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.     

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.     

Reactions and textures in grossular–wollastonite–scapolite calc–silicate granulites from Maligawila, Sri Lanka: evidence for high-temperature isobaric cooling in the meta-sediments of the Highland Complex

Grossular–wollastonite–scapolite calc–silicate granulites from Maligawila in the Buttala klippe, which form part of the overthrusted rocks of the Highland Complex of Sri Lanka, preserve a number of spectacular coronas and replacement textures that could be effectively used to infer their P–T–fluid history. These textures include coronas of garnet, garnet–quartz, and garnet–quartz–calcite at the grain boundaries of wollastonite, scapolite, and calcite as well as calcite–plagioclase and calcite–quartz symplectites or finer grains after scapolite and wollastonite respectively. Other textures include a double rind of coronal scapolite and coronal garnet between matrix garnet and calcite. The reactions that produced these coronas and replacement textures, except those involving clinopyroxene, are modelled in the CaO–Al₂O₃–SiO₂–CO₂ system using the reduced activities. Calculated examples of T–X_CO2 and P–X_CO2 projections indicate that the peak metamorphic temperature of about 900–875 °C at a pressure of 9 kbar and the peak metamorphic fluid composition is constrained to be low in X_CO2 (0.1<X_CO2<0.30). Interpretation of the textural features on the basis of the partial grids revealed that the calc–silicate granulites underwent high-temperature isobaric cooling, from about 900–875 °C to a temperature below 675 °C, following the peak metamorphism. The late-stage cooling was accompanied by an influx of hydrous fluids. The calc–silicate granulites provide evidence for high-temperature isobaric cooling in the meta-sediments of the Highland Complex, earlier considered by some workers to be confined exclusively to the meta-igneous rocks. The coronal scapolite may have formed under open-system metasomatism.     

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.     

Fluid-bearing alkaline carbonate melts as the medium for the formation of diamonds in the Earth''s mantle: an experimental study

We have experimentally studied the formation of diamonds in alkaline carbonate–carbon and carbonate–fluid–carbon systems at 5.7–7.0 GPa and 1150–1700 °C, using a split-sphere multi-anvil apparatus (BARS). The starting carbonate and fluid-generating materials were placed into Pt and Au ampoules. The main specific feature of the studied systems is a long period of induction, which precedes the nucleation and growth of diamonds. The period of induction considerably increases with decreasing P and T, but decreases when adding a C–O–H fluid to the system. In the range of P and T corresponding to the formation of diamonds in nature, this period lasts for tens of hours. The reactivity of the studied systems with respect to the diamond nucleation and growth decreases in this sequence: Na₂CO₃–H₂C₂O₄·2H₂O–C>K₂CO₃–H₂C₂O₄·2H₂O–C>>Na₂CO₃–C>K₂CO₃–C. The diamond morphology is independent of P and T, and is mainly governed by the composition of the crystallization medium. The stable growth form is a cubo-octahedron in the Na₂CO₃ melt, and an octahedron in the K₂CO₃ melt. Regardless of the composition of the carbonate melt, only octahedral diamond crystals formed in the presence of the C–O–H fluid. The growth rates of diamond varied in the range from 1.7 μm/h at 1420 °C to 0.1–0.01 μm/h at 1150 °C, and were used to estimate, for the first time, the possible duration of the crystallization of natural diamonds. From the analysis of the experimental results and the petrological evidence for the formation of diamonds in nature, we suggest that fluid-bearing alkaline carbonate melts are, most likely, the medium for the nucleation and growth of diamonds in the Earth's upper mantle.     

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.     

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.     

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.     

