Solubility of cassiterite in evolved granitic melts: effect of T, fO2, and additional volatiles

The aim of this experimental study was to determine the solubility of cassiterite in natural topaz- and cassiterite-bearing granite melts at temperatures close to the solidus. Profiles of Sn concentrations at glass–crystal (SnO₂) interface were determined following the method of (Harrison, T.M., Watson, E.B., 1983. Kinetics of zircon dissolution and zirconium diffusion in granitic melts of variable water content. Contributions to Mineralogy and Petrology 84, 66–72). The cassiterite concentration calculated at the SnO₂–glass interface is the SnO₂ solubility. Experiments were performed at 700–850 °C and 2 kbar using a natural F-bearing peraluminous granitic melt with 2.8 wt.% normative corundum. Slightly H₂O-undersaturated to H₂O-saturated melt compositions were chosen in order to minimize the loss of Sn to the noble element capsule walls. At the nickel–nickel oxide assemblage (Ni–NiO) oxygen fugacity buffer, the solubility of cassiterite in melts containing 1.12 wt.% F increases from 0.32 to 1.20 wt.% SnO₂ with an increasing temperature from 700 to 850 °C. At the Ni–NiO buffer and a given corundum content, SnO₂ solubility increases by 10% to 20% relative to an increase of F from 0 to 1.12 wt.%. SnO₂ solubility increases by 20% relative to increasing Cl content from 0 to 0.37 wt.% in synthetic granitic melts at 850 °C. We show that Cl is at least as important as F in controlling SnO₂ solubility in evolved peraluminous melts at oxygen fugacities close to the Ni–NiO buffer. In addition to the strong effects of temperature and fO₂ on SnO₂ solubility, an additional controlling parameter is the amount of excess Al (corundum content). At Ni–NiO and 850 °C, SnO₂ solubility increases from 0.47 to 1.10 wt.% SnO₂ as the normative corundum content increases from 0.1 to 2.8 wt.%. At oxidizing conditions (Ni–NiO +2 to +3), Sn is mainly incorporated as Sn⁴⁺ and the effect of excess Al seems to be significantly weaker than at reducing conditions.     

Application of the QUILF thermobarometer to the peralkaline trachytes and pantellerites of the Eburru volcanic complex, East African Rift, Kenya

The Quaternary Eburru volcanic complex in the south-central Kenya Rift consists of pantelleritic trachytes and pantellerites. The phenocryst assemblage in the trachytes is sanidine + fayalite + ferrohedenbergite + aenigmatite ± quartz ± ilmenite ± magnetite ± pyrrhotite ± pyrite. In the pantellerites, the assemblage is sanidine + quartz + ferrohedenbergite + fayalite + aenigmatite + ferrorichterite + pyrrhotite ± apatite, although fayalite, ferrohedenbergite and ilmenite are absent from more evolved rocks (e.g. with SiO₂ > 71%). QUILF temperature calculations for the trachytes range from 709 to 793 °C and for the pantellerites 668–708 °C, the latter temperatures being among the lowest recorded for peralkaline silicic magmas. The QUILF thermobarometer demonstrates that the Eburru magmas crystallized at relatively low oxidation states (ΔFMQ + 0.5 to − 1.6) for both trachytes and pantellerites. The trachytes and pantellerites evolved along separate liquid lines of descent, the trachytes possibly deriving from a more mafic parent by fractional crystallization and the pantellerites from extreme fractionation of comenditic magmas.     

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.     

New P–T constraints on the Tamayen glaucophane‐bearing rocks,eastern Taiwan: Perple_X modelling results and geodynamic implications

