Iterative thermodynamic modelling—Part 1: A theoretical scoring technique and a computer program (Bingo-Antidote)

This paper introduces the software solution Bingo-Antidote for thermodynamic calculations at equilibrium based on iterative thermodynamic models. It describes a hybrid strategy combining the strength of Gibbs energy minimization (GEM) and inverse thermobarometry models based on the comparison between the modelled and observed mineral assemblage, modes and compositions. The overall technique relies on quantitative compositional maps acquired by electron probe micro-analyser for obtaining a mutually consistent set of observed data such as bulk rock and mineral compositions. Thus it offers the opportunity to investigate metamorphic rocks on a microscale. The scoring part Bingo integrates three statistical model quality factors for the assemblage, for the mineral modes, for the mineral compositions combined in a global evaluation criterion that quantifies how the model reproduces the observations for the investigated volume. The input parameters of GEM affecting the model quality such as pressure, temperature and eventually some components of the bulk composition (e.g. the molar amount of hydrogen, carbon or oxygen) or activity variables of fluids and gases (e.g. , , f(O₂)) can be optimized by inversion in Antidote using several mapping stages followed by a direct search optimization. Examples of iterative models based on compositional maps processed with Bingo-Antidote demonstrate the utility of the program. In contrast to the qualitative interpretation of phase diagrams, the inversion maximizes the benefits of GEM and permits the derivation of statistically ‘optimal’ pressure–temperature conditions for well-equilibrated samples. In addition, Bingo-Antidote opens new avenues for petrological investigations such as the generation of chemical potential landscape maps.     

Mineral equilibrium constraints on the feasibility of diffusive H2O-fluxed melting in the continental crust

Generation of granitic melt is believed to occur predominantly by melting through the breakdown of hydrous minerals. However, melting due to the influx of H₂O has been recognized in anatectic amphibolite facies tonalitic grey gneisses, metagreywackes and low-P metapelites, and has consequently been proposed as an alternative mechanism for the generation of granitic melt. Melting induced by H₂O addition is recognized from voluminous melt production at relatively low temperature, where hydrous minerals are stable and anhydrous minerals are preferentially consumed during melting. Mineral equilibrium modelling to determine the P–T conditions, melt volumes, melting reactions and viable H₂O sources reveals that the process is not restricted to specific compositions or P–T conditions, although lower pressure and lithologies with a low hydrous mineral content are more favourable. Melting reactions in all lithologies primarily consume quartz and feldspars to yield 5–6 mol.% melt for each mol.% of H₂O added. remains constant at ~0.70 to 0.77 during progressive melting as long as alkali feldspar is present. Once alkali feldspar is exhausted, plagioclase becomes the main reactant, producing more tonalitic melt compositions with gradually higher . Our results demonstrate that, at the site of melting, melting is driven by diffusion of H₂O into the target rock along chemical potential gradients, rather than the advective flow of a mechanically distinct water-rich fluid phase. Melting will initiate and proceed as long as a gradient exists between the H₂O source and target lithology. Our calculations show that an ordinary magma, such as an I-type magma with typical H₂O content, has a high enough to be a viable H₂O source, allowing diffusive H₂O-fluxed melting to produce melt proportions and fertility comparable to that of dehydration melting. However, high degrees of partial melting require a considerable amount of H₂O, which necessitates a continuously advecting H₂O source such as a magma conduit or melt-bearing shear zone. A magmatic H₂O source at emplacement level will undergo a similar amount of crystallization as the melt fraction produced in the target rock such that there will be no net melt production. Considering that shear-zone hosted magma conduits are localized features, diffusive H₂O-fluxed melting is likely to only be viable in a small fraction of the anatectic orogenic crust. Although it may play an important role in locally raising melt volumes and modifying magma chemistry through mingling and hybridization, it does not appear to, of itself, be able to generate significant volumes of granitic melt.     

Evolution of metamorphic fluid recorded in granulite facies metacarbonate rocks from the middle segment of the Mogok metamorphic belt in central Myanmar

