions include the following: (1) Peridotite Fo+Opx+Cpx can be carbonated with increasing pressure, or decreasing temperature, to yield Fo+Opx+Cpx+Cd (Cd=calcic dolomite), Fo+Opx+Cd, Fo+Opx+Cm (Cm=calcic magnesite), and finally Qz+Cm. (2) Free CO₂ cannot exist in subsolidus mantle peridotite with normal temperature distributions; it is stored as carbonate, Cd. (3) The CO₂ bubbles in peridotite nodules do not represent free CO₂ in mantle peridotite along normal geotherms. (4) CO₂ is as effective as H₂O in causing incipient melting, our preferred explanation for the low-velocity zone. (5) Fusion of peridotite with CO₂ at depths shallower than 80 km produces basic magmas, becoming more SiO₂-undersaturated with depth. (6) The solubility of CO₂ in mantle magmas is less than about 5 wt% at depths to 80 km, increasing abruptly to about 40 wt% at 80 km and deeper. (7) Deeper than 80 km, the first liquids produced are carbonatitic, changing towards kimberlitic and eventually, at considerably higher temperatures, to basic magmas. (8) Kimberlite and carbonatite magmas rising from the asthenosphere must evolve CO₂ at depths 100-80 km, which contributes to their explosive emplacement. (9) Fractional crystallization of CO₂-bearing SiO₂-undersaturated basic magmas at most pressures can yield residual kimberlite and carbonatite magmas.     

Deep crustal carbonates as CO2 fluid sources: Evidence from metasomatic reaction zones

Metasomatic reaction zones which developed at marble-pelitic schist contacts in a granulite facies terrane in West Greenland contain a consistent sequence of five mineralogical zones. Outward from the carbonates the zones are characterized by the assemblages grossular-diopside-meionite (I), meionite-anorthite-diopside (II), anorthite-diopside-edenitic hornblende (III), anorthite-enstatite (IV), plagioclase-almandine-sillimanite (V). Sphene is superceded by ilmenite between zones (II) and (III); quartz is present in all zones except zone I. Scapolite, plagioclase, clinopyroxene and mica exhibit a small degree of compositional variation which correlates with distance from the carbonate. These small compositional variations are superimposed on a strong CaO chemical potential gradient. Compositional features, zone distributions and CaO activity calculations demonstrate that the zones developed in response to CaO diffusion along a chemical potential gradient of 2 kcal/m. The CaO source appears to be carbonate rocks which release calcium as decarbonation reactions proceed. The maximum volume of CO₂ released in this process, and that released during discontinuous reactions in the marbles, will contribute a total volume of CO₂ approximately equivalent to the volume of carbonate in the rock. Calculations demonstrate that a terrane consisting of as little as 8% carbonate will release sufficient CO₂ to result in complete dehydration of an amphibolite terrane, at deep crustal conditions. Dehydration through CO₂ release will be accomplished either through rapid burial, which would prevent both equilibration of mineral assemblages and CO₂ release at intermediate crustal levels, or through diffusion-driven metasomatic reactions which would lead to CO₂ release primarily at the high temperatures of deep crustal environments. The latter process would be the dominant CO₂ source at deep crustal levels if carbonate rocks occur predominately as relatively thin layers.     

Ancient mantle lithosphere beneath the Khanka massif in the Russian Far East: in situ Re–Os evidence

The Os‐isotope compositions of sulphides in mantle xenoliths hosted by Late Miocene alkali basalts from the Sviyaginsky volcano, Russian Far East, reveal the presence of Archaean–Proterozoic subcontinental lithospheric mantle beneath the Khanka massif. Their T_MA and T_RD model ages reveal similar peaks at 1.1 and 0.8 Ga suggesting later thermotectonic events in the subcontinental lithospheric mantle, whereas T_RD model ages range back to 2.8 ± 0.5 (2σ) Ga. The events recognized in the subcontinental lithospheric mantle are consistent with those recorded in the crust of the Khanka massif. The sulphide Os‐isotope data show that the subcontinental lithospheric mantle beneath the Khanka massif had formed at least by the Mesoproterozoic, and was subsequently metasomatized by juvenile crustal‐growth events related to the evolution of the Altaids. The Khanka massif is further proposed to have tectonic affinity to the Siberia Craton and should originate from it accordingly.     

