Crystallization rates of shock melts in three martian basalts: Experimental simulation with implications for meteoroid dimensions

Dynamic crystallization experiments have been performed on synthetic glasses representative of shock-generated melts observed in Los Angeles, Sayh al Uhaymir 150 and Dar al Gani 476 martian basalts. On the basis of qualitative (texture) and quantitative (fractal analysis) results, we show that melt pockets in Los Angeles cooled at a rate of 1040-1560 °C/h. Sayh al Uhaymir 150 and Dar al Gani 476 melt pockets cooled at 780 °C/h. Conductive cooling models, for a range of meteoroid diameters (10-50 cm), indicate that the minimum meteoroid diameter was small, on the order of 10-15 cm and that melt pockets cooled from post-shock temperatures within minutes. Our results also have bearing on shock implanted martian atmospheric components because it is during cooling that the melt pockets have the potential to lose gases. Modeling of argon diffusion in a spherical melt pocket indicates that during cooling and quench crystallization ∼4-60% of trapped martian atmospheric argon may be lost from the melt pocket through diffusive transport.     

Chromite in komatiites: 3D morphologies with implications for crystallization mechanisms

High-resolution X-ray computed tomography has been carried out on a suite of komatiite samples representing a range of volcanic facies, chromite contents and degrees of alteration and metamorphism, to reveal the wide range of sizes, shapes and degrees of clustering that chromite grains display as a function of cooling history. Dendrites are spectacularly skeletal chromite grains formed during very rapid crystallization of supercooled melt in spinifex zones close to flow tops. At slower cooling rates in the interiors of thick flows, chromite forms predominantly euhedral grains. Large clusters (up to a dozen of grains) are characteristic of liquidus chromite, whereas fine dustings of mostly individual ~20-μm grains form by in situ crystallization from trapped intercumulus liquid. Chromite in coarse-grained olivine cumulates from komatiitic dunite bodies occurs in two forms: as clusters or chains of euhedral crystals, developing into “chicken-wire” texture where chromite is present in supra-cotectic proportions; and as strongly dendritic, semi-poikilitic grains. These dendritic grains are likely to have formed by rapid crescumulate growth from magma that was close to its liquidus temperature but supersaturated with chromite. In some cases, this process seems to have been favoured by nucleation of chromite on the margins of sulphide liquid blebs. This texture is a good evidence for the predominantly cumulus origin of oikocrysts and in situ origin of heteradcumulate textures. Our 3D textural analysis confirms that the morphology of chromite crystals is a distinctive indicator of crystallization environment even in highly altered rocks.     

Early Palaeozoic sub-arc chromitite-bearing peridotite in the Kudi ophiolite on the westernmost Tibetan Plateau

ABSTRACT

A chromite deposit was discovered in the Kudi ophiolite in the Palaeozoic western Kunlun orogenic belt. Chromite forms elongated (<2 m in width) and banded chromitite bodies (<0.1 m in width for each band) in dunite and podiform chromitite bodies (<1.5 m in width) in harzburgite. Dunite is classified into two types. Type I dunite hosting massive and banded chromitites shows low Fo in olivine (88.1–90.9), moderate Cr^# [=Cr/(Cr + Al), 0.47–0.56] in chromite, and a positively sloped primitive mantle-normalized platinum group elements (PGE) pattern, suggesting that it is a cumulate of a mafic melt. Harzburgite and type II dunite show olivine with high Fo (>91.1) and chromite with moderate to high Cr^# (0.44–0.61), and flat to negatively sloped primitive mantle-normalized PGE patterns, indicating that they are residual mantle peridotite after partial melting. Chromite in all three types of chromitites has relatively uniform moderate values Cr^# ranging from 0.43 to 0.56. Massive chromitite contains euhedral chromite with high TiO₂ (0.40–0.43 wt.%) and has a positively sloped primitive mantle-normalized PGE pattern, suggesting that it represents a cumulate of a melt. Rocks containing disseminated and banded chromite show overall low total PGE, < 117 ppb, and a negatively sloped primitive mantle-normalized PGE pattern. Chromite grains in these two types of occurrences are irregular in shape and enclose olivine grains, suggesting that chromite formed later than olivine. We suggest that chromite-oversaturated melt penetrated into the pre-existing dunite and crystallized chromite. The oxygen fugacity (fO₂ values of chromitites and peridotites are high, ranging from FMQ+0.8 (0.8 logarithmic unit above the fayalite-magnetite-quartz buffer) to FMQ+2.3 for chromitites and from FMQ+0.9 to FMQ+2.8 for peridotites (dunite and harzburgite). The mineral compositions and high fO₂ values as well as estimated parental magma compositions of the chromitites suggest that the Kudi ophiolite formed in a sub-arc setting.     