The Mogok metamorphic belt of Palaeogene age, which records subduction‐ and collision‐related events between the Indian and Eurasian plates, lies along the western margin of the Shan plateau in central Myanmar and continues northwards to the eastern Himalayan syntaxis. Reaction textures of clinohumite‐ and scapolite‐bearing assemblages in Mogok granulite facies metacarbonate rocks provide insights into the drastic change in fluid composition during exhumation of the collision zone. Characteristic high‐grade assemblages of marble and calcsilicate rock are clinohumite+forsterite+spinel+phlogopite+pargasite/edenite+calcite+dolomite, and scapolite+diopside+anorthite+quartz+calcite respectively. Calculated petrogenetic grids in CaO–MgO–Al₂O₃–SiO₂–H₂O–CO₂ and subsets of this system were employed to deduce the pressure–temperature–fluid evolution of the clinohumite‐ and scapolite‐bearing assemblages. These assemblages suggest higher temperature (>780–810°C) and [=CO₂/(CO₂+H₂O) >0.17–0.60] values in the metamorphic fluid for the peak granulite facies stage, assuming a pressure of 0.8 GPa. Calcite grains commonly show exsolution textures with dolomite particles, and their reintegrated compositions yield temperatures of 720–880°C. Retrograde reactions are mainly characterized by a reaction zone consisting of a dolomite layer and a symplectitic aggregate of tremolite and dolomite grown between clinohumite and calcite in marble, and a replacement texture of scapolite by clinozoisite in calcsilicate rock. These textures indicate that the retrograde reactions developed under lower temperature (<620°C) and (<0.08–0.16) conditions, assuming a pressure of 0.5 GPa. The metacarbonate rocks share metamorphic temperatures similar to the Mogok paragneiss at the peak granulite facies stage. The values of the metacarbonate rock at peak metamorphic stage are, however, distinctly higher than those previously deduced from carbonate mineral‐free paragneiss. Primary clinohumite, phlogopite and pargasite/edenite in marble have F‐rich compositions, and scapolite in calcsilicate rock contains Cl, suggesting a contrast in the halogen compositions of the metamorphic fluids between these two lithologies. The metamorphic fluid compositions were probably buffered within each lithology, and the effective migration of metamorphic fluid, which would have extensively changed the fluid compositions, did not occur during the prograde granulite facies stage throughout the Mogok metamorphic belt. The lower conditions of the Mogok metacarbonate rocks during the retrograde stage distinctly contrast with higher conditions recorded in metacarbonate rocks from other metamorphic belts of granulite facies. The characteristic low conditions were probably due to far‐ranging infiltration of H₂O‐dominant fluid throughout the middle segment of the Mogok metamorphic belt under low‐amphibolite facies conditions during the exhumation and hydration stage.     

The effect of subduction on the sulphur,carbon and redox budget of lithospheric mantle

Subduction of hydrated lithospheric mantle introduces HO, ferric iron, oxidized carbon and sulphur to the subduction zone system. The fate of these components is poorly known, but is intimately linked to the global geochemical cycles of iron, carbon and sulphur, the genesis of arc‐related ore deposits, the temporal evolution of mantle redox state and subduction‐related earthquakes and magmatism. thermocalc is used to provide first‐order constraints on the effect of subduction zone metamorphism on metamorphic redistribution of iron, carbon, sulphur and water in ultramafic rocks via construction of P?T and T‐X(O) pseudosections with open system calculation of the effect of fluid loss. The calculations replicate observed mineral assemblages in high‐P to low‐T ultramafic rocks at P?T conditions consistent with those suggested by other workers. The results are consistent with open system fluid loss without significant fluid infiltration. Water loss is complete by 850 C, the corresponding depth of fluid loss being consistent with that inferred for earthquakes in subducting slabs. Losses of carbon and sulphur are relatively minor, at around <5% and <1%, respectively, so it is envisaged that most carbon and sulphur subducted in ultramafic lithologies is transported to >5 GPa, below the depths of the source zone for arc volcanoes. Oxygen activity for rocks in closed systems that evolve with a fixed redox budget is calculated to change from ΔFMQ ?1 at 350 C to over ΔFMQ +3 at 850 C. This result emphasizes the need to consider redox budget as well as oxygen activity when the results of experiments performed at fixed oxygen activity relative to some buffer are interpreted in the context of natural systems. In open systems, devolatilization is calculated to increase the redox budget and oxygen activity of the residue via loss of methane and HS at the brucite‐out and serpentine‐out reactions respectively. No fluid‐induced mechanism for oxidation of sub‐arc mantle by transfer of redox budget from hydrated ultramafic lithologies to the overlying sub‐arc mantle was identified, although further thermodynamic data on fluid species such as S are required to confirm this.     

Phase equilibria for graphitic metapelite including solution of CO2 in melt and cordierite: implications for dehydration,partial melting and graphite precipitation