Fluid-assisted granulite metamorphism: A continental journey

Lower crustal granulites, which constitute the base of all continents, belong to two series: high-pressure granulites generated by crustal thickening (subduction) and (ultra)high-temperature granulites associated with crustal extension. Fluid inclusions and metasomatic features indicate that the latter were metamorphosed in the presence of low-water activity fluids (high-density CO₂ and brines), which have invaded the lower crust at peak metamorphic conditions (fluid-assisted granulite metamorphism). High-pressure and (ultra)high-temperature granulites commonly occur along elongated paired belts. They were formed, from the early Proterozoic onwards, during a small number of active periods lasting a few hundreds of m.y. These periods were separated from each other by longer periods of stability. Each period ended with the formation of a supercontinent whose amalgamation coincided with low- to medium pressure (ultra)high-temperature granulite metamorphism, immediately before continental break-up. It is proposed that large quantities of mantle-derived CO₂ stored in the lower crust at the final stage of supercontinent amalgamation, are released into the hydro- and atmosphere during breakup of the supercontinent. Fluid-assisted granulite metamorphism, therefore, appears to be an important mechanism for transferring deep mantle fluids towards the Earth's surface. Possible consequences were, for example, the sudden end of Proterozoic glaciations, as well as the post-Cambrian explosion of life.     

Metamorphic evolution of ultrahigh-temperature Fe- and Al-rich granulites in the south Yenisei Ridge and tectonic implications

This study provides the first evidence for the occurrence of ultrahigh-temperature (UHT) granulite-facies metamorphism in the Yenisei Ridge (Angara–Kan block). UHT metamorphism is documented in Fe-Al-rich metapelites on the basis of the garnet–hypersthene–sillimanite–cordierite–plagioclase–biotite–spinel–quartz–K-feldspar assemblage. Microtextural relationships and compositional data for paragneisses of the Kan complex attest to three distinct metamorphic episodes: (M1) pre-peak prograde (820?900°C/5.5–7 kbar), (M2) peak UHT (920–1000°C/7–9 kbar), and (M3) post-peak retrograde (770?900°C/5.5–7.5 kbar). The observed counterclockwise P–T evolution at a high geothermal gradient (dT/dP = 100–200°C/kbar) suggests that UHT metamorphic assemblages were formed in an overall extensional tectonic setting accompanied by underplating of mantle-derived mafic magmas, which may be sourced from ~1750 Ma giant radiating dike swarms linked to the Vilyuy mantle plume as part of the Trans-Siberian LIP. The broad synchroneity of UHT metamorphism (1744 ± 26 Ma; monazite–zircon isochron age) and rift-related endogenic activity in the region can provide an additional line of evidence for the two-stage evolution of granulite-facies metamorphism in the Angara–Kan block. The Aldan–Stanovoy, Anabar, and Baikal basement inliers of high-grade metamorphic rocks within the Siberian craton record two Paleoproterozoic peaks (1.9 and 1.75 Ga) of granulite-facies metamorphism. The synchronous sequence of tectonothermal events at the periphery of the large Precambrian Laurentian, Baltica, and Siberian cratons provide convincing evidence for their spatial proximity over a wide time interval, which is consistent with the most recent paleomagnetic reconstructions of the Proterozoic supercontinent Nuna.     

Composition and evolution of the continental crust: Retrospect and prospect

Until the middle of the 20th century, the continental crust was considered to be dominantly granitic. This hypothesis was revised after the Second World War when several new studies led to the realization that the continental crust is dominantly made of metamorphic rocks. Magmatic rocks were emplaced at peak metamorphic conditions in domains, which can be defined by geophysical discontinuities. Low to medium-grade metamorphic rocks constitute the upper crust, granitic migmatites and intrusive granites occur in the middle crust, and the lower crust, situated between the Conrad and Moho discontinuities, comprises charnockites and granulites. The continental crust acquired its final structure during metamorphic episodes associated with mantle upwelling, which mostly occurred in supercontinents prior to their disruption, during which the base of the crust experienced ultrahigh temperatures (>1000 °C, ultrahigh temperature granulite-facies metamorphism). Heat is provided by underplating of mantle-derived mafic magmas, as well as by a massive influx of low H₂O activity mantle fluids, i.e. high-density CO₂ and high-salinity brines. These fluids are initially stored in ultrahigh temperature domains, and subsequently infiltrate the lower crust, where they generate anhydrous granulite mineral assemblages. The brines can reach upper crustal levels, possibly even the surface, along major shear zones, where granitoids are generated through brine streaming in addition to those formed by dehydration melting in upper crustal levels.     