New pseudosection modelling was applied to better constrain the P–T conditions and evolution of glaucophane‐bearing rocks in the Tamayen block of the Yuli belt, recognized as the world's youngest known blueschist complex. Based on the predominant clinoamphibole, textural relationships, and mineral compositions, these glaucophane‐bearing high‐P rocks can be divided into four types. We focused on the three containing garnet. The chief phase assemblages are (in decreasing mode): amphibole + quartz + epidote + garnet + chlorite + rutile/titanite (Type‐I), phengite + amphibole + quartz + garnet + chlorite + epidote + titanite + biotite + magnetite (Type‐II), and amphibole + quartz + albite + epidote + garnet + rutile + hematite + titanite (Type‐III). Amphibole exhibits compositional zoning from core to rim as follows: glaucophane → pargasitic amphibole → actinolite (Type‐I), barroisite → Mg‐katophorite/taramite → Fe‐glaucophane (Type‐II), glaucophane → winchite (Type‐III). Using petrographic data, mineral compositions and Perple_X modelling (pseudosections and superimposed isopleths), peak P–T conditions were determined as 13 ± 1 kbar and 550 ± 40 °C for Type‐I, 10.5 ± 0.5 kbar and 560 ± 30 °C for Type‐II (thermal peak) and 11 ± 1 kbar and 530 ± 30 °C for Type‐III. The calculations yield higher pressures and temperatures than previously thought; the difference is ~1–6 kbar and 50–200 °C. The three rock types record similar P–T retrograde paths with clockwise trajectories; all rocks followed trajectories with substantial pressure decrease under near‐isothermal conditions (Type‐I and Type‐III), with the probable exception of Type‐II where decompression followed colder geotherms. The P–T paths suggest a tectonic environment in which the rocks were exhumed from maximum depths of ~45 km within a subduction channel along a relative cold geothermal gradient of ~11–14 °C km^?1.     

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.     

Corundum + quartz and Mg-staurolite bearing granulite from the Limpopo Belt, southern Africa: Implications for a P–T path

A new occurrence of the rare corundum + quartz assemblage and magnesian staurolite has been found in a gedrite–garnet rock from the Central Zone of the Neoarchean Limpopo Belt in Zimbabwe. Poikiloblastic garnet in the sample contains numerous inclusions of corundum + quartz ± sillimanite, magnesian staurolite + sapphirine ± orthopyroxene, and sapphirine + sillimanite assemblages, as well as monophase inclusions. Corundum, often containing subhedral to rounded quartz, occurs as subhedral to euhedral inclusions in the garnet. Quartz and corundum occur in direct grain contact with no evidence of a reaction texture. The textures and Fe–Mg ratios of staurolite inclusions and the host garnet suggest a prograde dehydration reaction of St → Grt + Crn + Qtz + H₂O to give the corundum + quartz assemblage. Peak conditions of 890–930 °C at 9–10 kbar are obtained from orthopyroxene + sapphirine and garnet + staurolite assemblages. A clockwise P–T path is inferred, with peak conditions being followed by retrograde conditions of 4–6 kbar and 500–570 °C. The presence of unusually magnesian staurolite (Mg / [Fe + Mg] = 0.47–0.53) and corundum + garnet assemblages provides evidence for early high-pressure metamorphism in the Central Zone, possibly close to eclogite facies. The prograde high-pressure event followed by high- to ultrahigh-temperature metamorphism and rapid uplifting of the Limpopo Belt could have occurred as a result of Neoarchean collisional orogeny involving the Zimbabwe and Kaapvaal Cratons.     

Fluid-induced high-temperature metasomatism at Rundv?gshetta in the Lützow-Holm Complex,East Antarctica: Implications for the role of brine during granulite formation

We report new petrological, phase equilibria modeling, and fluid inclusion data for pelitic and mafic granulites from Rundv?gshetta in the highest-grade region of the Neoproterozoic Lützow-Holm Complex(LHC),East Antarctica, and provide unequivocal evidence for fluid-rock interaction and high-temperature metasomatism in the presence of brine fluid. The studied locality is composed dominantly of well-foliated pelitic granulite(K-feldspar+quartz+sillimanite+garnet+ilmenite) with foliation-parallel bands and/or layers of mafic granulite(plagioclase+orthopyroxene+garnet+ilmenite+quartz+biotite). The boundary between the two lithologies is defined by thin(about 1 -20 cm in thick) garnet-rich layers with a common mineral assemblage of garnet+plagioclase+quartz+ilmenite+biotite ? orthopyroxene. Systematic increase of grossular and decrease of pyrope contents in garnet as well as decreasing Mg/(Fe+Mg) ratio of biotite from the pelitic granulite to garnet-rich rock and mafic granulite suggest that the garnet-rich layer was formed by metasomatic interaction between the two granulite lithologies. Phase equilibria modeling in the system NCKFMASHTO demonstrates that the metasomatism took place at 850 -860℃, which is slightly lower than the peak metamorphism of this region, and the modal abundance of garnet is the highest along the metapeliteemetabasite boundary(up to 40%), which is consistent with the field and thin section observations. The occurrence of brine(7.0 -10.9 wt.% Na Cleqfor ice melting or 25.1 -25.5 wt.% NaC leqfor hydrohalite melting) fluid inclusions as a primary phase trapped within plagioclase in the garnet-rich layer and the occurrence of Cl-rich biotite(Cl = 0.22 -0.60 wt.%) in the metasomatic rock compared to that in pelitic(0.15 -0.24 wt.%) and mafic(0.06-0.13 wt.%) granulites suggest infiltration of brine fluid could have given rise to the high-temperature metasomatism. The fluid might have been derived from external sources possibly related to the formation of major suture zones formed during the Gondwana amalgamation.     

