Conditions of condensate rim formation on the surface of lunar regolith particles

Condensate objects observed in the lunar regolith are distinctly separated on the basis of morpho-logical and chemical characteristics into droplets condensed during the expansion of an impact-generated vapor cloud and films condensed on the relatively cold surface of mineral particles. Using the analyses of both condensate forms and experimental data on the evaporation of melt corresponding to a typical lunar highland rock of the gabbro-anorthosite composition from Apollo 16 sample 68415.40, the temperature conditions of vapor condensation during lunar impact events were estimated. The comparison of condensate compositions with the analyses of vapors from the evaporation experiment showed that, compared with the compositions of droplet-type condensates, the condensate rims were formed from a vapor with high contents of refractory CaO and Al₂O₃ and at very different condensation temperatures. The enrichment of vapor in CaO and Al₂O₃ could be attained only at high temperatures of melt evaporation (higher than ∼ 1850°C according to experimental data). The estimated condensation temperatures of droplets are significantly lower, ∼1750–1500°C. Rim-type condensates were produced by vapor quenching on the relatively cold surface of a solid mineral particle, which resulted in almost complete precipitation of all major components of the silicate vapor without fractionation in accordance with their individual volatilities.     

Lunar rock-rain: Diverse silicate impact-vapor condensates in an Apollo-14 regolith breccia

Apollo 14 regolith breccia 14076, long known to be uniquely endowed with high-alumina, silica-poor (HASP) material of evaporation-residue origin, has been found to contain a diverse suite of complementary condensates, dubbed GASP (gas-associated spheroidal precipitates). GASP occurs in two forms: as glassy or extremely fine grained quenched-melt spheroids, mostly less than 5 μm across; and as quenched textured clasts up to 200 μm across. In two of the clasts, origin by aggregation of spheroidal GASP is confirmed by the presence of relict spheroids. GASP is distinctively depleted in the same refractory major oxides that are characteristically enriched in HASP: Al₂O₃ and CaO. Among the larger GASP spheroids, Al₂O₃ is seldom >1 wt%; among the clasts, excluding two instances of apparent contamination by Na- and K-rich substrate-derived melt, bulk Al₂O₃ averages 0.3 wt%. Depletion of Al₂O₃ and CaO is also manifested by pyroxene compositions in some clasts; e.g., in the largest clast, En₈₂Wo_0.45 with 0.07 wt% Al₂O₃. Although GASP bulk compositions are nearly pure SiO₂ + MgO + FeO, they are nonetheless highly diverse. Spheroid compositions range in mg from 7 to 84 mol%, and in FeO/SiO₂ (weight ratio) from 0.002 to 0.67. Bulk compositions and textures of many GASP spheroids suggest that liquid immiscibility occurred prior to quenching; implying that these materials were, some time after condensation, at temperatures of ∼1680 °C. Textural evidence for immiscibility includes lobate boundaries between silicic and mafic domains, and a general tendency for quenched mafic silicates to be concentrated into a few limited patches rather than evenly dispersed. The parent melt of the largest clast’s pyroxene is inferred to have formed as a partial melt within the parent aggregation of GASP matter, compositionally near the pyroxene + cristobalite + melt eutectic and thus at ∼1500 °C. A few GASP spheroids show possible signs of in-flight collision-coalescence, but aggregation of the much larger clasts probably took place in mushy puddles on the lunar surface. Little mixing took place between these GASP puddles and the related HASP, probably because GASP condensation did not commence until after an intermediate stage during which, while neither net evaporation nor net condensation took place, expansion of the vapor cloud carried the eventual GASP matter well apart from the HASP. Considering the characteristic length-scale of lunar regolith mixing, the concentration of both GASP and HASP into this single unique regolith sample (14076) is most consistent with a parent crater size (diameter) of 10-100 km. I speculate that the 14076 regolith may have been unusually situated, almost directly uprange from an unusually oblique large impact. Mercurian analogs of the 14076 impact condensates may have significant implications for remote sensing.     

Volatility inversion of silicon and magnesium oxides during the evaporation of HASP glasses on the moon

An inversion of SiO₂ and MgO volatility occurs during high-temperature melt evaporation in the CaO–MgO–Al₂O₃–SiO₂ (CMAS) system. This results in that SiO₂, which is usually more volatile than MgO, becomes less volatile during the evaporation of melts enriched in the refractory oxides CaO and Al₂O₃. The volatility inversion is adequately explained within the theory of acid–base interaction of silicate melt components developed by D.S. Korzhinskii. The compositions of high-Al₂O₃ and SiO₂-poor glasses (known as HASP glasses) from the lunar regolith show a systematic decrease in MgO/SiO₂ with increasing CaO content, which is a direct consequence of the influence of acid–base effects.     