When graphite is present, carbon‐bearing species dissolve in the C‐O‐H fluid and lower the activity of water (). Accordingly, metamorphic reactions that involve water, namely dehydration and partial melting reactions, adjust their P–T positions to accommodate the change of . In this modelling study, pseudosections are calculated for graphite‐bearing systems that are either closed or that progressively lose fluid and/or melt. The diagrams incorporate a new model of CO₂ solubility in felsic melts that we derived to be compatible with a recently published melt model. As the result of the lowered in the carbon‐bearing systems, the temperature displacements of the solidus can be as large as 50 °C at low pressures in cordierite‐bearing zones (<4 kbar), but are smaller than 15 °C at mid‐pressure P–T conditions (4–9 kbar). In the supersolidus region, the phase relations among silicate minerals + melt are very close to those in carbon‐free systems. The fluid CO₂ content increases as temperature increases in the supersolidus assemblages. The CO₂‐rich fluid can be stable in granulite facies conditions in an oxidized system. In graphitic systems, melt and/or cordierite dominate the CO₂ budget of high‐grade rocks. During cooling, the fluid that exsolves from such crystalizing melt is CO₂‐rich. In addition to the phase relations, the pseudosections presented in this study enable researchers to quantitatively investigate the evolution of phase modes, including graphite, along specific metamorphic P–T paths. At low pressures in the cordierite stability field, graphite is predicted to precipitate as the pressure increases or temperature decreases in the subsolidus assemblages, or temperature increases in the region of melt + fluid coexistence. On the other hand, the graphite abundance remains nearly constant along the mid‐pressure P–T series, but the graphite mode in the supersolidus region may increase due to residual enrichment if the melt is extracted. The modelling results show that metamorphic processes in closed systems lead to only small changes in graphite mode (a few tenths of a per cent). This strongly suggests that open‐system behaviours are required for large amounts of graphite deposition, including fluid infiltration and mixing or residual enrichment processes in high‐grade rocks. In addition to P–T pseudosections, P/T–X_O diagrams (X_O = O/(H + O) in the fluid) illustrate the thermodynamic features of internal buffering from another perspective, and explore the dependence of phase relations on the externally imposed redox state. If the system is equilibrated with CO₂ or CH₄‐rich infiltrating fluid, the temperature displacements of metamorphic reactions can be larger than 50 °C, compared with carbon‐free systems.     

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.     

Activity–composition relations for the calculation of partial melting equilibria in metabasic rocks

A set of thermodynamic models is presented that, for the first time, allows partial melting equilibria to be calculated for metabasic rocks. The models consist of new activity–composition relations combined with end‐member thermodynamic properties from the Holland & Powell dataset, version 6. They allow for forward modelling in the system NaO–CaO–KO–FeO–MgO–AlO–SiO–HO–TiO–FeO. In particular, new activity–composition relations are presented for silicate melt of broadly trondhjemitic–tonalitic composition, and for augitic clinopyroxene with Si–Al mixing on the tetrahedral sites, while existing activity–composition relations for hornblende are extended to include KO and TiO. Calibration of the activity–composition relations was carried out with the aim of reproducing major experimental phase‐in/phase‐out boundaries that define the amphibolite–granulite transition, across a range of bulk compositions, at ≤13 kbar.     

The origin of chloritoid – 3‐mica pseudomorph growth in staurolite–muscovite schist,Bangriposi (Eastern India)

At Bangriposi, variable stages in replacement of staurolite by chloritoid – Na–K–Ca mica shimmer aggregates in muscovite schists provides insight into the complex interplay between fluid flow, mass transfer, and dissolution–precipitation during pseudomorph growth. Idioblastic chloritoid growing into mica caps without causing visible deformation, and monomineralic chloritoid veins (up to 300 μm wide) within shimmer aggregates replacing staurolite attest to chloritoid nucleation in fluid‐filled conduits along staurolite grain boundaries and crystallographic planes. The growth of shimmer aggregates initiated along staurolite margins, and advanced inwards into decomposing staurolite along networks of crystallographically controlled fluid‐filled conduits. Coalescence among alteration zones adjacent to channel fills led to dismemberment and the eventual demise of staurolite. Mass balance calculation within a volume‐fixed, silica‐conserved reference frame indicate the shimmer aggregates grew via precipitation from fluids in response to mass transport that led to the addition of H₂O, K₂O, Na₂O and CaO in the reaction zone, and Al₂O₃ was transported outward from the inward‐retreating margin of decomposing staurolite. This aided precipitation of chloritoid in veins and in the outer collars, and as disseminated grains in the shimmer aggregates at mid‐crustal condition (~520 ± 20 °C, 5.5 ± 2.0 kbar). Computation using one‐dimensional transport equation suggests that staurolite decomposition involved advection dominating over diffusive transport; the permeation of externally derived H₂O caused flattening of chemical potential gradients in H₂O and aqueous species, for example, and , computed using the Gibbs method. This suggests that staurolite decomposition was promoted by the infiltration of a large volume of H₂O that flattened existing chemical potential gradients. In the initial stages of replacement, chloritoid super‐saturation in fluid caused preferential nucleation and growth of chloritoid at staurolite grain boundaries and in crystallographic planes. As reaction progressed, further chloritoid nucleation was halted, but chloritoid continued to grow as the 3‐mica aggregates continued to replace the remaining staurolite in situ, while the chloritoid‐compatible elements were transported in the water‐rich phase facilitating continued growth of the existing chloritoid grains.     