Martian regolith in Elephant Moraine 79001 shock melts? Evidence from major element composition and sulfur speciation

Shock veins and melt pockets in Lithology A of Martian meteorite Elephant Moraine (EETA) 79001 have been investigated using electron microprobe (EM) analysis, petrography and X-ray Absorption Near Edge Structure (XANES) spectroscopy to determine elemental abundances and sulfur speciation (S²⁻ versus S⁶⁺). The results constrain the materials that melted to form the shock glasses and identify the source of their high sulfur abundances. The XANES spectra for EETA79001 glasses show a sharp peak at 2.471 keV characteristic of crystalline sulfides and a broad peak centered at 2.477 keV similar to that obtained for sulfide-saturated glass standards analyzed in this study. Sulfate peaks at 2.482 keV were not observed. Bulk compositions of EETA79001 shock melts were estimated by averaging defocused EM analyses. Vein and melt pocket glasses are enriched in Al, Ca, Na and S, and depleted in Fe, Mg and Cr compared to the whole rock. Petrographic observations show preferential melting and mobilization of plagioclase and pyrrhotite associated with melt pocket and vein margins, contributing to the enrichments. Estimates of shock melt bulk compositions obtained from glass analyses are biased towards Fe- and Mg- depletions because, in general, basaltic melts produced from groundmass minerals (plagioclase and clinopyroxene) will quench to a glass, whereas ultramafic melts produced from olivine and low-Ca pyroxene megacrysts crystallize during the quench. We also note that the bulk composition of the shock melt pocket cannot be determined from the average composition of the glass but must also include the crystals that grew from the melt - pyroxene (En_72-75Fs_20-21Wo_5-7) and olivine (Fo_75-80). Reconstruction of glass + crystal analyses gives a bulk composition for the melt pocket that approaches that of lithology A of the meteorite, reflecting bulk melting of everything except xenolith chromite.Our results show that EETA79001 shock veins and melt pockets represent local mineral melts formed by shock impedance contrasts, which can account for the observed compositional anomalies compared to the whole rock sample. The observation that melts produced during shock commonly deviate from the bulk composition of the host rock has been well documented from chondrites, rocks from terrestrial impact structures and other Martian meteorites. The bulk composition of shock melts reflects the proportions of minerals melted; large melt pockets encompass more minerals and approach the whole rock whereas small melt pockets and thin veins reflect local mineralogy. In the latter, the modal abundance of sulfide globules may reach up to 15 vol%. We conclude the shock melt pockets in EETA79001 lithology A contain no significant proportion of Martian regolith.     

Petrogenesis of olivine-phyric shergottite Yamato 980459, revisited

Primitive magmas provide critical information on mantle sources, but most Martian meteorites crystallized from fractionated melts. An olivine-phyric shergottite, Yamato 980459 (Y-980459), has been interpreted to represent a primary melt, because its olivine megacrysts have magnesian cores (Fo84-86) that appear to be in equilibrium with the Y-980459 whole-rock composition based on Fe-Mg partitioning. However, crystal size distribution (CSD) plots for Y-980459 olivines show a size gap, suggesting a cumulus origin for some megacrysts. Because melting experiments using the Y-980459 whole-rock composition have been used to infer the thermal structure and volatile contents of the Martian mantle, the interpretation that this rock is primitive should be scrutinized.We report major, minor and trace element compositions of Y-980459 olivines and compare them with results from melting experiments (both hydrous and anhydrous) and thermodynamic calculations. Cores of the olivine megacrysts have major and minor element contents identical to those of the most magnesian olivines from the experiments, but they differ slightly from those of thermodynamic calculations. This is probably because the Y-980459 whole-rock composition lies near the limit of the range of liquids used to calibrate these models. The megacryst cores (Fo80-85) exhibit minor and trace element (Mn-Ni-Co-Cr-V) characteristics distinct from other olivines (megacryst rims and groundmass olivines, Fo < 80), implying that the megacryst cores crystallized under more reduced conditions (∼IW + 1).Y-980459 contains pyroxenes with orthopyroxene cores mantled by pigeonite and augite. We also found some reversely zoned pyroxenes that have augite cores (low-Mg#) mantled by orthopyroxenes (high-Mg#), although they are uncommon. These reversely zoned pyroxenes are interpreted to have grown initially as atoll-like crystals with later crystallization filling in the hollow centers, implying disequilibrium crystallization at a moderate cooling rate (3-7 °C/h). The calculated REE pattern of a melt in equilibrium with normally zoned pyroxene is parallel to those of glass and the Y-980459 whole-rock as well as other depleted olivine-phyric shergottites, suggesting that Y-980459 was derived from a depleted mantle reservoir.Considering the CSD patterns of Y-980459 olivines, we propose that the olivine megacrysts are cumulus crystals which probably formed in a feeder conduit by continuous melt replenishment, and the parent melt composition was indistinguishable from the Y-980459 whole-rock with 0-2 wt% of H₂O and 0-5 wt% of CO₂. The final magma pulse entrained these cumulus olivines and then crystallized groundmass olivines and pyroxenes. Although Y-980459 contains small amounts of cumulus olivine (<∼6 vol%), we conclude that the Y-980459 whole-rock composition closely approximates a Martian primary melt composition.     

