Depths of Partial Crystallization of H2O-bearing MORB: Phase Equilibria Simulations of Basalts at the MAR near Ascension Island (7 11{degrees}S)

Phase equilibria simulations were performed on naturally quenchedbasaltic glasses to determine crystallization conditions priorto eruption of magmas at the Mid-Atlantic Ridge (MAR) east ofAscension Island (7–11°S). The results indicate thatmid-ocean ridge basalt (MORB) magmas beneath different segmentsof the MAR have crystallized over a wide range of pressures(100–900 MPa). However, each segment seems to have a specificcrystallization history. Nearly isobaric crystallization conditions(100–300 MPa) were obtained for the geochemically enrichedMORB magmas of the central segments, whereas normal (N)-MORBmagmas of the bounding segments are characterized by polybariccrystallization conditions (200–900 MPa). In addition,our results demonstrate close to anhydrous crystallization conditionsof N-MORBs, whereas geochemically enriched MORBs were successfullymodeled in the presence of 0·4–1 wt% H₂O in theparental melts. These estimates are in agreement with direct(Fourier transform IR) measurements of H₂O abundances in basalticglasses and melt inclusions for selected samples. Water contentsdetermined in the parental melts are in the range 0·04–0·09and 0·30–0·55 wt% H₂O for depleted and enrichedMORBs, respectively. Our results are in general agreement (within±200 MPa) with previous approaches used to evaluate pressureestimates in MORB. However, the determination of pre-eruptiveconditions of MORBs, including temperature and water contentin addition to pressure, requires the improvement of magma crystallizationmodels to simulate liquid lines of descent in the presence ofsmall amounts of water. KEY WORDS: MORB; Mid-Atlantic Ridge; depth of crystallization; water abundances; phase equilibria calculations; cotectic crystallization; pressure estimates; polybaric fractionation     

Experimental constraints on ultrapotassic magmatism from the Bohemian Massif (durbachite series, Czech Republic)

The equilibrium phase relations of a mafic durbachite (53 wt.% SiO₂) from the Třebíč pluton, representative of the Variscan ultrapotassic magmatism of the Bohemian Massif (338–335 Ma), have been determined as a function of temperature (900–1,100°C), pressure (100–200 MPa), and H₂O activity (1.1–6.1 wt.% H₂O in the melt). Two oxygen fugacity ranges were investigated: close to the Ni–NiO (NNO) buffer and 2.6 log unit above NNO buffer (∆NNO + 2.6). At 1,100°C, olivine is the liquidus phase and co-crystallized with phlogopite and augite at 1,000°C for the whole range of investigated pressure and water content in the melt. At 900°C, the mineral assemblage consists of augite and phlogopite, whereas olivine is not stable. The stability field of both alkali feldspar and plagioclase is restricted to low pressure (100 MPa) at nearly water-saturated conditions (<3–4 wt.% H₂O) and T < 900°C. A comparison between experimental products and natural minerals indicates that mafic durbachites have a near-liquidus assemblage of olivine, augite, Ti-rich phlogopite, apatite and zircon, followed by alkali feldspar and plagioclase, similar to the mineral assemblage of minette magma. Natural amphibole, diopside and orthopyroxene were not reproduced experimentally and probably result from sub-solidus reactions, whereas biotite re-equilibrated at low temperature. The crystallization sequence olivine followed by phlogopite and augite reproduces the sequence inferred in many mica-lamprophyre rocks. The similar fractionation trends observed for durbachites and minettes indicate that mafic durbachites are probably the plutonic equivalents of minettes and that K- and Mg-rich magmas in the Bohemian Massif may have been generated from partial melting of a phlogopite–clinopyroxene-bearing metasomatized peridotite. Experimental melt compositions also suggest that felsic durbachites can be generated by simple fractionation of a more mafic parent and mixing with mantle-derived components at mid crustal pressures.     

