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Sample records for magma oxidation state

  1. Oxidation State of Iron in the Izu-Bonin Arc Initial Magma and Its Influence Factors

    Science.gov (United States)

    Li, H.; Arculus, R. J.; Brandl, P. A.; Hamada, M.; Savov, I. P.; Zhu, S.; Hickey-Vargas, R.; Tepley, F. J., III; Meffre, S.; Yogodzinski, G. M.; McCarthy, A.; Barth, A. P.; Kanayama, K.; Kusano, Y.; Sun, W.

    2014-12-01

    The redox state of mantle-derived magmas is a controversial issue, especially whether island arc basalts are more oxidized than those from mid-ocean ridges. Usually, arc magmas have higher Fe3+/Fe2+ and calculated oxygen fugacity (fO2) than mid-ocean ridge basalts (MORB). It is the high fO2 of arc magma that apparently delays onset of sulfide fractionation and sequestration of precious/base metals thereby facilitating the formation of many giant gold-copper deposits typically associated with subduction zones. But due to a paucity of Fe3+/Fe2+ data for primary mantle-derived arc magmas, the cause for high fO2 of these magma types is still controversial; causes may include inter alia subduction-released oxidized material addition to the mantle wedge source of arc magma, partial melting of subducted slab, and redox changes occurring during ascent of the magma. Fortunately, IODP expedition 351 drilling at IODP Site U1438 in the Amami-Sankaku Basin of the northwestern Philipine Sea, adjacent to the proto-Izu-Bonin Arc at the Kyushu-Palau Ridge (KPR), recovered not only volcaniclastics derived from the inception of Izu-Bonin Mariana (IBM) arc in the Eocene, but also similar materials for the Arc's subsequent evolution through to the Late Oligocene and abandonment of the KPR as a remnant arc. Samples of the pre-Arc oceanic crustal basement were also recovered enabling us to determine the fO2of the mantle preceding arc inception. As the oxidation state of iron in basaltic glass directly relates to the fO2 , the Fe3+/∑Fe ratio [Fe3+/(Fe3++ Fe2+)] of basaltic glass are quantified by synchrotron-facilitated micro X-ray Absorption Near Edge Structure (XANES) spectroscopy to reflect its fO2. Fe K-edge µ-XANES spectra were recorded in fluorescence mode at Beamline 15U1, Shanghai Synchrotron Radiation Facility (SSRF). Synthetic silicate glass with known Fe3+/∑Fe ratio was used in data handling. The experimental results as well as preliminary data from IODP Expedition 351

  2. Quantitative evaluation of the effect of H2O degassing on the oxidation state of magmas

    Science.gov (United States)

    Lange, R. A.; Waters, L.

    2014-12-01

    The extent to which degassing of the H2O component affects the oxidation state of hydrous magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of various magmas, whereas our focus is on the H2O component. There are two ways that degassing of H2O by itself may cause oxidation: (1) the reaction: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt), and/or (2) if dissolved water preferentially enhances the activity of ferrous vs. ferric iron in magmatic liquids. In this study, a comparison is made between the pre-eruptive oxidation states of 14 crystal-poor, jet-black obsidian samples (obtained from two Fe-Ti oxides) and their post-eruptive values (analyzed with the Wilson 1960 titration method tested against USGS standards). The obsidians are from Medicine Lake (CA), Long Valley (CA), and the western Mexican arc; all have low FeOT (1.1-2.1 wt%), rendering their Fe2+/Fe3+ ratios highly sensitive to the possible effects of substantial H2O degassing. The Fe-Ti oxide thermometer/oxybarometer of Ghiorso and Evans, (2008) gave temperatures for the 14 samples that range for 720 to 940°C and ΔNNO values of -0.9 to +1.4. With temperature known, the plagioclase-liquid hygrometer was applied and show that ≤ 6.5 wt% H2O was dissolved in the melts prior to eruption. In addition, pre-eruptive Cl and S concentrations were constrained on the basis of apatite analyses (Webster et al., 2009) and sulfur concentrations needed for saturation with pyrrhotite (Clemente et al., 2004), respectively. Maximum pre-eruptive chlorine and sulfur contents are 6000 and 200 ppm, respectively. After eruption, the rhyolites lost nearly all of their volatiles. Our results indicate no detectable change between pre- and post-eruptive Fe2+ concentrations, with an average deviation of ± 0.1 wt % FeO. Although degassing of large concentrations of S and/or Cl may affect the oxidation state of magmas, at the pre-eruptive levels

  3. Oxidation state inherited from the magma source and implications for mineralization: Late Jurassic to Early Cretaceous granitoids, Central Lhasa subterrane, Tibet

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    Cao, MingJian; Qin, KeZhang; Li, GuangMing; Evans, Noreen J.; McInnes, Brent I. A.; Li, JinXiang; Zhao, JunXing

    2018-03-01

    Arc magmas are more oxidized than mid-ocean ridge basalts; however, there is continuing debate as to whether this higher oxidation state is inherited from the source magma or developed during late-stage magmatic differentiation processes. Well-constrained Late Jurassic to Early Cretaceous arc-related intermediate to felsic rocks derived from distinct magma sources provide us with a good opportunity to resolve this enigma. A series of granitoids from the western Central Lhasa subterrane were analyzed for whole-rock magnetic susceptibility, Fe2O3/FeO ratios, and trace elements in zircon. Compared to Late Jurassic samples (1.8 ± 2.0 × 10-4 emu g-1 oe-1, Fe3+/Fetotal = 0.32 ± 0.07, zircon Ce4+/Ce3+* = 15.0 ± 13.4), Early Cretaceous rocks show higher whole-rock magnetic susceptibility (5.8 ± 2.5 × 10-4 emu g-1 oe-1), Fe3+/Fetotal ratios (0.43 ± 0.04), and zircon Ce4+/Ce3+* values (23.9 ± 22.3). In addition, positive correlations among whole-rock magnetic susceptibility, Fe3+/Fetotal ratios, and zircon Ce4+/Ce3+* reveal a slight increase in oxidation state from fO2 = QFM to NNO in the Late Jurassic to fO2 = ˜NNO in the Early Cretaceous. Obvious linear correlation between oxidation indices (whole-rock magnetic susceptibility, zircon Ce4+/Ce3+*) and source signatures (zircon ɛHf(t), TDM C ages) indicates that the oxidation state was predominantly inherited from the source with only a minor contribution from magmatic differentiation. Thus, the sources for both the Late Jurassic and Early Cretaceous rocks were probably influenced by mantle wedge-derived magma, contributing to the increased fO2. Compared to ore-forming rocks at giant porphyry Cu deposits, the relatively low oxidation state (QFM to NNO) and negative ɛHf(t) (-16 to 0) of the studied granitoids implies relative infertility. However, this study demonstrates two potential fast and effective indices ( fO2 and ɛHf(t)) to evaluate the fertility of granitoids for porphyry-style mineralization. In an

  4. No effect of H2O degassing on the oxidation state of hydrous rhyolite magmas: a comparison of pre- and post-eruptive Fe2+ concentrations in six obsidian samples from the Mexican and Cascade arcs

    Science.gov (United States)

    Waters, L.; Lange, R. A.

    2011-12-01

    The extent to which degassing affects the oxidation state of arc magmas is widely debated. Several researchers have examined how degassing of mixed H-C-O-S-Cl fluids may change the Fe3+/FeT ratio of magmas, and it has been proposed that degassing may induce either oxidation or reduction depending on the initial oxidation state. A commonly proposed oxidation reaction is related to H2O degassing: H2O (melt) + 2FeO (melt) = H2 (fluid) + Fe2O3 (melt). Another mechanism by which H2O degassing can affect the iron redox state is if dissolved water affects the activity of ferrous and/or ferric iron in the melt. Although Moore et al. (1995) presented experiments showing no evidence of an affect of dissolved water on the activity of the ferric-ferrous ratio in silicate melts, other experimental results (e.g., Baker and Rutherford, 1996; Gaillard et al., 2001; 2003) indicate that there may be such an effect in rhyolite liquids. It has long been understood that rhyolites, owing to their low total iron concentrations, are more sensitive than other magma types to degassing-induced change in redox state. Therefore, a rigorous test of whether H2O degassing affects the redox state of arc magmas is best evaluated on rhyolites. In this study, a comparison is made between the pre-eruptive (pre-degassing) Fe2+ concentrations in six, phenocryst-poor (volatiles, as indicated by the low loss on ignition values (LOI ≤ 0.7 wt%). In order to test how much oxidation of ferrous iron occurred as a consequence of that degassing, we measured the ferrous iron concentration in the bulk samples by titration, using the Wilson (1960) method, which was successfully tested again three USGS and one Canadian Geological Survey standards. Our results indicate no detectable change within analytical error between pre- and post-eruptive FeO concentrations, with an average deviation of 0.09 wt% and a maximum deviation of 0.15 wt%. Our results show that H2O degassing has no effect on the redox state of

  5. Rapid mixing and short storage timescale in the magma dynamics of a steady-state volcano

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    Petrone, Chiara Maria; Braschi, Eleonora; Francalanci, Lorella; Casalini, Martina; Tommasini, Simone

    2018-06-01

    Steady-state volcanic activity implies equilibrium between the rate of magma replenishment and eruption of compositionally homogeneous magmas, lasting for tens to thousands of years in an open conduit system. The Present-day activity of Stromboli volcano (Aeolian Islands, Southern Italy) has long been recognised as typical of a steady-state volcano, with a shallow magmatic reservoir (highly porphyritic or hp-magma) continuously refilled by more mafic magma (with low phenocryst content or lp-magma) at a constant rate and accompanied by mixing, crystallisation and eruption. Our aim is to clarify the timescale and dynamics of the plumbing system at the establishment of the Present-day steady-state activity (volcanoes.

  6. Intraplate mantle oxidation by volatile-rich silicic magmas

    Energy Technology Data Exchange (ETDEWEB)

    Martin, Audrey M.; Médard, Etienne; Righter, Kevin; Lanzirotti, Antonio

    2017-11-01

    The upper subcontinental lithospheric mantle below the French Massif Central is more oxidized than the average continental lithosphere, although the origin of this anomaly remains unknown. Using iron oxidation analysis in clinopyroxene, oxybarometry, and melt inclusions in mantle xenoliths, we show that widespread infiltration of volatile (HCSO)-rich silicic melts played a major role in this oxidation. We propose the first comprehensive model of magmatism and mantle oxidation at an intraplate setting. Two oxidizing events occurred: (1) a 365–286 Ma old magmatic episode that produced alkaline vaugnerites, potassic lamprophyres, and K-rich calc-alkaline granitoids, related to the N–S Rhenohercynian subduction, and (2) < 30 Ma old magmatism related to W–E extension, producing carbonatites and hydrous potassic trachytes. These melts were capable of locally increasing the subcontinental lithospheric mantle fO2 to FMQ + 2.4. Both events originate from the melting of a metasomatized lithosphere containing carbonate + phlogopite ± amphibole. The persistence of this volatile-rich lithospheric source implies the potential for new episodes of volatile-rich magmatism. Similarities with worldwide magmatism also show that the importance of volatiles and the oxidation of the mantle in intraplate regions is underestimated.

  7. Onset of solid state mantle convection and mixing during magma ocean solidification

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    Maurice, Maxime; Tosi, Nicola; Samuel, Henri; Plesa, Ana-Catalina; Hüttig, Christian; Breuer, Doris

    2017-04-01

    The fractional crystallization of a magma ocean can cause the formation of a compositional layering that can play a fundamental role for the subsequent long-term dynamics of the interior, for the evolution of geochemical reservoirs, and for surface tectonics. In order to assess to what extent primordial compositional heterogeneities generated by magma ocean solidification can be preserved, we investigate the solidification of a whole-mantle Martian magma ocean, and in particular the conditions that allow solid state convection to start mixing the mantle before solidification is completed. To this end, we performed 2-D numerical simulations in a cylindrical geometry. We treat the liquid magma ocean in a parametrized way while we self-consistently solve the conservation equations of thermochemical convection in the growing solid cumulates accounting for pressure-, temperature- and, where it applies, melt-dependent viscosity as well as parametrized yield stress to account for plastic yielding. By testing the effects of different cooling rates and convective vigor, we show that for a lifetime of the liquid magma ocean of 1 Myr or longer, the onset of solid state convection prior to complete mantle crystallization is likely and that a significant part of the compositional heterogeneities generated by fractionation can be erased by efficient mantle mixing.

  8. Magmas near the critical degassing pressure drive volcanic unrest towards a critical state

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    Chiodini, Giovanni; Paonita, Antonio; Aiuppa, Alessandro; Costa, Antonio; Caliro, Stefano; De Martino, Prospero; Acocella, Valerio; Vandemeulebrouck, Jean

    2016-01-01

    During the reawaking of a volcano, magmas migrating through the shallow crust have to pass through hydrothermal fluids and rocks. The resulting magma–hydrothermal interactions are still poorly understood, which impairs the ability to interpret volcano monitoring signals and perform hazard assessments. Here we use the results of physical and volatile saturation models to demonstrate that magmatic volatiles released by decompressing magmas at a critical degassing pressure (CDP) can drive volcanic unrest towards a critical state. We show that, at the CDP, the abrupt and voluminous release of H2O-rich magmatic gases can heat hydrothermal fluids and rocks, triggering an accelerating deformation that can ultimately culminate in rock failure and eruption. We propose that magma could be approaching the CDP at Campi Flegrei, a volcano in the metropolitan area of Naples, one of the most densely inhabited areas in the world, and where accelerating deformation and heating are currently being observed. PMID:27996976

  9. Coexistence and mixing of magmas in the late precambrian Itaporanga batholith, State of Paraiba, Northeastern Brazil

    International Nuclear Information System (INIS)

    Mariano, G.; Sial, A.N.

    1990-01-01

    The Precambrian Cachoeirinha-Salgueiro Fold Belt (CSF) located in the western portion of the states of Pernambuco and Paraiba is intruded, in its northern portion, by several coarsely porphyritic potassic calc-alkalic batholiths. These batholiths were syntectonically emplaced in relation to the Brasiliano cycle (=Pan-African) and are commonly associated with potassium diorites suggesting coexistence and mixing between felsic and mafic magmas. In the Itaporanga batholith three petrographic domains were mapped. A hybrid zone characterized by intense mechanical mixing of granite to granodiorite and potassium diorite magmas is located towards the border of the batholith. A commingling zone where felsic porphyritic granite to granodiorite and potassium diorite rocks are individualized at outcrop scale is located towards the center of the batholith. Finally a felsic porphyritic facies occur in the hybrid zone. Similarity among chemical analyses of amphiboles from potassium dioritic enclaves of the Itaporanga batholith and from the potassium diorite stock east of it suggest a common source for both magmas. This hypothesis is corroborated by similar REE patterns for potassium dioritic enclaves of the Itaporanga batholith and for the potassium diorite stock. The batholith shows a well developed foliation which dips towards its core suggesting that the present level of exposure represents the root zone of a diapir, where intense interaction between felsic and mafic magmas took place. (author)

  10. Formation of thick stratiform Fe-Ti oxide layers in layered intrusion and frequent replenishment of fractionated mafic magma: Evidence from the Panzhihua intrusion, SW China

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    Song, Xie-Yan; Qi, Hua-Wen; Hu, Rui-Zhong; Chen, Lie-Meng; Yu, Song-Yue; Zhang, Jia-Fei

    2013-03-01

    Panzhihua intrusion is one of the largest layered intrusions that hosts huge stratiform Fe-Ti oxide layers in the central part of the Emeishan large igneous province, SW China. Up to 60 m thick stratiform massive Fe-Ti oxide layers containing 85 modal% of magnetite and ilmenite and overlying magnetite gabbro compose cyclic units of the Lower Zone of the intrusion. The cyclic units of the Middle Zone consist of magnetite gabbro and overlying gabbro. In these cyclic units, contents of Fe2O3(t), TiO2 and Cr and Fe3+/Ti4+ ratio of the rocks decrease upward, Cr content of magnetite and forsterite percentage of olivine decrease as well. The Upper Zone consists of apatite gabbro characterized by enrichment of incompatible elements (e.g., 12-18 ppm La, 20-28 ppm Y) and increasing of Fe3+/Ti4+ ratio (from 1.3 to 2.3) upward. These features indicate that the Panzhihua intrusion was repeatedly recharged by more primitive magma and evolved magmas had been extracted. Calculations using MELTS indicate that extensive fractionation of olivine and clinopyroxene in deep level resulted in increasing Fe and Ti contents in the magma. When these Fe-Ti-enriched magmas were emplaced along the base of the Panzhihua intrusion, Fe-Ti oxides became an early crystallization phase, leading to a residual magma of lower density. We propose that the unusually thick stratiform Fe-Ti oxide layers resulted from coupling of gravity settling and sorting of the crystallized Fe-Ti oxides from Fe-Ti-enriched magmas and frequent magma replenishment along the floor of the magma chamber.

  11. A Holistic Model That Physicochemically Links Iron Oxide - Apatite and Iron Oxide - Copper - Gold Deposits to Magmas

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    Simon, A. C.; Reich, M.; Knipping, J.; Bilenker, L.; Barra, F.; Deditius, A.; Lundstrom, C.; Bindeman, I. N.

    2015-12-01

    Iron oxide-apatite (IOA) and iron oxide-copper-gold deposits (IOCG) are important sources of their namesake metals and increasingly for rare earth metals in apatite. Studies of natural systems document that IOA and IOCG deposits are often spatially and temporally related with one another and coeval magmatism. However, a genetic model that accounts for observations of natural systems remains elusive, with few observational data able to distinguish among working hypotheses that invoke meteoric fluid, magmatic-hydrothermal fluid, and immiscible melts. Here, we use Fe and O isotope data and high-resolution trace element (e.g., Ti, V, Mn, Al) data of individual magnetite grains from the world-class Los Colorados (LC) IOA deposit in the Chilean Iron Belt to elucidate the origin of IOA and IOCG deposits. Values of d56Fe range from 0.08‰ to 0.26‰, which are within the global range of ~0.06‰ to 0.5‰ for magnetite formed at magmatic conditions. Values of δ18O for magnetite and actinolite are 2.04‰ and 6.08‰, respectively, consistent with magmatic values. Ti, V, Al, and Mn are enriched in magnetite cores and decrease systematically from core to rim. Plotting [Al + Mn] vs. [Ti + V] indicates that magnetite cores are consistent with magmatic and/or magmatic-hydrothermal (i.e., porphyry) magnetites. Decreasing Al, Mn, Ti, V is consistent with a cooling trend from porphyry to Kiruna to IOCG systems. The data from LC are consistent with the following new genetic model for IOA and IOCG systems: 1) magnetite cores crystallize from silicate melt; 2) these magnetite crystals are nucleation sites for aqueous fluid that exsolves and scavenges inter alia Fe, P, S, Cu, Au from silicate melt; 3) the magnetite-fluid suspension is less dense that the surrounding magma, allowing ascent; 4) as the suspension ascends, magnetite grows in equilibrium with the fluid and takes on a magmatic-hydrothermal character (i.e., lower Al, Mn, Ti, V); 5) during ascent, magnetite, apatite and

  12. Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

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    Pahlevan, K.; Karato, S. I.

    2016-12-01

    Models of the Moon-forming giant impact extensively melt and partially vaporize the silicate Earth and deliver a substantial mass of metal to the Earth's core. The subsequent evolution of the terrestrial magma ocean and overlying vapor atmosphere over the ensuing 105-6 years has been largely constrained by theoretical models with remnant signatures from this epoch proving somewhat elusive. We have calculated equilibrium hydrogen isotopic fractionation between the magma ocean and overlying steam atmosphere to determine the extent to which H isotopes trace the evolution during this epoch. By analogy with the modern silicate Earth, the magma ocean-steam atmosphere system is often assumed to be chemically oxidized (log fO2 QFM) with the dominant atmospheric vapor species taken to be water vapor. However, the terrestrial magma ocean - having held metallic droplets in suspension - may also exhibit a much more reducing character (log fO2 IW) such that equilibration with the overlying atmosphere renders molecular hydrogen the dominant H-bearing vapor species. This variable - the redox state of the magma ocean - has not been explicitly included in prior models of the coupled evolution of the magma ocean-steam atmosphere system. We find that the redox state of the magma ocean influences not only the vapor speciation and liquid-vapor partitioning of hydrogen but also the equilibrium isotopic fractionation during the crystallization epoch. The liquid-vapor isotopic fractionation of H is substantial under reducing conditions and can generate measurable D/H signatures in the crystallization products but is largely muted in an oxidizing magma ocean and steam atmosphere. We couple equilibrium isotopic fractionation with magma ocean crystallization calculations to forward model the behavior of hydrogen isotopes during this epoch and find that the distribution of H isotopes in the silicate Earth immediately following crystallization represents an oxybarometer for the terrestrial

  13. From magma-poor Ocean Continent Transitions to steady state oceanic spreading: the balance between tectonic and magmatic processes

    Science.gov (United States)

    Gillard, Morgane; Manatschal, Gianreto; Autin, Julia; Decarlis, Alessandro; Sauter, Daniel

    2016-04-01

    The evolution of magma-poor rifted margins is linked to the development of a transition zone whose basement is neither clearly continental nor oceanic. The development of this Ocean-Continent Transition (OCT) is generally associated to the exhumation of serpentinized mantle along one or several detachment faults. That model is supported by numerous observations (IODP wells, dredges, fossil margins) and by numerical modelling. However, if the initiation of detachment faults in a magma-poor setting tends to be better understood by numerous studies in various area, the transition with the first steady state oceanic crust and the associated processes remain enigmatic and poorly studied. Indeed, this latest stage of evolution appears to be extremely gradual and involves strong interactions between tectonic processes and magmatism. Contrary to the proximal part of the exhumed domain where we can observe magmatic activity linked to the exhumation process (exhumation of gabbros, small amount of basalts above the exhumed mantle), in the most distal part the magmatic system appears to be independent and more active. In particular, we can observe large amounts of extrusive material above a previously exhumed and faulted basement (e.g. Alps, Australia-Antarctica margins). It seems that some faults can play the role of feeder systems for the magma in this area. Magmatic underplating is also important, as suggested by basement uplift and anomalously thick crust (e.g. East Indian margin). It results that the transition with the first steady state oceanic crust is marked by the presence of a hybrid basement, composed by exhumed mantle and magmatic material, whose formation is linked to several tectonic and magmatic events. One could argue that this basement is not clearly different from an oceanic basement. However, we consider that true, steady state oceanic crust only exists, if the entire rock association forming the crust is created during a single event, at a localized

  14. Coupled interactions between volatile activity and Fe oxidation state during arc crustal processes

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    Humphreys, Madeleine C.S.; Brooker, R; Fraser, D.C.; Burgisser, A; Mangan, Margaret T.; McCammon, C

    2015-01-01

    Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

  15. Ore-forming adakitic porphyry produced by fractional crystallization of oxidized basaltic magmas in a subcrustal chamber (Jiamate, East Junggar, NW China)

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    Hong, Tao; Xu, Xing-Wang; Gao, Jun; Peters, Stephen; Zhang, Di; Jielili, Reyaniguli; Xiang, Peng; Li, Hao; Wu, Chu; You, Jun; Liu, Jie; Ke, Qiang

    2018-01-01

    Adakitic intrusions are supposed to have a close genetic and spatial relationship to porphyry Cu deposits. However, the genesis of adakitic intrusions is still under dispute. Here, we describe newly discovered intrusive complex rocks, which are composed of ore-bearing, layered magnetite-bearing gabbroic and adakitic rocks in Jiamate, East Junggar, NW China. These Jiamate Complex intrusions have diagnostic petrologic, geochronologic and geochemical signatures that indicate they were all generated from the same oxidized precursor magma source. Additionally, these layered rocks underwent the same fractional crystallization process as the ore-bearing adakitic rocks in the adjacent Kalaxiangar Porphyry Cu Belt (KPCB) in an oceanic island arc (OIA) setting. The rocks studied for this paper include layered magnetite-bearing gabbroic intrusive rocks that contain: (1) gradual contact changes between lithological units of mafic and intermediate rocks, (2) geochemical signatures that are the same as those found in oceanic island arc (OIA) rocks, (3) typical adakitic geochemistry, and (4) similar characteristics and apparent fractional crystallization relationships of ultra-basic to basic rocks to those in the nearby Beitashan Formation and to ore-bearing adakitic rocks in the KPCB. They also display similar zircon U-Pb and zircon Hf model ages.The Jiamate Complex intrusions contain intergrowths of magnetite and layered gabbro, and the intermediate-acidic intrusions of the Complex display typical adakitic affinities. Moreover, in conjunction with previously published geochronological and geochemistry data of the mafic rocks in the Beitashan Formation and in the KPCB area, additional data generated for the Jiamate Complex intrusions rocks indicate that they were formed from fractional crystallization processes. The Jiamate Complex intrusions most likely were derived from a metasomatized mantle wedge that was underplated at the root of the Saur oceanic island arc (Saur OIA). The

  16. Ore-forming adakitic porphyry produced by fractional crystallization of oxidized basaltic magmas in a subcrustal chamber (Jiamate, East Junggar, NW China)

    Science.gov (United States)

    Hong, Tao; Xu, Xing-Wang; Gao, Jun; Peters, Stephen G.; Zhang, Di; Jielili, Reyaniguli; Xiang, Peng; Li, Hao; Wu, Chu; You, Jun; Liu, Jie; Ke, Qiang

    2018-01-01

    Adakitic intrusions are supposed to have a close genetic and spatial relationship to porphyry Cu deposits. However, the genesis of adakitic intrusions is still under dispute. Here, we describe newly discovered intrusive complex rocks, which are composed of ore-bearing, layered magnetite-bearing gabbroic and adakitic rocks in Jiamate, East Junggar, NW China. These Jiamate Complex intrusions have diagnostic petrologic, geochronologic and geochemical signatures that indicate they were all generated from the same oxidized precursor magma source. Additionally, these layered rocks underwent the same fractional crystallization process as the ore-bearing adakitic rocks in the adjacent Kalaxiangar Porphyry Cu Belt (KPCB) in an oceanic island arc (OIA) setting. The rocks studied for this paper include layered magnetite-bearing gabbroic intrusive rocks that contain: (1) gradual contact changes between lithological units of mafic and intermediate rocks, (2) geochemical signatures that are the same as those found in oceanic island arc (OIA) rocks, (3) typical adakitic geochemistry, and (4) similar characteristics and apparent fractional crystallization relationships of ultra-basic to basic rocks to those in the nearby Beitashan Formation and to ore-bearing adakitic rocks in the KPCB. They also display similar zircon U-Pb and zircon Hf model ages. The Jiamate Complex intrusions contain intergrowths of magnetite and layered gabbro, and the intermediate-acidic intrusions of the Complex display typical adakitic affinities. Moreover, in conjunction with previously published geochronological and geochemistry data of the mafic rocks in the Beitashan Formation and in the KPCB area, additional data generated for the Jiamate Complex intrusions rocks indicate that they were formed from fractional crystallization processes. The Jiamate Complex intrusions most likely were derived from a metasomatized mantle wedge that was underplated at the root of the Saur oceanic island arc (Saur OIA

  17. Experimental Study of Lunar and SNC Magmas

    Science.gov (United States)

    Rutherford, Malcolm J.

    1998-01-01

    The research described in this progress report involved the study of petrological, geochemical and volcanic processes that occur on the Moon and the SNC parent body, generally accepted to be Mars. The link between these studies is that they focus on two terrestrial-type parent bodies somewhat smaller than earth, and the fact that they focus on the role of volatiles in magmatic processes and on processes of magma evolution on these planets. The work on the lunar volcanic glasses has resulted in some exciting new discoveries over the years of this grant. We discovered small metal blebs initially in the Al5 green glass, and determined the significant importance of this metal in fixing the oxidation state of the parent magma (Fogel and Rutherford, 1995). More recently, we discovered a variety of metal blebs in the Al7 orange glass. Some of these Fe-Ni metal blebs were in the glass; others were in olivine phenocrysts. The importance of these metal spheres is that they fix the oxidation state of the parent magma during the eruption, and also indicate changes during the eruption (Weitz et al., 1997) They also yield important information about the composition of the gas phase present, the gas which drove the lunar fire-fountaining. One of the more exciting and controversial findings in our research over the past year has been the possible fractionation of H from D during shock (experimental) of hornblende bearing samples (Minitti et al., 1997). This research is directed at explaining some of the low H2O and high D/H observed in hydrous phases in the SNC meteorites.

  18. Magnetic susceptibility of Variscan granite-types of the Spanish Central System and the redox state of magma

    Energy Technology Data Exchange (ETDEWEB)

    Villaseca, C.; Ruiz-Martínez, V.C.; Pérez-Soba, C.

    2017-07-01

    Magnetic susceptibility (MS) has been measured in Variscan granites from central Spain. They yield values in the order of 15 to 180μSI units for S- and I-type granites, indicating that both types belong to the ilmenite series. Only samples from magnetite-bearing leucogranites from the I-type La Pedriza massif show high MS values, in the order of 500-1400μSI, reflecting the presence of this ferromagnetic mineral. Mineral chemistry of magmatic Fe-rich minerals (mainly biotite) suggests similar oxidation values for both granite types. MS values change in highly fractionated granites accordingly either with the presence of rare new Fe-oxide phases (some I-type leucogranites) or with the marked modal amount decrease of Fe-rich minerals (I- and S-type leucogranites). The redox state in highly fractionated granite melts is mostly controlled by magmatic processes that modify redox conditions inherited from the source region. Thus, the occurrence of magnetite or ilmenite in granites is primarily controlled by the oxidation state of the source material but also by the differentiation degree of the granite melt. The presence of magnetite in some Variscan I-type leucogranites might be a consequence of crystal fractionation processes in a more limited mafic mineral assemblage than in S-type granite melts.

  19. Molybdenite saturation in silicic magmas: Occurrence and petrological implications

    Science.gov (United States)

    Audetat, A.; Dolejs, D.; Lowenstern, J. B.

    2011-01-01

    We identified molybdenite (MoS2) as an accessory magmatic phase in 13 out of 27 felsic magma systems examined worldwide. The molybdenite occurs as small (molybdenite-saturated samples reveal 1-13 ppm Mo in the melt and geochemical signatures that imply a strong link to continental rift basalt-rhyolite associations. In contrast, arc-associated rhyolites are rarely molybdenite-saturated, despite similar Mo concentrations. This systematic dependence on tectonic setting seems to reflect the higher oxidation state of arc magmas compared with within-plate magmas. A thermodynamic model devised to investigate the effects of T, f O2 and f S2 on molybdenite solubility reliably predicts measured Mo concentrations in molybdenite-saturated samples if the magmas are assumed to have been saturated also in pyrrhotite. Whereas pyrrhotite microphenocrysts have been observed in some of these samples, they have not been observed from other molybdenite-bearing magmas. Based on the strong influence of f S2 on molybdenite solubility we calculate that also these latter magmas must have been at (or very close to) pyrrhotite saturation. In this case the Mo concentration of molybdenite-saturated melts can be used to constrain both magmatic f O2 and f S2 if temperature is known independently (e.g. by zircon saturation thermometry). Our model thus permits evaluation of magmatic f S2, which is an important variable but is difficult to estimate otherwise, particularly in slowly cooled rocks. ?? The Author 2011. Published by Oxford University Press. All rights reserved.

  20. Oxidation-state maxima in plutonium chemistry

    International Nuclear Information System (INIS)

    Silver, G.L.

    2013-01-01

    Maxima in the fractions of the trivalent and hexavalent oxidation states of plutonium are inherent in the algebra of its disproportionation reactions. The maxima do not support overall disproportionation equations as satisfactory representations of aqueous plutonium. (author)

  1. Magma Chambers, Thermal Energy, and the Unsuccessful Search for a Magma Chamber Thermostat

    Science.gov (United States)

    Glazner, A. F.

    2015-12-01

    Although the traditional concept that plutons are the frozen corpses of huge, highly liquid magma chambers ("big red blobs") is losing favor, the related notion that magma bodies can spend long periods of time (~106years) in a mushy, highly crystalline state is widely accepted. However, analysis of the thermal balance of magmatic systems indicates that it is difficult to maintain a significant portion in a simmering, mushy state, whether or not the system is eutectic-like. Magma bodies cool primarily by loss of heat to the Earth's surface. The balance between cooling via energy loss to the surface and heating via magma accretion can be denoted as M = ρLa/q, where ρ is magma density, L is latent heat of crystallization, a is the vertical rate of magma accretion, and q is surface heat flux. If M>1, then magma accretion outpaces cooling and a magma chamber forms. For reasonable values of ρ, L, and q, the rate of accretion amust be > ~15 mm/yr to form a persistent volume above the solidus. This rate is extremely high, an order of magnitude faster than estimated pluton-filling rates, and would produce a body 10 km thick in 700 ka, an order of magnitude faster than geochronology indicates. Regardless of the rate of magma supply, the proportion of crystals in the system must vary dramatically with depth at any given time owing to transfer of heat. Mechanical stirring (e.g., by convection) could serve to homogenize crystal content in a magma body, but this is unachievable in crystal-rich, locked-up magma. Without convection the lower part of the magma body becomes much hotter than the top—a process familiar to anyone who has scorched a pot of oatmeal. Thermal models that succeed in producing persistent, large bodies of magma rely on scenarios that are unrealistic (e.g., omitting heat loss to the planet's surface), self-fulfilling prophecies (e.g., setting unnaturally high temperatures as fixed boundary conditions), or physically unreasonable (e.g., magma is intruded

  2. The Mineralogy, Geochemistry, and Redox State of Multivalent Cations During the Crystallization of Primitive Shergottitic Liquids at Various (f)O2. Insights into the (f)O2 Fugacity of the Martian Mantle and Crustal Influences on Redox Conditions of Martian Magmas.

    Science.gov (United States)

    Shearer, C. K.; Bell, A. S.; Burger, P. V.; Papike, J. J.; Jones, J.; Le, L.; Muttik, N.

    2016-01-01

    The (f)O2 [oxygen fugacity] of crystallization for martian basalts has been estimated in various studies to range from IW-1 to QFM+4 [1-3]. A striking geochemical feature of the shergottites is the large range in initial Sr isotopic ratios and initial epsilon(sup Nd) values. Studies by observed that within the shergottite group the (f)O2 [oxygen fugacity] of crystallization is highly correlated with these chemical and isotopic characteristics with depleted shergottites generally crystallizing at reduced conditions and enriched shergottites crystallizing under more oxidizing conditions. More recent work has shown that (f)O2 [oxygen fugacity] changed during the crystallization of these magmas from one order of magnitude in Y980459 (Y98) to several orders of magnitude in Larkman Nunatak 06319. These real or apparent variations within single shergottitic magmas have been attributed to mixing of a xenocrystic olivine component, volatile loss-water disassociation, auto-oxidation during crystallization of mafic phases, and assimilation of an oxidizing crustal component (e.g. sulfate). In contrast to the shergottites, augite basalts such as NWA 8159 are highly depleted yet appear to be highly oxidized (e.g. QFM+4). As a first step in attempting to unravel petrologic complexities that influence (f)O2 [oxygen fugacity] in martian magmas, this study explores the effect of (f)O2 [oxygen fugacity] on the liquid line of descent (LLD) for a primitive shergottite liquid composition (Y98). The results of this study will provide a fundamental basis for reconstructing the record of (f)O2 [oxygen fugacity] in shergottites and other martian basalts, its effect on both mineral chemistries and valence state partitioning, and a means for examining the role of crystallization (and other more complex processes) on the petrologic linkages between olivine-phyric and pyroxene-plagioclase shergottites.

  3. Thermodynamic Ground States of Complex Oxide Heterointerfaces

    DEFF Research Database (Denmark)

    Gunkel, F.; Hoffmann-Eifert, S.; Heinen, R. A.

    2017-01-01

    The formation mechanism of 2-dimensional electron gases (2DEGs) at heterointerfaces between nominally insulating oxides is addressed with a thermodynamical approach. We provide a comprehensive analysis of the thermodynamic ground states of various 2DEG systems directly probed in high temperature...

  4. Higher Americium Oxidation State Research Roadmap

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Law, Jack D. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Goff, George S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burns, Jon D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lumetta, Gregg J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sinkov, Sergey I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shehee, Thomas C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hobbs, David T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-12-18

    The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained under the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non

  5. Mafic microgranular enclave swarms in the Chenar granitoid stock, NW of Kerman, Iran: evidence for magma mingling

    Science.gov (United States)

    Arvin, M.; Dargahi, S.; Babaei, A. A.

    2004-10-01

    Mafic microgranular enclaves (MME) are common in the Early to Middle Miocene Chenar granitoid stock, northwest of Kerman, which is a part of Central Iranian Eocene volcanic belt. They occur individually and in homogeneous or heterogeneous swarms. The MME form a number of two-dimensional structural arrangements, such as dykes, small rafts, vortices, folded lens-shapes and late swarms. The enclaves are elongated, rounded to non-elongated and subrounded in shape and often show some size-sorting parallel to direction of flow. Variation in the elongation of enclaves could reflect variations in the viscosity of the enclave, the time available for enclave deformation and differential strain during flow of the host granitoid magma. The most effective mechanism in the formation of enclave swarms in the Chenar granitoid stock was velocity gradient-related convection currents in the granitoid magma chamber. Gravitational sorting and the break-up of heterogeneous dykes also form MME swarms. The MME (mainly diorite to diorite gabbro) have igneous mineralogy and texture, and are marked by sharp contacts next to their host granitoid rocks. The contact is often marked by a chilled margin with no sign of solid state deformation. Evidence of disequilibrium is manifested in feldspars by oscillatory zoning, resorbed rims, mantling and punctuated growth, together with overgrowth of clinopyroxene/amphibole on quartz crystals, the acicular habit of apatites and the development of Fe-Ti oxides along clinopyroxene cleavages. These observations suggest that the MMEs are derived from a hybrid-magma formed as a result of the intrusion of a mafic magma into the base of a felsic magma chamber. The density contrast between hybrid-magma and the overlying felsic magma was reduced by the release of dissolved fluids and the ascent of exsolved gas bubbles from the mafic magma into the hybrid zone. Further convection in the magma chamber dispersed the hybridized magma as globules in the upper parts of

  6. The Meaning of "Magma"

    Science.gov (United States)

    Bartley, J. M.; Glazner, A. F.; Coleman, D. S.

    2016-12-01

    Magma is a fundamental constituent of the Earth, and its properties, origin, evolution, and significance bear on issues ranging from volcanic hazards to planetary evolution. Unfortunately, published usages indicate that the term "magma" means distinctly different things to different people and this can lead to miscommunication among Earth scientists and between scientists and the public. Erupting lava clearly is magma; the question is whether partially molten rock imaged at depth and too crystal-rich to flow should also be called magma. At crystal fractions > 50%, flow can only occur via crystal deformation and solution-reprecipitation. As the solid fraction increases to 90% or more, the material becomes a welded crystal framework with melt in dispersed pores and/or along grain boundaries. Seismic images commonly describe such volumes of a few % melt as magma, yet the rheological differences between melt-rich and melt-poor materials make it vital not to confuse a large rock volume that contains a small melt fraction with melt-rich material. To ensure this, we suggest that "magma" be reserved for melt-rich materials that undergo bulk fluid flow on timescales consonant with volcanic eruptions. Other terms should be used for more crystal-rich and largely immobile partially molten rock (e.g., "crystal mush," "rigid sponge"). The distinction is imprecise but useful. For the press, the public, and even earth scientists who do not study magmatic systems, "magma" conjures up flowing lava; reports of a large "magma" body that contains a few percent melt can engender the mistaken perception of a vast amount of eruptible magma. For researchers, physical processes like crystal settling are commonly invoked to account for features in plutonic rocks, but many such processes are only possible in melt-rich materials.

  7. Photochemical oxidants: state of the science.

    Science.gov (United States)

    Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

    1999-01-01

    Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

  8. Plutonium disproportionation. Hydrolysis and local oxidation-state maxima

    International Nuclear Information System (INIS)

    Silver, G.L.

    2014-01-01

    Local maxima in the fractions of the trivalent and hexavalent oxidation states are inherent in the algebra of Pu disproportionation reactions. A new method predicts the pH and the oxidation-state fractions at maximum. Tabulated results illustrate the effects of the Pu oxidation number and Pu(IV) hydrolysis on the maxima. This method suggests a new laboratory approach for discovering Pu oxidation-state maxima. (author)

  9. Origin and evolution of the Pirituba aluminous calc-alkalic magma, state of Sao Paulo, SE Brazil

    International Nuclear Information System (INIS)

    Wernick, Eberhard

    1999-01-01

    The origin and evolution of the Late Proterozoic calc-alkalic Pirituba magmatism near the city of Sao Paulo, State of Sao Paulo, SE Brazil, are presented and discussed on the basis of geological, petrographic, mineralogical, chemical (rocks and minerals), isotopic and zircon typology data. (author)

  10. Contamination of mantle magmas by crustal contributions: evidence from the brasiliano mobile belt in the State of Espirito Santo, Brazil

    International Nuclear Information System (INIS)

    Wiedemann, Cristina M.; mendes, Julio C.; Ludka, Isabel P.

    1995-01-01

    In the beginning of the late orogenic phase of the Pan african/Brasiliano Mobile Belt, in Espirito Santo and Rio de Janeiro States, along the Brazilian coast, tholeiitic gabbros intruded the coast Small bodies of clinopyroxene -gabbro-norites, hornblendi-gabbros and clinoorthopyroxenes -pyroxenites/hornblendites typical tholeiitic AFM-trends. The series of rocks reveal evidence of crustal contamination, but no signs of in situ mixing with granitic melts. The geochemical characteristics of the tholeiitic series and suites of magmatites,- present in the different evolutionary stages of the post-collisional magmatic arc, in the Brasiliano Coastal Mobile belt, in the States of Espirito Santo and Rio de Janeiro-, are regarded as an important tool for the recognition of a further contamination process of an already enriched mantle, at crustal levels, during Late Proterozoic/Early Paleozoic times. 33 refs., 11 figs., 2 tabs

  11. Mush Column Magma Chambers

    Science.gov (United States)

    Marsh, B. D.

    2002-12-01

    Magma chambers are a necessary concept in understanding the chemical and physical evolution of magma. The concept may well be similar to a transfer function in circuit or time series analysis. It does what needs to be done to transform source magma into eruptible magma. In gravity and geodetic interpretations the causative body is (usually of necessity) geometrically simple and of limited vertical extent; it is clearly difficult to `see' through the uppermost manifestation of the concentrated magma. The presence of plutons in the upper crust has reinforced the view that magma chambers are large pots of magma, but as in the physical representation of a transfer function, actual magma chambers are clearly distinct from virtual magma chambers. Two key features to understanding magmatic systems are that they are vertically integrated over large distances (e.g., 30-100 km), and that all local magmatic processes are controlled by solidification fronts. Heat transfer considerations show that any viable volcanic system must be supported by a vertically extensive plumbing system. Field and geophysical studies point to a common theme of an interconnected stack of sill-like structures extending to great depth. This is a magmatic Mush Column. The large-scale (10s of km) structure resembles the vertical structure inferred at large volcanic centers like Hawaii (e.g., Ryan et al.), and the fine scale (10s to 100s of m) structure is exemplified by ophiolites and deeply eroded sill complexes like the Ferrar dolerites of the McMurdo Dry Valleys, Antarctica. The local length scales of the sill reservoirs and interconnecting conduits produce a rich spectrum of crystallization environments with distinct solidification time scales. Extensive horizontal and vertical mushy walls provide conditions conducive to specific processes of differentiation from solidification front instability to sidewall porous flow and wall rock slumping. The size, strength, and time series of eruptive behavior

  12. Io's theothermal (sulfur) - Lithosphere cycle inferred from sulfur solubility modeling of Pele's magma supply

    Science.gov (United States)

    Battaglia, Steven M.; Stewart, Michael A.; Kieffer, Susan W.

    2014-06-01

    Surface deposits of volatile compounds such as water (Earth) or sulfur (Io) on volcanically active bodies suggest that a magmatic distillation process works to concentrate volatiles in surface reservoirs. On Earth, this is the combined hydrologic and tectonic cycle. On Io, sulfurous compounds are transferred from the interior to the surface reservoirs through a combination of a mantle-sourced magmatic system, vertical cycling of the lithosphere, and a sulfur-dominated crustal thermal system that we here call the "theothermal" system. We present a geochemical analysis of this process using previously inferred temperature and oxygen fugacity constraints of Pele's basaltic magma to determine the behavior of sulfur in the ionian magmas. Sulfate to sulfide ratios of Pele's magma are -4.084 ± 0.6 and -6.442 ± 0.7 log10 units, comparable to or lower than those of mid-ocean ridge basalts. This reflects the similarity of Io's oxidation state with Earth's depleted mantle as previously suggested by Zolotov and Fegley (Zolotov, M.Y., Fegley, B. [2000]. Geophys. Res. Lett. 27, 2789-2792). Our calculated limits of sulfur solubility in melts from Pele's patera (˜1100-1140 ppm) are also comparable to terrestrial mid-ocean ridge basalts, reflecting a compositional similarity of mantle sources. We propose that the excess sulfur obvious on Io's surface comes from two sources: (1) an insoluble sulfide liquid phase in the magma and (2) theothermal near-surface recycling.

  13. Crustal thermal state and origin of silicic magma in Iceland: the case of Torfajökull, Ljósufjöll and Snæfellsjökull volcanoes

    Science.gov (United States)

    Martin, E.; Sigmarsson, O.

    2007-05-01

    Pleistocene and Holocene peralkaline rhyolites from Torfajökull (South Iceland Volcanic Zone) and Ljósufjöll central volcanoes and trachytes from Snæfellsjökull (Snæfellsnes Volcanic Zone) allow the assessment of the mechanism for silicic magma genesis as a function of geographical location and crustal geothermal gradient. The low δ18O (2.4‰) and low Sr concentration (12.2 ppm) measured in Torfajökull rhyolites are best explained by partial melting of hydrated metabasaltic crust followed by major fractionation of feldspar. In contrast, very high 87Sr/86Sr (0.70473) and low Ba (8.7 ppm) and Sr (1.2 ppm) concentrations measured in Ljósufjöll silicic lavas are best explained by fractional crystallisation and subsequent 87Rb decay. Snæfellsjökull trachytes are also generated by fractional crystallisation, with less than 10% crustal assimilation, as inferred from their δ18O. The fact that silicic magmas within, or close to, the rift zone are principally generated by crustal melting whereas those from off-rift zones are better explained by fractional crystallisation clearly illustrates the controlling influence of the thermal state of the crust on silicic magma genesis in Iceland.

  14. The Surtsey Magma Series.

    Science.gov (United States)

    Schipper, C Ian; Jakobsson, Sveinn P; White, James D L; Michael Palin, J; Bush-Marcinowski, Tim

    2015-06-26

    The volcanic island of Surtsey (Vestmannaeyjar, Iceland) is the product of a 3.5-year-long eruption that began in November 1963. Observations of magma-water interaction during pyroclastic episodes made Surtsey the type example of shallow-to-emergent phreatomagmatic eruptions. Here, in part to mark the 50(th) anniversary of this canonical eruption, we present previously unpublished major-element whole-rock compositions, and new major and trace-element compositions of sideromelane glasses in tephra collected by observers and retrieved from the 1979 drill core. Compositions became progressively more primitive as the eruption progressed, with abrupt changes corresponding to shifts between the eruption's four edifices. Trace-element ratios indicate that the chemical variation is best explained by mixing of different proportions of depleted ridge-like basalt, with ponded, enriched alkalic basalt similar to that of Iceland's Eastern Volcanic Zone; however, the systematic offset of Surtsey compositions to lower Nb/Zr than other Vestmannaeyjar lavas indicates that these mixing end members are as-yet poorly contained by compositions in the literature. As the southwestern-most volcano in the Vestmannaeyjar, the geochemistry of the Surtsey Magma Series exemplifies processes occurring within ephemeral magma bodies on the extreme leading edge of a propagating off-axis rift in the vicinity of the Iceland plume.

  15. Lunar magma transport phenomena

    Science.gov (United States)

    Spera, Frank J.

    1992-01-01

    An outline of magma transport theory relevant to the evolution of a possible Lunar Magma Ocean and the origin and transport history of the later phase of mare basaltic volcanism is presented. A simple model is proposed to evaluate the extent of fractionation as magma traverses the cold lunar lithosphere. If Apollo green glasses are primitive and have not undergone significant fractionation en route to the surface, then mean ascent rates of 10 m/s and cracks of widths greater than 40 m are indicated. Lunar tephra and vesiculated basalts suggest that a volatile component plays a role in eruption dynamics. The predominant vapor species appear to be CO CO2, and COS. Near the lunar surface, the vapor fraction expands enormously and vapor internal energy is converted to mixture kinetic energy with the concomitant high-speed ejection of vapor and pyroclasts to form lunary fire fountain deposits such as the Apollo 17 orange and black glasses and Apollo 15 green glass.

  16. Comparative Magma Oceanography

    Science.gov (United States)

    Jones, J. H.

    1999-01-01

    The question of whether the Earth ever passed through a magma ocean stage is of considerable interest. Geochemical evidence strongly suggests that the Moon had a magma ocean and the evidence is mounting that the same was true for Mars. Analyses of martian (SNC) meteorites have yielded insights into the differentiation history of Mars, and consequently, it is interesting to compare that planet to the Earth. Three primary features of Mars contrast strongly to those of the Earth: (i) the extremely ancient ages of the martian core, mantle, and crust (about 4.55 b.y.); (ii) the highly depleted nature of the martian mantle; and (iii) the extreme ranges of Nd isotopic compositions that arise within the crust and depleted mantle. The easiest way to explain the ages and diverse isotopic compositions of martian basalts is to postulate that Mars had an early magma ocean. Cumulates of this magma ocean were later remelted to form the SNC meteorite suite and some of these melts assimilated crustal materials enriched in incompatible elements. The REE pattern of the crust assimilated by these SNC magmas was LREE enriched. If this pattern is typical of the crust as a whole, the martian crust is probably similar in composition to melts generated by small degrees of partial melting (about 5%) of a primitive source. Higher degrees of partial melting would cause the crustal LREE pattern to be essentially flat. In the context of a magma ocean model, where large degrees of partial melting presumably prevailed, the crust would have to be dominated by late-stage, LREE-enriched residual liquids. Regardless of the exact physical setting, Nd and W isotopic evidence indicates that martian geochemical reservoirs must have formed early and that they have not been efficiently remixed since. The important point is that in both the Moon and Mars we see evidence of a magma ocean phase and that we recognize it as such. Several lines of theoretical inference point to an early Earth that was also hot

  17. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  18. Magma chamber processes in central volcanic systems of Iceland

    DEFF Research Database (Denmark)

    Þórarinsson, Sigurjón Böðvar; Tegner, Christian

    2009-01-01

    are composed of 2-10 m thick melanocratic layers rich in clinopyroxene and sometimes olivine, relative to the thicker overlying leucocratic oxide gabbros. While the overall compositional variation is limited (Mg# clinopyroxene 72-84; An% plagioclase 56-85), the melanocratic bases display spikes in Mg# and Cr2O......3 of clinopyroxene and magnetite indicative of magma replenishment. Some macrorhythmic units show mineral trends indicative of up-section fractional crystallisation over up to 100 m, whereas others show little variation. Two populations of plagioclase crystals (large, An-rich and small, less An......-rich) indicate that the recharge magma carried plagioclase xenocrysts (high An-type). The lack of evolved gabbros suggests formation in a dynamic magma chamber with frequent recharge, tapping and fractionation. Modelling of these compositional trends shows that the parent magma was similar to known transitional...

  19. Redox Evolution in Magma Oceans Due to Ferric/Ferrous Iron Partitioning

    Science.gov (United States)

    Schaefer, L.; Elkins-Tanton, L. T.; Pahlevan, K.

    2017-12-01

    A long-standing puzzle in the evolution of the Earth is that while the present day upper mantle has an oxygen fugacity close to the QFM buffer, core formation during accretion would have occurred at much lower oxygen fugacities close to IW. We present a new model based on experimental evidence that normal solidification and differentiation processes in the terrestrial magma ocean may explain both core formation and the current oxygen fugacity of the mantle without resorting to a change in source material or process. A commonly made assumption is that ferric iron (Fe3+) is negligible at such low oxygen fugacities [1]. However, recent work on Fe3+/Fe2+ ratios in molten silicates [2-4] suggests that the Fe3+ content should increase at high pressure for a given oxygen fugacity. While disproportionation was not observed in these experiments, it may nonetheless be occurring in the melt at high pressure [5]. Therefore, there may be non-negligible amounts of Fe3+ formed through metal-silicate equilibration at high pressures within the magma ocean. Homogenization of the mantle and further partitioning of Fe2+/Fe3+ as the magma ocean crystallizes may explain the oxygen fugacity of the Earth's mantle without requiring additional oxidation mechanisms. We present here models using different parameterizations for the Fe2+/Fe3+ thermodynamic relationships in silicate melts to constrain the evolution of the redox state of the magma ocean as it crystallizes. The model begins with metal-silicate partitioning at high pressure to form the core and set the initial Fe3+ abundance. Combined with previous work on oxygen absorption by magma oceans due to escape of H from H2O [6], we show that the upper layers of solidifying magma oceans should be more oxidized than the lower mantle. This model also suggests that large terrestrial planets should have more oxidized mantles than small planets. From a redox perspective, no change in the composition of the Earth's accreting material needs to be

  20. The oxidation state of Fe in glasses from the Kerguelen Large Igneous Province: Evidence for the changing oxidation state of the Indian Ocean Basin

    Science.gov (United States)

    Peterson, M. E.; Stolper, E.; Brounce, M. N.; Eiler, J. M.; Wallace, P. J.