Millennial timescale resolution of rhyolite magma recharge at Tarawera volcano: insights from quartz chemistry and melt inclusions

Most rhyolite eruption episodes of Tarawera volcano have emitted several physiochemically distinct magma batches (∼1–10 km³). These episodes were separated on a millennial timescale. The magma batches were relatively homogeneous in temperature and composition at pumice scale (>4 cm), but experienced isolated crystallisation histories. At the sub-cm scale, matrix glasses have trace element compositions (Sr, Ba, Rb) that vary by factors up to 2.5, indicating incomplete mixing of separate melts. Some quartz-hosted melt inclusions are depleted in compatible trace elements (Sr, Ti, Ba) compared to enclosing matrix glasses. This could reflect re-melting of felsic crystals deeper in the crystal pile. Individual quartz crystals display a variety of cathodoluminescence brightness and Ti zoning patterns including rapid changes in melt chemistry and/or temperature (∼50–100°C), and point to multi-cycle crystallisation histories. The Tarawera magma system consisted of a crystal-rich mass containing waxing and waning melt pockets that were periodically recharged by silicic melts driven by basaltic intrusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Evolution of the trachydacite and pantellerite magmas of the bimodal volcanic association of Dzarta-Khuduk, Central Mongolia: Investigation of inclusions in minerals

Using various methods of melt inclusion investigation, including electron and ion microprobe techniques, we estimated the composition, evolution, and formation conditions of melts producing the trachydacites and pantellerites of the Late Paleozoic bimodal volcanic association of Dzarta-Khuduk, Central Mongolia. Primary crystalline and melt inclusions were detected in anorthoclase from trachydacites and quartz from pantellerites and pantelleritic tuffs. Among the crystalline inclusions, we identified hedenbergite, fluorapatite, and pyrrhotite in the trachydacites and F-arfvedsonite, fluorite, ilmenite, and the rare REE diorthosilicate chevkinite in the pantellerites. Melt inclusions in anorthoclase from the trachydacites are composed of glass, a gas phase, and daughter minerals (F-arfvedsonite, fluorite, villiaumite, and anorthoclase rim on the inclusion wall). Melt inclusions in quartz from the pantellerites are composed of glass, a gas phase, and a fine-grained salt aggregate consisting of Li, Na, and Ca fluorides (griceite, villiaumite, and fluorite). Melt inclusions in quartz crystalloclasts from the pantelleritic tuffs are composed of homogeneous silicate glasses. The phenocrysts of the trachydacites and pantellerites crystallized at temperatures of 1060–1000°C. During thermometric experiments with quartz-hosted melt inclusions from the pantellerites, the formation of immiscible silicate and salt (fluoride) melts was observed at a temperature of 800°C. Homogeneous melt inclusions in anorthoclase from the trachydacites have both trachydacite and rhyolite compositions (wt %): 68–70 SiO₂, 12–13 Al₂O₃, 0.34–0.74 TiO₂, 5–7 FeO, 0.4–0.9 CaO, and 9–12 Na₂O + K₂O. The agpaitic index ranges from 0.92 to 1.24. The glasses of homogenized melt inclusions in quartz from the pantellerites and pantelleritic tuffs have rhyolitic compositions. Compared with the homogeneous glasses trapped in anorthoclase of the trachydacites, quartz-hosted inclusions from the pantellerites show higher SiO₂ (72–78 wt %) and lower Al₂O₃ contents (7.8–10.0 wt %). They also contain 0.14–0.26 wt % TiO₂, 2.5–4.9 wt % FeO, 9–11 wt % Na₂O + K₂O, and 0.9–0.15 wt % CaO and show an agpaitic index of 1.2–2.05. Homogeneous melt inclusions in quartz from the pantelleritic tuffs contain 69–72 wt % SiO₂. The contents of other major components, including TiO₂, Al₂O₃, FeO, and CaO, are close to those in the homogeneous glasses of quartzhosted melt inclusions in the pantellerites. The contents of Na₂O + K₂O are 4–10 wt %, and the agpaitic index is 1.0–1.6. The glasses of melt inclusions from each rock group show distinctive volatile compositions. The H₂O content is up to 0.08 wt % in anorthoclase of the trachydacites, 0.4–1.4 wt % in quartz of the pantellerites, and up to 5 wt % in quartz of the pantelleritic tuffs. The content of F in the glasses of melt inclusions in the phenocrysts of the trachydacites is no higher than 0.67 wt %, and up to 1.4–2.8 wt % in quartz from the pantellerites. The Cl content is up to 0.2 wt % in the glasses of melt inclusions in the minerals of the trachydacites and up to 0.5 wt % in the glasses of quartz-hosted melt inclusions from the pantellerites. The investigation of trace elements in the homogenized glasses of melt inclusions in minerals showed that the trachydacites and pantellerites were formed from strongly evolved rare-metal alkaline silicate melts with high contents of Li, Zr, Rb, Y, Hf, Th, U, and REE. The analysis of the composition of homogeneous melt inclusions in the minerals of the above rocks allowed us to distinguish magmatic processes resulting in the enrichment of these rocks in trace and rare earth elements. The most important processes are the crystallization differentiation and immiscible separation of silicate and fluoride salt melts. It was also shown that all the melts studied evolved in spatially separated magma chambers. This caused the differences in the character of melt evolution between the trachydacites and pantellerites. During the final stages of differentiation, when the magmatic system was saturated with respect to ore elements, Na-Ca fluoride melts were separated and extracted considerable amounts of Li.     