Experimental synthesis and phase relations of phengitic muscovite from 6.5 to 11 GPa in a calcareous metapelite from the Dabie Mountains, China

The stability and phase relations of phengitic muscovite in a metapelitic bulk composition containing a mixed H₂O+CO₂ fluid were investigated at 6.5–11 GPa, 750–1050°C in synthesis experiments performed in a multianvil apparatus. Starting material consisted of a natural calcareous metapelite from the coesite zone of the Dabie Mountains, China, ultrahigh-pressure metamorphic complex that had experienced peak metamorphic pressures greater than 3 GPa. The sample contains a total of 2.1 wt.% H₂O and 6.3 wt.% CO₂ bound in hydrous and carbonate minerals. No additional fluid was added to the starting material. Phengite is stable in this bulk composition from 6.5 to 9 GPa at 900°C and coexists with an eclogitic phase assemblage consisting of garnet, omphacite, coesite, rutile, and fluid. Phengite dehydrates to produce K-hollandite between 8 and 11 GPa, 750–900°C. Phengite melting/dissolution occurs between 900°C and 975°C at 6.5–8 GPa and is associated with the appearance of kyanite in the phase assemblage. The formation of K-hollandite is accompanied by the appearance of magnesite and topaz-OH in the phase assemblage as well as by significant increases in the grossular content of garnet (average X_grs=0.52, X_py=0.19) and the jadeite content of omphacite (X_jd=0.92). Mass balance indicates that the volatile content of the fluid phase changes markedly at the phengite/K-hollandite phase boundary. At P≤8 GPa, fluid coexisting with phengite appears to be relatively CO₂-rich (XCO₂/XH₂O=2.2), whereas fluid coexisting with K-hollandite and magnesite at 11 GPa is rich in H₂O (XCO₂/XH₂O=0.2). Analysis of quench material and mass balance calculations indicate that fluids at all pressures and temperatures examined contain an abundance of dissolved solutes (approximately 40 mol% at 8 GPa, 60 mol% at 11 GPa) that act to dilute the volatile content of the fluid phase. The average phengite content of muscovite is positively correlated with pressure and ranges from 3.62 Si per formula unit (pfu) at 6.5 GPa to 3.80 Si pfu at 9 GPa. The extent of the phengite substitution in muscovite in this bulk composition appears to be limited to a maximum of 3.80–3.85 Si pfu at P=9 GPa. These experiments show that phengite should be stable in metasediments in mature subduction zones to depths of up to 300 km even under conditions in which aH₂O1. Other high-pressure hydrous phases such as lawsonite, MgMgAl-pumpellyite, and topaz-OH that may form in subducted sediments do not occur within the phengite stability field in this system, and may require more H₂O-rich fluid compositions in order to form. The wide range of conditions under which phengite occurs and its participation in mixed volatile reactions that may buffer the composition of the fluid phase suggest that phengite may significantly influence the nature of metasomatic fluids released from deeply subducted sediments at depths of up to 300 km at convergent plate boundaries.     

Conditions of pocket formation in the Oktyabrskaya tourmaline-rich gem pegmatite (the Malkhan field, Central Transbaikalia, Russia)

Coexisting melt (MI), fluid-melt (FMI) and fluid (FI) inclusions in quartz from the Oktaybrskaya pegmatite, central Transbaikalia, have been studied and the thermodynamic modeling of PVTX-properties of aqueous orthoboric-acid fluids has been carried out to define the conditions of pocket formation. At room temperature, FMI in early pocket quartz and in quartz from the coarse-grained quartz–oligoclase host pegmatite contain crystalline aggregates and an orthoboric-acid fluid. The portion of FMI in inclusion assemblages decreases and the volume of fluid in inclusions increases from the early to the late growth zones in the pocket quartz. No FMI have been found in the late growth zones. Significant variations of solid/fluid ratios in the neighboring FMI result from heterogeneous entrapment of coexisting melts and fluids by a host mineral. Raman spectroscopy, SEM EDS and EMPA indicate that the crystalline aggregates in FMI are dominated by mica minerals of the boron-rich muscovite–nanpingite CsAl₂[AlSi₃O₁₀](OH,F)₂ series as well as lepidolite. Topaz, quartz, potassium feldspar and several unidentified minerals occur in much lower amounts. Fluid isolations in FMI and FI have similar total salinity (4–8 wt.% NaCl eq.) and H₃BO₃ contents (12–16 wt.%). The melt inclusions in host-pegmatite quartz homogenize at 570–600 °C. The silicate crystalline aggregates in large inclusions in pocket quartz completely melt at 615 °C. However, even after those inclusions were significantly overheated at 650±10 °C and 2.5 kbar during 24 h they remained non-homogeneous and displayed two types: (i) glass+unmelted crystals and (ii) fluid+glass. The FMI glasses contain 1.94–2.73 wt.% F, 2.51 wt.% B₂O₃, 3.64–5.20 wt.% Cs₂O, 0.54 wt.% Li₂O, 0.57 wt.% Ta₂O₅, 0.10 wt.% Nb₂O₅, 0.12 wt.% BeO. The H₂O content of the glass could exceed 12 wt.%. Such compositions suggest that the residual melts of the latest magmatic stage were strongly enriched in H₂O, B, F, Cs and contained elevated concentrations of Li, Be, Ta, and Nb. FMI microthermometry showed that those melts could have crystallized at 615–550 °C.

