Intrinsic oxygen fugacities of diogenites and mesosiderite clasts

Oxygen fugacities of diogenite and mesosiderite clast material were measured with the double ZrO₂ cell technique between 800° and 1150°C. The samples were taken from large clasts in the diogenites Johnstown (En₇₃) and Tatahouine (En₇₅), and the mesosiderites Estherville (En₈₁), West Point (Fo₈₈) and Emery (En₆₈). Fugacity values for all except Emery plot near the wüstite-iron buffer curve and are interpreted as indicating similar source regions and environments of crystallization for the two suites. Emery orthopyroxene records a lower fugacity, close to the fayalite-quartz-iron buffer curve, probably as a result of equilibration with the mesosiderite matrix assemblage. The similarity of redox conditions experienced by mesosiderite orthopyroxenite and diogenites is not sufficient to require a single parent body and, if the common achondrites were derived from Vesta, mesosiderites probably came from a different body.     

Orthopyroxene-olivine assemblages in diogenites and mesosiderites

Diogenites contain equilibrated orthopyroxene-olivine assemblages. Mn is very regularly partitioned between olivine and orthopyroxene in pallasites, diogenites and synthetic eucrite melts, with an $\text{FeO}\text{MnO}$ partition ratio for olivine versus orthopyroxene of 1.6 by weight over a very wide range of FeO contents. In contrast to diogenites, Fe and Mn are not regularly partitioned between the olivine and orthopyroxene of mesosiderites and these minerals were not in equilibrium. Mesosiderite olivine differs from diogenite olivine in $\text{Fe}\text{Mn}$ and $\text{Ca}\text{Mn}$ ratios. Lack of olivine-orthopyroxene equilibrium suggests that olivine in mesosiderites was derived not from a pyroxenite component analogous to diogenites but from dunites.     

Petrology and shock metamorphism of the olivine-phyric shergottite Yamato 980459: Evidence for a two-stage cooling and a single-stage ejection history

The basaltic Martian meteorite Yamato 980459 consists of large olivine phenocrysts and often prismatic pyroxenes set into a fine-grained groundmass of smaller more Fe-rich olivine, chromite, and an interstitial residual material displaying quenching textures of dendritic olivine, chain-like augite and sulfide droplets in a glassy matrix. Yamato 980459 is, thus, the only Martian meteorite without plagioclase/maskelynite. Olivine is compositionally zoned from a Mg-rich core to a Fe-rich rim with the outer few micrometers being especially rich in iron. With Fo₈₄ the cores are the most magnesian olivines found in Martian meteorites so far. Pyroxenes are also mostly composite crystals of large orthopyroxene cores and thin Ca-rich overgrowths. Separate pigeonite and augites are rare. On basis of the mineral compositions, the cooling rates determined from crystal morphologies, and crystal grain size distributions it is deduced that the parent magma of Yamato 980459 initially cooled under near equilibrium conditions e.g., in a magma chamber allowing chromite and the Mg-rich silicates to form as cumulus phases. Fractional crystallization at higher cooling rates and a low degree of undercooling let to the formation of the Ca-, Al-, and Fe-rich overgrowths on olivine and orthopyroxene while the magma was ascending towards the Martian surface. Finally and before plagioclase and also phosphates could precipitate, the magma was very quickly erupted quenching the remaining melt to glass, dendritic silicates and sulfide droplets. The shape preferred orientation of olivine and pyroxene suggests a quick, thin outflow of lava. According to the shock effects found in the minerals of Yamato 980459, the meteorite experienced an equilibration shock pressure of about 20-25 GPa. Its near surface position allowed the ejection from the planet’s surface already by a single impact event and at relatively low shock pressures.     

Thermal and redox equilibrium conditions of the upper-mantle xenoliths from the Quaternary volcanoes of NW Spitsbergen,Svalbard Archipelago