    2017-12-01

    Oxygen fugacity (ƒO2) is a thermodynamic property of silicate magmas that can be influenced by volcanic processes such as melting, crystal fractionation, and degassing. Lavas erupted as part of large igneous provinces (LIPs) may reflect the impingement of mantle plumes on the lithosphere, and thus could provide constraints on the ƒO2 of plumes responsible for generation of LIPs. The Kerguelen plateau was emplaced during the break up of Gondwana and the initial opening of the Indian Ocean. Elevated 207Pb/204Pb and 208Pb/204Pb ratios at low 206Pb/204Pb suggests that continental lithosphere from Gondwana is present in the asthenosphere of this region. The Sr-Nd-Pb-He isotopic compositions of the Kerguelen lavas are variable and have been used to infer that the mantle sources of these lavas reflect contributions from the depleted upper mantle, a common plume component, and the EM1 mantle component (perhaps recycled lower continental crust; e.g. Frey et al., 2002). The ƒO2 of the lavas of the Kerguelen LIP may thus reflect mixing of the upper mantle (i.e., near QFM), the plume component, and continental crust. We present new μ-XANES measurements of Fe3+/ΣFe ratios in a suite of 21 submarine glasses from Kerguelen. Over a narrow range in MgO (6.5-7.5 wt%), these glasses have Fe3+/ΣFe ratios of 0.16-0.18, corresponding to an ƒO2 of QFM+0.23 to +0.38 (at 1 atm, 1200°C). The H2O/Ce and Cl/K ratios of these glasses suggest that they did not assimilate significant amounts of altered oceanic crust. Also, S-FeOT variations indicate that the magmas are near sulfide saturation. These lavas were erupted in 1000 m of water, precluding significant loss of S to a vapor phase. At a given MgO content, samples from Kerguelen have similar to higher Fe3+/ΣFe ratios than the average values found in samples from along the Indian mid-ocean ridge, which could indicate a more oxidized mantle source. In addition, increases in Fe3+/ΣFe ratios of the Kerguelen samples, over a narrow

  1. Tube pumices as strain markers of the ductile-brittle transition during magma fragmentation

    Science.gov (United States)

    Martí, J.; Soriano, C.; Dingwell, D. B.

    1999-12-01

    Magma fragmentation-the process by which relatively slow-moving magma transforms into a violent gas flow carrying fragments of magma-is the defining feature of explosive volcanism. Yet of all the processes involved in explosively erupting systems, fragmentation is possibly the least understood. Several theoretical and laboratory studies on magma degassing and fragmentation have produced a general picture of the sequence of events leading to the fragmentation of silicic magma. But there remains a debate over whether magma fragmentation is a consequence of the textural evolution of magma to a foamed state where disintegration of walls separating bubbles becomes inevitable due to a foam-collapse criterion, or whether magma is fragmented purely by stresses that exceed its tensile strength. Here we show that tube pumice-where extreme bubble elongation is observed-is a well-preserved magmatic `strain marker' of the stress state immediately before and during fragmentation. Structural elements in the pumice record the evolution of the magma's mechanical response from viscous behaviour (foaming and foam elongation) through the plastic or viscoelastic stage, and finally to brittle behaviour. These observations directly support the hypothesis that fragmentation occurs when magma undergoes a ductile-brittle transition and stresses exceed the magma's tensile strength.

  2. MAGMA: analysis of two-channel microarrays made easy.

    Science.gov (United States)

    Rehrauer, Hubert; Zoller, Stefan; Schlapbach, Ralph

    2007-07-01

    The web application MAGMA provides a simple and intuitive interface to identify differentially expressed genes from two-channel microarray data. While the underlying algorithms are not superior to those of similar web applications, MAGMA is particularly user friendly and can be used without prior training. The user interface guides the novice user through the most typical microarray analysis workflow consisting of data upload, annotation, normalization and statistical analysis. It automatically generates R-scripts that document MAGMA's entire data processing steps, thereby allowing the user to regenerate all results in his local R installation. The implementation of MAGMA follows the model-view-controller design pattern that strictly separates the R-based statistical data processing, the web-representation and the application logic. This modular design makes the application flexible and easily extendible by experts in one of the fields: statistical microarray analysis, web design or software development. State-of-the-art Java Server Faces technology was used to generate the web interface and to perform user input processing. MAGMA's object-oriented modular framework makes it easily extendible and applicable to other fields and demonstrates that modern Java technology is also suitable for rather small and concise academic projects. MAGMA is freely available at www.magma-fgcz.uzh.ch.

  3. Superheat in magma oceans

    Science.gov (United States)

    Jakes, Petr

    1992-01-01

    The existence of 'totally molten' planets implies the existence of a superheat (excess of heat) in the magma reservoirs since the heat buffer (i.e., presence of crystals having high latent heat of fusion) does not exist in a large, completely molten reservoir. Any addition of impacting material results in increase of the temperature of the melt and under favorable circumstances heat is stored. The behavior of superheat melts is little understood; therefore, we experimentally examined properties and behavior of excess heat melts at atmospheric pressures and inert gas atmosphere. Highly siliceous melts (70 percent SiO2) were chosen for the experiments because of the possibility of quenching such melts into glasses, the slow rate of reaction in highly siliceous composition, and the fact that such melts are present in terrestrial impact craters and impact-generated glasses. Results from the investigation are presented.

  4. Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

    International Nuclear Information System (INIS)

    Ma, Wen; Yildiz, Bilge; Herbert, F. William; Senanayake, Sanjaya D.

    2015-01-01

    The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr 1+ , Zr 2+ , and Zr 3+ as non-equilibrium oxidation states, in addition to Zr 4+ in the stoichiometric ZrO 2 . This finding resolves the long-debated question of whether it is possible to form any valence states between Zr 0 and Zr 4+ at the metal-oxide interface. The presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr

  5. Numerical modeling of magma-repository interactions

    NARCIS (Netherlands)

    Bokhove, Onno

    2001-01-01

    This report explains the numerical programs behind a comprehensive modeling effort of magma-repository interactions. Magma-repository interactions occur when a magma dike with high-volatile content magma ascends through surrounding rock and encounters a tunnel or drift filled with either a magmatic

  6. Oxidatively generated DNA/RNA damage in psychological stress states

    DEFF Research Database (Denmark)

    Jørgensen, Anders

    2013-01-01

    age-related somatic disorders. The overall aim of the PhD project was to investigate the relation between psychopathology, psychological stress, stress hormone secretion and oxidatively generated DNA and RNA damage, as measured by the urinary excretion of markers of whole-body DNA/RNA oxidation (8...... between the 24 h urinary cortisol excretion and the excretion of 8-oxodG/8-oxoGuo, determined in the same samples. Collectively, the studies could not confirm an association between psychological stress and oxidative stress on nucleic acids. Systemic oxidatively generated DNA/RNA damage was increased......Both non-pathological psychological stress states and mental disorders are associated with molecular, cellular and epidemiological signs of accelerated aging. Oxidative stress on nucleic acids is a critical component of cellular and organismal aging, and a suggested pathogenic mechanism in several...

  7. Charge state of oxide layer of SIMOX-structures

    CERN Document Server

    Askinazi, A Y; Dmitriev, V A; Miloglyadova, L V

    2001-01-01

    The charge state of the oxide layer of the SIMOX-structures, obtained in the course of forming the oxide layers, bricked up in the silicon volume, through the oxygen ions implantation into the Si, is studied. The charge state of the given structures is studied through the method of the layer-by-layer profiling, which makes it possible to obtain the dependence of the plane zones potential on the oxide layer thickness. It is established, that during the process of the SIMOX-structures formation in the oxide layer near the boundary with the Si there appear defects, responsible for the charge. The radiation from the near-the-ultraviolet (NUV) area without the applied electric field neutralizes the given charge. The simultaneous impact of the NUV-radiation and electric field leads to the formation of significantly positive charge

  8. Magma emplacement in 3D

    Science.gov (United States)

    Gorczyk, W.; Vogt, K.

    2017-12-01

    Magma intrusion is a major material transfer process in Earth's continental crust. Yet, the mechanical behavior of the intruding magma and its host are a matter of debate. In this study, we present a series of numerical thermo-mechanical experiments on mafic magma emplacement in 3D.In our model, we place the magmatic source region (40 km diameter) at the base of the mantle lithosphere and connect it to the crust by a 3 km wide channel, which may have evolved at early stages of magmatism during rapid ascent of hot magmatic fluids/melts. Our results demonstrate continental crustal response due to magma intrusion. We observe change in intrusion geometries between dikes, cone-sheets, sills, plutons, ponds, funnels, finger-shaped and stock-like intrusions as well as injection time. The rheology and temperature of the host-rock are the main controlling factors in the transition between these different modes of intrusion. Viscous deformation in the warm and deep crust favours host rock displacement and magma pools along the crust-mantle boundary forming deep-seated plutons or magma ponds in the lower to middle-crust. Brittle deformation in the cool and shallow crust induces cone-shaped fractures in the host rock and enables emplacement of finger- or stock-like intrusions at shallow or intermediate depth. A combination of viscous and brittle deformation forms funnel-shaped intrusions in the middle-crust. Low-density source magma results in T-shaped intrusions in cross-section with magma sheets at the surface.

  9. Effect of microorganisms on the plutonium oxidation states

    International Nuclear Information System (INIS)

    Lukšienė, Benedikta; Druteikienė, Rūta; Pečiulytė, Dalia; Baltrūnas, Dalis; Remeikis, Vidmantas; Paškevičius, Algimantas

    2012-01-01

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to 239 Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: ► Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). ► Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. ► Tested fungi did not show peculiarities to alter Pu oxidation state. ► The modified radiochemical method was applied to differentiate Pu oxidation states.

  10. Effect of microorganisms on the plutonium oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Luksiene, Benedikta, E-mail: bena@ar.fi.lt [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Druteikiene, Ruta [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Peciulyte, Dalia [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania); Baltrunas, Dalis; Remeikis, Vidmantas [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Paskevicius, Algimantas [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania)

    2012-03-15

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to {sup 239}Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: Black-Right-Pointing-Pointer Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). Black-Right-Pointing-Pointer Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. Black-Right-Pointing-Pointer Tested fungi did not show peculiarities to alter Pu oxidation state. Black-Right-Pointing-Pointer The modified radiochemical method was applied to differentiate Pu oxidation states.

  11. Re-appraisal of the Magma-rich versus Magma-poor Paradigm at Rifted Margins: consequences for breakup processes

    Science.gov (United States)

    Tugend, J.; Gillard, M.; Manatschal, G.; Nirrengarten, M.; Harkin, C. J.; Epin, M. E.; Sauter, D.; Autin, J.; Kusznir, N. J.; McDermott, K.

    2017-12-01

    Rifted margins are often classified based on their magmatic budget only. Magma-rich margins are commonly considered to have excess decompression melting at lithospheric breakup compared with steady state seafloor spreading while magma-poor margins have suppressed melting. New observations derived from high quality geophysical data sets and drill-hole data have revealed the diversity of rifted margin architecture and variable distribution of magmatism. Recent studies suggest, however, that rifted margins have more complex and polyphase tectono-magmatic evolutions than previously assumed and cannot be characterized based on the observed volume of magma alone. We compare the magmatic budget related to lithospheric breakup along two high-resolution long-offset deep reflection seismic profiles across the SE-Indian (magma-poor) and Uruguayan (magma-rich) rifted margins. Resolving the volume of magmatic additions is difficult. Interpretations are non-unique and several of them appear plausible for each case involving variable magmatic volumes and mechanisms to achieve lithospheric breakup. A supposedly 'magma-poor' rifted margin (SE-India) may show a 'magma-rich' lithospheric breakup whereas a 'magma-rich' rifted margin (Uruguay) does not necessarily show excess magmatism at lithospheric breakup compared with steady-state seafloor spreading. This questions the paradigm that rifted margins can be subdivided in either magma-poor or magma-rich margins. The Uruguayan and other magma-rich rifted margins appear characterized by an early onset of decompression melting relative to crustal breakup. For the converse, where the onset of decompression melting is late compared with the timing of crustal breakup, mantle exhumation can occur (e.g. SE-India). Our work highlights the difficulty in determining a magmatic budget at rifted margins based on seismic reflection data alone, showing the limitations of margin classification based solely on magmatic volumes. The timing of

  12. Iron Redox Systematics of Shergottites and Martian Magmas

    Science.gov (United States)

    Righter, Kevin; Danielson, L. R.; Martin, A. M.; Newville, M.; Choi, Y.

    2010-01-01

    Martian meteorites record a range of oxygen fugacities from near the IW buffer to above FMQ buffer [1]. In terrestrial magmas, Fe(3+)/ SigmaFe for this fO2 range are between 0 and 0.25 [2]. Such variation will affect the stability of oxides, pyroxenes, and how the melt equilibrates with volatile species. An understanding of the variation of Fe(3+)/SigmaFe for martian magmas is lacking, and previous work has been on FeO-poor and Al2O3-rich terrestrial basalts. We have initiated a study of the iron redox systematics of martian magmas to better understand FeO and Fe2O3 stability, the stability of magnetite, and the low Ca/high Ca pyroxene [3] ratios observed at the surface.

  13. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

    Energy Technology Data Exchange (ETDEWEB)

    Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Marry K.; Tyliszczak, T.; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

    2015-09-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.

  14. Chromium Oxidation State in Planetary Basalts: Oxygen Fugacity Indicator and Critical Variable for Cr-Spinel Stability

    Science.gov (United States)

    Bell, A. S.; Burger, P. V.; Le, Loan; Papike, J. J.; Jone, J.; Shearer, C. K.

    2014-01-01

    Cr is a ubiquitous and relatively abundant minor element in basaltic, planetary magmas. At the reduced oxidation states (oxidation state of Cr in in silicate melts. Here we present a series of 1-bar gas mixing experiments performed with a Fe-rich basaltic melt in which have determined the Cr redox ratio of the melt at over a range of fO2 values by measuring this quantity in olivine with X-ray Absorption Near Edge Spectroscopy (XANES). The measured Cr redox ratio of the olivine phenocrysts can be readily converted to the ratio present in the conjugate melt via the ratio of crystal-liquid partition coefficients for Cr3+ and Cr2+. We have applied these results to modeling Cr spinel stability and Cr redox ratios in a primitive, iron-rich martian basalt.

  15. Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

    International Nuclear Information System (INIS)

    Morss, L.R.

    1992-01-01

    The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

  16. Oxidative Stress and Heart Failure in Altered Thyroid States

    Directory of Open Access Journals (Sweden)

    Pallavi Mishra

    2012-01-01

    Full Text Available Increased or reduced action of thyroid hormone on certain molecular pathways in the heart and vasculature causes relevant cardiovascular derangements. It is well established that hyperthyroidism induces a hyperdynamic cardiovascular state, which is associated with a faster heart rate, enhanced left ventricular systolic and diastolic function whereas hypothyroidism is characterized by the opposite changes. Hyperthyroidism and hypothyroidism represent opposite clinical conditions, albeit not mirror images. Recent experimental and clinical studies have suggested the involvement of ROS tissue damage under altered thyroid status. Altered-thyroid state-linked changes in heart modify their susceptibility to oxidants and the extent of the oxidative damage they suffer following oxidative challenge. Chronic increase in the cellular levels of ROS can lead to a catastrophic cycle of DNA damage, mitochondrial dysfunction, further ROS generation and cellular injury. Thus, these cellular events might play an important role in the development and progression of myocardial remodeling and heart failure in altered thyroid states (hypo- and hyper-thyroidism. The present review aims at elucidating the various signaling pathways mediated via ROS and their modulation under altered thyroid state and the possibility of antioxidant therapy.

  17. Weak solutions of magma equations

    International Nuclear Information System (INIS)

    Krishnan, E.V.

    1999-01-01

    Periodic solutions in terms of Jacobian cosine elliptic functions have been obtained for a set of values of two physical parameters for the magma equation which do not reduce to solitary-wave solutions. It was also obtained solitary-wave solutions for another set of these parameters as an infinite period limit of periodic solutions in terms of Weierstrass and Jacobian elliptic functions

  18. Magma flow through elastic-walled dikes

    NARCIS (Netherlands)

    Bokhove, Onno; Woods, A.W.; de Boer, A

    2005-01-01

    A convection–diffusion model for the averaged flow of a viscous, incompressible magma through an elastic medium is considered. The magma flows through a dike from a magma reservoir to the Earth’s surface; only changes in dike width and velocity over large vertical length scales relative to the

  19. Evolution of the Oxidation State of the Earth's Mantle

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, E.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3(+) at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. In our previous experiments on shergottite compositions, variable fO2, T, and P less than 4 GPa, Fe3(+)/sigma Fe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3(+)/sigma Fe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3(+). Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Preliminary multi-anvil experiments with Knippa basalt as the starting composition were conducted at 5-7 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal to Fe3(+)/2(+). Experiments are underway to produce glassy samples that can be measured by EELS and XANES, and are conducted at higher pressures.

  20. Corrosion-product transport, oxidation state and remedial measures

    International Nuclear Information System (INIS)

    Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

    1998-10-01

    The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. Efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness and as a monitor of system corrosion effects. The discussion is based mostly on the results of observations from Ontario Hydro plants, and their comparisons with pressurized-water reactors. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of layup and various startup conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on CPT on the primary side of SGs are also discussed. (author)

  1. Corrosion-product transport, oxidation state and remedial measures

    International Nuclear Information System (INIS)

    Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

    1998-01-01

    The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. The efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness, and as a monitor of system corrosion effects. The discussion is based mostly on the results and observations from Ontario Hydro plants, and their comparisons with PWRs. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of lay-up and various start-up conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on corrosion-product transport on the primary side of steam generators are also discussed. (author)

  2. Influence of oxidation state on the pH dependence of hydrous iridium oxide films

    International Nuclear Information System (INIS)

    Steegstra, Patrick; Ahlberg, Elisabet

    2012-01-01

    Many electrochemical reactions taking place in aqueous solution consume or produce protons. The pH in the diffusion layer can therefore be significantly altered during the reaction and there is a need for in situ pH measurements tracing this near surface pH. In the present paper the rotating ring disc technique was used to measure near surface pH changes during oxygen reduction, utilising hydrous iridium oxide as the pH sensing probe. Before such experiments a good understanding of the pH sensing properties of these films is required and the impact of the oxidation state of the film on the pH sensing properties was investigated as well as the influence of solution redox species. The pH sensitivity (depicted by dE/dpH) was found to depend on the average oxidation state of the film in a manner resembling the cyclic voltammetry response. In all cases the pH response is “supernernstian” with more than one proton per electron. The origin of this behaviour is discussed in the context of acid-base properties of the film and the existence of both hydrous and anhydrous oxide phases. The pH response depends also on the redox properties of the solution but can be optimised for various purposes by conditioning the film at different potentials. This was clearly illustrated by adding hydrogen peroxide, an intermediate in the oxygen reduction reaction, to the solution. It was shown that hydrous iridium oxide can be used as a reliable in situ pH sensor provided that care is taken to optimise the oxidation state of the film.

  3. Pentavalent Uranium Chemistry - Synthetic Pursuit Of A Rare Oxidation State

    Energy Technology Data Exchange (ETDEWEB)

    Graves, Christopher R [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

    2009-01-01

    This feature article presents a comprehensive overview of pentavalent uranium systems in non-aqueous solution with a focus on the various synthetic avenues employed to access this unusual and very important oxidation state. Selected characterization data and theoretical aspects are also included. The purpose is to provide a perspective on this rapidly evolving field and identify new possibilities for future developments in pentavalent uranium chemistry.

  4. Study of uranium oxidation states in geological material.

    Science.gov (United States)

    Pidchenko, I; Salminen-Paatero, S; Rothe, J; Suksi, J

    2013-10-01

    A wet chemical method to determine uranium (U) oxidation states in geological material has been developed and tested. The problem faced in oxidation state determinations with wet chemical methods is that U redox state may change when extracted from the sample material, thereby leading to erroneous results. In order to quantify and monitor U redox behavior during the acidic extraction in the procedure, an analysis of added isotopic redox tracers, (236)U(VI) and (232)U(IV), and of variations in natural uranium isotope ratio ((234)U/(238)U) of indigenous U(IV) and U(VI) fractions was performed. Two sample materials with varying redox activity, U bearing rock and U-rich clayey lignite sediment, were used for the tests. The Fe(II)/Fe(III) redox-pair of the mineral phases was postulated as a potentially disturbing redox agent. The impact of Fe(III) on U was studied by reducing Fe(III) with ascorbic acid, which was added to the extraction solution. We observed that ascorbic acid protected most of the U from oxidation. The measured (234)U/(238)U ratio in U(IV) and U(VI) fractions in the sediment samples provided a unique tool to quantify U oxidation caused by Fe(III). Annealing (sample heating) to temperatures above 500 °C was supposed to heal ionizing radiation induced defects in the material that can disturb U redox state during extraction. Good agreement between two independent methods was obtained for DL-1a material: an average 38% of U(IV) determined by redox tracer corrected wet chemistry and 45% for XANES. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Studies of the Tc oxidation states in humic acid solutions

    International Nuclear Information System (INIS)

    Wang Bo; Liu Dejun; Yao Jun

    2010-01-01

    The oxidation state is an important aspect of the speciation of Tc in groundwater that contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg L -1 and the Tc (Ⅶ) concentration range is about 10 -8 mol l -1 . The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation methods were carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (IPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (Ⅳ) and Tc (Ⅶ) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentrations are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (Ⅶ) is very stable in the Tc (Ⅶ)-humic acid system during a 350 days experimental period, and the Tc (Ⅳ) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (Ⅶ) in aqueous solutions under anaerobic conditions. That is means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

  6. Studies of Tc oxidation states in humic acid solutions

    International Nuclear Information System (INIS)

    Wang Bo; Liu Dejun; Yao Jun

    2011-01-01

    The oxidation state of Tc is an important aspect of the speciation in groundwater which contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg/L and the Tc (VII) concentration is about 10 -8 mol/L. The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation method was carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (TPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (IV) and Tc (VII) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentration are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (VII) is very stable in the Tc (VII)-humic acid system during a 350 days experimental period, and the Tc (IV) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (VII) in aqueous solutions under anaerobic conditions. That means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

  7. Caldera resurgence driven by magma viscosity contrasts.

    Science.gov (United States)

    Galetto, Federico; Acocella, Valerio; Caricchi, Luca

    2017-11-24

    Calderas are impressive volcanic depressions commonly produced by major eruptions. Equally impressive is the uplift of the caldera floor that may follow, dubbed caldera resurgence, resulting from magma accumulation and accompanied by minor eruptions. Why magma accumulates, driving resurgence instead of feeding large eruptions, is one of the least understood processes in volcanology. Here we use thermal and experimental models to define the conditions promoting resurgence. Thermal modelling suggests that a magma reservoir develops a growing transition zone with relatively low viscosity contrast with respect to any newly injected magma. Experiments show that this viscosity contrast provides a rheological barrier, impeding the propagation through dikes of the new injected magma, which stagnates and promotes resurgence. In explaining resurgence and its related features, we provide the theoretical background to account for the transition from magma eruption to accumulation, which is essential not only to develop resurgence, but also large magma reservoirs.

  8. Study on the solid state chemistry of ternary uranium oxides

    International Nuclear Information System (INIS)

    Yamashita, Toshiyuki

    1988-03-01

    With the increase of burnup of uranium oxide fuels, various kinds of fission products are formed, and the oxygen atoms combined with the consumed heavy atoms are freed. The solid state chemical and/or thermodynamic properties of these elements at high temperatures are complex, and have not been well clarified. In the present report, an approach was taken that the chemical interactions between UO 2 and these fission products can be regarded as causing overlapped effects of composing ternary uranium oxides, and formation reactions and phase behavior were studied for several ternary uranium oxides with typical fission product elements such as alkaline earth metals and rare earth elements. Precise determination methods for the composition of ternary uranium oxides were developed. The estimated accuracies for x and y values in M y U 1-y O 2+x were ± 0.006 and ± 0.004, respectively. The thermodynamic properties and the lattice parameters of the phases in the Ca-U-O and Pr-U-O systems were discussed in relation to the composition determined by the methods. Crystal structure analyses of cadmium monouranates were made with X-ray diffraction method. (author) 197 refs

  9. Optoelectronic properties of valence-state-controlled amorphous niobium oxide

    Science.gov (United States)

    Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira; Katayama, Shota; Matsushima, Koichi; Itagaki, Naho; Yoshida, Hisao; Ohta, Hiromichi

    2016-06-01

    In order to understand the optoelectronic properties of amorphous niobium oxide (a-NbO x ), we have investigated the valence states, local structures, electrical resistivity, and optical absorption of a-NbO x thin films with various oxygen contents. It was found that the valence states of Nb ion in a-NbO x films can be controlled from 5+  to 4+  by reducing oxygen pressure during film deposition at room temperature, together with changing the oxide-ion arrangement around Nb ion from Nb2O5-like to NbO2-like local structure. As a result, a four orders of magnitude reduction in the electrical resistivity of a-NbO x films was observed with decreasing oxygen content, due to the carrier generation caused by the appearance and increase of an oxygen-vacancy-related subgap state working as an electron donor. The tunable optoelectronic properties of a-NbO x films by valence-state-control with oxygen-vacancy formation will be useful for potential flexible optoelectronic device applications.

  10. Predicting spent fuel oxidation states in a tuff repository

    International Nuclear Information System (INIS)

    Einziger, R.E.; Woodley, R.E.

    1987-01-01

    Nevada Nuclear Waste Storage Investigations Project (NNWSI) is studying the suitability of the tuffaceous rocks at Yucca Mountain as a waste repository for spent fuel disposal. The oxidation state of the LWR spent fuel in the moist air environment of a tuff repository could be a significant factor in determining its leaching and dissolution characteristics. Predictions as to which oxidation states would be present are important in analyzing such a repository and thus the present study was undertaken. A set of TGA (thermogravimetric analysis) tests were conducted on well-controlled samples of irradiated PWR fuel with time and temperature as the only variables. The tests were conducted between 140 and 225 0 C for a duration up to 2200 hours. The weight gain curves were analyzed in terms of diffusion through a layer of U 3 O 7 , diffusion into the grains to form a solid solution, a simplified empirical representation of a combination of grain boundary diffusion and bulk grain oxidation. Reaction rate constants were determined in each case, but analysis of these data could not establish a definitive mechanism. 21 refs., 10 figs., 3 tabs

  11. The oxidation state of sulfur in apatite: A new oxybarometer?

    Science.gov (United States)

    Fiege, A.; Konecke, B.; Kim, Y.; Simon, A. C.; Becker, U.; Parat, F.

    2016-12-01

    Oxygen fugacity (fO2) of magmatic and hydrothermal systems influences, for instance, crystallization and degassing processes as well as metal solubilities in melts and fluids. Apatite is a ubiquitous mineral in magmatic and hydrothermal environments that can record and preserve volatile zonation. It can contain several thousand μg/g of the redox sensitive element sulfur (S), making S-in-apatite a potential fO2 sensor. Despite the polyvalent properties of S (e.g., S2-, S4+, S6+), the oxidation state and incorporation mechanisms of S in the apatite structure are poorly understood. In this study, the oxidation state of S-in-apatite as a function of fO2 is investigated using X-ray absorption near-edge structures (XANES) spectroscopy at the S K-edge. Apatites crystallized from lamproitic melts at 1000°C, 300 MPa and over a broad range of fO2 and sulfur fugacities (fS2) were measured. Peaks corresponding to S6+ ( 2482 eV), S4+ ( 2478 eV) and S2- ( 2470 eV) were identified in apatite. The integrated S6+/STotal (STotal = S6+ + S4+ + S2-) peak area ratios show a distinct positive correlation with fO2, increasing from 0.17 at FMQ+0 to 0.96 at FMQ+3. Ab-initio calculations were performed to further understand the energetics and geometry of incorporation of S6+, S4+ and S2- into the apatite (F-, Cl-, OH-) end-members. The results confirm that apatite can contain three different oxidations states of S (S6+, S4+, S2-) as a function of fO2. This makes apatite probably the first geologically relevant mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions. We emphasize that the strong dependence of the S oxidation state in apatite as a function of fO2 is also coupled with changing S content of apatite and co-existing melt (i.e., with changing fS2), resulting in a complex correlation between [1] apatite-melt (or fluid) partitioning, [2] redox conditions and [3] the melt and/or fluid composition, making the application of previously

  12. Pressure effect on Fe3+/FeT in silicate melts and applications to magma redox, particularly in magma oceans

    Science.gov (United States)

    Zhang, H.; Hirschmann, M. M.

    2014-12-01

    The proportions of Fe3+ and Fe2+ in magmas reflect the redox conditions of their origin and influence the chemical and physical properties of natural silicate liquids, but the relationship between Fe3+/FeT and oxygen fugacity depends on pressure owing to different molar volumes and compressibilities of Fe3+ and Fe2+ in silicates. An important case where the effect of pressure effect may be important is in magma oceans, where well mixed (and therefore potentially uniform Fe3+/FeT) experiencses a wide range of pressures, and therefore can impart different ƒO2 at different depths, influencing magma ocean degassing and early atmospheres, as well as chemical gradients within magma oceans. To investigate the effect of pressure on magmatic Fe3+/FeT we conducted high pressure expeirments on ƒO2-buffered andestic liquids. Quenched glasses were analyzed by Mössbauer spectroscopy. To verify the accuracy of Mössbauer determinations of Fe3+/FeT in glasses, we also conducted low temperature Mössbauer studies to determine differences in the recoilless fraction (ƒ) of Fe2+ and Fe3. These indicate that room temperature Mössbauer determinations of on Fe3+/FeT glasses are systematically high by 4% compared to recoilless-fraction corrected ratios. Up to 7 GPa, pressure decreases Fe3+/FeT, at fixed ƒO2 relative to metal-oxide buffers, meaning that an isochemical magma will become more reduced with decreasing pressure. Consequently, for small planetary bodies such as the Moon or Mercury, atmospheres overlying their MO will be highly reducing, consisting chiefly of H2 and CO. The same may also be true for Mars. The trend may reverse at higher pressure, as is the case for solid peridotite, and so for Earth, Venus, and possibly Mars, more oxidized atmospheres above MO are possible. Diamond anvil experiments are underway to examine this hypothesis.

  13. Sulfur diffusion in dacitic melt at various oxidation states: Implications for volcanic degassing

    Science.gov (United States)

    Lierenfeld, Matthias Bernhard; Zajacz, Zoltán; Bachmann, Olivier; Ulmer, Peter

    2018-04-01

    The diffusivity of S in a hydrous dacitic melt (4.5-6.0 wt.% H2O) has been investigated in the temperature (T) and pressure (P) range of 950 °C to 1100 °C and 200 to 250 MPa, respectively. Three series of experiments were conducted at relatively low oxygen fugacity (fO2) conditions [0.8 log units below fayalite-magnetite-quartz equilibrium (FMQ -0.8); referred to as "low fO2"] and high fO2 conditions (FMQ +2.5; referred to as "high fO2") to determine if the diffusivity of S is affected by its oxidation state and speciation. Sulfur concentration profiles were measured by electron microprobe and the diffusion coefficient (D) was calculated by fitting these profiles. Sulfur diffusion is approximately one order of magnitude faster when S is dominantly present as sulfide species (low fO2) in comparison to the sulfate dominated experiments (high fO2). The following Arrhenian equations were obtained for high and low fO2 conditions at 200 MPa: high fO2: D = 10-5.92±0.86 * exp ({-137.3±21.5 kJ/mol}/{RT}) low fO2: D = 10-5.18±1.39 * exp ({-125.7±34.4 kJ/mol}/{RT}) where D is the average diffusion coefficient in m2 s-1, R is the gas constant in 8.3144 J mol-1 K-1 and T is the temperature in K. Our results demonstrate for the first time in natural melts that S diffusion is strongly sensitive to fO2. Our S diffusivities under low fO2 conditions are only slightly slower of those found for H2O, suggesting that S can be rather efficiently purged from reduced dacitic melts during volcanic eruptions. However, for more oxidized systems (e.g. subduction zones), S diffusion will be much slower and will hinder equilibrium syn-eruptive degassing during rapid decompression. Therefore, we conclude that the "excess" measured during many explosive volcanic eruptions in arcs is dominantly derived from S-rich bubble accumulation in the eruptible portion of the magma reservoir.

  14. Chelation and stabilization of berkelium in oxidation state +IV

    Science.gov (United States)

    Deblonde, Gauthier J.-P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.; An, Dahlia D.; Illy, Marie-Claire; Ralston, Corie Y.; Brabec, Jiri; de Jong, Wibe A.; Strong, Roland K.; Abergel, Rebecca J.

    2017-09-01

    Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin—a mammalian metal transporter—in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.

  15. The 3550 year BP-1944 A.D.magma-plumbing system of Somma-Vesuvius: constraints on its behaviour and present state through a review of Sr-Nd isotope data

    Directory of Open Access Journals (Sweden)

    G. Mastrolorenzo

    2004-06-01

    Full Text Available Vesuvius, dominating the densely-populated Neapolitan area, is one of the most dangerous volcanoes in the World. Its destructive power derives from energetic subplinian and plinian eruptions, such as the one which occurred in 79 A.D. Generally such large-scale events follow a long period of quiescence; a behaviour interpreted as the gradual build-up of magma volumes between periods of major activity. After the 1631 subplinian eruption until the last 1944 A.D. eruption, it experienced an almost continuous and less energetic explosive/effusive activity. The erupted magmas are characterized by undersaturated potassic to ultrapotassic nature, and compositional and Sr-isotopic variability. Furthermore geobarometric studies indicate two different crystallization depths located at 4 and >11 km, respectively. According to most of the recent literature, the eruptions were triggered by the injection in a shallower magma chamber, of isotopically distinct magma batches derived from heterogeneous mantle source(s and/or contamination processes occurred within the deep reservoir. In our review of petrochemical data, we consider the period between the 3550 years BP plinian eruption and the 472 A.D. sub-plinian eruption, which includes 79 A.D. event, and the most recent period of activity which started in 1631 A.D. and lasted up to the 1944 A.D. eruption, characterized by a near continuous effusive/explosive activity. For both periods we identify a correlation between Sr-isotopical features of magmas and their crystallization depth. In particular, we show that pyroxenes have Sr-isotopic ratios lower than 0.7074 and an equilibrium crystallization depth of 22-11 km. Moreover feldspars have higher 87Sr/86Sr values (0.7075-7 and an equilibrium crystallization depth of about 4 km. Therefore the most radiogenic magmas did not derive from a deeper reservoir but their higher Sr-isotopic ratios have been acquired at a shallower depth likely by crustal contamination

  16. Partially molten magma ocean model

    International Nuclear Information System (INIS)

    Shirley, D.N.

    1983-01-01

    The properties of the lunar crust and upper mantle can be explained if the outer 300-400 km of the moon was initially only partially molten rather than fully molten. The top of the partially molten region contained about 20% melt and decreased to 0% at 300-400 km depth. Nuclei of anorthositic crust formed over localized bodies of magma segregated from the partial melt, then grew peripherally until they coverd the moon. Throughout most of its growth period the anorthosite crust floated on a layer of magma a few km thick. The thickness of this layer is regulated by the opposing forces of loss of material by fractional crystallization and addition of magma from the partial melt below. Concentrations of Sr, Eu, and Sm in pristine ferroan anorthosites are found to be consistent with this model, as are trends for the ferroan anorthosites and Mg-rich suites on a diagram of An in plagioclase vs. mg in mafics. Clustering of Eu, Sr, and mg values found among pristine ferroan anorthosites are predicted by this model

  17. Grain to outcrop-scale frozen moments of dynamic magma mixing in the syenite magma chamber, Yelagiri Alkaline Complex, South India

    Directory of Open Access Journals (Sweden)

    M.L. Renjith

    2014-11-01

    Full Text Available Magma mixing process is unusual in the petrogenesis of felsic rocks associated with alkaline complex worldwide. Here we present a rare example of magma mixing in syenite from the Yelagiri Alkaline Complex, South India. Yelagiri syenite is a reversely zoned massif with shoshonitic (Na2O + K2O=5–10 wt.%, Na2O/K2O = 0.5–2, TiO2 <0.7 wt.% and metaluminous character. Systematic modal variation of plagioclase (An11–16 Ab82–88, K-feldspar (Or27–95 Ab5–61, diopside (En34–40Fs11–18Wo46–49, biotite, and Ca-amphibole (edenite build up three syenite facies within it and imply the role of in-situ fractional crystallization (FC. Evidences such as (1 disequilibrium micro-textures in feldspars, (2 microgranular mafic enclaves (MME and (3 synplutonic dykes signify mixing of shoshonitic mafic magma (MgO = 4–5 wt.%, SiO2 = 54–59 wt.%, K2O/Na2O = 0.4–0.9 with syenite. Molecular-scale mixing of mafic magma resulted disequilibrium growth of feldspars in syenite. Physical entity of mafic magma preserved as MME due to high thermal-rheological contrast with syenite magma show various hybridization through chemical exchange, mechanical dilution enhanced by chaotic advection and phenocryst migration. In synplutonic dykes, disaggregation and mixing of mafic magma was confined within the conduit of injection. Major-oxides mass balance test quantified that approximately 0.6 portions of mafic magma had interacted with most evolved syenite magma and generated most hybridized MME and dyke samples. It is unique that all the rock types (syenite, MME and synplutonic dykes share similar shoshonitic and metaluminous character; mineral chemistry, REE content, coherent geochemical variation in Harker diagram suggest that mixing of magma between similar composition. Outcrop-scale features of crystal accumulation and flow fabrics also significant along with MME and synplutonic dykes in syenite suggesting that Yelagiri syenite magma chamber had evolved

  18. Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

    International Nuclear Information System (INIS)

    Meublat, L.

    1989-10-01

    The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), CIO 2 + RuF 6 - , a new compound well identified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

  19. Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

    International Nuclear Information System (INIS)

    Meublat, L.

    1989-01-01

    The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), ClO 2 + RuF 6 - , a new compound well idendified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

  20. Zircon reveals protracted magma storage and recycling beneath Mount St. Helens

    Science.gov (United States)

    Claiborne, L.L.; Miller, C.F.; Flanagan, D.M.; Clynne, M.A.; Wooden, J.L.

    2010-01-01

    Current data and models for Mount St. Helens volcano (Washington, United States) suggest relatively rapid transport from magma genesis to eruption, with no evidence for protracted storage or recycling of magmas. However, we show here that complex zircon age populations extending back hundreds of thousands of years from eruption age indicate that magmas regularly stall in the crust, cool and crystallize beneath the volcano, and are then rejuvenated and incorporated by hotter, young magmas on their way to the surface. Estimated dissolution times suggest that entrained zircon generally resided in rejuvenating magmas for no more than about a century. Zircon elemental compositions reflect the increasing influence of mafic input into the system through time, recording growth from hotter, less evolved magmas tens of thousands of years prior to the appearance of mafic magmas at the surface, or changes in whole-rock geochemistry and petrology, and providing a new, time-correlated record of this evolution independent of the eruption history. Zircon data thus reveal the history of the hidden, long-lived intrusive portion of the Mount St. Helens system, where melt and crystals are stored for as long as hundreds of thousands of years and interact with fresh influxes of magmas that traverse the intrusive reservoir before erupting. ?? 2010 Geological Society of America.

  1. Shallow magma diversions during explosive diatreme-forming eruptions.

    Science.gov (United States)

    Le Corvec, Nicolas; Muirhead, James D; White, James D L

    2018-04-13

    The diversion of magma is an important mechanism that may lead to the relocation of a volcanic vent. Magma diversion is known to occur during explosive volcanic eruptions generating subterranean excavation and remobilization of country and volcanic rocks. However, feedbacks between explosive crater formation and intrusion processes have not been considered previously, despite their importance for understanding evolving hazards during volcanic eruptions. Here, we apply numerical modeling to test the impacts of excavation and subsequent infilling of diatreme structures on stress states and intrusion geometries during the formation of maar-diatreme complexes. Explosive excavation and infilling of diatremes affects local stress states which inhibits magma ascent and drives lateral diversion at various depths, which are expected to promote intra-diatreme explosions, host rock mixing, and vent migration. Our models demonstrate novel mechanisms explaining the generation of saucer-shaped sills, linked with magma diversion and enhanced intra-diatreme explosive fragmentation during maar-diatreme volcanism. Similar mechanisms will occur at other volcanic vents producing crater-forming eruptions.

  2. Intestinal Oxidative State Can Alter Nutrient and Drug Bioavailability

    Directory of Open Access Journals (Sweden)

    Faria Ana

    2009-01-01

    Full Text Available Organic cations (OCs are substances of endogenous (e.g., dopamine, choline or exogenous (e.g., drugs like cimetidine origin that are positively charged at physiological ph. since many of these compounds can not pass the cell membrane freely, their transport in or out of cells must be mediated by specific transport systems. Transport by organic cation transporters (OCTs can be regulated rapidly by altering their trafficking and/or affinities in response to stimuli. However, for example, a specific disease could lead to modifications in the expression of OCTs. Chronic exposure to oxidative stress has been suggested to alter regulation and functional activity of proteins through several pathways. According to results from a previous work, oxidation-reduction pathways were thought to be involved in intestinal organic cation uptake modulation. The present work was performed in order to evaluate the influence of oxidative stressors, especially glutathione, on the intestinal organic cation absorption. For this purpose, the effect of compounds with different redox potential (glutathione, an endogenous antioxidant, and procyanidins, diet antioxidants was assessed on MPP+ (1-methyl-4-phenylpyridinium iodide uptake in an enterocyte cell line (Caco-2. Caco-2 cells were subcultured with two different media conditions (physiological: 5 mM glucose, referred as control cells; and high-glucose: 25 mM glucose, referred as HG cells. In HG cells, the uptake was significantly lower than in control cells. Redox changing interventions affected Mpp+ uptake, both in control and in high-glucose Caco-2 cells. Cellular glutathione levels could have an important impact on membrane transporter activity. The results indicate that modifications in the cellular oxidative state modulate MPP+ uptake by Caco-2 cells. Such modifications may reflect in changes of nutrient and drug bioavailability.

  3. Persistence of oxidation state III of gold in thione coordination

    Science.gov (United States)

    Jääskeläinen, Sirpa; Koskinen, Laura; Kultamaa, Matti; Haukka, Matti; Hirva, Pipsa

    2017-05-01

    Ligands N,N'-tetramethylthiourea and 2-mercapto-1-methyl-imidazole form stable Au(III) complexes [AuCl3(N,N'-tetramethylthiourea)] (1) and [AuCl3(2-mercapto-1-methyl-imidazole)] (2) instead of reducing the Au(III) metal center into Au(I), which would be typical for the attachment of sulfur donors. Compounds 1 and 2 were characterized by spectroscopic methods and by X-ray crystallography. The spectroscopic details were explained by simulation of the UV-Vis spectra via the TD-DFT method. Additionally, computational DFT studies were performed in order to find the reason for the unusual oxidation state in the crystalline materials. The preference for Au(III) can be explained via various weak intra- and intermolecular interactions present in the solid state structures. The nature of the interactions was further investigated by topological charge density analysis via the QTAIM method.

  4. Primitive magmas at five Cascade volcanic fields: Melts from hot, heterogeneous sub-arc mantle

    Science.gov (United States)

    Bacon, C.R.; Bruggman, P.E.; Christiansen, R.L.; Clynne, M.A.; Donnelly-Nolan, J. M.; Hildreth, W.

    1997-01-01

    Major and trace element concentrations, including REE by isotope dilution, and Sr, Nd, Pb, and O isotope ratios have been determined for 38 mafic lavas from the Mount Adams, Crater Lake, Mount Shasta, Medicine Lake, and Lassen volcanic fields, in the Cascade arc, northwestern part of the United States. Many of the samples have a high Mg# [100Mg/(Mg + FeT) > 60] and Ni content (>140 ppm) such that we consider them to be primitive. We recognize three end-member primitive magma groups in the Cascades, characterized mainly by their trace-element and alkali-metal abundances: (1) High-alumina olivine tholeiite (HAOT) has trace element abundances similar to N-MORB, except for slightly elevated LILE, and has Eu/Eu* > 1. (2) Arc basalt and basaltic andesite have notably higher LILE contents, generally have higher SiO2 contents, are more oxidized, and have higher Cr for a given Ni abundance than HAOT. These lavas show relative depletion in HFSE, have lower HREE and higher LREE than HAOT, and have smaller Eu/Eu* (0.94-1.06). (3) Alkali basalt from the Simcoe volcanic field east of Mount Adams represents the third end-member, which contributes an intraplate geochemical signature to magma compositions. Notable geochemical features among the volcanic fields are: (1) Mount Adams rocks are richest in Fe and most incompatible elements including HFSE; (2) the most incompatible-element depleted lavas occur at Medicine Lake; (3) all centers have relatively primitive lavas with high LILE/HFSE ratios but only the Mount Adams, Lassen, and Medicine Lake volcanic fields also have relatively primitive rocks with an intraplate geochemical signature; (4) there is a tendency for increasing 87Sr/86Sr, 207Pb/204Pb, and ??18O and decreasing 206Pb/204Pb and 143Nd/144Nd from north to south. The three end-member Cascade magma types reflect contributions from three mantle components: depleted sub-arc mantle modestly enriched in LILE during ancient subduction; a modern, hydrous subduction component

  5. Proteomic indicators of oxidation and hydration state in colorectal cancer

    Directory of Open Access Journals (Sweden)

    Jeffrey M. Dick

    2016-07-01

    Full Text Available New integrative approaches are needed to harness the potential of rapidly growing datasets of protein expression and microbial community composition in colorectal cancer. Chemical and thermodynamic models offer theoretical tools to describe populations of biomacromolecules and their relative potential for formation in different microenvironmental conditions. The average oxidation state of carbon (ZC can be calculated as an elemental ratio from the chemical formulas of proteins, and water demand per residue ( ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O is computed by writing the overall formation reactions of proteins from basis species. Using results reported in proteomic studies of clinical samples, many datasets exhibit higher mean ZC or ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O of proteins in carcinoma or adenoma compared to normal tissue. In contrast, average protein compositions in bacterial genomes often have lower ZC for bacteria enriched in fecal samples from cancer patients compared to healthy donors. In thermodynamic calculations, the potential for formation of the cancer-related proteins is energetically favored by changes in the chemical activity of H2O and fugacity of O2 that reflect the compositional differences. The compositional analysis suggests that a systematic change in chemical composition is an essential feature of cancer proteomes, and the thermodynamic descriptions show that the observed proteomic transformations in host tissue could be promoted by relatively high microenvironmental oxidation and hydration states.

  6. Composition and oxidation state of sulfur in atmospheric particulate matter

    Directory of Open Access Journals (Sweden)

    A. F. Longo

    2016-10-01

    Full Text Available The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS and X-ray fluorescence (XRF microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

  7. Interaction of coeval felsic and mafic magmas from the Kanker ...

    Indian Academy of Sciences (India)

    66

    20 crystallization of the latter, results in hybrid magmas under the influence of thermal and. 21 chemical exchange. The mechanical exchange occurs between the coexisting magmas due to. 22 viscosity contrast, if the mafic magma enters slightly later into the magma chamber, when the. 23 felsic magma started to crystallize.

  8. Oxidation states of Fe and Ti in blue sapphire

    International Nuclear Information System (INIS)

    Wongrawang, P; Wongkokua, W; Monarumit, N; Thammajak, N; Wathanakul, P

    2016-01-01

    X-ray absorption near-edge spectroscopy (XANES) can be used to study the oxidation state of a dilute system such as transition metal defects in solid-state samples. In blue sapphire, Fe and Ti are defects that cause the blue color. Inter-valence charge transfer (IVCT) between Fe 2+ and Ti 4+ has been proposed to describe the optical color’s origin. However, the existence of divalent iron cations has not been thoroughly investigated. Fluorescent XANES is therefore employed to study K-edge absorptions of Fe and Ti cations in various blue sapphire samples including natural, synthetic, diffused and heat-treated sapphires. All the samples showed an Fe absorption edge at 7124 eV, corresponding to the Fe 3+ state; and Ti at 4984 eV, corresponding to Ti 4+ . From these results, we propose Fe 3+ -Ti 4+ mixed acceptor states located at 1.75 eV and 2.14 eV above the valence band of corundum, that correspond to 710 nm and 580 nm bands of UV–vis absorption spectra, to describe the cause of the color of blue sapphire. (paper)

  9. Magma Mixing: Magmatic Enclaves in Morne Micotrin, Dominica

    Science.gov (United States)

    Hickernell, S.; Frey, H. M.; Manon, M. R. F.; Waters, L. E.

    2017-12-01

    Magmatic enclaves in volcanic rocks provide direct evidence of magma mingling/mixing within a magma reservoir and may reinvigorate the system and trigger eruption, as documented at the Soufriere Hills in Montserrat. Lava domes on the neighboring island of Dominica also contain multiple enclave populations and may be evidence for similar magma chamber processes. The central dome of Micotrin is at the head of the Roseau Valley, which was filled with 3 km3 of pyroclastic deposits from eruptions spanning 65 - 25 ka. There appear to be two distinct types of enclaves in the crystal-rich Micotrin andesites (60 wt% SiO2), fine-grained and coarse-grained. Fine-grained mafic enclaves (52 wt% SiO2) vary in size from 1 to 15 cm in diameter, whereas the coarse-grained enclaves are generally larger and range from 3-20 cm. Fine-grained enclaves are saturated in plag (35%) + opx (35%) + cpx (20%) + oxides (10%). Average pyroxenes are 0.01 to 0.02 cm in size, whereas plagioclase averages 0.05 cm and up to 0.1 cm. The texture of the fine-grained enclaves is cumulate-like, devoid of microlites and matrix glass. Coarse-grained enclaves lack cpx and have different modal abundances and textures: plag (75%) + opx (10%) + oxides (5%) + plag microlites (10%). Plagioclase are 0.1 cm in size and orthopyroxenes average 0.05 cm. The coarse-grained enclaves are highly vesicular, a notable difference from the host as well as the fine-grained enclaves. The boundaries of both the fine- and coarse-grained enclaves are quite sharp and distinct and there do not appear to be enclave minerals disaggregated in the host rock. Temperatures were determined by two oxides. The fine-grained enclaves had two populations of magnetite, yielding 847 + 21° and 920 + 17°C. The coarse-grained enclave was 890 + 42 °C, but the oxides were extensively exsolved. Plagioclase composition in both coarse and fine-grained samples was comparable, ranging from An50 to An80. Despite compositional similarity the textures of

  10. Rapid differentiation in a sill-like magma reservoir: a case study from the campi flegrei caldera.

    Science.gov (United States)

    Pappalardo, Lucia; Mastrolorenzo, Giuseppe

    2012-01-01

    In recent decades, geophysical investigations have detected wide magma reservoirs beneath quiescent calderas. However, the discovery of partially melted horizons inside the crust is not sufficient to put constraints on capability of reservoirs to supply cataclysmic eruptions, which strictly depends on the chemical-physical properties of magmas (composition, viscosity, gas content etc.), and thus on their differentiation histories. In this study, by using geochemical, isotopic and textural records of rocks erupted from the high-risk Campi Flegrei caldera, we show that the alkaline magmas have evolved toward a critical state of explosive behaviour over a time span shorter than the repose time of most volcanic systems and that these magmas have risen rapidly toward the surface. Moreover, similar results on the depth and timescale of magma storage were previously obtained for the neighbouring Somma-Vesuvius volcano. This consistency suggests that there might be a unique long-lived magma pool beneath the whole Neapolitan area.

  11. Determination of the oxidation states of metals and metalloids: An analytical review

    Science.gov (United States)

    Vodyanitskii, Yu. N.

    2013-12-01

    The hazard of many heavy metals/metalloids in the soil depends on their oxidation state. The problem of determining the oxidation state has been solved due to the use of synchrotron radiation methods with the analysis of the X-ray absorption near-edge structure (XANES). The determination of the oxidation state is of special importance for some hazardous heavy elements (arsenic, antimony, selenium, chromium, uranium, and vanadium). The mobility and hazard of each of these elements depend on its oxidation state. The mobilities are higher at lower oxidation states of As, Cr, V, and Se and at higher oxidation states of Sb and U. The determination of the oxidation state of arsenic has allowed revealing its fixation features in the rhizosphere of hydrophytes. The known oxidation states of chromium and uranium are used for the retention of these elements on geochemical barriers. Different oxidation states have been established for vanadium displacing iron in goethite. The determination of the oxidation state of manganese in the rhizosphere and the photosynthetic apparatus of plants is of special importance for agricultural chemists.

  12. U-series isotopes in arc magma

    Energy Technology Data Exchange (ETDEWEB)

    Hawkesworth, C.; Turner, S.; McDermott, F.; Peate, D.; Van Calsteren, P.

    1997-12-31

    Thorium is not readily mobilized in the fluid component along destructive plate margins. Uranium is mobilized, and the resultant fractionation in U/Th can be used to estimate the rates of transfer slab derived components through the mantle wedge. The variations in Th/Yb, and by implication in the fractionation-corrected Th abundances of arc magmas largely depend on the contributions from subducted sediments. It is inferred that the distinctive high Th/Ta ratios of subduction related magmas primarily reflect the Th/Ta ratios of the subducted sediments, and that such high Th/Ta ratios are generated by processes other than those associated with recent subduction-related magmatism. Uranium and thorium isotopes have also been used to evaluate magma residence times within the crust. Thus, separated minerals and groundmass from six rocks erupted in the last 4,000 years from Soufriere on St. Vincent in the Lesser Antilles, scatter about a 50,000 year errorchron on the U-Th equiline diagram (Heath et al., 1977). Models are currently being developed to investigate how such apparent ages may relate to calculated replenishment times in steady state systems. Bulk continental crust has a lower U/Th ratio (0.25) than at least some estimates for the bulk Earth (0.26) and the depleted upper mantle (0.39). However, the island arc rocks with low U/Th ratios appear to have inherited those from subducted sediments, and arc rocks with a low sediment contribution have significantly higher U/Th. Consequently, the U/Th ratios of new crustal material generated along destructive plate margins are significantly higher than those of bulk continental crust. The low average U/Th of bulk crust may be primarily due to different crust generation processes in the Archaean, when U would be less mobile because conditions were less oxidising, and when residual garnet may have had more of a role in crust generation processes. Extended abstract. 4 figs., 23 refs.

  13. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    International Nuclear Information System (INIS)

    Schacht, L.; Navarrete, J.; Schacht, P.; Ramirez, M. A.

    2010-01-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  14. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

    2010-07-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  15. Manganese oxidation state mediates toxicity in PC12 cells

    International Nuclear Information System (INIS)

    Reaney, S.H.; Smith, D.R.