Crystallization of quartz–feldspar pegmatite matrix leads to the formation of H₂O-, B- and F-enriched residual melts and associated fluids (prototypes of pockets). Fluids of different compositions and residual melts of different liquidus–solidus P–T-conditions would form pockets with various internal fluid pressures. During crystallization, those melts release more aqueous fluids resulting in a further increase of the fluid pressure in pockets. A significant overpressure and a possible pressure gradient between the neighboring pockets would induce fracturing of pockets and “fluid explosions”. The fracturing commonly results in the crushing of pocket walls, formation of new fractures connecting adjacent pockets, heterogenization and mixing of pocket fluids. Such newly formed fluids would interact with a primary pegmatite matrix along the fractures and cause autometasomatic alteration, recrystallization, leaching and formation of “primary–secondary” pockets.     

Partitioning of boron among melt, brine and vapor in the system haplogranite–H2O–NaCl at 800 °C and 100 MPa

Fluid-saturated experiments were conducted to investigate the partitioning of boron among haplogranitic melt, aqueous vapor and brine at 800 °C and 100 MPa. Experiments were carried out in cold-seal pressure vessels for 1 to 21 days, and utilized powdered synthetic subaluminous haplogranite glass doped with 1000 ppm B (crystalline H₃BO₃) and variable amounts of NaCl and H₂O at a fluid/haplogranite mass RATIO=1:1. Run-product glasses were analyzed for boron concentration by secondary ion mass spectrometry (SIMS) and for major elements and chlorine by electron microprobe. The composition of the coexisting fluid was calculated by mass balance. Boron partition coefficients between aqueous vapor and hydrous granitic melt range from 3.1 to 6.3, and demonstrate a clear preference of boron for the vapor over the hydrous melt. Partition coefficients between brine and hydrous granitic melt vary from 0.45 to 1.1, suggesting that boron has no preference for the brine or the melt. The bulk fluid–melt partition coefficients for low-salinity and high-salinity experiments are D_B^(vapor/melt)=4.6±1.3 and D_B^(brine/melt)=0.91±0.49, respectively. The corresponding vapor–brine partition coefficient is 5.0±3.1, demonstrating that boron partitions preferentially into the vapor over the brine at the conditions of this study. The preferential incorporation of boron in the aqueous vapor is controlled by borate speciation and solution mechanism. The dominant borate species in aqueous fluids, H₃BO₃^o, is highly soluble in aqueous vapor (X_B2O3=0.187); however, B₂O₃ is immiscible in NaCl liquid. Consequently, concentrations of boron in aqueous vapor are significantly higher than in the coexisting brine. Furthermore, Na–B complexing in the melt at high chlorine fluid contents stabilizes boron in the melt thereby contributing to the non-preferential partitioning of boron between brine and melt. The commonly observed association of tourmalinization (boron metasomatism), brecciation and ore deposition in nature is consistent with the preferential partitioning of boron into aqueous vapor of magmatic-hydrothermal systems predicted by this study.     