Upper-mantle xenoliths in Cenozoic basalts of northwestern Spitsbergen are rocks of peridotite (spinel lherzolites) and pyroxenite (amphibole-containing garnet and garnet-free clinopyroxenites, garnet clinopyroxenites, and garnet and garnet-free websterites) series. The upper-mantle section in the depth range 50–100 km is composed of spinel peridotites; at depths of 80–100 km pyroxenites (probably, dikes or sills) appear. The equilibrium conditions of parageneses are as follows: in the peridotites—730–1180 °C, 13–27 kbar, and oxygen fugacity of − 1.5 to + 0.3 log. un.; in the pyroxenites—1100–1310 °C, 22–33 kbar. The pyroxenite minerals have been found to contain exsolved structures, such as orthopyroxene lamellae in clinopyroxene and, vice versa, clinopyroxene lamella in orthopyroxene. The formation temperatures of unexsolved phases in orthopyroxene and clinopyroxene are nearly 100–150 °C higher than the temperatures of the lamellae–matrix equilibrium and the equilibrium of minerals in the rock. The normal distribution of cations in the spinel structure and the equilibrium distribution of Fe^2 + between the M1 and M2 sublattices in the orthopyroxenes point to the high rate of xenolith ascent from the rock crystallization zone to the surface. All studied Spitsbergen rock-forming minerals from mantle xenoliths contain volatiles in their structure: OH⁻, crystal hydrate water H₂O_cryst, and molecules with characteristic CH and CO groups. The first two components are predominant, and the total content of water (OH– + H₂O_cryst) increases in the series olivine → garnet → orthopyroxene → clinopyroxene. The presence of these volatiles in the nominally anhydrous minerals (NAM) crystallized at high temperatures and pressures in the peridotites and pyroxenites testifies to the high strength of the volatile–mineral bond. The possibility of preservation of volatiles is confirmed by the results of comprehensive thermal and mass-spectral analyses of olivines and clinopyroxene, whose structures retain these components up to 1300 °C. The composition of hypothetic C–O–H fluid in equilibrium (in the presence of free carbon) with the underlying mantle rocks varies from aqueous (> 80% H₂O) to aqueous–carbonic (~ 60% H₂O). The fluid becomes essentially aqueous when the oxygen activity in the system decreases. However, there is no strict dependence of the redox conditions on the depth of formation of xenoliths.     

Olivines and olivine coronas in mesosiderites

Olivines and their surrounding coronas in mesosiderites have been studied texturally and compositionally by optical and microprobe methods. Most olivine is compositionally homogeneous but some is irregularly zoned. It ranges from Fo_58–92 and shows no consistent pattern of distribution within and between mesosiderites. Olivine occurs as large single crystals or as partially recrystallized mineral clasts, except for two lithic clasts. One is in Emery, the other in Vaca Muerta, and they are both shock-modified olivine orthopyroxenites. $\text{FeO}\text{MnO}$ ratios in olivine exhibit a variety of differing trends and range from 22–46, most commonly 35–40. These values are lower than those in olivine from diogenites sensu stricto (45–50) and have therefore experienced a different history. Some of the olivine clasts could have coexisted with some of the large orthopyroxene clasts as equilibrium assemblages, but some could not. Much of the olivine may be derived from mesosiderite olivine orthopyroxenites, which differ from diogenites sensu stricto. More magnesian olivine may be a residue from one or more source rocks, with varying degrees of melting. These events probably occurred in a highly evolved and differentiated parent body.Fine-grained coronas surround olivine, except for those in impact-melt group mesosiderites (Simondium, Hainholz, Pinnaroo) and those without tridymite in their matrices (Bondoc, Veramin). Coronas consist largely of orthopyroxene, plagioclase, clinopyroxene, chromite, merrillite and ilmenite and are similar to the matrix, but lack metal and tridymite. Coronas contain abundant orthopyroxene but are unusually rich in chromite (up to 7%) and merrillite (up to 20%). The outer parts of the corona grade into the matrix, but have little or no metal and tridymite. Texturally the innermost part of the corona can be divided into three stages of development: I Radiating acicular; II Intermediate; III Granular. Stage I is the result of the greatest disequilibrium between olivine and matrix orthopyroxene and Stage III has the least disequilibrium. Coronas are the result of the reaction olivine + tridymite = orthopyroxene, probably because FeO (and MgO) diffuse from olivine to tridymite in the matrix. Absence of metal and concentration of chromite in the corona are probably the result of an FeO potential gradient away from the olivine. Merrillite concentrations are a result of P₂O₅ migration into the corona but are controlled by the availability of calcic pyroxene, or possibly plagioclase. Although the coronas are texturally similar to terrestrial and lunar counterparts, they are unique and represent different kinds of reactions marked by a large degree of intra-corona diffusion under dry conditions. Opaque oxide-silicate-metal buffer assemblages yield apparent equilibration conditions of about 840°C and fO₂ near 10^?20. Poikiloblastic pyroxene textures in some coronas suggest a closing of reaction systems between 900 and 1000°C and such systems may record a higher temperature stage of development.     