    2005-01-01

    The role of the manganese (Mn) oxidation state on cellular Mn uptake and toxicity is not well understood. Therefore, undifferentiated PC12 cells were exposed to 0-200 μM Mn(II)-chloride or Mn(III)-pyrophosphate for 24 h, after which cellular manganese levels were measured along with measures of cell viability, function, and cytotoxicity (trypan blue exclusion, medium lactate dehydrogenase (LDH), 8-isoprostanes, cellular ATP, dopamine, serotonin, H-ferritin, transferrin receptor (TfR), Mn-superoxide dismutase (MnSOD), and copper-zinc superoxide dismutase (CuZnSOD) protein levels). Exposures to Mn(III) >10 μM produced 2- to 5-fold higher cellular manganese levels than equimolar exposures to Mn(II). Cell viability and ATP levels both decreased at the highest Mn(II) and Mn(III) exposures (150-200 μM), while Mn(III) exposures produced increases in LDH activity at lower exposures (≥50 μM) than did Mn(II) (200 μM only). Mn(II) reduced cellular dopamine levels more than Mn(III), especially at the highest exposures (50% reduced at 200 μM Mn(II)). In contrast, Mn(III) produced a >70% reduction in cellular serotonin at all exposures compared to Mn(II). Different cellular responses to Mn(II) exposures compared to Mn(III) were also observed for H-ferritin, TfR, and MnSOD protein levels. Notably, these differential effects of Mn(II) versus Mn(III) exposures on cellular toxicity could not simply be accounted for by the different cellular levels of manganese. These results suggest that the oxidation state of manganese exposures plays an important role in mediating manganese cytotoxicity

  16. Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

    Science.gov (United States)

    Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

    2009-01-01

    The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated

  17. Depth of origin of magma in eruptions.

    Science.gov (United States)

    Becerril, Laura; Galindo, Ines; Gudmundsson, Agust; Morales, Jose Maria

    2013-09-26

    Many volcanic hazard factors--such as the likelihood and duration of an eruption, the eruption style, and the probability of its triggering large landslides or caldera collapses--relate to the depth of the magma source. Yet, the magma source depths are commonly poorly known, even in frequently erupting volcanoes such as Hekla in Iceland and Etna in Italy. Here we show how the length-thickness ratios of feeder dykes can be used to estimate the depth to the source magma chamber. Using this method, accurately measured volcanic fissures/feeder-dykes in El Hierro (Canary Islands) indicate a source depth of 11-15 km, which coincides with the main cloud of earthquake foci surrounding the magma chamber associated with the 2011-2012 eruption of El Hierro. The method can be used on widely available GPS and InSAR data to calculate the depths to the source magma chambers of active volcanoes worldwide.

  18. Volcanic emission of radionuclides and magma dynamics

    International Nuclear Information System (INIS)

    Lambert, G.; Le Cloarec, M.F.; Ardouin, B.; Le Roulley, J.C.

    1985-01-01

    210 Pb, 210 Bi and 210 Po, the last decay products of the 238 U series, are highly enriched in volcanic plumes, relative to the magma composition. Moreover this enrichment varies over time and from volcano to volcano. A model is proposed to describe 8 years of measurements of Mt. Etna gaseous emissions. The lead and bismuth coefficients of partition between gaseous and condensated phases in the magma are determined by comparing their concentrations in lava flows and condensated volatiles. In the case of volatile radionuclides, an escaping time is calculated which appears to be related to the volcanic activity. Finally, it is shown that that magma which is degassing can already be partly degassed; it should be considered as a mixture of a few to 50% of deep non-degassed magma with a well degassed superficial magma cell. (orig.)

  19. The problem of oxidation state stabilisation and some regularities of a Periodic system of the elements

    International Nuclear Information System (INIS)

    Kiselev, Yurii M; Tretyakov, Yuri D

    1999-01-01

    The general principles of the concept of oxidation state stabilisation are formulated. Problems associated with the preparation and provision of the highest valent forms of transition elements are considered. The empirical data concerning the synthesis of new compounds of rare-earth elements and d elements in unusually high oxidation states are analysed. The possibility of occurrence of the oxidation states + 9 and + 10 for some elements (for example, for iridium and platinum in tetraoxo ions) are discussed. Approaches to the realisation of these states are outlined and it is demonstrated that solid phases or matrices containing alkali metal cations are the most promising systems for the stabilisation of these high oxidation states. Selected thermodynamic features typical of metal halides and oxides and the regularities of the changes in the extreme oxidation states of d elements are considered. The bibliography includes 266 references.

  20. Shear thinning behaviors in magmas

    Science.gov (United States)

    Vetere, F. P.; Cassetta, M.; Perugini, D.

    2017-12-01

    Studies on magma rheology are of fundamental importance to understanding magmatic processes from depth to surface. Since viscosity is one of the most important parameter controlling eruption mechanisms, as well as lava flow emplacement, a comprehensive knowledge on the evolution of magma viscosities during crystallization is required. We present new viscosity data on partly crystalized basalt, andesite and analogue lavas comparable to those erupted on Mercury's northern volcanic plains. High-temperature viscosity measurements were performed using a rotational Anton Paar RheolabQC viscometer head at the PVRG labs, in Perugia (Italy) (http://pvrg.unipg.it). The relative proportion of phases in each experimental run were determined by image analysis on BS-SEM images at different magnifications; phases are glasses, clinopyroxene, spinel, plagioclase for the basalt, plagioclase and spinel for the andesite and pure enstatite and clinopyroxenes, for the analogue Mercury's composition. Glass and crystalline fractions determined by image analysis well correlate with compositions of residual melts. In order to constrain the viscosity (η) variations as a function of crystallinity, shear rate (γ) was varied from 0.1 to 5 s-1. Viscosity vs. time at constant temperature shows a typical S-shape curve. In particular, for basaltic composition η vary from 3.1-3.8 Pa s [log η] at 1493 K and crystallinity of 19 area % as γ vary from 1.0 to 0.1 s-1; the andesite viscosity evolution is 3.2 and 3.7 Pa s [log η] as γ varies from 1 to 0.1 at 1493 K and crystal content of 17 area %; finally, Mercury's analogue composition was investigated at different temperature ranging from 1533 to 1502 K (Vetere et al., 2017). Results, for γ = 0.1, 1.0 and 5.0 s-1, show viscosity variation between 2.7-4.0, 2.5-3.4 and 2.0-3.0 [log η inPa s] respectively while crystallinity vary from 9 to 27 (area %). As viscosity decreases as shear rate increases, these data points to a shear thinning behaviour

  1. Melt recharge, f O2-T conditions, and metal fertility of felsic magmas: zircon trace element chemistry of Cu-Au porphyries in the Sanjiang orogenic belt, southwest China

    Science.gov (United States)

    Meng, Xuyang; Mao, Jingwen; Zhang, Changqing; Zhang, Dongyang; Liu, Huan

    2018-06-01

    The magmatic hydrothermal Pulang Cu deposit (Triassic) and the Beiya Au-Cu deposits (Eocene) are located in the Sanjiang copper porphyry belt, southwest China. Zircon chemistry was used to constrain the magmatic evolution and oxidation state of the porphyries. The results show that porphyries of the Beiya district formed from an early oxidized melt and a later relatively reduced and more evolved magma, whereas Pulang experienced a normal Cu porphyry evolutionary trend. The Pulang porphyries crystallized from more oxidized magma (ΔFMQ + 2.9-4.6, average = 4.0 ± 1.0, n = 3) with an average temperature of 709 ± 6 °C compared to the Beiya porphyries (ΔFMQ + 0.6-3.5, average = 1.9 ± 1.3, n = 5) with a mean magmatic temperature of 780 ± 22 °C. These data, combined with data from other Cu- and Au-rich porphyries in the Sanjiang belt (i.e., Machangjing Cu, Yao'an Au), are consistent with previous experimental work showing that elevated Cu and Au solubilities in magma require oxidizing conditions. A compilation of existing geochemical data for magmatic zircons from fertile and barren porphyry systems worldwide establishes an optimal diagnostic interval on CeIV/CeIII-TTi-in-zircon and (Eu/Eu*)N plots for generating magmatic hydrothermal Cu-Au deposits.

  2. Effect of particle size on iron nanoparticle oxidation state

    International Nuclear Information System (INIS)

    Lombardo, Jeffrey J.; Lysaght, Andrew C.; Goberman, Daniel G.; Chiu, Wilson K.S.

    2012-01-01

    Selecting catalyst particles is a very important part of carbon nanotube growth, although the properties of these nanoscale particles are unclear. In this article iron nanoparticles are analyzed through the use of atomic force microscopy and x-ray photoelectron spectroscopy in order to understand how the size affects the chemical composition of nanoparticles and thus their physical structure. Initially, atomic force microscopy was used to confirm the presence of iron particles, and to determine the average size of the particles. Next an analytical model was developed to estimate particle size as a function of deposition time using inputs from atomic force microscopy measurement. X-ray photoelectron spectroscopy analysis was then performed with a focus on the spectra relating to the 2p Fe electrons to study the chemical state of the particles as a function of time. It was shown that as the size of nanoparticles decreased, the oxidation state of the particles changed due to a high proportion of atoms on the surface.

  3. Quantum confinement-induced tunable exciton states in graphene oxide.

    Science.gov (United States)

    Lee, Dongwook; Seo, Jiwon; Zhu, Xi; Lee, Jiyoul; Shin, Hyeon-Jin; Cole, Jacqueline M; Shin, Taeho; Lee, Jaichan; Lee, Hangil; Su, Haibin

    2013-01-01

    Graphene oxide has recently been considered to be a potential replacement for cadmium-based quantum dots due to its expected high fluorescence. Although previously reported, the origin of the luminescence in graphene oxide is still controversial. Here, we report the presence of core/valence excitons in graphene-based materials, a basic ingredient for optical devices, induced by quantum confinement. Electron confinement in the unreacted graphitic regions of graphene oxide was probed by high resolution X-ray absorption near edge structure spectroscopy and first-principles calculations. Using experiments and simulations, we were able to tune the core/valence exciton energy by manipulating the size of graphitic regions through the degree of oxidation. The binding energy of an exciton in highly oxidized graphene oxide is similar to that in organic electroluminescent materials. These results open the possibility of graphene oxide-based optoelectronic device technology.

  4. Numerical modeling of bubble dynamics in magmas

    Science.gov (United States)

    Huber, Christian; Su, Yanqing; Parmigiani, Andrea

    2014-05-01

    Understanding the complex non-linear physics that governs volcanic eruptions is contingent on our ability to characterize the dynamics of bubbles and its effect on the ascending magma. The exsolution and migration of bubbles has also a great impact on the heat and mass transport in and out of magma bodies stored at shallow depths in the crust. Multiphase systems like magmas are by definition heterogeneous at small scales. Although mixture theory or homogenization methods are convenient to represent multiphase systems as a homogeneous equivalent media, these approaches do not inform us on possible feedbacks at the pore-scale and can be significantly misleading. In this presentation, we discuss the development and application of bubble-scale multiphase flow modeling to address the following questions : How do bubbles impact heat and mass transport in magma chambers ? How efficient are chemical exchanges between the melt and bubbles during magma decompression? What is the role of hydrodynamic interactions on the deformation of bubbles while the magma is sheared? Addressing these questions requires powerful numerical methods that accurately model the balance between viscous, capillary and pressure stresses. We discuss how these bubble-scale models can provide important constraints on the dynamics of magmas stored at shallow depth or ascending to the surface during an eruption.

  5. Evidence for seismogenic fracture of silicic magma.

    Science.gov (United States)

    Tuffen, Hugh; Smith, Rosanna; Sammonds, Peter R

    2008-05-22

    It has long been assumed that seismogenic faulting is confined to cool, brittle rocks, with a temperature upper limit of approximately 600 degrees C (ref. 1). This thinking underpins our understanding of volcanic earthquakes, which are assumed to occur in cold rocks surrounding moving magma. However, the recent discovery of abundant brittle-ductile fault textures in silicic lavas has led to the counter-intuitive hypothesis that seismic events may be triggered by fracture and faulting within the erupting magma itself. This hypothesis is supported by recent observations of growing lava domes, where microearthquake swarms have coincided with the emplacement of gouge-covered lava spines, leading to models of seismogenic stick-slip along shallow shear zones in the magma. But can fracturing or faulting in high-temperature, eruptible magma really generate measurable seismic events? Here we deform high-temperature silica-rich magmas under simulated volcanic conditions in order to test the hypothesis that high-temperature magma fracture is seismogenic. The acoustic emissions recorded during experiments show that seismogenic rupture may occur in both crystal-rich and crystal-free silicic magmas at eruptive temperatures, extending the range of known conditions for seismogenic faulting.

  6. Examining shear processes during magma ascent

    Science.gov (United States)

    Kendrick, J. E.; Wallace, P. A.; Coats, R.; Lamur, A.; Lavallée, Y.

    2017-12-01

    Lava dome eruptions are prone to rapid shifts from effusive to explosive behaviour which reflects the rheology of magma. Magma rheology is governed by composition, porosity and crystal content, which during ascent evolves to yield a rock-like, viscous suspension in the upper conduit. Geophysical monitoring, laboratory experiments and detailed field studies offer the opportunity to explore the complexities associated with the ascent and eruption of such magmas, which rest at a pivotal position with regard to the glass transition, allowing them to either flow or fracture. Crystal interaction during flow results in strain-partitioning and shear-thinning behaviour of the suspension. In a conduit, such characteristics favour the formation of localised shear zones as strain is concentrated along conduit margins, where magma can rupture and heal in repetitive cycles. Sheared magmas often record a history of deformation in the form of: grain size reduction; anisotropic permeable fluid pathways; mineral reactions; injection features; recrystallisation; and magnetic anomalies, providing a signature of the repetitive earthquakes often observed during lava dome eruptions. The repetitive fracture of magma at ( fixed) depth in the conduit and the fault-like products exhumed at spine surfaces indicate that the last hundreds of meters of ascent may be controlled by frictional slip. Experiments on a low-to-high velocity rotary shear apparatus indicate that shear stress on a slip plane is highly velocity dependent, and here we examine how this influences magma ascent and its characteristic geophysical signals.

  7. Magma Mixing: Why Picrites are Not So Hot

    Science.gov (United States)

    Natland, J. H.

    2010-12-01

    Oxide gabbros or ferrogabbros are the late, low-temperature differentiates of tholeiitic magma and usually form as cumulates that can have 2-30% of the magmatic oxides, ilmenite and magnetite. They are common in the ocean crust and are likely ubiquitous wherever extensive tholeiitic magmatism has occurred, especially beneath thick lava piles such as at Hawaii, Iceland, oceanic plateaus, island arcs and ancient continental crust. When intruded by hot primitive magma including picrite, the oxide-bearing portions of these rocks are readily partially melted or assimilated into the magma and contribute to it a degree of iron and titanium enrichment that is not reflective of the mantle source of the primitive magma. The most extreme examples of such mixing are meimechites and ferropicrites, but this type of end-member mixing is even common in MORB. To the extent this process occurs, the eruptive picrite cannot be used to estimate compositions of partial melts of mantle rocks, nor their eruptive or potential temperatures, using olivine-liquid FeO-MgO backtrack procedures. Most picrites have glasses with compositions approximating those expected from low-pressure multiphase cotectic crystallization, and olivine that on average crystallized from liquids of nearly those compositions. The hallmark of such rocks is the presence of minerals other than olivine among phenocrysts (plagioclase at Iceland, clinopyroxene at many oceanic islands), Fe- and Ti-rich chromian spinel (ankaramites, ferropicrites and meimichites), and in some cases the presence of iron-rich olivine (hortonolite ~Fo65 in ferropicrites), Ti-rich kaersutitic amphibole and even apatite (meimechites); the latter two derive from late-stage, hydrous and geochemically enriched metamorphic or alkalic assimilants. This type of mixing, however, does not necessarily involve depleted and enriched mixing components. To avoid such mixing, primitive melts have to rise primarily through upper mantle rocks of near-zero melt

  8. Solid state solubility of copper oxides in hydroxyapatite

    Science.gov (United States)

    Zykin, Mikhail A.; Vasiliev, Alexander V.; Trusov, Lev A.; Dinnebier, Robert E.; Jansen, Martin; Kazin, Pavel E.

    2018-06-01

    Samples containing copper oxide doped hydroxyapatite with the composition Ca10(PO4)6(CuxOH1-x-δ)2, x = 0.054 - 0.582, in the mixture with CuO/Cu2O were prepared by a solid-state high-temperature treatment at varying annealing temperatures and at different partial water vapor and oxygen pressures. The crystal structures of the apatite compounds were refined using powder X-ray diffraction patterns and the content of copper ions x in the apatite was determined. Copper ions enter exclusively into the apatite trigonal channels formally substituting protons of OH-groups and the hexagonal cell parameters grow approximately linearly with x, the channel volume mostly expanding while the remaining volume of the crystal lattice changing only slightly. The equilibrium copper content in the apatite increases drastically, by almost a factor of 10 with the annealing temperature rising from 800° to 1200°C. The reduction of the water partial pressure leads to a further increase of x, while the dependence of x on the oxygen partial pressure exhibits a maximum. The observed relations are consistent with the proposed chemical reactions implying the copper introduction is followed by the release of a considerable quantity of gaseous products - water and oxygen. The analysis of interatomic distances suggests that the maximum content of copper ions in the channel cannot exceed 2/3.

  9. Stabilization of actinides and lanthanides in unusually high oxidation states

    International Nuclear Information System (INIS)

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO 3 or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF 5 /HF solution or Pu(VII) in Li 5 PuO 6 ). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs

  10. Comments on 'Generation of Deccan Trap magmas'

    Indian Academy of Sciences (India)

    R.Narasimhan(krishtel emaging)1461 1996 Oct 15 13:05:22

    Comments on 'Generation of Deccan Trap magmas' by Gautam Sen ... Department of Geology & Geophysics, School of Ocean & Earth Science & Technology (SOEST), University of .... Mahoney J J, Sheth H C, Chandrasekharan D and Peng Z.

  11. The Boycott effect in magma chambers

    Science.gov (United States)

    Blanchette, F.; Peacock, T.; Bush, J. W. M.

    2004-03-01

    We investigate the plausibility of the stratified Boycott effect as a source of layering in magma chambers. Crystal settling within the magma chamber will generate buoyant fluid near the sloping sidewalls whose vertical ascent may be limited by the ambient stratification associated with vertical gradients in SiO2. The resulting flow may be marked by a layered structure, each layer taking the form of a convection cell spanning the lateral extent of the magma chamber. Using parameters relevant to magma chambers, we estimate that such convection cells would be established over a timescale of a month and have a depth on the order of 4m, which is roughly consistent with field observations of strata within solidified chambers.

  12. Depths of Magma Chambers in the Icelandic Crust

    Science.gov (United States)

    Kelley, D. F.; Kapostasy, D. D.; Barton, M.

    2004-05-01

    There is considerable interest in the structure and thermal state of the crust in Iceland, which lies across the Mid Atlantic Ridge. However, interpretations of seismic and gravity data yield conflicting views of the nature of the lower crust. Some interpretations prefer a model in which the lower crust (15-25 km) is relatively cool and solid, whereas other interpretations, based largely on gravity data, prefer a model in which the lower crust is relatively warm and possibly partially molten. Knowledge of the depth of magma chambers is critical to constrain the geothermal gradient in Icelandic crust and to resolve discrepancies in interpretation of geophysical data. Analyses of aphyric lavas and of glasses in Icelandic lavas erupted from 11 volcanic centers have been compiled. The compositions are picritic and basaltic with SiO2 - 47 to 50 wt%, MgO - 6 to 15wt%, FeO - 8 to 14wt%, to, Na2O - 1.3 to 3.3 wt%, and K2O - 0.03-46 wt%. The pressures of equilibration of these liquids with ol, high-Ca pyx and plag were estimated qualitatively from projections into the pseudoternary system Ol-Di-Silica using methods described by Walker and coworkers and Grove and coworkers. The results (ca. 0.5 GPa) indicate crystallization in magma chambers located at about 16 km depth. Equilibration pressures were also calculated using the method described by Yang and coworkers and by a modified version of this method. Calculated pressures (0.45±0.15 GPa) indicate magma chambers located at 15±4 km depth. Equilibration pressures for Rekjanes Ridge glasses determined using the same techniques are 0.2±0.1 GPa, corresponding to depths of 7.6±3 km. The results indicate the presence of magma chambers in the deep Icelandic crust and that the latter is relatively warm. Shallower chambers (3-7 km) have been identified from seismic studies suggesting a complex magma plumbing system. The results also confirm that magma chambers beneath Iceland are located at greater depths than those beneath the

  13. The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States.

    Science.gov (United States)

    Matheu, Roc; Ghaderian, Abolfazl; Francas, Laia; Chernev, Petko; Ertem, Mehmed; Benet-Buchholz, Jordi; Batista, Victor; Haumann, Michael; Gimbert-Suriñach, Carolina; Sala, Xavier; Llobet, Antoni

    2018-06-13

    The Ru complex [RuII(bda-κ-N2O2)(N-NH2)2], 1, (bda2- = (2,2'-bipyridine)-6,6'-dicarboxylate; N-NH2 = 4-(pyridin-4-yl)aniline) is used as a synthetic intermediate to prepare Ru-bda complexes that contain the NO+, acetonitrile (MeCN) or H2O ligands at oxidation states II and III. Complex 1 reacts with excess NO+ to form a Ru complex where the aryl amine ligands N-NH2 in 1 are transformed into diazonium salts (N-N2+ = 4-(pyridin-4-yl)benzenediazonium)) together with the formation of a new Ru-NO group at the equatorial zone, to generate [RuII(bda-κ-N2O)(NO)(N-N2)2]3+, 23+. Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature leading to complex [RuII(bda-κ-N2O)(MeCN)(N-NH2)2], 3. Finally in acidic aqueous solutions solvent water coordinates the Ru center forming {[RuII(bda-κ-(NO)3)(H2O)(N-NH3)2](H2O)n}2+, 42+, that is strongly hydrogen bonded with additional water molecules at the second coordination sphere. We have additionally characterized the one electron oxidized complex {[RuIII(bda-κ-(NO)3.5)(H2O)(N-NH3)2](H2O)n}3+, 53+. The coordination mode of the complexes has been studied both in the solid state and in solution through single-crystal XRD, X-ray absorption spectroscopy, variable-temperature NMR and DFT calculations. While the κ-N2O is the main coordination mode for 23+ and 3, an equilibrium that involves isomers with κ-N2O and κ-NO2 coordination modes and neighboring hydrogen bonded water molecules is observed for 42+ and 53+. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Silicic magma generation at Askja volcano, Iceland

    Science.gov (United States)

    Sigmarsson, O.

    2009-04-01

    Rate of magma differentiation is an important parameter for hazard assessment at active volcanoes. However, estimates of these rates depend on proper understanding of the underlying magmatic processes and magma generation. Differences in isotope ratios of O, Th and B between silicic and in contemporaneous basaltic magmas have been used to emphasize their origin by partial melting of hydrothermally altered metabasaltic crust in the rift-zones favoured by a strong geothermal gradient. An alternative model for the origin of silicic magmas in the Iceland has been proposed based on U-series results. Young mantle-derived mafic protolith is thought to be metasomatized and partially melted to form the silicic end-member. However, this model underestimates the compositional variations of the hydrothermally-altered basaltic crust. New data on U-Th disequilibria and O-isotopes in basalts and dacites from Askja volcano reveal a strong correlation between (230Th/232Th) and delta 18O. The 1875 AD dacite has the lowest Th- and O isotope ratios (0.94 and -0.24 per mille, respectively) whereas tephra of evolved basaltic composition, erupted 2 months earlier, has significantly higher values (1.03 and 2.8 per mille, respectively). Highest values are observed in the most recent basalts (erupted in 1920 and 1961) inside the Askja caldera complex and out on the associated fissure swarm (Sveinagja basalt). This correlation also holds for older magma such as an early Holocene dacites, which eruption may have been provoked by rapid glacier thinning. Silicic magmas at Askja volcano thus bear geochemical signatures that are best explained by partial melting of extensively hydrothermally altered crust and that the silicic magma source has remained constant during the Holocene at least. Once these silicic magmas are formed they appear to erupt rapidly rather than mixing and mingling with the incoming basalt heat-source that explains lack of icelandites and the bi-modal volcanism at Askja

  15. A microbial-mineralization-inspired approach for synthesis of manganese oxide nanostructures with controlled oxidation states and morphologies

    Energy Technology Data Exchange (ETDEWEB)

    Oba, Manabu; Oaki, Yuya; Imai, Hiroaki [Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan)

    2010-12-21

    Manganese oxide nanostructures are synthesized by a route inspired by microbial mineralization in nature. The combination of organic molecules, which include antioxidizing and chelating agents, facilitates the parallel control of oxidation states and morphologies in an aqueous solution at room temperature. Divalent manganese hydroxide (Mn(OH){sub 2}) is selectively obtained as a stable dried powder by using a combination of ascorbic acid as an antioxidizing agent and other organic molecules with the ability to chelate to manganese ions. The topotactic oxidation of the resultant Mn(OH){sub 2} leads to the selective formation of trivalent manganese oxyhydroxide ({beta}-MnOOH) and trivalent/tetravalent sodium manganese oxide (birnessite, Na{sub 0.55}Mn{sub 2}O{sub 4}.1.5H{sub 2}O). For microbial mineralization in nature, similar synthetic routes via intermediates have been proposed in earlier works. Therefore, these synthetic routes, which include in the present study the parallel control over oxidation states and morphologies of manganese oxides, can be regarded as new biomimetic routes for synthesis of transition metal oxide nanostructures. As a potential application, it is demonstrated that the resultant {beta}-MnOOH nanostructures perform as a cathode material for lithium ion batteries. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. The 2006-2009 activity of the Ubinas volcano (Peru): Petrology of the 2006 eruptive products and insights into genesis of andesite magmas, magma recharge and plumbing system

    Science.gov (United States)

    Rivera, Marco; Thouret, Jean-Claude; Samaniego, Pablo; Le Pennec, Jean-Luc

    2014-01-01

    Following a fumarolic episode that started six months earlier, the most recent eruptive activity of the Ubinas volcano (south Peru) began on 27 March 2006, intensified between April and October 2006 and slowly declined until December 2009. The chronology of the explosive episode and the extent and composition of the erupted material are documented with an emphasis on ballistic ejecta. A petrological study of the juvenile products allows us to infer the magmatic processes related to the 2006-2009 eruptions of the andesitic Ubinas volcano. The juvenile magma erupted during the 2006 activity shows a homogeneous bulk-rock andesitic composition (56.7-57.6 wt.% SiO2), which belongs to a medium- to high-K calc-alkaline series. The mineral assemblage of the ballistic blocks and tephra consists of plagioclase > two-pyroxenes > Fe-Ti oxide and rare olivine and amphibole set in a groundmass of the same minerals with a dacitic composition (66-67 wt.% SiO2). Thermo-barometric data, based on two-pyroxene and amphibole stability, records a magma temperature of 998 ± 14 °C and a pressure of 476 ± 36 MPa. Widespread mineralogical and textural features point to a disequilibrium process in the erupted andesite magma. These features include inversely zoned "sieve textures" in plagioclase, inversely zoned clinopyroxene, and olivine crystals with reaction and thin overgrowth rims. They indicate that the pre-eruptive magmatic processes were dominated by recharge of a hotter mafic magma into a shallow reservoir, where magma mingling occurred and triggered the eruption. Prior to 2006, a probable recharge of a mafic magma produced strong convection and partial homogenization in the reservoir, as well as a pressure increase and higher magma ascent rate after four years of fumarolic activity. Mafic magmas do not prevail in the Ubinas pre-historical lavas and tephras. However, mafic andesites have been erupted during historical times (e.g. AD 1667 and 2006-2009 vulcanian eruptions). Hence

  17. Oxidation under electron bombardment. A tool for studying the initial states of silicon oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Carriere, B.; Deville, J.P.; El Maachi, A.

    1987-06-01

    The exciting beam of an Auger electron spectrometer has been used to monitor the oxidation of silicon single crystals at room temperature and very low pressures of oxygen (approx. 10/sup -7/ Torr). This process allows us to build ultra-thin layers of silica on silicon (down to 30 A) but it is mostly used to investigate the mechanisms of the initial stages of oxidation. Auger spectra recorded continuously during the oxidation process provide information on (1) the nature of the silicon-oxygen chemical bonds which are interpreted through fine structure in the Auger peak, and (2) the kinetics of oxide formation which are deduced from curves of Auger signal versus time. An account is given of the contribution of these Auger studies to the description of the intermediate oxide layer during the reaction between silicon and oxygen and the influence of surface structural disorder, induced mainly by argon-ion bombardment, is discussed in terms of reactivity and oxide coverage.

  18. Decadal to monthly timescales of magma transfer and reservoir growth at a caldera volcano.

    Science.gov (United States)

    Druitt, T H; Costa, F; Deloule, E; Dungan, M; Scaillet, B

    2012-02-01

    Caldera-forming volcanic eruptions are low-frequency, high-impact events capable of discharging tens to thousands of cubic kilometres of magma explosively on timescales of hours to days, with devastating effects on local and global scales. Because no such eruption has been monitored during its long build-up phase, the precursor phenomena are not well understood. Geophysical signals obtained during recent episodes of unrest at calderas such as Yellowstone, USA, and Campi Flegrei, Italy, are difficult to interpret, and the conditions necessary for large eruptions are poorly constrained. Here we present a study of pre-eruptive magmatic processes and their timescales using chemically zoned crystals from the 'Minoan' caldera-forming eruption of Santorini volcano, Greece, which occurred in the late 1600s BC. The results provide insights into how rapidly large silicic systems may pass from a quiescent state to one on the edge of eruption. Despite the large volume of erupted magma (40-60 cubic kilometres), and the 18,000-year gestation period between the Minoan eruption and the previous major eruption, most crystals in the Minoan magma record processes that occurred less than about 100 years before the eruption. Recharge of the magma reservoir by large volumes of silicic magma (and some mafic magma) occurred during the century before eruption, and mixing between different silicic magma batches was still taking place during the final months. Final assembly of large silicic magma reservoirs may occur on timescales that are geologically very short by comparison with the preceding repose period, with major growth phases immediately before eruption. These observations have implications for the monitoring of long-dormant, but potentially active, caldera systems.

  19. Trace element and isotopic effects arising from magma migration beneath mid-ocean ridges

    International Nuclear Information System (INIS)

    Kenyon, P.M.

    1990-01-01

    The trace element concentrations and isotopic ratios in the magma erupted on mid-ocean ridges may differ from those in the source material due to physical effects such as porous flow dispersion, exchange of trace elements between the fluid and solid phases during magma migration, and convective mixing in magma chambers. These differences are in addition to those produced by better known processes such as fractional crystallization and partial melting. The effects of the three former processes are described. It is predicted that magma typically reaches the sub-ridge magma chambers with a spatial heterogeneity only slightly reduced from that of the source material, but with a subdued variation in time. Convective mixing then further reduces the spatial heterogeneity. Application of the results for convective mixing to a recent Fourier analysis of 87 Sr/ 86 Sr variations along the Mid-Atlantic Ridge suggests that the falloff in amplitude of variation observed with decreasing wavelength in the Mid-Atlantic Ridge data cannot be explained by convective mixing in magma chambers. Instead, it is postulated that this falloff is due to the mechanics of the production and/or the solid-state convective mixing of chemical and isotopic heterogeneities in the solid mantle. (orig.)

  20. Interface Controlled Oxidation States in Layered Cobalt Oxide Nanoislands on Gold

    DEFF Research Database (Denmark)

    Walton, Alexander; Fester, Jakob; Bajdich, Michal

    2015-01-01

    Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER; half of the catalytic “water splitting” reaction), particularly when promoted with gold. However, the surface chemistry of cobalt oxides and in particular the nature of the synergistic effect...

  1. Origin of interface states and oxide charges generated by ionizing radiation

    International Nuclear Information System (INIS)

    Sah, C.T.

    1976-01-01

    The randomly located trivalent silicon atoms are shown to account for the thermally generated interface states at the SiO 2 -Si interface. The interface state density is greatly reduced in water containing ambients at low temperatures (450 0 C) by forming trivalent silicon hydroxide bonds. Interface states are regenerated when the /triple bond/Si-OH bonds are broken by ionizing radiation and the OH ions are drifted away. In the bulk of the oxide film, the trivalent silicon and the interstitial oxygen donor centers are shown to be responsible for the heat and radiation generated positive space charge build-up (oxide charge) in thermally grown silicon oxide

  2. Radiographic visualization of magma dynamics in an erupting volcano.

    Science.gov (United States)

    Tanaka, Hiroyuki K M; Kusagaya, Taro; Shinohara, Hiroshi

    2014-03-10

    Radiographic imaging of magma dynamics in a volcanic conduit provides detailed information about ascent and descent of magma, the magma flow rate, the conduit diameter and inflation and deflation of magma due to volatile expansion and release. Here we report the first radiographic observation of the ascent and descent of magma along a conduit utilizing atmospheric (cosmic ray) muons (muography) with dynamic radiographic imaging. Time sequential radiographic images show that the top of the magma column ascends right beneath the crater floor through which the eruption column was observed. In addition to the visualization of this magma inflation, we report a sequence of images that show magma descending. We further propose that the monitoring of temporal variations in the gas volume fraction of magma as well as its position in a conduit can be used to support existing eruption prediction procedures.

  3. Rapid Crystallization of the Bishop Magma

    Science.gov (United States)

    Gualda, G. A.; Anderson, A. T.; Sutton, S. R.

    2007-12-01

    Substantial effort has been made to understand the longevity of rhyolitic magmas, and particular attention has been paid to the systems in the Long Valley area (California). Recent geochronological data suggest discrete magma bodies that existed for hundreds of thousands of years. Zircon crystallization ages for the Bishop Tuff span 100-200 ka, and were interpreted to reflect slow crystallization of a liquid-rich magma. Here we use the diffusional relaxation of Ti zoning in quartz to investigate the longevity of the Bishop magma. We have used such an approach to show the short timescales of crystallization of Ti-rich rims on quartz from early- erupted Bishop Tuff. We have now recognized Ti-rich cores in quartz that can be used to derive the timescales of their crystallization. We studied four samples of the early-erupted Bishop. Hand-picked crystals were mounted on glass slides and polished. Cathodoluminescence (CL) images were obtained using the electron microprobe at the University of Chicago. Ti zoning was documented using the GeoSoilEnviroCARS x-ray microprobe at the Advanced Photon Source (Argonne National Lab). Quartz crystals in all 4 samples include up to 3 Ti-bearing zones: a central core (50-100 μm in diameter, ca. 50 ppm Ti), a volumetrically predominant interior (~40 ppm Ti), and in some crystals a 50-100 μm thick rim (50 ppm Ti). Maximum estimates of core residence times were calculated using a 1D diffusion model, as the time needed to smooth an infinitely steep profile to fit the observed profile. Surprisingly, even for the largest crystals studied - ca. 2 mm in diameter - core residence times are less than 1 ka. Calculated growth rates imply that even cm-sized crystals crystallized in less than 10 ka. Crystal size distribution data show that crystals larger than 3 mm are exceedingly rare, such that the important inference is that the bulk of the crystallization of the early-erupted Bishop magma occurred in only a few thousand years. This timescale

  4. Contraction or expansion of the Moon's crust during magma ocean freezing?

    Science.gov (United States)

    Elkins-Tanton, Linda T; Bercovici, David

    2014-09-13

    The lack of contraction features on the Moon has been used to argue that the Moon underwent limited secular cooling, and thus had a relatively cool initial state. A cool early state in turn limits the depth of the lunar magma ocean. Recent GRAIL gravity measurements, however, suggest that dikes were emplaced in the lower crust, requiring global lunar expansion. Starting from the magma ocean state, we show that solidification of the lunar magma ocean would most likely result in expansion of the young lunar crust, and that viscous relaxation of the crust would prevent early tectonic features of contraction or expansion from being recorded permanently. The most likely process for creating the expansion recorded by the dikes is melting during cumulate overturn of the newly solidified lunar mantle. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

  5. Towards a Predictive Thermodynamic Model of Oxidation States of Uranium Incorporated in Fe (hydr) oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S. [Univ. of North Texas, Denton, TX (United States)

    2013-01-01

    -Level Excited States: Consequences For X-Ray Absorption Spectroscopy”, J. Elec. Spectros. and Related Phenom., 200, 174 (2015) describes our first application of these methods. As well as applications to problems and materials of direct interest for our PNNL colleagues, we have pursued applications of fundamental theoretical significance for the analysis and interpretation of XPS and XAS spectra. These studies are important for the development of the fields of core-level spectroscopies as well as to advance our capabilities for applications of interest to our PNNL colleagues. An excellent example is our study of the surface core-level shifts, SCLS, for the surface and bulk atoms of an oxide that provides a new approach to understanding how the surface electronic of oxides differs from that in the bulk of the material. This work has the potential to lead to a new key to understanding the reactivity of oxide surfaces. Our theoretical studies use cluster models with finite numbers of atoms to describe the properties of condensed phases and crystals. This approach has allowed us to focus on the local atomistic, chemical interactions. For these clusters, we obtain orbitals and spinors through the solution of the Hartree-Fock, HF, and the fully relativistic Dirac HF equations. These orbitals are used to form configuration mixing wavefunctions which treat the many-body effects responsible for the open shell angular momentum coupling and for the satellites of the core-level spectra. Our efforts have been in two complementary directions. As well as the applications described above, we have placed major emphasis on the enhancement and extension of our theoretical and computational capabilities so that we can treat complex systems with a greater range of many-body effects. Noteworthy accomplishments in terms of method development and enhancement have included: (1) An improvement in our treatment of the large matrices that must be handled when many-body effects are treated. (2

  6. Ion bombardment effects on surface states in selected oxide systems: rutile and alkaline earth titanates

    International Nuclear Information System (INIS)

    Gruen, D.M.

    1978-01-01

    In this paper, the nature of the surface states of n-type TiO 2 and SrTiO 3 is discussed and the role of ion bombardment in modifying the properties of these states is elucidated. Insofar as possible, the interrelationships between oxide nonstoichiometry, surface states, ion bombardment effects and photoelectrolysis are explored

  7. Oxidation Kinetics of Copper: An Experiment in Solid State Chemistry.

    Science.gov (United States)

    Ebisuzaki, Y.; Sanborn, W. B.

    1985-01-01

    Oxidation kinetics in metals and the role defects play in diffusion-controlled reactions are discussed as background for a junior/senior-level experiment in the physical or inorganic chemistry laboratory. Procedures used and typical data obtained are provided for the experiment. (JN)

  8. Plutonium uptake by Scenedesmus obliquus as a function of isotope and oxidation state

    International Nuclear Information System (INIS)

    Tkacik, M.F.; Giesy, J.P.; Wilhite, E.L.; Corey, J.C.

    1979-01-01

    Uptake of 238 Pu 4+ , 238 Pu 6+ , 239 Pu 4+ and 239 Pu 6+ by the green alga Scenedesmus obliquus (Turp) Kutz was studied to determine whether isotope or oxidation state differences affect Pu uptake from aqueous medium by algal cells. At equivalent 238 Pu and 239 PU concentrations, even when initial oxidation states differed, accumulations of these isotopes by S.obliquus were not significantly (p>0.05) different. Plutonium accumulation by S.obliquus was log-linear. (author)

  9. Magma wagging and whirling in volcanic conduits

    Science.gov (United States)

    Liao, Yang; Bercovici, David; Jellinek, Mark

    2018-02-01

    Seismic tremor characterized by 0.5-7 Hz ground oscillations commonly occur before and during eruptions at silicic volcanoes with widely ranging vent geometries and edifice structures. The ubiquitous characteristics of this tremor imply that its causes are potentially common to silicic volcanoes. Here we revisit and extend to three dimensions the magma-wagging model for tremor (Jellinek and Bercovici, 2011; Bercovici et al., 2013), wherein a stiff magma column rising in a vertical conduit oscillates against a surrounding foamy annulus of bubbly magma, giving rise to tremor. While prior studies were restricted to two-dimensional lateral oscillations, here we explore three-dimensional motion and additional modes of oscillations. In the absence of viscous damping, the magma column undergoes 'whirling' motion: the center of each horizontal section of the column traces an elliptical trajectory. In the presence of viscous effect we identify new 'coiling' and 'uncoiling' column bending shapes with relatively higher and comparable rates of dissipation to the original two-dimensional magma wagging model. We also calculate the seismic P-wave response of the crustal material around the volcanic conduit to the new whirling motions and propose seismic diagnostics for different wagging patterns using the time-lag between seismic stations. We test our model by analyzing pre-eruptive seismic data from the 2009 eruption of Redoubt Volcano. In addition to suggesting that the occurrence of elliptical whirling motion more than 1 week before the eruption, our analysis of seismic time-lags also implies that the 2009 eruption was accompanied by qualitative changes in the magma wagging behavior including fluctuations in eccentricity and a reversal in the direction of elliptical whirling motion when the eruption was immediately impending.

  10. Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

    Energy Technology Data Exchange (ETDEWEB)

    Baltrusaitis, Jonas, E-mail: job314@lehigh.edu [Department of Chemical Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015 (United States); PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Mendoza-Sanchez, Beatriz [CRANN, Chemistry School, Trinity College Dublin, Dublin (Ireland); Fernandez, Vincent [Institut des Matériaux Jean Rouxel, 2 rue de la Houssinière, BP 32229, F-44322 Nantes Cedex 3 (France); Veenstra, Rick [PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Dukstiene, Nijole [Department of Physical and Inorganic Chemistry, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas (Lithuania); Roberts, Adam [Kratos Analytical Ltd, Trafford Wharf Road, Wharfside, Manchester, M17 1GP (United Kingdom); Fairley, Neal [Casa Software Ltd, Bay House, 5 Grosvenor Terrace, Teignmouth, Devon TQ14 8NE (United Kingdom)

    2015-01-30

    Highlights: • We analyzed and modeled spectral envelopes of complex molybdenum oxides. • Molybdenum oxide films of varying valence and crystallinity were synthesized. • MoO{sub 3} and MoO{sub 2} line shapes from experimental data were created. • Informed amorphous sample model (IASM) developed. • Amorphous molybdenum oxide XPS envelopes were interpreted. - Abstract: Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

  11. SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

    Energy Technology Data Exchange (ETDEWEB)

    Steven Shaffer; Sean Kelly; Subhasish Mukerjee; David Schumann; Gail Geiger; Kevin Keegan; John Noetzel; Larry Chick

    2003-12-08

    The objective of Phase I under this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustion engine. This technical progress report covers work performed by Delphi from January 1, 2003 to June 30, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; and Task 9 Stack Testing with Coal-Based Reformate.

  12. Artificial magma and applications of the blasting technique

    Energy Technology Data Exchange (ETDEWEB)

    Ichioka, K [Chugoku Kaki KK, Japan

    1974-01-01

    Artifical magma is discussed. Solid magma is a high temperature source and fluid magma is also a heat carrier. Iron ores are examples of solid magma, silica-borate is an example of a hydrophobic heat carrier magma assuming a liquid phase at 600/sup 0/C, and S, Ag, Pb, etc. are also examples of heat carrier magma. In addition to these examples, basic salts such as NaNO/sub 3/, KNO/sub 3/, NaCl, CaCl, KCl, BaCl, and Na/sub 4/B/sub 4/O/sub 7/ can be used as artifical magma. These are artifical magmas or heat mediums capable of capturing geothermal heat when circulated inside volcanoes. The blasting technique's applications in geothermal wells are also discussed. The technique can be used to expand a well's diameter, repair the well bottom, regenerate old wells, clean wells, or cut steel pipe. Two figures and one table are provided.

  13. Limitations on the Estimation of Parental Magma Temperature Using Olivine-melt Equilibria: Hotspots Not So Hot

    Science.gov (United States)

    Natland, J. H.

    2004-12-01

    Estimates of temperatures of magmas parental to picritic tholeiites using olivine-melt equilibria and FeO-MgO relationships depend strongly on the assumption that a liquid composition, usually a glass, is related to the most magnesian olivine in the rock, or to an olivine composition in equilibrium with mantle peridotite, along an olivine-controlled liquid line of descent. The liquid Fe2+/Fe3+ also has to be known; where data exist, average values from wet chemical determinations are used. Crystallization histories of tholeiitic picrites from islands, spreading ridges, and large igneous provinces, however, usually reveal them to be hybrid rocks that are assembled by two types of magma mixing: 1) between a) differentiated magmas that are on olivine-plagioclase or olivine-plagioclase-clinopyroxene cotectics and b) crystal sludges with abundant olivine that may have accumulated from liquids crystallizing olivine alone; and 2) between primitive magma strains in which olivine crystallized either alone or with other silicate minerals at elevated pressure on separate liquid lines of descent. Many picrites give evidence that both types of mixing have occurred. If either type has occurred, the assumption of olivine-control linking a glass and an olivine composition can only circumstantially be correct. Oxidation state can also be underestimated and therefore FeO contents overestimated if basalts have degassed S, as at Hawaii. In Case 1, hybrid host glass compositions often have higher FeO at given MgO content than liquids which produced many olivine crystals in the rock. In Case 2, the separate parental melt strains are revealed by diversity of compositions of both melt inclusions and Cr-spinel and are most often interpreted to mean local heterogeneity of the mantle source. The inclusions do not always affirm an olivine-controlled liquid line of descent. Instead, inclusions with Gorgona, but not in MORB. Where fresh glass is lacking (e.g., Gorgona), bulk-rock compositions

  14. SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

    Energy Technology Data Exchange (ETDEWEB)

    Steven Shaffer; Sean Kelly; Subhasish Mukerjee; David Schumann; Gail Geiger; Kevin Keegan; Larry Chick

    2004-05-07

    The objective of this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustion engine. This technical progress report covers work performed by Delphi from July 1, 2003 to December 31, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; Task 9 Stack Testing with Coal-Based Reformate; and Task 10 Technology Transfer from SECA CORE Technology Program. In this reporting period, unless otherwise noted Task 6--System Fabrication and Task 7--System Testing will be reported within Task 1 System Design and Integration. Task 8--Program Management, Task 9--Stack Testing with Coal Based Reformate, and Task 10--Technology Transfer from SECA CORE Technology Program will be reported on in the Executive Summary section of this report.

  15. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  16. Loki Patera: A Magma Sea Story

    Science.gov (United States)

    Veeder, G. J.; Matson, D. L.; Rathbun, A. G.

    2005-01-01

    We consider Loki Patera on Io as the surface expression of a large uniform body of magma. Our model of the Loki magma sea is some 200 km across; larger than a lake but smaller than an ocean. The depth of the magma sea is unknown, but assumed to be deep enough that bottom effects can be ignored. Edge effects at the shore line can be ignored to first order for most of the interior area. In particular, we take the dark material within Loki Patera as a thin solidified lava crust whose hydrostatic shape follows Io's isostatic surface (approx. 1815 km radius of curvature). The dark surface of Loki appears to be very smooth on both regional and local (subresolution) scales. The thermal contrast between the low and high albedo areas within Loki is consistent with the observed global correlation. The composition of the model magma sea is basaltic and saturated with dissolved SO2 at depth. Its average, almost isothermal, temperature is at the liquidus for basalt. Additional information is included in the original extended abstract.

  17. Probing magma reservoirs to improve volcano forecasts

    Science.gov (United States)

    Lowenstern, Jacob B.; Sisson, Thomas W.; Hurwitz, Shaul

    2017-01-01

    When it comes to forecasting eruptions, volcano observatories rely mostly on real-time signals from earthquakes, ground deformation, and gas discharge, combined with probabilistic assessments based on past behavior [Sparks and Cashman, 2017]. There is comparatively less reliance on geophysical and petrological understanding of subsurface magma reservoirs.

  18. Iron Redox Systematics of Martian Magmas

    Science.gov (United States)

    Righter, K.; Danielson, L.; Martin, A.; Pando, K.; Sutton, S.; Newville, M.

    2011-01-01

    Martian magmas are known to be FeO-rich and the dominant FeO-bearing mineral at many sites visited by the Mars Exploration rovers (MER) is magnetite [1]. Morris et al. [1] propose that the magnetite appears to be igneous in origin, rather than of secondary origin. However, magnetite is not typically found in experimental studies of martian magmatic rocks [2,3]. Magnetite stability in terrestrial magmas is well understood, as are the stability of FeO and Fe2O3 in terrestrial magmas [4,5]. In order to better understand the variation of FeO and Fe2O3, and the stability of magnetite (and other FeO-bearing phases) in martian magmas we have undertaken an experimental study with two emphases. First we document the stability of magnetite with temperature and fO2 in a shergottite bulk composition. Second, we determine the FeO and Fe2O3 contents of the same shergottite bulk composition at 1 bar and variable fO2 at 1250 C, and at variable pressure. These two goals will help define not only magnetite stability, but pyroxene-melt equilibria that are also dependent upon fO2.

  19. Unusual Iron Redox Systematics of Martian Magmas

    Science.gov (United States)

    Danielson, L.; Righter, K.; Pando, K.; Morris, R. V.; Graff, T.; Agresti, D.; Martin, A.; Sutton, S.; Newville, M.; Lanzirotti, A.

    2012-01-01

    Martian magmas are known to be FeO-rich and the dominant FeO-bearing mineral at many sites visited by the Mars Exploration rovers (MER) is magnetite. Morris et al. proposed that the magnetite appears to be igneous in origin, rather than of secondary origin. However, magnetite is not typically found in experimental studies of martian magmatic rocks. Magnetite stability in terrestrial magmas is well understood, as are the stabilities of FeO and Fe2O3 in terrestrial magmas. In order to better understand the variation of FeO and Fe2O3, and the stability of magnetite (and other FeO-bearing phases) in martian magmas, we have undertaken an experimental study with two emphases. First, we determine the FeO and Fe2O3 contents of super- and sub-liquidus glasses from a shergottite bulk composition at 1 bar to 4 GPa, and variable fO2. Second, we document the stability of magnetite with temperature and fO2 in a shergottite bulk composition.

  20. Magma-poor vs. magma-rich continental rifting and breakup in the Labrador Sea

    Science.gov (United States)

    Gouiza, M.; Paton, D.

    2017-12-01

    Magma-poor and magma-rich rifted margins show distinct structural and stratigraphic geometries during the rift to breakup period. In magma-poor margins, crustal stretching is accommodated mainly by brittle faulting and the formation of wide rift basins shaped by numerous graben and half-graben structures. Continental breakup and oceanic crust accretion are often preceded by a localised phase of (hyper-) extension where the upper mantle is embrittled, serpentinized, and exhumed to the surface. In magma-rich margins, the rift basin is narrow and extension is accompanied by a large magmatic supply. Continental breakup and oceanic crust accretion is preceded by the emplacement of a thick volcanic crust juxtaposing and underplating a moderately thinned continental crust. Both magma-poor and magma-rich rifting occur in response to lithospheric extension but the driving forces and processes are believed to be different. In the former extension is assumed to be driven by plate boundary forces, while in the latter extension is supposed to be controlled by sublithospheric mantle dynamics. However, this view fails in explaining observations from many Atlantic conjugate margins where magma-poor and magma-rich segments alternate in a relatively abrupt fashion. This is the case of the Labrador margin where the northern segment shows major magmatic supply during most of the syn-rift phase which culminate in the emplacement of a thick volcanic crust in the transitional domain along with high density bodies underplating the thinned continental crust; while the southern segment is characterized mainly by brittle extension, mantle seprentinization and exhumation prior to continental breakup. In this work, we use seismic and potential field data to describe the crustal and structural architectures of the Labrador margin, and investigate the tectonic and mechanical processes of rifting that may have controlled the magmatic supply in the different segments of the margin.

  1. The mechanics of shallow magma reservoir outgassing

    Science.gov (United States)

    Parmigiani, A.; Degruyter, W.; Leclaire, S.; Huber, C.; Bachmann, O.

    2017-08-01

    Magma degassing fundamentally controls the Earth's volatile cycles. The large amount of gas expelled into the atmosphere during volcanic eruptions (i.e., volcanic outgassing) is the most obvious display of magmatic volatile release. However, owing to the large intrusive:extrusive ratio, and considering the paucity of volatiles left in intrusive rocks after final solidification, volcanic outgassing likely constitutes only a small fraction of the overall mass of magmatic volatiles released to the Earth's surface. Therefore, as most magmas stall on their way to the surface, outgassing of uneruptible, crystal-rich magma storage regions will play a dominant role in closing the balance of volatile element cycling between the mantle and the surface. We use a numerical approach to study the migration of a magmatic volatile phase (MVP) in crystal-rich magma bodies ("mush zones") at the pore scale. Our results suggest that buoyancy-driven outgassing is efficient over crystal volume fractions between 0.4 and 0.7 (for mm-sized crystals). We parameterize our pore-scale results for MVP migration in a thermomechanical magma reservoir model to study outgassing under dynamical conditions where cooling controls the evolution of the proportion of crystal, gas, and melt phases and to investigate the role of the reservoir size and the temperature-dependent viscoelastic response of the crust on outgassing efficiency. We find that buoyancy-driven outgassing allows for a maximum of 40-50% volatiles to leave the reservoir over the 0.4-0.7 crystal volume fractions, implying that a significant amount of outgassing must occur at high crystal content (>0.7) through veining and/or capillary fracturing.

  2. Io: Loki Patera as a Magma Sea

    Science.gov (United States)

    Matson, Dennis L.; Davies, Ashley Gerard; Veeder, Glenn J.; Rathbun, Julie A.; Johnson, Torrence V.; Castillo, Julie C.

    2006-01-01

    We develop a physical model for Loki Patera as a magma sea. We calculate the total volume of magma moving through the Loki Patera volcanic system every resurfacing cycle (approx.540 days) and the resulting variation in thermal emission. The rate of magma solidification at times reaches 3 x 10(exp 6) kg per second, with a total solidified volume averaging 100 cu km per year. A simulation of gas physical chemistry evolution yields the crust porosity profile and the timescale when it will become dense enough to founder in a manner consistent with observations. The Loki Patera surface temperature distribution shows that different areas are at different life cycle stages. On a regional scale, however, there can be coordinated activity, indicated by the wave of thermal change which progresses from Loki Patera's SW quadrant toward the NE at a rate of approx.1 km per day. Using the observed surface temperature distribution, we test several mechanisms for resurfacing Loki Patera, finding that resurfacing with lava flows is not realistic. Only the crustal foundering process is consistent with observations. These tests also discovered that sinking crust has a 'heat deficit' which promotes the solidification of additional magma onto the sinking plate ("bulking up"). In the limiting case, the mass of sinking material can increase to a mass of approx.3 times that of the foundering plate. With all this solid matter sinking, there is a compensating upward motion in the liquid magma. This can be in excess of 2 m per year. In this manner, solid-liquid convection is occurring in the sea.

  3. Approaches to Determining the Oxidation State of Nitrogen and Carbon Atoms in Organic Compounds for High School Students

    Science.gov (United States)

    Jurowski, Kamil; Krzeczkowska, Malgorzata Krystyna; Jurowska, Anna

    2015-01-01

    The concept of oxidation state (or oxidation number) and related issues have always been difficult for students. In addition, there are misunderstandings and obscurities, which can cause improper balancing of the chemical equations (mostly in organic reactions). In particular, these problems are related to determination of the oxidation state of…

  4. Phase Behavior and Equations of State of the Actinide Oxides

    Science.gov (United States)

    Chidester, B.; Pardo, O. S.; Panero, W. R.; Fischer, R. A.; Thompson, E. C.; Heinz, D. L.; Prescher, C.; Prakapenka, V. B.; Campbell, A.