Evolution of metamorphic fluids in shear zones: The record from the emeralds of Habachtal, Tauern Window, Austria

Fluid inclusions in emeralds from the Habachtal, Central Tauern Window, have been studied by microthermometry. Results allow a detailed reconstruction of trapping history and evolution of the metamorphic fluids during the Middle Alpine Tauernkristallisation metamorphic event and some of the subsequent cooling period. Five different types of fluid inclusions, corresponding to at least five trapping periods, have been distinguished. In general, the earliest primary (type 1) inclusions, which occur as negative crystals or thin long tubes, are represented by low salinity ( < 10 wt. % NaCl equivalent) aqueous fluids with or without CO₂ with up to X_CO2 ≈ 0.04. Later primary type 2 inclusions are distinguished by different morphologies and distribution patterns. Lower salinity CO₂-free brines and CO₂-bearing denser inclusions with higher CO₂ contents (up to X_CO2 ≈ 0.11) are characteristic of this stage. The type 2 inclusions may also occur as pseudosecondary arrays. The effects of necking have been studied, and found to be considerable in the type 1 primary inclusions. This mechanism has occasionally resulted in the appearance of almost pure CO₂ fluids. The possibility of fluid immiscibility has been examined, and rejected, for the apparent “coexistence” of primary brine and CO₂-bearing inclusions. Instead, mixing of fluids which fluctuated between two different compositions is proposed. The fluctuation was probably due to the sequence of hydration reactions during the Tauernkristallisation. Maximum trapping pressures (3.6 kbar) obtained for stage 1 of the Tauernkristallisation are thought to represent a situation where sublithostatic fluid pressures exested in shear zones during the crystallisation period of many of the emerald cores and coexisting biotite and actinolite. Maximum fluid pressures of 7 kbar were obtained from the type 2 inclusions. This is similar to pressure estimates obtained from mineral equilibria. At least four phases of deformation are indicated by the trapping history. A pressure-temperature-time path for the Tauernkristallisation and the subsequent cooling/uplift period has been constructed for the Habachtal area, using the maximum pressure estimates obtained in this work together with previously existing data. In the cooling period, fluid pressures lower than the lithostatic load again prevailed. This difference, about 1–2 kbar, was probably due to late stage fracturing and/or the development of an open system. At least two more phases of minor deformation and three more stages of entrapment have been defined for this period. During this time, fluids gradually evolved towards more CO₂-poor, and less saline compositions. The present work shows that the possibility of fluctuations in fluid pressures must be considered seriously when attempting to define the PT cooling path from fluid inclusions in metamorphic rocks, especially those in shear zones. Postulations of retrograde PT paths based on fluid inclusions alone may result in pressure estimates which are too low.     

The preservation of high-pressure rocks during exhumation: metagranites and metapelites

Metagranites in the NKFMASH system require external hydration during prograde high-pressure metamorphism in order to equilibrate to ambient HP conditions by producing more siliceous muscovite. Any lack of external fluid or the disappearance of biotite stops re-equilibration and thus prevents recording of high-pressure conditions. The same hydration reactions cause dehydration during exhumation. Orthogneiss from shear zones or adjacent to metapelites and metabasites will take up external fluid during subduction and record the highest P–T conditions, but will also be the first to dehydrate upon exhumation, now hydrating other lithologies and probably refuelling shearzones.

The (de)hydration behavior of Ca-bearing metagranitoids is similar to that in the Ca-free system. However, the anorthite component of plagioclase decomposes with increasing pressure to form either (clino)zoisite or a grossular-rich garnet. Both reactions are fluid-consuming. If H₂O is supplied from an external source, the garnet-bearing assemblage can record P–T conditions up to very high pressures, but dehydrates again during heating and/or decompression to form a more Fe-rich garnet and Al-rich mica(s). The garnet compositions observed in natural HP-metagranites are mostly too Fe-rich to be formed in the presence of an H₂O-rich fluid.

N(C)KFMASH metapelites generally have a more complex mineralogy and succession of mineral assemblages along a P–T path. The H₂O contained in hydrous silicates like chlorite and chloritoid is only partly released, but partly transferred to other minerals like paragonite, glaucophane or phengite during subduction and further dehydration during exhumation is common. The mineral assemblage preserved by the rock may then record P–T conditions way below those of the actual pressure and temperature peak of the path. Contouring of the P–T pseudosection of a specific metapelite composition with mode isopleths for H₂O shows which P–T conditions along a given path are the ones most likely recorded by the rock.     