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.     

基于DFT方法的注热蒸汽开采CH4吸附机理

为探究不同煤阶煤吸附CH₄和H₂O吸附机理,采用量子化学方法中的密度泛函理论（DFT）,在B3LYP/6-31G基组上计算了不同煤阶煤的大分子稳定构型及煤分别吸附CH₄、H₂O及CH₄与H₂O共存条件下的吸附能和电荷转移情况。研究结果表明:煤吸附CH₄为物理吸附,随着煤阶升高,煤吸附CH₄能力增强;吸附H₂O时以氢键形式作用,其中煤中含氧官能团为氢键供体,H₂O中-OH为氢键受体,随着煤阶升高,吸附H₂O能力减弱;当H₂O与CH₄共存时,H₂O抢占CH₄吸附位,导致煤优先吸附H₂O,使吸附态CH₄减少,游离态CH₄增多。从分子水平完善了煤吸附甲烷和H₂O的吸附机理,为注热蒸汽开发煤层气奠定了吸附理论基础。      

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.     

Magnetite compositions and oxygen fugacities of the Khibina magmatic system

Most titanomagnetite in the Khibina alkaline igneous complex, sampled through 500 m of a vertical cross-section, is represented by Ti-rich varieties. The ulvöspinel component is most commonly around 55 mol%, rarely reaching up to 80 mol%.

We calculated an f_O2–T diagram for magnetite + ilmenite + titanite + clinopyroxene + nepheline + alkali feldspar and magnetite + titanite+ clinopyroxene + nepheline + alkali feldspar phase assemblages at a hedenbergite activity of 0.2. The diagram shows that magnetites with 55 mol% of ulvöspinel crystallized at oxygen fugacities just slightly below the quartz–fayalite–magnetite buffer. More Ti-rich varieties crystallized at higher temperatures and slightly lower ΔQMF values, whereas more Ti-poor magnetites crystallized at or below about 650 °C.

Under the redox conditions estimated for the apatite-bearing intrusion of the Khibina complex (close to the QFM buffer), substantial quantities of methane may only form during cooling below 400 °C in equilibrium with magma. However, even at higher orthomagmatic temperatures and redox conditions corresponding to ΔQMF = 0, the hydrogen content in the early magmatic stage is not negligible. This hydrogen present in the gas phase at magmatic temperatures may migrate to colder parts of a solidifying magma chamber and trigger Fischer-Tropsch-type reactions there. We propose therefore, that methane in peralkaline systems may form in three distinct stages: orthomagmatic and late-magmatic in equilibrium with a melt and — due to Fischer-Tropsch-type reactions — post-magmatic in equilibrium with a local mineral assemblage.     