The geochemistry and provenance of Apollo 16 mafic glasses

The regolith of the Apollo 16 lunar landing site is composed mainly of feldspathic lithologies but mafic lithologies are also present. A large proportion of the mafic material occurs as glass. We determined the major element composition of 280 mafic glasses (>10 wt% FeO) from six different Apollo 16 soil samples. A small proportion (5%) of the glasses are of volcanic origin with picritic compositions. Most, however, are of impact origin. Approximately half of the mafic impact glasses are of basaltic composition and half are of noritic composition with high concentrations of incompatible elements. A small fraction have compositions consistent with impact mixtures of mare material and material of the feldspathic highlands. On the basis of major-element chemistry, we identified six mafic glass groups: VLT picritic glass, low-Ti basaltic glass, high-Ti basaltic glass, high-Al basaltic glass, KREEPy glass, and basaltic-andesite glass. These glass groups encompass 60% of the total mafic glasses studied. Trace-element analyses by secondary ion mass spectroscopy for representative examples of each glass group (31 total analyses) support the major-element classifications and groupings. The lack of basaltic glass in Apollo 16 ancient regolith breccias, which provide snapshots of the Apollo 16 soil just after the infall of Imbrium ejecta, leads us to infer that most (if not all) of the basaltic glass was emplaced as ejecta from small- or moderate-sized impacts into the maria surrounding the Apollo 16 site after the Imbrium impact. The high-Ti basaltic glasses likely represent a new type of basalt from Mare Tranquillitatis, whereas the low-Ti and high-Al basaltic glasses possibly represent the composition of the basalts in Mare Nectaris. Both the low-Ti and high-Al basaltic glasses are enriched in light-REEs, which hints at the presence of a KREEP-bearing source region beneath Mare Nectaris. The basaltic andesite glasses have compositions that are siliceous, ferroan, alkali-rich, and moderately titaniferous; they are unlike any previously recognized lunar lithology or glass group. Their likely provenance is within the Procellarum KREEP Terrane, but they are not found within the Apollo 16 ancient regolith breccias and therefore were likely deposited at the Apollo 16 site post-Imbrium. The basaltic-andesite glasses are the most ferroan variety of KREEP yet discovered.     

On the origin of impact glass in the Apollo 16 regolith

This study addresses the issue of what fraction of the impact glass in the regolith of a lunar landing site derives from local impacts (those within a few kilometers of the site) as opposed to distant impacts (10 or more kilometers away). Among 10,323 fragments from the 64-210-μm grain-size fraction of three Apollo 16 regolith samples, 14% are impact glasses, that is, fragments consisting wholly or largely of glass produced in a crater-forming impact. Another 16% are agglutinates formed by impacts of micrometeorites into regolith. We analyzed the glass in 1559 fragments for major- and minor-element concentrations by electron probe microanalysis and a subset of 112 of the fragments that are homogeneous impact glasses for trace elements by secondary ion mass spectrometry. Of the impact glasses, 75% are substantially different in composition from either the Apollo 16 regolith or any mixture of rocks of which the regolith is mainly composed. About 40% of the impact glasses are richer in Fe, Mg, and Ti, as well as K, P, and Sm, than are common rocks of the feldspathic highlands. These glasses must originate from craters in maria or the Procellarum KREEP Terrane. Of the feldspathic impact glasses, some are substantially more magnesian (greater MgO/FeO) or have substantially lower concentrations of incompatible elements than the regolith of the Apollo 16 site. Many of these, however, are in the range of feldspathic lunar meteorites, most of which derive from points in the feldspathic highlands distant from the Procellarum KREEP Terrane. These observations indicate that a significant proportion of the impact glass in the Apollo 16 regolith is from craters occurring 100 km or more from the landing site. In contrast, the composition of glass in agglutinates, on average, is similar to the composition of the Apollo 16 regolith, consistent with local origin.     

Variscan amphibolite-facies rocks from the Kurtoğlu metamorphic complex (Gümüşhane area,Eastern Pontides,Turkey)

The Kurtoğlu metamorphic complex, that forms part of the pre-Liassic basement of the Sakarya zone in northern Turkey, consists of at least two tectonic units. Blueschist-facies rocks of unknown metamorphic age in the southern part of the complex are tectonically overlain by Variscan low-pressure high-temperature metamorphic rocks. The latter comprise mica schists and fine-grained gneisses, cut by metaleucogranitic dikes, as well as migmatitic biotite gneisses and subordinate amphibolite intercalations. Structural data indicate that metamorphism and penetrative deformation occurred after dyke intrusion. Peak metamorphic conditions of the mica schists, fine-grained gneisses and metaleucogranites are estimated to ∼650°C and ∼0.4 GPa, based on phase relationships in the system NCKFMASH, Fe–Mg partitioning between garnet and biotite as well as garnet-aluminosilicate-quartz-plagioclase (GASP) and garnet-plagioclase-biotite-quartz (GBPQ) barometry. Peak temperatures of the migmatitic biotite gneisses and amphibolite intercalations are not well constrained but might have been significantly higher (690–740°C), as suggested from hornblende-plagioclase thermometry. ⁴⁰Ar–³⁹Ar incremental dating on muscovite and biotite fractions from the mica schists and fine-grained gneisses yielded plateau ages of ∼323 Ma. Significantly older model ages of ∼329 and ∼337 Ma were obtained on muscovite fractions from two metaleucogranite samples. These fractions contain both relict igneous and newly formed metamorphic muscovite.     