Jadeite–garnet glaucophane schists in the Bizan area,Sambagawa metamorphic belt,eastern Shikoku,Japan: significance and extent of eclogite facies metamorphism

Eclogite facies metamorphic rocks have been discovered from the Bizan area of eastern Shikoku, Sambagawa metamorphic belt. The eclogitic jadeite–garnet glaucophane schists occur as lenticular or sheet‐like bodies in the pelitic schist matrix, with the peak mineral assemblage of garnet + glaucophane + jadeite + phengite + quartz. The jadeitic clinopyroxene (X_Jd 0.46–0.75) is found exclusively as inclusions in porphyroblastic garnet. The eclogite metamorphism is characterized by prograde development from epidote–blueschist to eclogite facies. Metamorphic P–T conditions estimated using pseudosection modelling are 580–600 °C and 18–20 kbar for eclogite facies. Compared with common mafic eclogites, the jadeite–garnet glaucophane schists have low CaO (4.4–4.5 wt%) and MgO (2.1–2.3 wt%) bulk‐rock compositions. The P–T– pseudosections show that low X_Ca bulk‐rock compositions favour the appearance of jadeite instead of omphacite under eclogite facies conditions. This is a unique example of low X_Ca bulk‐rock composition triggered to form jadeite at eclogite facies conditions. Two significant types of eclogitic metamorphism have been distinguished in the Sambagawa metamorphic belt, that is, a low‐T type and subsequent high‐T type eclogitic metamorphic events. The jadeite–garnet glaucophane schists experienced low‐T type eclogite facies metamorphism, and the P–T path is similar to lawsonite‐bearing eclogites recently reported from the Kotsu area in eastern Shikoku. During subduction of the oceanic plate (Izanagi plate), the hangingwall cooled gradually, and the geothermal gradient along the subduction zone progressively decreased and formed low‐T type eclogitic metamorphic rocks. A subsequent warm subduction event associated with an approaching spreading ridge caused the high‐T type eclogitic metamorphism within a single subduction zone.     

Metamorphic imprint of accretion and ridge subduction in the Pan‐African Damara Belt,Namibia

Ridge subduction is an inescapable plate tectonic process, but has only been documented in modern circum‐Pacific environments and not yet been recognized from suture zones associated with supercontinent assembly, likely because its imprint is obliterated by later collision. The formation of the Pan‐African Damara Belt of central Namibia involved northward subduction of the Khomas Sea underneath the Congo Craton, prior to final suturing of the Congo and Kalahari Cratons. The accretionary history of the Belt is preserved in the Southern and Southern Marginal Zones, which consist of turbiditic metasedimentary and intercalcated mafic rocks with MORB affinity. Two localities in the Kuiseb and Gaub canyons reveal that aluminous metapelites contain a fabric‐defining assemblage of fine‐grained muscovite, chlorite, biotite, quartz and graphite that is overprinted by randomly oriented porphyroblasts and poikiloblasts of garnet, staurolite, kyanite and biotite. Associated metamafic rocks consist of hornblende, chlorite, epidote, rutile and quartz, with actinolite cores preserved in amphibole porphyroblasts. Metamorphic conditions for the fabric‐defining assemblage are estimated at ～10 kbar and 540–560 C, whereas peak metamorphism likely occurred at 10–10.5 kbar and 600 C. Consequently, these rocks preserve a two‐stage prograde metamorphic history, where initial tectonic burial was followed by relatively rapid, near‐isobaric heating without attendant deformation to peak metamorphic conditions. We propose that initial burial occurred through subduction and underplating to the accretionary prism, before ridge subduction and opening of a slab window heated the rocks to peak metamorphic conditions. The exceptional preservation of the tectono‐thermal imprint of the accretionary orogenic stage is due to the relatively soft, largely aborted collision that characterized the Damara orogeny, which can be attributed to the confined extent of the Khomas Sea.     

