Evolution of fluids associated with metasedimentary sequences from Chaves (North Portugal)

In order to identify and characterise fluids associated with metamorphic rocks from the Chaves region (North Portugal), fluid inclusions were studied in quartz veinlets, concordant with the main foliation, in graphitic-rich and nongraphitic-rich lithologies from areas with distinct metamorphic grade. The study indicates multiple fluid circulation events with a variety of compositions, broadly within the C–H–O–N–salt system. Primary fluid inclusions in quartz contain low salinity aqueous–carbonic, H₂O–CH₄–N₂–NaCl fluids that were trapped near the peak of regional metamorphism, which occurred during or immediately after D2. The calculated P–T conditions for the western area of Chaves (CW) is P=300–350 MPa and T500 °C, and for the eastern area (CE), P=200–250 MPa and T=400–450 °C. A first generation of secondary fluid inclusions is restricted to discrete cracks at the grain boundaries of quartz and consists of low salinity aqueous–carbonic, H₂O–CO₂–CH₄–N₂–NaCl fluids. P–T conditions from the fluid inclusions indicate that they were trapped during a thermal event, probably related with the emplacement of the two-mica granites.

A second generation of secondary inclusions occurs in intergranular fractures and is characterised by two types of aqueous inclusions. One type is a low salinity, H₂O–NaCl fluid and the second consists of a high salinity, H₂O–NaCl–CaCl₂ fluid. These fluid inclusions are not related to the metamorphic process and have been trapped after D3 at relatively low P (hydrostatic)–T conditions (P<100 MPa and T<300 °C).

Both the early H₂O–CH₄–N₂–NaCl fluids in quartz from the graphitic-rich lithologies and the later H₂O–CO₂–CH₄–N₂–NaCl carbonic fluid in quartz from graphitic-rich and nongraphitic-rich lithologies seem to have a common origin and evolution. They have low salinity, probably resulting from connate waters that were diluted by the water released from mineral dehydration during metamorphism. Their main component is water, but the early H₂O–CH₄–N₂–NaCl fluids are enriched in CH₄ due to interaction with the C-rich host rocks.

From the early H₂O–CH₄–N₂–NaCl to the later aqueous–carbonic H₂O–CO₂–CH₄–N₂–NaCl fluids, there is an enrichment in CO₂ that is more significant for the fluids associated with nongraphitic-rich lithologies.

The aqueous–carbonic fluids, enriched in H₂O and CH₄, are primarily associated with graphitic-rich lithologies. However, the aqueous–carbonic CO₂-rich fluids were found in both graphitic and nongraphitic-rich units from both the CW and CE studied areas, which are of medium and low metamorphic grade, respectively.     

Status report on stability of K-rich phases at mantle conditions

Experimental research on K-rich phases and observations from diamond inclusions, UHP metamorphic rocks, and xenoliths provide insights about the hosts for potassium at mantle conditions. K-rich clinopyroxene (Kcpx–KM³⁺Si₂O₆) can be an important component in clinopyroxenes at P>4 GPa, dependent upon coexisting K-bearing phases (solid or liquid) but not, apparently, upon temperature. Maximum Kcpx content can reach 25 mol%, with 17 mol% the highest reported in nature. Partitioning ^(K)D_(cpx/liquid) above 7 GPa=0.1–0.2 require ultrapotassic liquids to form highly potassic cpx or critical solid reactions, e.g., between Kspar and Di. Phlogopite can be stable to about 8 GPa at 1250 °C where either amphibole or liquid forms. When fluorine is present, it generally increases in Phl upon increasing P (and probably T) to about 6 GPa, but reactions forming amphibole and/or KMgF₃ limit F content between 6 and 8 GPa. The perovskite KMgF₃ is stable up to 10 GPa and 1400 °C as subsolidus breakdown products of phlogopite upon increasing P. ^(M4)K-substituted potassic richterite (ideally K(KCa)Mg₅Si₈O₂₂(OH,F)₂) is produced in K-rich peridotites above 6 GPa and in Di+Phl from 6 to 13 GPa. K content of amphibole is positively correlated with P; Al and F content decrease with P. In the system 1Kspar+1H₂O K-cymrite (hydrous hexasanidine–KAlSi₃O₈·nH₂O–Kcym) is stable from 2.5 GPa at 400 to 1200 °C and 9 GPa; Kcym can be a supersolidus phase. Formation of Kcym is sensitive to water content, not forming within experiments with H₂O2O>Kspar. Phase X, a potassium di-magnesium acid disilicate ((K_1−x−n)₂(Mg_1−nM_n³⁺)₂Si₂O₇H_2x), forms in mafic compositions at T=1150–1400 °C and P=9–17 GPa and is a potential host for K and H₂O at mantle conditions with a low-T geotherm or in subducting slabs. The composition of phase-X is not fixed but actually represents a solid solution in the stoichiometries □₂Mg₂Si₂O₇H₂–(K□)Mg₂Si₂O₇H–K₂Mg₂Si₂O₇ (□=vacancy), apparently stable only near the central composition. K-hollandite, KAlSi₃O₈, is possibly the most important K-rich phase at very high pressure, as it appears to be stable to conditions near the core–mantle boundary, 95 GPa and 2300 °C. Other K-rich phases are considered.     