Microstructures of olivine-plagioclase corona in meta-ultramafic rocks from Sefuri Mountains, NW Kyushu, Japan

Two types of reaction rims occur between olivine and plagioclase in ultramafic rocks from the Sefuri Mountains, NW Kyushu, Japan, which were metamorphosed under granulite-facies conditions. One occurs as a thin film of orthopyroxene along the boundary between olivine and plagioclase (orthopyroxene zone). The other is composed of two zones: symplectite of calcic amphibole and spinel on the plagioclase-side (symplectite zone) and calcic amphibole with sporadic orthopyroxene on the olivine-side (tremolite zone). In the tremolite zone, calcic amphibole shows a systematic decrease in Al content and increase in Mg/(Fe +Mg) with decreasing distance from olivine. Local equilibria maintained during the diffusion-controlled corona-forming reaction enable us to apply equilibrium thermodynamics to calcic amphibole and adjacent orthopyroxene. An integrated formulation of the Gibbs method for an Fe–Mg exchange reaction constrains the equilibrium temperature recorded in the tremolite zone to be 600–710 °C. It is significantly lower than the temperature of the granulite-facies metamorphism (800–900 °C) estimated using conventional geothermobarometry. Except for H₂O, the association of calcic amphibole and spinel in the symplectite zone is chemically equivalent to the association of olivine, plagioclase and orthopyroxene that was stable before the corona formation. This suggests that the following orthopyroxene-consuming reaction describes the paragenetic change taking place between 800–900 °C and 600–710 °C, olivine + plagioclase + orthopyroxene + aqueous fluid = calcic amphibole + spinel. In contrast, the overall reaction inferred from microstructures produces orthopyroxene as well as calcic amphibole and spinel at the expense of olivine and plagioclase. This reaction requires removal mainly of MgO that is also responsible for destabilizing the local association of olivine and plagioclase. These features suggest that the presence of orthopyroxene as a product in the corona is not always indicative of an orthopyroxene-producing reaction being responsible for the change of paragenetic relation. Microstructural features should be carefully applied to infer the reaction describing paragenetic change by which we argue the P–T path of the rocks.     

Experimental abiotic synthesis of methanol in seafloor hydrothermal systems during diking events

The abiotic synthesis of organic compounds in seafloor hydrothermal systems is one mechanism through which the subsurface environment could be supplied with reduced carbon. A flow-through, fixed-bed laboratory reactor vessel, the Catalytic Reactor Vessel (CRV) system, has been developed to investigate mineral–surface promoted organic synthesis at temperatures up to 400°C and pressures up to 30 MPa, conditions relevant to seafloor hydrothermal systems. Here we present evidence that metastable methanol can be directly synthesized from a gas-rich CO₂–H₂–H₂O mixture in the presence of a mineral substrate. Experiments have been performed without a substrate, with quartz, and with a mixture of quartz and magnetite. Temperatures and pressures in the experiments ranged from 200°C to 350°C and from 15 to 18 MPa, respectively. Maximum conversion of 5.8×10⁻⁴% CO₂ to CH₃OH per hour was measured using a mixture of magnetite and quartz in the reactor. After passivation of the stainless steel reactor vessel, experiments demonstrate that methanol is formed at temperatures up to 350°C in the presence of magnetite, and that the formation rate decreases over time. The experiments also show a loss of surface reactivity at 310°C and a regeneration of surface reactivity with increased temperature up to 350°C. Concentrations of CO₂ and H₂ used in the experiments simulate periodic, localized and dynamic conditions occurring within the seafloor during and immediately following magmatic diking events. High concentrations of CO₂ and H₂ may be generated by dike injection accompanied by exsolution of CO₂ and reaction of dissolved H₂O with FeO in the magma to form H₂. The experiments described here examine how the ephemeral formation of an H₂–CO₂-rich vapor phase within seafloor hydrothermal systems may supply reactants for abiotic organic synthesis reactions. These experiments show that the presence of specific minerals can promote the abiotic synthesis of simple organic molecules from common inorganic reactants such H₂O, CO₂ and H₂ under geologically realistic conditions.     

Phase equilibrium modelling of the amphibolite facies metamorphism in the Yelapa-Chimo Metamorphic Complex,Mexico