Gold solubility in oxidized and reduced, water-saturated mafic melt

We have performed experiments to evaluate Au solubility in natural, water-saturated basaltic melts as a function of oxygen fugacity. Experiments were carried out at 1000 °C and 200 MPa, and oxygen fugacity was controlled at the fayalite-magnetite-quartz (FMQ) oxygen fugacity buffer and FMQ + 4. All experiments were saturated with a metal-chloride aqueous solution loaded initially as a 10 wt% NaCl eq. fluid. The stable phase assemblage at FMQ consists of basalt melt, olivine, clinopyroxene, a single-phase aqueous fluid, and metallic Au. The stable phase assemblage at FMQ + 4 consists of basalt melt, clinopyroxene, magnetite-spinel solid solution, a single-phase aqueous fluid, and metallic Au. Silicate glasses (i.e., quenched melt) and their contained crystalline material were analyzed by using both electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Measured Au concentrations in the quenched melt range from 4.8 μg g⁻¹ to 0.64 μg g⁻¹ at FMQ + 4, and 0.54 μg g⁻¹ to 0.1 μg g⁻¹ at FMQ. The measured solubility of Au in olivine and clinopyroxene was consistently below the LA-ICP-MS limit of detection (i.e., 0.1 μg g⁻¹). These melt solubility data place important limitations on the dissolved Au content of water-saturated, Cl- and S-bearing basaltic liquids at geologically relevant fO₂ values. The new data are compared to published, experimentally-determined values for Au solubility in dry and hydrous silicate liquids spanning the compositional range from basalt to rhyolite, and the effects of melt composition, oxygen fugacity, pressure and temperature are discussed.     

An absarokite from a phlogopite lherzolite source

An absarokite (SiO₂ 47.72 wt %, K₂O 3.41 wt %) occurs in the Katamata volcano, SW Japan. The rock carries phenocrysts of olivine, phlogopite, clinopyroxene, and hornblende. Chemical compositions of bulk rock (FeO^*/ MgO 0.73) and minerals (Mg-rich olivine and phlogopite, Cr-rich chromite) suggest that the absarokite is not differentiated. Melting experiments at high pressures on the Katamata absarokite have been conducted. The completely anhydrous absarokite melt coexists with olivine, orthopyroxene, and clinopyroxene at 1310° C and 1.0 GPa. The melt with 3.29 wt % of H₂O also coexists with the above three phases at 1230° C and 1.4 GPa; phlogopite appears at temperatures more than 80° C below the liquidus. On the other hand, the melt is not saturated with lherzolite minerals in the presence of 5.13 wt % of H₂O and crystallizes olivine and phlogopite as liquidus phases; the stability limit of phlogopite is little affected at least by the present variation of H₂O content in the absarokite melt. It is suggested that the absarokite magma was segregated from the upper mantle at 1170° C and 1.7 GPa leaving a phlogopite lherzolite as a residual material on the basis of the above experimental results and the petrographical observation that olivine and phlogopite crystallize at an earlier stage of crystallization sequence than clinopyroxene. The contribution of phlogopite at the stage of melting processes is also suggested by the geochemical characteristics that the absarokite is more enriched in Rb, K, and Ba and depleted in Ca and Na than a typical alkali olivine basalt from the same volcanic field.     