High-pressure experimental growth of diamond using C–K2CO3–KCl as an analogue for Cl-bearing carbonate fluid

High-pressure, high-temperature diamond growth experiments have been conducted in the system C–K₂CO₃–KCl at 1050–1420 °C, 7.0–7.7 GPa. KCl is of interest because of the strong effect of halogens on the phase relations of carbonate-rich systems [Geophys. Res. Lett. 30 (2003) 1022] and because of the occurrence of KCl coexisting with alkali silicate–carbonate fluids in natural-coated diamond [Geochim. Cosmochim. Acta 64 (2000) 717]. We have used system C–K₂CO₃–KCl as an analogue for these mantle fluids in diamond growth experiments. The presence of KCl reduces the potassium carbonate liquidus to ≤1000 °C at 7.7 GPa, allowing it to act as a solvent catalyst for diamond growth at temperatures below the continental geotherm. This is a reduction on the minimum diamond growth temperature reported in the alkali-carbonate–C–O–H system [Lithos 60 (2002) 145]. Diamond growth using carbonate solvent catalysts is characterised by a relatively long induction period. However, the addition of KCl also reduced the period for diamond growth in carbonate to 5 min; no such induction period appears to be necessary. It is suggested that KCl destabilises carbonate, allowing greater solubility and diffusion of carbon.     

Carbonatite melt–CO2 fluid inclusions in mantle xenoliths from Tenerife, Canary Islands: a story of trapping, immiscibility and fluid–rock interaction in the upper mantle

Three types of fluid inclusions have been identified in olivine porphyroclasts in the spinel harzburgite and lherzolite xenoliths from Tenerife: pure CO₂ (Type A); carbonate-rich CO₂–SO₂ mixtures (Type B); and polyphase inclusions dominated by silicate glass±fluid±sp±silicate±sulfide±carbonate (Type C). Type A inclusions commonly exhibit a “coating” (a few microns thick) consisting of an aggregate of a platy, hydrous Mg–Fe–Si phase, most likely talc, together with very small amounts of halite, dolomite and other phases. Larger crystals (e.g. (Na,K)Cl, dolomite, spinel, sulfide and phlogopite) may be found on either side of the “coating”, towards the wall of the host mineral or towards the inclusion center. These different fluids were formed through the immiscible separations and fluid–wall-rock reactions from a common, volatile-rich, siliceous, alkaline carbonatite melt infiltrating the upper mantle beneath the Tenerife. First, the original siliceous carbonatite melt is separated from a mixed CO₂–H₂O–NaCl fluid and a silicate/silicocarbonatite melt (preserved in Type A inclusions). The reaction of the carbonaceous silicate melt with the wall-rock minerals gave rise to large poikilitic orthopyroxene and clinopyroxene grains, and smaller neoblasts. During the metasomatic processes, the consumption of the silicate part of the melt produced carbonate-enriched Type B CO₂–SO₂ fluids which were trapped in exsolved orthopyroxene porphyroclasts. At the later stages, the interstitial silicate/silicocarbonatite fluids were trapped as Type C inclusions. At a temperature above 650 °C, the mixed CO₂–H₂O–NaCl fluid inside the Type A inclusions were separated into CO₂-rich fluid and H₂O–NaCl brine. At T<650 °C, the residual silicate melt reacted with the host olivine, forming a reaction rim or “coating” along the inclusion walls consisting of talc (or possibly serpentine) together with minute crystals of NaCl, KCl, carbonates and sulfides, leaving a residual CO₂ fluid. The homogenization temperatures of +2 to +25 °C obtained from the Type A CO₂ inclusions reflect the densities of the residual CO₂ after its reactions with the olivine host, and are unrelated to the initial fluid density or the external pressure at the time of trapping. The latter are restricted by the estimated crystallization temperatures of 1000–1200 °C, and the spinel lherzolite phase assemblage of the xenolith, which is 0.7–1.7 GPa.     