Electron Probe Microanalysis of Bromine in Minerals and Glasses with Correction for Spectral Interference from Aluminium,and Comparison with Microbeam Synchrotron X‐Ray Fluorescence Spectrometry

The strong spectral interference between Br‐ and Al‐induced X‐ray lines hampers the utilisation of electron probe microanalysis (EPMA) for measuring Br mass fractions in Al‐bearing minerals and glasses. Through measuring Br‐free Al‐bearing materials, we established an EPMA method to quantify the overlap from AlKα on BrLβ, which can be expressed as a linear function of the Al₂O₃ content. The count rate of the BrLβ peak signal was enhanced by high beam currents and long measurement times. Application of this EPMA method to Al‐ and Br‐bearing materials, such as sodalite and scapolite, and to five experimental glasses yielded Br mass fractions (in the range of 250–4000 μg g^?1) that are consistent with those measured by microbeam synchrotron X‐ray fluorescence (μ‐SXRF) spectrometry. The EPMA method has an estimated detection limit of ~ 100–300 μg g^?1. We propose that this method is useful for measuring Br mass fractions (hundreds to thousands of μg g^?1) in Al‐bearing minerals and glasses, including those produced in Br‐doped experiments. In addition, the natural marialitic scapolite (ON70) from Mpwapwa (Tanzania) containing homogeneously distributed high mass fractions of Br (2058 ± 56 μg g^?1) and Cl (1.98 ± 0.03% m/m) is an ideal reference material for future in situ analyses.     

The Blacktail Creek Tuff: an analytical and experimental study of rhyolites from the Heise volcanic field,Yellowstone hotspot system

The magma storage conditions of the 6.62 Ma Blacktail Creek Tuff eruption, belonging to the Heise volcanic field (6.62–4.45 Ma old) of the Yellowstone hotspot system, have been investigated by combining thermobarometric and experimental approaches. The results from different geothermometers (e.g., Fe–Ti oxides, feldspar pairs, apatite and zircon solubility, and Ti in quartz) indicate a pre-eruptive temperature in the range 825–875 °C. The temperature estimated using two-pyroxene pairs varies in a range of 810–950 °C, but the pyroxenes are probably not in equilibrium with each other, and the analytical results of melt inclusion in pyroxenes indicate a complex history for clinopyroxene, which hosts two compositionally different inclusion types. One natural Blacktail Creek Tuff rock sample has been used to determine experimentally the equilibrium phase assemblages in the pressure range 100–500 MPa and a water activity range 0.1–1.0. The experiments have been performed at fluid-present conditions, with a fluid phase composed of H₂O and CO₂, as well as at fluid-absent conditions. The stability of the quartzo-feldspathic phases is similar in both types of experiments, but the presence of mafic minerals such as biotite and clinopyroxene is strongly dependent on the experimental approach. Possible explanations are given for this discrepancy which may have strong impacts on the choice of appropriate experimental approaches for the determination of magma storage conditions. The comparison of the composition of natural phases and of experimentally synthesized phases confirms magma storage temperatures of 845–875 °C. Melt water contents of 1.5–2.5 wt% H₂O are required to reproduce the natural Blacktail Creek Tuff mineral assemblage at these temperatures. Using the Ti-in-quartz barometer and the Qz–Ab–Or proportions of natural matrix glasses, coexisting with quartz, plagioclase and sanidine, the depth of magma storage is estimated to be in a pressure range between 130 and 250 MPa.     

Experimental study into the petrogenesis of crystal-rich basaltic to andesitic magmas at Arenal volcano