Pressure-Temperature Path Recorded in the Yangkou Garnet Peridotite, in Su-Lu Ultrahigh-pressure Metamorphic Belt, Eastern China

Chemical variations along with changes in microstructure ofthe principal constituent minerals make it possible to identifyat least four equilibrium stages in the evolution of the Yangkougarnet peridotite in the Su-Lu ultrahigh-pressure metamorphicbelt, eastern China: Stage I—a primary garnet lherzolitestage represented by coarse-grained (a few millimeters size)porphyroclastic aluminous pyroxenes + chromian spinel ±garnet; Stage II—an ultrahigh-pressure (UHP) stage definedby fine-grained matrix phases (0·1–0·3 mmsize) of garnet + extremely low-Al orthopyroxene + high-Na clinopyroxene+ chromite; Stage III—a medium-pressure stage definedby fine-grained mineral aggregates (<0·1–0·2mm size) mainly composed of aluminous spinel + high-Al orthopyroxenein the matrix; Stage IV—an amphibolite- to greenschist-faciesstage defined by poikiloblastic amphibole. Orthopyroxene–clinopyroxenethermometry and an empirical spinel barometer give temperaturesof around 800–830°C and pressures of 1·2–2·9GPa for porphyroclasts of Stage I. Garnet–orthopyroxene,garnet–clinopyroxene and empirical spinel geothermobarometersgive relatively uniform P–T conditions for the matrixgarnet–orthopyroxene–clinopyroxene–chromiteassemblage of Stage II (     

An example of ultrahigh-temperature metamorphism: orthopyroxene–sillimanite–garnet, sapphirine–quartz and spinel–quartz parageneses in Al–Mg granulites from In Hihaou, In Ouzzal, Hoggar

Quartz Al–Mg granulites exposed at In Hihaou, In Ouzzal (NW Hoggar), preserve an unusual high-grade mineral association stable at temperatures up to 1050°C, involving the parageneses orthopyroxene–sillimanite–garnet–quartz, sapphirine–quartz and spinel–quartz. The phase relationships within the FMAS system show that a continuum exists between the earlier prograde reaction textures and those of the later decompressive event. The following mineral reactions involving sillimanite are deduced: (1) Grt+Qtz→Opx+Sil, (2) Opx+Sil→Grt+Spr+Qtz, (3) Grt+Sil+Qtz→Crd, (4) Grt+Sil→Crd+Spr, (5) Grt+Sil+Spr→Crd+Spl, (6) Grt+Sil→Crd+Spl, (7) Grt+Crd+Sil→Spl+Qtz and (8) Grt+Sil→Spl+Qtz. Minerals in quartz Al–Mg granulites display compositional variations consistent with the observed reactions. The Mg/(Mg+Fe²⁺) range of the main minerals is as follows: cordierite (0.81–0.97), sapphirine (0.77–0.88), orthopyroxene (0.65–0.81), garnet (0.33–0.64) and spinel (0.23–0.56). The reaction textures and the evolution of the mineral assemblages in the quartz Al–Mg granulites indicate a clockwise P–T trajectory characterized by peak conditions of at least 10 kbar and 1050°C, followed by decompression from 10 to 6 kbar at a temperature of at least 900°C.     

Acapulcoite-lodranite meteorites: Ultramafic asteroidal partial melt residues

Acapulcoites (most ancient Hf-W ages are 4,563.1?±?0.8 Ma), lodranites (most ancient Hf-W ages are 4,562.6?±?0.9 Ma) and rocks transitional between them are ancient residues of different degrees of partial melting of a chondritic source lithology (e.g., as indicated by the occurrence of relict chondrules in 9 acapulcoites), although the precise chondrite type is unknown. Acapulcoites are relatively fine- grained (～150–230?μm) rocks with equigranular, achondritic textures and consist of olivine, orthopyroxene, Ca-rich clinopyroxene, plagioclase, metallic Fe,Ni, troilite, chromite and phosphates. Lodranites are coarser grained (540–700?μm), with similar equigranular, recrystallized textures, mineral compositions and contents, although some are significantly depleted in eutectic Fe,Ni-FeS and plagioclase- clinopyroxene partial melts. The acapulcoite-lodranite clan is most readily distinguished from other groups of primitive achondrites (e.g., winoanites/IAB irons) by oxygen isotopic compositions, although more than 50% of meteorites classified as acapulcoites currently lack supporting oxygen isotopic data. The heat source for melting of acapulcoites-lodranites was internal to the parent body, most likely ²⁶Al, although some authors suggest it was shock melting. Acapulcoites experienced lower temperatures of ～980–1170?°C and lower degrees of partial melting (～1–4?vol.%) and lodranites higher temperatures of ～1150–1200?°C and higher degrees (～5?≥?10?vol.%) of partial melting. Hand-specimen and thin section observations indicate movement of Fe,Ni-FeS, basaltic, and phosphate melts in veins over micrometer to centimeter distances. Mineralogical, chemical and isotopic properties, Cosmic Ray Exposure (CRE) ages which cluster around 4–6 Ma and the occurrence of some meteorites consisting of both acapulcoite and lodranite material, indicate that these meteorites come from one parent body and were most likely ejected in one impact event. Whereas the precise parent asteroid of these meteorites is unknown, there is general agreement that it was an S-type object. There is nearly total agreement that the acapulcoite-lodranite parent body was <～100?km in radius and, based on the precise Pb–Pb age for Acapulco of 4555.9?±?0.6 Ma, combined with the Hf/W and U/Pb records and cooling rates deduced from mineralogical and other investigations, that the parent body was fragmented during its cooling which the U/Pb system dates at precisely 4556?±?1 Ma. Hf-W chronometry suggests that the parent body of the acapulcoites-lodranites and, in fact, the parent bodies of all “primitive achondrites” accreted slightly later than those of the differentiated achondrites and, thus, had lower contents of ²⁶Al, the heat producing radionuclide largely responsible for heating of both primitive and differentiated achondrites. Thus, the acapulcoite-lodranite parent body never experienced the high degrees of melting responsible for the formation of the differentiated meteorites, but arrested its melting history at relatively low degrees of ～15?vol.%.     