Formation of Al-rich titanite (CaTiSiO4O–CaAlSiO4OH) reaction rims on ilmenite in metamorphic rocks as a function of fH2O and fO2

Reaction rims of titanite on ilmenite are described in samples from four terranes of amphibolite-facies metapelites and amphibolites namely the Tamil Nadu area, southern India; the Val Strona area of the Ivrea-Verbano Zone, northern Italy, the Bamble Sector, southern Norway, and the northwestern Austroalpine Ötztal Complex. The titanite rims, and hence the stability of titanite (CaTiSiO₄O) and Al–OH titanite, i.e. vuaganatite (hypothetical end-member CaAlSiO₄OH), are discussed in the light of fH₂O- and fO₂-buffered equilibria involving clinopyroxene, amphibole, biotite, ilmenite, magnetite, and quartz in the systems CaO–FeO/Fe₂O₃–TiO₂–SiO₂–H₂O–O₂ (CFTSH) and CaO–FeO/Fe₂O₃–Al₂O₃–SiO₂–H₂O–O₂ (CFASH) present in each of the examples. Textural evidence suggests that titanite reaction rims on ilmenite in rocks from Tamil Nadu, Val Strona, and the Bamble Sector originated most likely due to hydration reactions such as clinopyroxene + ilmenite + quartz + H₂O = amphibole + titanite and oxidation reactions such as amphibole + ilmenite + O₂ = titanite + magnetite + quartz + H₂O during amphibolite-facies metamorphism, or, as in the case of the Ötztal Complex, during a subsequent greenschist-facies overprint. Overstepping of these reactions requires fH₂O and fO₂ to be high for titanite formation, which is also in accordance with equilibria involving Al–OH titanite. This study shows that, in addition to P, T, bulk–rock composition and composition of the coexisting fluid, fO₂ and fH₂O also play an important role in the formation of Al-bearing titanite during amphibolite- and greenschist-facies metamorphism.     

Ultra high temperature-metamorphism and its significance in the Central Indian Tectonic Zone

In the present study from the southern margin of the Central Indian Tectonic Zone, it is demonstrated how the metamorphic P–T path of ultrahigh-temperature granulite terranes can be reconstructed using the metamorphic transition in corundum granulites from early biotite melting to later FMAS solid–solid reaction. The extreme metamorphism in these rocks caused two-stage biotite melting, resulting in initial porphyroblastic garnet₁ and later sapphirine–spinel₁ incongruent solid mineral assemblages. During this process, the leucocratic and melanocratic layers in the corundum granulites evolved from an initial silica-oversaturated to a later silica-undersaturated domain. In the melanocratic layer, this allowed localized concentration of sapphirine-spinel₁ and residual sillimanite₁, producing an extremely restitic assemblage, at the culmination of peak metamorphism, BM₁. BM₁ is constrained at  1000 °C at relatively deep crustal levels (P  9 kbar) from the stability of ferroaugite in a co-metamorphosed Iron Formation granulite. During subsequent metamorphism (BM₂), the reaction path and history in the corundum granulites shifted to the restitic domain allowing reacting sapphirine, spinel₁ and sillimanite to produce coronal garnet₂–corundum assemblage via a FMAS univariant reaction. In the final stages of reaction history, biotite₂–sillimanite₂–spinel₂ assemblage was produced after garnet₂–corundum due to localized melt–crystal interaction. The metamorphic sequence, when interpreted with the help of a newly constructed, qualitative KFMASH petrogenetic grid, reveals successive stages of heating, increasing pressure and cooling around the KFMASH invariant point, [Opx,Crd], which is consistent with a counterclockwise metamorphic P–T path. The near isobaric nature of post-peak cooling (ΔT  250–300 °C) is also evident from multistage pyroxene exsolution and by the appearance of lamellar and coronal garnets in the Iron Formation granulites. This study provides the first tight constraint for ultrahigh-T metamorphism along a counter clockwise P–T trajectory in the Central Indian Tectonic zone, and has important bearing for terrane correlations in this part of East Gondwanaland. In addition, the new KFMASH grid allows evaluation of metamorphic phase relations in ultrahigh-T, corundum-bearing and corundum-absent aluminous granulites.     

Coesite inclusions and prograde compositional zonation of garnet in whiteschist of the HP-UHPM Kokchetav massif, Kazakhstan: a record of progressive UHP metamorphism

Coarse-grained whiteschist, containing the assemblage: garnet+kyanite+phengite+talc+quartz/coesite, is an abundant constituent of the ultrahigh-pressure metamorphic (UHPM) belt in the Kulet region of the Kokchetav massif of Kazakhstan.

Garnet displays prograde compositional zonation, with decreasing spessartine and increasing pyrope components, from core to rim. Cores were recrystallized at T=380°C (inner) to 580°C (outer) at P<10 kbar (garnet–ilmenite geothermometry, margarite+quartz stability), and mantles at T=720–760°C and P_H20=34–36 kbar (coesite+graphite stability, phengite geobarometer, KFMASH system reaction equilibria). Textural evidence indicates that rims grew during decompression and cooling, within the Qtz-stability field.

Silica inclusions (quartz and/or coesite) of various textural types within garnets display a systematic zonal distribution. Cores contain abundant inclusions of euhedral quartz (type 1 inclusions). Inner mantle regions contain inclusions of polycrystalline quartz pseudomorphs after coesite (type 2), with minute dusty micro-inclusions of chlorite, and more rarely, talc and kyanite in their cores; intense radial and concentric fractures are well developed in the garnet. Intermediate mantle regions contain bimineralic inclusions with coesite cores and palisade quartz rims (type 3), which are also surrounded by radial fractures. Subhedral inclusions of pure coesite without quartz overgrowths or radial fractures (type 4) occur in the outer part of the mantle. Garnet rims are silica-inclusion-free.