Arenal volcano is nearly unique among arc volcanoes with its 42 year long (1968–2010) continuous, small-scale activity erupting compositionally monotonous basaltic andesites that also dominate the entire, ~7000 year long, eruptive history. Only mineral zoning records reveal that basaltic andesites are the result of complex, open-system processes deriving minerals from a variety of crystallization environments and including the episodic injections of basalt. The condition of the mafic input as well as the generation of crystal-rich basaltic andesites of the recent, 1968–2010, and earlier eruptions were addressed by an experimental study at 200 MPa, 900–1,050 °C, oxidizing and fluid-saturated conditions with various fluid compositions [H₂O/(H₂O + CO₂) = 0.3–1]. Phase equilibria were determined using a phenocryst-poor (~3 vol%) Arenal-like basalt (50.5?wt% SiO₂) from a nearby scoria cone containing olivine (Fo₉₂), plagioclase (An₈₆), clinopyroxene (Mg# = 82) and magnetite (X_ulvö = 0.13). Experimental melts generally reproduce observed compositional trends among Arenal samples. Small differences between experimental melts and natural rocks can be explained by open-system processes. At low pressure (200 MPa), the mineral assemblage as well as the mineral compositions of the natural basalt were reproduced at 1,000 °C and high water activity. The residual melt at these conditions is basaltic andesitic (55 wt% SiO₂) with 5 wt% H₂O. The evolution to more evolved magmas observed at Arenal occurred under fluid-saturated conditions but variable fluid compositions. At 1,000 °C and 200 MPa, a decrease of water content by approximately 1 wt% induces significant changes of the mineral assemblage from olivine + clinopyroxene + plagioclase (5 wt% H₂O in the melt) to clinopyroxene + plagioclase + orthopyroxene (4 wt% H₂O in the melt). Both assemblages are observed in crystal-rich basalt (15 vol%) and basaltic andesites. Experimental data indicate that the lack of orthopyroxene and the presence of amphibole, also observed in basaltic andesitic tephra units, is due to crystallization at nearly water-saturated conditions and temperatures lower than 950 °C. The enigmatic two compositional groups previously known as low- and high-Al₂O₃ samples at Arenal volcano may be explained by low- and high-pressure crystallization, respectively. Using high-Al as signal of deeper crystallization, first magmas of the 1968–2010 eruption evolved deep in the crust and ascent was relatively fast leaving little time for significant compositional overprint by shallower level crystallization.     

Storage conditions of Bezymianny Volcano parental magmas: results of phase equilibria experiments at 100 and 700 MPa

The crystallization sequence of a basaltic andesite from Bezymianny Volcano, Kamchatka, Russia, was simulated experimentally at 100 and 700 MPa at various water activities (aH₂O) to investigate the compositional evolution of residual liquids. The temperature (T) range of the experiments was 950–1,150 °C, aH₂O varied between 0.1 and 1, and the log of oxygen fugacity (fO₂) varied between quartz–fayalite–magnetite (QFM) and QFM + 4.1. The comparison of the experimentally produced liquids and natural samples was used to constrain the pressure (P)–T–aH₂O–fO₂ conditions of the Bezymianny parental magma in the intra-crustal magma plumbing system. The phase equilibria constraints suggest that parental basaltic andesite magmas should contain ~2–2.5 wt% H₂O; they can be stored in upper crustal levels at a depth of ~15 km, and at this depth they start to crystallize at ~1,110 °C. The subsequent chemical evolution of this parental magma most probably proceeded as decompressional crystallization occurred during magma ascent. The final depths at which crystallization products accumulated prior to eruption are not well constrained experimentally but should not be shallower than 3–4 km because amphibole is present in natural magmas (>150 MPa). Thus, the major volume of Bezymianny andesites was produced in a mid-crustal magma chamber as a result of decompressional crystallization of parental basaltic andesites, accompanied by mixing with silicic products from the earlier stages of magma fractionation. In addition, these processes are complicated by the release of volatiles due to magma degassing, which occurs at various stages during magma ascent.     

Subduction initiation and ophiolite crust: new insights from IODP drilling

International Ocean Discovery Program (IODP) Expedition 352 recovered a high-fidelity record of volcanism related to subduction initiation in the Bonin fore-arc. Two sites (U1440 and U1441) located in deep water nearer to the trench recovered basalts and related rocks; two sites (U1439 and U1442) located in shallower water further from the trench recovered boninites and related rocks. Drilling in both areas ended in dolerites inferred to be sheeted intrusive rocks. The basalts apparently erupted immediately after subduction initiation and have compositions similar to those of the most depleted basalts generated by rapid sea-floor spreading at mid-ocean ridges, with little or no slab input. Subsequent melting to generate boninites involved more depleted mantle and hotter and deeper subducted components as subduction progressed and volcanism migrated away from the trench. This volcanic sequence is akin to that recorded by many ophiolites, supporting a direct link between subduction initiation, fore-arc spreading, and ophiolite genesis.     