    2017-12-01

    The distribution of the long-lived heat-producing actinide elements U and Th in the deep Earth has important implications for the dynamics of the mantle and possibly the energy budget of Earth's core. The low shear velocities of the Large Low-Shear Velocity Provinces (LLSVPs) on the core-mantle boundary suggests that these regions are at least partially molten and may contain concentrated amounts of the radioactive elements, as well as other large cations such as the rare Earth elements. As such, by exploring the phase behavior of actinide-bearing minerals at extreme conditions, some insight into the mineralogy, formation, and geochemical and geodynamical effects of these regions can be gained. We have performed in situ high-pressure, high-temperature synchrotron X-ray diffraction experiments and calculations on two actinide oxide materials, UO2 and ThO2, to determine their phase behavior at the extreme conditions of the lower mantle. Experiments on ThO2 reached 60 GPa and 2500 K, and experiments on UO2 reached 95 GPa and 2500 K. We find that ThO2 exists in the fluorite-type structure to 20 GPa at high temperatures, at which point it transforms to the high-pressure cotunnite-type structure and remains thus up to 60 GPa. At room temperature, an anomalous expansion of the fluorite structure is observed prior to the transition, and may signal anion sub-lattice disorder. Similarly, UO2 exists in the fluorite-type structure at ambient conditions and up to 28 GPa at high temperatures. Above these pressures, we have observed a previously unidentified phase of UO2 with a tetragonal structure as the lower-temperature phase and the cotunnite-type phase at higher temperatures. Above 78 GPa, UO2 undergoes another transition or possible dissociation into two separate oxide phases. These phase diagrams suggest that the actinides could exist as oxides in solid solution with other analogous phases (e.g. ZrO2) in the cotunnite-type structure throughout much of Earth's lower mantle.

  5. On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Kiselev, Yurii M [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation)

    2009-01-31

    The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

  6. On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

    International Nuclear Information System (INIS)

    Kiselev, Yurii M

    2009-01-01

    The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

  7. Adsorption properties versus oxidation states of rutile TiO2(110)

    DEFF Research Database (Denmark)

    Martinez, Umberto; Hammer, Bjørk

    2011-01-01

    Using density functional theory we have studied the adsorption properties of different atoms and molecules deposited on a stoichiometric, reduced, and oxidized rutile TiO2(110) surface. Depending on the oxidation state of the surface, electrons can flow from or to the substrate and, therefore...... of the charge flow depends on the oxidation state of the rutile surface and on the adsorption site. Generally, the charging effect leads to more stable complexes. However, the increase in the binding energy of the adsorbates is highly dependent on the electronic states of the surface prior to the adsorption...... event. In this work we have analyzed in details these mechanisms and we have also established a direct correlation between the enhanced binding energy of the adsorbates and the induced gap states...

  8. Microanalysis of iron oxidation state in iron oxides using X Ray Absorption Near Edge Structure (XANES)

    Science.gov (United States)

    Sutton, S. R.; Delaney, J.; Bajt, S.; Rivers, M. L.; Smith, J. V.

    1993-01-01

    An exploratory application of x ray absorption near edge structure (XANES) analysis using the synchrotron x ray microprobe was undertaken to obtain Fe XANES spectra on individual sub-millimeter grains in conventional polished sections. The experiments concentrated on determinations of Fe valence in a suite of iron oxide minerals for which independent estimates of the iron speciation could be made by electron microprobe analysis and x ray diffraction.

  9. The high-K calc-alkalic Serra da Lagoinha batholith, States of Ceara and Paraiba (Northeastern region, Brazil): coexistence and mixing of dioritic and quartz monzonitic to granitic magmas

    International Nuclear Information System (INIS)

    Mariano, Gorki; Sobreira, Mauricio de Nassau de Mattos

    1999-01-01

    The Serra da Lagoinha batholith (SLB) has an outcrop area of 200 km 2 is located in the Borborema Province, northeastern Brazil, and intrudes schists and phylites at the border of the Cachoeirinha-Salgueiro fold belt. Its southern border is defined by a major curved NE-SW sinistral transcurrent shear zone (Boqueirao dos Cochos) connecting the E-W dextral shear zones of Patos to the north and Pernambuco to the south. The SLB has three lithologic domains: the felsic porphyritic domain composed of K-feldspar megacrystic monzonitic, quartz monzonitic, quartz monzodioritic, granitic to granodioritic rocks; the k-dioritic domain composed of biotite (quartz) dioritic to tonalitic rocks and the hybrid domain composed of monzonitic and biotite (quartz) dioritic rocks. Field evidences show that these lithologic domains were produced by the coexistence and mixing of K-diorites with potassic monzonitic to granodioritic magmas. The mafic rocks are enriched in Nb, ba, and Zr and LREE in relation to the felsic porphyritic rocks. The REE patterns for mafic and felsic rocks are similar and enriched in the LREE in relation to the HREE, with (La/Yb) N varying from 22.43 to 36.10 for the felsic and from 27.21 to 58.87 for the mafic rocks. Al Τ in amphibole geobarometer (Hollister 1987) shows that amphibole crystallization in the SLB occurred at approximately 4.5 kbar. Geothermometry based on the coexistence of amphibole and plagioclase, (Blundy and Holland 1990) gives a temperature of 742 deg C. Whole rock Oxygen isotope data showed average values for mafic of δ 18 O = + 7.9 permil SMOW and for the felsic rocks of δ 18 O + 9.1 permil SMOW , suggesting either isotopic equilibrium of coexistent magmas of distinct sources or crystal fractionation process controlling the evolution from mafic to felsic rocks. Quartz corrected values for the felsic porphyritic rocks averaged δ 18 O = + 9.2 permil, suggesting that the whole rock data represent magmatic values. Sm-Nd systematics show T

  10. Magnetotelluric Investigations of the Yellowstone Caldera: Understanding the Emplacement of Crustal Magma Bodies

    Science.gov (United States)

    Gurrola, R. M.; Neal, B. A.; Bennington, N. L.; Cronin, R.; Fry, B.; Hart, L.; Imamura, N.; Kelbert, A.; Bowles-martinez, E.; Miller, D. J.; Scholz, K. J.; Schultz, A.

    2017-12-01

    Wideband magnetotellurics (MT) presents an ideal method for imaging conductive shallow magma bodies associated with contemporary Yellowstone-Snake River Plain (YSRP) magmatism. Particularly, how do these magma bodies accumulate in the mid to upper crust underlying the Yellowstone Caldera, and furthermore, what role do hydrothermal fluids play in their ascent? During the summer 2017 field season, two field teams from Oregon State University and the University of Wisconsin-Madison installed forty-four wideband MT stations within and around the caldera, and using data slated for joint 3-D inversion with existing seismic data, two 2-D vertical conductivity sections of the crust and upper mantle were constructed. These models, in turn, provide preliminary insight into the emplacement of crustal magma bodies and hydrothermal processes in the YSRP region.

  11. Deep magma transport at Kilauea volcano, Hawaii

    Science.gov (United States)

    Wright, T.L.; Klein, F.W.

    2006-01-01

    The shallow part of Kilauea's magma system is conceptually well-understood. Long-period and short-period (brittle-failure) earthquake swarms outline a near-vertical magma transport path beneath Kilauea's summit to 20 km depth. A gravity high centered above the magma transport path demonstrates that Kilauea's shallow magma system, established early in the volcano's history, has remained fixed in place. Low seismicity at 4-7 km outlines a storage region from which magma is supplied for eruptions and intrusions. Brittle-failure earthquake swarms shallower than 5 km beneath the rift zones accompany dike emplacement. Sparse earthquakes extend to a decollement at 10-12 km along which the south flank of Kilauea is sliding seaward. This zone below 5 km can sustain aseismic magma transport, consistent with recent tomographic studies. Long-period earthquake clusters deeper than 40 km occur parallel to and offshore of Kilauea's south coast, defining the deepest seismic response to magma transport from the Hawaiian hot spot. A path connecting the shallow and deep long-period earthquakes is defined by mainshock-aftershock locations of brittle-failure earthquakes unique to Kilauea whose hypocenters are deeper than 25 km with magnitudes from 4.4 to 5.2. Separation of deep and shallow long-period clusters occurs as the shallow plumbing moves with the volcanic edifice, while the deep plumbing is centered over the hotspot. Recent GPS data agrees with the volcano-propagation vector from Kauai to Maui, suggesting that Pacific plate motion, azimuth 293.5?? and rate of 7.4 cm/yr, has been constant over Kilauea's lifetime. However, volcano propagation on the island of Hawaii, azimuth 325??, rate 13 cm/yr, requires southwesterly migration of the locus of melting within the broad hotspot. Deep, long-period earthquakes lie west of the extrapolated position of Kilauea backward in time along a plate-motion vector, requiring southwesterly migration of Kilauea's magma source. Assumed ages of 0

  12. The oxidation states of elements in pure and Ca-doped BiCuSeO thermoelectric oxides

    International Nuclear Information System (INIS)

    Hsiao, Chun-Lung; Qi, Xiaoding

    2016-01-01

    Bi 1−x Ca x CuSeO (x = 0–0.3) was synthesized at 650 °C in an air-tight system flowing with pure argon. The Ca doping resulted in an increase in the thermoelectric figure of merit (ZT) as the consequence of increased carrier concentration. X-ray photoelectron spectroscopy (XPS) was carried out to check the oxidation states in Bi 1−x Ca x CuSeO. The results indicated that in addition to the expected Bi 3+ and Cu 1+ , there existed Bi 2+ and Cu 2+ in the undoped BiCuSeO, whereas in the Ca-doped BiCuSeO, Bi 4+ , Cu 3+ and Cu 2+ were observed. The Ca dopant was confirmed to be in the 2+ oxidation state. Two broad peaks centered at 54.22 and 58.59 eV were recorded in the vicinity around the binding energy of Se 3d. The former is often observed in the Se-containing intermetallics while the latter is often found in the Se-containing oxides, indicating that along with the expected Se–Cu bonding, a bonding between Se and O may also exist. Based on the XPS results, the charge compensation mechanisms were proposed for Bi 1−x Ca x CuSeO, which may shed some light on the origins of charge carriers. BiCuSeO based oxides have recently be discovered to have a large ZT comparable to the best alloys currently in use, because of the large Seebeck coefficient and small thermal conductivity. However, their electrical conductivity is lower compared to the best thermoelectrics. This work may provide some hints for the further improvement of ZT in BiCuSeO based oxides. - Graphical abstract: The oxidation states, charge compensation mechanisms, and origins of charge carriers in Bi 1−x Ca x CuSeO thermoelectrics. Display Omitted

  13. Evolution of silicic magmas in the Kos-Nisyros volcanic center: cycles associated with caldera collapse

    Science.gov (United States)

    Ruprecht, J. S.; Bachmann, O.; Deering, C. D.; Huber, C.; Skopelitis, A.; Schnyder, C.

    2010-12-01

    Multiple eruptions of silicic magma (dacite and rhyolites) occurred over the last ~ 3 My in the Kos-Nisyros volcanic center (eastern Aegean sea). Over the course of this period, magmas have changed from hornblende-biotite rich units with low eruption temperatures (≤750-800 °C; Kefalos and Kos units) to hotter (>800-850 °C), pyroxene-bearing units (Nisyros units) and are transitioning back to colder magmas (Yali units). Using bulk-rock compositions, mineral chemistry, and zircon Hf isotopes, we show that the two different types of silicic magmas followed the same differentiation trend; they all evolved by crystal fractionation (and minor assimilation) from parents with intermediate compositions characterized by high Sr/Y and low Nb content, following a wet, high oxygen fugacity liquid line of descent typical of subduction zones. As the transition between the Kos-Kefalos and Nisyros-type magmas occurred immediately and abruptly after the major caldera collapse in the area (the 161 ky Kos Plateau Tuff; KPT), we suggest that the efficient emptying of the magma chamber during the KPT drew most of the eruptible magma out and partly froze the silicic magma source zone in the upper crust due to rapid unloading, decompression and resulting crystallization. Therefore, the system had to reinstate a shallow silicic production zone from more mafic parents, recharged at temperatures typically around 850-900 °C from the mid to lower crust. The first silicic eruptions evolving from these parents after the caldera collapse (Nisyros units) were thus slightly hotter and less evolved than the Kefalos-Kos package. However, with time, the upper crustal intermediate mush grew and cooled, leading to interstitial melt compositions reaching again the highly-evolved, cold state that prevailed prior to the Kefalos-Kos. The recent (albeit not precisely dated) eruption of the high-SiO2 rhyolite of Yali suggests that another large, potentially explosive magma chamber is presently building

  14. Ab initio molecular dynamics simulation of aqueous solution of nitric oxide in different formal oxidation states

    Science.gov (United States)

    Venâncio, Mateus F.; Rocha, Willian R.

    2015-10-01

    Ab initio molecular dynamics simulations were used to investigate the early chemical events involved in the dynamics of nitric oxide (NOrad), nitrosonium cation (NO+) and nitroxide anion (NO-) in aqueous solution. The NO+ ion is very reactive in aqueous solution having a lifetime of ∼4 × 10-13 s, which is shorter than the value of 3 × 10-10 s predicted experimentally. The NO+ reacts generating the nitrous acid as an intermediate and the NO2- ion as the final product. The dynamics of NOrad revealed the reversibly formation of a transient anion radical species HONOrad -.

  15. Formation and evolution of a lunar core from ilmenite-rich magma ocean cumulates

    NARCIS (Netherlands)

    de Vries, J.; van den Berg, A.P.; van Westrenen, W.

    2010-01-01

    In the absence of comprehensive seismic data coverage, the size, composition and physical state of the lunar core are still debated. It has been suggested that a dense ilmenite-rich layer, which originally crystallised near the top of the lunar magma ocean, may have sunk to the centre of the Moon to

  16. Magma Dynamics in Dome-Building Volcanoes

    Science.gov (United States)

    Kendrick, J. E.; Lavallée, Y.; Hornby, A. J.; Schaefer, L. N.; Oommen, T.; Di Toro, G.; Hirose, T.

    2014-12-01

    The frequent and, as yet, unpredictable transition from effusive to explosive volcanic behaviour is common to active composite volcanoes, yet our understanding of the processes which control this evolution is poor. The rheology of magma, dictated by its composition, porosity and crystal content, is integral to eruption behaviour and during ascent magma behaves in an increasingly rock-like manner. This behaviour, on short timescales in the upper conduit, provides exceptionally dynamic conditions that favour strain localisation and failure. Seismicity released by this process can be mimicked by damage accumulation that releases acoustic signals on the laboratory scale, showing that the failure of magma is intrinsically strain-rate dependent. This character aids the development of shear zones in the conduit, which commonly fracture seismogenically, producing fault surfaces that control the last hundreds of meters of ascent by frictional slip. High-velocity rotary shear (HVR) experiments demonstrate that at ambient temperatures, gouge behaves according to Byerlee's rule at low slip velocities. At rock-rock interfaces, mechanical work induces comminution of asperities and heating which, if sufficient, may induce melting and formation of pseudotachylyte. The viscosity of the melt, so generated, controls the subsequent lubrication or resistance to slip along the fault plane thanks to non-Newtonian suspension rheology. The bulk composition, mineralogy and glass content of the magma all influence frictional behaviour, which supersedes buoyancy as the controlling factor in magma ascent. In the conduit of dome-building volcanoes, the fracture and slip processes are further complicated: slip-rate along the conduit margin fluctuates. The shear-thinning frictional melt yields a tendency for extremely unstable slip thanks to its pivotal position with regard to the glass transition. This thermo-kinetic transition bestows the viscoelastic melt with the ability to either flow or

  17. Long term storage of explosively erupted magma at Nevado de Toluca volcano, Mexico

    Science.gov (United States)

    Arce, J. L.; Gardner, J.; Macias, J. L.

    2007-12-01

    Dacitic magmas production is common in subduction-related volcanoes, occurring in those with a long period of activity as a result of the magmatic evolution. However, in this evolution many factors (i.e. crystal fractionation, assimilation, magma mixing) can interact to produce dacites. Nevado de Toluca volcano (4,680 masl; 19°09'N; 99°45'W) Central Mexico has recorded a long period of time producing dacites explosively, at least during 42 ka of activity, involving several km3 of magma, with two important Plinian-type eruptions occurred at ~21.7 ka (Lower Toluca Pumice) and ~10.5 ka (Upper Toluca Pumice). Questions like, what was the mechanism responsible to produce voluminous dacitic magma and how the volatiles and pressure changed in the Nevado de Toluca system, remain without answers. Dacites from the Lower Toluca Pumice (LTP) contain plagioclase, amphibole, iron-titanium oxides, and minor resorbed biotite, set in a glassy-vesicular matrix and the Upper Toluca Pumice (UTP) dacites contain the same mineral phases plus orthopyroxene. Ilmenite- ulvospinel geothermometry yielded a temperature of ~860°C for the LTP dacite, a little hotter than the UTP (~ 840°C). Based on hydrothermal experiments data, amphibole is stable above 100 MPa under 900°C, while plagioclase crystallizes up to 250-100 MPa at temperatures of 850-900°C. Pyroxene occurs only at pressures of 200-100 MPa with its respective temperatures of 825-900°C. Water contents in the LTP magma (2-3.5 wt %) are similar to that calculated for the UTP magma (1.3-3.6 wt %). So, there are only small changes in temperature and pressure from ~21.7 ka to 10.5 ka. It is noteworthy that orthopyroxene is absent in the LTP, however reaction-rimmed biotite (probably xenocrystic) is commonly observed in all dacites. Hence, almost all dacitic magmas seem to be stored at relatively similar pressures, water contents, and temperatures. All of these data could suggest repetitive basic magma injections producing the

  18. Modeling the Daly Gap: The Influence of Latent Heat Production in Controlling Magma Extraction and Eruption

    Science.gov (United States)

    Nelson, B. K.; Ghiorso, M. S.; Bachmann, O.; Dufek, J.

    2011-12-01

    A century-old issue in volcanology is the origin of the gap in chemical compositions observed in magmatic series on ocean islands and arcs - the "Daly Gap". If the gap forms during differentiation from a mafic parent, models that predict the dynamics of magma extraction as a function of chemical composition must simulate a process that results in volumetrically biased, bimodal compositions of erupted magmas. The probability of magma extraction is controlled by magma dynamical processes, which have a complex response to magmatic heat evolution. Heat loss from the magmatic system is far from a simple, monotonic function of time. It is modified by the crystallization sequence, chamber margin heat flux, and is buffered by latent heat production. We use chemical and thermal calculations of MELTS (Ghiorso & Sack, 1995) as input to the physical model of QUANTUM (Dufek & Bachmann, 2010) to predict crystallinity windows of most probable magma extraction. We modeled two case studies: volcanism on Tenerife, Canary Islands, and the Campanian Ignimbrite (CI) of Campi Flegrei, Italy. Both preserve a basanitic to phonolitic lineage and have comparable total alkali concentrations; however, CI has high and Tenerife has low K2O/Na2O. Modeled thermal histories of differentiation for the two sequences contrast strongly. In Tenerife, the rate of latent heat production is almost always greater than sensible heat production, with spikes in the ratio of latent to sensible heats of up to 40 associated with the appearance of Fe-Ti oxides at near 50% crystallization. This punctuated heat production must cause magma temperature change to stall or slow in time. The extended time spent at ≈50% crystallinity, associated with dynamical processes that enhance melt extraction near 50% crystallinity, suggests the magma composition at this interval should be common. In Tenerife, the modeled composition coincides with that of the first peak in the bimodal frequency-composition distribution. In our

  19. Nature of the magma storage system beneath the Damavand volcano (N. Iran): An integrated study

    Science.gov (United States)

    Eskandari, Amir; Amini, Sadraddin; De Rosa, Rosanna; Donato, Paola

    2018-02-01

    Damavand intraplate stratovolcano constructed upon a moderately thick crust (58-67 km) over the last 2 Ma. The erupted products are dominantly trachyandesite-trachyte (TT) lavas and pyroclasts, with minor mafic magmas including tephrite-basanite-trachybasalt and alkali olivine basalts emplaced as cinder cones at the base of the stratovolcano. The TT products are characterized by a mineral assemblage of clinopyroxene (diopside-augite), orthopyroxene (clinoenstatite), feldspar (An2-58, Ab6-69, Or2-56), high Ti phlogopite, F-apatite, Fesbnd Ti oxides, and minor amounts of olivine (Fo73-80), amphibole and zircon, whereas olivine (Fo78-88), high Mg# (80-89) diopside, feldspar, apatite and Fesbnd Ti oxide occur in the mafic magmas. The presence of hydrous and anhydrous minerals, normal zonings, mafic cumulates, and the composition of magmatic inclusions in the TT products suggest evolutionary processes in polybaric conditions. In the same way, disequilibrium textures - including orthopyroxene mantled with clinopyroxene, reaction rim of phlogopite and amphibole, the coexistence of olivine and orthopyroxene, reverse, oscillatory and complex zonings of pyroxene and feldspar crystals - suggest magmatic evolutions in open systems with a varying temperature, oxygen fugacity, water as well as pressure and, to a lesser extent, melt chemistry. Mineral assemblages are used to model the physicochemical conditions and assess default parameters for the thermodynamic simulation of crystallization using MELTS software to track the P-T-H2O-ƒO2 evolution of the magma plumbing system. Thermobarometry and MELTS models estimated the initial nucleation depth at 16-17 kb (56-60 km) for olivine (Fo89) and high Al diopside crystals occurring in the mafic primary magma; it then stopped and underwent fractionation between 8 and 10 kb (28-35 km), corresponding with Moho depth, and continued to differentiate in the lower crust, in agreement with the geophysical models. The mafic rocks were formed

  20. 99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

    Science.gov (United States)

    McGregor, Donna; Burton-Pye, Benjamin P; Mbomekalle, Israel M; Aparicio, Pablo A; Romo, Susanna; López, Xavier; Poblet, Josep M; Francesconi, Lynn C

    2012-08-20

    The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers. Separation and storage of the long-lived (99)Tc in an appropriate and stable waste-form is an important issue that needs to be addressed. Considering metal oxide solid-state materials as potential storage matrixes for Tc, we are examining the redox speciation of Tc on the molecular level using polyoxometalates (POMs) as models. In this study we investigate the electrochemistry of Tc complexes of the monovacant Wells-Dawson isomers, α(1)-P(2)W(17)O(61)(10-) (α1) and α(2)-P(2)W(17)O(61)(10-) (α2) to identify features of metal oxide materials that can stabilize the immobile Tc(IV) oxidation state accessed from the synthesized Tc(V)O species and to interrogate other possible oxidation states available to Tc within these materials. The experimental results are consistent with density functional theory (DFT) calculations. Electrochemistry of K(7-n)H(n)[Tc(V)O(α(1)-P(2)W(17)O(61))] (Tc(V)O-α1), K(7-n)H(n)[Tc(V)O(α(2)-P(2)W(17)O(61))] (Tc(V)O-α2) and their rhenium analogues as a function of pH show that the Tc-containing derivatives are always more readily reduced than their Re analogues. Both Tc and Re are reduced more readily in the lacunary α1 site as compared to the α2 site. The DFT calculations elucidate that the highest oxidation state attainable for Re is VII while, under the same electrochemistry conditions, the highest oxidation state for Tc is VI. The M(V)→ M(IV) reduction processes for Tc(V)O-α1 are not pH dependent or only slightly pH dependent suggesting that protonation does not accompany reduction of this species unlike the M(V)O-α2 (M = (99)Tc, Re) and Re(V)O-α1 where M(V/IV) reduction process must occur hand in hand with protonation of the terminal M═O to

  1. The crustal magma storage system of Volcán Quizapu, Chile, and the effects of magma mixing on magma diversity

    Science.gov (United States)

    Bergantz, George W.; Cooper, Kari M.; Hildreth, Edward; Ruprecht, Phillipp

    2012-01-01

    Crystal zoning as well as temperature and pressure estimates from phenocryst phase equilibria are used to constrain the architecture of the intermediate-sized magmatic system (some tens of km3) of Volcán Quizapu, Chile, and to document the textural and compositional effects of magma mixing. In contrast to most arc magma systems, where multiple episodes of open-system behavior obscure the evidence of major magma chamber events (e.g. melt extraction, magma mixing), the Quizapu magma system shows limited petrographic complexity in two large historical eruptions (1846–1847 and 1932) that have contrasting eruptive styles. Quizapu magmas and peripheral mafic magmas exhibit a simple binary mixing relationship. At the mafic end, basaltic andesite to andesite recharge magmas complement the record from peripheral cones and show the same limited range of compositions. The silicic end-member composition is almost identical in both eruptions of Quizapu. The effusive 1846–1847 eruption records significant mixing between the mafic and silicic end-members, resulting in hybridized andesites and mingled dacites. These two compositionally simple eruptions at Volcán Quizapu present a rare opportunity to isolate particular aspects of magma evolution—formation of homogeneous dacite magma and late-stage magma mixing—from other magma chamber processes. Crystal zoning, trace element compositions, and crystal-size distributions provide evidence for spatial separation of the mafic and silicic magmas. Dacite-derived plagioclase phenocrysts (i.e. An25–40) show a narrow range in composition and limited zonation, suggesting growth from a compositionally restricted melt. Dacite-derived amphibole phenocrysts show similar restricted compositions and furthermore constrain, together with more mafic amphibole phenocrysts, the architecture of the magmatic system at Volcán Quizapu to be compositionally and thermally zoned, in which an andesitic mush is overlain by a homogeneous dacitic

  2. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

    2010-11-05

    A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

  3. Oxidation state analyses of uranium with emphasis on chemical speciation in geological media

    International Nuclear Information System (INIS)

    Ervanne, H.

    2004-01-01

    This thesis focuses on chemical methods suitable for the determination of uranium redox species in geological materials. Nd-coprecipitation method was studied for the determination of uranium oxidation states in ground waters. This method is ideally suited for the separation of uranium oxidation states in the field, which means that problems associated with the instability of U(IV) during transport are avoided. An alternative method, such as ion exchange, is recommended for the analysis of high saline and calcium- and iron-rich ground waters. U(IV)/Utot was 2.8-7.2% in ground waters in oxidizing conditions and 60-93% in anoxic conditions. From thermodynamic model calculations applied to results from anoxic ground waters it was concluded that uranium can act as redox buffer in granitic ground waters. An ion exchange method was developed for the analysis of uranium oxidation states in different solid materials of geological origin. These included uranium minerals, uraniumbearing minerals, fracture coatings and bulk rock. U(IV)/Utot was 50-70% in uraninites, 5.8-8.7% in secondary uranium minerals, 15-49% in different fracture coatings and 64- 77% in samples from deep bedrock. In the uranium-bearing minerals, U(IV)/Utot was 33-43% (allanites), 5.9% (fergusonite) and 93% (monazite). Although the ion exchange method gave reliable results, there is a risk for the conversion of uranium oxidation states during analysis of heterogeneous samples due to the redox reactions that take place in the presence of some iron compounds. This risk was investigated in a study of several common iron-bearing minerals. The risk for conversion of uranium oxidation states can be screened by sample selection and minimized with use of a redox buffer compound such as polyacrylic acid (PAA). In studies of several carboxylic acids, PAA was found to be the most suitable for extending the application of the method. The stability of uranium oxidation states during analysis and the selectivity

  4. The oxidation state of Fe in MORB glasses and the oxygen fugacity of the upper mantle

    Science.gov (United States)

    Cottrell, Elizabeth; Kelley, Katherine A.

    2011-05-01

    Micro-analytical determination of Fe3+/∑Fe ratios in mid-ocean ridge basalt (MORB) glasses using micro X-ray absorption near edge structure (μ-XANES) spectroscopy reveals a substantially more oxidized upper mantle than determined by previous studies. Here, we show that global MORBs yield average Fe3+/∑Fe ratios of 0.16 ± 0.01 (n = 103), which trace back to primary MORB melts equilibrated at the conditions of the quartz-fayalite-magnetite (QFM) buffer. Our results necessitate an upward revision of the Fe3+/∑Fe ratios of MORBs, mantle oxygen fugacity, and the ferric iron content of the mantle relative to previous wet chemical determinations. We show that only 0.01 (absolute, or Co-variations of Fe3+/∑Fe ratios in global MORB with indices of low-pressure fractional crystallization are consistent with Fe3+ behaving incompatibly in shallow MORB magma chambers. MORB Fe3+/∑Fe ratios do not, however, vary with indices of the extent of mantle melting (e.g., Na2O(8)) or water concentration. We offer two hypotheses to explain these observations: The bulk partition coefficient of Fe3+ may be higher during peridotite melting than previously thought, and may vary with temperature, or redox exchange between sulfide and sulfate species could buffer mantle melting at ~ QFM. Both explanations, in combination with the measured MORB Fe3+/∑Fe ratios, point to a fertile MORB source with greater than 0.3 wt.% Fe2O3.

  5. The Origin of Tholeiitic and Calc-Alkaline Trends in Arc Magmas

    Science.gov (United States)

    Luffi, P. I.; Lee, C.

    2012-12-01

    It has long been recognized that tholeiitic (TH, high-Fe/Mg) and calc-alkaline (CA, low-Fe/Mg) magmatic series define the two most important igneous differentiation trends shaping Earth's crust. While oceanic crust formation at mid-ocean ridges is typically confined to a TH trend, arc magmatism at convergent margins, considered to significantly contribute to continent formation, generates both TH and CA trends. Thus, the origin of these trends - a key issue to understanding how continental crust forms - is matter of ongoing debate. Prevalent factors thought to contribute to the TH-CA duality are: 1) redox conditions (oxygen fugacity, fO2) and H2O contents in magmas, which control the onset and abundance of high-Fe/Mg oxide mineral fractionation; 2) crystallization depths that regulate the fractionating solid assemblage and thereby the solid/liquid Kd(Fe-Mg). Relying on an extensive geochemical dataset of modern arc volcanics and thermodynamic phase equilibria modeling, here we examine the validity and relative importance of these factors in arc petrogenesis. First, to discriminate igneous rocks more efficiently, we formulate an improved CA/TH index solely based on FeO-MgO systematics. We then confirm on a quantitative basis that, on regional scales, arcs formed on thick crust tend to be more calk-alkaline than those emplaced on thinner crust are, and show that the effect of fO2 on the CA/TH index in arc magmas is more significant than that of H2O. Importantly, we demonstrate that CA trends typical for continental arcs only form when crystal fractionation is accompanied by the assimilation of oxidized crustal components; in the absence of buffering oxidized assimilants fractionating magmas follow a TH trend more common in island arcs, irrespective of their H2O content and initial fO2 level. We find that high-pressure fractionation of amphibole and garnet in arc magmas occurs too late to have a significant influence on the CA/TH index; in addition, garnet-melt and

  6. Oxidation of extracellular cysteine/cystine redox state in bleomycin-induced lung fibrosis.

    Science.gov (United States)

    Iyer, Smita S; Ramirez, Allan M; Ritzenthaler, Jeffrey D; Torres-Gonzalez, Edilson; Roser-Page, Susanne; Mora, Ana L; Brigham, Kenneth L; Jones, Dean P; Roman, Jesse; Rojas, Mauricio

    2009-01-01

    Several lines of evidence indicate that depletion of glutathione (GSH), a critical thiol antioxidant, is associated with the pathogenesis of idiopathic pulmonary fibrosis (IPF). However, GSH synthesis depends on the amino acid cysteine (Cys), and relatively little is known about the regulation of Cys in fibrosis. Cys and its disulfide, cystine (CySS), constitute the most abundant low-molecular weight thiol/disulfide redox couple in the plasma, and the Cys/CySS redox state (E(h) Cys/CySS) is oxidized in association with age and smoking, known risk factors for IPF. Furthermore, oxidized E(h) Cys/CySS in the culture media of lung fibroblasts stimulates proliferation and expression of transitional matrix components. The present study was undertaken to determine whether bleomycin-induced lung fibrosis is associated with a decrease in Cys and/or an oxidation of the Cys/CySS redox state and to determine whether these changes were associated with changes in E(h) GSH/glutathione disulfide (GSSG). We observed distinct effects on plasma GSH and Cys redox systems during the progression of bleomycin-induced lung injury. Plasma E(h) GSH/GSSG was selectively oxidized during the proinflammatory phase, whereas oxidation of E(h) Cys/CySS occurred at the fibrotic phase. In the epithelial lining fluid, oxidation of E(h) Cys/CySS was due to decreased food intake. Thus the data show that decreased precursor availability and enhanced oxidation of Cys each contribute to the oxidation of extracellular Cys/CySS redox state in bleomycin-induced lung fibrosis.

  7. Magma ocean formation due to giant impacts

    Science.gov (United States)

    Tonks, W. B.; Melosh, H. J.

    1993-01-01

    The thermal effects of giant impacts are studied by estimating the melt volume generated by the initial shock wave and corresponding magma ocean depths. Additionally, the effects of the planet's initial temperature on the generated melt volume are examined. The shock pressure required to completely melt the material is determined using the Hugoniot curve plotted in pressure-entropy space. Once the melting pressure is known, an impact melting model is used to estimate the radial distance melting occurred from the impact site. The melt region's geometry then determines the associated melt volume. The model is also used to estimate the partial melt volume. Magma ocean depths resulting from both excavated and retained melt are calculated, and the melt fraction not excavated during the formation of the crater is estimated. The fraction of a planet melted by the initial shock wave is also estimated using the model.

  8. Illuminating magma shearing processes via synchrotron imaging

    Science.gov (United States)

    Lavallée, Yan; Cai, Biao; Coats, Rebecca; Kendrick, Jackie E.; von Aulock, Felix W.; Wallace, Paul A.; Le Gall, Nolwenn; Godinho, Jose; Dobson, Katherine; Atwood, Robert; Holness, Marian; Lee, Peter D.

    2017-04-01

    Our understanding of geomaterial behaviour and processes has long fallen short due to inaccessibility into material as "something" happens. In volcanology, research strategies have increasingly sought to illuminate the subsurface of materials at all scales, from the use of muon tomography to image the inside of volcanoes to the use of seismic tomography to image magmatic bodies in the crust, and most recently, we have added synchrotron-based x-ray tomography to image the inside of material as we test it under controlled conditions. Here, we will explore some of the novel findings made on the evolution of magma during shearing. These will include observations and discussions of magma flow and failure as well as petrological reaction kinetics.

  9. The Acoculco caldera magmas: genesis, evolution and relation with the Acoculco geothermal system

    Science.gov (United States)

    Sosa-Ceballos, G.; Macías, J. L.; Avellán, D.

    2017-12-01

    The Acoculco Caldera Complex (ACC) is located at the eastern part of the Trans Mexican Volcanic Belt; México. This caldera complex have been active since 2.7 Ma through reactivations of the system or associated magmatism. Therefore the ACC is an excellent case scenario to investigate the relation between the magmatic heat supply and the evolution processes that modified magmatic reservoirs in a potential geothermal field. We investigated the origin and the magmatic processes (magma mixing, assimilation and crystallization) that modified the ACC rocks by petrography, major oxides-trace element geochemistry, and isotopic analysis. Magma mixing is considered as the heat supply that maintain active the magmatic system, whereas assimilation yielded insights about the depth at which processes occurred. In addition, we performed a series of hydrothermal experiments in order to constrain the storage depth for the magma tapped during the caldera collapse. Rocks from the ACC were catalogued as pre, syn and post caldera. The post caldera rocks are peralkaline rhyolites, in contrast to all other rocks that are subalkaline. Our investigation is focus to investigate if the collapse modified the plumbing system and the depth at which magmas stagnate and recorded the magmatic processes.

  10. DetOx: a program for determining anomalous scattering factors of mixed-oxidation-state species.

    Science.gov (United States)

    Sutton, Karim J; Barnett, Sarah A; Christensen, Kirsten E; Nowell, Harriott; Thompson, Amber L; Allan, David R; Cooper, Richard I

    2013-01-01

    Overlapping absorption edges will occur when an element is present in multiple oxidation states within a material. DetOx is a program for partitioning overlapping X-ray absorption spectra into contributions from individual atomic species and computing the dependence of the anomalous scattering factors on X-ray energy. It is demonstrated how these results can be used in combination with X-ray diffraction data to determine the oxidation state of ions at specific sites in a mixed-valance material, GaCl(2).

  11. Pressure waves in a supersaturated bubbly magma

    Science.gov (United States)

    Kurzon, I.; Lyakhovsky, V.; Navon, O.; Chouet, B.

    2011-01-01

    We study the interaction of acoustic pressure waves with an expanding bubbly magma. The expansion of magma is the result of bubble growth during or following magma decompression and leads to two competing processes that affect pressure waves. On the one hand, growth in vesicularity leads to increased damping and decreased wave amplitudes, and on the other hand, a decrease in the effective bulk modulus of the bubbly mixture reduces wave velocity, which in turn, reduces damping and may lead to wave amplification. The additional acoustic energy originates from the chemical energy released during bubble growth. We examine this phenomenon analytically to identify conditions under which amplification of pressure waves is possible. These conditions are further examined numerically to shed light on the frequency and phase dependencies in relation to the interaction of waves and growing bubbles. Amplification is possible at low frequencies and when the growth rate of bubbles reaches an optimum value for which the wave velocity decreases sufficiently to overcome the increased damping of the vesicular material. We examine two amplification phase-dependent effects: (1) a tensile-phase effect in which the inserted wave adds to the process of bubble growth, utilizing the energy associated with the gas overpressure in the bubble and therefore converting a large proportion of this energy into additional acoustic energy, and (2) a compressive-phase effect in which the pressure wave works against the growing bubbles and a large amount of its acoustic energy is dissipated during the first cycle, but later enough energy is gained to amplify the second cycle. These two effects provide additional new possible mechanisms for the amplification phase seen in Long-Period (LP) and Very-Long-Period (VLP) seismic signals originating in magma-filled cracks.

  12. Yamato 980459: Crystallization of Martian Magnesian Magma

    Science.gov (United States)

    Koizumi, E.; Mikouchi, T.; McKay, G.; Monkawa, A.; Chokai, J.; Miyamoto, M.

    2004-01-01

    Recently, several basaltic shergottites have been found that include magnesian olivines as a major minerals. These have been called olivinephyric shergottites. Yamato 980459, which is a new martian meteorite recovered from the Antarctica by the Japanese Antarctic expedition, is one of them. This meteorite is different from other olivine-phyric shergottites in several key features and will give us important clues to understand crystallization of martian meteorites and the evolution of Martian magma.

  13. Studies of surface states in zinc oxide nanopowders

    Science.gov (United States)

    Peters, Raul Mugabe

    The surface of ZnO semiconductor nanosystems is a key performance-defining factor in numerous applications. In this work we present experimental results for the surface defect-related properties of ZnO nanoscale systems. Surface photovoltage spectroscopy was used to determine the defect level energies within the band gap, the conduction vs. valence band nature of the defect-related transitions, and to probe key dynamic parameters of the surface on a number of commercially available ZnO nanopowders. In our experimental setup, surface photovoltage characterization is conducted in high vacuum in tandem with in situ oxygen remote plasma treatments. Surface photovoltage investigations of the as-received and plasma-processed samples revealed a number of common spectral features related to surface states. Furthermore, we observed significant plasma-induced changes in the surface defect properties. Ex situ positron annihilation and photoluminescence measurements were performed on the studied samples and correlated with surface photovoltage results. The average positron lifetimes were found to be substantially longer than in a bulk single crystalline sample, which is consistent with the model of grains with defect-rich surface and subsurface layers. Compression of the powders into pellets yielded reduction of the average positron lifetimes. Surface photovoltage, positron annihilation, and photoluminescence spectra consistently showed sample-to-sample differences due to the variation in the overall quality of the nanopowders, which partially obscures observation of the scaling effects. However, the results demonstrated that our approach is efficient in detecting specific surface states in nanoscale ZnO specimens and in elucidating their nature.

  14. Conformational Toggling of Yeast Iso-1-Cytochrome c in the Oxidized and Reduced States

    Science.gov (United States)

    Yang, Zhongzheng; Zhu, Jing; Ying, Tianlei; Jiang, Xianwang; Zhang, Xu; Wu, Houming; Liu, Maili; Tan, Xiangshi; Cao, Chunyang; Huang, Zhong-Xian

    2011-01-01

    To convert cyt c into a peroxidase-like metalloenzyme, the P71H mutant was designed to introduce a distal histidine. Unexpectedly, its peroxidase activity was found even lower than that of the native, and that the axial ligation of heme iron was changed to His71/His18 in the oxidized state, while to Met80/His18 in the reduced state, characterized by UV-visible, circular dichroism, and resonance Raman spectroscopy. To further probe the functional importance of Pro71 in oxidation state dependent conformational changes occurred in cyt c, the solution structures of P71H mutant in both oxidation states were determined. The structures indicate that the half molecule of cyt c (aa 50–102) presents a kind of “zigzag riveting ruler” structure, residues at certain positions of this region such as Pro71, Lys73 can move a big distance by altering the tertiary structure while maintaining the secondary structures. This finding provides a molecular insight into conformational toggling in different oxidation states of cyt c that is principle significance to its biological functions in electron transfer and apoptosis. Structural analysis also reveals that Pro71 functions as a key hydrophobic patch in the folding of the polypeptide of the region (aa 50–102), to prevent heme pocket from the solvent. PMID:22087268

  15. How does the architecture of a fault system controls magma upward migration through the crust?

    Science.gov (United States)

    Iturrieta, P. C.; Cembrano, J. M.; Stanton-Yonge, A.; Hurtado, D.

    2017-12-01

    The orientation and relative disposition of adjacent faults locally disrupt the regional stress field, thus enhancing magma flow through previous or newly created favorable conduits. Moreover, the brittle-plastic transition (BPT), due to its stronger rheology, governs the average state of stress of shallower portions of the fault system. Furthermore, the BPT may coincide with the location of transient magma reservoirs, from which dikes can propagate upwards into the upper crust, shaping the inner structure of the volcanic arc. In this work, we examine the stress distribution in strike-slip duplexes with variable geometry, along with the critical fluid overpressure ratio (CFOP), which is the minimum value required for individual faults to fracture in tension. We also determine the stress state disruption of the fault system when a dike is emplaced, to answer open questions such as: what is the nature of favorable pathways for magma to migrate? what is the architecture influence on the feedback between fault system kinematics and magma injection? To this end, we present a 3D coupled hydro-mechanical finite element model of the continental lithosphere, where faults are represented as continuum volumes with an elastic-plastic rheology. Magma flow upon fracturing is modeled through non-linear Stoke's flow, coupling solid and fluid equilibrium. A non-linear sensitivity analysis is performed in function of tectonic, rheology and geometry inputs, to assess which are the first-order factors that governs the nature of dike emplacement. Results show that the CFOP is heterogeneously distributed in the fault system, and within individual fault segments. Minimum values are displayed near fault intersections, where local kinematics superimpose on regional tectonic loading. Furthermore, when magma is transported through a fault segment, the CFOP is now minimized in faults with non-favorable orientations. This suggests that these faults act as transient pathways for magma to

  16. The Impact of Environmental Factors in Influencing Epigenetics Related to Oxidative States in the Cardiovascular System

    Directory of Open Access Journals (Sweden)

    Francesco Angelini

    2017-01-01

    Full Text Available Oxidative states exert a significant influence on a wide range of biological and molecular processes and functions. When their balance is shifted towards enhanced amounts of free radicals, pathological phenomena can occur, as the generation of reactive oxygen species (ROS in tissue microenvironment or in the systemic circulation can be detrimental. Epidemic chronic diseases of western societies, such as cardiovascular disease, obesity, and diabetes correlate with the imbalance of redox homeostasis. Current advances in our understanding of epigenetics have revealed a parallel scenario showing the influence of oxidative stress as a major regulator of epigenetic gene regulation via modification of DNA methylation, histones, and microRNAs. This has provided both the biological link and a potential molecular explanation between oxidative stress and cardiovascular/metabolic phenomena. Accordingly, in this review, we will provide current insights on the physiological and pathological impact of changes in oxidative states on cardiovascular disorders, by specifically focusing on the influence of epigenetic regulation. A special emphasis will highlight the effect on epigenetic regulation of human’s current life habits, external and environmental factors, including food intake, tobacco, air pollution, and antioxidant-based approaches. Additionally, the strategy to quantify oxidative states in humans in order to determine which biological marker could best match a subject’s profile will be discussed.

  17. Advancing dynamic and thermodynamic modelling of magma oceans

    Science.gov (United States)

    Bower, Dan; Wolf, Aaron; Sanan, Patrick; Tackley, Paul

    2017-04-01

    The techniques for modelling low melt-fraction dynamics in planetary interiors are well-established by supplementing the Stokes equations with Darcy's Law. But modelling high-melt fraction phenomena, relevant to the earliest phase of magma ocean cooling, necessitates parameterisations to capture the dynamics of turbulent flow that are otherwise unresolvable in numerical models. Furthermore, it requires knowledge about the material properties of both solid and melt mantle phases, the latter of which are poorly described by typical equations of state. To address these challenges, we present (1) a new interior evolution model that, in a single formulation, captures both solid and melt dynamics and hence charts the complete cooling trajectory of a planetary mantle, and (2) a physical and intuitive extension of a "Hard Sphere" liquid equation of state (EOS) to describe silicate melt properties for the pressure-temperature (P-T) range of Earth's mantle. Together, these two advancements provide a comprehensive and versatile modelling framework for probing the far-reaching consequences of magma ocean cooling and crystallisation for Earth and other rocky planets. The interior evolution model accounts for heat transfer by conduction, convection, latent heat, and gravitational separation. It uses the finite volume method to ensure energy conservation at each time-step and accesses advanced time integration algorithms by interfacing with PETSc. This ensures it accurately and efficiently computes the dynamics throughout the magma ocean, including within the ultra-thin thermal boundary layers (modelling capabilities. The thermodynamics of mantle melting are represented using a pseudo-one-component model, which retains the simplicity of a standard one-component model while introducing a finite temperature interval for melting (important for multi-component systems). Our new high P-T liquid EOS accurately captures the energetics and physical properties of the partially molten

  18. Adakitic magmas: modern analogues of Archaean granitoids

    Science.gov (United States)

    Martin, Hervé

    1999-03-01

    Both geochemical and experimental petrological research indicate that Archaean continental crust was generated by partial melting of an Archaean tholeiite transformed into a garnet-bearing amphibolite or eclogite. The geodynamic context of tholeiite melting is the subject of controversy. It is assumed to be either (1) subduction (melting of a hot subducting slab), or (2) hot spot (melting of underplated basalts). These hypotheses are considered in the light of modern adakite genesis. Adakites are intermediate to felsic volcanic rocks, andesitic to rhyolitic in composition (basaltic members are lacking). They have trondhjemitic affinities (high-Na 2O contents and K 2O/Na 2O˜0.5) and their Mg no. (0.5), Ni (20-40 ppm) and Cr (30-50 ppm) contents are higher than in typical calc-alkaline magmas. Sr contents are high (>300 ppm, until 2000 ppm) and REE show strongly fractionated patterns with very low heavy REE (HREE) contents (Yb≤1.8 ppm, Y≤18 ppm). Consequently, high Sr/Y and La/Yb ratios are typical and discriminating features of adakitic magmas, indicative of melting of a mafic source where garnet and/or hornblende are residual phases. Adakitic magmas are only found in subduction zone environments, exclusively where the subduction and/or the subducted slab are young (subducted and where the adakitic character of the lavas correlates well with the young age of the subducting oceanic lithosphere. In typical subduction zones, the subducted lithosphere is older than 20 Ma, it is cool and the geothermal gradient along the Benioff plane is low such that the oceanic crust dehydrates before it reaches the solidus temperature of hydrated tholeiite. Consequently, the basaltic slab cannot melt. The released large ion lithophile element (LILE)-rich fluids rise up into the mantle wedge, inducing both its metasomatism and partial melting. Afterwards, the residue is made up of olivine+clinopyroxene+orthopyroxene, such that the partial melts are HREE-rich (low La/Yb and Sr

  19. Oxidation states of Fe in LaNi1-xFexO3

    International Nuclear Information System (INIS)

    Goeta, A.E.; Falcon, H.; Carbonio, R.

    1994-01-01

    The distribution of oxidation states in perovskites of the type LaA 1-x B x O 3 (A and B transition metal ions) can be ''tailored'' by x variation. In particular, in LaNiO 3 it has been shown that Fe substitution for Ni foces some Ni 3+ into Ni 2+ , while some Fe 3+ changes into the unusual Fe 4+ state. In addition, the existence of mixed oxidation states of Fe and/or Ni in LaNi 1-x Fe x O 3 has been related to its catalytic activity in hydrogen peroxide decomposition. The Fe 4+ population, obtained using Moessbauer spectroscopy, was found to be constant for all the analyzed annealing temperatures for x = 0.25 concentration, where the isomer shift difference for both states is the highest and the catalytic activity is maximum. (orig.)

  20. Facile solid-state synthesis of oxidation-resistant metal nanoparticles at ambient conditions

    Science.gov (United States)

    Lee, Kyu Hyung; Jung, Hyuk Joon; Lee, Ju Hee; Kim, Kyungtae; Lee, Byeongno; Nam, Dohyun; Kim, Chung Man; Jung, Myung-Hwa; Hur, Nam Hwi

    2018-05-01

    A simple and scalable method for the synthesis of metal nanoparticles in the solid-state was developed, which can produce nanoparticles in the absence of solvents. Nanoparticles of coinage metals were synthesized by grinding solid hydrazine and the metal precursors in their acetates and oxides at 25 °C. The silver and gold acetates converted completely within 6 min into Ag and Au nanoparticles, respectively, while complete conversion of the copper acetate to the Cu sub-micrometer particles took about 2 h. Metal oxide precursors were also converted into metal nanoparticles by grinding alone. The resulting particles exhibit distinctive crystalline lattice fringes, indicating the formation of highly crystalline phases. The Cu sub-micrometer particles are better resistant to oxidation and exhibit higher conductivity compared to conventional Cu nanoparticles. This solid-state method was also applied for the synthesis of platinum group metals and intermetallic Cu3Au, which can be further extended to synthesize other metal nanoparticles.

  1. Temporal Evolution of Volcanic and Plutonic Magmas Related to Porphyry Copper Ores Based on Zircon Geochemistry

    Science.gov (United States)

    Dilles, J. H.; Lee, R. G.; Wooden, J. L.; Koleszar, A. M.

    2015-12-01

    Porphyry Cu (Mo-Au) and epithermal Au-Ag ores are globally associated with shallow hydrous, strongly oxidized, and sulfur-rich arc intrusions. In many localities, long-lived magmatism includes evolution from early andesitic volcanic (v) and plutonic (p) rocks to later dacitic or rhyolitic compositions dominated by plutons. We compare zircon compositions from three igneous suites with different time spans: Yerington, USA (1 m.y., p>v), El Salvador, Chile (4 m.y., p>v), and Yanacocha, Peru (6 m.y., v>p). At Yerington granite dikes and ores formed in one event, at ES in 2 to 3 events spanning 3 m.y., and at Yanacocha in 6 events spanning 5 m.y. At both ES and Yanacocha, high-Al amphiboles likely crystallized at high temperature in the mid-crust and attest to deep magmas that periodically recharged the shallow chambers. At Yanacocha, these amphiboles contain anhydrite inclusions that require magmas were sulfur-rich and strongly oxidized (~NNO+2). The Ti-in-zircon geothermometer provides estimates of 920º to 620º C for zircon crystallization, and records both core to rim cooling and locally high temperature rim overgrowths. Ore-related silicic porphyries yield near-solidus crystallization temperatures of 750-650°C consistent with low zircon saturation temperatures. The latter zircons have large positive Ce/Ce* and small negative Eu/Eu*≥0.4 anomalies attesting to strongly oxidized conditions (Ballard et al., 2001), which we propose result from crystallization and SO2 loss to the magmatic-hydrothermal ore fluid (Dilles et al., 2015). The Hf, REE, Y, U, and Th contents of zircons are diverse in the magma suites, and Th/U vs Yb/Gd plots suggest a dominant role of crystal fractionation with lesser roles for both crustal contamination and mixing with high temperature deep-sourced mafic magma. Ce/Sm vs Yb/Gd plots suggest that magma REE contents at contamination are most evident in pre-ore magmas, whereas ore-forming intrusions at low temperatures are dominated by crystal

  2. How different oxidation states of crystalline myoglobin are influenced by X-rays.

    Science.gov (United States)

    Hersleth, Hans-Petter; Andersson, K Kristoffer

    2011-06-01

    X-ray induced radiation damage of protein crystals is well known to occur even at cryogenic temperatures. Redox active sites like metal sites seem especially vulnerable for these radiation-induced reductions. It is essential to know correctly the oxidation state of metal sites in protein crystal structures to be able to interpret the structure-function relation. Through previous structural studies, we have tried to characterise and understand the reactions between myoglobin and peroxides. These reaction intermediates are relevant because myoglobin is proposed to take part as scavenger of reactive oxygen species during oxidative stress, and because these intermediates are similar among the haem peroxidases and oxygenases. We have in our previous studies shown that these different myoglobin states are influenced by the X-rays used. In this study, we have in detail investigated the impact that X-rays have on these different oxidation states of myoglobin. An underlying goal has been to find a way to be able to determine mostly unreduced states. We have by using single-crystal light absorption spectroscopy found that the different oxidation states of myoglobin are to a different extent influenced by the X-rays (e.g. ferric Fe(III) myoglobin is faster reduced than ferryl Fe(IV)═O myoglobin). We observe that the higher oxidation states are not reduced to normal ferrous Fe(II) or ferric Fe(III) states, but end up in some intermediate and possibly artificial states. For ferric myoglobin, it seems that annealing of the radiation-induced/reduced state can reversibly more or less give the starting point (ferric myoglobin). Both scavengers and different dose-rates might influence to which extent the different states are affected by the X-rays. Our study shows that it is essential to do a time/dose monitoring of the influence X-rays have on each specific redox-state with spectroscopic techniques like single-crystal light absorption spectroscopy. This will determine to which

  3. Templated electrodeposition of Ag7NO11 nanowires with very high oxidation states of silver

    NARCIS (Netherlands)

    Rodijk, E.J.B.; Maijenburg, A.W.; Maas, M.G.; Blank, David H.A.; ten Elshof, Johan E.