Type 1 inclusions in garnet cores represent the low-P, low-T precursor stage to UHPM recrystallization, and attest to the persistence of low-P assemblages in the coesite-stability field. Coesites in inclusion types 2, 3, and 4 are interpreted to have sequentially crystallized by net transfer reaction (kyanite+talc=garnet+coesite+H₂O), and were sequestered within the garnet with progressively decreasing amounts of intragranular aqueous fluid.

During the retrograde evolution of the rock, all three inclusion types diverged from the host garnet P–T path at the coesite–quartz equilibrium, and followed a trajectory parallel to the equilibrium boundary resulting in inclusion overpressure. Coesite in type 2 inclusions suffered rapid intragranular H₂O-catalysed transformation to quartz, and ruptured the host garnet at about 600°C (when inclusion P27 kbar, garnet host P9 kbar). Instantaneous decompression to the host garnet P–T path, passed through the kyanite+talc=chlorite+quartz reaction equilibrium, resulting in the dusty micro-assemblage in inclusion cores. Type 3 inclusions suffered a lower volumetric proportion transformation to quartz at the coesite–quartz equilibrium, and finally underwent rupture and decompression when T<400°C, facilitating coesite preservation. Type 4 coesite inclusions are interpreted to have suffered minimal transformation to quartz and proceeded to surface temperature conditions along or near the coesite–quartz equilibrium boundary.     

Metamorphic evolution, mineral chemistry and thermobarometry of schists and orthogneisses hosting ultra-high pressure eclogites in the Dabieshan of central China

As is typical of ultra-high pressure (UHP) terrains, the regional extent of the UHP terrain in the Dabieshan of central China is highly speculative, since the volume of eclogites and paragneisses preserving unequivocal evidence of coesite and/or diamond stability is very small. By contrast, the common garnet (X_Mn=0.18–0.45)–phengite (Si=3.2–3.35)–zoned epidote (Ps_38–97)–biotite–titanite–two feldspars–quartz assemblages in the more extensive orthogneisses have been previously thought to have formed under low P–T conditions of ca. 400±50°C at 4 kbar. However, certain orthogneiss samples preserve garnets with X_Ca up to 0.50, rutile inclusions within titanite or epidote and relict phengite inclusions within epidote with Si contents p.f.u. of up to 3.49 — overlapping with the highest values (3.49–3.62) recorded for phengites in samples of undoubted UHP schists. These and other mineral composition features (such as A-site deficiencies in the highest Si phengites, Na in garnets linked to Y+Yb substitution and Al F Ti₋₁ O₋₁ substitution in titanites) are taken to be pointers towards the orthogneisses having experienced a similar metamorphic evolution to the associated UHP schists and eclogites. Re-evaluated garnet–phengite and garnet–biotite Fe/Mg exchange thermometry and calculated 5 rutile+3 grossular+2SiO₂+H₂O=5 titanite+2 zoisite equilibria indicate that the orthogneisses may indeed have followed a common subduction-related clockwise P–T path with the UHP paragneisses and eclogites through conditions of P_max at ca. 690°C–715°C and 36 kbar to T_max at ca. 710°C–755°C and 18 kbar, prior to extensive re-crystallisation and re-equilibration of these ductile orthogneisses at ca. 400°C–450°C and 6 kbar. The consequential conclusion, that it is no longer necessary to resort to models of tectonic juxtapositioning to explain the spatial association of these Dabieshan orthogneisses with undoubted UHP lithologies, has far-reaching implications for the interpretation of controversial gneiss–eclogite relationships in other UHP metamorphic terrains.     

Review of the systematics of CO2–H2O fluid inclusions

Aqueous solutions that contain volatile (gas) components are one of the most important types of fluid in the Earth's crust. The record that such fluids have left in the form of fluid inclusions in minerals provides a wealth of insight into the geochemical and petrologic processes in which the fluids participated. This article reviews the systematics of CO₂–H₂O fluid inclusions as a starting point for interpreting the chemically more complex systems. The phase relations of the binary are described with respect to a qualitative P–T–X model, and isoplethic–isochoric paths through this model are used to explain the equilibrium and non-equilibrium behaviour of fluid inclusions during microthermometric heating and cooling. The P–T–X framework is then used to discuss the various modes of fluid inclusion entrapment, and how the resulting assemblage textures can be used to interpret the P–T conditions, phase states, and evolution paths of the parent solutions. Finally, quantitative methods are reviewed by which bulk molar volume and composition of CO₂–H₂O fluid inclusions can be determined from microthermometric observations of phase transitions.     