A Practical Method for Accurate Measurement of Trace Level Fluorine in Mg‐ and Fe‐Bearing Minerals and Glasses Using Electron Probe Microanalysis

Fluorine plays an important role in magmatic and hydrothermal processes, but due to its low abundance in geological samples determining F is difficult by electron probe microanalysis. By using a W‐Si multi‐layered pseudocrystal as the diffraction crystal instead of thallium acid phthalate (TAP), count rates were considerably higher, which however introduced spectral interferences between FKα and FeLα and MgKβ lines when normal integral mode is applied. In this study, we developed a protocol using a W‐Si multi‐layered pseudocrystal for measuring accurately trace level F in both minerals and glasses. First, we used differential mode with an optimised PHA (pulse height analysis) setting in signal processing, instead of normal integral mode, which completely eliminated the second‐order MgKβ line. Second, the overlap of the first‐order FeLα on FKα peak, which cannot be filtered by modifying the PHA setting, was calibrated quantitatively using F‐free minerals and silicate glasses. Applying this two‐step method, F was determined in a number of reference glasses, as well as in glasses synthesised from powders of the rock reference materials AC‐E, GS‐N and DR‐N. Our data are consistent within error with F concentrations determined by other methods, demonstrating the reliability of this method.     

Test of the Ballhaus–Berry–Green <Emphasis Type="Italic">Ol–Opx–Sp</Emphasis> oxybarometer and calibration of a new equation for estimating the redox state of melts saturated with olivine and spinel

Testing the Ballhaus–Berry–Green Ol–Opx–Sp oxybarometer (BBG) on independent experimental data indicates that it overestimates the oxygen fugacity by 0.6–1.3 log units under mildly reduced conditions (near the C–CO buffer) and by as much as 2–3 log units under reduced conditions (at the IW buffer and below it). A newly developed oxibarometer is suggested to minimize this effect and enhance the capabilities of redoxometry of low-pressure mineral associations, including magmatic melts undersaturated with respect to orthopyroxene (Opx). The new empirical equation of the oxybarometer is applicable to a wide range of mafic–ultramafic magmas of normal alkalinity, including terrestrial, lunar, and meteoritic systems under pressures of 0.001–25 kbar and oxygen fugacity ranging from IW–3 to NNO + 1. The derived regression fits the ΔQFM values of the calibration dataset (154 experiments) accurate to ~0.5 log units. The new oxybarometer eliminates systematic errors when redox parameters are evaluated for the reduced region (from IW–3 to C–CO) and for crystallization of magmas without Opx on the liquidus. The efficiency of the suggested model is demonstrated by its application to natural rocks: (1) low-Ti lunar basalts, (2) tholeiites from the Shatsky Rise, (3) Siberian flood basalts, (4) rocks of the layered series of the Yoko-Dovyren intrusion, and (5) mantle xenoliths collected in southern Siberia, Mongolia, China, and the southern Russian Far East. The values yielded by such oxybarometers for intrusive rocks, which underwent long-lasting cooling and postcumulus reequilibration, should be regarded with reserve.     

New Compositional and Structural Constraints on the Smithsonian Microanalytical Reference Materials: Amphiboles from Kakanui and Arenal

The amphiboles from Kakanui and Arenal are two natural minerals that have been used worldwide as microanalytical reference materials, but their compositions and crystal structures are still poorly constrained. In this paper, we report new data on H₂O and trace element mass fractions and single-crystal structural refinement of these two amphiboles. H₂O mass fractions of the Kakanui and Arenal amphiboles determined via Karl-Fischer titration are 0.92 ± 0.18 (2s) and 1.56 ± 0.22% m/m (2s), respectively; these values estimated based on crystal-structure refinement are 0.86 and 1.46% m/m, respectively. Trace element mass fractions measured via LA-ICP-MS in two laboratories are in good agreement, and spots from five fragments for both Kakanui and Arenal amphiboles are generally consistent within reproducibility precision (2s). Our measurements indicate a better homogeneity for the amphiboles from Kakanui than that from Arenal. According to the latest scheme for amphibole classification and nomenclature (Hawthorne et al. 2012), the sample from Arenal is a (partially dehydrogenated) pargasite, and that from Kakanui is a kaersutite. The significant amount of oxo-component and that ^CTi⁴⁺ content is strongly ordered at the M(1) site for both amphiboles indicate crystallisation under high fO₂ conditions.