The Yelapa-Chimo Metamorphic Complex forms part of the Jalisco Block in western Mexico and exposes a wide range of Early Cretaceous metamorphic rocks;such as paragneiss,orthogneiss,amphibolites,and migmatites.However,the pressure-temperature(P-T)conditions of metamorphism and partial melting remain poorly studied in the region.To elucidate metamorphic P-T conditions,phase equilibrium modelling was applied to two sillimanite-garnet paragneisses,one amphibole-orthogneiss,and one amphibolite.Sillimanite-garnet paragneisses exhibit a lepidoblastic texture with a biotite+sillimanite+kyanite+garnet+quartz+plagioclase+K-feldspar mineral assemblage.Amphibole-orthogneiss and amphibolite display a nematoblastic texture with an amphibole+(1)plagioclase+quartz+(1)titanite assemblage and an amphibole+(2)plagioclase+(2)titanite+ilmenite retrograde mineral assemblage.Pseudosections calculated for the two sillimanite-garnet paragneiss samples show P-T peak conditions at~6-7.5 kbar and~725-740℃.The results for amphibole-orthogneiss and the amphibolite yield P-T peak conditions at~8.5-10 kbar and~690-710℃.The mode models imply that metasedimentary and metaigneous units can produce up to~20 vol%and~10 vol%of melt,respectively.Modelling within a closed system during isobaric heating suggests that melt compositions of metasedimentary and metaigneous units are likely to have direct implications for the petrogenesis of the Puerto Vallarta Batholith.Our new data indicate that the Yelapa-Chimo Metamorphic Complex evolved through a metamorphic gradient between~23-33℃km^-1and the metamorphic rocks formed at depths between~22 km and~30 km with a burial rate of~2.0 km Ma^-1.Finally,the P-T data for both metasedimentary and metaigneous rocks provide new constraints on an accretionary framework,which is responsible for generating metamorphism and partial melting in the YelapaChimo Metamorphic Complex during the Early Cretaceous.     

Metamorphic evolution of calcsilicate granulites near Battye Glacier, northern Prince Charles Mountains, East Antarctica

Calcsilicate granulites of probable Middle Proterozoic age ( c .1000–1100  Ma) in the vicinity of Battye Glacier, northern Prince Charles Mountains, East Antarctica, contain prograde metamorphic assemblages comprising various combinations of wollastonite, scapolite, clinopyroxene, An-rich plagioclase, calcite, quartz, titanite and, rarely, orthoclase, ilmenite, phlogopite and graphite. Comparison of the prograde assemblages with calculated and experimentally determined phase relations in the simple CaO–Al₂O₃–SiO₂–CO₂–H₂O system suggests peak metamorphism at ≥835 °C in the presence (in wollastonite-bearing assemblages at least) of a CO₂-bearing fluid ( X _CO≥0.3) at a probable pressure of 6–7  kbar.
Well-preserved retrograde reaction textures represent: (1) breakdown of scapolite to anorthite+calcite±quartz; (2) formation of grossular–andradite garnet and, locally, (3) epidote, both principally by reactions involving scapolite breakdown products and clinopyroxene; (4) local coupled replacement of clinopyroxene and ilmenite by hornblende and titanite, respectively; and finally (5) local sericitization of prograde and retrograde plagioclase. These retrograde reactions are interpreted to be the result of cooling and variable infiltration by H₂O-rich fluids, possibly derived from crystallizing pegmatitic intrusions and segregations that may be partial melts, which are common throughout the area.     