Thermodynamic modelling of C–O–H fluids

H₂O, CO₂, CH₄, CO, H₂ and O₂ are the most important species in crustal fluids. The composition of these C–O–H fluids can be calculated if the pressure, temperature, carbon activity, and either the oxygen fugacity or the atomic H/O ratio of the fluid is known. The calculation methods are discussed and calculation results are illustrated with isobaric T–X_i, P–T, and isobaric–isothermal ternary C–O–H diagrams. Fluid inclusion compositions, in particular, the X_CO2/(X_CO2+X_CH4) ratio, can be used for C–O–H model calculations. However, care should be taken about possible post-entrapment changes, which may have modified the chemical composition of the fluid inclusion.     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

Fluid inclusions in granulites, granulitized eclogites and garnet clinopyroxenites from the Dabie–Sulu terranes, eastern China

Minor granulites (believed to be pre-Triassic), surrounded by abundant amphibolite-facies orthogneiss, occur in the same region as the well-documented Triassic high- and ultrahigh-pressure (HP and UHP) eclogites in the Dabie–Sulu terranes, eastern China. Moreover, some eclogites and garnet clinopyroxenites have been metamorphosed at granulite- to amphibolite-facies conditions during exhumation. Granulitized HP eclogites/garnet clinopyroxenites at Huangweihe and Baizhangyan record estimated eclogite-facies metamorphic conditions of 775–805 °C and ≥15 kbar, followed by granulite- to amphibolite-facies overprint of ca. 750–800 °C and 6–11 kbar. The presence of (Na, Ca, Ba, Sr)-feldspars in garnet and omphacite corresponds to amphibolite-facies conditions. Metamorphic mineral assemblages and P–T estimates for felsic granulite at Huangtuling and mafic granulite at Huilanshan indicate peak conditions of 850 °C and 12 kbar for the granulite-facies metamorphism and 700 °C and 6 kbar for amphibolite-facies retrograde metamorphism. Cordierite–orthopyroxene and ferropargasite–plagioclase coronas and symplectites around garnet record a strong, rapid decompression, possibly contemporaneous with the uplift of neighbouring HP/UHP eclogites.

Carbonic fluid (CO₂-rich) inclusions are predominant in both HP granulites and granulitized HP/UHP eclogites/garnet clinopyroxenites. They have low densities, having been reset during decompression. Minor amounts of CH₄ and/or N₂ as well as carbonate are present. In the granulitized HP/UHP eclogites/garnet clinopyroxenites, early fluids are high-salinity brines with minor N₂, whereas low-salinity fluids formed during retrogression. Syn-granulite-facies carbonic fluid inclusions occur either in quartz rods in clinopyroxene (granulitized HP garnet clinopyxeronite) or in quartz blebs in garnet and quartz matrices (UHP eclogite). For HP granulites, a limited number of primary CO₂ and mixed H₂O–CO₂(liquid) inclusions have also been observed in undeformed quartz inclusions within garnet, orthopyroxene, and plagioclase which contain abundant, low-density CO₂±carbonate inclusions. It is suggested that the primary fluid in the HP granulites was high-density CO₂, mixed with a significant quantity of water. The water was consumed by retrograde metamorphic mineral reactions and may also have been responsible for metasomatic reactions (“giant myrmekites”) occurring at quartz–feldspar boundaries. Compared with the UHP eclogites in this region, the granulites were exhumed in the presence of massive, externally derived carbonic fluids and subsequently limited low-salinity aqueous fluids, probably derived from the surrounding gneisses.     

Biotite stability in peraluminous granitic melts: Compositional dependence and application to the generation of two-mica granites in the South Bohemian batholith (Bohemian Massif, Czech Republic)

Crystallization experiments have been conducted in the system Na₂O–K₂O–MgO–FeO–Al₂O₃–SiO₂–H₂O (with 4% normative corundum) in order to constrain the stability of biotite as a function of water activity and the Mg# of biotite [Mg/(Mg +Fe_total)] in equilibrium with peraluminous granitic melts. The temperature at which biotite breakdown starts is strongly dependent on the Mg# of biotite. At 500 MPa, the temperature of biotite breakdown to form orthopyroxene increases from 750 °C to 830 °C, as the Mg# of biotite increases from 0.4 to 0.5. Considering that the system investigated is relevant for Ca-poor peraluminous biotite-bearing rocks (metapelites), the biotite dehydration curves obtained are used to discuss the melting reactions and the temperatures that lead to the formation of two distinct types of two-mica granites found in the South Bohemian batholith (specifically the Eisgarn and Deštná granites). The phase relationships were determined experimentally for the composition of these two granites in order to constrain the composition of the biotite in equilibrium with the melt in the protoliths. We demonstrate that Eisgarn granitic melts may have been generated at temperatures in the range 830–850 °C from melting reactions involving biotite with a Mg# up to 0.5 as a reactant. In contrast, Deštná granitic melts cannot have been generated from dehydration melting reactions involving biotite.     