Crystallization sequences of Ca-Al-rich inclusions from Allende: An experimental study

The equilibrium crystallization sequence at 1 atmosphere in air of a melt corresponding in composition to the average composition of Type B Ca-Al-rich inclusions from the Allende meteorite is: spinel (1550°C) → melilite (1400°C; Åk22) → anorthite (1260°C) → Ti-Al-rich clinopyroxene (1230°C; “Ti-fassaite”). The melilite becomes increasingly åkermanitic with decreasing temperature. The pyroxene is similar in composition to fassaites from Type B inclusions. Preliminary results suggest that the crystallization sequence is similar at oxygen fugacities near the iron-wüstite buffer.The results of these experiments have been integrated with available phase equilibrium data in the system CaO-MgO-Al₂O₃-SiO₂TiO₂ and a phase diagram for predicting the crystallization sequences of liquids with compositions of coarse-grained Ca-Al-rich inclusions has been developed.Available bulk compositions of coarse-grained inclusions form a well-defined trend in terms of major elements, extending from Type A and Bl inclusions near the spinel-melilite join to more pyroxene-rich Type B2 inclusions. The trend deviates from the expected sequence of solid condensates from a nebular gas at P = 10^?3 atm if pure diopside is assumed to be the clinopyroxene that condenses. The Type A-B1 end of the trend is similar in composition to calculated equilibrium condensates at 1202–1227°C and the trend as a whole parallels the sequence of condensates expected from diopside condensation at ~ 1170°C. The trend is consistent to first order with the condensation of solid Ti-rich fassaite in place of pure diopside at higher temperatures than those at which pure diopside is predicted to condense. Partially molten condensates may be likely in this case or if the nebular pressure is higher than 10^?3 atm.     

Challenges in constraining the P–T conditions of mafic granulites: An example from the northern Trans‐North China Orogen

Some mafic granulites in the Sanggan area of the northern Trans‐North China Orogen (TNCO) have a relatively simple mineralogy with low energy grain shapes that are compatible with an assumption of equilibrium, but the rock‐forming minerals show variations in composition that create challenges for thermobarometry. The mafic granulites, which occur as apparently disrupted dyke‐like bodies in tonalite–trondhjemite–granodiorite gneisses, are divided into two types based on petrography and chemical composition. Type 1 mafic granulites are fine‐ to medium‐grained with an equilibrated texture and an assemblage of plagioclase+clinopyroxene+garnet+magnetite+ilmenite and sometimes minor hornblende±orthopyroxene. Type 2 mafic granulites are coarse‐grained and hornblende bearing with a peak assemblage of garnet+clinopyroxene+plagioclase+hornblende and variably developed coronae and symplectites of plagioclase+hornblende+orthopyroxene partially replacing porphyroblastic garnet±clinopyroxene. SIMS U–Pb dating of metamorphic zircon from two type 1 mafic granulites yields metamorphic ages of c. 1.84 and 1.83 Ga, consistent with published ages of the type 2 mafic granulites. Based on phase equilibrium modelling, we use the common overlap of P–T fields defined by the mineral assemblage limits, and the mole proportion and composition isopleths of different minerals in each sample to quantify the metamorphic conditions. For type 1 granulites, overlap of the mineral proportion and composition fields for each of three samples yields similar P–T conditions of 710–880°C at 0.57–0.79 GPa, 820–850°C at 0.59–0.63 GPa and 800–860°C at 0.59–0.68 GPa. For the type 2 granulites, overlaying the peak assemblage fields for three samples yields common P–T conditions of 870–890°C at 1.1–1.2 GPa. For the retrograde assemblage, overlap of the mineral proportion and composition fields for each sample yields similar P–T conditions of 820–840°C at 0.85–0.88 GPa, 860–880°C at 0.83–0.86 GPa and 880–930°C at 0.89–0.95 GPa. The P–T conditions appear distinct between the two types of mafic granulite, with the mineralogically simple type 1 mafic granulites recording the lowest pressures. However, there are significant uncertainties associated with these results. For the granulites, there are uncertainties related to the determination of modes and composition of the equilibration volume, particularly estimation of O and H₂O contents, and in the phase equilibrium modelling there are uncertainties that propagate through the calculation of mole proportions and mineral compositions. The compound uncertainties on pressure and temperature for high‐T granulites are large and the results of our study show that it may be unwise to rely on P–T conditions determined from the simple intersection of calculated mineral composition isopleths alone. Since the samples in this study are from a limited area—a few hundred square metres—we infer that they record a single P–T path involving both decompression and cooling. However, there is no evidence of the high‐P granulite facies event at 1.93–1.90 Ga that is recorded elsewhere in the TNCO, which suggests that the precursor basic dykes were emplaced late during the assembly of the North China Craton.     