Mantle petrology and mineralogy of the Thetford Mines Ophiolite Complex

The Ordovician Thetford Mines ophiolite complex (TMOC) formed by boninite-fed seafloor-spreading, probably in a fore-arc environment. The mantle section is dominated by foliated harzburgite (≤ 5–6% clinopyroxene), cut by dunitic (± chromitite cores) and orthopyroxenitic veins and dykes. Contrasting structures, textures and mineral compositions allow us to subdivide the mantle. The granular-textured rocks of the Duck Lake Block (DLB) have two steeply-dipping foliations. The older foliation strikes NW, is sub-perpendicular to the Moho, and is interpreted to have resulted from upflow of the asthenosphere beneath the spreading ridge. This fabric is overprinted by a 2nd ductile foliation striking ENE, oriented sub-parallel to the Moho, which we interpreted as having formed by crust–mantle shear as the lithosphere migrated away from the spreading ridge. The DLB mantle has a limited range of spinel Cr# (100Cr / (Cr + Al) = 51–71). Comparison with experimentally determined residual spinel compositions (equilibrium melting) implies a maximum loss of 27–38% melt if the protolith had a fertile MORB mantle composition. However, interstitial-textured clinopyroxene may have high TiO₂ (< 0.04wt.%) and Na₂O (< 0.27wt.%), and some interstitial spinel has higher TiO₂ (< 0.09wt.%), suggesting interaction with (or crystallization from) an “impregnating” melt. Interstitial tremolitic amphibole also indicates the passage of late hydrous fluids. The harzburgite in the Caribou Mountain Block (CMB) has a porphyroclastic texture, with a strong, locally mylonitic foliation striking roughly N–S, parallel to the orientation of seafloor-spreading related paleo-normal faults in the crust. These fabrics and textures imply a colder, lithospheric deformation, possibly related to tectonic denudation (oceanic core complex). This would explain problematic lava/mantle contacts, favour infiltration of seawater, serpentinization, and reduced fO₂ conditions. The CMB mantle shows a wider range of mineral compositions than the DLB, with spinel Cr# (28–86) implying ≤ 15–45% of equilibrium melting. Locally higher TiO₂ in spinel (< 0.05wt.%) and clinopyroxene (< 0.11wt.%), a local rimward decrease in spinel Cr#, clinopyroxene Cr#, and olivine Fo-content, and traces of interstitial amphibole, are attributed to the circulation of an evolved hydrous melt during peridotite deformation. This suggests that the lower limit to the extent of melting inferred for the CMB (15%), established on the basis of Al-rich spinel rims and neoblasts, is probably too low. On the other hand, the higher inferred degree of depletion of the CMB is probably unaffected by the metasomatic overprint and is a more robust conclusion.     

The Fedorivka layered intrusion (Korosten Pluton, Ukraine): An example of highly differentiated ferrobasaltic evolution

This study documents the petrography and whole-rock major and trace element geochemistry of 38 samples mainly from a drill core through the entire Fedorivka layered intrusion (Korosten Pluton), as well as mineral compositions (microprobe analyses and separated mineral fraction analyses of plagioclase, ilmenite, magnetite and apatite) of 10 samples. The Fedorivka layered intrusion can be divided into 4 lithostratigraphic units: a Lower Zone (LZ, 72 m thick), a Main Zone (MZ, 160 m thick), and an Upper Border Zone, itself subdivided into 2 sub-zones (UBZ₂, 40 m thick; UBZ₁, 50 m thick). Igneous lamination defines the cumulate texture, but primary cumulus minerals have been affected by trapped liquid crystallization and subsolidus recrystallization. The dominant cumulus assemblage in MZ and UBZ₂ is andesine (An_39–42), iron-rich olivine (Fo_32–42), augite (En_29–35Fs_24–29Wo_42–44), ilmenite (Hem_1–6), Ti-magnetite (Usp_52–78), and apatite. The data reveal a continuous evolution from the floor of the intrusion (LZ) to the top of MZ, due to fractional crystallization, and an inverse evolution in UBZ, resulting from crystallization downwards from the roof. The whole-rock Fe/Mg ratio and incompatible element contents (e.g. Rb, Nb, Zr, REE) increase in the fractionating magma, whereas compatible elements (e.g. V, Cr) steadily decrease. The intercumulus melt remained trapped in the UBZ cumulates due to rapid cooling and lack of compaction, and cumulus mineral compositions re-equilibrated (e.g. olivine, Fe–Ti oxides). In LZ, the intercumulus melt was able to partially or totally escape. The major element composition of the MZ cumulates can be approximated by a mixing (linear) relationship between a plagioclase pole and a mafic pole, the latter being made up of all mafic minerals in (nearly) constant relative proportions. By analogy with the ferrobasaltic/jotunitic liquid line of descent, defined in Rogaland, S. Norway, and its conjugated cumulates occurring in the Transition Zone of the Bjerkreim-Sokndal intrusion (Rogaland, a monzonitic (57% SiO₂) melt is inferred to be in equilibrium with the MZ cumulates. The conjugated cumulate composition falls (within error) on the locus of cotectic compositions fixed by the 2-pole linear relationship. Ulvöspinel is the only Ti phase in some magnetites that have been protected from oxidation. QUIlF equilibria in these samples show that magnetite and olivine in MZ have retained their liquidus compositions during subsolidus cooling. This permits calculation of liquidus fO₂ conditions, which vary during fractionation from ΔFMQ = 0.7 to − 1.4 log units. Low fO₂ values are also evidenced by the late appearance of cumulus magnetite (Fo₄₂) and the high V³⁺-content of the melt, reflected in the high V-content of the first liquidus magnetite (up to 1.85% V).     