Crystallization of Chromite and Chromium Solubility in Basaltic Melts

The equilibrium between chromite and melt has been determinedon four basalts at temperatures of 1200–1400?C over arange of oxygen fugacity (f_o2) and pressures of 1 atm and 10kb. The Cr content of chromite-saturated melts at 1300?C and1 atm ranges from 0?05 wt.% Cr₂O₃ at a log f_o2= –3 to1?4 wt.% at a log f_o2=–12?8. The Cr²⁺/Cr³⁺ of melt increaseswith decreasing f_o2 and is estimated by assuming a constantpartitioning of Cr³⁺ between chromite and melt at constant temperature.The estimated values of Cr²⁺/Cr³⁺ in the melt are at f_o2 valuesof 4–5 orders of magnitude lower than the equivalent Fe²⁺/Fe³⁺values. The Cr/(Cr+Al) of chromite coexisting with melt at constanttemperature changes little with variation of f_o2 below log f_o2=–6.Five experiments at 10 kb indicate that Cr₂O₃ dissolved in themelt is slightly higher and the Cr/(Cr + Al) of coexisting chromiteis slightly lower than experiments at 1 atm pressure. Thus variationin total pressure cannot explain the large variations of Cr/(Cr+ Al) that are common to mid-ocean ridge basalt (MORB) chromite. Experiments on a MORB at 1 atm at f_o2 values close to fayalite-magnetite-quartz(FMQ) buffer showed that the Al₂O₃ content of melt is highlysensitive to the crystallization or melting of plagioclase,and consequently coexisting chromite shows a large change inCr/(Cr + Al). It would appear, therefore, that mixing of a MORBmagma containing plagioclase with a hotter MORB magma undersaturatedin plagioclase may give rise to the large range of Cr/(Cr +Al) observed in some MORB chromite.     

Temperature dependence of sulfide and sulfate solubility in olivine-saturated basaltic magmas

The sulfur concentration at pyrrhotite- and anhydrite-saturation in primitive hydrous basaltic melt of the 2001-2002 eruption of Mt. Etna was determined at 200 MPa, T = 1050-1250 °C and at log fO₂ from FMQ to FMQ+2.2 (FMQ is Fayalite-Magnetite-Quartz oxygen buffer). At 1050 °C Au sample containers were used. A double-capsule technique, using a single crystal olivine sample container closed with an olivine piston, embedded in a sealed Au₈₀Pd₂₀ capsule, was developed to perform experiments in S-bearing hydrous basaltic systems at T > 1050 °C. Pyrrhotite is found to be a stable phase coexisting with melt at FMQ-FMQ+0.3, whereas anhydrite is stable at FMQ+1.4-FMQ+2.2. The S concentration in the melt increases almost linearly from 0.12 ± 0.01 to 0.39 ± 0.02 wt.% S at FeS-saturation and from 0.74 ± 0.01 to 1.08 ± 0.04 wt.% S at anhydrite-saturation with T ranging from 1050-1250 °C. The relationships between S concentration at pyrrhotite and/or anhydrite saturation, MgO content of the olivine-saturated melt, T, and log fO₂ observed in this study and from previous data are used to develop an empirical model for estimating the magmatic T and fO₂ from the S and MgO concentrations of H₂O-bearing olivine-saturated basaltic melts. The model can also be used to determine maximum S concentrations, if fO₂ and MgO content of the melt are known. The application of the model to compositions of melt inclusions in olivines from Mt. Etna indicates that the most primitive magmas trapped in inclusions might have been stored at log fO₂ slightly higher than FMQ+1 and at T = 1100-1150 °C, whereas more evolved melts could have been trapped at T ? 1100 °C. These values are in a good agreement with the estimates obtained by other independent methods reported in the literature.     