Phase Chemistry Study of the Zabuye Salt Lake Brine: Isothermal Evaporation at 15°C and 25°C

Zabuye Salt Lake in Tibet, China is a carbonate-type salt lake, which has some unique characteristics that make it different from other types of salt lakes. The lake is at the latter period in its evolution and contains liquid and solid resources. Its brine is rich in Li, B, K and other useful minor elements that are of great economic value. We studied the concentration behavior of these elements and the crystallization paths of salts during isothermal evaporation of brine at 15°C and 25°C. The crystallization sequence of the primary salts from the brine at 25°C is halite (NaCl) → aphthitalite (3K2SO4·Na2SO4) → zabuyelite (Li2CO3)→ trona (Na2CO3·NaHCO3·2H2O) → thermonatrite (Na2CO3·H2O) → sylvite (KCl), while the sequence is halite (NaCl) → sylvite (KCl) → trona (Na2CO3·NaHCO3·2H2O) → zabuyelite (Li2CO3) → thermonatrite (Na2CO3·H2O) → aphthitalite (3K2SO4·Na2SO4) at 15°C. They are in accordance with the metastable phase diagram of the Na+, K+-Cl?, CO32?, SO42?-H2O quinary system at 25°C, except for Na2CO3·7H2O which is replaced by trona and thermonatrite. In the 25°C experiment, zabuyelite (Li2CO3) was precipitated in the early stage because Li2CO3 is supersaturated in the brine at 25°C, in contrast with that at 15°C, it precipitated in the later stage. Potash was precipitated in the middle and late stages in both experiments, while boron was concentrated in the early and middle stages and precipitated in the late stage.     

The Asama igneous complex, central Japan: An ultramafic-mafic layered intrusion in the Mikabu greenstone belt, Sambagawa metamorphic terrain

The Asama igneous complex comprises layered mafic and ultramafic plutonic rocks exposed over about 500×6000 m in the Mikabu greenstone belt, Sambagawa metamorphic terrain of Mie Prefecture; its margins terminate by faults, and there is no trace of chilled rocks. The exposed layered sequence is about 460 m thick, and includes dunite, plagioclase wehrlite, olivine gabbro and two-pyroxene gabbro. The crystallization sequence of essential cumulus minerals is olivine, followed by plagioclase and clinopyroxene together, and finally the appearance of orthopyroxene. Olivine systematically varies in composition from Fo₈₉ to Fo₇₈ with stratigraphic height in the lower to middle portion of the layered sequence. The composition of clinopyroxene changes from Ca₄₉Mg₄₆Fe₅ to Ca₄₀Mg₄₇Fe₁₃ upward in the layered sequence; cumulus orthopyroxene, which occurs at the top of the exposed layered sequence, has a composition of Ca₂Mg₇₄Fe₂₄. Cumulus chromite occurs as disseminated grains in peridotitic rocks, and tends to increase its Fe³⁺/(Cr+Al+Fe³⁺) ratio with stratigraphic height. The most aluminous chromite [Cr/(Cr+Al) = 0.48] occurs in dunite that crystallized shortly before plagioclase began to separate as an essential phase. The Cr/(Cr+Al) ratio of the most aluminous chromite, coupled with the crystallization order of essential minerals, suggests that the Asama parental magma was moderately enriched in plagioclase and clinopyroxene components in the normative mineral diagram plagioclase-clinopyroxene-orthopyroxene. It was similar to a Hawaiian tholeiite and different from the Bushveld and Great “Dyke” parental magmas that were more enriched in orthopyroxene component; it also differed from mid-oceanic ridge basalts that are more depleted in the orthopyroxene component. The Asama clinopyroxene and chromite show characteristically high TiO₂ contents and are also similar to those in Hawaiian tholeiites. The Asama igneous complex probably resulted from the crystallization of a magma of a Hawaiian (oceanic-island) tholeiite composition and formed in an oceanic island regime.     