UHT metamorphism on Seram,eastern Indonesia: reaction microstructures and P–T evolution of spinel‐bearing garnet–sillimanite granulites from the Kobipoto Complex

The island of Seram, part of the northern limb of the Banda Arc in eastern Indonesia, exposes an extensive Mio‐Pliocene granulite facies migmatite complex (the Kobipoto Complex) comprising voluminous leucosome‐rich diatexites and scarcer Al–Fe‐rich residual granulites. The migmatites are intimately associated with ultramafic rocks of predominantly lherzolitic composition that were exhumed by substantial lithospheric extension beneath low‐angle detachment faults; heat supplied by the lherzolites was evidently a major driver for the granulite facies metamorphism and accompanying anatexis. Residual garnet–sillimanite granulites sampled from the Kobipoto Mountains, central Seram, contain scarce garnet‐hosted inclusions of hercynite spinel (~1.5 wt% ZnO) + quartz (± ilmenite) in direct grain‐boundary contact – an assemblage potentially indicative of metamorphism under ultrahigh‐temperature (UHT) conditions. thermocalc ‘Average P–T’ reactions and melanosome‐specific thermocalc , T–M_O, and P–T pseudosections in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (NCKFMASHTO) chemical system, supported by Ti‐in‐garnet thermobarometry, are permissive of the rock having experienced a clockwise P–T path peaking at 925 °C and 9 kbar – thus narrowly reaching UHT conditions – before undergoing near‐isothermal decompression to ~750 °C and ~4 kbar. Spinel + quartz assemblages are interpreted to have formed at or just after the metamorphic peak from localized reactions between sillimanite, ilmenite and surrounding garnet. Further decompression of the rock resulted in the formation of complex reaction microstructures comprising cordierite ± plagioclase coronae around garnet, and symplectic intergrowths of cordierite + spinel + ilmenite around sillimanite. Small grains of sapphirine + corundum developed subsequently within spinel by localized quartz‐absent reactions. The post‐peak evolution of the granulites may be related to previously published U–Pb zircon and ⁴⁰Ar/³⁹Ar ages of c. 16 Ma, further substantiating the claim for the Kobipoto Complex granulites having recorded Earth's youngest‐identified episode of UHT metamorphism, albeit at slightly lower temperature and higher pressure than previously inferred. The Kobipoto Complex granulites demonstrate how UHT conditions may be achieved in the ‘modern’ Earth by extreme lithospheric extension, which, in this instance, was driven by slab rollback of the Banda Arc.     

A statistical analysis of the distribution of cordierite and biotite in hornfels from the Bugaboo contact aureole: implications for the kinetics of porphyroblast crystallization

The three‐dimensional disposition of cordierite and biotite crystals in a hornfels from the contact aureole of the Bugaboo Batholith is quantified using high‐resolution X‐ray micro‐computed tomography and global as well as scale‐dependent pattern statistics. The results demonstrate a random distribution of cordierite and biotite crystal sizes for all scales across the entire rock volume studied indicative of interface‐controlled prograde metamorphic reaction kinetics. The reaction considered responsible for the mineral assemblage and the formation of cordierite and biotite in the hornfels is Ms + Chl + Qtz = Crd + And + Bt + . Rock‐specific phase equilibria point to metamorphic conditions of ~520 –550 °C and 3 kbar for this reaction. The common approach to approximate the shape of crystals as spherical underestimates the influence of the Strauss hard‐core process on rock texture and may be misinterpreted to reflect ordering of crystal sizes by inhibition of nucleation and growth commonly associated with diffusion‐controlled reaction kinetics. According to our findings, Strauss hard‐core ordering develops at length scales equal to and less than the average major axis of the crystal population. This is significantly larger than what is obtained if a spherical crystal geometry would be assumed, and increases with deviation from sphericity. For the cordierite and biotite populations investigated in this research, Strauss hard‐core ordering developed at length scales of up to ～2.2 and 1.25 mm, respectively, which is almost 1 mm longer than the scales that would be obtained if a spherical geometry would have been assumed. Our results highlight the importance of a critical assessment of the geometrical model assumptions commonly applied in the three‐dimensional analysis of crystal size distributions, and underline the need for a quantitative understanding of interface processes in order to appreciate their role in the kinetics of contact metamorphic reactions and rock texture formation.     

Details of the gabbro‐to‐eclogite transition determined from microtextures and calculated chemical potential relationships