Phase relations in silicic systems at one-atmosphere pressure

An important control on magma rheology is the extent to which the magma crystallizes during ascent as a result of the effective undercooling created by volatile exsolution. To assess this undercooling, we need to know the final (anhydrous) one-atmosphere phase relations of silicic magmas. For this reason, we have performed one-atmosphere controlled-fO₂ crystallization experiments on dacitic to rhyolitic melt compositions (67–78 wt% SiO₂) and determined equilibrium phase assemblages, melt fractions, and some phase compositions over a range of temperatures. Experiments were run at oxygen fugacities between NNO+1 and NNO+2 and temperatures of 1,000 to 1,250°C. Constant phase compositions and sample crystallinities in runs longer than 3.5 days suggest that these runs closely approached compositional equilibrium. Additionally, melting experiments with similar compositions yielded results closely resembling those obtained in crystallization experiments. All samples have liquidus temperatures between 1,250 and 1,200 °C, with plagioclase the liquidus phase for the two most mafic samples and quartz for the most silicic sample. When associated glass compositions are projected into the Qz-Ab-Or system they define a revised one-atmosphere quartz-feldspar cotectic 5–10% less quartz normative than previously estimated. Glass compositions from each sample plot along this cotectic between 1,100 and 1,000 °C, consistent with the plagioclase-quartz co-crystallization textures found in runs at these temperatures. This cotectic constrains glass compositions to a maximum silica content of 76±1 wt% SiO₂. Reported glass compositions in excess of 77 wt% SiO₂ in volcanic samples suggest non-equilibrium crystallization, perhaps a consequence of large melt undercoolings.Editorial responsibility: I. Carmichael     

Formation conditions of aluminum-rich chondrules

We have studied the formation conditions of Al-rich chondrules by doing isothermal and dynamic crystallization experiments at one atmosphere on four different chondrule analogue compositions within the pure CaO-MgO-Al₂O₃-SiO₂ system. For the dynamic crystallization experiments, we cooled from both liquidus and subliquidus peak temperatures (T_max), at cooling rates from 5-1000 °C/h. The starting compositions include two with anorthite and two with forsterite as the dominant liquidus phases, all at or near spinel-saturation. One of each pair evolves towards diopside crystallization, and the others cordierite or enstatite crystallization, giving a total of four completely different crystallization sequences analogous to the four basic varieties of Al-rich chondrule recently proposed. Bulk composition is the main controlling factor, both in terms of mineralogy and texture. The textures of the anorthite-rich compositions are more sensitive to T_max than they are to cooling rate, whereas the textures of the forsterite-rich compositions are more sensitive to cooling rate. Comparisons of natural Al-rich chondrules having similar compositions to our synthetic analogues indicate that the natural objects reflect a range of peak heating temperatures, ∼1400-1500 °C, and cooling rates of 10-500 °C/h for porphyritic chondrules and possibly higher (1000 °C/h) for barred chondrules. These conditions are consistent with the conditions inferred for ferromagnesian chondrules but differ from those inferred for some calcium-aluminum-rich inclusions.     

Mullite-corundum-spinel-cordierite-plagioclase xenoliths in the Skaergaard Marginal Border Group: multi-stage interaction between metasediments and basaltic magma

Metapelitic country rocks were contact- and pyro-metamorphosed by the Tertiary Skaergaard Intrusion, East Greenland. In an initial stage of heating, while they were probably still in place within the host rock contact aureole, they overstepped a range of equilibrium and disequilibrium melting reactions and produced both a granitic melt and very refractory spinel+cordierite+plagioclase±corundum residuals. Parts of these refractory rocks were then subjected to another melting event after being entrained as xenoliths into the Skaergaard Marginal Border Group, where they experienced a temperature of about 1,000°C at a pressure of about 650 bars and at an oxygen fugacity about 0.2–0.5 log units below the FMQ buffer. Here, they underwent bulk melting, but did not mix with the Skaergaard magma, presumably because of the high viscosity contrast. The Al-rich melts crystallized to an assemblage of corundum+mullite+sillimanite+ plagioclase+spinel+rutile±tridymite±cordierite and they reacted with the surrounding basalt producing a strongly cryptically zoned rim of plagioclase (An₅₅ close to the basalt to An₉₀ close to the Al-rich melt). The assemblage in the inner parts of the xenoliths provides textural evidence for disequilibrium growth due to slow diffusivities in the highly viscous, probably water-free Al-rich melt. Later interaction of lower temperature ferrobasaltic to granophyric melts with the xenoliths along their margins and along cracks led to consumption of corundum and mullite and to the stable assemblage of spinel+cordierite+plagioclase+quartz+K-feldspar +magnetite+ilmenite at about 800°C.     