Origin of the Oceanic Lithosphere

In a global examination of mid-ocean ridge basalt (MORB) glasscompositions, we find that Na₈–Fe₈–depth variationsdo not support modeling of MORBs as aggregates of melt compositionsgenerated over a large range of temperature and pressure. However,the Na₈–Fe₈ variations are consistent with the compositionalsystematics of solidus melts in the plagioclase–spinellherzolite transition in the CaO–MgO–Al₂O₃–SiO₂–Na₂O–FeO(CMASNF) system. For natural compositions, the P–T rangefor melt extraction is estimated to be 1·2–1·5GPa and 1250–1280°C. This P–T range is a closematch with the maximum P–T conditions for explosive pressure-releasevaporization of carbonate-bearing melts. It is proposed thatfracturing of the lithosphere induces explosive formation andescape of CO₂ vapor. This provides the vehicle for extractionof MORBs at a relatively uniform T and P. The upper portionof the CO₂-bearing and slightly melted seismic low-velocityzone flows toward the ridge, rises at the ridge axis to lower-lithospheredepths, melts much more extensively during this rise, and releasesMORB melts to the surface driven by explosively escaping CO₂vapor. The residue and overlying crust produced by this meltingthen migrate away from the ridge axis as new oceanic lithosphere.The entire process of oceanic lithosphere creation involvesonly the upper 140 km. When lithospheric stresses shift fractureformation to other localities, escape of CO₂ ceases, the vehiclefor transporting melt to the surface disappears, and ridgesdie. Inverse correlations of Na₈ vs Fe₈ for MORB glasses areexplained by mantle heterogeneity, and positive variations superimposedon the inverse variations are consistent with progressive extractionof melts from short, ascending melting columns. The uniformlylow temperatures of MORB extraction are not consistent withthe existence of hot plumes on or close to ocean ridges. Inthis modeling, the southern Atlantic mantle from Bouvet to about26°N is relatively homogeneous, whereas the Atlantic mantlenorth of about 26°N shows significant long-range heterogeneity.The mantle between the Charlie Gibbs and Jan Mayen fracturezones is strongly enriched in FeO/MgO, perhaps by a trappedfragment of basaltic crust. Iceland is explained as the productof this enrichment, not a hot plume. The East Pacific Rise,Galapagos Ridge, Gorda Ridge, and Juan de Fuca Ridge samplemantle that is heterogeneous over short distances. The mantlebeneath the Red Sea is enriched in FeO/MgO relative to the mantlebeneath the northern Indian Ocean.     

The origin and evolution of the parental magmas of frontal volcanoes in Kamchatka: Evidence from magmatic inclusions in olivine from Zhupanovsky volcano

The paper presents data on naturally quenched melt inclusions in olivine (Fo 69–84) from Late Pleistocene pyroclastic rocks of Zhupanovsky volcano in the frontal zone of the Eastern Volcanic Belt of Kamchatka. The composition of the melt inclusions provides insight into the latest crystallization stages (∼70% crystallization) of the parental melt (∼46.4 wt % SiO₂, ∼2.5 wt % H₂O, ∼0.3 wt % S), which proceeded at decompression and started at a depth of approximately 10 km from the surface. The crystallization temperature was estimated at 1100 ± 20°C at an oxygen fugacity of ΔFMQ = 0.9–1.7. The melts evolved due to the simultaneous crystallization of olivine, plagioclase, pyroxene, chromite, and magnetite (Ol: Pl: Cpx: (Crt-Mt) ∼ 13: 54: 24: 4) along the tholeiite evolutionary trend and became progressively enriched in FeO, SiO₂, Na₂O, and K₂O and depleted in MgO, CaO, and Al₂O₃. Melt crystallization was associated with the segregation of fluid rich in S-bearing compounds and, to a lesser extent, in H₂O and Cl. The primary melt of Zhupanovsky volcano (whose composition was estimated from data on the most primitive melt inclusions) had a composition of low-Si (∼45 wt % SiO₂) picrobasalt (∼14 wt % MgO), as is typical of parental melts in Kamchatka and other island arcs, and was different from MORB. This primary melt could be derived by ∼8% melting of mantle peridotite of composition close to the MORB source, under pressures of 1.5 ± 0.2 GPa and temperatures 20–30°C lower than the solidus temperature of “dry” peridotite (1230–1240°C). Melting was induced by the interaction of the hot peridotite with a hydrous component that was brought to the mantle from the subducted slab and was also responsible for the enrichment of the Zhupanovsky magmas in LREE, LILE, B, Cl, Th, U, and Pb. The hydrous component in the magma source of Zhupanovsky volcano was produced by the partial slab melting under water-saturated conditions at temperatures of 760–810°C and pressures of ∼3.5 GPa. As the depth of the subducted slab beneath Kamchatkan volcanoes varies from 100 to 125 km, the composition of the hydrous component drastically changes from relatively low-temperature H₂O-rich fluid to higher temperature H₂O-bearing melt. The geothermal gradient at the surface of the slab within the depth range of 100–125 km beneath Kamchatka was estimated at 4°C/km.     