    2011-01-01

    The templated electrodeposition of 200 nm diameter nanowires of the argentic oxynitrate Ag(Ag3O4)2NO3 phase is reported. Their high surface-to-volume ratio and the high average oxidation state of Ag make these wires promising candidates for nanoscale redox processes in which both a high volumetric

  4. Investigation of the oxidation states of Pu isotopes in a hydrochloric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Lee, M.H. [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, P. O. Box 105, Yuseong, Daejeon 305-353 (Korea, Republic of)], E-mail: mhlee@kaeri.re.kr; Kim, J.Y.; Kim, W.H.; Jung, E.C.; Jee, K.Y. [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, P. O. Box 105, Yuseong, Daejeon 305-353 (Korea, Republic of)

    2008-12-15

    The characteristics of the oxidation states of Pu in a hydrochloric acid solution were investigated and the results were applied to a separating of Pu isotopes from IAEA reference soils. The oxidation states of Pu(III) and Pu(IV) were prepared by adding hydroxylamine hydrochloride and sodium nitrite to a Pu stock solution, respectively. Also, the oxidation state of Pu(VI) was adjusted with concentrated HNO{sub 3} and HClO{sub 4}. The stability of the various oxidation states of plutonium in a HCl solution with elapsed time after preparation were found to be in the following order: Pu(III){approx}Pu(VI)>Pu(IV)>Pu(V). The chemical recoveries of Pu(IV) in a 9 M HCl solution with an anion exchange resin were similar to those of Pu(VI). This method for the determination of Pu isotopes with an anion exchange resin in a 9 M HCl medium was applied to IAEA reference soils where the activity concentrations of {sup 239,240}Pu and {sup 238}Pu in IAEA-375 and IAEA-326 were consistent with the reference values reported by the IAEA.

  5. Teaching the Properties of Chromium's Oxidation States with a Case Study Method

    Science.gov (United States)

    Ozdilek, Zehra

    2015-01-01

    The purpose of this study was to investigate how a mixed-method case study affects pre-service science teachers' awareness of hexavalent chromium pollution and content knowledge about the properties of chromium's different oxidation states. The study was conducted in Turkey with 55 sophomores during the fall semester of 2013-2014. The students…

  6. The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

    KAUST Repository

    LaGrow, Alec P.; Knudsen, Kristian; AlYami, Noktan; Anjum, Dalaver H.; Bakr, Osman

    2015-01-01

    of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape

  7. Regulation of Ca2+ release from mitochondria by the oxidation-reduction state of pyridine nucleotides

    Science.gov (United States)

    Lehninger, Albert L.; Vercesi, Anibal; Bababunmi, Enitan A.

    1978-01-01

    Mitochondria from normal rat liver and heart, and also Ehrlich tumor cells, respiring on succinate as energy source in the presence of rotenone (to prevent net electron flow to oxygen from the endogenous pyridine nucleotides), rapidly take up Ca2+ and retain it so long as the pyridine nucleotides are kept in the reduced state. When acetoacetate is added to bring the pyridine nucleotides into a more oxidized state, Ca2+ is released to the medium. A subsequent addition of a reductant of the pyridine nucleotides such as β-hydroxybutyrate, glutamate, or isocitrate causes reuptake of the released Ca2+. Successive cycles of Ca2+ release and uptake can be induced by shifting the redox state of the pyridine nucleotides to more oxidized and more reduced states, respectively. Similar observations were made when succinate oxidation was replaced as energy source by ascorbate oxidation or by the hydrolysis of ATP. These and other observations form the basis of a hypothesis for feedback regulation of Ca2+-dependent substrate- or energy-mobilizing enzymatic reactions by the uptake or release of mitochondrial Ca2+, mediated by the cytosolic phosphate potential and the ATP-dependent reduction of mitochondrial pyridine nucleotides by reversal of electron transport. Images PMID:25436

  8. Measurements of the oxidation state and concentration of plutonium in interstitial waters of the Irish Sea

    International Nuclear Information System (INIS)

    Nelson, D.M.; Lovett, M.B.

    1980-01-01

    The question of plutonium movement in interstitial waters resulting from diffusion along concentration gradients or from advective flow is addressed. The results of measurements of both the concentration and the oxidation state of plutonium in interstitial water collected from sediments near the Windscale discharge, in the solid phases of these sediments and in seawater and suspended solids collected at the coring locations are discussed

  9. Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

    Science.gov (United States)

    Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

    2015-11-05

    Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major

  10. Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

    International Nuclear Information System (INIS)

    Reed, Donald Timothy; Borkowski, Marian; Lucchini, Jean-Francois; Ams, David; Richmann, M.K.; Khaing, H.; Swanson, J.S.

    2010-01-01

    The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.

  11. The influence of magma viscosity on convection within a magma chamber

    Science.gov (United States)

    Schubert, M.; Driesner, T.; Ulmer, P.

    2012-12-01

    Magmatic-hydrothermal ore deposits are the most important sources of metals like Cu, Mo, W and Sn and a major resource for Au. It is well accepted that they are formed by the release of magmatic fluids from a batholith-sized magma body. Traditionally, it has been assumed that crystallization-induced volatile saturation (called "second boiling") is the main mechanism for fluid release, typically operating over thousands to tens of thousands of years (Candela, 1991). From an analysis of alteration halo geometries caused by magmatic fluids, Cathles and Shannon (2007) suggested much shorter timescales in the order of hundreds of years. Such rapid release of fluids cannot be explained by second boiling as the rate of solidification scales with the slow conduction of heat away from the system. However, rapid fluid release is possible if convection is assumed within the magma chamber. The magma would degas in the upper part of the magma chamber and volatile poor magma would sink down again. Such, the rates of degassing can be much higher than due to cooling only. We developed a convection model using Navier-Stokes equations provided by the computational fluid dynamics platform OpenFOAM that gives the possibility to use externally derived meshes with complex (natural) geometries. We implemented a temperature, pressure, composition and crystal fraction dependent viscosity (Ardia et al., 2008; Giordano et al., 2008; Moore et al., 1998) and a temperature, pressure, composition dependent density (Lange1994). We found that the new viscosity and density models strongly affect convection within the magma chamber. The dependence of viscosity on crystal fraction has a particularly strong effect as the steep viscosity increase at the critical crystal fraction leads to steep decrease of convection velocity. As the magma chamber is cooling from outside to inside a purely conductive layer is developing along the edges of the magma chamber. Convection continues in the inner part of the

  12. Cost-benefit analyses for the development of magma power

    International Nuclear Information System (INIS)

    Haraden, John

    1992-01-01

    Magma power is the potential generation of electricity from shallow magma bodies in the crust of the Earth. Considerable uncertainty still surrounds the development of magma power, but most of that uncertainty may be eliminated by drilling the first deep magma well. The uncertainty presents no serious impediments to the private drilling of the well. For reasons unrelated to the uncertainty, there may be no private drilling and there may be justification for public drilling. In this paper, we present cost-benefit analyses for private and public drilling of the well. Both analyses indicate there is incentive for drilling. (Author)

  13. Origin of deep subgap states in amorphous indium gallium zinc oxide: Chemically disordered coordination of oxygen

    International Nuclear Information System (INIS)

    Sallis, S.; Williams, D. S.; Butler, K. T.; Walsh, A.; Quackenbush, N. F.; Junda, M.; Podraza, N. J.; Fischer, D. A.; Woicik, J. C.; White, B. E.; Piper, L. F. J.

    2014-01-01

    The origin of the deep subgap states in amorphous indium gallium zinc oxide (a-IGZO), whether intrinsic to the amorphous structure or not, has serious implications for the development of p-type transparent amorphous oxide semiconductors. We report that the deep subgap feature in a-IGZO originates from local variations in the oxygen coordination and not from oxygen vacancies. This is shown by the positive correlation between oxygen composition and subgap intensity as observed with X-ray photoelectron spectroscopy. We also demonstrate that the subgap feature is not intrinsic to the amorphous phase because the deep subgap feature can be removed by low-temperature annealing in a reducing environment. Atomistic calculations of a-IGZO reveal that the subgap state originates from certain oxygen environments associated with the disorder. Specifically, the subgap states originate from oxygen environments with a lower coordination number and/or a larger metal-oxygen separation.

  14. Origin of deep subgap states in amorphous indium gallium zinc oxide: Chemically disordered coordination of oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Sallis, S.; Williams, D. S. [Materials Science and Engineering, Binghamton University, Binghamton, New York 13902 (United States); Butler, K. T.; Walsh, A. [Center for Sustainable Technologies and Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom); Quackenbush, N. F. [Department of Physics, Applied Physics, and Astronomy, Binghamton University, Binghamton, New York 13902 (United States); Junda, M.; Podraza, N. J. [Department of Physics and Astronomy, University of Toledo, Toledo, Ohio 43606 (United States); Fischer, D. A.; Woicik, J. C. [Materials Science and Engineering Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); White, B. E.; Piper, L. F. J., E-mail: lpiper@binghamton.edu [Department of Physics, Applied Physics, and Astronomy, Binghamton University, Binghamton, New York 13902 (United States); Materials Science and Engineering, Binghamton University, Binghamton, New York 13902 (United States)

    2014-06-09

    The origin of the deep subgap states in amorphous indium gallium zinc oxide (a-IGZO), whether intrinsic to the amorphous structure or not, has serious implications for the development of p-type transparent amorphous oxide semiconductors. We report that the deep subgap feature in a-IGZO originates from local variations in the oxygen coordination and not from oxygen vacancies. This is shown by the positive correlation between oxygen composition and subgap intensity as observed with X-ray photoelectron spectroscopy. We also demonstrate that the subgap feature is not intrinsic to the amorphous phase because the deep subgap feature can be removed by low-temperature annealing in a reducing environment. Atomistic calculations of a-IGZO reveal that the subgap state originates from certain oxygen environments associated with the disorder. Specifically, the subgap states originate from oxygen environments with a lower coordination number and/or a larger metal-oxygen separation.

  15. Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Wenchuan [Univ. of California, Berkeley, CA (United States)

    1994-11-01

    X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S2 state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S2 state with the g~4 electron paramagnetic resonance (EPR) signal (S2-g4 state) was compared with that in the S2 state with multiline signal (S2-MLS state) and the S1 state. The S2-g4 state has a higher XAS inflection point energy than that of the S1 state, indicating the oxidation of Mn in the advance from the S1 to the S2-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S2-g4 state is different from that in the S2-MLS or the S1 state. In the S2-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 Å and 2.85 Å. Very little distance disorder exists in the second shell of the S1 or S2-MLS states. The third shell of the S2-g4 state at about 3.3 Å also contains increased heterogeneity relative to that of the S2-MLS or the S1 state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct "pure" S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S1 → S2 transition.

  16. Outgassing From Open And Closed Magma Foams

    Science.gov (United States)

    von Aulock, Felix W.; Kennedy, Ben M.; Maksimenko, Anton; Wadsworth, Fabian B.; Lavallée, Yan

    2017-06-01

    During magma ascent, bubbles nucleate, grow, coalesce, and form a variably permeable porous network. The volcanic system opens and closes as bubble walls reorganize, seal or fail. In this contribution we cause obsidian to nucleate and grow bubbles to high gas volume fraction at atmospheric pressure by heating samples to 950 ºC for different times and we image the growth through a furnace. Following the experiment, we imaged the internal pore structure of selected samples in 3D and then dissected for analysis of textures and dissolved water content remnant in the glass. We demonstrate that in these high viscosity systems, during foaming and subsequent foam-maturation, bubbles near a free surface resorb via diffusion to produce an impermeable skin of melt around a foam. The skin thickens nonlinearly through time. The water concentrations at the outer and inner skin margins reflect the solubility of water in the melt at the partial pressure of water in atmospheric and water-rich bubble conditions, respectively. In this regime, mass transfer of water out of the system is diffusion limited and the sample shrinks slowly. In a second set of experiments in which we polished off the skin of the foamed samples and placed them back in the furnace, we observe rapid sample contraction and collapse of the connected pore network under surface tension as the system efficiently outgasses. In this regime, mass transfer of water is permeability limited. The mechanisms described here are relevant to the evolution of pore network heterogeneity in permeable magmas. We conclude that diffusion-driven skin formation can efficiently seal connectivity in foams. When rupture of melt film around gas bubbles (i.e. skin removal) occurs, then rapid outgassing and consequent foam collapse modulate gas pressurisation in the vesiculated magma.

  17. Experimental Constraints on a Vesta Magma Ocean

    Science.gov (United States)

    Hoff, C.; Jones, J. H.; Le, L.

    2014-01-01

    A magma ocean model was devised to relate eucrites (basalts) and diogenites (orthopyroxenites), which are found mixed together as clasts in a suite of polymict breccias known as howardites. The intimate association of eucritic and diogenitic clasts in howardites argues strongly that these three classes of achondritic meteorites all originated from the same planetoid. Reflectance spectral evidence (including that from the DAWN mission) has long suggested that Vesta is indeed the Eucrite Parent Body. Specifically, the magma ocean model was generated as follows: (i) the bulk Vesta composition was taken to be 0.3 CV chondrite + 0.7 L chondrite but using only 10% of the Na2O from this mixture; (ii) this composition is allowed to crystallize at 500 bar until approx. 80% of the system is solid olivine + low-Ca pyroxene; (iii) the remaining 20% liquid crystallizes at one bar from 1250C to 1110C, a temperature slightly above the eucrite solidus. All crystallization calculations were performed using MELTS. In this model, diogenites are produced by cocrystallization of olivine and pyroxene in the >1250C temperature regime, with Main Group eucrite liquids being generated in the 1300-1250C temperature interval. Low-Ca pyroxene reappears at 1210C in the one-bar calculations and fractionates the residual liquid to produce evolved eucrite compositions (Stannern Trend). We have attempted to experimentally reproduce the magma ocean. In the MELTS calculation, the change from 500 bar to one bar results in a shift of the olivine:low-Ca pyroxene boundary so that the 1250C liquid is now in the olivine field and, consequently, olivine should be the first-crystallizing phase, followed by low-Ca pyroxene at 1210C, and plagioclase at 1170C. Because at one bar the olivine:low-Ca pyroxene boundary is a peritectic, fractional crystallization of the 1210C liquid proceeds with only pyroxene crystallization until plagioclase appears. Thus, the predictions of the MELTS calculation are clear and

  18. Outgassing from Open and Closed Magma Foams

    Directory of Open Access Journals (Sweden)

    Felix W. von Aulock

    2017-06-01

    Full Text Available During magma ascent, bubbles nucleate, grow, coalesce, and form a variably permeable porous network. The reorganization, failing and sealing of bubble walls may contribute to the opening and closing of the volcanic system. In this contribution we cause obsidian to nucleate and grow bubbles to high gas volume fraction at atmospheric pressure by heating samples to 950°C for different times and we image the growth through a furnace. Following the experiment, we imaged the internal pore structure of selected samples in 3D and then dissected for analysis of textures and dissolved water content remnant in the glass. We demonstrate that in these high viscosity systems, during foaming and subsequent foam-maturation, bubbles near a free surface resorb via diffusion to produce an impermeable skin of melt around a foam. The skin thickens non-linearly through time. The water concentrations at the outer and inner skin margins reflect the solubility of water in the melt at the partial pressure of water in atmospheric and water-rich bubble conditions, respectively. In this regime, mass transfer of water out of the system is diffusion limited and the sample shrinks slowly. In a second set of experiments in which we polished off the skin of the foamed samples and placed them back in the furnace to allow open system outgassing, we observe rapid sample contraction and collapse of the connected pore network under surface tension as the system efficiently outgasses. In this regime, mass transfer of water is permeability limited. We conclude that diffusion-driven skin formation can efficiently seal connectivity in foams. When rupture of melt film around gas bubbles (i.e., skin removal occurs, then rapid outgassing and consequent foam collapse modulate gas pressurization in the vesiculated magma. The mechanisms described here are relevant to the evolution of pore network heterogeneity in permeable magmas.

  19. Method of isolation of traces of americium by using the +6 oxidation state properties

    International Nuclear Information System (INIS)

    Kwinta, Jean; Michel, Jean-Jacques

    1969-05-01

    The authors present a method to separate traces of americium from a solution containing fission products and actinides. This method comprises the following steps: firstly, the oxidation of americium at the +6 state by ammonium persulfate and carrying over of actinides and III and IV lanthanides by lanthanum fluoride; secondly, the reduction by hydrazine of the oxidized americium and carrying over of the reduced americium by lutetium fluoride; and thirdly, the americium-lutetium separation by selective extractions either with di 2 ethyl hexyl phosphoric acid, or by fractionated elution on an anionic resin column by a mixture of nitric acid and methanol [fr

  20. Special relativity derived from spacetime magma.

    Science.gov (United States)

    Greensite, Fred

    2014-01-01

    We present a derivation of relativistic spacetime largely untethered from specific physical considerations, in constrast to the many physically-based derivations that have appeared in the last few decades. The argument proceeds from the inherent magma (groupoid) existing on the union of spacetime frame components [Formula: see text] and Euclidean [Formula: see text] which is consistent with an "inversion symmetry" constraint from which the Minkowski norm results. In this context, the latter is also characterized as one member of a class of "inverse norms" which play major roles with respect to various unital [Formula: see text]-algebras more generally.

  1. Special relativity derived from spacetime magma.

    Directory of Open Access Journals (Sweden)

    Fred Greensite

    Full Text Available We present a derivation of relativistic spacetime largely untethered from specific physical considerations, in constrast to the many physically-based derivations that have appeared in the last few decades. The argument proceeds from the inherent magma (groupoid existing on the union of spacetime frame components [Formula: see text] and Euclidean [Formula: see text] which is consistent with an "inversion symmetry" constraint from which the Minkowski norm results. In this context, the latter is also characterized as one member of a class of "inverse norms" which play major roles with respect to various unital [Formula: see text]-algebras more generally.

  2. Dynamics of differentiation in magma reservoirs

    Science.gov (United States)

    Jaupart, Claude; Tait, Stephen

    1995-09-01

    In large magma chambers, gradients of temperature and composition develop due to cooling and to fractional crystallization. Unstable density differences lead to differential motions between melt and crystals, and a major goal is to explain how this might result in chemical differentiation of magma. Arriving at a full description of the physics of crystallizing magma chambers is a challenge because of the large number of processes potentially involved, the many coupled variables, and the different geometrical shapes. Furthermore, perturbations are caused by the reinjection of melt from a deep source, eruption to the Earth's surface, and the assimilation of country rock. Physical models of increasing complexity have been developed with emphasis on three fundamental approaches. One is, given that large gradients in temperature and composition may occur, to specify how to apply thermodynamic constraints so that coexisting liquid and solid compositions may be calculated. The second is to leave the differentiation trend as the solution to be found, i.e., to specify how cooling occurs and to predict the evolution of the composition of the residual liquid and of the solid forming. The third is to simplify the physics so that the effects of coupled heat and mass transfer may be studied with a reduced set of variables. The complex shapes of magma chambers imply that boundary layers develop with density gradients at various angles to gravity, leading to various convective flows and profiles qf liquid stratification. Early studies were mainly concerned with describing fluid flow in the liquid interior of large reservoirs, due to gradients developed at the margins. More recent work has focused on the internal structure and flow field of boundary layers and in particular on the gradients of solid fraction and interstitial melt composition which develop within them. Crystal settling may occur in a surprisingly diverse range of regimes and may lead to intermittent deposition

  3. Extracellular redox state: refining the definition of oxidative stress in aging.

    Science.gov (United States)

    Jones, Dean P

    2006-01-01

    Oxidative stress in aging can result from an imbalance of prooxidants and antioxidants with excessive, destructive free radical chemistry. Thiol systems are important in the control of these processes, both by protecting against damage and serving in redox signaling mechanisms to sense danger and repair the damage. Studies by a number of research groups in collaboration with the Emory Clinical Biomarkers Laboratory show that the redox state of the central tissue antioxidant, glutathione (GSH), can be measured in human plasma and provides a quantitative systemic indicator of oxidative stress. Plasma GSH/GSSG redox in humans becomes oxidized with age, in response to chemotherapy, as a consequence of cigarette smoking, and in association with common age-related diseases (e.g., type 2 diabetes, cardiovascular disease). However, the GSH/GSSG redox is not equilibrated with the larger plasma cysteine/cystine (Cys/CySS) pool, and the Cys/CySS redox varies with age in a pattern that is distinct from that of GSH/GSSG redox. Furthermore, in vitro studies show that variation in Cys/CySS redox over the range found in vivo affects signaling pathways, which control cell proliferation and oxidant-induced apoptosis. The results point to the conclusion that free radical scavenging antioxidants are of increased importance when thiol/disulfide redox states are oxidized. Because thiol/disulfide redox states, per se, function in redox signaling and control as well as antioxidant protection, GSH/GSSG and Cys/CySS redox states may provide central parameters to link environmental influences and progression of changes associated with aging.

  4. The Oxidation State of Fe in MORB Glasses and the Oxygen Fugacity of the Upper Mantle

    Energy Technology Data Exchange (ETDEWEB)

    E Cottrell; K Kelley

    2011-12-31

    Micro-analytical determination of Fe{sup 3+}/{Sigma}Fe ratios in mid-ocean ridge basalt (MORB) glasses using micro X-ray absorption near edge structure ({mu}-XANES) spectroscopy reveals a substantially more oxidized upper mantle than determined by previous studies. Here, we show that global MORBs yield average Fe{sup 3+}/{Sigma}Fe ratios of 0.16 {+-} 0.01 (n = 103), which trace back to primary MORB melts equilibrated at the conditions of the quartz-fayalite-magnetite (QFM) buffer. Our results necessitate an upward revision of the Fe{sup 3+}/{Sigma}Fe ratios of MORBs, mantle oxygen fugacity, and the ferric iron content of the mantle relative to previous wet chemical determinations. We show that only 0.01 (absolute, or < 10%) of the difference between Fe{sup 3+}/{Sigma}Fe ratios determined by micro-colorimety and XANES can be attributed to the Moessbauer-based XANES calibration. The difference must instead derive from a bias between micro-colorimetry performed on experimental vs. natural basalts. Co-variations of Fe{sup 3+}/{Sigma}Fe ratios in global MORB with indices of low-pressure fractional crystallization are consistent with Fe{sup 3+} behaving incompatibly in shallow MORB magma chambers. MORB Fe{sup 3+}/{Sigma}Fe ratios do not, however, vary with indices of the extent of mantle melting (e.g., Na{sub 2}O(8)) or water concentration. We offer two hypotheses to explain these observations: The bulk partition coefficient of Fe{sup 3+} may be higher during peridotite melting than previously thought, and may vary with temperature, or redox exchange between sulfide and sulfate species could buffer mantle melting at {approx} QFM. Both explanations, in combination with the measured MORB Fe{sup 3+}/{Sigma}Fe ratios, point to a fertile MORB source with greater than 0.3 wt.% Fe{sub 2}O{sub 3}.

  5. Magma evolution inside the 1631 Vesuvius magma chamber and eruption triggering

    Science.gov (United States)

    Stoppa, Francesco; Principe, Claudia; Schiazza, Mariangela; Liu, Yu; Giosa, Paola; Crocetti, Sergio

    2017-03-01

    Vesuvius is a high-risk volcano and the 1631 Plinian eruption is a reference event for the next episode of explosive unrest. A complete stratigraphic and petrographic description of 1631 pyroclastics is given in this study. During the 1631 eruption a phonolite was firstly erupted followed by a tephritic phonolite and finally a phonolitic tephrite, indicating a layered magma chamber. We suggest that phonolitic basanite is a good candidate to be the primitive parental-melt of the 1631 eruption. Composition of apatite from the 1631 pyroclastics is different from those of CO2-rich melts indicating negligible CO2 content during magma evolution. Cross checking calculations, using PETROGRAPH and PELE software, accounts for multistage evolution up to phonolite starting from a phonolitic basanite melt similar to the Vesuvius medieval lavas. The model implies crystal settling of clinopyroxene and olivine at 6 kbar and 1220°C, clinopyroxene plus leucite at a pressure ranging from 2.5 to 0.5 kbar and temperature ranging from 1140 to 940°C. Inside the phonolitic magma chamber K-feldspar and leucite would coexist at a temperature ranging from from 940 to 840°C and at a pressure ranging from 2.5 to0.5 kbar. Thus crystal fractionation is certainly a necessary and probably a sufficient condition to evolve the melt from phono tephritic to phonolitic in the 1631 magma chamber. We speculate that phonolitic tephrite magma refilling from deeper levels destabilised the chamber and triggered the eruption, as testified by the seismic precursor phenomena before 1631 unrest.

  6. Magma evolution inside the 1631 Vesuvius magma chamber and eruption triggering

    Directory of Open Access Journals (Sweden)

    Stoppa Francesco

    2017-03-01

    Full Text Available Vesuvius is a high-risk volcano and the 1631 Plinian eruption is a reference event for the next episode of explosive unrest. A complete stratigraphic and petrographic description of 1631 pyroclastics is given in this study. During the 1631 eruption a phonolite was firstly erupted followed by a tephritic phonolite and finally a phonolitic tephrite, indicating a layered magma chamber. We suggest that phonolitic basanite is a good candidate to be the primitive parental-melt of the 1631 eruption. Composition of apatite from the 1631 pyroclastics is different from those of CO2-rich melts indicating negligible CO2 content during magma evolution. Cross checking calculations, using PETROGRAPH and PELE software, accounts for multistage evolution up to phonolite starting from a phonolitic basanite melt similar to the Vesuvius medieval lavas. The model implies crystal settling of clinopyroxene and olivine at 6 kbar and 1220°C, clinopyroxene plus leucite at a pressure ranging from 2.5 to 0.5 kbar and temperature ranging from 1140 to 940°C. Inside the phonolitic magma chamber K-feldspar and leucite would coexist at a temperature ranging from from 940 to 840°C and at a pressure ranging from 2.5 to0.5 kbar. Thus crystal fractionation is certainly a necessary and probably a sufficient condition to evolve the melt from phono tephritic to phonolitic in the 1631 magma chamber. We speculate that phonolitic tephrite magma refilling from deeper levels destabilised the chamber and triggered the eruption, as testified by the seismic precursor phenomena before 1631 unrest.

  7. Mantle to surface degassing of alkalic magmas at Erebus volcano, Antarctica

    Science.gov (United States)

    Oppenheimer, C.; Moretti, R.; Kyle, P.R.; Eschenbacher, A.; Lowenstern, J. B.; Hervig, R.L.; Dunbar, N.W.

    2011-01-01

    Continental intraplate volcanoes, such as Erebus volcano, Antarctica, are associated with extensional tectonics, mantle upwelling and high heat flow. Typically, erupted magmas are alkaline and rich in volatiles (especially CO2), inherited from low degrees of partial melting of mantle sources. We examine the degassing of the magmatic system at Erebus volcano using melt inclusion data and high temporal resolution open-path Fourier transform infrared (FTIR) spectroscopic measurements of gas emissions from the active lava lake. Remarkably different gas signatures are associated with passive and explosive gas emissions, representative of volatile contents and redox conditions that reveal contrasting shallow and deep degassing sources. We show that this unexpected degassing signature provides a unique probe for magma differentiation and transfer of CO2-rich oxidised fluids from the mantle to the surface, and evaluate how these processes operate in time and space. Extensive crystallisation driven by CO2 fluxing is responsible for isobaric fractionation of parental basanite magmas close to their source depth. Magma deeper than 4kbar equilibrates under vapour-buffered conditions. At shallower depths, CO2-rich fluids accumulate and are then released either via convection-driven, open-system gas loss or as closed-system slugs that ascend and result in Strombolian eruptions in the lava lake. The open-system gases have a reduced state (below the QFM buffer) whereas the closed-system gases preserve their deep oxidised signatures (close to the NNO buffer). ?? 2011 Elsevier B.V.

  8. General regularity of the oxidation potential variations and high oxidation states in the second half of the actinide series

    International Nuclear Information System (INIS)

    Spitsyn, V.I.; Vokhmin, V.G.; Ionova, G.V.; Pershina, V.G.

    1984-01-01

    Oxidation potentials (OP) PHI(4/3), PHI(5/3), PHI(6/3), PHI(5/4) and PHI(6/5) are calculated for the members of the actinide series. A semiemperic relation combining OP with explicit terms for ground level energies of actinide ions in Russell-Saunders approximation as well as known values of formal OP relative to the normal hydrogen electrode potential are used as an extrapolation function. It is shown that an increase of PHI(4/3) OP which occurs after Bsub(k) explains a low stability of the oxidation state 4 in solutions for actinides of the second half of the series. PHI(5/3) and PHI(5/4) OP in the section starting with Cm have the minimum at Cf. PHI(6/3) OP for Cm, Bk, Cf and Es are practically the same but for Cm, Bk and Es they are smaller than PHI(5/3) OP. A principle possibility of Bk(6), Cf(6) and Es(6) preparation is shown

  9. In situ oxidation state profiling of nickel hexacyanoferrate derivatized electrodes using line-imaging Raman spectroscopy and multivariate calibration

    International Nuclear Information System (INIS)

    Haight, S.M.; Schwartz, D.T.

    1999-01-01

    Metal hexacyanoferrate compounds show promise as electrochemically switchable ion exchange materials for use in the cleanup of radioactive wastes such as those found in storage basins and underground tanks at the Department of Energy's Hanford Nuclear Reservation. Reported is the use of line-imaging Raman spectroscopy for the in situ determination of oxidation state profiles in nickel hexacyanoferrate derivatized electrodes under potential control in an electrochemical cell. Line-imaging Raman spectroscopy is used to collect 256 contiguous Raman spectra every ∼5 microm from thin films (ca. 80 nm) formed by electrochemical derivatization of nickel electrodes. The cyanide stretching region of the Raman spectrum of the film is shown to be sensitive to iron oxidation state and is modeled by both univariate and multivariate correlations. Although both correlations fit the calibration set well, the multivariate (principle component regression or PCR) model's predictions of oxidation state are less sensitive to noise in the spectrum, yielding a much smoother oxidation state profile than the univariate model. Oxidation state profiles with spatial resolution of approximately 5 microm are shown for a nickel hexacyanoferrate derivatized electrode in reduced, intermediate, and oxidized states. In situ oxidation state profiles indicate that the 647.1 nm laser illumination photo-oxidizes the derivatized electrodes. This observation is confirmed using photoelectrochemical methods

  10. Storage conditions of the mafic and silicic magmas at Cotopaxi, Ecuador

    Science.gov (United States)

    Martel, Caroline; Andújar, Joan; Mothes, Patricia; Scaillet, Bruno; Pichavant, Michel; Molina, Indira

    2018-04-01

    The 2015 reactivation of the Cotopaxi volcano urges us to understand the complex eruptive dynamics of Cotopaxi for better management of a potential major crisis in the near future. Cotopaxi has commonly transitioned from andesitic eruptions of strombolian style (lava flows and scoria ballistics) or nuées ardentes (pyroclastic flows and ash falls) to highly explosive rhyolitic ignimbrites (pumiceous pyroclastic flows), which entail drastically different risks. To better interpret geophysical and geochemical signals, Cotopaxi magma storage conditions were determined via existing phase-equilibrium experiments that used starting materials chemically close to the Cotopaxi andesites and rhyolites. The results suggest that Cotopaxi's most mafic andesites (last erupted products) can be stored over a large range of depth from 7 km to ≥16 km below the summit (pressure from 200 to ≥400 MPa), 1000 °C, NNO +2, and contain 4.5-6.0±0.7 wt% H2O dissolved in the melt in equilibrium with 30-40% phenocrysts of plagioclase, two pyroxenes, and Fe-Ti oxides. These mafic andesites sometimes evolve towards more silicic andesites by cooling to 950 °C. Rhyolitic magmas are stored at 200-300 MPa (i.e. 7-11 km below the summit), 750 °C, NNO +2, and contain 6-8 wt% H2O dissolved in a nearly aphyric melt (<5% phenocrysts of plagioclase, biotite, and Fe-Ti oxides). Although the andesites produce the rhyolitic magmas by fractional crystallization, the Cotopaxi eruptive history suggests reactivation of either reservoirs at distinct times, likely reflecting flux or time fluctuations during deep magma recharge.

  11. Radiation oxidation of polypropylene: A solid-state 13C NMR study using selective isotopic labeling

    International Nuclear Information System (INIS)

    Mowery, Daniel M.; Assink, Roger A.; Derzon, Dora K.; Klamo, Sara B.; Bernstein, Robert; Clough, Roger L.

    2007-01-01

    Polypropylene samples, in which the three different carbon atoms along the chain were selectively labeled with carbon-13, were subjected to radiation under inert and air atmospheres, and to post-irradiation exposure in air at various temperatures. By using solid-state 13 C NMR measurements at room temperature, we have been able to identify and quantify the oxidation products. The isotopic labeling provides insight into chemical reaction mechanisms, since oxidation products can be traced back to their positions of origin on the macromolecule. The major products include peroxides and alcohols, both formed at tertiary carbon sites along the chain. Other products include methyl ketones, acids, esters, peresters, and hemiketals formed from reaction at the tertiary carbon, together with in-chain ketones and esters from reaction at the secondary chain carbon. No evidence is found of products arising from reactions at the methyl side chain. Significant temperature-dependent differences are apparent; for example much higher yields of chain-end methyl ketones, which are the indicator product of chain scission, are generated for both elevated temperature irradiation and for post-irradiation treatment at elevated temperatures. Time-dependent plots of yields of the various oxidation products have been obtained under a wide range of conditions, including the post-irradiation oxidation of a sample at room temperature in air that has been monitored for 2 years. Radiation-oxidation products of polypropylene are contrasted to products measured for 13 C-labeled polyethylene in an earlier investigation: the peroxides formed in irradiated polypropylene are remarkably longer lived, the non-peroxidic products are significantly different, and the overall ratios of oxidation products in polypropylene change relatively little as a function of the extent of oxidation

  12. Microbial utilization of low molecular weight organic substrates in soil depends on their carbon oxidation state

    Science.gov (United States)

    Gunina, Anna; Smith, Andrew; Jones, Davey; Kuzyakov, Yakov

    2017-04-01

    Removal of low molecular weight organic substances (LMWOS), originating from plants and microorganisms, from soil solution is regulated by microbial uptake. In addition to the concentration of LMWOS in soil solution, the chemical properties of each substance (e.g. C oxidation state, number of C atoms, number of -COOH groups) can affect their uptake and subsequent partitioning of C within the soil microbial community. The aim of this study was to trace the initial fate of three dominant classes of LMWOS in soil (sugars, carboxylic and amino acids), including their removal from solution and utilization by microorganisms, and to reveal the effect of substance chemical properties on these processes. Soil solution, spiked at natural abundance levels with 14C-labelled glucose, fructose, malate, succinate, formate, alanine or glycine, was added to the soil and 14C was traced in the dissolved organic carbon (DOC), CO2, cytosol and soil organic carbon (SOC) over 24 hours. The half-life time of all LMWOS in the DOC (T1 /2-solution) varied between 0.6-5.0 min showing extremely fast initial uptake of LMWOS. The T1 /2-solution of substances was dependent on C oxidation state, indicating that less oxidized organic substances (with C oxidation state "0") were retained longer in soil solution than oxidized substances. The LMWOS-C T1 /2-fast, characterizing the half-life time of 14C in the fast mineralization pool, ranged between 30 and 80 min, with the T1 /2-fast of carboxylic acids (malic acid) being the fastest and the T1 /2-fast of amino acids (glycine) being the slowest. An absence of correlation between T1 /2-fast and either C oxidation state, number of C atoms, or number of -COOH groups suggests that intercellular metabolic pathways are more important for LMWOS transformation in soil than their basic chemical properties. The CO2 release during LMWOS mineralization accounted for 20-90% of 14C applied. Mineralization of LMWOS was the least for sugars and the greatest for

  13. Influence of steam generator surface state on corrosion and oxide formation

    International Nuclear Information System (INIS)

    Mazenc, Arnaud; Leclercq, Stephanie; Seyeux, Antoine; Galtayries, Anouk; Marcus, Philippe

    2012-09-01

    The corrosion and release of nickel-based alloy Steam Generator tubes are partly due to their surface state. Among the most important parameters influencing the corrosion, the effect of grain size and the effect of grain crystallographic orientation have been chosen to be studied. The aim of this study is to determine how these parameters have an impact on the corrosion of Steam Generator tubes. Thermal treatments (700 deg. C and 1050 deg. C) have been performed on several samples in Alloy 690 to obtain homogeneous grain sizes, varying from 25 μm to 110 μm. Two samples have been oxidised for four days in a recirculating autoclave, reproducing primary conditions. The changes of oxide composition and thickness were examined by ToF-SIMS on samples exposed to primary water conditions. The intensity profiles versus thicknesses of characteristic oxide anions, such as CrO - , NiO - or FeO - enable us to evaluate the effect of grain size and crystallographic orientation on the formation of an enriched inner chromium layer. As regards to the grain size, there was no effect on the growth, but smaller grains led to a chromium-rich oxide layer. The effect of crystallographic orientation was observed on the oxidation kinetics and the composition of oxide scales. (authors)

  14. Characterization of Interface State in Silicon Carbide Metal Oxide Semiconductor Capacitors

    Science.gov (United States)

    Kao, Wei-Chieh

    Silicon carbide (SiC) has always been considered as an excellent material for high temperature and high power devices. Since SiC is the only compound semiconductor whose native oxide is silicon dioxide (SiO2), it puts SiC in a unique position. Although SiC metal oxide semiconductor (MOS) technology has made significant progress in recent years, there are still a number of issues to be overcome before more commercial SiC devices can enter the market. The prevailing issues surrounding SiC MOSFET devices are the low channel mobility, the low quality of the oxide layer and the high interface state density at the SiC/SiO2 interface. Consequently, there is a need for research to be performed in order to have a better understanding of the factors causing the poor SiC/SiO2 interface properties. In this work, we investigated the generation lifetime in SiC materials by using the pulsed metal oxide semiconductor (MOS) capacitor method and measured the interface state density distribution at the SiC/SiO2 interface by using the conductance measurement and the high-low frequency capacitance technique. These measurement techniques have been performed on n-type and p-type SiC MOS capacitors. In the course of our investigation, we observed fast interface states at semiconductor-dielectric interfaces in SiC MOS capacitors that underwent three different interface passivation processes, such states were detected in the nitrided samples but not observed in PSG-passivated samples. This result indicate that the lack of fast states at PSG-passivated interface is one of the main reasons for higher channel mobility in PSG MOSFETs. In addition, the effect of mobile ions in the oxide on the response time of interface states has been investigated. In the last chapter we propose additional methods of investigation that can help elucidate the origin of the particular interface states, enabling a more complete understanding of the SiC/SiO2 material system.

  15. A magnetic route to measure the average oxidation state of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS).

    Science.gov (United States)

    Shen, Xiong-Fei; Ding, Yun-Shuang; Liu, Jia; Han, Zhao-Hui; Budnick, Joseph I; Hines, William A; Suib, Steven L

    2005-05-04

    A magnetic route has been applied for measurement of the average oxidation state (AOS) of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS). The method gives AOS measurement results in good agreement with titration methods. A maximum analysis deviation error of +/-7% is obtained from 10 sample measurements. The magnetic method is able to (1) confirm the presence of mixed-valent manganese and (2) evaluate AOS and the spin states of d electrons of both single oxidation state and mixed-valent state Mn in manganese oxides. In addition, the magnetic method may be extended to (1) determine AOS of Mn in manganese oxide OMS with dopant "diamagnetic" ions, such as reducible V5+ (3d0) ions, which is inappropriate for the titration method due to interference of redox reactions between these dopant ions and titration reagents, such as KMnO4, (2) evaluate the dopant "paramagnetic" ions that are present as clusters or in the OMS framework, and (3) determine AOS of other mixed-valent/single oxidation state ion systems, such as Mo3+(3d3)-Mo4+(3d2) systems and Fe3+ in FeCl3.

  16. Intrusion of basaltic magma into a crystallizing granitic magma chamber: The Cordillera del Paine pluton in southern Chile

    Science.gov (United States)

    Michael, Peter J.

    1991-10-01

    The Cordillera del Paine pluton in the southernmost Andes of Chile represents a deeply dissected magma chamber where mafic magma intruded into crystallizing granitic magma. Throughout much of the 10x15 km pluton, there is a sharp and continuous boundary at a remarkably constant elevation of 1,100 m that separates granitic rocks (Cordillera del Paine or CP granite: 69 77% SiO2) which make up the upper levels of the pluton from mafic and comingled rocks (Paine Mafic Complex or PMC: 45 60% SiO2) which dominate the lower exposures of the pluton. Chilled, crenulate, disrupted contacts of mafic rock against granite demonstrate that partly crystallized granite was intruded by mafic magma which solidified prior to complete crystallization of the granitic magma. The boundary at 1,100 m was a large and stable density contrast between the denser, hotter mafic magma and cooler granitic magma. The granitic magma was more solidified near the margins of the chamber when mafic intrusion occurred, and the PMC is less disrupted by granites there. Near the pluton margins, the PMC grades upward irregularly from cumulate gabbros to monzodiorites. Mafic magma differentiated largely by fractional crystallization as indicated by the presence of cumulate rocks and by the low levels of compatible elements in most PMC rocks. The compositional gap between the PMC and CP granite indicates that mixing (blending) of granitic magma into the mafic magma was less important, although it is apparent from mineral assemblages in mafic rocks. Granitic magma may have incorporated small amounts of mafic liquid that had evolved to >60% SiO2 by crystallization. Mixing was inhibited by the extent of crystallization of the granite, and by the thermal contrast and the stable density contrast between the magmas. PMC gabbros display disequilibrium mineral assemblages including early formed zoned olivine (with orthopyroxene coronas), clinopyroxene, calcic plagioclase and paragasite and later-formed amphibole

  17. Solid state chemistry of rare earth oxides. Final report, September 1, 1950--July 31, 1977

    International Nuclear Information System (INIS)

    Eyring, L.

    1977-07-01

    Work under Contract E(11-1)-1109 and its antecedents has been primarily for the purpose of obtaining detailed thermodynamic, kinetic and structural information on the complex rare earth oxides of praseodymium and terbium. These systems exhibit homologous series of ordered phases, order-disorder transformations, wide-range nonstoichiometric phases, chemical hysteresis in two-phase regions and many other solid state reaction phenomena. Fluorite-related materials of importance to ERDA occur as nuclear fuels, radiation power sources, insulators and solid electrolytes. The rare earth oxides serve directly as model systems for such similar materials and, in a more general sense, they serve as models of solids in general since they exhibit nearly the full range of solid state properties

  18. Geophysical Evidence for the Locations, Shapes and Sizes, and Internal Structures of Magma Chambers beneath Regions of Quaternary Volcanism

    Science.gov (United States)

    Iyer, H. M.

    1984-04-01

    at the onset of melting of rocks and to delineate in three dimensions the shape of the partly melted zone. Similarly, decreases in density and electrical resistivity in rocks during melting, can be detected. Seismic refraction and reflection are not yet used extensively in magma chamber studies. In a study, in the Yellowstone region, seismic delays occurring in a fan-shooting configuration and time-term modelling show the presence of an intense molten zone in the upper crust. Deep seismic sounding (a combination of seismic refraction and reflection) and modelling amplitude and velocity changes of diffracted seismic waves from explosions and earthquakes, have enabled mapping of small and large magma chambers beneath many volcanoes in Kamchatka, U.S.S.R. Teleseismic P-wave residuals have been used to model low-velocity bodies, interpreted as magma chambers, in several Quaternary volcanic centres in the U.S.A. The results show that magma chambers with volumes of a few hundred to a few thousand cubic kilometres volume seem to be confined to regions of silicic volcanism. Many of the magma bodies seem to have upper-mantle roots implying that they are not isolated pockets of partial melt, but may be deriving their magma supplies from deeper parental sources. Medium or large crustal magma chambers are absent in the andesitic volcanoes of western United States and the basaltic Kilauea volcano, Hawaii. However, regional velocity models of the Oregon Cascades and Hawaii show evidence for the presence of magma reservoirs in the upper mantle. The transport of magma to the upper crust in these regions probably occurs rapidly through narrow conduits, with transient storage occurring in small chambers of a few cubic kilometres volume. Very little use has been made of the gravity and magnetic maps to model magma chambers. The number of available case histories, though few, indicate that these data can be very useful to give constraints on the density and temperature in magma chambers

  19. Discovering Mathematics with Magma Reducing the Abstract to the Concrete

    CERN Document Server

    Bosma, Wieb

    2006-01-01

    With a design based on the ontology and semantics of algebra, Magma enables users to rapidly formulate and perform calculations in the more abstract parts of mathematics. This book introduces the role Magma plays in advanced mathematical research through 14 case studies which, in most cases, describe computations underpinning theoretical results.

  20. Zircons reveal magma fluxes in the Earth's crust.

    Science.gov (United States)

    Caricchi, Luca; Simpson, Guy; Schaltegger, Urs

    2014-07-24

    Magma fluxes regulate the planetary thermal budget, the growth of continents and the frequency and magnitude of volcanic eruptions, and play a part in the genesis and size of magmatic ore deposits. However, because a large fraction of the magma produced on the Earth does not erupt at the surface, determinations of magma fluxes are rare and this compromises our ability to establish a link between global heat transfer and large-scale geological processes. Here we show that age distributions of zircons, a mineral often present in crustal magmatic rocks, in combination with thermal modelling, provide an accurate means of retrieving magma fluxes. The characteristics of zircon age populations vary significantly and systematically as a function of the flux and total volume of magma accumulated in the Earth's crust. Our approach produces results that are consistent with independent determinations of magma fluxes and volumes of magmatic systems. Analysis of existing age population data sets using our method suggests that porphyry-type deposits, plutons and large eruptions each require magma input over different timescales at different characteristic average fluxes. We anticipate that more extensive and complete magma flux data sets will serve to clarify the control that the global heat flux exerts on the frequency of geological events such as volcanic eruptions, and to determine the main factors controlling the distribution of resources on our planet.

  1. Solid State Electrochemical Sensors for Nitrogen Oxide (NOx) Detection in Lean Exhaust Gases

    OpenAIRE

    Rheaume, Jonathan Michael

    2010-01-01

    Solid state electrochemical sensors that measure nitrogen oxides (NOx) in lean exhaust have been investigated in order to help meet future on-board diagnostic (OBD) regulations for diesel vehicles. This impedancemetric detection technology consists of a planar, single cell sensor design with various sensing electrode materials and yttria-stabilized zirconia (YSZ) as the electrolyte. No reference to ambient air is required. An impedance analysis method yields a signal that is proportional to t...

  2. Arsenic (+3 oxidation state) methyltransferase and the inorganic arsenic methylation phenotype

    International Nuclear Information System (INIS)

    Li Jiaxin; Waters, Stephen B.; Drobna, Zuzana; Devesa, Vicenta; Styblo, Miroslav; Thomas, David J.

    2005-01-01

    Inorganic arsenic is enzymatically methylated; hence, its ingestion results in exposure to the parent compound and various methylated arsenicals. Both experimental and epidemiological evidences suggest that some of the adverse health effects associated with chronic exposure to inorganic arsenic may be mediated by these methylated metabolites. If i As methylation is an activation process, then the phenotype for inorganic arsenic methylation may determine risk associated with exposure to this metalloid. We examined inorganic arsenic methylation phenotypes and arsenic (+3 oxidation state) methyltransferase genotypes in four species: three that methylate inorganic arsenic (human (Homo sapiens), rat (Rattus norwegicus), and mouse (Mus musculus)) and one that does not methylate inorganic arsenic (chimpanzee, Pan troglodytes). The predicted protein products from arsenic (+3 oxidation state) methyltransferase are similar in size for rat (369 amino acid residues), mouse (376 residues), and human (375 residues). By comparison, a 275-nucleotide deletion beginning at nucleotide 612 in the chimpanzee gene sequence causes a frameshift that leads to a nonsense mutation for a premature stop codon after amino acid 205. The null phenotype for inorganic arsenic methylation in the chimpanzee is likely due to the deletion in the gene for arsenic (+3 oxidation state) methyltransferase that yields an inactive truncated protein. This lineage-specific loss of function caused by the deletion event must have occurred in the Pan lineage after Homo-Pan divergence about 5 million years ago

  3. Oxidized Nitrogen Balance over 15 Months at Rural and Urban New York State Locations

    Science.gov (United States)

    Schwab, J. J.; Ninneman, M.; Marto, J.; Edgerton, E. S.; Blanchard, C. L.; Shaw, S. L.

    2017-12-01

    Continuous measurements of oxidized nitrogen species (NO, NO2, and HNO3), families of species (NOy, alkyl nitrates [or ANs], and peroxyacetyl nitrates [or PANs]), and particle nitrate (pNO3) were carried out for a fifteen-month period from August 2016 through October 2017 at two locations in New York State. The two sites were a rural research station at Pinnacle State Park in Addison, NY and an urban research station at Queens College in New York City. Four different chemiluminescence analyzers with various converters and denuders were employed to make these measurements. Instrumentation used for the study will be described, as well as some of the challenges created by combining data from these independent analyzers to address the oxidized nitrogen budget at the two sites. The Pinnacle State Park site often experiences quite clean air with low ppb levels of total NOy and a greater fraction of oxidized nitrogen products (NOz species). This contrasts with the urban Queens College location, which experiences stronger NOx sources. Seasonal differences in the NOx/NOy and NOz/NOy ratios, and the makeup of the NOz species, are also significant and will be explored in the presentation.

  4. Temperature evolution during magma ascent in basaltic effusive eruptions: A numerical application to Stromboli volcano

    Science.gov (United States)

    La Spina, G.; Burton, M.; de'Michieli Vitturi, M.

    2015-09-01

    The dynamics of magma ascent are controlled by the complex, interdependent processes of crystallisation, rheological evolution, gas exsolution, outgassing, non-ideal gas expansion and temperature evolution. Temperature changes within the conduit, in particular, play a key role on ascent dynamics, since temperature strongly controls the crystallisation process, which in turn has an impact on viscosity and thus on magma ascent rate. The cooling produced by gas expansion is opposed by the heat produced by crystallisation, and therefore the temperature profile within the conduit is quite complex. This complexity means that unravelling the dynamics controlling magma ascent requires a numerical model. Unfortunately, comprehensive, integrated models with full thermodynamic treatment of multiple phases and rheological evolution are challenging to produce, due to the numerical challenges involved. Until now, models have tended to focus on aspects of the problem, without a holistic approach in which petrological, thermodynamic, rheological and degassing processes, and their interactions, were all explicitly addressed and quantified. Here, we present a new, multiphase steady-state model for magma ascent in which the main physical and chemical processes, such as crystallisation, degassing, outgassing, rheological evolution and temperature variations, are quantitatively calculated. Basaltic magma's crystallisation and flow are sensitive to initial temperature and volatile content, and therefore we investigate temperature variations during magma ascent in a basaltic system with a range of volatile contents. As a test case, we use one of the most well-studied recent basaltic effusive eruptions: the 2007 eruption of Stromboli, Italy. Assuming equilibrium crystallisation and exsolution, we compare the solutions obtained both with and without an isothermal constraint, finding that temperature variations within the conduit have a significant influence on the ascent dynamics and

  5. Single Crystal Growth of Pure Co3+ Oxidation State Material LaSrCoO4

    Directory of Open Access Journals (Sweden)

    Hanjie Guo

    2016-08-01

    Full Text Available We report on the single crystal growth of the single-layer perovskite cobaltate LaSrCoO4 that was grown by the optical floating zone method using high oxygen pressures. Phase purity and single crystallinity were confirmed by X-ray diffraction techniques. The pure Co3+ oxidation state was confirmed by X-ray absorbtion spectroscopy measurements. A transition to a spin glass state is observed at ∼7 K in magnetic susceptibility and specific heat measurements.

  6. Magma fluxes and recurreance rate of eruptions at Nevado de Toluca volcano (Mexico)

    Science.gov (United States)

    Weber, Gregor; Probst, Line; Arce, José L.; Caricchi, Luca

    2017-04-01

    Forecasting the frequency and size of volcanic eruptions is a long-term goal for hazard mitigation. The frequency at which a given crustal magmatic system is driven towards a critical state and the magnitude of the resulting volcanic events are linked to the supply rate of fresh magma, crustal properties, and tectonic setting. Our ability to forecast the recurrence rate of eruptions is hampered by the lack of data on key variables such as the average magma flux locally and globally. The aim of this project is to identify the average magma supply rate and injection frequency for eruptions of different magnitude and eruptive style. We centred our study at Nevado de Toluca in Mexico, a subduction-related volcano with an eruptive history spanning about 1.5 million years of comparatively well documented effusive and explosive eruptions dominantly of dacitic composition. We carry out in-situ high precision zircon geochronology for a sequence of eruptions of different magnitude to obtain a distribution of crystal ages from which average crustal magma fluxes can be calculated. Eruptive fluxes will be constrained by extracting lava flow volumes from a digital elevation model. A combination of whole rock and mineral chemistry will provide quantitative insights on petrogenetic processes and on the frequency at which intensive parameters changed within the magma reservoir before the eruptions. Our results will be integrated in a global database including other volcanic systems and literature data to attempt to identify similarities and differences between magmatic reservoirs feeding volcanic eruptions of different magnitude. The final target of this project is to identify the physical factors controlling the recurrence rate of volcanic eruptions at regional and global scale.

  7. Raman spectroscopic study of the oxidation state of Eu in molten LiCl-KCl

    Energy Technology Data Exchange (ETDEWEB)

    Park, Seung; Yun, Jong-Il [KAIST, Daejeon(Korea, Republic of)

    2016-10-15

    Spectroscopy can provide high reliability for the quantitative analysis of such system. The molar absorptivity of Eu(II) at 325 nm is reported as about 1645 M{sup -1}cm{sup -1}, which is too high to apply to higher concentration. A high-temperature Raman spectroscopy has been set and employed for analyzing the molecular structure and coordination complex and investigating the oxidation state of europium in molten LiCl-KCl. Europium can be present in divalent state while many other lanthanides exist in trivalent state. The thermodynamic properties of europium ions have been studied using electrochemical methods, spectroscopic methods, and EPR technique. Although there has been discrepancy of the reduced amount of europium in previous works, the majority of Eu(III) is thought to be reduced to Eu(II) in molten LiCl-KCl spontaneously at relatively low concentration (< 7.5 × 10{sup -4} M). Raman spectroscopy was employed to investigate the oxidation state of EuClx in LiCl-KCl at 500 .deg. C. The Raman scattering results suggest the majority of trivalent europium is reduced to divalent state with the composition change by vaporization. The Raman bands show highly asymmetric structure, quite different from regular octahedral structure.

  8. Stability of oxidized iron species and the redox budget of slab-derived fluids

    Science.gov (United States)

    Sanchez-Valle, C.; Hin, R.; Testemale, D.; Borca, C.; Grolimund, D.