Liquids in equilibrium with peridotitic mineral assemblages at high water pressures

Pressure-temperature conditions for which “andesitic” liquids (～60% SiO₂) may coexist with mineral assemblages of the type magnesian olivine + orthopyroxene + clinopyroxene±amphibole±phlogopite have been investigated, both by means of partial melting experiments on the pyrolite model composition, and by experiments involving addition of olivine to andesite or basaltic andesite compositions at or near their liquidus temperatures. In the latter experiments, reaction relationships between quartz-normative liquid and olivine were made to proceed until olivine persisted. The composition of the final liquid in equilibrium with olivine (plus pyroxenes etc.) was then estimated by microprobe analysis of its quench products (glass, quench crystals). The inferred liquid compositions were tested for equilibrium with coexisting crystals using criteria based on mass balance within the total assemblage, equilibrium element partition relationships, and the requirement that the liquidus temperatures and near-liquidus crystalline phases of these compositions should closely match the temperature of the original olivine-addition experiment and the crystalline phases developed during it. At 1000° C–1050° C, liquids which satisfy these criteria for equilibrium with assemblages which include olivine are “andesitic” (58–60% SiO₂, 5–12% normative Qz) only at water pressures ≤ 10kb. At 15 kb, liquids in equilibrium with olivine at 1000° C and 980° C have ～56% SiO₂, high alkali contents, and 5–10% normative olivine. Similar compositions are in equilibrium with orthopyroxene and garnet alone at 20 kb. These results show that andesitic magmas are unlikely to be produced by melting of a peridotitic mantle at pressures >10 kb (depths>35 km). If hydrous, but otherwise geochemically primitive peridotitic compositions are partially melted at pressures<10 kb, then “andesitic” products will be much more magnesian and poorer in alkalies than typical natural andesites. These conclusions raise serious difficulties for models of andesite genesis by the melting of hydrous peridotitic mantle immediately overlying Benioff zones.     

Cognate clinopyroxene from Paleogene mantle xenolith-bearing basanite lavas (East Serbia, SE Europe): the role of dissolution of mantle orthopyroxene

The study focuses on clinopyroxene from mantle xenolith-bearing East Serbian basanites and suggests that dissolution of mantle orthopyroxene played an important role in at least some stages of the crystallization of these alkaline magmas. Five compositional types of clinopyroxene are distinguished, some of them having different textural forms: megacrysts (Type-A), green/colourless-cored phenocrysts (Type-B), overgrowths and sieve-textured cores (Type-C), rims and matrix clinopyroxene (Type-D), and clinopyroxene from the reaction rims around orthopyroxene xenocrysts (Type-E). Type-A is high-Al diopside that probably crystallized at near-liquidus conditions either directly from the host basanite or from compositionally similar magmas in previous magmatic episodes. Type-B cores show high ^VIAl/^IVAl≥1 and low Mg# of mostly <75 and are interpreted as typical xenocrysts. Type-C, D and E are interpreted as typical cognate clinopyroxene. Type-D has Mg#<78, Al₂O₃?=?6–13?wt.%, TiO₂?=?1.5–4.5?wt.%, and Na₂O?=?0.4–0.8?wt.% and compositionally similar clinopyroxene is calculated by MELTS as a phase in equilibrium with the last 30?% of melt starting from the average host lava composition. Type-C has Mg#?=?72–89, Al₂O₃?=?4.5–9.5?wt.%, TiO₂?=?1–2.5?wt.%, Na₂O?=?0.35–1?wt.% and Cr₂O₃?=?0.1–1.5?wt.%. This clinopyroxene has some compositional similarities to Type-E occurring exclusively around mantle orthopyroxene. Cr/Al vs Al/Ti and Cr/Al vs Na/Ti plots revealed that Type-C clinopyroxene can crystallize from a mixture of the host basanite magma and 2–20?wt.% mantle orthopyroxene. Sieve-textured Type-C crystals show characteristics of experimentally produced skeletal clinopyroxene formed by orthopyroxene dissolution suggesting that crystallization of Type-C was both texturally and compositionally controlled by orthopyroxene breakdown. According to FeO/MgO^cpx/melt modelling the first clinopyroxene precipitating from the host basanite was Type-A (T?~?1250?°C, p?~?1.5?GPa). Dissolution of orthopyroxene produced decreasing FeO/MgO^melt and crystallization of Type-E and sieve-textured Type-C clinopyroxene (0.3–0.8?GPa and 1200–1050?°C). The melt composition gradually shifted towards higher FeO/MgO^melt ratios precipitating more evolved Type-C and Type-D approaching near-solidus conditions (<0.3?GPa; ~950?°C).     