An Experimental Study of Water and Carbon Dioxide Solubilities in Mid-Ocean Ridge Basaltic Liquids. Part II: Applications to Degassing

Degassing processes in basaltic magmas rich in both water andcarbon dioxide can be modeled using the solubilities of theendmember systems and the assumption of Henry's law. Suitesof vapor-saturated basaltic melts having a range of initialCO₂/H₂O ratios and erupted over a narrow depth interval willdefine negatively sloped arrays on an H₂O vs CO₂ plot. It isimportant that all of the major volatile species be consideredsimultaneously when interpreting trends in dissolved volatilespecies concentrations in magmas. Based on measured concentrations of water and carbon dioxidein basaltic glasses, the composition of the vapor phase at 1200°Cthat could coexist with a basaltic melt and the pressure atwhich it would be vapor saturated can be calculated. The rangein vapor compositions in equilibrium with submarine basaltsreflects the range in water contents in the melts characteristicof each environment. The ranges in the molar proportion of CO₂in vapor phases (X_CO2) calculated to be in equilibrium withsubmarine tholeiitic glasses are 0•93–1•00 formid-ocean ridge basalts (MORB), 0•60–0•99 forglasses from Kilauea [representative of ocean island basalts(OIB)] and 0–0•94 for glasses from back-arc basins(BABB). MORB glasses from spreading centers ranging from slow(e.g. the Mid-Atlantic Ridge) to fast (e.g. East Pacific Rise,9–13°N) are commonly supersaturated with respect toCO₂-rich vapor, resulting from magma ascent rates so rapid thatmagmas erupt on the sea-floor without having been fully degassedby bubble nucleation and growth during ascent. In contrast tothe MORB glasses, volatile contents in submarine glasses fromKilauea are consistent with having been in equilibrium witha vapor phase containing 60–100 mol% CO₂ at the pressureof eruption, reflecting differences in average magma transportrates during eruptions at mid-ocean ridges and hotspot volcanoes. Degassing during decompression of tholeiitic basaltic magmais characterized by strong partitioning of CO₂ into the vaporphase. During open system degassing, CO₂ is rapidly removedfrom the melt with negligible loss of water, until a pressureis reached at which the melt is in equilibrium with nearly purewater vapor. From this pressure downward, the water contentof the melt follows the water solubility curve. During closedsystem degassing, water and CO₂ contents in vapor-saturatedbasaltic magmas will depend strongly on the vapor compositionas determined by the initial volatile concentrations. Deviationfrom open system behavior, toward lower dissolved H₂O and CO₂saturation concentrations at a given pressure, will be greatestin melts having high total volatile concentrations and highCO₂:H₂O ratios. Closed system degassing of basaltic melts havingthe low initial H₂O and CO₂ contents typical of MORB and OIB,however, are similar to the open system case. KEY WORDS: mid-ocean ridge basalts; water and carbon dioxide solubility; degassing     

The temperature dependence of the speciation of water in NaAlSi3O8-KAlSi3O8 melts: an application of fictive temperatures derived from synthetic fluid-inclusions

 The speciation of water dissolved in glasses along the join NaAlSi₃O₈-KAlSi₃O₈ has been investigated using infrared spectroscopy. Hydrous melts have been hydrothermally synthesized by chemical equilibration of cylinders of bubble-free anhydrous start glasses with water at 1040^° C and 2 kbar. These melts have been isobarically and rapidly (200^° C/s) “drop”-quenched to room temperature and then subsequently depressurized. The speciation of water in the quenched glasses reflects the state of water speciation at a temperature (the so-called fictive temperature) where the quenched-in structure of the glasses closely corresponds to the melt structure at equilibrium. This fictive temperature is detectable as the macroscopically measureable glass transition temperature of these melt compositions. A separate set of experiments using vesicular samples of the same chemistry has precisely defined the glass transition temperature of these melts (±5^° C) on the basis of homogenization temperatures for water-filled fluid inclusions (Romano et al. 1994). The spectroscopic data on the speciation of water in these quenched glasses has been quantified using experimentally determined absorptivities for OH and H₂O for each individual melt composition. The knowledge of glass transition temperatures, together with quantitative speciation data permits an analysis of the temperature dependence of the water speciation over the 113^° C range of fictive temperatures obtained for these water-saturated melts. The variation of water speciation, cast as the equilibrium constant K where K = [H₂O] [O _m ]/[OH]² is plotted versus the fictive temperature of the melt to obtain the temperature dependence of speciation. Such a plot describes a single linear trend of the logarithm of the equilibrium constant versus reciprocal temperature, implying that the exchange of K for Na has little influence on melt speciation of water. The enthalpy derived from temperature dependence is 36.5(±5) kJ/mol. The results indicate a large variation in speciation with temperature and an insensitivity of the speciation to the K–Na exchange. Received: 8 March 1995/Accepted: 6 June 1995     