The influence of Cr on the garnet–spinel transition in the Earth''s mantle: experiments in the system MgO–Cr2O3–SiO2 and thermodynamic modelling

The position of the transition from spinel peridotite to garnet peridotite in a simplified chemical composition has been determined experimentally at high pressures and high temperatures. The univariant reaction MgCr₂O₄+2Mg₂Si₂O₆=Mg₃Cr₂Si₃O₁₂+Mg₂SiO₄, has a negative slope in P–T space between 1200 °C and 1600 °C. The experimental results, combined with assessed thermodynamic data for MgCr₂O₄, MgSiO₃ and Mg₂SiO₄ give the entropy and enthalpy of formation of knorringite garnet (Mg₃Cr₂Si₃O₁₂). Thermodynamic calculations in simplified chemical compositions indicate that Cr shifts the garnet-in reaction to much higher pressures than previously anticipated. Moreover, in Cr-bearing systems a pressure–temperature field exists where garnet and spinel coexist. The width of this divariant field strongly depends on the Cr/(Cr+Al) of the system.     

Fluids in metamorphic rocks

Basic principles for the study of fluid inclusions in metamorphic rocks are reviewed and illustrated. A major problem relates to the number of inclusions, possibly formed on a wide range of P–T conditions, having also suffered, in most cases, extensive changes after initial trapping. The interpretation of fluid inclusion data can only be done by comparison with independent P–T estimates derived from coexisting minerals, but this requires a precise knowledge of the chronology of inclusion formation in respect to their mineral host.

The three essential steps in any fluid inclusion investigation are described: observation, measurements, and interpretation. Observation, with a conventional petrographic microscope, leads to the identification and relative chronology of a limited number of fluid types (same overall composition, eventually changes in fluid density). For the chronology, the notion of GIS (Group of synchronous inclusions) is introduced. It should serve as a systematic basis for the rest of the study. Microthermometry measurements, completed by nondestructive analyses (mostly micro-Raman), specify the composition and density of the different fluid types. The major problem of density variability can be significantly reduced by simple considerations of the shape of density histograms, allowing elimination of a great number of inclusions having suffered late perturbations. Finally, the interpretation is based on the comparison between few isochores, representative of the whole inclusion population, and P–T mineral data. Essential is a clear perception of the relative chronology between the different isochores. When this is possible, as illustrated by the complicated case of the granulites from Central Kola Peninsula, a good interpretation of the fluid inclusion data can be done. If not, fluid inclusions will not tell much about the metamorphic evolution of the rocks in which they occur.     

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.     

A high precision U–Pb age of metamorphic rutile in coesite-bearing eclogite from the Dabie Mountains in central China: a new constraint on the cooling history

This paper first reports a high precision U–Pb age of 218±1.2 Ma for rutile in coesite-bearing eclogite from Jinheqiao in the Dabie Mounteins, east–central China. This work shows that the U–Pb mineral (rutile+omphacite) isochron age of 218±2.5 Ma and conventional rutile U–Pb concordia age of 218±1.2 Ma obtained by common Pb correction based on the Pb isotopic composition of omphacite in the same eclogite sample are consistent, proving that the omphacite with low U/Pb ratio (μ=2.8) can be used for common Pb correction in U–Pb dating of rutile. Oxygen isotope analysis of rutile aliquots gave the consistent δ¹⁸O values of −6.1±0.1%, demonstrating oxygen isotope homogenization in the rutile of different grains as inclusion in garnet and grain in matrix. Oxygen isotope thermometry yields temperatures of 695±35 and 460±15 °C for quartz–garnet and quartz–rutile pairs, respectively. These oxygen isotopic observations suggest that the diffusion of oxygen in rutile as inclusion in garnet is not controlled by garnet. According to field-based thermochronological studies of rutile, an estimate of the T_c of about 460 °C for U–Pb system in rutile under rapid cooling conditions (20 °C/Ma) was advised. Based on this U–Pb age as well as the reported chronological data with their corresponding metamorphic and/or closure temperature, an improved T–t path has been constructed. The T–t path confirms that the UHPM rocks in South Dabie experienced a rapid cooling following the peak metamorphism before 220 Ma and a long isothermal stage from 213 to 180 Ma around 425 °C.     