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

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

The Geology of the Great 'Dyke', Zimbabwe: The Ultramafic Rocks

Textural and mineral chemistry data for the ultramafic sequenceof the Hartley Complex are presented with the object of evaluatingemplacement mechanisms, crystallization history and sub-solidusre-equilibration processes for the Great ‘Dyke’.Mineral chemistry indicates in situ crystallizaration for theultramafic sequence, whereas textural evidence suggests thatlimited crystal settling of chromite took place. It is concludedthat crystallization of cumulus phases occurred at or near thefloor of the magma chamber. The mineral chemistry indicates that the volume of magma fromwhich each unit crystallized was significantly smaller thanthat represented by the stratigraphic succession of the HartleyComplex. The magma chamber may effectively have been part ofan open system during the crystallization of the ultramaficsequence. The results are consistent with the concept of a stratifiedmagma chamber and the process of double-diffusion convection. Modelling of the liquid line of descent and crystallizationsequences indicate that none of the previously proposed initialliquid compositions are likely to have constituted the parentalmagma of the Great ‘Dyke’. Rather than komatüticor exceptionally high magnesium liquids, as previously suggested,a parental magma with about 15 per cent MgO, similar to thecomposition of the chill phase of a dyke parallel to and inclose proximity to the East Dyke is in closest agreement withthe observed and modelled results. Chromite compositions are strongly related to textural and mineralogicalenvironments. Seam chromitites are higher in Cr, Mg and Fe³⁺than chromites enclosed in silicates. Chromite enclosed in cumulusolivine is higher in Fe²⁺ than that in coexisting pyroxenesbut there is little difference in the proportions of the trivalentcaptions. Seam chromitites are considered to have precipitatedin response to increases in foi associated with periodic influxesof magma into the magma chamber. The higher ferric iron contentof the seam chromitites compared with the chromite enclosedin the silicates is consistent with such a mechanism. Compositional zoning in olivine and pyroxene adjacent to enclosedchromite grains is interpreted as reflecting subsolidus re-equilibrationwith cooling. Zoning profiles exhibit strong crystallographiccontrol. Computer modelling using finite difference approximationshas allowed controlling factors to be assessed by optimizationof the modelled parameters to give closest agreement to themeasured results. Interdiffusion coefficients and distributioncoefficients for Fe²⁺ and Mg for olivine and pyroxene with chromiteare modelled and compared with published data. Indicated blockingtemperatures for olivine are of the order of 600 °C to 700°C and 750 °C to 850 °C for orthopyroxene. Thuschromites enclosed in orthopyroxene are more Mg-rich than thoseenclosed in olivine. Coarse-grained seam chromitites have beenlittle modified subsequent to crystallization but the compositionsof the associated silicates have been influenced by the modalabundance of the chromite. Geothermometers based on chromite-silicate equilibria are probablynot applicable to layered intrusions, but information on thermalhistories may be provided by evaluation of the diffusion profiles.     

Experimental modelling of corona textures

Formation of corona textures along olivine–plagioclase and orthopyroxene–plagioclase interfaces has been experimentally reproduced at 670 and 700 °C and 5 kbar with either a pure H₂O fluid phase or 0.1 and 37 m NaCl–H₂O solution fluid. In these experiments, we investigate the interaction of primary olivine and/or orthopyroxene and plagioclase in powders and polished crystals, and in small samples of a natural gabbro. The experiments result in the formation of corona textures with several layers of different assemblages (according to the experimental conditions) consisting of garnet (grossular), clinopyroxene, orthopyroxene, amphibole, chlorite and phlogopite. The experiments show major differences in the number of layers, the mineral assemblages and mineral composition, and in the trends of composition of plagioclase in coronas around olivine and orthopyroxene. The fluid phase composition influences the corona assemblages and the composition of the minerals in the experimental coronas; for example, garnet appears in the coronas in the second experiment where the NaCl–H₂O ratio is low. Experimental modelling of corona textures confirms a model of simultaneous growth of layers by the mechanism of diffusion metasomatism with participation of a fluid phase through which mass is transferred. Zoning in the experimental coronas shows opposing diffusion of Al and Ca from plagioclase and Mg and Fe from olivine/orthopyroxene; difference in the mobility of the components is inferred from observations in the coronas. The experimental corona textures are compared with natural coronas from the Belomorian belt (Baltic shield), developed at 670–690 °C and 7–8 kbar, and the Marun‐Keu complex (Polar Urals), developed at 670–700 °C and 14–16 kbar, where the corona textures correspond to a transitional stage of the gabbro‐to‐eclogite transformation.     