Fluid+melt intrusions in lechatelierite from the Popigai suevites: A product of dynamic interaction melts and fluids during the shock melting of the target gneiss

The paper presents data on lechatelierite form suevites of the Daldyn Formation in the Popigai astrobleme. Some of the lechatelierite samples show a complicated structure and contain block of diaplectic quartz glass and dynamic “intrusions” of glasses of types I, II, and III. The glasses of types I and II abound in fluid inclusions and display evidence of partial homogenization with lechatelierite. The glasses of type III are clearly separated from all other glasses but show evidence of dynamic interaction with them in the molten state. Fluid inclusions in the glasses of types I and II are syngenetic but have notably different densities from those of completely liquid or gaseous inclusions at 20°C. As is indicated by cryometric data, the liquid phase of the inclusions is aqueous solution of low salinity (5–8 wt % NaCl_equiv). The bulk petrochemistry of the glasses of type I characterizes them as highly silicic (96.04 wt % SiO₂ on average), with elevated K and Na concentrations (Na₂O + K₂O = 0.72 wt % on average), with 0.73 wt % Al₂O₃ (on average) and analytical totals 1.97 wt % less than 100%. The glasses of type II are also rich in SiO₂ (91.51 wt % SiO₂ on average) but contain a broader spectrum of concentrations of major oxides (totaling 5.53 wt % on average) and deficient analytical totals (by 2.96 wt % on average). The glasses of type III are completely equal to impactites produced by melting gneisses of the Popigai astrobleme. The glasses of type I are interpreted to be the intrusion products of the “early” highly mobile and H₂O-rich fluid+melt mixtures, whose protolithic material was K-Na feldspars of the target rocks. The derivation of these melts was associated with the capturing of much silica and water at a highly mobile behavior of K and Na and an inert behavior of Al. The glasses of type II were produced by the extensive mixing of silica and water at the limited involvement of apogneiss melts, and these glasses are sometimes deficient in Al. The glasses of type III are usual mixed apogneiss melts. Excess silica in the glasses of types I and II and their richness in water and deficiency in Al suggest impact anatexis and the selective separation of components during their derivation; the parental fluid-melt mixtures of these glasses were derived from such “hydrous” varieties of the target gneisses as diaphthorized and fractured rocks. The evolution and partial vitrification of lechatelierite and the glasses of types I and II proceeded under residual shock pressures, as follows from data on the dense (from ∼0.5 to 1 g/cm³) aqueous inclusions in these glasses, which suggest that the inclusions were captured in the glasses under pressures from ∼0.8 to 3.3 GPa. It follows that our lechatelierite samples have a complex multistage genesis, and their quenching facilitated the preservation of “intrusions” of various stages of shock melting, including the products of the “early” impact anatexis of the gneisses with the selective separation of components at the active participation of water.     

The effects of metamorphism on O and Fe isotope compositions in the Biwabik Iron Formation, northern Minnesota

The Biwabik Iron Formation of Minnesota (1.9 Ga) underwent contact metamorphism by intrusion of the Duluth Complex (1.1 Ga). Apparent quartz–magnetite oxygen isotope temperatures decrease from ∼700°C at the contact to ∼375°C at 2.6 km distance (normal to the contact in 3D). Metamorphic pigeonite at the contact, however, indicates that peak temperatures were greater than 825°C. The apparent O isotope temperatures, therefore, reflect cooling, and not peak metamorphic conditions. Magnetite was reset in δ¹⁸O as a function of grain size, indicating that isotopic exchange was controlled by diffusion of oxygen in magnetite for samples from above the grunerite isograd. Apparent quartz–magnetite O isotope temperatures are similar to calculated closure temperatures for oxygen diffusion in magnetite at a cooling rate of ∼5.6°C/kyr, which suggests that the Biwabik Iron Formation cooled from ∼825 to 400°C in ∼75 kyr at the contact with the Duluth Complex. Isotopic exchange during metamorphism also occurred for Fe, where magnetite–Fe silicate fractionations decrease with increasing metamorphic grade. Correlations between quartz–magnetite O isotope fractionations and magnetite–iron silicate Fe isotope fractionations suggest that both reflect cooling, where the closure temperature for Fe was higher than for O. The net effect of metamorphism on δ¹⁸O–δ⁵⁶Fe variations in magnetite is a strong increase in δ¹⁸O_Mt and a mild decrease in δ⁵⁶Fe with increasing metamorphic grade, relative to the isotopic compositions that are expected at the low temperatures of initial magnetite formation. If metamorphism of Iron Formations occurs in a closed system, bulk O and Fe isotope compositions may be preserved, although re-equilibration among the minerals may occur for both O and Fe isotopes. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Melting experiments on the enstatite-diopside join at 70–224 kbar,including the melting of diopside