New insights into the occurrence of C-depleted carbon in the mantle from two closely associated kimberlites: Letlhakane and Orapa, Botswana

Carbon isotope measurements on diamonds from the Letlhakane kimberlite, and the analyses of their inclusions, permit the examination of km-scale mantle-composition variations by comparing the results with those for the nearby Orapa kimberlite. Diamonds from Letlhakane have a wide range in carbon isotopic composition (−3‰ to −21‰); however, the relative abundance of diamonds depleted in ¹³C is significantly lower than in the Orapa kimberlite. Most of the ¹³C-depleted diamonds belong to the eclogictic or websteritic paragenesis. The relative abundance of inclusions in diamonds and their composition indicate that there are significant differences in petrology in the mantle below the two locations. At Letlhakane, peridotitic compositions are more prevalent than at Orapa and the protolith of P-Type inclusions in diamonds may have experienced a higher degree of partial melting at Letlhakane compared to Orapa. P/T estimates for both W- and E-Type diamonds indicate that a region of ¹³C-depletion may exist beneath the two kimberlites. The relationships between carbon isotopic composition of the host diamond and the Al₂O₃/Cr₂O₃ ratios of their websteritic and eclogitic garnet inclusions indicate that the low δ¹³C regions may represent a primary mantle feature, unrelated to a crustal component.     

P–T paths reconstruction of a collisional event: The example of the Thiviers-Payzac Unit in the Variscan French Massif Central

Because of late metamorphic and tectonic overprints, the reconstruction of prograde parts of P–T paths is often difficult. In the SW Variscan French Massif Central, the Thiviers-Payzac Unit (TPU) is the uppermost allochthon emplaced above underlying units. The TPU experienced a Barrovian metamorphism coeval with a top-to-the-NW ductile shearing (D2 event) in Early Carboniferous times (ca. 360–350 Ma). The tectonic setting of the D2 event, compression or synconvergence extension, remains unclear. Using the THERMOCALC software and the model system MnNCKFMASH, the peak P–T conditions are estimated from garnet rims and matrix minerals and the prograde evolution is deduced from garnet core compositions. The combination of these two approaches demonstrates that the TPU experienced pressure and temperature increases before reaching peak conditions at 6.6–9.0 +/− 1.2 kbar and 615–655 +/− 35 °C. This kind of P–T path shows that the regional D2 event corresponds to crustal thickening.     

Mineral and fluid inclusions in zircon of UHP metamorphic rocks from the CCSD-main drill hole: A record of metamorphism and fluid activity

The Chinese Continental Scientific Drilling (CCSD) main drill hole (0–3000 m) in Donghai, southern Sulu orogen, consists of eclogite, paragneiss, orthogneiss, schist and garnet peridotite. Detailed investigations of Raman, cathodoluminescence, and microprobe analyses show that zircons from most eclogites, gneisses and schists have oscillatory zoned magmatic cores with low-pressure mineral inclusions of Qtz, Pl, Kf and Ap, and a metamorphic rim with relatively uniform luminescence and eclogite-facies mineral inclusions of Grt, Omp, Phn, Coe and Rt. The chemical compositions of the UHP metamorphic mineral inclusions in zircon are similar to those from the matrix of the host rocks. Similar UHP metamorphic P–T conditions of about 770 °C and 32 kbar were estimated from coexisting minerals in zircon and in the matrix. These observations suggest that all investigated lithologies experienced a joint in situ UHP metamorphism during continental deep subduction. In rare cases, magmatic cores of zircon contain coesite and omphacite inclusions and show patchy and irregular luminescence, implying that the cores have been largely altered possibly by fluid–mineral interaction during UHP metamorphism.

Abundant H₂O–CO₂, H₂O- or CO₂-dominated fluid inclusions with low to medium salinities occur isolated or clustered in the magmatic cores of some zircons, coexisting with low-P mineral inclusions. These fluid inclusions should have been trapped during magmatic crystallization and thus as primary. Only few H₂O- and/or CO₂-dominated fluid inclusions were found to occur together with UHP mineral inclusions in zircons of metamorphic origin, indicating that UHP metamorphism occurred under relatively dry conditions. The diversity in fluid inclusion populations in UHP rocks from different depths suggests a closed fluid system, without large-scale fluid migration during subduction and exhumation.     