Permian‐aged metagabbros from the eclogite type‐locality in the eastern European Alps were partially to completely transformed to eclogite during Eoalpine intracontinental subduction. Microtextures developed along a preserved fluid infiltration and reaction front in the gabbros record the incipient gabbro‐to‐eclogite transition, allowing the details of the eclogitization process to be investigated. Original, anorthite‐rich igneous plagioclase is pervasively replaced by fine‐grained intergrowths of clinozoisite, kyanite and Na‐rich plagioclase. Where plagioclase was in contact with igneous orthopyroxene, 100–200 μm thick bimineralic coronae of symplectic kyanite and diopsidic clinopyroxene form along the edges of the grains. The rims of igneous orthopyroxene develop a complementary bimineralic corona of diopsidic clinopyroxene and garnet. Igneous clinopyroxene does not show any breakdown textures; however, jadeite content gradually increases towards the rims. In addition, exsolution lamellae inherited from the igneous clinopyroxene become progressively more jadeitic as eclogitization proceeds. Given that the igneous plagioclase is pervasively replaced by clinozoisite, kyanite and Na‐rich plagioclase, whereas kyanite–diopside symplectites are confined to narrow rim zones, we suggest that the development of these textures was controlled by the (im)mobility of different elements on different length scales. The presence of hydrous minerals in the core of anhydrous plagioclase indicates that H₂O diffusivity occurred on a mm‐scale. By contrast, the size of the anhydrous diopside–kyanite and diopside–garnet symplectites indicate that Fe–Mg–Ca–Na diffusivity was limited to a 10s of μm scale. Chemical potential relations calculated in the idealized NCASH chemical system show that the clinozoisite–kyanite–albite intergrowths formed due to an increase of μH₂O to plagioclase, whereas all other elements remained effectively immobile on the scale of this texture. Fluid conditions indicated by this texture span from virtually dry conditions (0.15) to H₂O‐saturation, and therefore does not imply that the rocks were ever fluid‐saturated. Calculations in the CMAS and NCFMAS systems show that the gabbro‐to‐eclogite transition is characterized by the growth of garnet, diopsidic clinopyroxene and kyanite due to diffusion of Ca (+ Na) and Mg (+ Fe) along a μCaO (+ Na₂O)–μMgO (+ FeO) chemical potential gradient developed between orthopyroxene and plagioclase compositional domains. The anhydrous nature of the textures indicate that the gabbro‐to‐eclogite transition is not driven by hydration; however, increased μH₂O acts as a catalyst that increases diffusivity of all elements and rates of dissolution–precipitation, allowing the overstepped metamorphic reactions to occur. Our results show that crustal eclogite formation requires low H₂O content, confirming that true eclogites are dry rocks.     

Isotopic signatures of Paleoproterozoic granitoids from the southern São Francisco Craton and implications for the evolution of the Transamazonian Orogeny

The southern São Francisco Craton, northeastern Brazil, consists of an Archean block surrounded by a Paleoproterozoic belt related to the Transamazonian Orogeny (ca. 2.0 Ga). A calc-alkaline plutonic arc developed within the belt and the granitoid plutons comprise two distinct groups. One group displays Archean T_DM ages (3.07–2.62 Ga), ε_Nd(t) values between −11.0 and −3.8 and high initial ⁸⁷Sr/⁸⁶Sr values, and it consists mainly of peraluminous granites. T_DM ages for the other group are Paleoproterozoic (2.43–2.27 Ga), and ε_Nd(t) values range between −2.8 and +1.3; the plutons are metaluminous tonalites (trondhjemites) to granodiorites. The Transamazonian granitoids can be related to contrasting source-regions, from mantle- to crust-derived ones. A number of them are probably derived from mixing of Paleoproterozoic juvenile material and variable proportions of Archean crust material. Magmatism related to deep faulting, during the compressional stages of the Transamazonian Orogeny, is a plausible model for granitoid generation. The contribution of mantle-derived material to the granitoid sources supports the idea that a significant episode of new crust formation occurred during the Transamazonian Orogeny.     

Structures,kinematic analysis,rheological parameters and temperature-pressure estimate of the Mesozoic Xingcheng-Taili ductile shear zone in the North China Craton

The NE to ENE trending Mesozoic Xingcheng-Taili ductile shear zone of the northeastern North China Craton was shaped by three phases of deformation. Deformation phase D₁ is characterized by a steep, generally E–W striking gneissosity. It was then overprinted by deformation phase D₂ with NE-sinistral shear with K-feldspar porphyroclasts forming a subhorizontal low-angle stretching lineation on a steep foliation. During deformation phase D₃, lateral motion accommodated by ENE sinistral strike-slip shear zones dominated. Associated fabrics developed at upper greenschist metamorphic facies conditions and show the deformation characteristics of middle- to shallow crustal levels. In some parts, the older structures have been in turn overprinted by late-stage sinistral D₃ shearing. Finite strain and kinematic vorticity in all deformed granitic rocks indicate a prolate ellipsoid (L-S tectonites) near plane strain. Simple shear-dominated general shear during D₃ deformation is probably of general significance. The quartz c-axis textures indicate prism-gliding with a dominant rhomb <a> slip and basal <a> slip system formed mainly at low-middle temperatures. Mineral deformation behavior, quartz c-axis textures, quartz grain size and the Kruhl thermometer demonstrate that the ductile shear zone developed under greenschist facies metamorphic conditions at deformation temperatures ranging from 400 to 500 °C. Dislocation creep is the main deformation mechanism at a shallow crustal level. Fractal analysis showed that the boundaries of recrystallized quartz grains had statistically self-similarities. Differential stresses deduced from dynamically recrystallized quartz grain size are at around 20–39 MPa, and strain rates in the order of 10⁻¹² to 10⁻¹⁴ s⁻¹. This indicates deformation of granitic rocks in the Xingcheng-Taili ductile shear zone at low strain rates, which is consistent with most other ductile shear zones. Hornblende-plagioclase thermometer and white mica barometer indicate metamorphic conditions of medium pressures at around ca. 3–5 kbar and temperatures of 400–500 °C within greenschist facies conditions. The main D₃ deformation of the ENE-trending sinistral strike-slip ductile shearing is related to the roll-back of the subducting Pacific plate beneath the North China Craton.     