 Melting relations on the enstatite−diopside (En, Mg₂Si₂O₆−Di, CaMgSi₂O₆) join, including the compositions of crystalline phases and melts coexisting along the solidi, were experimentally determined in the pressure range 70–224 kbar with a split-sphere anvil apparatus (USSA-2000). Melting is peritectic in enstatite-rich compositions at 70–124 kbar (1840–2100° C) and eutectic at higher pressures, while the diopside-rich clinopyroxene melts azeotropically at 70–165 kbar and up to 300° C lower temperatures than the eutectic. Orthopyroxene is replaced with enstatite-rich clinopyroxene at 120 kbar and 2090°C. First garnet with 17 mol% Di forms on the solidus at 158 kbar and 2100° C. Two garnets coexist on the solidus at 165–183 kbar and 2100° C, garnet coexists with CaSiO₃ perovskite at 183–224 kbar (2100–2230° C) and two coexisting perovskites are stable at higher pressures. The melting curve of diopside was determined at 80–170 kbar; the slope becomes negative at 140 kbar and 2155° C. At 170 kbar and 2100° C, diopside with 96% Di breaks down to garnet with 89% Di and CaSiO₃ perovskite. The new data were used to calculate an improved temperature-pressure phase diagram for the CMAS system, which can be useful for estimating the mineralogy of the Earth's upper mantle. Received: 15 October 1994 / Accepted: 15 October 1995     

Phosphorus solubility mechanisms in haplogranitic aluminosilicate glass and melt: effect of temperature and aluminum content

The solubility behavior of phosphorus in glasses and melts in the system Na₂O-Al₂O₃-SiO₂-P₂O₅ has been examined as a function of temperature and Al₂O₃ content with microRaman spectroscopy. The Al₂O₃ was added (2, 4, 5, 6, and 8 mol% Al₂O₃) to melts with 80 mol% SiO₂ and ∼2 mol% P₂O₅. The compositions range from peralkaline, via meta-aluminous to peraluminous. Raman spectra were obtained of both the phosphorus-free and phosphorous-bearing glasses and melts between 25 and 1218 °C. The Raman spectrum of Al-free, P-bearing glass exhibits a characteristic strong band near 940 cm⁻¹ assigned to P=O stretching in orthophosphate complexes together with a weaker band near 1000 cm⁻¹ assigned P₂O₇ complexes. With increasing Al content, the proportion of P₂O₇ initially increases relative to PO₄ and is joined by AlPO₄ complexes which exhibit a characteristic P-O stretch mode slightly above 1100 cm⁻¹. The latter complex appears to dominate in meta-aluminosilicate glass and is the only phosphate complex in peraluminous glasses. When P-bearing peralkaline silicate and aluminosilicate glasses are transformed to supercooled melts, there is a rapid decrease in PO₄/P₂O₇ so that in the molten state, PO₄ units are barely discernible. The P₂O₇/AlPO₄ abundance ratio in peralkaline compositions increases with increasing temperature. This decrease in PO₄/P₂O₇ with increasing temperature results in depolymerization of the silicate melts. Dissolved P₂O₅ in peraluminous glass and melts forms AlPO₄ complexes only. This solution mechanism has no discernible influence on the aluminosilicate melt structure. There is no effect of temperature on this solution mechanism. Received: 7 October 1997 / Accepted: 11 May 1998     

Sr isotope systematics during melt generation by intrusion of basalt into continental crust

We have studied the Sr isotopic composition of partial melts of biotite granite generated experimentally and by intrusion of basalt into the Sierra Nevada Batholith. The experiments employed large, 3-cm cubes of granite to duplicate natural grain-boundary textures and were performed in air over the temperature interval 1000–1250 °C, to simulate basalt-induced wall rock and xenolith melting in the shallow crust. In both the experimental and natural analogs, fusion of plagioclase + alkali-feldspar ± quartz and biotite + plagioclase ± quartz results in the formation of colorless and brown melt (quenched to glass) respectively. Accordant with this melting behavior, brown glasses are enriched in radiogenic Sr and MgO, FeO, CaO, and TiO₂ relative to colorless glasses. These results support recent studies indicating that the isotopic compositions of crustal melts can reflect the relative contributions of mineral phases entering the melt, rather than the isotopic composition of the bulk source rock. In addition, we show that at shallow-crustal conditions preferential breakdown of biotite leads to initial high-⁸⁷Sr/⁸⁶Sr, low-Sr concentration melts. However, as the degree of melting increases, melts become less radiogenic yet are more enriched in elemental Sr due to loss of biotite from the restite and increased consumption of feldspars. Our results therefore suggest, if partial melts of granitic crust segregate rapidly during episodic magmatic underplating, successive melt batches can evolve from high-⁸⁷Sr/⁸⁶Sr to low-⁸⁷Sr/⁸⁶Sr liquids as melting progresses. Received: 25 August 1998 / Accepted: 10 March 1999     

Magmatic infiltration and melting in the lower crust and upper mantle beneath the Cima volcanic field,California