Ti-content of high-Ca pyroxenes as a petrogenetic indicator: an experimental study of Mafic Alkaline Rocks from the Mt. Erebus volcanic region,Antarctica

We report chemical and mineralogical data for one atmosphere melting experiments conducted on alkalic rocks from the Mt. Erebus volcanic region: DVDP2 basanite, two hawaiites (DVDP2 and a nepheline-bearing variety), and an anorthoclase phonolite. Temperatures between 1,224 and 1,049°C were investigated at f_O2~QFM. DVDP2 basanite appears to be an intermediate pressure liquid or a cumulate, because only olivine coexists with melt from above 1,224–1,160°C. High-Ca pyroxene joins olivine in the crystallization sequence at 1,138°C. These minerals are joined by plagioclase at a temperature between 1,120 and 1,104°C. In contrast, DVDP2 hawaiite appears to be relatively evolved, because it is multiply saturated with olivine, plagioclase, and high-Ca pyroxene near its liquidus (between 1,120 and 1,104°C). Plagioclase crystallizes in the Ne-hawaiite by 1,160°C followed by olivine below 1,120°C. The liquidus of anorthoclase phonolite is between the lowest temperatures investigated, 1,089 and 1,049°C, and plagioclase is the liquidus mineral. Our results indicate that DVDP2 hawaiite can be derived from a DVDP2 basanitic parental magma by crystal fractionation at low pressures, that the nepheline hawaiite is an olivine cumulate, and that the liquids parental to the anorthoclase phonolite represent the end products of crystal fractionation. They also allow us to illustrate how the Ti-content of pyroxene may be used as a petrogenetic indicator of processes and events in the evolution of the Erebus volcanic system.     

The melting and crystallisation behaviour of a natural clinopyroxene-ilmenite intergrowth

The anhydrous solidus of a natural clinopyroxene-ilmenite intergrowth from the kimberlite pipe at Monastery was found to be 1300° C at 20 kb increasing to 1470 ° C at 47 kb. The slope of the solidus is 6 ° C/kb, with a constant melting interval of approximately 140 ° C. Clinopyroxene was the liquidus phase in all but one case, and the ilmenite-out curve coincided with the beginning of melting. Controlled cooling experiments resulted in liquidus clinopyroxene crystals surrounded by intergrowths of clinopyroxene and ilmenite. The experimental and natural intergrowths are texturally, crystallographically and chemically similar. These results support the view that the natural clinopyroxene-ilmenite intergrowths found in kimberlites are a product of eutectic crystallisation in the upper mantle. Compositional similarities between the liquidus clinopyroxene and discrete clinopyroxene nodules from kimberlite suggest that the latter are possibly related to the clinopyroxene-ilmenite intergrowths by fractional crystallisation. Differences between the temperatures of equilibration obtained for clinopyroxenes from the natural intergrowths, and the beginning of melting on the clinopyroxene-ilmenite join, may be the result of hydrous melting in the former case, or as a consequence of the natural intergrowths existing as mantle veins or pegmatites at the ambient temperature prior to their incorporation in the kimberlite.     

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.     

Crystallization, melt inclusion, and redox history of a Martian meteorite: Olivine-phyric shergottite Larkman Nunatak 06319

The Larkman Nunatak (LAR) 06319 olivine-phyric shergottite is composed of zoned megacrysts of olivine (Fo_76-55 from core to rim), pyroxene (from core to rim En₇₀Fs₂₅Wo₅, En₅₀Fs₂₅Wo₂₅, and En₄₅Fs₄₅Wo₁₀), and Cr-rich spinel in a matrix of maskelynite (An₅₂Ab₄₅), pyroxene (En_30-40Fs_40-55Wo_10-25,), olivine (Fo₅₀), Fe-Ti oxides, sulfides, phosphates, Si-rich glass, and baddeleyite. LAR 06319 experienced equilibration shock pressures of 30-35 GPa based on the presence of localized shock melts, mechanical deformation of olivine and pyroxene, and complete transformation of plagioclase to maskelynite with no relict birefringence. The various phases and textures of this picritic basalt can be explained by closed system differentiation of a shergottitic melt. Recalculated parent melt compositions obtained from melt inclusions located in the core of the olivine megacrysts (Fo_>72) resemble those of other shergottite parent melts and whole-rock compositions, albeit with a lower Ca content. These compositions were used in the MELTS software to reproduce the crystallization sequence. Four types of spinel and two types of ilmenite reflect changes in oxygen fugacity during igneous differentiation. Detailed oxybarometry using olivine-pyroxene-spinel and ilmenite-titanomagnetite assemblages indicates initial crystallization of the megacrysts at 2 log units below the Fayalite-Magnetite-Quartz buffer (FMQ - 2), followed by crystallization of the groundmass over a range of FMQ - 1 to FMQ + 0.3. Variation is nearly continuous throughout the differentiation sequence.LAR 06319 is the first member of the enriched shergottite subgroup whose bulk composition, and that of melt inclusions in its most primitive olivines, approximates that of the parental melt. The study of this picritic basalt indicates that oxidation of more than two log units of FMQ can occur during magmatic fractional crystallization and ascent. Some part of the wide range of oxygen fugacities recorded in shergottites may consequently be due to this process. The relatively reduced conditions at the beginning of the crystallization sequence of LAR 06319 may imply that the enriched shergottite mantle reservoir is slightly more reduced than previously thought. As a result, the total range of Martian mantle oxygen fugacities is probably limited to FMQ − 4 to − 2. This narrow range could have been generated during the slow crystallization of a magma ocean, a process favored to explain the origin of shergottite mantle reservoirs.     