Matrix rheology effects on reaction rim growth I: evidence from orthopyroxene rim growth experiments

The rim-forming reaction quartz + olivine = orthopyroxene is used to investigate the effect of matrix rheology on rim growth rates. Orthopyroxene rim growth around olivine grains in quartz matrix is compared to rim growth around quartz grains in an olivine matrix. At constant P–T , within one single capsule, orthopyroxene rims grow faster around quartz clasts in olivine matrix than around olivine clasts in quartz matrix. Fourier transform infra-red spectra indicate that the entire samples are water saturated because of water adsorption on the reactant grain surfaces. The increased orthopyroxene growth rates in olivine matrix as opposed to quartz matrix are interpreted in terms of matrix rheology, where in the two different matrix-inclusion arrangements the olivine matrix behaves 'softer' and the quartz matrix 'more rigid'. The strain energy associated with accommodation of the negative reaction volume is higher for the quartz than the olivine matrix and reduces the free energy that drives orthopyroxene rim growth. Growth textures in both kinds of orthopyroxene rims indicate that the diffusivity of MgO slightly exceeds the diffusivity of SiO₂. The relative mobility of MgO and SiO₂ at given P , T , f H₂O seems to be controlled by energy minimization during orthopyroxene growth at the compressive Ol/Opx interface. Our experiments provide evidence for two previously overlooked effects relevant to rim growth reactions in metamorphic rocks: (i) diffusivity along chemical potential gradients to reaction sites is a function of rheology and (ii) the relative diffusivity of components during reaction rim or corona growth is a function of local volume changes at the rim's interfaces.     

Oxidized, magnetite-series, rapakivi-type granites of Carajás, Brazil: Implications for classification and petrogenesis of A-type granites

The varying geochemical and petrogenetic nature of A-type granites is a controversial issue. The oxidized, magnetite-series A-type granites, defined by Anderson and Bender [Anderson, J.L., Bender, E.E., 1989. Nature and origin of Proterozoic A-type granitic magmatism in the southwestern United States of America. Lithos 23, 19–52.], are the most problematic as they do not strictly follow the original definition of A-type granites, and approach calc-alkaline and I-type granites in some aspects. The oxidized Jamon suite A-type granites of the Carajás province of the Amazonian craton are compared with the magnetite-series granites of Laurentia, and other representative A-type granites, including Finnish rapakivi and Lachlan Fold Belt A-type granites, as well as with calc-alkaline, I-type orogenic granites. The geochemistry and petrogenesis of different groups of A-types granites are discussed with an emphasis on oxidized A-type granites in order to define their geochemical signatures and to clarify the processes involved in their petrogenesis. Oxidized A-type granites are clearly distinguished from calc-alkaline Cordilleran granites not only regarding trace element composition, as previously demonstrated, but also in their major element geochemistry. Oxidized A-type granites have high whole-rock FeO_t/(FeO_t + MgO), TiO₂/MgO, and K₂O/Na₂O and low Al₂O₃ and CaO compared to calc-alkaline granites. The contrast of Al₂O₃ contents in these two granite groups is remarkable. The CaO/(FeO_t + MgO + TiO₂) vs. CaO + Al₂O₃ and CaO/(FeO_t + MgO + TiO₂) vs. Al₂O₃ diagrams are proposed to distinguish A-type and calc-alkaline granites. Whole-rock FeO_t/(FeO_t + MgO) and the FeO_t/(FeO_t + MgO) vs. Al₂O₃ and FeO_t/(FeO_t + MgO) vs. Al₂O₃/(K₂O/Na₂O) diagrams are suggested for discrimination of oxidized and reduced A-type granites. Experimental data indicate that, besides pressure, the nature of A-type granites is dependent of ƒO₂ conditions and the water content of magma sources. Oxidized A-type magmas are considered to be derived from melts with appreciable water contents (≥ 4 wt.%), originating from lower crustal quartz-feldspathic igneous sources under oxidizing conditions, and which had clinopyroxene as an important residual phase. Reduced A-type granites may be derived from quartz-feldspathic igneous sources with a metasedimentary component or, alternatively, from differentiated tholeiitic sources. The imprint of the different magma sources is largely responsible for the geochemical and petrological contrasts between distinct A-type granite groups. Assuming conditions near the NNO buffer as a minimum for oxidized granites, magnetite-bearing granites formed near FMQ buffer conditions are not stricto sensu oxidized granites and a correspondence between oxidized and reduced A-type granites and, respectively, magnetite-series and ilmenite-series granites is not always observed.     