 Xenoliths of lower crustal and upper mantle rocks from the Cima volcanic field (CVF) commonly contain glass pockets, veins, and planar trains of glass and/or fluid inclusions in primary minerals. Glass pockets occupy spaces formerly occupied by primary minerals of the host rocks, but there is a general lack of correspondence between the composition of the glass and that of the replaced primary minerals. The melting is considered to have been induced by infiltration of basaltic magma and differentiates of basaltic magma from complex conduits formed by hydraulic fracturing of the mantle and crustal rocks, and to have occurred during the episode of CVF magmatism between ∼7.5 Ma and present. Variable compositions of quenched melts resulted from mixing of introduced melts and products of melting of primary minerals, reaction with primary minerals, partial crystallization, and fractionation resulting from melt and volatile expulsion upon entrainment of the xenoliths. High silica melts ( >∼60% SiO₂) may result by mixing introduced melts with siliceous melts produced by reaction of orthopyroxene. Other quenched melt compositions range from those comparable to the host basalts to those with intermediate Si compositions and elevated Al, alkalis, Ti, P, and S; groundmass compositions of CVF basalts are consistent with infiltration of fractionates of those basalts, but near-solidus melting may also contribute to formation of glass with intermediate silica contents with infiltration only of volatile constituents. Received: 15 June 1995 / Accepted: 13 December 1995     

Primordial compositions of refractory inclusions

Bulk chemical and O-, Mg- and Si-isotopic compositions were measured for each of 17 Types A and B refractory inclusions from CV3 chondrites. After bulk chemical compositions were corrected for non-representative sampling in the laboratory, the Mg- and Si-isotopic compositions of each inclusion were used to calculate its original chemical composition assuming that the heavy-isotope enrichments of these elements are due to Rayleigh fractionation that accompanied their evaporation from CMAS liquids. The resulting pre-evaporation chemical compositions are consistent with those predicted by equilibrium thermodynamic calculations for high-temperature nebular condensates, but only if different inclusions condensed from nebular regions that ranged in total pressure from 10⁻⁶ to 10⁻¹ bar, regardless of whether they formed in a system of solar composition or in one enriched in dust of ordinary chondrite composition relative to gas by a factor of 10 compared to solar composition. This is similar to the range of total pressures predicted by dynamic models of the solar nebula for regions whose temperatures are in the range of silicate condensation temperatures. Alternatively, if departure from equilibrium condensation and/or non-representative sampling of condensates in the nebula occurred, the inferred range of total pressure could be smaller. Simple kinetic modeling of evaporation successfully reproduces observed chemical compositions of most inclusions from their inferred pre-evaporation compositions, suggesting that closed-system isotopic exchange processes did not have a significant effect on their isotopic compositions. Comparison of pre-evaporation compositions with observed ones indicates that 80% of the enrichment in refractory CaO + Al₂O₃ relative to more volatile MgO + SiO₂ is due to initial condensation and 20% due to subsequent evaporation for both Types A and B inclusions.     

Petrological constraints on the cooling history of high-temperature garnet peridotite massifs in lower Austria

High-temperature peridotite massifs occur as lensoid bodies with high-pressure granulites in the southern Bohemian massif. In lower Austria the peridotites comprise garnet lherzolites lacking primary spinel, rare garnet and garnet-spinel harzburgites, and harzburgites containing Cr-rich primary spinel instead of garnet. These phase assemblages suggest initial high-pressure equilibration and are consistent with results from garnet-orthopyroxene geobarometry indicating equilibration at around 3–3.5 GPa. Maximum temperature estimates obtained on core compositions of coexisting minerals from the peridotites are not higher than ca. 1100 °C. In contrast, pyroxene megacryst compositions, garnet exsolution textures in the garnet pyroxenites, and results from geothermometry indicate much higher original equilibration temperatures in most of the pyroxenites (up to 1400 °C). High temperatures, modal zoning, the occasional presence of Mg-rich garnetites and chemical evidence suggest that the pyroxenites are cumulates which crystallized from low-degree melts derived from the sub-lithospheric mantle. Isothermal interpolation of the high temperatures to an upper mantle adiabat suggests that the melts were derived from a minimum depth of 180–200 km. The formation of small garnet II grains and garnet exsolution lamellae in the pyroxenites and pyroxene megacrysts may reflect isobaric cooling of the cumulates from temperatures above 1400 °C to ca. 1100–1200 °C (at 3–3.5 GPa) to approach the ambient lithospheric isotherm. This model differs from other models in which the formation of garnet II was explained by an increase in pressure during cooling in a subduction zone. Isobaric cooling was followed by near-isothermal decompression from 3–3.5 GPa to 1.5–2 GPa at 1000–1200 °C, as indicated by the increase of Al in pyroxenes near garnet. Further cooling in the spinel lherzolite stability field is indicated by spinel exsolution lamellae in pyroxenes from lherzolites. The formation of symplectites and kelyphites indicate sub-millimetre scale re-equilibration during exhumation in the course of the Carboniferous collision in the Bohemian massif. The peridotite massifs represent fragments of normal (non-cratonic) lithospheric mantle from a Paleozoic convergent plate margin. Received: 22 July 1996 / Accepted 28 February 1997