Fluid record of rock exhumation across the brittle–ductile transition during formation of a Metamorphic Core Complex (Naxos Island,Cyclades, Greece)

Fluid inclusions trapped in quartz veins hosted by a leucogneiss from the southern part of the Naxos Metamorphic Core Complex (Attic‐Cycladic‐Massif, Greece) were studied to determine the evolution of the fluid record of metamorphic rocks during their exhumation across the ductile/brittle transition. Three sets of quartz veins (V‐M2, V‐BD & V‐B) are distinguished. The V‐M2 and V‐BD are totally or, respectively, partially transposed into the foliation of the leucogneiss. They formed by hydrofracturing alternating with ductile deformation accommodated by crystal‐plastic deformation. The V‐B is discordant to the foliation and formed by fracturing during exhumation without subsequent ductile transposition. Fluids trapped during crystal–plastic deformation comprise two very distinct fluid types, namely a CO₂‐rich fluid and a high‐salinity brine, that are interpreted to represent immiscible fluids generated from metamorphic reactions and the crystallization of magmas respectively. They were initially trapped at ～625 °C and 400 MPa and then remobilized during subsequent ductile deformation resulting in various degrees of mixing of the two end‐members with later trapping conditions of ～350 °C and 140 MPa. In contrast, brittle microcracks contain aqueous fluids trapped at 250 °C and 80 MPa. All veins display a similar δ¹³C pointing to carbon that was trapped at depth and then preserved in the fluid inclusions throughout the exhumation history. In contrast, the δD signature is marked by a drastic difference between (i) V‐M2 and V‐BD veins that are dominated by carbonic, aqueous‐carbonic and high‐salinity fluids of metamorphic and magmatic origin characterized by δD between ?56‰ and ?66‰, and (ii) V‐B veins that are dominated by aqueous fluids of meteoric origin characterized by δD between ?40‰ and ?46‰. The retrograde P–T pathway implies that the brittle/ductile transition separates two structurally, chemically and thermally distinct fluid reservoirs, namely (i) the ductile crust into which fluids originating from crystallizing magmas and fluids in equilibrium with metamorphic rocks circulate through a geothermal gradient of 30 °C km^?1 at lithostatic pressure, and (ii) the brittle upper crust through which meteoric fluids percolate through a high geothermal gradient of 55 °C km^?1 at hydrostatic pressure.     

Geochemistry, Nd Isotopic Characteristics of Metamorphic Complexes in Northern Hebei： Implications for Crustal Accretion