    2017-12-01

    The high oxidation state of subduction zone magmas compared to magmas from other locations might result from the influx of oxidized fluid from the subducted oceanic plate into the mantle wedge. However, the nature of the chemical agent(s) and the mechanism responsible for the transfer of the oxidized signature from the slab to the mantle wedge remains poorly understood. In this contribution, we will discuss the oxidizing capacity of slab-derived fluids in the light of experimental results of the solubility and speciation of iron in high-pressure fluids that mimic the slab flux. Iron-bearing mineral assemblages were equilibrated with chlorinated aqueous fluids and hydrous granitic melts at different oxygen fugacities relevant for the present day crust/mantle. The concentration of iron and the distribution of stability of oxidized iron species were monitored up to 2.5 GPa and 800 °C using a combination of diamond trap experiments and XANES measurements in diamond anvil cells. The results illustrate the role of coordination chemistry involving halogen and polymerized species in the stability of oxidized iron in the fluids. The concentration of Fe3+ in the fluids progressively decreases as temperature increases, regardless of fluid composition and pressure. This implies that the fluid capacity to transport Fe3+ at high temperature may be limited, even at the redox conditions relevant for the present day crust and mantle. With the new experimental results, we place constrains on the oxidizing capacity of Fe-bearing metasomatic fluids and discuss the transfer of the oxidizing signature and the conditions for the genesis of oxidized arc magmas.

  9. Magma heating by decompression-driven crystallization beneath andesite volcanoes.

    Science.gov (United States)

    Blundy, Jon; Cashman, Kathy; Humphreys, Madeleine

    2006-09-07

    Explosive volcanic eruptions are driven by exsolution of H2O-rich vapour from silicic magma. Eruption dynamics involve a complex interplay between nucleation and growth of vapour bubbles and crystallization, generating highly nonlinear variation in the physical properties of magma as it ascends beneath a volcano. This makes explosive volcanism difficult to model and, ultimately, to predict. A key unknown is the temperature variation in magma rising through the sub-volcanic system, as it loses gas and crystallizes en route. Thermodynamic modelling of magma that degasses, but does not crystallize, indicates that both cooling and heating are possible. Hitherto it has not been possible to evaluate such alternatives because of the difficulty of tracking temperature variations in moving magma several kilometres below the surface. Here we extend recent work on glassy melt inclusions trapped in plagioclase crystals to develop a method for tracking pressure-temperature-crystallinity paths in magma beneath two active andesite volcanoes. We use dissolved H2O in melt inclusions to constrain the pressure of H2O at the time an inclusion became sealed, incompatible trace element concentrations to calculate the corresponding magma crystallinity and plagioclase-melt geothermometry to determine the temperature. These data are allied to ilmenite-magnetite geothermometry to show that the temperature of ascending magma increases by up to 100 degrees C, owing to the release of latent heat of crystallization. This heating can account for several common textural features of andesitic magmas, which might otherwise be erroneously attributed to pre-eruptive magma mixing.

  10. Molecular water oxidation mechanisms followed by transition metals: state of the art.

    Science.gov (United States)

    Sala, Xavier; Maji, Somnath; Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Llobet, Antoni

    2014-02-18

    One clean alternative to fossil fuels would be to split water using sunlight. However, to achieve this goal, researchers still need to fully understand and control several key chemical reactions. One of them is the catalytic oxidation of water to molecular oxygen, which also occurs at the oxygen evolving center of photosystem II in green plants and algae. Despite its importance for biology and renewable energy, the mechanism of this reaction is not fully understood. Transition metal water oxidation catalysts in homogeneous media offer a superb platform for researchers to investigate and extract the crucial information to describe the different steps involved in this complex reaction accurately. The mechanistic information extracted at a molecular level allows researchers to understand both the factors that govern this reaction and the ones that derail the system to cause decomposition. As a result, rugged and efficient water oxidation catalysts with potential technological applications can be developed. In this Account, we discuss the current mechanistic understanding of the water oxidation reaction catalyzed by transition metals in the homogeneous phase, based on work developed in our laboratories and complemented by research from other groups. Rather than reviewing all of the catalysts described to date, we focus systematically on the several key elements and their rationale from molecules studied in homogeneous media. We organize these catalysts based on how the crucial oxygen-oxygen bond step takes place, whether via a water nucleophilic attack or via the interaction of two M-O units, rather than based on the nuclearity of the water oxidation catalysts. Furthermore we have used DFT methodology to characterize key intermediates and transition states. The combination of both theory and experiments has allowed us to get a complete view of the water oxidation cycle for the different catalysts studied. Finally, we also describe the various deactivation pathways for

  11. Application of powerful oxidizers in the synthesis of new high-oxidation state actinide and related species

    International Nuclear Information System (INIS)

    Yeh, S.M.

    1984-11-01

    The fluorinating and oxide scavenging ability of XeF 6 have been studied by bringing XeF 6 into interaction with oxide-fluoride compounds of the third-transition-series elements (W, Re and Os) and uranium, in their highest oxidation states. A + MOF 5 - and A + M 2 O 2 F 9 - (A = K or Cs, M = W or U) were converted to A + MF 7 - by XeF 6 , but the rhenium and osmium compounds, K + ReO 2 F 4 - and XeF 5 + OsO 3 F 3 - , resisted interaction with XeF 6 . Strong interactions between XeF 2 or KrF 2 and the solvent have been observed for their solutions in anhydrous HF. Both XeF 2 and KrF 2 are seen to be effective in breaking up the polymeric (HF)/sub n/ chains. Only weak interactions occur between cations and anions of KrF + AuF 6 - and Kr 2 F 3 + AuF 6 - in HF. The AuF 6 - anions are slightly distorted from O/sub h/ symmetry. Kr 2 F 3 + cations in HF have the same dissymmetric V-shape which occurs in crystalline salts. A low-temperature orthorhombic form, β-ReF 6 + SbF 6 - , a high-temperature rhombohedral form, α-ReF 6 + SbF 6 - , and a ReF 6 + AuF 6 - have been prepared. These compounds possess only kinetic stability at ambient temperature and at approx. 20 0 C are best represented as ReF 6 + ReF 7 MF 6 - MF 5 . Thermochemical energy evaluations indicate that the ionization potential of ReF 6 is 261 kcal mole -1 and that the fluoride-ion affinity of ReF 6 + is -214 kcal mole -1 . This is more exothermal than the corresponding process for IF 6 + (-208 kcal mole -1 ). In contrast, ReOF 5 is shown to be a better fluoro-base than IOF 5 and also is a better base than ReF 7 . ReOF 4 + MF 6 - (M = Sb, Au and As) salts are of higher thermal stability than their ReF 6 + MF 6 - analogues

  12. Synchrotron Micro-XANES Measurements of Vanadium Oxidation State in Glasses as a Function of Oxygen Fugacity: Experimental Calibration of Data Relevant to Partition Coefficient Determination

    Science.gov (United States)

    Delaney, J. S.; Sutton, S. R.; Newville, M.; Jones, J. H.; Hanson, B.; Dyar, M. D.; Schreiber, H.

    2000-01-01

    Oxidation state microanalyses for V in glass have been made by calibrating XANES spectral features with optical spectroscopic measurements. The oxidation state change with fugacity of O2 will strongly influence partitioning results.

  13. Longevity of magma in the near subsurface

    International Nuclear Information System (INIS)

    Marsh, B.D.; Resmini, R.G.

    1992-01-01

    Small, sporadic occurrences of basaltic volcanism are particularly difficult to evaluate in terms of long term threat to mankind because of their short overall eruptive history. Insight into future eruptive vigor and possible subsurface magma storage may be furnished by studying the ages of crystals in the eruptive products themselves. In this paper, the authors do this by applying the method of crystal size distribution theory (CSD) to a stack of basaltic lavas within the Nevada test site; namely the Dome Mtn. lavas. Preliminary results suggest a pre-eruptive residence time of 10 - 20 years, decreasing with decreasing age of lava within the sequence. These times are similar to those found by M.T. Mangan for the 1959 Kilauea (Hawaii) eruptions, and may suggest a relatively vigorous magmatic system at this time some 8 m.y. ago. Work is progressing on a greatly expanded CSD analysis of the Dome Mtn. lavas

  14. Chemical state analysis of oxidation products on steel surface by conversion electron Moessbauer spectrometry

    International Nuclear Information System (INIS)

    Ujihira, Yusuke; Nomura, Kiyoshi

    1978-01-01

    The polished NT-70H steel (Fe: 95.97%, C: 0.56%, diameter: 5 cm, thickness: 0.5 cm) was immersed in deionized water or in solutions containing (0.25 -- 0.5) M of chloride, sulfate and nitrate ions. The chemical states of oxidation products of iron on the surface were identified through the analysis of conversion electron Moessbauer spectra (CEMS). CEMS of the steel surface, which had been dipped in deionized water, revealed that γ-FeOOH was formed on the surface. The thickness of γ-FeOOH layer increased with the increase of the duration of dipping. Dissolved oxygen in the solution played an essential role in the oxidation of iron to γ-FeOOH. Oxidation product of iron dipped in the 0.5 M sodium chloride solution was identified as γ-FeOOH. Amorphous paramagnetic iron (III) compound tended to form in the presence of hydrogen peroxide or ammonium ions in the solutions. The increase of alkalinity of the solution up to pH 12 suppressed the oxidation rate and assisted the formation of green rust, which was confirmed by the appearance of the quadrupole splitting peaks of the green rust. In the 0.25 M sodium sulfate solution, oxidation of the steel surface proceeded slowly and the quadrupole splitting peaks of Fe(OH) 2 were seen in the CEMS. The peak intensity of Fe(OH) 2 gradually decreased and that of γ-FeOOH increased by the extension of immersion of steel in the solution. Magnetite (Fe 3 O 4 ) layer was developed beneath the γ-FeOOH layer, when steel was dipped in 0.5 M sodium nitrate solution. However, the peaks of Fe 3 O 4 were not seen on CEMS of steel surface immersed in 0.5 M ammonium nitrate solution. Thus, applying the feasibility of CEMS for the characterization of oxidated compounds of iron on the steel surface formed by the immersion in solutions, the oxidation mechanism of the steel surface was discussed based upon the results of chemical state analyses. (author)

  15. Permeability During Magma Expansion and Compaction

    Science.gov (United States)

    Gonnermann, Helge. M.; Giachetti, Thomas; Fliedner, Céline; Nguyen, Chinh T.; Houghton, Bruce F.; Crozier, Joshua A.; Carey, Rebecca J.

    2017-12-01

    Plinian lapilli from the 1060 Common Era Glass Mountain rhyolitic eruption of Medicine Lake Volcano, California, were collected and analyzed for vesicularity and permeability. A subset of the samples were deformed at a temperature of 975°, under shear and normal stress, and postdeformation porosities and permeabilities were measured. Almost all undeformed samples fall within a narrow range of vesicularity (0.7-0.9), encompassing permeabilities between approximately 10-15 m2 and 10-10 m2. A percolation threshold of approximately 0.7 is required to fit the data by a power law, whereas a percolation threshold of approximately 0.5 is estimated by fitting connected and total vesicularity using percolation modeling. The Glass Mountain samples completely overlap with a range of explosively erupted silicic samples, and it remains unclear whether the erupting magmas became permeable at porosities of approximately 0.7 or at lower values. Sample deformation resulted in compaction and vesicle connectivity either increased or decreased. At small strains permeability of some samples increased, but at higher strains permeability decreased. Samples remain permeable down to vesicularities of less than 0.2, consistent with a potential hysteresis in permeability-porosity between expansion (vesiculation) and compaction (outgassing). We attribute this to retention of vesicle interconnectivity, albeit at reduced vesicle size, as well as bubble coalescence during shear deformation. We provide an equation that approximates the change in permeability during compaction. Based on a comparison with data from effusively erupted silicic samples, we propose that this equation can be used to model the change in permeability during compaction of effusively erupting magmas.

  16. Variations in magma supply rate at Kilauea Volcano, Hawaii

    Science.gov (United States)

    Dvorak, John J.; Dzurisin, Daniel

    1993-01-01

    When an eruption of Kilauea lasts more than 4 months, so that a well-defined conduit has time to develop, magma moves freely through the volcano from a deep source to the eruptive site at a constant rate of 0.09 km3/yr. At other times, the magma supply rate to Kilauea, estimated from geodetic measurements of surface displacements, may be different. For example, after a large withdrawal of magma from the summit reservoir, such as during a rift zone eruption, the magma supply rate is high initially but then lessens and exponentially decays as the reservoir refills. Different episodes of refilling may have different average rates of magma supply. During four year-long episodes in the 1960s, the annual rate of refilling varied from 0.02 to 0.18 km3/yr, bracketing the sustained eruptive rate of 0.09 km3/yr. For decade-long or longer periods, our estimate of magma supply rate is based on long-term changes in eruptive rate. We use eruptive rate because after a few dozen eruptions the volume of magma that passes through the summit reservoir is much larger than the net change of volume of magma stored within Kilauea. The low eruptive rate of 0.009 km3/yr between 1840 and 1950, compared to an average eruptive rate of 0.05 km3/yr since 1950, suggests that the magma supply rate was lower between 1840 and 1950 than it has been since 1950. An obvious difference in activity before and since 1950 was the frequency of rift zone eruptions: eight rift zone eruptions occurred between 1840 and 1950, but more than 20 rift zone eruptions have occurred since 1950. The frequency of rift zone eruptions influences magma supply rate by suddenly lowering pressure of the summit magma reservoir, which feeds magma to rift zone eruptions. A temporary drop of reservoir pressure means a larger-than-normal pressure difference between the reservoir and a deeper source, so magma is forced to move upward into Kilauea at a faster rate.

  17. Drilling Magma for Science, Volcano Monitoring, and Energy

    Science.gov (United States)

    Eichelberger, J. C.; Lavallée, Y.; Blankenship, D.

    2017-12-01

    Magma chambers are central to understanding magma evolution, formation of continental crust, volcanism, and renewal of hydrothermal systems. Information from geology, petrology, laboratory experiments, and geophysical imagery has led to little consensus except a trend to see magma systems as being crystal-dominant (mush) rather than melt dominant. At high melt viscosities, crystal-liquid fractionation may be achieved by separation of melt from mush rather than crystals from liquid suspension. That the dominant volume has properties more akin to solid than liquid might explain the difficulty in detecting magma geophysically. Recently, geothermal drilling has intersected silicic magma at the following depths and SiO2 contents are: Puna, Hawaii, 2.5 km, 67 wt%; Menengai, Kenya 2.1 km, 67 wt%; Krafla, Iceland, 2.1 km, 75 wt%. Some similarities are: 1) Drillers encountered a "soft", sticky formation; 2) Cuttings or chips of clear quenched glass were recovered; 3) The source of the glass flowed up the well; 4) Transition from solid rock to recovering crystal-poor glass occurred in tens of meters, apparently without an intervening mush zone. Near-liquidus magma at the roof despite rapid heat loss there presents a paradox that may be explained by very recent intrusion of magma, rise of liquidus magma to the roof replacing partially crystallized magma, or extremely skewed representation of melt over mush in cuttings (Carrigan et al, this session). The latter is known to occur by filter pressing of ooze into lava lake coreholes (Helz, this session), but cannot be verified in actual magma without coring. Coring to reveal gradients in phase composition and proportions is required for testing any magma chamber model. Success in drilling into and controlling magma at all three locations, in coring lava lakes to over 1100 C, and in numerical modeling of coring at Krafla conditions (Su, this session) show this to be feasible. Other unprecedented experiments are using the known

  18. Room air versus carbon dioxide pneumoperitoneum: effects on oxidative state, apoptosis and histology of splanchnic organs.

    Science.gov (United States)

    Ypsilantis, Petros; Lambropoulou, Maria; Tentes, Ioannis; Chryssidou, Maria; Georgantas, Themistoklis; Simopoulos, Constantinos

    2016-04-01

    Although CO2 is the insufflation gas of choice in laparoscopic procedures, room air is usually used in natural orifice transluminal endoscopic surgery. The aim of the present study was to compare the safety of room air versus CO2 pneumoperitoneum in terms of their effect on the oxidative state, apoptosis and tissue injury of splanchnic organs. Eighteen Wistar rats were assigned to three groups (n = 6 per group) and were subjected to 8 mm Hg room air (group Pne-Air) or CO2 pneumoperitoneum (group Pne-CO2) or sham operation for 60 min. Forty-five minutes postdeflation, tissue samples were excised from the liver, stomach, ileum and kidneys for reduced glutathione-to-glutathione disulfide (GSH/GSSG) ratio, caspase-8 and caspase-3 and hypoxia-inducible factor-1α (HIF-1α) immunohistochemical assessment and histopathologic examination. GSH/GSSG ratio substantially declined in both pneumoperitoneum groups. No change was noted in HIF-1α expression. Mild upregulation of caspase-8 and caspase-3 was noted in both pneumoperitoneum groups being less pronounced in group Pne-Air. Histopathologic score was increased in all organs studied, but the stomach, in both pneumoperitoneum groups. Pneumoperitoneum established by either room air or CO2 induced substantial oxidative stress, mild apoptosis and mild tissue injury in splanchnic organs. While air pneumoperitoneum conferred a less pronounced apoptotic effect, the oxidative state and histopathologic profile of splanchnic organs did not differ between insufflation gases.

  19. The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

    Science.gov (United States)

    Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

    2017-10-01

    Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

  20. Short lived radionuclides in gases and magmas: contribution to the study of degassing and of the dynamics of magmatic reservoirs

    International Nuclear Information System (INIS)

    Gauthier, P.J.

    1998-01-01

    Crystallization and magma degassing at Stromboli (Italy) and Merapi (Indonesia) volcanoes are studied through 230 Th- 226 Ra- 210 Pb and 210 Pb- 210 Bi- 210 Po disequilibria in lavas and gases. An attempt to date crystallization by internal isochrones in ( 226 Ra)/Ba - ( 230 Th)/Ba and ( 210 Pb)/Pb - ( 226 Ra)/Pb diagrams reveals the complex evolution of these arc magmas. Several models (instantaneous but non simultaneous crystallization of the different mineral phases; continuous crystallization) are proposed to explain the lack of simple isochrones. The influence of other magmatic processes (assimilation, magma reinjection, degassing...) is discussed. The role played by radon loss from magmas (controlled by the ex solution of major gas species) on 210 Pb- 226 Ra disequilibria in lavas is examined through a model of dynamic degassing. At Stromboli, the magma reservoir has reached a steady-state and is rapidly renewed, thus explaining (Pb/Ra) ratios close to 1. At Merapi, the evolution of the reservoir is controlled by a succession of low dynamics degassing periods ( 2 analyses in the volcanic plume. The contribution of Etna as a source of atmospheric pollution is estimated during periods of contrasted volcanic activity and is compared to the volcanic emissions worldwide. (author)

  1. Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements.

    Science.gov (United States)

    Huang, Wei; Jiang, Ning; Schwarz, W H Eugen; Yang, Ping; Li, Jun

    2017-08-04

    The geometric and electronic ground-state structures of 30 isomers of six MS 4 molecules (M=Group 8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density functional theory and correlated wavefunction approaches. The MS 4 species were compared to analogous MO 4 species recently investigated (W. Huang, W.-H. Xu, W. H. E. Schwarz, J. Li, Inorg. Chem. 2016, 55, 4616). A metal oxidation state (MOS) with a high value of eight appeared in the low-spin singlet T d geometric species (Os,Hs)S 4 and (Ru,Os,Hs)O 4 , whereas a low MOS of two appeared in the high-spin septet D 2d species Fe(S 2 ) 2 and (slightly excited) metastable Fe(O 2 ) 2 . The ground states of all other molecules had intermediate MOS values, with S 2- , S 2 2- , S 2 1- (and O 2- , O 1- , O 2 2- , O 2 1- ) ligands bonded by ionic, covalent, and correlative contributions. The known tendencies toward lower MOS on going from oxides to sulfides, from Hs to Os to Ru, and from Pu to Sm, and the specific behavior of Fe, were found to arise from the different atomic orbital energies and radii of the (n-1)p core and (n-1)d and (n-2)f valence shells of the metal atoms in row n of the periodic table. The comparative results of the electronic and geometric structures of the MO 4 and MS 4 species provides insight into the periodicity of oxidation states and bonding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Visible light photoreactivity from hybridization states between carbon nitride bandgap states and valence states in Nb and Ti oxides

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hosik, E-mail: hosiklee@gmail.com [School of Mechanical and Advanced Materials Engineering, Ulsan National Institute of Science and Technology (UNIST), Unist-gil 100 Eonyang-eup, Ulsan 689-798 (Korea, Republic of); Ohno, Takahisa, E-mail: OHNO.Takahisa@nims.go.jp [Global Research Center for Environment and Energy based on Nanomaterials Science (GREEN), National Institute for Material Science, 1-2-1 Sengen, Tsukuba (Japan); Computational Materials Science Unit (CMSU), National Institute for Materials Science (NIMS), Tsukuba, Ibaraki 305-0047 (Japan)

    2013-03-29

    Highlights: ► Origin of bandgap reduction for visible photoreactivity is suggested. ► Carbon nitride adsorption in interlayer space can induce the bandgap reduction. ► The electronic structures are studied by density functional theory calculations. - Abstract: For better efficiency as photocatalysts, N-doping for visible light reactivity has been intensively studied in Lamellar niobic and titanic solid acids (HNb{sub 3}O{sub 8}, H{sub 2}Ti{sub 4}O{sub 9}), and its microscopic structures have been debated in this decade. We calculate the layered solid acids’ structures and bandgaps. Bandgap reduction by carbon nitride adsorption in interlayer space is observed computationally. It originates from localized nitrogen states which form delocalized top-valence states by hybridizing with the host oxygen states and can contribute to photo-current.

  3. Introducing a Simple Equation to Express Oxidation States as an Alternative to Using Rules Associated with Words Alone

    Science.gov (United States)

    Minkiewicz, Piotr; Darewicz, Malgorzata; Iwaniak, Anna

    2018-01-01

    A simple equation to calculate the oxidation states (oxidation numbers) of individual atoms in molecules and ions may be introduced instead of rules associated with words alone. The equation includes two of three categories of bonds, classified as proposed by Goodstein: number of bonds with more electronegative atoms and number of bonds with less…

  4. Forecasting magma-chamber rupture at Santorini volcano, Greece.

    Science.gov (United States)

    Browning, John; Drymoni, Kyriaki; Gudmundsson, Agust

    2015-10-28

    How much magma needs to be added to a shallow magma chamber to cause rupture, dyke injection, and a potential eruption? Models that yield reliable answers to this question are needed in order to facilitate eruption forecasting. Development of a long-lived shallow magma chamber requires periodic influx of magmas from a parental body at depth. This redistribution process does not necessarily cause an eruption but produces a net volume change that can be measured geodetically by inversion techniques. Using continuum-mechanics and fracture-mechanics principles, we calculate the amount of magma contained at shallow depth beneath Santorini volcano, Greece. We demonstrate through structural analysis of dykes exposed within the Santorini caldera, previously published data on the volume of recent eruptions, and geodetic measurements of the 2011-2012 unrest period, that the measured 0.02% increase in volume of Santorini's shallow magma chamber was associated with magmatic excess pressure increase of around 1.1 MPa. This excess pressure was high enough to bring the chamber roof close to rupture and dyke injection. For volcanoes with known typical extrusion and intrusion (dyke) volumes, the new methodology presented here makes it possible to forecast the conditions for magma-chamber failure and dyke injection at any geodetically well-monitored volcano.

  5. Homogeneity of Continuum Model of an Unsteady State Fixed Bed Reactor for Lean CH4 Oxidation

    Directory of Open Access Journals (Sweden)

    Subagjo

    2014-07-01

    Full Text Available In this study, the homogeneity of the continuum model of a fixed bed reactor operated in steady state and unsteady state systems for lean CH4 oxidation is investigated. The steady-state fixed bed reactor system was operated under once-through direction, while the unsteady-state fixed bed reactor system was operated under flow reversal. The governing equations consisting of mass and energy balances were solved using the FlexPDE software package, version 6. The model selection is indispensable for an effective calculation since the simulation of a reverse flow reactor is time-consuming. The homogeneous and heterogeneous models for steady state operation gave similar conversions and temperature profiles, with a deviation of 0.12 to 0.14%. For reverse flow operation, the deviations of the continuum models of thepseudo-homogeneous and heterogeneous models were in the range of 25-65%. It is suggested that pseudo-homogeneous models can be applied to steady state systems, whereas heterogeneous models have to be applied to unsteady state systems.

  6. SOLID STATE ENERGY CONVERSION ALLIANCE (SECA) SOLID OXIDE FUEL CELL PROGRAM

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Minh; Jim Powers

    2003-10-01

    This report summarizes the work performed for April 2003--September 2003 reporting period under Cooperative Agreement DE-FC26-01NT41245 for the U.S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid State Energy Conversion Alliance (SECA) Solid oxide Fuel Cell Program''. During this reporting period, the conceptual system design activity was completed. The system design, including strategies for startup, normal operation and shutdown, was defined. Sealant and stack materials for the solid oxide fuel cell (SOFC) stack were identified which are capable of meeting the thermal cycling and degradation requirements. A cell module was tested which achieved a stable performance of 0.238 W/cm{sup 2} at 95% fuel utilization. The external fuel processor design was completed and fabrication begun. Several other advances were made on various aspects of the SOFC system, which are detailed in this report.

  7. SOLID STATE ENERGY CONVERSION ALLIANCE (SECA) SOLID OXIDE FUEL CELL PROGRAM

    Energy Technology Data Exchange (ETDEWEB)

    Unknown

    2003-06-01

    This report summarizes the progress made during the September 2001-March 2002 reporting period under Cooperative Agreement DE-FC26-01NT41245 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program''. The program focuses on the development of a low-cost, high-performance 3-to-10-kW solid oxide fuel cell (SOFC) system suitable for a broad spectrum of power-generation applications. The overall objective of the program is to demonstrate a modular SOFC system that can be configured to create highly efficient, cost-competitive, and environmentally benign power plants tailored to specific markets. When fully developed, the system will meet the efficiency, performance, life, and cost goals for future commercial power plants.

  8. Surface State Capture Cross-Section at the Interface between Silicon and Hafnium Oxide

    Directory of Open Access Journals (Sweden)

    Fu-Chien Chiu

    2013-01-01

    Full Text Available The interfacial properties between silicon and hafnium oxide (HfO2 are explored by the gated-diode method and the subthreshold measurement. The density of interface-trapped charges, the current induced by surface defect centers, the surface recombination velocity, and the surface state capture cross-section are obtained in this work. Among the interfacial properties, the surface state capture cross-section is approximately constant even if the postdeposition annealing condition is changed. This effective capture cross-section of surface states is about 2.4 × 10−15 cm2, which may be an inherent nature in the HfO2/Si interface.

  9. Control of lipid oxidation during exercise: role of energy state and mitochondrial factors

    DEFF Research Database (Denmark)

    Sahlin, K; Harris, R C

    2008-01-01

    Despite considerable progress during recent years our understanding of how lipid oxidation (LOx) is controlled during exercise remains incomplete. This review focuses on the role of mitochondria and energy state in the control of LOx. LOx increases in parallel with increased energy demand up...... to an exercise intensity of about 50-60% of VO(2max) after which the contribution of lipid decreases. The switch from lipid to carbohydrate (CHO) is of energetic advantage due to the increased ATP/O(2) yield. In the low-intensity domain (energy state will stimulate both LOx...... during high-intensity exercise. Another potential mechanism, suggested in this review, is that Acyl-CoA synthetase (ACS), an initial step in LCFA catabolism, functions as a regulator of LOx. ACS activity is suggested to be under control of CoASH and energy state. Furthermore, evidence exists...

  10. Optically induced bistable states in metal/tunnel-oxide/semiconductor /MTOS/ junctions

    Science.gov (United States)

    Lai, S. K.; Dressendorfer, P. V.; Ma, T. P.; Barker, R. C.

    1981-01-01

    A new switching phenomenon in metal-oxide semiconductor tunnel junction has been discovered. With a sufficiently large negative bias applied to the electrode, incident visible light of intensity greater than about 1 microW/sq cm causes the reverse-biased junction to switch from a low-current to a high-current state. It is believed that hot-electron-induced impact ionization provides the positive feedback necessary for switching, and causes the junction to remain in its high-current state after the optical excitation is removed. The junction may be switched back to the low-current state electrically. The basic junction characteristics have been measured, and a simple model for the switching phenomenon has been developed.

  11. Bonding of xenon to oxygen in magmas at depth

    Science.gov (United States)

    Leroy, Clémence; Sanloup, Chrystèle; Bureau, Hélène; Schmidt, Burkhard C.; Konôpková, Zuzana; Raepsaet, Caroline

    2018-02-01

    The field of noble gases chemistry has witnessed amazing advances in the last decade with over 100 compounds reported including Xe oxides and Xe-Fe alloys stable at the pressure-temperature conditions of planetary interiors. The chemistry of Xe with planetary materials is nonetheless still mostly ignored, while Xe isotopes are used to trace a variety of key planetary processes from atmosphere formation to underground nuclear tests. It is indeed difficult to incorporate the possibility of Xe reactivity at depth in isotopic geochemical models without a precise knowledge of its chemical environment. The structure of Xe doped hydrous silica-rich melts is investigated by in situ high energy synchrotron X-ray diffraction using resistive heating diamond anvil cells. Obtained pair distribution functions reveal the oxidation of Xe between 0.2 GPa and 4 GPa at high T up to 1000 K. In addition to the usual interatomic distances, a contribution at 2.05 ± 0.05 Å is observed. This contribution is not observed in the undoped melt, and is interpreted as the Xe-O bond, with a coordination number of about 12 consistent with Xe insertion in rings of the melt structure. Xe solubility measurements by electron microprobe and particle induced X-rays emission analysis confirm that Xe and Ar have similar solubility values in wt% in silicate melts. These values are nonetheless an order of magnitude higher than those theoretically calculated for Xe. The formation of Xe-O bonds explains the enhanced solubility of Xe in deep continental crust magmas, revealing a mechanism that could store Xe and fractionate its isotopes. Xenon is indeed atypical among noble gases, the atmosphere being notably depleted in elemental Xe, and very strongly depleted in Xe light isotopes. These observations are known as the 'missing' Xe paradox, and could be solved by the present findings.

  12. Shallow magma diversions during explosive maar-diatreme eruptions in mafic volcanic fields

    Science.gov (United States)

    Le Corvec, N.; Muirhead, J.; White, J. D. L.

    2017-12-01

    Maar-diatremes are inverted conical structures formed by subterranean excavation and remobilization of country rocks during explosive volcanism and common in mafic volcanic fields. We focus on impacts of excavation and filling of maar-diatremes on the local state of stress, and its subsequent influence on underlying feeder dikes, which are critical for understanding the development of intrusive networks that feed surface eruptions. We address this issue using finite element models in COMSOL Multiphysics®. Inverted conical structures of varying sizes are excavated in a gravitationally loaded elastic half-space, and then progressively filled with volcaniclastic material, resulting in changes in the orientations and magnitudes of stresses generated within surrounding rocks and within the filling portion of the maar-diatreme. Our results show that rapid unloading during maar-diatreme excavation generates a horizontal compressive stress state beneath diatremes. These stresses allow magma to divert laterally as saucer-shaped sills and circumferential dikes at varying depths in the shallow feeder system, and produce intrusion geometries consistent with both field observations from exhumed volcanic fields and conceptual models of diatreme growth. Stresses generated in these models also provide an explanation for the evolving locations of fragmentation zones over the course of diatreme's filling. In particular, results from this study suggest that: (1) extensional stresses at the base of the diatreme fill favor magma ascent in the lower half of the structure, and possibly promote volatile exsolution and magma fragmentation; and (2) increased filling of diatremes creates a shallow compressive stress state that can inhibit magma ascent to the surface, promoting widespread intra-diatreme explosions, efficient mixing of host rock, and upward widening of the diatreme structure.

  13. Evolution of the Oxidation State of the Earth's Mantle: Challenges of High Pressure Quenching

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, R.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3+ at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. Experiments of more mafic compositions and at higher pressures commonly form a polyphase quench intergrowth composed primarily of pyroxenes, with interstitial glass which hosts nearly all of the more volatile minor elements. In our previous experiments on shergottite compositions, variable fO2, T, and P is less than 4 GPa, Fe3+/TotFe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3+/TotFe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3+. Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Experiments with Knippa basalt as the starting composition were conducted at 1-8 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products from 7-8 GPa quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal Fe3+/2+. A number of different approaches have been employed to produce glassy samples that can be measured by EELS and XANES. A more intermediate andesite was used in one experiment, and decompression during quenching was attempted after, but both resulted in a finer grained polyphase texture. Experiments are currently underway to test different capsule materials may affect quench texture. A preliminary experiment using liquid nitrogen to greatly enhance the rate of cooling of the assembly has also been attempted and this technique will be

  14. Evidence for on-going inflation of the Socorro Magma Body, New Mexico, from interferometric synthetic aperture radar imaging

    Science.gov (United States)

    Fialko, Yuri; Simons, Mark

    Interferometric synthetic aperture radar (InSAR) imaging of the central Rio Grande rift (New Mexico, USA) during 1992-1999 reveals a crustal uplift of several centimeters that spatially coincides with the seismologically determined outline of the Socorro magma body, one of the largest currently active magma intrusions in the Earth’s continental crust. Modeling of interferograms shows that the observed deformation may be due to elastic opening of a sill-like intrusion at a rate of a few millimeters per year. Despite an apparent constancy of the geodetically determined uplift rate, thermodynamic arguments suggest that it is unlikely that the Socorro magma body has formed via steady state elastic inflation.

  15. Magma paths at Piton de la Fournaise Volcano

    OpenAIRE

    Michon , Laurent; Ferrazzini , Valérie; Di Muro , Andrea

    2016-01-01

    International audience; Several patterns of magma paths have been proposed since the 1980s for Piton de la Fournaise volcano. Given the significant differences, which are presented here, we propose a reappraisal of the magma intrusion paths using a 17-years-long database of volcano-tectonic seismic events and a detailed mapping of the scoria cones. At the edifice scale, the magma propagates along two N120 trending rift zones. They are wide, linear, spotted by small to large scoria cones and r...

  16. Magma Expansion and Fragmentation in a Propagating Dike (Invited)

    Science.gov (United States)

    Jaupart, C. P.; Taisne, B.

    2010-12-01

    The influence of magma expansion due to volatile exsolution and gas dilation on dike propagation is studied using a new numerical code. Many natural magmas contain sufficient amounts of volatiles for fragmentation to occur well below Earth's surface. Magma fragmentation has been studied for volcanic flows through open conduits but it should also occur within dikes that rise towards Earth's surface. We consider the flow of a volatile-rich magma in a hydraulic fracture. The mixture of melt and gas is treated as a compressible viscous fluid below the fragmentation level and as a gas phase carrying melt droplets above it. A numerical code solves for elastic deformation of host rocks, the flow of the magmatic mixture and fracturing at the dike tip. With volatile-free magma, a dike fed at a constant rate in a uniform medium adopts a constant shape and width and rises at a constant velocity. With volatiles involved, magma expands and hence the volume flux of magma increases. With no fragmentation, this enhanced flux leads to acceleration of the dike. Simple scaling laws allow accurate predictions of dike width and ascent rate for a wide range of conditions. With fragmentation, dike behavior is markedly different. Due to the sharp drop of head loss that occurs in gas-rich fragmented material, large internal overpressures develop below the tip and induce swelling of the nose region, leading to deceleration of the dike. Thus, the paradoxical result is that, with no viscous impediment on magma flow and a large buoyancy force, the dike stalls. This process may account for some of the tuffisite veins and intrusions that are found in and around magma conduits, notably in the Unzen drillhole, Japan. We apply these results to the two-month long period of volcanic unrest that preceded the May 1980 eruption of Mount St Helens. An initial phase of rapid earthquake migration from the 7-8 km deep reservoir to shallow levels was followed by very slow progression of magma within the

  17. Short-circuiting magma differentiation from basalt straight to rhyolite?

    Science.gov (United States)

    Ruprecht, P.; Winslow, H.

    2017-12-01

    Silicic magmas are the product of varying degrees of crystal fractionation and crustal assimilation/melting. Both processes lead to differentiation that is step-wise rather than continuous for example during melt separation from a crystal mush (Dufek and Bachmann, 2010). However, differentiation is rarely efficient enough to evolve directly from a basaltic to a rhyolitic magma. At Volcán Puyehue-Cordón Caulle, Chile, the magma series is dominated by crystal fractionation where mixing trends between primitive and felsic end members in the bulk rock compositions are almost absent (e.g. P, FeO, TiO2 vs. SiO2). How effective fraction is in this magmatic system is not well-known. The 2011-12 eruption at Cordón Caulle provides new constraints that rhyolitic melts may be derived directly from a basaltic mush. Minor, but ubiquitous mafic, crystal-rich enclaves co-erupted with the predominantly rhyolitic near-aphyric magma. These enclaves are among the most primitive compositions erupted at Puyehue-Cordón Caulle and geochemically resemble closely basaltic magmas that are >10 ka old (Singer et al. 2008) and that have been identified as a parental tholeiitic mantle-derived magma (Schmidt and Jagoutz, 2017) for the Southern Andean Volcanic Zone. The vesiculated nature, the presence of a microlite-rich groundmass, and a lack of a Eu anomaly in these encalves suggest that they represent recharge magma/mush rather than sub-solidus cumulates and therefore have potentially a direct petrogenetic link to the erupted rhyolites. Our results indicate that under some conditions crystal fractionation can be very effective and the presence of rhyolitic magmas does not require an extensive polybaric plumbing system. Instead, primitive mantle-derived magmas source directly evolved magmas. In the case, of the magma system beneath Puyehue-Cordón Caulle, which had three historic rhyolitic eruptions (1921-22, 1960, 2011-12) these results raise the question whether rhyolite magma extraction

  18. Genesis of felsic plutonic magmas and their igneous enclaves

    DEFF Research Database (Denmark)

    Clemens, John D.; Maas, Roland; Waight, Tod Earle

    2016-01-01

    -type Pyalong pluton was emplaced, apparently along an east-west-orientated fracture zone. Around 367 Ma, the main I-type Baynton pluton intruded as numerous shallow-dipping sheets. The last plutonic event was the intrusion of the broad, thin, flat-lying, and crosscutting sheet of the I-type Beauvallet pluton...... the relatively high abundance of igneous-textured microgranular enclaves (MEs). The MEs show neither chemical nor isotope mixing trends with each other or with the host magmas. Variations in the Baynton magmas were derived from the heterogeneity of the source terrane, with individual magma batches formed from...

  19. Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

    Directory of Open Access Journals (Sweden)

    Effendy Mohammad

    2016-01-01

    Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

  20. Quantitative chemical state XPS analysis of first row transition metals, oxides and hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Biesinger, M C; Payne, B P; McIntryre, N S [Department of Chemistry, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Hart, B R; Lau, L Wm [Surface Science Western, Room G1, Western Science Centre, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Grosvenor, A P [Department of Chemistry, Gunning/Lemieux Chemistry Centre, University of Alberta, Edmonton, Alberta, T6G 2G2 (Canada); Smart, R StC [ACeSSS, Applied Centre for Structural and Synchrotron Studies, University of South Australia, Mawson Lakes, SA 5095 (Australia)], E-mail: biesingr@uwo.ca

    2008-03-15

    Practical quantitative chemical state X-ray photoelectron spectroscopy (XPS) analysis of first row transition metals, oxides and hydroxides is challenging due to the complexity of their M 2p spectra. Complex multiplet splitting, shake-up and plasmon loss structure can play a role in the interpretation of the chemical states present. This paper will show practical curve fitting procedures for the quantitative measurement of different chemical states for metal oxides and hydroxides from a survey of transition metals. It will also discuss some of the limitations and pitfalls present as well as give practical examples of their successful use. These curve-fitting procedures are based on 1) standard spectra from quality reference samples, 2) a survey of appropriate literature databases and/or a compilation of literature references, 3) fitting of multiplet split spectra based on spectra of numerous reference materials and theoretical modelling, 4) spectral subtractions routines, again using reference spectra, and 5) specific literature references where fitting procedures are available.

  1. Quantitative chemical state XPS analysis of first row transition metals, oxides and hydroxides

    International Nuclear Information System (INIS)

    Biesinger, M C; Payne, B P; McIntryre, N S; Hart, B R; Lau, L Wm; Grosvenor, A P; Smart, R StC

    2008-01-01

    Practical quantitative chemical state X-ray photoelectron spectroscopy (XPS) analysis of first row transition metals, oxides and hydroxides is challenging due to the complexity of their M 2p spectra. Complex multiplet splitting, shake-up and plasmon loss structure can play a role in the interpretation of the chemical states present. This paper will show practical curve fitting procedures for the quantitative measurement of different chemical states for metal oxides and hydroxides from a survey of transition metals. It will also discuss some of the limitations and pitfalls present as well as give practical examples of their successful use. These curve-fitting procedures are based on 1) standard spectra from quality reference samples, 2) a survey of appropriate literature databases and/or a compilation of literature references, 3) fitting of multiplet split spectra based on spectra of numerous reference materials and theoretical modelling, 4) spectral subtractions routines, again using reference spectra, and 5) specific literature references where fitting procedures are available

  2. Why Is There an Abrupt Transition from Solid Rock to Low Crystallinity Magma in Drilled Magma Bodies?

    Science.gov (United States)

    Eichelberger, J. C.; Carrigan, C. R.; Sun, Y.; Lavallée, Y.

    2017-12-01

    We report on a preliminary evaluation, from basic principles of heat and mass transfer, on the unexpectedly abrupt transition from cuttings of solid rock to fragments of crystal poor glass during drilling into magma bodies. Our analysis is based on conditions determined and inferred for the 2009 IDDP-1 well in Krafla Caldera, which entered apparently liquidus rhyolite magma at about 900oC at a depth of 2104 m. Simple conduction would predict some 30 m of crystallization and partial crystallization since the latest time the magma could have been intruded, approximately 30 years prior to discovery by drilling. Option 1: The expected crystallization of magma has occurred but interstitial melt remains. The pressure difference between lithostatic load of about 50 MPa on the mush and 20 MPa hydrostatic pressure in the well causes pore melt to flow from the permeable mush into the borehole, where it becomes the source of the quenched melt chips. To be viable, this mechanism must work over the time frame of a day. Option 2: The expected crystallization is occurring, but high Rayleigh number thermal convection in the magma chamber continuously displaces crystallizing roof magma by liquidus magma from the interior of the body. To be viable, this mechanism must result in overturning magma in the chamber on a time scale that is much shorter than that of crystallization. Option 3: Flow-induced crystal migration away from zones of high shear created during drilling into magma may preferentially produce low-crystal-content melt at the boundary of the borehole, which is then sampled.

  3. Solid-state electrochromic cell with anodic iridium oxide film electrodes

    International Nuclear Information System (INIS)

    Dautremont-Smith, W.C.; Beni, G.; Schiavone, L.M.; Shay, J.L.

    1979-01-01

    A new solid-state electrochromic cell has been fabricated using an anodic iridium oxide film (AIROF) display electrode. The cell has the symmetric sandwich structure AIROFvertical-barNafionvertical-barAIROF, with the Nafion solid electrolyte opacified by an in situ precipitation technique. A symmetric square-wave voltage of 1.5 V amplitude produces clearly perceivable color changes from pale to dark blue-gray in approx. =1 sec when viewed in diffuse reflection. Good open-circuit optical memory is exhibited:

  4. N-Oxide-N-oxide interactions and Cl...Cl halogen bonds in pentachloropyridine N-oxide: the many-body approach to interactions in the crystal state.

    Science.gov (United States)

    Wzgarda-Raj, Kinga; Rybarczyk-Pirek, Agnieszka J; Wojtulewski, Sławomir; Palusiak, Marcin

    2018-02-01

    Pentachloropyridine N-oxide, C 5 Cl 5 NO, crystallizes in the monoclinic space group P2 1 /c. In the crystal structure, molecules are linked by C-Cl...Cl halogen bonds into infinite ribbons extending along the crystallographic [100] direction. These molecular aggregates are further stabilized by very short intermolecular N-oxide-N-oxide interactions into herringbone motifs. Computations based on quantum chemistry methods allowed for a more detailed description of the N-oxide-N-oxide interactions and Cl...Cl halogen bonds. For this purpose, Hirshfeld surface analysis and the many-body approach to interaction energy were applied.

  5. Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments

    Science.gov (United States)

    Stoliker, Deborah L.; Campbell, Kate M.; Fox, Patricia M.; Singer, David M.; Kaviani, Nazila; Carey, Minna; Peck, Nicole E.; Barger, John R.; Kent, Douglas B.; Davis, James A.

    2013-01-01

    Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

  6. Water Partitioning in Planetary Embryos and Protoplanets with Magma Oceans

    Science.gov (United States)

    Ikoma, M.; Elkins-Tanton, L.; Hamano, K.; Suckale, J.

    2018-06-01

    The water content of magma oceans is widely accepted as a key factor that determines whether a terrestrial planet is habitable. Water ocean mass is determined as a result not only of water delivery and loss, but also of water partitioning among several reservoirs. Here we review our current understanding of water partitioning among the atmosphere, magma ocean, and solid mantle of accreting planetary embryos and protoplanets just after giant collisions. Magma oceans are readily formed in planetary embryos and protoplanets in their accretion phase. Significant amounts of water are partitioned into magma oceans, provided the planetary building blocks are water-rich enough. Particularly important but still quite uncertain issues are how much water the planetary building blocks contain initially and how water goes out of the solidifying mantle and is finally degassed to the atmosphere. Constraints from both solar-system explorations and exoplanet observations and also from laboratory experiments are needed to resolve these issues.

  7. Understanding the rheology of two and three-phase magmas

    Science.gov (United States)

    Coats, R.; Cai, B.; Kendrick, J. E.; Wallace, P. A.; Hornby, A. J.; Miwa, T.; von Aulock, F. W.; Ashworth, J. D.; Godinho, J.; Atwood, R. C.; Lee, P. D.; Lavallée, Y.

    2017-12-01

    The rheology of magma plays a fundamental role in determining the style of a volcanic eruption, be it explosive or effusive. Understanding how magmas respond to changes in stress/ strain conditions may help to enhance eruption forecast models. The presence of crystals and bubbles in magmas alter the viscosity of suspensions and favor a non-Newtonian response. Thus, with the aim of grasping the rheological behavior of volcanic materials, uniaxial compressive tests were performed on natural and synthetic samples. A suite of variably porous (10-32 vol.%), highly crystalline ( 50 vol.%) dacite from the 1991-95 eruption of Mt Unzen, Japan, was selected as the natural material, while synthetic samples were sintered with desired porosities (Diamond Light Source. Unexpectedly, these observations suggest that fractures nucleate in crystals due to crystal interactions, before propagating through the interstitial melt. This ongoing study promises to uncover the way crystal-bearing magmas flow or fail, necessary to constrain magmatic processes and volcanic hazards.

  8. Implications of magma transfer between multiple reservoirs on eruption cycling.

    Science.gov (United States)

    Elsworth, Derek; Mattioli, Glen; Taron, Joshua; Voight, Barry; Herd, Richard

    2008-10-10

    Volcanic eruptions are episodic despite being supplied by melt at a nearly constant rate. We used histories of magma efflux and surface deformation to geodetically image magma transfer within the deep crustal plumbing of the Soufrière Hills volcano on Montserrat, West Indies. For three cycles of effusion followed by discrete pauses, supply of the system from the deep crust and mantle was continuous. During periods of reinitiated high surface efflux, magma rose quickly and synchronously from a deflating mid-crustal reservoir (at about 12 kilometers) augmented from depth. During repose, the lower reservoir refilled from the deep supply, with only minor discharge transiting the upper chamber to surface. These observations are consistent with a model involving the continuous supply of magma from the deep crust and mantle into a voluminous and compliant mid-crustal reservoir, episodically valved below a shallow reservoir (at about 6 kilometers).

  9. Production and Preservation of Sulfide Layering in Mercury's Magma Ocean

    Science.gov (United States)

    Boukare, C.-E.; Parman, S. W.; Parmentier, E. M.; Anzures, B. A.

    2018-05-01

    Mercury's magma ocean (MMO) would have been sulfur-rich. At some point during MMO solidification, it likely became sulfide saturated. Here we present physiochemical models exploring sulfide layer formation and stability.

  10. Seismic Tremors and Three-Dimensional Magma Wagging

    Science.gov (United States)

    Liao, Y.; Bercovici, D.

    2015-12-01

    Seismic tremor is a feature shared by many silicic volcanoes and is a precursor of volcanic eruption. Many of the characteristics of tremors, including their frequency band from 0.5 Hz to 7 Hz, are common for volcanoes with very different geophysical and geochemical properties. The ubiquitous characteristics of tremor imply that it results from some generation mechanism that is common to all volcanoes, instead of being unique to each volcano. Here we present new analysis on the magma-wagging mechanism that has been proposed to generate tremor. The model is based on the suggestion given by previous work (Jellinek & Bercovici 2011; Bercovici et.al. 2013) that the magma column is surrounded by a compressible, bubble-rich foam annulus while rising inside the volcanic conduit, and that the lateral oscillation of the magma inside the annulus causes observable tremor. Unlike the previous two-dimensional wagging model where the displacement of the magma column is restricted to one vertical plane, the three-dimensional model we employ allows the magma column to bend in different directions and has angular motion as well. Our preliminary results show that, without damping from viscous deformation of the magma column, the system retains angular momentum and develops elliptical motion (i.e., the horizontal displacement traces an ellipse). In this ''inviscid'' limit, the magma column can also develop instabilities with higher frequencies than what is found in the original two-dimensional model. Lateral motion can also be out of phase for various depths in the magma column leading to a coiled wagging motion. For the viscous-magma model, we predict a similar damping rate for the uncoiled magma column as in the two-dimensional model, and faster damping for the coiled magma column. The higher damping thus requires the existence of a forcing mechanism to sustain the oscillation, for example the gas-driven Bernoulli effect proposed by Bercovici et al (2013). Finally, using our new 3

  11. Nanoscale probing of bandgap states on oxide particles using electron energy-loss spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Qianlang [School for the Engineering of Matter, Transport and Energy, Arizona State University, 85287 AZ (United States); March, Katia [Laboratoire de Physique des Solides, Bâtiment 510, Université Paris-Sud, 91405 Orsay Cedex (France); Crozier, Peter A., E-mail: CROZIER@asu.edu [School for the Engineering of Matter, Transport and Energy, Arizona State University, 85287 AZ (United States)

    2017-07-15

    Surface and near-surface electronic states were probed with nanometer spatial resolution in MgO and TiO{sub 2} anatase nanoparticles using ultra-high energy resolution electron energy-loss spectroscopy (EELS) coupled to a scanning transmission electron microscope (STEM). This combination allows the surface electronic structure determined with spectroscopy to be correlated with nanoparticle size, morphology, facet etc. By acquiring the spectra in aloof beam mode, radiation damage to the surface can be significantly reduced while maintaining the nanometer spatial resolution. MgO and TiO{sub 2} showed very different bandgap features associated with the surface/sub-surface layer of the nanoparticles. Spectral simulations based on dielectric theory and density of states models showed that a plateau feature found in the pre-bandgap region in the spectra from (100) surfaces of 60 nm MgO nanocubes is consistent with a thin hydroxide surface layer. The spectroscopy shows that this hydroxide species gives rise to a broad filled surface state at 1.1 eV above the MgO valence band. At the surfaces of TiO{sub 2} nanoparticles, pronounced peaks were observed in the bandgap region, which could not be well fitted to defect states. In this case, the high refractive index and large particle size may make Cherenkov or guided light modes the likely causes of the peaks. - Highlights: • Bandgap states detected with aloof beam monochromated EELS on oxide nanoparticle surfaces. • Dielectric theory applied to simulate the spectra and interpret surface structure. • Density of states models also be employed to understand the surface electronic structure. • In MgO, one states associate with water species was found close to the valence band edge. • In anatase, two mid-gap states associated with point defects were found.

  12. Adsorption of CO, CO2, H2, and H2O on titania surfaces with different oxidation states

    International Nuclear Information System (INIS)

    Raupp, G.B.; Dumesic, J.A.

    1985-01-01

    The adsorptive properties of titania surfaces with different oxidation states were proved by temperature-programmed desorption (TPD) of CO, H 2 , CO 2 , and H 2 O. Auger electron spectroscopy and X-ray photoelectron spectroscopy revealed that vacuum annealing an oxidized titanium foil at temperatures from 300 to 800 K was an effective means of systematically varying the average surface oxidation state from Ti 4+ to Ti 2+ . Carbon monoxide weakly adsorbed (desorption energy of 44-49 kJ x mol -1 ) in a carbonyl fashion on coordinatively unsaturated cation sites. Titania surfaces were inert with respect to H 2 adsorption and dissociation. Carbon dioxide adsorbed in a linear molecular fashion. Water adsorbed both molecularly and dissociatively. Results are discussed in terms of the role of titania oxidation state in CO hydrogenation over titania-supported metal catalysts. 74 references, 7 figures

  13. Magma chamber interaction giving rise to asymmetric oscillations

    Science.gov (United States)

    Walwer, D.; Ghil, M.; Calais, E.

    2017-12-01

    Geodetic time series at four volcanoes (Okmok, Akutan, Shishaldin, and Réunion) are processed using Multi-channel Singular Spectrum Analysis (M-SSA) and reveal sawtooth-shaped oscillations ; the latter are characterized by short intervals of fast inflations followed by longer intervals of slower deflations. At Okmok and Akutan, the oscillations are first damped and then accentuated. At Okmok, the increase in amplitude of the oscillations is followed by an eruption. We first show that the dynamics of these four volcanoes bears similarities with that of a simple nonlinear, dissipative oscillator, indicating that the inflation-deflation episodes are relaxation oscillations. These observations imply that ab initio dynamical models of magma chambers should possess an asymmetric oscillatory regime. Next, based on the work of Whitehead and Helfrich [1991], we show that a model of two magma chambers — connected by a cylindrical conduit in which the magma viscosity depends on temperature — gives rise to asymmetric overpressure oscillations in the magma reservoirs. These oscillations lead to surface deformations that are consistent with those observed at the four volcanoes in this study. This relaxation oscillation regime occurs only when the vertical temperature gradient in the host rock between the two magma chambers is large enough and when the magma flux entering the volcanic system is sufficiently high. The magma being supplied by a deeper source region, the input flux depends on the pressure difference between the source and the deepest reservoir. When this difference is not sufficiently high, the magma flux exponentially decreases, leading to damped oscillations as observed at Akutan and Okmok. The combination of observational and modeling results clearly supports the role of relaxation oscillations in the dynamics of volcanic systems.

  14. Crystalline heterogeneities and instabilities in thermally convecting magma chamber

    Science.gov (United States)

    Culha, C.; Suckale, J.; Qin, Z.