Mantle diversity beneath the Colombian Andes, Northern Volcanic Zone: Constraints from Sr and Nd isotopes

In order to provide mantle and crustal constraints during the evolution of the Colombian Andes, Sr and Nd isotopic studies were performed in xenoliths from the Mercaderes region, Northern Volcanic Zone, Colombia. Xenoliths are found in the Granatifera Tuff, a deposit of Cenozoic age, in which mantle- and crustal-derived xenoliths are present in bombs and fragments of andesites and lamprophyres compositions. Garnet-bearing xenoliths are the most abundant mantle-derived rocks, but websterites (garnet-free xenoliths) and spinel-bearing peridotites are also present in minor amounts. Amphibolites, pyroxenites, granulites, and gneisses represent the lower crustal xenolith assemblage. Isotopic signatures for the mantle xenoliths, together with field, petrographic, mineral, and whole-rock chemistry and pressure–temperature estimates, suggest three main sources for these mantle xenoliths: garnet-free websterite xenoliths derived from a source region with low P and T (16 kbar, 1065 °C) and MORB isotopic signature, ⁸⁷Sr/⁸⁶Sr ratio of 0.7030, and ¹⁴³Nd/¹⁴⁴Nd ratio of 0.5129. Garnet-bearing peridotite and websterite xenoliths derived from two different sources in the mantle: i) a source with intermediate P and T (29–35 kbar, 1250–1295 °C) conditions, similar to that of sub-oceanic geotherm, with an OIB isotopic signature (⁸⁷Sr/⁸⁶Sr ratio of 0.7043 and ¹⁴³Nd/¹⁴⁴Nd ratio of 0.5129); and ii) another source with P and T conditions similar to those of a sub-continental geotherm (>38 kbar, 1140–1175 °C) and OIB isotopic characteristics (⁸⁷Sr/⁸⁶Sr ratio=0.7041 and ¹⁴³Nd/¹⁴⁴Nd ratio=0.5135).     

Intermediate high-pressure exhumation of the northern segment of the Sanbagawa belt, Saruta-gawa area, central Shikoku, Japan

The retrograde chemical zonal structure of amphibole in hematite-bearing basic and quartz schists from the higher grade zone in the Saruta-gawa area of the Sanbagawa belt was studied to investigate the relationships between the prograde and retrograde P–T paths of the Sanbagawa metamorphism. This amphibole coexists with chlorite, epidote, muscovite, albite, quartz and hematite, and is composed of Al-rich core and Al-poor mantle. The core is fairly homogeneous and has a barroisitic composition. In the mantle part, ^[B]Na increases with decreasing ^[4]Al towards the margins, which have winchite–magnesioriebeckite compositions. The barroisite–winchite–magnesioriebeckite composite crystal is sometimes rimmed by actinolite and/or winchite with low ^[4]Al and ^[B]Na. The Al-rich core and Al-poor mantle are regarded as prograde and retrograde products, respectively. The retrograde mantle in the Saruta-gawa area: (1) is systematically richer in ^[B]Na [0.40–1.73 per formula unit (pfu; for O=23)] than that from the same grade zone in the Asemi-gawa area (0.19–0.78 pfu), about 8 km south of the studied area; (2) tends to be ^[B]Na-poorer (less than 1.73 pfu) than prograde sodic amphibole (up to 1.93 ^[B]Na pfu) produced in the peak temperature stage from the lower grade zone in the same and other areas; and (3) extends its compositional range towards higher ^[B]Na and lower ^[4]Al than prograde-formed amphibole from the same grade zone in the same area. These zonal characteristics imply that (1) the Saruta-gawa samples experienced retrograde metamorphism under higher P/T conditions than the Asemi-gawa samples, (2) the retrograde P–T path of the Saruta-gawa area passes on the lower pressure side of the metamorphic field gradient, and (3) the Saruta-gawa samples underwent retrograde metamorphism under higher P/T conditions than the prograde metamorphism. The higher P/T conditions of the retrograde metamorphism suggests an increasing dP/dT of the geotherm during exhumation. Retrograde P–T conditions during the formation of magnesioriebeckite can be roughly estimated at 7–8 kbar, 400–450°C based on semi-quantitative phase relations of actinolite–winchite–magnesioriebeckite–barroisite series associated with chlorite, epidote, muscovite, albite, quartz and hematite.     

The Homestead kimberlite, central Montana, USA: mineralogy, xenocrysts, and upper-mantle xenoliths

The Homestead kimberlite was emplaced in lower Cretaceous marine shale and siltstone in the Grassrange area of central Montana. The Grassrange area includes aillikite, alnoite, carbonatite, kimberlite, and monchiquite and is situated within the Archean Wyoming craton. The kimberlite contains 25–30 modal% olivine as xenocrysts and phenocrysts in a matrix of phlogopite, monticellite, diopside, serpentine, chlorite, hydrous Ca–Al–Na silicates, perovskite, and spinel. The rock is kimberlite based on mineralogy, the presence of atoll-textured groundmass spinels, and kimberlitic core-rim zoning of groundmass spinels and groundmass phlogopites.

Garnet xenocrysts are mainly Cr-pyropes, of which 2–12% are G10 compositions, crustal almandines are rare and eclogitic garnets are absent. Spinel xenocrysts have MgO and Cr₂O₃ contents ranging into the diamond inclusion field. Mg-ilmenite xenocrysts contain 7–11 wt.% MgO and 0.8–1.9 wt.% Cr₂O₃, with (Fe⁺³/Fe^tot) from 0.17–0.31. Olivine is the only obvious megacryst mineral present. One microdiamond was recovered from caustic fusion of a 45-kg sample.