Redox state of iron in peralkaline rhyolitic glass/melt: X-ray absorption micro-spectroscopy experiments at high temperature

Assessing the ferric-ferrous ratio in magmas prior to eruption remains a challenging task. X-ray absorption near-edge structure (μXANES) spectra were collected at the iron K-edge in water-rich peralkaline silicic melt/glass inclusions trapped in quartz. These experiments were carried out between 800 and 20 °C. The chemical environment of iron was also determined in the naturally quenched samples (glass inclusions and matrix glass) and in the peralkaline rhyolitic reference glasses, with variable [Fe³⁺ / ∑Fe] ratios.In the reference glasses, both the intensity of the pre-peaks (Fe²⁺, Fe³⁺) and site geometry of iron change as the oxidation state increases. Fourfold-coordinated Fe³⁺ prevails in highly oxidised peralkaline silicic glasses, using alkalis for charge balance. The position of the pre-edge centroid of the 1s-3d transition correlates with the Fe³⁺ / ΣFe ratios that allowed calibration of the redox state of iron of our natural samples.At high temperatures, Fe²⁺ dominates in the pre-edge structure of melt inclusions. Upon cooling down to 20 °C, the intensity of the Fe³⁺ peak increases, the centroid position of the pre-edge features shifts by nearly 0.5 eV and the main edge moves slightly towards higher energies. The slower the cooling rate, the higher the ferric iron contribution. Iterative μXANES experiments performed on the same samples show that the process is reversible. However, this apparent oxidation of iron upon cooling is an artefact of changes in Fe coordination. It implies that the [Fe³⁺ / ΣFe] ratio of glassy samples, measured at 20 °C, may be overestimated by a factor > 1.7, and that this ratio cannot be reliably retrieved by probing naturally cooled glass inclusions, and most silicate glasses. High temperature μXANES experiments led first to an assessment of the ferric-ferrous ratio in the water-rich peralkaline melt in pre-eruptive magmatic conditions and second to the determination of the corresponding oxygen fugacity at 740 °C.     

Subduction Influence on Oxygen Fugacity and Trace and Volatile Elements in Basalts Across the Cascade Volcanic Arc