    2016-12-01

    A volcanic vent can supply different densities of crystals over an eruption time period. This has been seen in Hawai'i's Kilauea Iki 1959 eruption; however it is not common for all Kilauea or basaltic eruptions. We ask the question: Under what conditions can homogenous magma chamber cultivate crystalline heterogeneities? In some laboratory experiments and numerical simulations, a horizontal variation is observed. The region where crystals reside is identified as a retention zone: convection velocity balances settling velocity. Simulations and experiments that observe retention zones assume crystals do not alter the convection in the fluid. However, a comparison of experiments and simulations of convecting magma with crystals suggest that large crystal volume densities and crystal sizes alter fluid flow considerably. We introduce a computational method that fully resolves the crystalline phase. To simulate basaltic magma chambers in thermal convection, we built a numerical solver of the Navier-Stoke's equation, continuity equation, and energy equation. The modeled magma is assumed to be a viscous, incompressible fluid with a liquid and solid phase. Crystals are spherical, rigid bodies. We create Rayleigh-Taylor instability through a cool top layer and hot bottom layer and update magma density while keeping crystal temperature and size constant. Our method provides a detailed picture of magma chambers, which we compare to other models and experiments to identify when and how crystals alter magma chamber convection. Alterations include stratification, differential settling and instabilities. These characteristics are dependent on viscosity, convection vigor, crystal volume density and crystal characteristics. We reveal that a volumetric crystal density variation may occur over an eruption time period, if right conditions are met to form stratifications and instabilities in magma chambers. These conditions are realistic for Kilauea Iki's 1959 eruption.

  15. Experimental Fractional Crystallization of the Lunar Magma Ocean

    Science.gov (United States)

    Rapp, J. F.; Draper, D. S.

    2012-01-01

    The current paradigm for lunar evolution is of crystallization of a global scale magma ocean, giving rise to the anorthositic crust and mafic cumulate interior. It is thought that all other lunar rocks have arisen from this differentiated interior. However, until recently this paradigm has remained untested experimentally. Presented here are the first experimental results of fractional crystallization of a Lunar Magma Ocean (LMO) using the Taylor Whole Moon (TWM) bulk lunar composition [1].

  16. The effect of interfaces on solid-state reactions between oxides

    International Nuclear Information System (INIS)

    Johnson, M.T.; Carter, C.B.

    1998-01-01

    A thin-film geometry has been used to study fundamental solid-state reaction processes occurring at interfaces in two spinel-forming oxide systems. In the first system, NiO/Al 2 O 3 , epitactic NiO films were deposited on various orientations of single-crystal α-Al 2 O 3 . In this case, the reaction kinetics were studied and correlated with the interfacial structure (or substrate orientation). In the second, In 2 O 3 /MgO, solid-state reactions were studied under the influence of an electric field. The electric field provides a driving force for mass transport that affects both the reaction process and the morphological stability of an interface

  17. Chemical states of fission products in irradiated uranium-plutonium mixed oxide fuel

    International Nuclear Information System (INIS)

    Kurosaki, Ken; Uno, Masayoshi; Yamanaka, Shinsuke

    1999-01-01

    The chemical states of fission products (FPs) in irradiated uranium-plutonium mixed oxide (MOX) fuel for the light water reactor (LWR) were estimated by thermodynamic equilibrium calculations on system of fuel and FPs by using ChemSage program. A stoichiometric MOX containing 6.1 wt. percent PuO 2 was taken as a loading fuel. The variation of chemical states of FPs was calculated as a function of oxygen potential. Some pieces of information obtained by the calculation were compared with the results of the post-irradiation examination (PIE) of UO 2 fuel. It was confirmed that the multicomponent and multiphase thermodynamic equilibrium calculation between fuel and FPs system was an effective tool for understanding the behavior of FPs in fuel. (author)

  18. Origin of major donor states in In–Ga–Zn oxide

    Energy Technology Data Exchange (ETDEWEB)

    Nakashima, Motoki; Oota, Masashi; Ishihara, Noritaka; Nonaka, Yusuke; Hirohashi, Takuya; Takahashi, Masahiro; Yamazaki, Shunpei [Semiconductor Energy Laboratory Co., Ltd., 398 Hase, Atsugi, Kanagawa 243-0036 (Japan); Obonai, Toshimitsu; Hosaka, Yasuharu; Koezuka, Junichi [Advanced Film Device Inc., 161-2 Masuzuka, Tsuga-machi, Tochigi, Tochigi 328-0114 (Japan)

    2014-12-07

    To clarify the origin of the major donor states in indium gallium zinc oxide (IGZO), we report measurement results and an analysis of several physical properties of IGZO thin films. Specifically, the concentration of H atoms and O vacancies (V{sub O}), carrier concentration, and conductivity are investigated by hard X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, thermal desorption spectroscopy, and Hall effect measurements. The results of these experiments suggest that the origin of major donor states is H occupancy of V{sub O} sites. Furthermore, we use first-principles calculations to investigate the influence of the coexistence of V{sub O} and H in crystalline InGaO{sub 3}(ZnO){sub m} (m = 1). The results indicate that when H is trapped in V{sub O}, a stable complex is created that serves as a shallow-level donor.

  19. Solid-State Electrochromic Device Consisting of Amorphous WO3 and Various Thin Oxide Layers

    Science.gov (United States)

    Shizukuishi, Makoto; Shimizu, Isamu; Inoue, Eiichi

    1980-11-01

    A mixed oxide containing Cr2O3 was introduced into an amorphous WO3 solid-state electrochromic device (ECD) in order to improve its colour memory effect. The electrochromic characteristics were greatly affected by the chemical constituents of a dielectric layer on the a-WO3 layer. Particularly, long memory effect and low power dissipation were attained in a solid-state ECD consisting of a-WO3 and Cr2O3\\cdotV2O5(50 wt.%). Some electrochromic characteristics of the a-WO3/Cr2O3\\cdotV2O5 ECD and the role of V2O5 were investigated.

  20. Long-living positron and positronium states in zeolites and microcrystalline oxides

    International Nuclear Information System (INIS)

    Kajcsos, Zs.; Liszkay, L.; Varga, L.; Lohonyai, L.; Lazar, K.

    1995-01-01

    Positron annihilation (PA) investigation were performed on zeolites (X, Y and ZSM-5) and on microcrystalline MgO, Al 2 O 3 and SiO 2 , providing long lifetime components attributed to o-Ps atoms. In addition to the positron lifetime (LT) measurements, the energy distribution (ED) of the annihilation gamma radiation spectrum was recorded in the 30 keV - 1.5 MeV range for different samples and was compared to reference distributions for Si and GaAs samples, where no long-living Ps states are formed. Apart from the strong correlation with the water content in the samples, the positron data collected testify much more pronounced positronium hosting features for powders of the mentioned oxides than for zeolites. Positron LT spectroscopy combined with recording of the ED of the annihilation radiation provides reliable information on the forming of long living 3γ states. (author) 15 refs.; 4 figs

  1. The state of itinerant charge carriers and thermoelectric effects in correlated oxide metals

    International Nuclear Information System (INIS)

    Kuzemsky, A.L.; Abdus Salam International Centre for Theoretical Physics, Trieste

    2000-10-01

    We analyzed the physics of transport processes and, in particular, the thermoelectric power in the mercurocuprates and other cuprates to get a better insight into the state of the carriers in these compounds. The actual problems related to the complicated mechanisms of carriers scattering above Tc are discussed. The experimental studies of thermoelectric power showed that the state of carriers in cuprates can be influenced by many complicated scattering processes, however the underlying mechanism for the linear decreasing of the TEP with increasing the temperature for most hole-doped HTSC cuprates is still not yet known. The actual problems related to the complicated mechanisms of carriers scattering above Tc are discussed for a few models of charge transport. A comparison between the analytical and experimental results is also made. It is concluded that the crucial factor for the understanding of the transport properties of correlated oxide metals is the nature of itinerant charge carriers, i.e. renormalized quasiparticles. (author)

  2. Probing the transition state region in catalytic CO oxidation on Ru

    Energy Technology Data Exchange (ETDEWEB)

    Ostrom, H. [Stockholm Univ. (Sweden); Oberg, H. [Stockholm Univ. (Sweden); Xin, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); LaRue, J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Beye, M. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Dell' Angela, M. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Gladh, J. [Stockholm Univ. (Sweden); Ng, M. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Sellberg, J. A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); Kaya, S. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mercurio, G. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Nordlund, D. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Hantschmann, M. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Hieke, F. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Kuhn, D. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Schlotter, W. F. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Dakovski, G. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Turner, J. J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Minitti, M. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mitra, A. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Moeller, S. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Fohlisch, A. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany); Wolf, M. [Fritz-Haber Institute of the Max-Planck-Society, Berlin (Germany); Wurth, W. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); DESY Photon Science, Hamburg (Germany); Persson, M. [The Univ. of Liverpool, Liverpool (United Kingdom); Norskov, J. K. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Abild-Pedersen, F. [Stanford Univ., Stanford, CA (United States); Ogasawara, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Pettersson, L. G. M. [Stockholm Univ. (Sweden); Nilsson, A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

    2015-02-12

    Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC–O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.

  3. Magma Dynamics at Yucca Mountain, Nevada

    International Nuclear Information System (INIS)

    D. Krier

    2005-01-01

    Small-volume basaltic volcanic activity at Yucca Mountain has been identified as one of the potential events that could lead to release of radioactive material from the U.S. Department of Energy (DOE) designated nuclear waste repository at Yucca Mountain. Release of material could occur indirectly as a result of magmatic dike intrusion into the repository (with no associated surface eruption) by changing groundwater flow paths, or as a result of an eruption (dike intrusion of the repository drifts, followed by surface eruption of contaminated ash) or volcanic ejection of material onto the Earth's surface and the redistribution of contaminated volcanic tephra. Either release method includes interaction between emplacement drifts and a magmatic dike or conduit, and natural (geologic) processes that might interrupt or halt igneous activity. This analysis provides summary information on two approaches to evaluate effects of disruption at the repository by basaltic igneous activity: (1) descriptions of the physical geometry of ascending basaltic dikes and their interaction with silicic host rocks similar in composition to the repository host rocks; and (2) a summary of calculations developed to quantify the response of emplacement drifts that have been flooded with magma and repressurized following blockage of an eruptive conduit. The purpose of these analyses is to explore the potential consequences that could occur during the full duration of an igneous event

  4. Magma Dynamics at Yucca Mountain, Nevada

    Energy Technology Data Exchange (ETDEWEB)

    D. Krier

    2005-08-29

    Small-volume basaltic volcanic activity at Yucca Mountain has been identified as one of the potential events that could lead to release of radioactive material from the U.S. Department of Energy (DOE) designated nuclear waste repository at Yucca Mountain. Release of material could occur indirectly as a result of magmatic dike intrusion into the repository (with no associated surface eruption) by changing groundwater flow paths, or as a result of an eruption (dike intrusion of the repository drifts, followed by surface eruption of contaminated ash) or volcanic ejection of material onto the Earth's surface and the redistribution of contaminated volcanic tephra. Either release method includes interaction between emplacement drifts and a magmatic dike or conduit, and natural (geologic) processes that might interrupt or halt igneous activity. This analysis provides summary information on two approaches to evaluate effects of disruption at the repository by basaltic igneous activity: (1) descriptions of the physical geometry of ascending basaltic dikes and their interaction with silicic host rocks similar in composition to the repository host rocks; and (2) a summary of calculations developed to quantify the response of emplacement drifts that have been flooded with magma and repressurized following blockage of an eruptive conduit. The purpose of these analyses is to explore the potential consequences that could occur during the full duration of an igneous event.

  5. Oxidative stress markers in hypertensive states of pregnancy: preterm and term disease.

    Directory of Open Access Journals (Sweden)

    Lesia Olha Kurlak

    2014-08-01

    Full Text Available Discussion continues as to whether de novo hypertension in pregnancy with significant proteinuria (pre-eclampsia; PE and non-proteinuric new hypertension (gestational hypertension; GH are parts of the same disease spectrum or represent different conditions. Non-pregnant hypertension, pregnancy and PE are all associated with oxidative stress. We have established a 6 weeks post-partum clinic for women who experienced a hypertensive pregnancy. We hypothesized that PE and GH could be distinguished by markers of oxidative stress; thiobarbituric acid reactive substances (TBARS and antioxidants (ferric ion reducing ability of plasma; FRAP. Since the severity of PE and GH is greater pre-term, we also compared pre-term and term disease. Fifty-eight women had term PE, 23 pre-term PE, 60 had term GH and 6 pre-term GH, 11 pre-existing (essential hypertension (EH without PE. Limited data were available from normotensive pregnancies (n=7 and non-pregnant controls (n=14. There were no differences in postpartum TBARS or FRAP between hypertensive states; TBARS (P=0.001 and FRAP (P=0.009 were lower in plasma of non-pregnant controls compared to recently-pregnant women. Interestingly FRAP was higher in preterm than term GH (P=0.013. In PE and GH, TBARS correlated with low density lipoprotein (LDL-cholesterol (P=0.036; this association strengthened with inclusion of EH ((P=0.011. The 10 year Framingham index for cardiovascular risk was positively associated with TBARS (P=0.003.Oxidative stress profiles do not differ between hypertensive states but appear to distinguish between recently-pregnant and non-pregnant states. This suggests that pregnancy may alter vascular integrity with changes remaining 6 weeks postpartum. LDL-cholesterol is a known determinant of oxidative stress in cardiovascular disease and we have shown this association to be present in hypertensive pregnancy further emphasizing that such a pregnancy may be revealing a pre-existing cardiovascular

  6. The fluid dynamics of a basaltic magma chamber replenished by influx of hot, dense ultrabasic magma

    Science.gov (United States)

    Huppert, Herbert E.; Sparks, R. Stephen J.

    1981-09-01

    This paper describes a fluid dynamical investigation of the influx of hot, dense ultrabasic magma into a reservoir containing lighter, fractionated basaltic magma. This situation is compared with that which develops when hot salty water is introduced under cold fresh water. Theoretical and empirical models for salt/water systems are adapted to develop a model for magmatic systems. A feature of the model is that the ultrabasic melt does not immediately mix with the basalt, but spreads out over the floor of the chamber, forming an independent layer. A non-turbulent interface forms between this layer and the overlying magma layer across which heat and mass are transferred by the process of molecular diffusion. Both layers convect vigorously as heat is transferred to the upper layer at a rate which greatly exceeds the heat lost to the surrounding country rock. The convection continues until the two layers have almost the same temperature. The compositions of the layers remain distinct due to the low diffusivity of mass compared to heat. The temperatures of the layers as functions of time and their cooling rate depend on their viscosities, their thermal properties, the density difference between the layers and their thicknesses. For a layer of ultrabasic melt (18% MgO) a few tens of metres thick at the base of a basaltic (10% MgO) magma chamber a few kilometres thick, the temperature of the layers will become nearly identical over a period of between a few months and a few years. During this time the turbulent convective velocities in the ultrabasic layer are far larger than the settling velocity of olivines which crystallise within the layer during cooling. Olivines only settle after the two layers have nearly reached thermal equilibrium. At this stage residual basaltic melt segregates as the olivines sediment in the lower layer. Depending on its density, the released basalt can either mix convectively with the overlying basalt layer, or can continue as a separate

  7. Theoretical studies of positron states and annihilation characteristics at the oxidized Cu(100) surface

    Energy Technology Data Exchange (ETDEWEB)

    Fazleev, N. G. [Department of Physics, Box 19059, University of Texas at Arlington, Arlington Texas 76019 (United States) and Institute of Physics, Kazan Federal University, Kremlevskaya18, Kazan 420008 (Russian Federation); Weiss, A. H. [Department of Physics, Box 19059, University of Texas at Arlington, Arlington Texas 76019 (United States)

    2013-04-19

    In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. An ab-initio study of the electronic properties of the Cu(100) missing row reconstructed surface at various on surface and sub-surface oxygen coverages has been performed on the basis of the density functional theory (DFT) using the Dmol3 code and the generalized gradient approximation (GGA). Surface structures in calculations have been constructed by adding oxygen atoms to various surface hollow and sub-surface octahedral sites of the 0.5 monolayer (ML) missing row reconstructed phase of the Cu(100) surface with oxygen coverages ranging from 0.5 to 1.5 ML. The charge redistribution at the surface and variations in atomic structure and chemical composition of the topmost layers associated with oxidation and surface reconstruction have been found to affect the spatial extent and localization of the positron surface state wave function and annihilation probabilities of surface trapped positrons with relevant core electrons. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). It has been shown that positron annihilation probabilities with Cu 3s and 3p core electrons decrease when total (on-surface and sub-surface) oxygen coverage of the Cu(100) surface increases up to 1 ML. The calculations show that for high oxygen coverage when total oxygen coverage is 1. 5 ML the positron is not bound to the surface.

  8. Obesity-Associated Oxidative Stress: Strategies Finalized to Improve Redox State

    Directory of Open Access Journals (Sweden)

    Valeria Gasperi

    2013-05-01

    Full Text Available Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance.

  9. Obesity-Associated Oxidative Stress: Strategies Finalized to Improve Redox State

    Science.gov (United States)

    Savini, Isabella; Catani, Maria Valeria; Evangelista, Daniela; Gasperi, Valeria; Avigliano, Luciana

    2013-01-01

    Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance. PMID:23698776

  10. Oxidation state of sulfur, iron and tin at the surface of float glasses

    International Nuclear Information System (INIS)

    Lagarde, P; Flank, A-M; Jupille, J; Montigaud, H

    2009-01-01

    Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO 3 ), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 μm 2 ) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

  11. Oxidation state of sulfur, iron and tin at the surface of float glasses

    Energy Technology Data Exchange (ETDEWEB)

    Lagarde, P; Flank, A-M [Synchrotron SOLEIL, l' Orme des Merisiers, BP 48 91192 Gif/Yvette cedex (France); Jupille, J [IMPMC, Universite P. and M. Curie, Campus de Boucicaut, 140 rue de Lourmel 75015 Paris (France); Montigaud, H [Saint-Gobain Recherche 39, quai Lucien Lefranc, BP 135 93303 Aubervilliers Cedex (France)

    2009-11-15

    Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO{sub 3}), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 {mu}m{sup 2}) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

  12. Derivation of intermediate to silicic magma from the basalt analyzed at the Vega 2 landing site, Venus.

    Science.gov (United States)

    Shellnutt, J Gregory

    2018-01-01

    Geochemical modeling using the basalt composition analyzed at the Vega 2 landing site indicates that intermediate to silicic liquids can be generated by fractional crystallization and equilibrium partial melting. Fractional crystallization modeling using variable pressures (0.01 GPa to 0.5 GPa) and relative oxidation states (FMQ 0 and FMQ -1) of either a wet (H2O = 0.5 wt%) or dry (H2O = 0 wt%) parental magma can yield silicic (SiO2 > 60 wt%) compositions that are similar to terrestrial ferroan rhyolite. Hydrous (H2O = 0.5 wt%) partial melting can yield intermediate (trachyandesite to andesite) to silicic (trachydacite) compositions at all pressures but requires relatively high temperatures (≥ 950°C) to generate the initial melt at intermediate to low pressure whereas at high pressure (0.5 GPa) the first melts will be generated at much lower temperatures (< 800°C). Anhydrous partial melt modeling yielded mafic (basaltic andesite) and alkaline compositions (trachybasalt) but the temperature required to produce the first liquid is very high (≥ 1130°C). Consequently, anhydrous partial melting is an unlikely process to generate derivative liquids. The modeling results indicate that, under certain conditions, the Vega 2 composition can generate silicic liquids that produce granitic and rhyolitic rocks. The implication is that silicic igneous rocks may form a small but important component of the northeast Aphrodite Terra.

  13. Towards the improvement of the oxidation resistance of Nb-silicides in situ composites: A solid state diffusion approach

    International Nuclear Information System (INIS)

    Mathieu, S.; Knittel, S.; François, M.; Portebois, L.; Mathieu, S.; Vilasi, M.

    2014-01-01

    Highlights: •Local equilibrium is attained during oxidation at phase boundaries (steady state conditions). •A solid state diffusion model explains the oxidation mechanism of Nb-silicides composites. •The Nb ss fraction is not the only parameters governing the oxidation rate of Nb-silicides. •Aluminium increases the thermodynamic activity of Si in the Nb-silicides composites. •The results indicate the need to develop a Nb–Ti–Hf–Al–Cr–Si thermodynamic database. -- Abstract: The present study focuses on the oxidation mechanism of Nb-silicide composites and on the effect of the composition on the oxidation rate at 1100 °C. A theoretical approach is proposed based on experimental results and used to optimise the oxidation resistance. The growth model based on multiphase diffusion was experimentally tested and confirmed by manufacturing seven composites with different compositions. It was also found that the effect of the composition has to be evaluated at 1100 °C within a short time duration (50 h), where the oxide scale and the internal oxidation zone both grow according to parabolic kinetics

  14. Effect of surface state on the oxidation behavior of welded 308L in simulated nominal primary water of PWR

    Science.gov (United States)

    Ming, Hongliang; Zhang, Zhiming; Wang, Jiazhen; Zhu, Ruolin; Ding, Jie; Wang, Jianqiu; Han, En-Hou; Ke, Wei

    2015-05-01

    The oxidation behavior of 308L weld metal (WM) with different surface state in the simulated nominal primary water of pressurized water reactor (PWR) was studied by scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analyzer and X-ray photoelectron spectroscopy (XPS). After 480 h immersion, a duplex oxide film composed of a Fe-rich outer layer (Fe3O4, Fe2O3 and a small amount of NiFe2O4, Ni(OH)2, Cr(OH)3 and (Ni, Fe)Cr2O4) and a Cr-rich inner layer (FeCr2O4 and NiCr2O4) can be formed on the 308L WM samples with different surface state. The surface state has no influence on the phase composition of the oxide films but obviously affects the thickness of the oxide films and the morphology of the oxides (number & size). With increasing the density of dislocations and subgrain boundaries in the cold-worked superficial layer, the thickness of the oxide film, the number and size of the oxides decrease.

  15. Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors

    Science.gov (United States)

    Qifeng Zheng; Zhiyong Cai; Zhenqiang Ma; Shaoqin Gong

    2015-01-01

    A novel type of highly flexible and all-solid-state supercapacitor that uses cellulose nanofibril (CNF)/reduced graphene oxide (RGO)/carbon nanotube (CNT) hybrid aerogels as electrodes and H2SO4 poly (vinyl alcohol) PVA gel as the electrolyte was developed and is reported here. These flexible solid-state supercapacitors...

  16. Moessbauer effect study of oxidation and coordination states of iron in some sodium borate glasse:;

    International Nuclear Information System (INIS)

    Eissa, N.A.; Sanad, A.M.; Youssef, S.M.; El-Henawii, S.A.; Gomaa, S.Sh.; Mostafa, A.G.

    1980-01-01

    A structural study of some sodium borate glasses containing iron was carried out applying ME spectroscopy. Both oxidation and coordination states of iron were investigated under the effect of gradual replacing of sodium carbonate by sodium nitrate in the glass batches. The glasses were melted in porcelain crucibles using an electrically heated furnace at 1000+-10 deg C, then were quenched on a steel plate at room temperature (R.T.). The ME source was 20 mCi radioactive Co-57 in chromium. The obtained ME spectra indicated that at lower sodium nitrate content both Fe 2+ and Fe 3+ are present in these glasses. At moderate concentrations some Fe 3+ ions were separated in a crystalline phase and the rest of the iron ions appeared as ferric ions in glassy state. At high sodium nitrate content only Fe 3+ ions in glassy state were detected. The values of the ME parameters for all iron ions indicated that all of them are in the octahedral coordination state. The density measurements confirm the separation of a crystalline phase at moderate sodium nitrate content. (author)

  17. Magma accumulation or second boiling - Investigating the ongoing deformation field at Montserrat, West Indies

    Science.gov (United States)

    Collinson, Amy; Neuberg, Jurgen; Pascal, Karen

    2016-04-01

    For over 20 years, Soufriere Hills Volcano, Montserrat has been in a state of volcanic unrest. Intermittent periods of dome building have been punctuated by explosive eruptions and dome collapse events, endangering the lives of the inhabitants of the island. The last episode of active magma extrusion was in February 2010, and the last explosive event (ash venting) in March 2012. Despite a lack of eruptive activity recently, the volcano continues to emit significant volumes of SO2 and shows an ongoing trend of island inflation. Through the aid of three-dimensional numerical modelling, using a finite element method, we explore the potential sources of the ongoing island inflation. We consider both magmatic (dykes and chamber) and tectonic sources. Whilst a magmatic source suggests the possibility for further eruption, a tectonic source may indicate cessation of volcanic activity. We show that a magmatic source is the most likely scenario, and illustrate the effect of different sources (shapes, characters and depths) on the surface displacement. Furthermore, through the inclusion of topographic data, we investigate how the topography may affect the displacement pattern at the surface. We investigate the conflicting scenarios of magma chamber resupply versus second boiling - crystallisation-induced degassing. Based on numerical modelling results, we suggest the required pressurisation is too high for crystallisation-induced degassing to be the dominant process - thereby suggesting magma accumulation may be ongoing. However, we show that second boiling may be a contributing factor, particularly when taking into account the local tectonics and regional stretching.

  18. A cascade of magmatic events during the assembly and eruption of a super-sized magma body

    Science.gov (United States)

    Allan, Aidan. S. R.; Barker, Simon J.; Millet, Marc-Alban; Morgan, Daniel J.; Rooyakkers, Shane M.; Schipper, C. Ian; Wilson, Colin J. N.

    2017-07-01

    We use comprehensive geochemical and petrological records from whole-rock samples, crystals, matrix glasses and melt inclusions to derive an integrated picture of the generation, accumulation and evacuation of 530 km3 of crystal-poor rhyolite in the 25.4 ka Oruanui supereruption (New Zealand). New data from plagioclase, orthopyroxene, amphibole, quartz, Fe-Ti oxides, matrix glasses, and plagioclase- and quartz-hosted melt inclusions, in samples spanning different phases of the eruption, are integrated with existing data to build a history of the magma system prior to and during eruption. A thermally and compositionally zoned, parental crystal-rich (mush) body was developed during two periods of intensive crystallisation, 70 and 10-15 kyr before the eruption. The mush top was quartz-bearing and as shallow as 3.5 km deep, and the roots quartz-free and extending to >10 km depth. Less than 600 year prior to the eruption, extraction of large volumes of 840 °C low-silica rhyolite melt with some crystal cargo (between 1 and 10%), began from this mush to form a melt-dominant (eruptible) body that eventually extended from 3.5 to 6 km depth. Crystals from all levels of the mush were entrained into the eruptible magma, as seen in mineral zonation and amphibole model pressures. Rapid translation of crystals from the mush to the eruptible magma is reflected in textural and compositional diversity in crystal cores and melt inclusion compositions, versus uniformity in the outermost rims. Prior to eruption the assembled eruptible magma body was not thermally or compositionally zoned and at temperatures of 790 °C, reflecting rapid cooling from the 840 °C low-silica rhyolite feedstock magma. A subordinate but significant volume (3-5 km3) of contrasting tholeiitic and calc-alkaline mafic material was co-erupted with the dominant rhyolite. These mafic clasts host crystals with compositions which demonstrate that there was some limited pre-eruptive physical interaction of mafic

  19. Quantum State-Resolved Collision Dynamics of Nitric Oxide at Ionic Liquid and Molten Metal Surfaces

    Science.gov (United States)

    Zutz, Amelia Marie

    Detailed molecular scale interactions at the gas-liquid interface are explored with quantum state-to-state resolved scattering of a jet-cooled beam of NO(2pi1/2; N = 0) from ionic liquid and molten metal surfaces. The scattered distributions are probed via laser-induced fluorescence methods, which yield rotational and spin-orbit state populations that elucidate the dynamics of energy transfer at the gas-liquid interface. These collision dynamics are explored as a function of incident collision energy, surface temperature, scattering angle, and liquid identity, all of which are found to substantially affect the degree of rotational, electronic and vibrational excitation of NO via collisions at the liquid surface. Rotational distributions observed reveal two distinct scattering pathways, (i) molecules that trap, thermalize and eventually desorb from the surface (trapping-desorption, TD), and (ii) those that undergo prompt recoil (impulsive scattering, IS) prior to complete equilibration with the liquid surface. Thermally desorbing NO molecules are found to have rotational temperatures close to, but slightly cooler than the surface temperature, indicative of rotational dependent sticking probabilities on liquid surfaces. Nitric oxide is a radical with multiple low-lying electronic states that serves as an ideal candidate for exploring nonadiabatic state-changing collision dynamics at the gas-liquid interface, which induce significant excitation from ground (2pi1/2) to excited (2pi 3/2) spin-orbit states. Molecular beam scattering of supersonically cooled NO from hot molten metals (Ga and Au, Ts = 300 - 1400 K) is also explored, which provide preliminary evidence for vibrational excitation of NO mediated by thermally populated electron-hole pairs in the hot, conducting liquid metals. The results highlight the presence of electronically nonadiabatic effects and build toward a more complete characterization of energy transfer dynamics at gas-liquid interfaces.

  20. The Magma Chamber Simulator: Modeling the Impact of Wall Rock Composition on Mafic Magmas during Assimilation-Fractional Crystallization

    Science.gov (United States)

    Creamer, J. B.; Spera, F. J.; Bohrson, W. A.; Ghiorso, M. S.

    2012-12-01

    Although stoichiometric titration is often used to model the process of concurrent Assimilation and Fractional Crystallization (AFC) within a compositionally evolving magma body, a more complete treatment of the problem involves simultaneous and self-consistent determination of stable phase relationships and separately evolving temperatures of both Magma (M) and Wall Rock (WR) that interact as a composite M-WR system. Here we present results of M-WR systems undergoing AFC forward modeled with the Magma Chamber Simulator (MCS), which uses the phase modeling capabilities of MELTS (Ghiorso & Sack 1995) as the thermodynamic basis. Simulations begin with one of a variety of mafic magmas (e.g. HAB, MORB, AOB) intruding a set mass of Wall Rock (e.g. lherzolite, gabbro, diorite, granite, metapelite), and heat is exchanged as the M-WR system proceeds towards thermal equilibrium. Depending on initial conditions, the early part of the evolution can involve closed system FC while the WR heats up. The WR behaves as a closed system until it is heated beyond the solidus to critical limit for melt fraction extraction (fc), ranging between 0.08 and 0.12 depending on WR characteristics including composition and, rheology and stress field. Once fc is exceeded, a portion of the anatectic liquid is assimilated into the Magma. The MCS simultaneously calculates mass and composition of the mineral assemblage (Magma cumulates and WR residue) and melt (anatectic and Magma) at each T along the equilibration trajectory. Sensible and latent heat lost or gained plus mass gained by the Magma are accounted for by the MCS via governing Energy Constrained- Recharge Assimilation Fractional Crystallization (EC-RAFC) equations. In a comparison of two representative MCS results, consider a granitic WR intruded by HAB melt (51 wt. % SiO2) at liquidus T in shallow crust (0.1 GPa) with a WR/M ratio of 1.25, fc of 0.1 and a QFM oxygen buffer. In the first example, the WR begins at a temperature of 100o

  1. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries.

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-12-23

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn 4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g -1 based on solid-state redox reaction of oxide ions.

  2. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-01-01

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

  3. Evolution of silicic magmas in the Kos-Nisyros volcanic center, Greece: a petrological cycle associated with caldera collapse

    Science.gov (United States)

    Bachmann, Olivier; Deering, Chad D.; Ruprecht, Janina S.; Huber, Christian; Skopelitis, Alexandra; Schnyder, Cedric

    2012-01-01

    Multiple eruptions of silicic magma (dacite and rhyolites) occurred over the last ~3 My in the Kos-Nisyros volcanic center (eastern Aegean sea). During this period, magmas have changed from hornblende-biotite-rich units with low eruption temperatures (≤750-800°C; Kefalos and Kos dacites and rhyolites) to hotter, pyroxene-bearing units (>800-850°C; Nisyros rhyodacites) and are transitioning back to cooler magmas (Yali rhyolites). New whole-rock compositions, mineral chemistry, and zircon Hf isotopes show that these three types of silicic magmas followed the same differentiation trend: they all evolved by crystal fractionation and minor crustal assimilation (AFC) from parents with intermediate compositions characterized by high Sr/Y and low Nb content, following a wet, high oxygen fugacity liquid line of descent typical of subduction zones. As the transition between the Kos-Kefalos and Nisyros-type magmas occurred immediately and abruptly after the major caldera collapse in the area (the 161 ka Kos Plateau Tuff; KPT), we suggest that the efficient emptying of the magma chamber during the KPT drew out most of the eruptible, volatile-charged magma and partly solidified the unerupted mush zone in the upper crust due to rapid unloading, decompression, and coincident crystallization. Subsequently, the system reestablished a shallow silicic production zone from more mafic parents, recharged from the mid to lower crust. The first silicic eruptions evolving from these parents after the caldera collapse (Nisyros units) were hotter (up to >100°C) than the caldera-forming event and erupted from reservoirs characterized by different mineral proportions (more plagioclase and less amphibole). We interpret such a change as a reflection of slightly drier conditions in the magmatic column after the caldera collapse due to the decompression event. With time, the upper crustal intermediate mush progressively transitioned into the cold-wet state that prevailed during the Kefalos

  4. Bayesian estimation of magma supply, storage, and eruption rates using a multiphysical volcano model: Kīlauea Volcano, 2000-2012

    Science.gov (United States)

    Anderson, Kyle R.; Poland, Michael P.

    2016-08-01

    Estimating rates of magma supply to the world's volcanoes remains one of the most fundamental aims of volcanology. Yet, supply rates can be difficult to estimate even at well-monitored volcanoes, in part because observations are noisy and are usually considered independently rather than as part of a holistic system. In this work we demonstrate a technique for probabilistically estimating time-variable rates of magma supply to a volcano through probabilistic constraint on storage and eruption rates. This approach utilizes Bayesian joint inversion of diverse datasets using predictions from a multiphysical volcano model, and independent prior information derived from previous geophysical, geochemical, and geological studies. The solution to the inverse problem takes the form of a probability density function which takes into account uncertainties in observations and prior information, and which we sample using a Markov chain Monte Carlo algorithm. Applying the technique to Kīlauea Volcano, we develop a model which relates magma flow rates with deformation of the volcano's surface, sulfur dioxide emission rates, lava flow field volumes, and composition of the volcano's basaltic magma. This model accounts for effects and processes mostly neglected in previous supply rate estimates at Kīlauea, including magma compressibility, loss of sulfur to the hydrothermal system, and potential magma storage in the volcano's deep rift zones. We jointly invert data and prior information to estimate rates of supply, storage, and eruption during three recent quasi-steady-state periods at the volcano. Results shed new light on the time-variability of magma supply to Kīlauea, which we find to have increased by 35-100% between 2001 and 2006 (from 0.11-0.17 to 0.18-0.28 km3/yr), before subsequently decreasing to 0.08-0.12 km3/yr by 2012. Changes in supply rate directly impact hazard at the volcano, and were largely responsible for an increase in eruption rate of 60-150% between 2001 and

  5. Bayesian estimation of magma supply, storage, and eruption rates using a multiphysical volcano model: Kīlauea Volcano, 2000–2012

    Science.gov (United States)

    Anderson, Kyle R.; Poland, Michael

    2016-01-01

    Estimating rates of magma supply to the world's volcanoes remains one of the most fundamental aims of volcanology. Yet, supply rates can be difficult to estimate even at well-monitored volcanoes, in part because observations are noisy and are usually considered independently rather than as part of a holistic system. In this work we demonstrate a technique for probabilistically estimating time-variable rates of magma supply to a volcano through probabilistic constraint on storage and eruption rates. This approach utilizes Bayesian joint inversion of diverse datasets using predictions from a multiphysical volcano model, and independent prior information derived from previous geophysical, geochemical, and geological studies. The solution to the inverse problem takes the form of a probability density function which takes into account uncertainties in observations and prior information, and which we sample using a Markov chain Monte Carlo algorithm. Applying the technique to Kīlauea Volcano, we develop a model which relates magma flow rates with deformation of the volcano's surface, sulfur dioxide emission rates, lava flow field volumes, and composition of the volcano's basaltic magma. This model accounts for effects and processes mostly neglected in previous supply rate estimates at Kīlauea, including magma compressibility, loss of sulfur to the hydrothermal system, and potential magma storage in the volcano's deep rift zones. We jointly invert data and prior information to estimate rates of supply, storage, and eruption during three recent quasi-steady-state periods at the volcano. Results shed new light on the time-variability of magma supply to Kīlauea, which we find to have increased by 35–100% between 2001 and 2006 (from 0.11–0.17 to 0.18–0.28 km3/yr), before subsequently decreasing to 0.08–0.12 km3/yr by 2012. Changes in supply rate directly impact hazard at the volcano, and were largely responsible for an increase in eruption rate of 60–150% between

  6. Role of the oxidation state of cerium on the ceria surfaces for silicate adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Seo, Jihoon [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Moon, Jinok [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Clean/CMP Technology Team, Memory, Samsung Electronics, Hwaseong (Korea, Republic of); Kim, Joo Hyun; Lee, Kangchun [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Hwang, Junha [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Materials R& D Center, K.C.Tech, Anseong (Korea, Republic of); Yoon, Heesung [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of); Yi, Dong Kee, E-mail: vitalis@mju.ac.kr [Department of Chemistry, Myongji University, Yongin (Korea, Republic of); Paik, Ungyu, E-mail: upaik@hanyang.ac.kr [WCD Department of Energy Engineering, Hanyang University, Seoul (Korea, Republic of)

    2016-12-15

    Highlights: • We investigated the role of Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surfaces for the silicate adsorption. • As the Ce{sup 3+} concentration increased from 19.3 to 27.6%, the surface density of −OH group increased from 0.34 to 0.72 OH/nm{sup 2}. • The Freundlich constant for the relative adsorption capacity (K{sub F}) and adsorption intensity (1/n) indicated that CeO{sub 2} NPs with high Ce{sup 3+} concentration show higher adsorption affinity with silicate ions. - Abstract: In this study, we have investigated the role of the Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surfaces for silicate adsorption. In aqueous medium, the Ce{sup 3+} sites lead to the formation of −OH groups at the CeO{sub 2} surface through H{sub 2}O dissociation. Silicate ions can adsorb onto the CeO{sub 2} surface through interaction with the −OH groups (−Ce−OH− + −Si−O{sup −} ↔ −Ce−O−Si− + OH{sup −}). As the Ce{sup 3+} concentration increased from 19.3 to 27.6%, the surface density of −OH group increased from 0.34 to 0.72 OH/nm{sup 2}. To evaluate the adsorption behaviors of silicate ions onto CeO{sub 2} NPs, we carried out an adsorption isothermal analysis, and the adsorption isotherm data followed the Freundlich model. The Freundlich constant for the relative adsorption capacity (K{sub F}) and adsorption intensity (1/n) indicated that CeO{sub 2} NPs with high Ce{sup 3+} concentration show higher adsorption affinity with silicate ions. As a result, we have demonstrated that the Ce oxidation state (Ce{sup 3+}/Ce{sup 4+}) on the CeO{sub 2} surface can have a significant influence on the silicate adsorption.

  7. Electronic state of ruthenium deposited onto oxide supports: An XPS study taking into account the final state effects

    International Nuclear Information System (INIS)

    Larichev, Yurii V.; Moroz, Boris L.; Bukhtiyarov, Valerii I.

    2011-01-01

    The electronic state of ruthenium in the supported Ru/EO x (EO x = MgO, Al 2 O 3 or SiO 2 ) catalysts prepared by with the use of Ru(OH)Cl 3 or Ru(acac) 3 (acac = acetylacetonate) and reduced with H 2 at 723 K is characterized by X-ray photoelectron spectroscopy (XPS) in the Ru 3d, Cl 2p and O 1s regions. The influence of the final state effects (the differential charging and variation of the relaxation energy) on the binding energy (BE) of Ru 3d 5/2 core level measured for supported Ru nanoparticles is estimated by comparison of the Fermi levels and the modified Auger parameters determined for the Ru/EO x samples with the corresponding characteristics of the bulk Ru metal. It is found that the negative shift of the Ru 3d 5/2 peak which is observed in the spectrum of ruthenium deposited onto MgO (BE = 279.5-279.7 eV) with respect to that of Ru black (BE = 280.2 eV) or ruthenium supported on γ-Al 2 O 3 and SiO 2 (BE = 280.4 eV) is caused not by the transfer of electron density from basic sites of MgO, as considered earlier, but by the differential charging of the supported Ru particles compared with the support surface. Correction for the differential charging value reveals that the initial state energies of ruthenium in the Ru/EO x systems are almost identical (BE = 280.5 ± 0.1 eV) irrespectively of acid-base properties of the support, the mean size of supported Ru crystallites (within the range of 2-10 nm) and the surface Cl content. The results obtained suggest that the difference in ammonia synthesis activity between the Ru catalysts supported on MgO and on the acidic supports is accounted for by not different electronic state of ruthenium on the surface of these oxides but by some other reasons.

  8. Petrology of the 1995/2000 Magma of Copahue, Argentina

    Science.gov (United States)

    Goss, A.; Varekamp, J. C.

    2001-05-01

    Phreatomagmatic eruptions of Copahue in July/August,1995 and July/August 2000 produced mixed juvenile clasts, silica-rich debris from the hydrothermal system, and magmatic scoria with 88 percent SiO2. These high-SiO2 clasts carry an as yet unidentified (crystobalite?), euhedral silica phase in great abundance, which is riddled with tan, primary melt inclusions. The mixed clasts have bands of mafic material with small euhedral olivine, clinopyroxene, and plagioclase that are mixed with an intermediate magma with coarser, resorbed phenocrysts of olivine, plagioclase, clino- and ortho- pyroxene, and rare occurrences of the silica phase. These ejecta are intimate mixtures of a relatively felsic magma similar to Pleistocene Copahue lavas and a mafic basaltic andesite, with minor contributions of a magma contaminated with silica-rich hydrothermal wallrock material. Two-pyroxene geothermometry indicates crystallization temperatures of 1020 deg - 1045 deg C. Glass inclusions (59-63 percent SiO2) in plagioclase and olivine crystals yield very low volatile contents in the melt (0.4-1.5 percent H2O). The 1995/2000 magmas resided at shallow level and degassed into the active volcano-hydrothermal system which discharges acid fluids into the Copahue crater lake and hot springs. More mafic magma intruded this shallow batch and the mixture rose into the hydrothermal system and assimilated siliceous wall rock. A Ti-diffusion profile in a magnetite crystal suggests that the period between magma mixing and eruption was on the order of 4-10 weeks, and the temperature difference between resident and intruding magma was about 50-60 oC.

  9. Solid-state ionics: Studies of lithium-conducting sulfide glasses and a superconducting oxide compound

    International Nuclear Information System (INIS)

    Ahn, Byung Tae.

    1989-01-01

    The first part of this work studies lithium-conducting sulfide glasses for battery applications, while the second part studies the thermodynamic properties of a superconducting oxide compound by using an oxide electrolyte. Lithium conducting glasses based on the SiS 2 -Li 2 S system are possible solid electrolytes for high-energy-density lithium batteries. The foremost requirement for solid electrolytes is that they should have high ionic conductivities. Unfortunately, most crystalline lithium conductors have low ionic conductivities at room temperature. However, glass ionic conductors show higher ionic conductivities than do crystalline forms of the same material. In addition to higher ionic conductivities, glasses appear to have several advantages over crystalline materials. These advantages include isotropic conductivity, absence of grain boundary effects, ease of glass forming, and the potential for a wide range of stability to oxidizing and reducing conditions. Using pyrolitic graphite-coated quartz ampoules, new ternary compounds and glasses in the SiS 2 -Li 2 S system were prepared. Several techniques were used to characterize the materials: powder x-ray diffraction, differential thermal analysis, differential scanning calorimetry, and AC impedance spectroscopy. The measured lithium conductivity of the sulfide glasses was one of the highest among the known solid lithium conductors. Measuring the equilibrium open circuit voltages assisted in determining the electrochemical stabilities of the ternary compounds and glasses with respect to pure Li. A solid-state ionic technique called oxygen coulometric titration was used to measure the thermodynamic stability, the oxygen stoichiometry, and the effects of the oxygen stoichiometry, and the effects of the oxygen stoichiometry and the cooling rate on superconductivity of the YBa 2 Cu 3 O 7-x compound were investigated

  10. Effect of charge state and stoichiometry on the structure and reactivity of nickel oxide clusters with CO

    Science.gov (United States)

    Johnson, Grant E.; Reilly, Nelly M.; Castleman, A. W., Jr.

    2009-02-01

    The collision induced fragmentation and reactivity of cationic and anionic nickel oxide clusters with carbon monoxide were studied experimentally using guided-ion-beam mass spectrometry. Anionic clusters with a stoichiometry containing one more oxygen atom than nickel atom (NiO2-, Ni2O3-, Ni3O4- and Ni4O5-) were found to exhibit dominant products resulting from the transfer of a single oxygen atom to CO, suggesting the formation of CO2. Of these four species, Ni2O3- and Ni4O5- were observed to be the most reactive having oxygen transfer products accounting for approximately 5% and 10% of the total ion intensity at a maximum pressure of 15 mTorr of CO. Our findings, therefore, indicate that anionic nickel oxide clusters containing an even number of nickel atoms and an odd number of oxygen atoms are more reactive than those with an odd number of nickel atoms and an even number of oxygen atoms. The majority of cationic nickel oxides, in contrast to anionic species, reacted preferentially through the adsorption of CO onto the cluster accompanied by the loss of either molecular O2 or nickel oxide units. The adsorption of CO onto positively charged nickel oxides, therefore, is exothermic enough to break apart the gas-phase clusters. Collision induced dissociation experiments, employing inert xenon gas, were also conducted to gain insight into the structural properties of nickel oxide clusters. The fragmentation products were found to vary considerably with size and stoichiometry as well as ionic charge state. In general, cationic clusters favored the collisional loss of molecular O2 while anionic clusters fragmented through the loss of both atomic oxygen and nickel oxide units. Our results provide insight into the effect of ionic charge state on the structure of nickel oxide clusters. Furthermore, we establish how the size and stoichiometry of nickel oxide clusters influences their ability to oxidize CO, an important reaction for environmental pollution abatement.

  11. Magma storage conditions of historic Plinian eruptions of Volcán de Colima, México

    Science.gov (United States)

    Macias, J.; Arce, J.; Sosa, G.; Gardner, J. E.; Saucedo, R.

    2013-12-01

    Volcán de Colima has a historical record with major explosive eruptions occurring every ~100 years (1606, 1690, 1818, and 1913) followed by intra-Plinian effusive activity. The 1818 and 1913 Plinian eruptions erupted andesitic magmas (Pl > Opx > Cpx >> Hbl + Fe-Ti oxides + Ap and rare resorbed Ol) with homogeneous bulk compositions (1913; 58.3 × 0.5 wt.% SiO2, 1818; 58.9 × 0.2 wt.% SiO2; Saucedo et al., 2010). Instead, intra-Plinian magmas are devoid of hornblende and have compositions of 59-61 wt. % in silica (Savov et al., 2008). Pre-eruptive temperatures of oxide Fe-Ti pairs in 1818 and 1913 products yielded temperatures of 830×20°C colder than intra-Plinian magmas usually >970°C (Luhr et al., 2002) depending on the mineral phase analyzed. Amphibole in 1818 and 1913 products consists of two populations: a) large xenocrysts, with plag-px-Fe-Ti oxide rims with equilibrium pressures and temperatures of 380 MPa and 950 °C (Ridolfi et al., 2010), and b) microphenocryst with equilibrium pressures and temperatures of 190-280 MPa and 870-910 °C, respectively. Some phenocrysts in the 1818 magma have a high pressure core overgrowth by a low pressure rim. In order to understand the storage conditions of Colima explosive magmas we carried out a set of hydrothermal experiments with a 1818 pumice sample. Experiments were water oversaturated and close to the oxygen fugacity of the NNO buffer. Experiments show that amphibole is stable at pressures greater than 75 MPa at 850°C, and greater than 100 MPa at 925°C. For the same range of temperature, plagioclase is stable at pressures below ~210 MPa and 100 MPa, respectively. Experimental plagioclase and experimental glass were analyzed and compared to those from the natural sample, yielding an approximate storage pressure of 210 MPa. This pressure is confirmed by the chemical equilibrium of microphenocrystic amphibole of the natural sample. Given the nearly equivalent composition of the most recent Plinain magmas is

  12. Pre-eruptive conditions of dacitic magma erupted during the 21.7 ka Plinian event at Nevado de Toluca volcano, Central Mexico

    Science.gov (United States)

    Arce, J. L.; Gardner, J. E.; Macías, J. L.

    2013-01-01

    The Nevado de Toluca volcano in Central Mexico has been active over the last ca. 42 ka, during which tens of km3 of pyroclastic material were erupted and two important Plinian-type eruptions occurred at ca. 21.7 ka (Lower Toluca Pumice: LTP) and ca. 10.5 ka (Upper Toluca Pumice: UTP). Samples from both the LTP and UTP contain plagioclase, amphibole, iron-titanium oxides, and minor anhedral biotite, set in a vesicular, rhyolitic, glassy matrix. In addition, UTP dacites contain orthopyroxene. Analysis of melt inclusions in plagioclase phenocrysts yields H2O contents of 2-3.5 wt.% for LTP and 1.3-3.6 wt.% for UTP samples. Ilmenite-ulvospinel geothermometry yields an average temperature of ~ 868 °C for the LTP magma (hotter than the UTP magma, ~ 842 °C; Arce et al., 2006), whereas amphibole-plagioclase geothermometry yields a temperature of 825-859 °C for the LTP magma. Water-saturated experiments using LTP dacite suggest that: (i) amphibole is stable above 100 MPa and below 900 °C; (ii) plagioclase crystallizes below 250-100 MPa at temperatures of 850-900 °C; and (iii) pyroxene is stable only below pressures of 200-100 MPa and temperatures of 825-900 °C. Comparison of natural and experimental data suggests that the LTP dacitic magma was stored at 150-200 MPa (5.8-7.7 km below the volcano summit). No differences in pressure found between 21.7 ka and 10.5 ka suggest that these two magmas were stored at similar depths. Orthopyroxene produced in lower temperature LTP experiments is compositionally different to those found in UTP natural samples, suggesting that they originated in two different magma batches. Whole-rock chemistry, petrographic features, and mineral compositions suggest that magma mixing was responsible for the generation of the dacitic Plinian LTP eruption.

  13. Remote Sensing the Thermosphere's State Using Emissions From Carbon Dioxide and Nitric Oxide

    Science.gov (United States)

    Weimer, D. R.; Mlynczak, M. G.; Doornbos, E.

    2017-12-01

    Measurements of emissions from nitric oxide and carbon dioxide in the thermosphere have strong correlations with properties that are very useful to the determination of thermospheric densities. We have compared emissions measured with the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument on the Thermosphere Ionosphere Mesosphere Energetics and Dynamics (TIMED) satellite with neutral density measurements from the Challenging Mini-satellite Payload (CHAMP), the Gravity Recovery and Climate Experiment (GRACE), the Ocean Circulation Explorer (GOCE), and the three Swarm satellites, spanning a time period of over 15 years. It has been found that nitric oxide emissions match changes in the exospheric temperatures that have been derived from the densities through use of the Naval Reasearch Laboratory Mass Spectrometer, Incoherent Scatter Radar Extended Model (NRLMSISE-00) thermosphere model. Similarly, our results indicate that the carbon dioxide emissions have annual and semiannual oscillations that correlate with changes in the amount of oxygen in the thermosphere, also determined by use of the NRLMSISE-00 model. These annual and semi-annual variations are found to have irregular amplitudes and phases, which make them very difficult to accurately predict. Prediction of exospheric temperatures through the use of geomagnetic indices also tends to be inexact. Therefore, it would be possible and very useful to use measurements of the thermosphere's infrared emissions for real-time tracking of the thermosphere's state, so that more accurate calculations of the density may be obtained.

  14. Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Minh

    2006-07-31

    This report summarizes the work performed for Phase I (October 2001 - August 2006) under Cooperative Agreement DE-FC26-01NT41245 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled 'Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program'. The program focuses on the development of a low-cost, high-performance 3-to-10-kW solid oxide fuel cell (SOFC) system suitable for a broad spectrum of power-generation applications. During Phase I of the program significant progress has been made in the area of SOFC technology. A high-efficiency low-cost system was designed and supporting technology developed such as fuel processing, controls, thermal management, and power electronics. Phase I culminated in the successful demonstration of a prototype system that achieved a peak efficiency of 41%, a high-volume cost of $724/kW, a peak power of 5.4 kW, and a degradation rate of 1.8% per 500 hours. . An improved prototype system was designed, assembled, and delivered to DOE/NETL at the end of the program. This prototype achieved an extraordinary peak efficiency of 49.6%.

  15. Determination of oxidation state of iron in normal and pathologically altered human aortic valves

    Energy Technology Data Exchange (ETDEWEB)

    Czapla-Masztafiak, J. [Institute of Nuclear Physics PAN, Radzikowskiego 152, 31-342 Kraków (Poland); Lis, G.J.; Gajda, M.; Jasek, E. [Department of Histology, Jagiellonian University Medical College, Kopernika 7, 31-034 Kraków (Poland); Czubek, U. [Department of Coronary Disease, Jagiellonian University Medical College, John Paul II Hospital, Prądnicka 80, 31-202 Kraków (Poland); Bolechała, F. [Department of Forensic Medicine, Jagiellonian University Medical College, Grzegórzecka 16, 31-531 Kraków (Poland); Borca, C. [Swiss Light Source, Paul Scherrer Institute, 5232 Villigen PSI (Switzerland); Kwiatek, W.M. [Institute of Nuclear Physics PAN, Radzikowskiego 152, 31-342 Kraków (Poland)

    2015-12-01

    In order to investigate changes in chemical state of iron in normal and pathologically altered human aortic valves X-ray absorption spectroscopy was applied. Since Fe is suspected to play detrimental role in aortic valve stenosis pathogenesis the oxidation state of this element has been determined. The experimental material consisted of 10 μm sections of valves excised during routine surgery and from autopsies. The experiment was performed at the MicroXAS beamline of the SLS synchrotron facility in Villigen (Switzerland). The Fe K-edge XANES spectra obtained from tissue samples were carefully analyzed and compared with the spectra of reference compounds containing iron in various chemical structures. The analysis of absorption edge position and shape of the spectra revealed that both chemical forms of iron are presented in valve tissue but Fe{sup 3+} is the predominant form. Small shift of the absorption edge toward higher energy in the spectra from stenotic valve samples indicates higher content of the Fe{sup 3+} form in pathological tissue. Such a phenomenon suggests the role of Fenton reaction and reactive oxygen species in the etiology of aortic valve stenosis. The comparison of pre-edge regions of XANES spectra for control and stenotic valve tissue confirmed no differences in local symmetry or spin state of iron in analyzed samples.