Metamorphic evolution of non‐equilibrated granulitized eclogite from Punta de li Tulchi (Variscan Sardinia) determined through texturally controlled thermodynamic modelling

The metamorphic evolution of a granulitized eclogite from Punta de li Tulchi, NE Sardinia, Italy, reconstructed utilizing a combined microstructural (symplectitic, coronitic and kelyphytic features) and thermodynamic approach, involved a complex metamorphic history with equilibrium attained only at a domainal scale. Microstructural analysis and mineral zoning allow recognition of reactants and products involved in successive balanced mineral reactions. The P–T conditions at which each microstructure was formed are constrained by calculating isochemical phase diagrams (pseudosections) for the composition of effectively reacting domains. A pre‐symplectite stage developed during prograde metamorphism under conditions ranging from 660–680 °C, 1.6–1.8 GPa to 660–700 °C at 1.7–2.1 GPa. Pseudosections calculated for subsequent clinopyroxene + plagioclase and orthopyroxene + plagioclase symplectitic coronae using the composition of effectively reacting microdomains suggest temperature in excess of 800 °C and pressures of 1.0–1.3 GPa. Modelling the development of later plagioclase + amphibole coronae around garnet during decompression yields conditions of 730–830 °C and 0.8–1.1 GPa. H₂O (wt%) isomodes indicate that the granulitized eclogites were H₂O‐undersaturated at peak‐P conditions and during most of the subsequent heating and decompression. This allowed the preservation of prograde garnet zoning in spite of the strong granulite facies overprint. The P–T evolution of Punta de li Tulchi granulitized eclogite is very similar in shape to that registered by other NE Sardinia retrogressed eclogites thus suggesting a common tectonic scenario for their evolution.     

Origin of ultramafic inclusions and megacrysts in a monchiquite dyke at Streap,inverness-shire,Scotland

Spinel lherzolite nodules, composed of olivine (Fo_88.7?89.2), clinepyroxene (6.5% Al₂O₃) and Al-rich spinel, and websterite nodules as well as megacrysts of clinopyroxene, orthopyroxene and magnetite occur in a monchiquite at Streap, Scotland. Petrographic data are given and microprobe analyses of coexisting phases in six spinel lherzolite nodules and one websterite nodule are reported, along with analyses of both types of pyroxene megacrysts. The spinel lherzolites show internal chemical homogeneity, and their mineral chemistries suggest equilibrium conditions of 1100–1200°C and 14–23 kb. The websterite nodules are, on the basis of mineral chemistry and petrography, considered to be crustal material. The megacrysts constitute a separate group, differing in composition from analogous phases in associated lherzolites and websterites as well as from monchiquite phenocryst phases, and show systematic chemical variations corresponding to low pressure crystal fractionation processes.     

Testing the fidelity of thermometers at ultrahigh temperatures

A highly residual granulite facies rock (sample RG07‐21) from Lunnyj Island in the Rauer Group, East Antarctica, presents an opportunity to compare different approaches to constraining peak temperature in high‐grade metamorphic rocks. Sample RG07‐21 is a coarse‐grained pelitic migmatite composed of abundant garnet and orthopyroxene along with quartz, biotite, cordierite, and plagioclase with accessory rutile, ilmenite, zircon, and monazite. The inferred sequence of mineral growth is consistent with a clockwise pressure–temperature (P–T) evolution when compared with a forward model (P–T pseudosection) for the whole‐rock chemical composition. Peak metamorphic conditions are estimated at 9 ± 0.5 kbar and 910 ± 50°C based on conventional Al‐in‐orthopyroxene thermobarometry, Zr‐in‐rutile thermometry, and calculated compositional isopleths. U–Pb ages from zircon rims and neocrystallized monazite grains yield ages of c. 514 Ma, suggesting that crystallization of both minerals occurred towards the end of the youngest pervasive metamorphic episode in the region known as the Prydz Tectonic Event. The rare earth element compositions of zircon and garnet are consistent with equilibrium growth of these minerals in the presence of melt. When comparing the thermometry methods used in this study, it is apparent that the Al‐in‐orthopyroxene thermobarometer provides the most reliable estimate of peak conditions. There is a strong textural correlation between the temperatures obtained using the Zr‐in‐rutile thermometer––maximum temperatures are recorded by a single rutile grain included within orthopyroxene, whereas other grains included in garnet, orthopyroxene, quartz, and biotite yield a range of temperatures down to 820°C. Ti‐in‐zircon thermometry returns significantly lower temperature estimates of 678–841°C. Estimates at the upper end of this range are consistent with growth of zircon from crystallizing melt at temperatures close to the elevated (H₂O undersaturated) solidus. Those estimates, significantly lower than the calculated temperature of this residual solidus, may reflect isolation of rutile from the effective equilibration volume leading to an activity of TiO₂ that is lower than the assumed value of unity.