Experimental study of the joins forsterite–diopside–leucite– and forsterite–leucite–åkermanite up to 2.3 GPa [P(H2O) = P(Total)] and variable temperatures: Its petrological significance

We conducted a series of melting experiments in the join forsterite–diopside–leucite under 0.1 and 2.3 GPa and in the join forsterite–leucite–åkermanite under 2.3 GPa to understand paragenetic relationships amongst different types of lamproitic and lamprophyric magmas with K-rich mafic and ultramafic volcanic (kamafugitic) rocks. Both the joins were studied in the presence of excess water. The experimental results of the join forsterite–diopside–leucite at 0.1 GPa show that the five-phase point of forsterite (Fo)_ss + diopside (Di)_ss + leucite (Lc)_ss + liquid (Liq) + vapour (V) (equivalent to ugandite lava) occurs at Fo₂Di₅₀Lc₄₈ at 880 ± 5 °C. Phlogopite appears as the last phase at 830 ± 15 °C. The final crystalline assemblage of forsterite_ss + diopside_ss + leucite_ss + phlogopite is similar to the phenocryst assemblage of missourite lava. Present study suggests that an olivine leucitite (ugandite) can be derived from an olivine italite, a slightly potassic peridotite and a leucitite magma.

A study of the join Fo–Di–Lc [P(H₂O) = P(Total)] at 2.3 GPa shows that liquid compositions penetrate the primary phase volumes of forsterite_ss, phlogopite_ss, kalsilitess, K-feldspar_ss and diopside_ss. It has the following three five-phase points: 1) one occurring at Fo₉Di₄₉Lc₄₂ and 1005 ± 5 °C, where liquid and vapour coexists with forsterite_ss, phlogopite_ss and diopside_ss (phlogopite-bearing madupite), 2) the second one at Fo₄Di₅₀Lc₄₆ and 990 ± 10 °C, where diopside_ss, K-feldspar_ss and phlogopite_ss coexist with liquid and vapour (pyroxene-bearing minette), and 3) the third one at Fo₃Di₂₁Lc₇₆ and 775 ± 5 °C, where phlogopite_ss, kalsilite_ss and K-feldspar_ss are in equilibrium with liquid plus vapour (kalsilite-bearing minette).

The experimental results of the join Fo–Lc–åkermanite (Ak) show that the join 40 penetrates the primary phase volumes of forsterite_ss, phlogopite_ss, kalsilite, K-feldspar_ss, diopside_ss and merwinite_ss. The data indicate the presence of four five-phase points: 1) one occurring at Fo₇Lc₄₂Ak₅₁ and 1165 ± 5 °C, where phlogopite_ss, forsterite_ss, diopside_ss coexists with liquid and vapour (olivine-bearing madupite), 2) the second one at Fo₃Lc₄₉Ak₄₈ and 1140 ± 10 °C, where a liquid is in equilibrium with phlogopite_ss, K-feldspar_ss, diopside_ss and vapour (pyroxene-bearing minette), 3) the third one at Fo₁₈Lc₂₁Ak₆₁ and 1255 ± 10 °C, where merwinite_ss, forsterite_ss and diopside_ss are in equilibrium with liquid and vapour (merwinite-bearing wherlite), and 4) the fourth one at Fo₅Lc_73.5Ak_21.5 and 770 ± 5 °C, where kalsilite_ss, phlogopite_ss and K-feldspar coexist with liquid and vapour (kalsilite-bearing minette). The present data suggest that high pressure heteromorphic equivalent of a katungite magma is represented by a kalsilite-bearing minette, a pyroxene-bearing minette, or an olivine-bearing madupite.