Fluids or melts derived from a subducting plate are often citedas a mechanism for the oxidation of arc magmas. What remainsunclear is the link between the fluid, oxygen fugacity, andother major and trace components, as well as the spatial distributionof the impact of those fluids. To test the potential effectsof addition of a subduction-derived fluid or melt to the sub-arcmantle, olivine-hosted melt inclusions from primitive basalticlavas sampled from across the central Oregon Cascades (43°–45°N)have been analyzed for major, trace and volatile elements andfO₂. Oxygen fugacity was determined in melt inclusions fromsulfur speciation determined by electron microprobe and fromolivine–chromite oxygen geobarometry. The overall rangein fO₂ based on sulfur speciation measurements is from <–0·25log units to + 1·9 log units (FMQ, where FMQ is fayalite–magnetite–quartzbuffer). Oxygen fugacity is positively correlated with fluid-mobiletrace element and light rare earth element contents in basaltsgenerated by relatively low-degree partial melting. Establishinga further correlation between fO₂ and fluid-mobile trace elementabundances with position along the arc requires the basaltsto be subdivided into shoshonitic, calc-alkaline, low-K tholeiiteand enriched intraplate basalt groups. Melt inclusions fromenriched intraplate and shoshonitic lavas show increasing fO₂and trace element abundances closer to the trench, whereas calc-alkalinemelt inclusions exhibit no significant across-arc variations.Low-K tholeiitic melt inclusions record an increase in incompatibletrace elements closer to the trench; however, there is no correlatedincrease in fO₂. The correlation observed in enriched intraplateand shoshonitic melt inclusions is interpreted to reflect aprogressively greater proportion of a fluid-rich, oxidized subductioncomponent in magmas generated nearer the subduction zone. Significantly,calc-alkaline melt inclusions with high ratios of large ionlithophile elements to high field strength elements, characteristicof ‘typical’ arc magmas, have oxidation states indistinguishablefrom low-K tholeiite and enriched intraplate basalt melt inclusions.The lack of across-arc geochemical variation in calc-alkalinemelt inclusions may suggest that these basalts are not necessarilythe most appropriate magmas for examining recent addition ofa subduction component to the sub-arc mantle. Flux and batchmelt model results produce a wide range of predicted amountsof melting and subduction component added to the mantle source;however, general trends characterized by increased melting andproportion of the subduction component from enriched intraplate,to low-K tholeiite, to calc-alkaline are robust. The model resultsdo not require enriched intraplate, low-K tholeiite and calc-alkalinemagmas to be produced from the same more fertile mantle source.However, enriched intraplate magmas, in contrast to calc-alkalineand low-K tholeiite magmas, cannot be generated from a depletedmantle source. Flux or batch melting of either the more fertileor depleted mantle sources used to generate the low-K tholeiite,calc-alkaline, and enriched intraplate magmas cannot reproduceshoshonitic compositions, which require a significantly depletedmantle source strongly metasomatized by a subduction component.The potential mantle source for shoshonitic basalts has a predictedfO₂ (after oxidation) from + 0·3 to + 2·4 logunits (FMQ) whereas the mantle source for low-K tholeiite, calc-alkaline,and enriched intraplate magmas may range from –1·1to + 0·7 log units (FMQ). KEY WORDS: basalt; Cascades; melt inclusions; oxidation state; volatiles     

Melting equilibria in multicomponent systems and liquidus/solidus convergence in mantle peridotite

The melting of undepleted mantle peridotite proceeds through a temperature interval which decreases with increasing pressure. If liquidus and solidus actually meet in the range 100–150 Kb, as suggested by Herzberg (1983), peridotite must transform there directly to a melt of its own composition. Thermodynamic analysis shows that such a liquidus/solidus meeting would be very unlikely in a system as chemically complex as mantle peridotite and would require that unanticipated phase equilibrium relations suppress all incongruent melting behavior. But Takahashi and Scarfe's (1985) preliminary experiments suggest that the upper mantle itself may indeed have a special composition with respect to phase equilibrium relations between liquids and solids at very high pressure. If so, mantle peridotite composition cannot be generated as a crystal accumulate or melting residue, because these two popular theories of origin are difficult to reconcile with a supposed eutecticlike composition. If upper mantle peridotite were itself a solidified liquid composition produced either as a partial melt or, more likely, as a crystallization residue of some more primitive melt composition representative of the whole mantle, an approach of liquidus to solidus might be expected at high pressure although the phase relations of Herzberg (1983) and Herzberg and O'Hara (1985) remain implausible.     

Dynamic crystallization of chondrule melts of porphyritic and radial pyroxene composition

Dynamic crystallization experiments in which heterogeneous nucleation is an important variable have been completed on four melts of chondrule composition. Compositions were chosen to best represent chondrules with porphyritic pyroxene and radial pyroxene textures. Experimental results show that heterogeneous nucleation is essential for the formation of porphyritic textures. Without preexisting nuclei, too much supercooling is established before crystallization is initiated and the textures are more likely to be dendritic or radial. In the near total absence of nuclei, radial textures can form at cooling rates as slow as 5°C/hr in this study. By varying the heterogeneous nucleation conditions and having a melt in which the appropriate phases are stable or metastable, analogs to most of the recognized chondrule textures can be produced in a single melt composition. Olivine inclusions in pyroxene can form readily during an experiment from a starting material which did not initially contain olivine crystals. Thus care must be taken in the assumption that olivine inclusions in pyroxene represent preexisting crystals.