A general model for the intrusion and evolution of 'mantle' garnet peridotites in high-pressure and ultra-high-pressure metamorphic terranes

Garnet‐bearing peridotite lenses are minor but significant components of most metamorphic terranes characterized by high‐temperature eclogite facies assemblages. Most peridotite intrudes when slabs of continental crust are subducted deeply (60–120 km) into the mantle, usually by following oceanic lithosphere down an established subduction zone. Peridotite is transferred from the resulting mantle wedge into the crustal footwall through brittle and/or ductile mechanisms. These ‘mantle’ peridotites vary petrographically, chemically, isotopically, chronologically and thermobarometrically from orogen to orogen, within orogens and even within individual terranes. The variations reflect: (1) derivation from different mantle sources (oceanic or continental lithosphere, asthenosphere); (2) perturbations while the mantle wedges were above subducting oceanic lithosphere; and (3) changes within the host crustal slabs during intrusion, subduction and exhumation. Peridotite caught within mantle wedges above oceanic subduction zones will tend to recrystallize and be contaminated by fluids derived from the subducting oceanic crust. These ‘subduction zone peridotites’ intrude during the subsequent subduction of continental crust. Low‐pressure protoliths introduced at shallow (serpentinite, plagioclase peridotite) and intermediate (spinel peridotite) mantle depths (20–50 km) may be carried to deeper levels within the host slab and undergo high‐pressure metamorphism along with the enclosing rocks. If subducted deeply enough, the peridotites will develop garnet‐bearing assemblages that are isofacial with, and give the same recrystallization ages as, the eclogite facies country rocks. Peridotites introduced at deeper levels (50–120 km) may already contain garnet when they intrude and will not necessarily be isofacial or isochronous with the enclosing crustal rocks. Some garnet peridotites recrystallize from spinel peridotite precursors at very high temperatures (c. 1200 °C) and may derive ultimately from the asthenosphere. Other peridotites are from old (>1 Ga), cold (c. 850 °C), subcontinental mantle (‘relict peridotites’) and seem to require the development of major intra‐cratonic faults to effect their intrusion.     

Very high-density carbonic fluid inclusions in sapphirine-bearing granulites from Tonagh Island in the Archean Napier Complex, East Antarctica: implications for CO2 infiltration during ultrahigh-temperature (T>1,100 °C) metamorphism

The ultrahigh-temperature (UHT) metamorphism of the Napier Complex is characterized by the presence of dry mineral assemblages, the stability of which requires anhydrous conditions. Typically, the presence of the index mineral orthopyroxene in more than one lithology indicates that H₂O activities were substantially low. In this study, we investigate a suite of UHT rocks comprising quartzo-feldspathic garnet gneiss, sapphirine granulite, garnet-orthopyroxene gneiss, and magnetite-quartz gneiss from Tonagh Island. High Al contents in orthopyroxene from sapphirine granulite, the presence of an equilibrium sapphirine-quartz assemblage, mesoperthite in quartzo-feldspathic garnet gneiss, and an inverted pigeonite-augite assemblage in magnetite-quartz gneiss indicate that the peak temperature conditions were higher than 1,000 °C. Petrology, mineral phase equilibria, and pressure-temperature computations presented in this study indicate that the Tonagh Island granulites experienced maximum P-T conditions of up to 9 kbar and 1,100 °C, which are comparable with previous P-T estimates for Tonagh and East Tonagh Islands. The textures and mineral reactions preserved by these UHT rocks are consistent with an isobaric cooling (IBC) history probably following an counterclockwise P-T path. We document the occurrence of very high-density CO₂-rich fluid inclusions in the UHT rocks from Tonagh Island and characterize their nature, composition, and density from systematic petrographic and microthermometric studies. Our study shows the common presence of carbonic fluid inclusions entrapped within sapphirine, quartz, garnet and orthopyroxene. Analysed fluid inclusions in sapphirine, and some in garnet and quartz, were trapped during mineral growth at UHT conditions as 'primary' inclusions. The melting temperatures of fluids in most cases lie in the range of -56.3 to -57.2 °C, close to the triple point for pure CO₂ (-56.6 °C). The only exceptions are fluid inclusions in magnetite-quartz gneiss, which show slight depression in their melting temperatures (-56.7 to -57.8 °C) suggesting traces of additional fluid species such as N₂ in the dominantly CO₂-rich fluid. Homogenization of pure CO₂ inclusions in the quartzo-feldspathic garnet gneiss, sapphirine granulite, and garnet-orthopyroxene gneiss occurs into the liquid phase at temperatures in the range of -34.9 to +4.2 °C. This translates into very high CO₂ densities in the range of 0.95-1.07 g/cm³. In the garnet-orthopyroxene gneiss, the composition and density of inclusions in the different minerals show systematic variation, with highest homogenization temperatures (lowest density) yielded by inclusions in garnet, as against inclusions with lowest homogenization (high density) in quartz. This could be a reflection of continued recrystallization of quartz with entrapment of late fluids along the IBC path. Very high-density CO₂ inclusions in sapphirine associated with quartz in the Tonagh Island rocks provide potential evidence for the involvement of CO₂-rich fluids during extreme crustal temperatures associated with UHT metamorphism. The estimated CO₂ isochores for sapphirine granulite intersect the counterclockwise P-T trajectory of Tonagh Island rocks at around 6-9 kbar at 1,100 °C, which corresponds to the peak metamorphic conditions of this terrane derived from mineral phase equilibria, and the stability field of sapphirine + quartz. Therefore, we infer that CO₂ was the dominant fluid species present during the peak metamorphism in Tonagh Island, and interpret that the fluid inclusions preserve traces of the synmetamorphic fluid from the UHT event. The stability of anhydrous minerals, such as orthopyroxene, in the study area might have been achieved by the lowering of H₂O activity through the influx of CO₂ at peak metamorphic conditions (>1,100 °C). Our microthermometric data support a counterclockwise P-T path for the Napier Complex.     