The middle segment of the northern margin of the North China Craton （NCC） consists mainly of metamorphosed Archean Dantazi Complex, Paleoproterozoic Hongqiyingzi Complex and unmetamorphosed gabbro-anorthosite-meta-alkaline granite, as well as metamorphosed Late Paleozoic mafic to granitoid rocks in the Damiao-Changshaoying area. The -2.49 Ga Dantazi Complex comprises dioritic-trondhjemitic-granodoritic-monzogranitic gneisses metamorphosed in amphibolite to granulite facies. Petrochemical characteristics reveal that most of the rocks belong to a medium- to high-potassium calc-alkaline series, and display Mg^# less than 40, right-declined REE patterns with no to obviously positive Eu anomalies, evidently negative Th, Nb, Ta and Ti anomalies in primitive mantlenormalized spider diagrams, εNd（t）=＋0.65 to -0.03, and depleted mantle model ages TDM=2.78-2.71 Ga. Study in petrogenesis indicates that the rocks were formed from magmatic mixing between mafic magma from the depleted mantle and granitoid magma from partial melting of recycled crustal mafic rocks in a continental margin setting. The 2.44-2.41 Ga Hongqiyingzi Complex is dominated by metamorphic mafic-granodioritic-monzogranitic gneisses, displaying similar petrochemical features to the Dantazi Complex, namely medium to high potassium calc-alkaline series, and the mafic rocks show evident change in LILEs, negative Th, Nb, Ta, Zr anomalies and positive P anomalies. And the other granitiod samples also exhibit negative Th, Nb, Ta, P and Ti anomalies. All rocks in the Hongqiyingzi Complex show right-declined REE patterns without Eu anomaly. The metamorphic mafic rocks with εNd（t） = -1.64 may not be an identical magmatic evolution series with granitoids that have εNd（t） values of ＋3.19 to ＋1.94 and TDM ages of 2.55-2.52 Ga. These granitic rocks originated from hybrid between mafic magma from the depleted mantle and magma from partial melting of juvenile crustal mafic rocks in an island arc setting. All the -311 Ma Late Paleozoic metamorphic mafic rocks and related granitic rocks show a medium-potassium calc-alkaline magmatic evolution series, characterized by high Mg^#, obviously negative Th, Nb, Ta anomalies and positive Sr anomalies, from no to strongly negative Ti anomalies and flat REE patterns with εNd（t） = ＋8.42, implying that the maflc magma was derived from the depleted mantle. However the other granitic rocks are characterized by right-declined REE patterns with no to evidently positive Eu anomalies, significantly low εNd（t） = -13.37 to -14.04, and TDM=1.97-1.96 Ga, revealing that the granitoid magma was derived from hybrid between maflc magma that came from -311 Ma depleted mantle and granitoid magma from Archean to Early Paleoproterozoic ancient crustal recycling. The geochemistry and Nd isotopic characteristics as well as the above geological and geochronological results indicate that the middle segment of the northern margin of the NCC mainly experienced four crustal growth episodes from Archean to Late Paleozoic, which were dominated by three continental marginal arc accretions （-2.49, -2.44 and 311 Ma）, except the 1.76-1.68 Ga episode related to post-collisional extension, revealing that the crustal accretion of this segment was chiefly generated from arc accretion and amalgamation to the NCC continental block.     

Fluid flow and Al transport during quartz-kyanite vein formation, Unst, Shetland Islands, Scotland

Quartz‐kyanite veins, adjacent alteration selvages and surrounding ‘precursor’ wall rocks in the Dalradian Saxa Vord Pelite of Unst in the Shetland Islands (Scotland) were investigated to constrain the geochemical alteration and mobility of Al associated with channelized metamorphic fluid infiltration during the Caledonian Orogeny. Thirty‐eight samples of veins, selvages and precursors were collected, examined using the petrographic microscope and electron microprobe, and geochemically analysed. With increasing grade, typical precursor mineral assemblages include, but are not limited to, chlorite+chloritoid, chlorite+chloritoid+kyanite, chlorite+chloritoid+staurolite and garnet+staurolite+kyanite+chloritoid. These assemblages coexist with quartz, white mica (muscovite, paragonite, margarite), and Fe‐Ti oxides. The mineral assemblage of the selvages does not change noticeably with metamorphic grade, and consists of chloritoid, kyanite, chlorite, quartz, white mica and Fe‐Ti oxides. Pseudosections for selvage and precursor bulk compositions indicate that the observed mineral assemblages were stable at regional metamorphic conditions of 550–600 °C and 0.8–1.1 GPa. A mass balance analysis was performed to assess the nature and magnitude of geochemical alteration that produced the selvages adjacent to the veins. On average, selvages lost about −26% mass relative to precursors. Mass losses of Na, K, Ca, Rb, Sr, Cs, Ba and volatiles were −30 to −60% and resulted from the destruction of white mica. Si was depleted from most selvages and transported locally to adjacent veins; average selvage Si losses were about −50%. Y and rare earth elements were added due to the growth of monazite in cracks cutting apatite. The mass balance analysis also suggests some addition of Ti occurred, consistent with the presence of rutile and hematite‐ilmenite solid solutions in veins. No major losses of Al from selvages were observed, but Al was added in some cases. Consequently, the Al needed to precipitate vein kyanite was not derived locally from the selvages. Veins more than an order of magnitude thicker than those typically observed in the field would be necessary to accommodate the Na and K lost from the selvages during alteration. Therefore, regional transport of Na and K out of the local rock system is inferred. In addition, to account for the observed abundances of kyanite in the veins, large fluid‐rock ratios (10²–10³ m³_fluid m⁻³_rock) and time‐integrated fluid fluxes in excess of ∼10⁴ m³_fluid m⁻²_rock are required owing to the small concentrations of Al in aqueous fluids. It is concluded that the quartz‐kyanite veins and their selvages were produced by regional‐scale advective mass transfer by means of focused fluid flow along a thrust fault zone. The results of this study provide field evidence for considerable Al mass transport at greenschist to amphibolite facies metamorphic conditions, possibly as a result of elevated concentrations of Al in metamorphic fluids due to alkali‐Al silicate complexing at high pressures.     

Geological Implications for the Deep-Derived Mafic Enclaves from Cenozoic Shoshonitic Rocks in Jianchuan-Dali Area,West Yunnan

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