Upper-mantle xenoliths up to 70 cm size are abundant and are some of the largest known garnet peridotite xenoliths in North America. The xenolith suite is dominated by dunites, and harzburgites containing garnet and/or spinel. Granulites are rare and eclogites are absent. Among 153 xenoliths, 7% are lherzolites, 61% are harzburgites, 31% are dunites, and 1% are orthopyroxenites. Three of 30 peridotite xenoliths that were analysed are low-Ca garnet–spinel harzburgites containing G10 garnets. Xenolith textures are mainly coarse granular, and only 5% are porphyroclastic.

Xenolith modal mineralogy and mineral compositions indicate ancient major-element depletion as observed in other Wyoming craton xenolith assemblages, followed by younger enrichment events evidenced by tectonized or undeformed veins of orthopyroxenite, clinopyroxenite, websterite, and the presence of phlogopite-bearing veins and disseminated phlogopite. Phlogopite-bearing veins may represent kimberlite-related addition and/or earlier K-metasomatism.

Xenolith thermobarometry using published two-pyroxene and Al-in-opx methods suggest that garnet–spinel peridotites are derived from 1180 to 1390 °C and 3.6 to 4.7 GPa, close to the diamond–graphite boundary and above a 38 mW/m² shield geotherm. Low-Ca garnet–spinel harzburgites with G10 garnets fall in about the same T and P range. Most spinel peridotites with assumed 2.0 GPa pressure are in the same T range, possibly indicating heating of the shallow mantle. Four of 79 Cr diopside xenocrysts have P–T estimates in the diamond stability field using published single-pyroxene P–T calculation methods.     

Basalt magma genesis and fractionation in collision- and extension-related provinces: A comparison between eastern, central and western Anatolia

Experimental studies of synthetic and natural basalt systems suggest that conditions of magma genesis and fractionation depend fundamentally on mantle temperatures and lithospheric stress fields. In general, compressional settings are more conducive to polybaric fractionation than extensional settings and in this regard, the Anatolian magmatic province offers a natural laboratory for comparing near-coeval basalt eruptions as a function of regional tectonics — compressional (collision-related) régimes dominating in eastern Anatolia and extensional tectonics characterizing a western province related to Aegean Sea opening. Projection of Plio-Quaternary basalt normative compositions from the Western Anatolia Extensional Province (WAEP), the Central Anatolian ‘Ova’ Province (CAOP), and Eastern Anatolia Compressional Province (EACP) are projected onto Ol–Ne–Cpx and Pl–Cpx–Ol planes in the simplified basalt system (Ne–Cpx–Ol–Qz), each showing distinctive liquid lines of descent. WAEP basalts are mostly constrained by low-pressure (< 0.5 GPa) cotectics while CAOP and EACP compositions conform to moderate and/or high-pressure (0.8–3.0 GPa) cotectics. Overall, a quasi-linear shift from moderate and/or high-pressure to low-pressure equilibria matches the westward transgression from compressional east Anatolia to the extensional west Anatolian–Aegean region. Comparison of their respective primary (mantle-equilibrated) magmas–simulated by normalizing their compositions to MgO = 15 wt.% (Mg-15)–with parameterized anhydrous and H₂O-undersaturated experimental melts suggests they segregated from spinel- to garnet-lherzolite mantle facies at pressures between c. 2 and 3 GPa (c. 70–100 km depth) under H₂O-undersaturated conditions. Interpolated potential temperatures (T_p) and lithospheric stretching factors (β) range as follows: (1) eastern Anatolian basalts associated with the Arabian foreland show T_p varying between 1250 and 1400 °C (except for the Karacalidag alkali basalts, south of the Bitlis–Zagros fracture zone, for which T_p ranges up to 1450 °C), for β values of 1.2–1.8. T_p values for central Anatolia (e.g. Sivas) range between 1300 and 1375 °C (except for Karapinar, Egrikuyu and Hasandag, which show < 1150 °C), and β values of 1.3–1.4. For western Anatolian basalts, T_p range mostly between 1250 and 1330 °C, except for a single value for Canakkale of 1400 °C and Kula sample showing T_p < 1200 °C, and β values of 1.3–2.0. Variation of these conditions is as great or greater than that between provinces, although there are clearly significant constraints on the inferred polybaric to low-pressure isobaric fractionation régimes. Covariation of total FeO, TiO₂, La/Yb, Ce/Sm, Zr/Y and Zr/Nb reflects small but significant differences in bulk composition and ambient melt fraction while the covariance of Ce/Sm and Sm/Yb is consistent with the segregation of primitive melts at the spinel- to garnet-lherzolite transition.