Abiogenic Fischer–Tropsch synthesis of hydrocarbons in alkaline igneous rocks; fluid inclusion, textural and isotopic evidence from the Lovozero complex, N.W. Russia

A detailed fluid inclusion study has been carried out on the hydrocarbon-bearing fluids found in the peralkaline complex, Lovozero. Petrographic, microthermometric, laser Raman and bulk gas data are presented and discussed in context with previously published data from Lovozero and similar hydrocarbon-bearing alkaline complexes in order to further understand the processes which have generated these hydrocarbons. CH₄-dominated inclusions have been identified in all Lovozero samples. They occur predominantly as secondary inclusions trapped along cleavage planes and healed fractures together with rare H₂O-dominant inclusions. They are consistently observed in close association with either arfvedsonite crystals, partially replaced by aegirine, aegirine crystals or areas of zeolitization. The majority of inclusions consist of a low-density fluid with CH₄ homogenisation temperatures between −25 and −120 °C. Those in near-surface hand specimens contain CH₄+H₂ (up to 40 mol%)±higher hydrocarbons. However, inclusions in borehole samples contain CH₄+higher hydrocarbons±H₂ indicating that, at depth, higher hydrocarbons are more likely to form. Estimated entrapment temperatures and pressures for these inclusions are 350 °C and 0.2–0.7 kbar. A population of high-density, liquid, CH₄-dominant inclusions have also been recorded, mainly in the borehole samples, homogenising between −78 and −99 °C. These consist of pure CH₄, trapped between 1.2 and 2.1 kbar and may represent an early CH₄-bearing fluid overprinted by the low-density population. The microthermometric and laser Raman data are in agreement with bulk gas data, which have recorded significant concentrations of H₂ and higher hydrocarbons up to C₆H₁₂ in these samples. These data, combined with published isotopic data for the gases CH₄, C₂H₆, H₂, He and Ar indicate that these hydrocarbons have an abiogenic, crustal origin and were generated during postmagmatic, low temperature, alteration reactions of the mineral assemblage. This would suggest that these data favour a model for formation of hydrocarbons through Fischer–Tropsch type reactions involving an early CO₂-rich fluid and H₂ derived from alteration reactions. This is in contrast to the late-magmatic model suggested for the formation of hydrocarbons in the similar peralkaline intrusion, Ilímaussaq, at temperatures between 400 and 500 °C.     

High-density early CO2 fluids in the ultrahigh-temperature granulites of Ihouhaouene (In Ouzzal, Algeria)

Fluid inclusion studies in rocks from the Lower Proterozoic granulites from western Hoggar (Algeria) provide new evidence for the hypothesis that a CO₂-rich, H₂O-poor fluid was present during the high-grade metamorphism. CO₂ inclusions represent the main fluid trapped in the Ihouhaouene ultrahigh-temperature (over 1000 °C) and high-pressure (10 to 14 kbar) granulites. The microthermometric and Raman microspectrometric measurements indicate that the carbonic fluid is mainly composed of CO₂ with minor amounts of CH₄ and N₂ detected in some inclusions (< 4 mol% CH₄). Carbonic fluid densities range from 1.18 to 0.57 g/cm³. The highest densities are recorded in superdense carbonic inclusions presenting evidence of the earliest trapping and they correspond to the fluid densities expected for the P–T conditions of the peak of metamorphism in the area previously determined from mineral geothermobarometers. Lower densities of carbonic fluids mainly result from the reequilibration of earlier trapped fluid inclusions during retrograde metamorphism and final uplift of the metamorphic terrane, but a new influx of carbonic fluids during the retrograde event remains possible. Carbonic fluids can be produced in situ from decarbonation reactions in interlayered impure marbles during the prograde event or derived from CO₂ flushing from underlying basic intrusions. The aqueous fluids present large variations of composition (0.5 to 30 wt.% NaCl equivalent) and densities (1.16 to 0.57 g/cm³). They clearly correspond to post-metamorphic fluids because they mainly occur along microfractures, they do not show any evidence of immiscibility with the carbonic fluids and mixed aquo-carbonic inclusions have not been observed. The percolation of aqueous fluids is related to the Pan-African tectonometamorphic event.     

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.