Metamorphism in Archaean greenstone belts: calculated fluid compositions and implications for gold mineralization

An inescapable consequence of the metamorphism of greenstone belt sequences is the release of a large volume of metamorphic fluid of low salinity with chemical characteristics controlled by the mineral assemblages involved in the devolatilization reactions. For mafic and ultramafic sequences, the composition of fluids released at upper greenschist to lower amphibolite facies conditions for the necessary relatively hot geotherm corresponds to those inferred for greenstone gold deposits (X_CO2= 0.2–0.3). This result follows from the calculation of mineral equilibria in the model system CaO–MgO–FeO–Al₂O₃–SiO₂–H₂O–CO₂, using a new, expanded, internally consistent dataset. Greenstone metamorphism cannot have involved much crustal over-thickening, because very shallow levels of greenstone belts are preserved. Such orogeny can be accounted for if compressive deformation of the crust is accompanied by thinning of the mantle lithosphere. In this case, the observed metamorphism, which was contemporaneous with deformation, is of the low-P high-T type. For this type of metamorphism, the metamorphic peak should have occurred earlier at deeper levels in the crust; i.e. the piezothermal array should be of the ‘deeper-earlier’type. However, at shallow crustal levels, the piezothermal array is likely to have been of ‘deeper-later’type, as a consequence of erosion. Thus, while the lower crust reached maximum temperatures, and partially melted to produce the observed granites, mid-crustal levels were releasing fluids prograde into shallow crustal levels that were already retrograde. We propose that these fluids are responsible for the gold mineralization. Thus, the contemporaneity of igneous activity and gold mineralization is a natural consequence of the thermal evolution, and does not mean that the mineralization has to be a consequence of igneous processes. Upward migration of metamorphic fluid, via appropriate structurally controlled pathways, will bring the fluid into contact with mineral assemblages that have equilibrated with a fluid with significantly lower X_CO2. These assemblages are therefore grossly out of equilibrium with the fluid. In the case of infiltrated metabasic rocks, intense carbonation and sulphidation is predicted. If, as seems reasonable, gold is mobilized by the fluid generated by devolatilization, then the combination of processes proposed, most of which are an inevitable consequence of the metamorphism, leads to the formation of greenstone gold deposits predominantly from metamorphic fluids.     

Contrasting Carbon and Oxygen Isotopic Evolution in Metacarbonates from the Kerala Khondalite Belt,Southern India

The Kerala Khondalite belt is a Proterozoic metasupracrustal granulite facies terrain in southern India comprising garnet-biotite gneiss, garnet-sillimanite gneiss and orthopyroxene granulites as major rock types. Calc-silicate rocks and marbles, occurring as minor lithologies in the Kerala Khondalite Belt, show different mineral assemblages and reaction histories of which indicate a metamorphic P-T-fluid history dominated by internal fluid buffering during the peak metamorphism, followed by external fluid influx during decompression. The carbon and oxygen isotopic compositions of calcite from three representative metacarbonate localities show contrasting evolutionary trends. The Ambasamudram marbles exhibit carbon and oxygen isotope ratios (δ¹³C ∼ 0‰ and δ¹⁸O ∼ 20‰) typical of middle to late Proterozoic marine carbonate sediments with minor variation ascribed to the isotopic exchange due to the devolatilization reactions. The δ¹³C and δ¹⁸O values of ∼ −9‰ and 11‰, respectively, for calcite from calc-silicate rocks at Nuliyam are considerably low and heterogeneous. The wollastonite formation here, possibly corresponds to an earlier event of fluid infiltration during prograde to peak metamorphism, which resulted in decarbonation and isotope resetting. Further, petrologic evidence supports a model of late carbonic fluid infiltration that has partially affected the calc-silicate rocks, with subsequent isotope resetting, more towards the contact between calc-silicate rock and charnockite. At Korani, only oxygen isotopes have been significantly lowered (δ¹⁸O ∼ 13‰) and the process involved might be a combination of metamorphic devolatilization accompanied by an aqueous fluid influx, supported by petrologic evidence. The stable isotope signatures obtained from the individual localities, thus indicate heterogeneous patterns of fluid evolution history within the same crustal segment.