  16. The effect of cerium valence states at cerium oxide nanoparticle surfaces on cell proliferation

    KAUST Repository

    Naganuma, Tamaki

    2014-05-01

    Understanding and controlling cell proliferation on biomaterial surfaces is critical for scaffold/artificial-niche design in tissue engineering. The mechanism by which underlying integrin ligates with functionalized biomaterials to induce cell proliferation is still not completely understood. In this study, poly-l-lactide (PL) scaffold surfaces were functionalized using layers of cerium oxide nanoparticles (CNPs), which have recently attracted attention for use in therapeutic application due to their catalytic ability of Ce4+ and Ce3+ sites. To isolate the influence of Ce valance states of CNPs on cell proliferation, human mesenchymal stem cells (hMSCs) and osteoblast-like cells (MG63) were cultured on the PL/CNP surfaces with dominant Ce4+ and Ce3+ regions. Despite cell type (hMSCs and MG63 cells), different surface features of Ce4+ and Ce3+ regions clearly promoted and inhibited cell spreading, migration and adhesion behavior, resulting in rapid and slow cell proliferation, respectively. Cell proliferation results of various modified CNPs with different surface charge and hydrophobicity/hydrophilicity, indicate that Ce valence states closely correlated with the specific cell morphologies and cell-material interactions that trigger cell proliferation. This finding suggests that the cell-material interactions, which influence cell proliferation, may be controlled by introduction of metal elements with different valence states onto the biomaterial surface. © 2014 Elsevier Ltd.

  17. Investigating the capability of ToF-SIMS to determine the oxidation state of Ce

    Science.gov (United States)

    Seed Ahmed, H. A. A.; Swart, H. C.; Kroon, R. E.

    2018-04-01

    The capability of time of flight secondary ion mass spectrometry (ToF-SIMS) to determine the oxidation state of Ce ions doped in a phosphor was investigated. Two samples of SiO2:Ce (4 mol%) with known Ce3+/Ce4+ relative concentrations were subjected to ToF-SIMS measurements. The spectra were very similar and no significant differences in the relative peak intensities were observed that would readily allow one to distinguish Ce3+ from Ce4+. Although ToF-SIMS was therefore not useful to distinguish the charge state of Ce ions doped in this phosphor material, the idea in principle was also tested on two other samples, namely CeF3 and CeF4 These contain Ce as part of the host (i.e. much higher concentration) and are fluorides, which is significant because ToF-SIMS has previously been reported to be able to distinguish Eu2+ from Eu3+ in Eu doped Sr5(PO4)3F phosphor. The spectrum of CeF4 contained a small peak related to Ce4+ which was not observed in the CeF3 spectrum, yet the peak related to the Ce3+ ions was found to be much more intense in the spectrum of CeF4 than CeF3, showing that the ToF-SIMS signals cannot be directly interpreted as retaining the charge state of the ions in the original material. Nevertheless, the significant differences in the Ce-related peaks in the ToF-SIMS spectra from CeF3 and CeF4 show that the charge state of Ce may be distinguished. This study shows that while in principle ToF-SIMS may be used to distinguish the charge state of Ce ions, this depends on the sample and it would not be easy to interpret the spectra without a standard or reference.

  18. Coherent diffractive imaging of solid state reactions in zinc oxide crystals

    Science.gov (United States)

    Leake, Steven J.; Harder, Ross; Robinson, Ian K.

    2011-11-01

    We investigated the doping of zinc oxide (ZnO) microcrystals with iron and nickel via in situ coherent x-ray diffractive imaging (CXDI) in vacuum. Evaporated thin metal films were deposited onto the ZnO microcrystals. A single crystal was selected and tracked through annealing cycles. A solid state reaction was observed in both iron and nickel experiments using CXDI. A combination of the shrink wrap and guided hybrid-input-output phasing methods were applied to retrieve the electron density. The resolution was 33 nm (half order) determined via the phase retrieval transfer function. The resulting images are nevertheless sensitive to sub-angstrom displacements. The exterior of the microcrystal was found to degrade dramatically. The annealing of ZnO microcrystals coated with metal thin films proved an unsuitable doping method. In addition the observed defect structure of one crystal was attributed to the presence of an array of defects and was found to change upon annealing.

  19. Oxidation-state distribution of plutonium in surface and subsurface waters at Thule, northwest Greenland

    DEFF Research Database (Denmark)

    McMahon, C.A.; Vintró, L.L.; Mitchell, P.I.

    2000-01-01

    (V, VI) (mean, 68 +/- 6%; n = 6), with little if any distinction apparent between surface and bottom waters. Further, the oxidation state distribution at stations close to the accident site is similar to that measured at Upernavik, remote from this site. It is also similar to the distribution observed...... in shelf waters at midlatitudes, suggesting that the underlying processes controlling plutonium speciation are insensitive to temperature over the range 0-25 degrees C. Measurements using tangential-flow ultrafiltration indicate that virtually all of the plutonium (including the fraction in a reduced...... chemical form) is present as fully dissolved species. Most of this plutonium would seem to be of weapons fallout origin, as the mean Pu-238/Pu-239,Pu-240 activity ratio in the water column (dissolved phase) at Thule (0.06 +/- 0.02; n = 10) is similar to the global fallout ratio at this latitude...

  20. State-of-the-art technologies of gallium oxide power devices

    Science.gov (United States)

    Higashiwaki, Masataka; Kuramata, Akito; Murakami, Hisashi; Kumagai, Yoshinao

    2017-08-01

    Gallium oxide (Ga2 O3 ) has gained increased attention for power devices due to its superior material properties and the availability of economical device-quality native substrates. This review illustrates recent advances in Ga2 O3 device technologies, beginning with an overview of the social circumstances that motivate the development of new-generation switching devices. Following an introduction to the material properties of Ga2 O3 from the viewpoint of power electronics, growth technologies of Ga2 O3 bulk single crystals and epitaxial thin films are discussed. The fabrication and performance of state-of-the-art Ga2 O3 transistors and diodes are then described. We conclude by identifying the directions and challenges of Ga2 O3 power device development in the near future.

  1. Coordination and Oxidation States of Iron Incorporated in Mesoporous MCM41

    International Nuclear Information System (INIS)

    Lazar, K.; Pal-Borbely, G.; Szegedi, A.; Beyer, H. K.

    2002-01-01

    Mesoporous Fe-MCM41 samples (Si/Fe=25) were synthesized and characterized under evacuation and reducing/oxidizing treatments by in situ FTIR and Moessbauer spectroscopies. Both Fe(II) and Fe(III) located in low coordination states in top layers of pore walls exhibit Lewis acidity and may participate in Fe(III) ↔ Fe(II) processes at low temperatures (570 K). Furthermore, Fe(III) ↔ Fe(II) cycles can be achieved and repeated with participation of the full amount of iron at higher temperatures (670 K). The accompanying formation of oxygen vacancies and restoration of the structure in the reverse process does not result in extended damages; the MCM41 structure retains its stability under the conditions applied.

  2. Carbon dioxide in magmas and implications for hydrothermal systems

    Science.gov (United States)

    Lowenstern, J. B.

    2001-01-01

    This review focuses on the solubility, origin, abundance, and degassing of carbon dioxide (CO2) in magma-hydrothermal systems, with applications for those workers interested in intrusion-related deposits of gold and other metals. The solubility of CO2 increases with pressure and magma alkalinity. Its solubility is low relative to that of H2O, so that fluids exsolved deep in the crust tend to have high CO2/H2O compared with fluids evolved closer to the surface. Similarly, CO2/H2O will typically decrease during progressive decompression- or crystallization-induced degassing. The temperature dependence of solubility is a function of the speciation of CO2, which dissolves in molecular form in rhyolites (retrograde temperature solubility), but exists as dissolved carbonate groups in basalts (prograde). Magnesite and dolomite are stable under a relatively wide range of mantle conditions, but melt just above the solidus, thereby contributing CO2 to mantle magmas. Graphite, diamond, and a free CO2-bearing fluid may be the primary carbon-bearing phases in other mantle source regions. Growing evidence suggests that most CO2 is contributed to arc magmas via recycling of subducted oceanic crust and its overlying sediment blanket. Additional carbon can be added to magmas during magma-wallrock interactions in the crust. Studies of fluid and melt inclusions from intrusive and extrusive igneous rocks yield ample evidence that many magmas are vapor saturated as deep as the mid crust (10-15 km) and that CO2 is an appreciable part of the exsolved vapor. Such is the case in both basaltic and some silicic magmas. Under most conditions, the presence of a CO2-bearing vapor does not hinder, and in fact may promote, the ascent and eruption of the host magma. Carbonic fluids are poorly miscible with aqueous fluids, particularly at high temperature and low pressure, so that the presence of CO2 can induce immiscibility both within the magmatic volatile phase and in hydrothermal systems

  3. On the Role of Mantle Overturn during Magma Ocean Solidification

    Science.gov (United States)

    Boukaré, C. E.; Parmentier, E.; Parman, S. W.

    2017-12-01

    Solidification of potential global magma ocean(s) (MO) early in the history of terrestrial planets may play a key role in the evolution of planetary interiors by setting initial conditions for their long-term evolution. Constraining this initial structure of solid mantles is thus crucial but remains poorly understood. MO fractional crystallization has been proposed to generate gravitationally unstable Fe-Mg chemical stratification capable of driving solid-state mantle overturn. Fractional solidification and overturn hypothesis, while only an ideal limiting case, can explain important geochemical features of both the Moon and Mars. Current overturn models consider generally post-MO overturn where the cumulate pile remains immobile until the end of MO solidification. However, if the cumulate pile overturns during MO solidification, the general picture of early planet evolution might differ significantly from the static crystallization models. We show that the timing of mantle overturn can be characterized with a dimensionless number measuring the ratio of the MO solidification time and the purely compositional overturn timescale. Syn-solidification overturn occurs if this dimensionless parameter, Rc, exceeds a critical value. Rc is mostly affected by the competition between the MO solidification time and mantle viscosity. Overturn that occurs during solidification can result in smaller scales of mantle chemical heterogeneity that could persist for long times thus influencing the whole evolution of a planetary body. We will discuss the effects of compaction/percolation on mantle viscosity. If partially molten cumulate do not have time to compact during MO solidification, viscosity of cumulates would be significantly lower as the interstitcial melt fraction would be large. Both solid mantle remelting during syn-solidification overturn and porous convection of melt retained with the cumulates are expected to reduce the degree of fractional crystallization. Syn

  4. Magma Transport from Deep to Shallow Crust and Eruption

    Science.gov (United States)

    White, R. S.; Greenfield, T. S.; Green, R. G.; Brandsdottir, B.; Hudson, T.; Woods, J.; Donaldson, C.; Ágústsdóttir, T.

    2016-12-01

    We have mapped magma transport paths from the deep (20 km) to the shallow (6 km) crust and in two cases to eventual surface eruption under several Icelandic volcanoes (Askja, Bardarbunga, Eyjafjallajokull, Upptyppingar). We use microearthquakes caused by brittle fracture to map magma on the move and tomographic seismic studies of velocity perturbations beneath volcanoes to map the magma storage regions. High-frequency brittle failure earthquakes with magnitudes of typically 0-2 occur where melt is forcing its way through the country rock, or where previously frozen melt is repeatedly re-broken in conduits and dykes. The Icelandic crust on the rift zones where these earthquakes occur is ductile at depths greater than 7 km beneath the surface, so the occurrence of brittle failure seismicity at depths as great as 20 km is indicative of high strain rates, for which magma movement is the most likely explanation. We suggest that high volatile pressures caused by the exsolution of carbon dioxide in the deep crust is driving the magma movement and seismicity at depths of 15-20 km. Eruptions from shallow crustal storage areas are likewise driven by volatile exsolution, though additional volatiles, and in particular water are also involved in the shallow crust.

  5. The role of magma mixing/mingling and cumulate melting in the Neapolitan Yellow Tuff caldera-forming eruption (Campi Flegrei, Southern Italy)

    Science.gov (United States)

    Forni, Francesca; Petricca, Eleonora; Bachmann, Olivier; Mollo, Silvio; De Astis, Gianfilippo; Piochi, Monica

    2018-06-01

    Understanding the mechanisms responsible for the generation of chemical gradients in high-volume ignimbrites is key to retrieve information on the processes that control the maturation and eruption of large silicic magmatic reservoirs. Over the last 60 ky, two large ignimbrites showing remarkable zoning were emplaced during caldera-forming eruptions at Campi Flegrei (i.e., Campanian Ignimbrite, CI, 39 ka and Neapolitan Yellow Tuff, NYT, 15 ka). While the CI displays linear compositional, thermal and crystallinity gradients, the NYT is a more complex ignimbrite characterized by crystal-poor magmas ranging in composition from trachy-andesites to phonolites. By combining major and trace element compositions of matrix glasses and mineral phases from juvenile clasts located at different stratigraphic heights along the NYT pyroclastic sequence, we interpret such compositional gradients as the result of mixing/mingling between three different magmas: (1) a resident evolved magma showing geochemical characteristics of a melt extracted from a cumulate mush dominated by clinopyroxene, plagioclase and oxides with minor sanidine and biotite; (2) a hotter and more mafic magma from recharge providing high-An plagioclase and high-Mg clinopyroxene crystals and (3) a compositionally intermediate magma derived from remelting of low temperature mineral phases (i.e., sanidine and biotite) within the cumulate crystal mush. We suggest that the presence of a refractory crystal mush, as documented by the occurrence of abundant crystal clots containing clinopyroxene, plagioclase and oxides, is the main reason for the lack of erupted crystal-rich material in the NYT. A comparison between the NYT and the CI, characterized by both crystal-poor extracted melts and crystal-rich magmas representing remobilized portions of a "mature" (i.e., sanidine dominated) cumulate residue, allows evaluation of the capability of crystal mushes of becoming eruptible upon recharge.

  6. In defense of Magnetite-Ilmenite Thermometry in the Bishop Tuff and its implication for gradients in silicic magma reservoirs

    Science.gov (United States)

    Evans, Bernard W; Hildreth, Edward; Bachmann, Olivier; Scaillet, Bruno

    2016-01-01

    Despite claims to the contrary, the compositions of magnetite and ilmenite in the Bishop Tuff correctly record the changing conditions of T and fO2 in the magma reservoir. In relatively reduced (∆NNO magmas (e.g., Bishop Tuff, Taupo units), Ti behaves compatibly (DTi ≈ 2-3.5), leading to a decrease in TiO2 activity in the melt with cooling and fractionation. In contrast, FeTi-oxides are poorer in TiO2 in more oxidized magmas (∆NNO > 1, e.g., Fish Canyon Tuff, Pinatubo), and the d(aTiO2)/dT slope can be negative. Biotite, FeTi-oxides, liquid, and possibly plagioclase largely maintained equilibrium in the Bishop Tuff magma (unlike the pyroxenes, and cores of quartz, sanidine, and zircon) prior ro and during a mixing event triggered by a deeper recharge, which, based on elemental diffusion profiles in minerals, took place at least several decades before eruption. Equilibrating phases and pumice compositions show evolving chemical variations that correlate well with mutually consistent temperatures based on the FeTi-oxides, sanidine-plagioclase, and ∆18O quartz-magnetite pairs. Early Bishop Tuff (EBT) temperatures are lower (700 to ~780‎°C) than temperatures (780 to >820°C) registered in Late Bishop Tuff (LBT), the latter defined here not strictly stratigraphically, but by the presence of orthopyroxene and reverse-zoned rims on quartz and sanidine. The claimed similarity in compositions, Zr-saturation temperatures and thermodynamically calculated temperatures (730-740°C) between EBT and less evolved LBT reflect the use of glass inclusions in quartz cores in LBT that were inherited from the low temperature rhyolitic part of the reservoir characteristic of the EBT. LBT temperatures as high as 820°C, the preservation of orthopyroxene, and the presence of reverse-zoned minerals (quartz, sanidine, zircons) are consistent with magma recharge at the base of the zoned reservoir, heating the cooler rhyolitic melt, partly remelting cumulate mush, and introducing

  7. Ultrathin reduced graphene oxide films as transparent top-contacts for light switchable solid-state molecular junctions

    DEFF Research Database (Denmark)

    Li, Tao; Jevric, Martyn; Hauptmann, Jonas Rahlf

    2013-01-01

    A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules. The electr......A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules...

  8. Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, K.D.; Sposito, G.

    2010-02-01

    Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

  9. Fault-magma interactions during early continental rifting: Seismicity of the Magadi-Natron-Manyara basins, Africa

    Science.gov (United States)

    Weinstein, A.; Oliva, S. J.; Ebinger, C. J.; Roecker, S.; Tiberi, C.; Aman, M.; Lambert, C.; Witkin, E.; Albaric, J.; Gautier, S.; Peyrat, S.; Muirhead, J. D.; Muzuka, A. N. N.; Mulibo, G.; Kianji, G.; Ferdinand-Wambura, R.; Msabi, M.; Rodzianko, A.; Hadfield, R.; Illsley-Kemp, F.; Fischer, T. P.

    2017-10-01

    Although magmatism may occur during the earliest stages of continental rifting, its role in strain accommodation remains weakly constrained by largely 2-D studies. We analyze seismicity data from a 13 month, 39-station broadband seismic array to determine the role of magma intrusion on state-of-stress and strain localization, and their along-strike variations. Precise earthquake locations using cluster analyses and a new 3-D velocity model reveal lower crustal earthquakes beneath the central basins and along projections of steep border faults that degas CO2. Seismicity forms several disks interpreted as sills at 6-10 km below a monogenetic cone field. The sills overlie a lower crustal magma chamber that may feed eruptions at Oldoinyo Lengai volcano. After determining a new ML scaling relation, we determine a b-value of 0.87 ± 0.03. Focal mechanisms for 65 earthquakes, and 13 from a catalogue prior to our array reveal an along-axis stress rotation of ˜60° in the magmatically active zone. New and prior mechanisms show predominantly normal slip along steep nodal planes, with extension directions ˜N90°E north and south of an active volcanic chain consistent with geodetic data, and ˜N150°E in the volcanic chain. The stress rotation facilitates strain transfer from border fault systems, the locus of early-stage deformation, to the zone of magma intrusion in the central rift. Our seismic, structural, and geochemistry results indicate that frequent lower crustal earthquakes are promoted by elevated pore pressures from volatile degassing along border faults, and hydraulic fracture around the margins of magma bodies. Results indicate that earthquakes are largely driven by stress state around inflating magma bodies.

  10. Fault-Magma Interactions during Early Continental Rifting: Seismicity of the Magadi-Natron-Manyara basins, Africa

    Science.gov (United States)

    Weinstein, A.; Oliva, S. J.; Ebinger, C.; Aman, M.; Lambert, C.; Roecker, S. W.; Tiberi, C.; Muirhead, J.

    2017-12-01

    Although magmatism may occur during the earliest stages of continental rifting, its role in strain accommodation remains weakly constrained by largely 2D studies. We analyze seismicity data from a 13-month, 39-station broadband seismic array to determine the role of magma intrusion on state-of-stress and strain localization, and their along-strike variations. Precise earthquake locations using cluster analyses and a new 3D velocity model reveal lower crustal earthquakes along projections of steep border faults that degas CO2. Seismicity forms several disks interpreted as sills at 6-10 km below a monogenetic cone field. The sills overlie a lower crustal magma chamber that may feed eruptions at Oldoinyo Lengai volcano. After determining a new ML scaling relation, we determine a b-value of 0.87 ± 0.03. Focal mechanisms for 66 earthquakes, and a longer time period of relocated earthquakes from global arrays reveal an along-axis stress rotation of 50 o ( N150 oE) in the magmatically active zone. Using Kostrov summation of local and teleseismic mechanisms, we find opening directions of N122ºE and N92ºE north and south of the magmatically active zone. The stress rotation facilitates strain transfer from border fault systems, the locus of early stage deformation, to the zone of magma intrusion in the central rift. Our seismic, structural, and geochemistry results indicate that frequent lower crustal earthquakes are promoted by elevated pore pressures from volatile degassing along border faults, and hydraulic fracture around the margins of magma bodies. Earthquakes are largely driven by stress state around inflating magma bodies, and more dike intrusions with surface faulting, eruptions, and earthquakes are expected.

  11. Linking rapid magma reservoir assembly and eruption trigger mechanisms at evolved Yellowstone-type supervolcanoes

    Science.gov (United States)

    Wotzlaw, J.F.; Bindeman, I.N.; Watts, Kathryn E.; Schmitt, A.K.; Caricchi, L.; Schaltegger, U.

    2014-01-01

    The geological record contains evidence of volcanic eruptions that were as much as two orders of magnitude larger than the most voluminous eruption experienced by modern civilizations, the A.D. 1815 Tambora (Indonesia) eruption. Perhaps nowhere on Earth are deposits of such supereruptions more prominent than in the Snake River Plain–Yellowstone Plateau (SRP-YP) volcanic province (northwest United States). While magmatic activity at Yellowstone is still ongoing, the Heise volcanic field in eastern Idaho represents the youngest complete caldera cycle in the SRP-YP, and thus is particularly instructive for current and future volcanic activity at Yellowstone. The Heise caldera cycle culminated 4.5 Ma ago in the eruption of the ∼1800 km3 Kilgore Tuff. Accessory zircons in the Kilgore Tuff display significant intercrystalline and intracrystalline oxygen isotopic heterogeneity, and the vast majority are 18O depleted. This suggests that zircons crystallized from isotopically distinct magma batches that were generated by remelting of subcaldera silicic rocks previously altered by low-δ18O meteoric-hydrothermal fluids. Prior to eruption these magma batches were assembled and homogenized into a single voluminous reservoir. U-Pb geochronology of isotopically diverse zircons using chemical abrasion–isotope dilution–thermal ionization mass spectrometry yielded indistinguishable crystallization ages with a weighted mean 206Pb/238U date of 4.4876 ± 0.0023 Ma (MSWD = 1.5; n = 24). These zircon crystallization ages are also indistinguishable from the sanidine 40Ar/39Ar dates, and thus zircons crystallized close to eruption. This requires that shallow crustal melting, assembly of isolated batches into a supervolcanic magma reservoir, homogenization, and eruption occurred extremely rapidly, within the resolution of our geochronology (103–104 yr). The crystal-scale image of the reservoir configuration, with several isolated magma batches, is very similar to the

  12. Magma storage in a strike-slip caldera.

    Science.gov (United States)

    Saxby, J; Gottsmann, J; Cashman, K; Gutiérrez, E

    2016-07-22

    Silicic calderas form during explosive volcanic eruptions when magma withdrawal triggers collapse along bounding faults. The nature of specific interactions between magmatism and tectonism in caldera-forming systems is, however, unclear. Regional stress patterns may control the location and geometry of magma reservoirs, which in turn may control the spatial and temporal development of faults. Here we provide new insight into strike-slip volcano-tectonic relations by analysing Bouguer gravity data from Ilopango caldera, El Salvador, which has a long history of catastrophic explosive eruptions. The observed low gravity beneath the caldera is aligned along the principal horizontal stress orientations of the El Salvador Fault Zone. Data inversion shows that the causative low-density structure extends to ca. 6 km depth, which we interpret as a shallow plumbing system comprising a fractured hydrothermal reservoir overlying a magmatic reservoir with vol% exsolved vapour. Fault-controlled localization of magma constrains potential vent locations for future eruptions.

  13. What can Fe stable isotopes tell us about magmas?

    DEFF Research Database (Denmark)

    Stausberg, Niklas

    the differentiation of magmas from the perspective of Fe stable isotopes, integrated with petrology, by studying igneous rocks and their constituent phases (minerals and glasses) from the Bushveld Complex, South Africa, Thingmuli, Iceland, Pantelleria, Italy, and the Bishop Tuff, USA. The findings are interpreted......The majority of the Earth’s crust is formed by magmas, and understanding their production and differentiation is important to interpret the geologic rock record. A powerful tool to investigate magmatic processes is the distribution of the stable isotopes of the major redox-sensitive element...... in magmas, Fe. Fe isotope compositions of magmatic rocks exhibit systematic differences, where the heaviest compositions are found in rhyolites and granites. Understanding of these systematics is complicated by a lack of constraints on Fe isotope fractionation among minerals and liquids under magmatic...

  14. The magma ocean as an impediment to lunar plate tectonics

    Science.gov (United States)

    Warren, Paul H.

    1993-01-01

    The primary impediment to plate tectonics on the moon was probably the great thickness of its crust and particularly its high crust/lithosphere thickness ratio. This in turn can be attributed to the preponderance of low-density feldspar over all other Al-compatible phases in the lunar interior. During the magma ocean epoch, the moon's crust/lithosphere thickness ratio was at the maximum theoretical value, approximately 1, and it remained high for a long time afterwards. A few large regions of thin crust were produced by basin-scale cratering approximately contemporaneous with the demise of the magma ocean. However, these regions probably also tend to have uncommonly thin lithosphere, since they were directly heated and indirectly enriched in K, Th, and U by the same cratering process. Thus, plate tectonics on the moon in the form of systematic lithosphere subduction was impeded by the magma ocean.

  15. Phenomena associated with magma expansion into a drift

    International Nuclear Information System (INIS)

    Gaffney, E.S.

    2002-01-01

    One of the significant threats to the proposed Yucca Mountain nuclear waste repository has been identified as the possibility of intersection of the underground structure by a basaltic intrusion. Based on the geology of the region, it is assumed that such an intrusion would consist of an alkali basalt similar to the nearby Lathrop Wells cone, which has been dated at about 78 ka. The threat of radioactive release may be either from eruption through the surface above the repository of basalt that had been contaminated or from migration through ground water of radionucleides released as a result of damage to waste packages that interact with the magma. As part of our study of these threats, we are analyzing the phenomena associated with magma expansion into drifts in tuff. The early phenomena of the encounter of volatile-rich basaltic magma with a drift are discussed here.

  16. Complexities in Shallow Magma Transport at Kilauea (Invited)

    Science.gov (United States)

    Swanson, D. A.

    2013-12-01

    The standard model of Kilauea's shallow plumbing system includes magma storage under the caldera and conduits in the southwest rift zone (SWRZ) and the east rift zone (ERZ). As a field geologist, I find that seemingly aberrant locations and trends of some eruptive vents indicate complexities in shallow magma transport not addressed by the standard model. This model is not wrong but instead incomplete, because it does not account for the development of offshoots from the main plumbing. These offshoots supply magma to the surface at places that tell us much about the complicated stress system within the volcano. Perhaps most readily grasped are fissures peripheral to the north and south sides of the caldera. Somehow magma can apparently be injected into caldera-bounding faults from the summit reservoir complex, but the process and pathways are unclear. Of more importance is the presence of fissures with ENE trends on the east side of the caldera, including Kilauea Iki. Is this a rift zone that forms an acute angle with the ERZ? I think there is another explanation: the main part of the ERZ has migrated ~5 km SSE during the past few tens of thousands of years owing to seaward movement of the south flank, but older parts of the rift zone can be reactivated. The fissures east of the caldera have the ERZ trend and may record such reactivation; this interpretation includes the location of the largest eruption (15th century) known from Kilauea. Whether or not this interpretation has validity, the question remains: what changes in the plumbing system allow magma to erupt east of the caldera? The SWRZ can be divided into two sections, the SWRZ proper and the seismically active part (SASWRZ) southeast of the SWRZ. The total width of both sections is ~4 km. The SWRZ might be migrating SSE, as is the ERZ. Fissures in the SWRZ proper trend SW. Fissures in the SASWRZ, however, have ENE trends like that of the ERZ, although, because of en echelon offsets, the fissure zone itself

  17. Solid state oxidation of phenols to quinones with sodium perborate on wet montmorillonite K10

    Energy Technology Data Exchange (ETDEWEB)

    Hashemi, Mohammed M.; Eftekhari-Sis, Bagher; Khalili, Behzad; Karimi-Jaberi, Zahed [Sharif University of Technology, Tehran (Iran, Islamic Republic of). Dept. of Chemistry]. E-mail: mhashemi@sharif.edu

    2005-09-15

    Phenols were oxidized to quinones using sodium perborate (SPB) on wet montmorillonite as oxidant. The reaction was carried out at ambient temperature on the solid phase under solvent free conditions. (author)

  18. Solid state oxidation of phenols to quinones with sodium perborate on wet montmorillonite K10

    International Nuclear Information System (INIS)

    Hashemi, Mohammed M.; Eftekhari-Sis, Bagher; Khalili, Behzad; Karimi-Jaberi, Zahed

    2005-01-01

    Phenols were oxidized to quinones using sodium perborate (SPB) on wet montmorillonite as oxidant. The reaction was carried out at ambient temperature on the solid phase under solvent free conditions. (author)

  19. Lunar Magma Ocean Crystallization: Constraints from Fractional Crystallization Experiments

    Science.gov (United States)

    Rapp, J. F.; Draper, D. S.

    2015-01-01

    The currently accepted paradigm of lunar formation is that of accretion from the ejecta of a giant impact, followed by crystallization of a global scale magma ocean. This model accounts for the formation of the anorthosite highlands crust, which is globally distributed and old, and the formation of the younger mare basalts which are derived from a source region that has experienced plagioclase extraction. Several attempts at modelling the crystallization of such a lunar magma ocean (LMO) have been made, but our ever-increasing knowledge of the lunar samples and surface have raised as many questions as these models have answered. Geodynamic models of lunar accretion suggest that shortly following accretion the bulk of the lunar mass was hot, likely at least above the solidus]. Models of LMO crystallization that assume a deep magma ocean are therefore geodynamically favorable, but they have been difficult to reconcile with a thick plagioclase-rich crust. A refractory element enriched bulk composition, a shallow magma ocean, or a combination of the two have been suggested as a way to produce enough plagioclase to account for the assumed thickness of the crust. Recently however, geophysical data from the GRAIL mission have indicated that the lunar anorthositic crust is not as thick as was initially estimated, which allows for both a deeper magma ocean and a bulk composition more similar to the terrestrial upper mantle. We report on experimental simulations of the fractional crystallization of a deep (approximately 100km) LMO with a terrestrial upper mantle-like (LPUM) bulk composition. Our experimental results will help to define the composition of the lunar crust and mantle cumulates, and allow us to consider important questions such as source regions of the mare basalts and Mg-suite, the role of mantle overturn after magma ocean crystallization and the nature of KREEP

  20. Failed magmatic eruptions: Late-stage cessation of magma ascent

    Science.gov (United States)

    Moran, S.C.; Newhall, C.; Roman, D.C.

    2011-01-01

    When a volcano becomes restless, a primary question is whether the unrest will lead to an eruption. Here we recognize four possible outcomes of a magmatic intrusion: "deep intrusion", "shallow intrusion", "sluggish/viscous magmatic eruption", and "rapid, often explosive magmatic eruption". We define "failed eruptions" as instances in which magma reaches but does not pass the "shallow intrusion" stage, i. e., when magma gets close to, but does not reach, the surface. Competing factors act to promote or hinder the eventual eruption of a magma intrusion. Fresh intrusion from depth, high magma gas content, rapid ascent rates that leave little time for enroute degassing, opening of pathways, and sudden decompression near the surface all act to promote eruption, whereas decreased magma supply from depth, slow ascent, significant enroute degassing and associated increases in viscosity, and impingement on structural barriers all act to hinder eruption. All of these factors interact in complex ways with variable results, but often cause magma to stall at some depth before reaching the surface. Although certain precursory phenomena, such as rapidly escalating seismic swarms or rates of degassing or deformation, are good indicators that an eruption is likely, such phenomena have also been observed in association with intrusions that have ultimately failed to erupt. A perpetual difficulty with quantifying the probability of eruption is a lack of data, particularly on instances of failed eruptions. This difficulty is being addressed in part through the WOVOdat database. Papers in this volume will be an additional resource for scientists grappling with the issue of whether or not an episode of unrest will lead to a magmatic eruption.

  1. Orientation of the eruption fissures controlled by a shallow magma chamber in Miyakejima

    Directory of Open Access Journals (Sweden)

    Nobuo Geshi

    2016-11-01

    Full Text Available Orientation of the eruption fissures and composition of the lavas of the Miyakejima volcano indicate tectonic influence of a shallow magma chamber on the distribution of eruption fissures. We examined the distributions and magmatic compositions of 23 fissures that formed within the last 2800 years, based on a field survey and a new dataset of 14C ages. The dominant orientation of the eruption fissures in the central portion of the volcano was found to be NE-SW, which is perpendicular to the direction of regional maximum horizontal compressive stress (σHmax. Magmas that show evidences of magma mixing between basaltic and andesitic magmas erupted mainly from the eruption fissures with a higher offset angle from the regional σHmax direction. The presence of a shallow dike-shaped magma chamber controls the distribution of the eruption fissures. The injection of basaltic magma into the shallow andesitic magma chamber caused the temporal rise of internal magmatic pressure in the shallow magma chamber. Dikes extending from the andesitic magma chamber intrude along the local compressive stress field which is generated by the internal excess pressure of the andesitic magma chamber. As the result, the eruption fissures trend parallel to the elongation direction of the shallow magma chamber. Injection of basaltic magma into the shallow andesitic magma chamber caused the magma mixing. Some basaltic dikes from the deep-seated magma chamber reach the ground surface without intersection with the andesitic magma chamber. The patterns of the eruption fissures can be modified in the future as was observed in the case of the destruction of the shallow magma chamber during the 2000 AD eruption.

  2. Oxidation of an aluminium-magnesium alloy in liquid state. Methodology of determination of mechanisms from not necessarily repeatable experiments

    International Nuclear Information System (INIS)

    Surla, Karine

    1998-01-01

    This research thesis reports the study of the oxidation of an aluminium-5 pc magnesium alloy in its liquid state in an oxygen environment, using thermogravimetric analysis and that of magnesium in its solid state. In a first part, the author reports a thermodynamic and bibliographical study on magnesium transformation in its solid state (Mg/O 2 and Mg/H 2 O systems, transformation with dry and humid synthetic air, oxidation inhibitors) and on Al-Mg alloy transformation in presence of oxygen (thermodynamic properties of aluminium-rich Al-Mg alloys, Al-Mg/O 2 /N 2 and Al-Mg/O 2 /N 2 /H 2 O systems). The next parts address the selection of reaction systems for the different cases (oxidation of solid magnesium in oxygen, oxidation of the Al-Mg alloy in oxygen), the modelling of the formation of magnesia from solid magnesium and from the Al-Mg alloy, and the modelling of the liquid Al-Mg A5182 alloy oxidation in oxygen [fr

  3. Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states

    Science.gov (United States)

    Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W.; Edmondson, Steve; Malmström, Eva

    2016-08-01

    We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been

  4. Isotopic evidence for multiple contributions to felsic magma chambers

    DEFF Research Database (Denmark)

    Waight, Tod Earle; Wiebe, R.A.; Krogstad, E.J.

    2007-01-01

    The Gouldsboro Granite forms part of the Coastal Maine Magmatic Province, a region characterized by granitic plutons that are intimately linked temporally and petrogenetically with abundant co-existing mafic magmas. The pluton is complex and preserves a felsic magma chamber underlain...... with identical isotopic compositions to more mafic dikes suggest that closed system fractionation may be occurring in deeper level chambers prior to injection to shallower levels. The granitic portion of the pluton has the highest Nd isotopic composition (eNd=+3.0) of plutons in the region whereas the mafic...

  5. Silicic magma differentiation in ascent conduits. Experimental constraints

    Science.gov (United States)

    Rodríguez, Carmen; Castro, Antonio

    2017-02-01

    Crystallization of water-bearing silicic magmas in a dynamic thermal boundary layer is reproduced experimentally by using the intrinsic thermal gradient of piston-cylinder assemblies. The standard AGV2 andesite under water-undersaturated conditions is set to crystallize in a dynamic thermal gradient of about 35 °C/mm in 10 mm length capsules. In the hotter area of the capsule, the temperature is initially set at 1200 °C and decreases by programmed cooling at two distinct rates of 0.6 and 9.6 °C/h. Experiments are conducted in horizontally arranged assemblies in a piston cylinder apparatus to avoid any effect of gravity settling and compaction of crystals in long duration runs. The results are conclusive about the effect of water-rich fluids that are expelled out the crystal-rich zone (mush), where water saturation is reached by second boiling in the interstitial liquid. Expelled fluids migrate to the magma ahead of the solidification front contributing to a progressive enrichment in the fluxed components SiO2, K2O and H2O. The composition of water-rich fluids is modelled by mass balance using the chemical composition of glasses (quenched melt). The results are the basis for a model of granite magma differentiation in thermally-zoned conduits with application of in-situ crystallization equations. The intriguing textural and compositional features of the typical autoliths, accompanying granodiorite-tonalite batholiths, can be explained following the results of this study, by critical phenomena leading to splitting of an initially homogeneous magma into two magma systems with sharp boundaries. Magma splitting in thermal boundary layers, formed at the margins of ascent conduits, may operate for several km distances during magma transport from deep sources at the lower crust or upper mantle. Accordingly, conduits may work as chromatographic columns contributing to increase the silica content of ascending magmas and, at the same time, leave behind residual mushes that

  6. Comparative assessment of five potential sites for magma: hydrothermal systems - geophysics

    Energy Technology Data Exchange (ETDEWEB)

    Kasameyer, P.

    1980-09-02

    As part of a comparative assessment for the Continental Scientific Drilling Program, geophysical data were used, to characterize and evaluate potential magma-hydrothermal targets at five drill sites in the western United States. The sites include Roosevelt Hot Springs, Utah, the Rio Grande Rift, New Mexico, and The Geysers-Clear Lake, Long Valley, and Salton Trough areas, California. This summary discusses the size, depth, temperature, and setting of each potential target, as well as relvant scientific questions about their natures and the certainty of their existence.

  7. The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

    KAUST Repository

    LaGrow, Alec P.

    2015-05-12

    The characteristics of bimetallic nanomaterials are dictated by their size, shape and elemental distribution. Solution synthesis is widely utilized to form nanomaterials, such as nanoparticles, with controlled size and shape. However, the effects of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape-controlled synthesis on the final shape of the nanomaterials and the elemental distribution within the alloy. We demonstrate that this strategy can tune the size of monodisperse PtM (M=Ni or Cu) alloy nanocrystals ranging from 3 to 16 nm with an octahedral shape using acetylacetonate or halide precursors of Pt(II), Pt(IV) and Ni or Cu (II). The nanoparticles formed from halide precursors showed an enrichment of platinum on their surfaces, and the bromides could oxidatively etch the nanoparticles during synthesis with the O2/Br- pair. The two nanocrystal precursors can be uti-lized independently and can control the size with a trend of Pt(acac)2

  8. Electrochemical and spectroscopic studies of some less stable oxidation states of selected lanthanide and actinide elements

    International Nuclear Information System (INIS)

    Hobart, D.E.

    1981-06-01

    Simultaneous observation of electrochemical and spectroscopic properties (spectroelectrochemistry) at optically transparent electrodes (OTE's) was used to study some less stable oxidation states of selected lanthanide and actinide elements. Cyclic voltammetry at microelectrodes was used in conjunction with spectroelectrochemistry for the study of redox couples. Additional analytical techniques were used. The formal reduction potential (E 0 ') values of the M(III)/M(II) redox couples in 1 M KCl at pH 6 were -0.34 +- 0.01 V for Eu, -1.18 +- 0.01 V for Yb, and -1.50 +- 0.01 V for Sm. Spectropotentiostatic determination of E 0 ' for the Eu(III)/Eu(II) redox couple yielded a value of -0.391 +- 0.005 V. Spectropotentiostatic measurement of the Ce(IV)/Ce(III) redox couple in concentrated carbonate solution gave E 0 ' equal to 0.051 +- 0.005 V, which is about 1.7 V less positive than the E 0 ' value in noncomplexing solution. This same difference in potential was observed for the E 0 ' values of the Pr(IV)/Pr(III) and Tb(IV)/Tb(III) redox couples in carbonate solution, and thus Pr(IV) and Tb(IV) were stabilized in this medium. The U(VI)/U(V)/U(IV) and U(IV)/U(III) redox couples were studied in 1 M KCl at OTE's. Spectropotentiostatic measurement of the Np(VI)/Np(V) redox couple in 1 M HClO 4 gave an E 0 ' value of 1.140 +- 0.005 V. An E 0 ' value of 0.46 +- 0.01 V for the Np(VII)/Np(VI) couple was found by voltammetry. Oxidation of Am(III) was studied in concentrated carbonate solution, and a reversible cyclic voltammogram for the Am(IV)/Am(III) couple yielded E 0 ' = 0.92 +- 0.01 V in this medium; this value was used to estimate the standard reduction potential (E 0 ) of the couple as 2.62 +- 0.01 V. Attempts to oxidize Cm(III) in concentrated carbonate solution were not successful which suggests that the predicted E 0 value for the Cm(IV)/Cm(III) redox couple may be in error

  9. Eutectic propeties of primitive Earth's magma ocean

    Science.gov (United States)

    Lo Nigro, G.; Andrault, D.; Bolfan-Casanova, N.; Perillat, J.-P.

    2009-04-01

    It is widely accepted that the early Earth was partially molten (if not completely) due to the high energy dissipated by terrestrial accretion [1]. After core formation, subsequent cooling of the magma ocean has led to fractional crystallization of the primitive mantle. The residual liquid corresponds to what is now called the fertile mantle or pyrolite. Melting relations of silicates have been extensively investigated using the multi-anvil press, for pressures between 3 and 25 GPa [2,3]. Using the quench technique, it has been shown that the pressure affects significantly the solidus and liquidus curves, and most probably the composition of the eutectic liquid. At higher pressures, up to 65 GPa, melting studies were performed on pyrolite starting material using the laser-heated diamond anvil cell (LH-DAC) technique [4]. However, the quench technique is not ideal to define melting criteria, and furthermore these studies were limited in pressure range of investigation. Finally, the use of pyrolite may not be relevant to study the melting eutectic temperature. At the core-mantle boundary conditions, melting temperature is documented by a single data point on (Mg,Fe)2SiO4 olivine, provided by shock wave experiments at around 130-140 GPa [5]. These previous results present large uncertainties of ~1000 K. The aim of this study is to determine the eutectic melting temperature in the chemically simplified system composed of the two major lower mantle phases, the MgSiO3 perovskite and MgO periclase. We investigated melting in-situ using the laser-heated diamond anvil cell coupled with angle dispersive X-ray diffraction at the ID27 beamline of the ESRF [6]. Melting relations were investigated in an extended P-T range comparable to those found in the Earth's lower mantle, i.e. from 25 to 120 GPa and up to more than 5000 K. Melting was evidenced from (a) disappearance of one of the two phases in the diffraction pattern, (b) drastic changes of the diffraction image itself, and

  10. Imaging magma plumbing beneath Askja volcano, Iceland

    Science.gov (United States)

    Greenfield, Tim; White, Robert S.

    2015-04-01

    Volcanoes during repose periods are not commonly monitored by dense instrumentation networks and so activity during periods of unrest is difficult to put in context. We have operated a dense seismic network of 3-component, broadband instruments around Askja, a large central volcano in the Northern Volcanic Zone, Iceland, since 2006. Askja last erupted in 1961, with a relatively small basaltic lava flow. Since 1975 the central caldera has been subsiding and there has been no indication of volcanic activity. Despite this, Askja has been one of the more seismically active volcanoes in Iceland. The majority of these events are due to an extensive geothermal area within the caldera and tectonically induced earthquakes to the northeast which are not related to the magma plumbing system. More intriguing are the less numerous deeper earthquakes at 12-24km depth, situated in three distinct areas within the volcanic system. These earthquakes often show a frequency content which is lower than the shallower activity, but they still show strong P and S wave arrivals indicative of brittle failure, despite their location being well below the brittle-ductile boundary, which, in Askja is ~7km bsl. These earthquakes indicate the presence of melt moving or degassing at depth while the volcano is not inflating, as only high strain rates or increased pore fluid pressures would cause brittle fracture in what is normally an aseismic region in the ductile zone. The lower frequency content must be the result of a slower source time function as earthquakes which are both high frequency and low frequency come from the same cluster, thereby discounting a highly attenuating lower crust. To image the plumbing system beneath Askja, local and regional earthquakes have been used as sources to solve for the velocity structure beneath the volcano. Travel-time tables were created using a finite difference technique and the residuals were used to solve simultaneously for both the earthquake locations

  11. The effect on phase separation of the oxidation state of molybdenum in a Na2O-B2O3-SiO2 glass

    International Nuclear Information System (INIS)

    Kawamoto, Y.; Clemens, K.; Tomozawa, M.; Warden, J.T.

    1981-01-01

    The effect of oxidation state on phase separation was studied for 13Na 2 O, 49B 2 O 3 , 38SiO 2 (mol%) glasses containing 1 mol% Mo oxide. The glasses were melted under various conditions to vary the oxidation states of Mo ions. The oxidation states of Mo ions were determined by chemical analysis and ESR. The crystallisation tendency, the immiscibility temperature, and the phase separation morphology of the glasses were examined by DTA, x-ray diffraction, opalescence method, and replica electron microscopy. Glasses containing Mo 4+ ions have a great tendency to precipitate MoO 2 crystals. The immiscibility temperature of glass goes through a minimum when the oxidation states of Mo ions are changed. It was suggested that there is an optimum oxidation state to prevent crystallisation and to suppress the phase separation tendency of this system. (author)

  12. Operando XAS Study of the Surface Oxidation State on a Monolayer IrOx on RuOx and Ru Oxide Based Nanoparticles for Oxygen Evolution in Acidic Media

    DEFF Research Database (Denmark)

    Pedersen, Anders Filsøe; Escribano, Maria Escudero; Sebok, Bela

    2018-01-01

    that the average Ir oxidation state change is strongly affected by the coverage of atomic O. The observed shifts in oxidation state suggest that the surface has a high coverage of O at potentials just below the potential where oxygen evolution is exergonic in free energy. This observation is consistent...

  13. Effect of high doses of L-ascorbic acid on the antioxidative/oxidative state in the rats

    DEFF Research Database (Denmark)

    Niemiec, T.; Sawosz, E.; Chwalibog, André

    2005-01-01

    The objective of this study was to determine the effects of mega-doses of vitamin C (0.3, 0.6 and 0.9% of diet) as a dietary supplement for rats on selected indices of the antioxidative/oxidative state in 40 growing Wistar rats (4x10). It was found that L-ascorbic acid and Total Antioxidative State...... (TAS) in plasma did not increase with increasing vitamin C supply. The results indicate that high doses of L-ascorbic acid (0.3 and 0.9 but not 0.6%) increased the concentration of this antioxidant in plasma. Supplementation of vitamin C above 0.3% to the diets had pro-oxidative effects on lipid...... structures, while application of 0.9% promoted oxidative degradation of rat livers....

  14. Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

    Energy Technology Data Exchange (ETDEWEB)

    Yamaura, Kazunari, E-mail: YAMAURA.Kazunari@nims.go.jp [Superconducting Properties Unit, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, North 10 West 8, Kita-ku, Sapporo, Hokkaido 060-0810 (Japan)

    2016-04-15

    High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO{sub 3}, LiOsO{sub 3}, and Na{sub 2}OsO{sub 4}, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal–insulator transition in NaOsO{sub 3}, a ferroelectric-like transition in LiOsO{sub 3}, and high-temperature ferrimagnetism driven by a local structural distortion in Ca{sub 2}FeOsO{sub 6} may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices. - Graphical Abstract: Flux-grown crystals of NaOsO{sub 3} under high-pressure and high-temperature conditions in a belt-type apparatus. The crystal shows a magnetically driven metal–insulator transition at a temperature of 410 K. - Highlights: • Short review of high-pressure crystal growth of solid-state osmium oxides. • Wide variety of magnetic properties of solid-state osmium oxides. • Perovskite and related dense structures stabilized at 3–17 GPa.

  15. Pu oxidation state distributions in suspensions of the Mont Terri Opalinus Clay isolate Sporomusa sp. MT-2.99

    Energy Technology Data Exchange (ETDEWEB)

    Moll, Henry [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry; Cherkouk, Andrea [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). HZDR Young Investigator Group; Bok, Frank [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    The time-dependent {sup 242}Pu oxidation state distribution in the presence of Sporomusa sp. cells as a function of pH with or without Na-pyruvate was analyzed. In all cases, the presence of bacterial cells enhanced removal of Pu from solution and accelerated Pu interaction reactions, e.g. biosorption and bioreduction.

  16. Pu oxidation state distributions in suspensions of the Mont Terri Opalinus Clay isolate Sporomusa sp. MT-2.99

    International Nuclear Information System (INIS)

    Moll, Henry; Cherkouk, Andrea; Bok, Frank

    2017-01-01

    The time-dependent "2"4"2Pu oxidation state distribution in the presence of Sporomusa sp. cells as a function of pH with or without Na-pyruvate was analyzed. In all cases, the presence of bacterial cells enhanced removal of Pu from solution and accelerated Pu interaction reactions, e.g. biosorption and bioreduction.

  17. Regulatory, Land Ownership, and Water Availability Factors for a Magma Well: Long Valley Caldera and Coso Hot Springs, California

    Energy Technology Data Exchange (ETDEWEB)

    Blackett, Robert

    1985-09-01

    The U.S. Department of Energy is currently engaged in a program to demonstrate the engineering feasibility of extracting thermal energy from high-level molten magma bodies. The program is being carried out under the direction of Sandia National Laboratories where a number of individual projects support the overall program. The existing program elements include (1) high-temperature materials compatibility testing; (2) studies of properties of melts of various compositions; and (3) the investigation of the economics of a magma energy extraction system. Another element of the program is being conducted with the cooperation of the U.S. Geological Survey, and involves locating and outlining magma bodies at selected sites using various geophysical techniques. The ultimate goal here will be to define the limits of a magma body as a drilling target. During an earlier phase of the program, more than twenty candidate study sites considered were evaluated based upon: (1) the likelihood of the presence of a shallow magma chamber, (2) the accessibility of the site, and (3) physical and institutional constraints associated with each site with respect to performing long-term experiments. From these early phase activities, the number of candidate sites were eventually narrowed to just 2. The sites currently under consideration are Coso Hot Springs and the Long Valley caldera (Figure 1). This report describes certain attributes of these sites in order to help identify potential problems related to: (1) state and federal regulations pertaining to geothermal development; (2) land ownership; and (3) water resource availability. The information sources used in this study were mainly maps, publications, and informative documents gathered from the California Division of Oil and Gas and the U.S. Department of the Interior. Environmental studies completed for the entire Long Valley caldera study area, and for portions of the Coso Hot Springs study area were also used for reference.

  18. Density of alkaline magmas at crustal and upper mantle conditions by X-ray absorption

    Science.gov (United States)

    Seifert, R.; Malfait, W.; Petitgirard, S.; Sanchez-Valle, C.

    2011-12-01

    Silicate melts are essential components of igneous processes and are directly involved in differentiation processes and heat transfer within the Earth. Studies of the physical properties of magmas (e.g., density, viscosity, conductivity, etc) are however challenging and experimental data at geologically relevant pressure and temperature conditions remain scarce. For example, there is virtually no data on the density at high pressure of alkaline magmas (e.g., phonolites) typically found in continental rift zone settings. We present in situ density measurements of alkaline magmas at crustal and upper mantle conditions using synchrotron X-ray absorption. Measurements were conducted on ID27 beamline at ESRF using a panoramic Paris-Edinburgh Press (PE Press). The starting material is a synthetic haplo-phonolite glass similar in composition to the Plateau flood phonolites from the Kenya rift [1]. The glass was synthesized at 1673 K and 2.0 GPa in a piston-cylinder apparatus at ETH Zurich and characterized using EPMA, FTIR and density measurements. The sample contains less than 200 ppm water and is free of CO2. Single-crystal diamond cylinders (Øin = 0.5 mm, height = 1 mm) were used as sample containers and placed in an assembly formed by hBN spacers, a graphite heater and a boron epoxy gasket [2]. The density was determined as a function of pressure (1.0 to 3.1 GPa) and temperature (1630-1860 K) from the X-ray absorption contrast at 20 keV between the sample and the diamond capsule. The molten state of the sample during the data collection was confirmed by X-ray diffraction measurements. Pressure and temperature were determined simultaneously from the equation of state of hBN and platinum using the the double isochor method [3].The results are combined with available density data at room conditions to derive the first experimental equation of state (EOS) of phonolitic liquids at crustal and upper mantle conditions. We will compare our results with recent reports of the

  19. Arsenic K-edge X-ray absorption near-edge spectroscopy to determine oxidation states of arsenic of a coastal aquifer–aquitard system

    International Nuclear Information System (INIS)

    Wang, Ya; Jiao, Jiu Jimmy; Zhu, Sanyuan; Li, Yiliang

    2013-01-01

    Determination of oxidation states of solid-phase arsenic in bulk sediments is a valuable step in the evaluation of its bioavailability and environmental fate in deposits, but is difficult when the sediments have low arsenic contents and heterogeneous distribution of arsenic species. As K-edge X-ray absorption near-edge spectroscopy (XANES) was used to determine quantitatively the oxidation states of arsenic in sediments collected from different depths of boreholes in the Pearl River Delta, China, where the highest aquatic arsenic concentration is 161.4 μg/L, but the highest solid arsenic content only 39.6 mg/kg. The results demonstrated that XANES is efficient in determining arsenic oxidation states of the sediments with low arsenic contents and multiple arsenic species. The study on the high-resolution vertical variations of arsenic oxidation states also indicated that these states are influenced strongly by groundwater activities. With the help of geochemical data, solid arsenic speciation, toxicity and availability were further discussed. -- Highlights: •XANES is efficient in determining arsenic oxidation states of the bulk sediments. •Distribution of arsenic oxidation states is consistent with geochemical conditions. •Arsenic oxidation states are influenced strongly by groundwater activities. -- As K-edge X-ray absorption near-edge spectroscopy is efficient in determining arsenic oxidation states of the bulk sediments with low arsenic contents and heterogeneous distribution of arsenic species

  20. Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy.

    Science.gov (United States)

    Wang, Y F; Singh, Shashi B; Limaye, Mukta V; Shao, Y C; Hsieh, S H; Chen, L Y; Hsueh, H C; Wang, H T; Chiou, J W; Yeh, Y C; Chen, C W; Chen, C H; Ray, Sekhar C; Wang, J; Pong, W F; Takagi, Y; Ohigashi, T; Yokoyama, T; Kosugi, N

    2015-10-20

    This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets.

  1. Oxidative Stress State Is Associated with Left Ventricular Mechanics Changes, Measured by Speckle Tracking in Essential Hypertensive Patients

    Directory of Open Access Journals (Sweden)

    Luis Antonio Moreno-Ruíz

    2015-01-01

    Full Text Available The oxidative stress state is characterized by an increase in oxygen reactive species that overwhelms the antioxidant defense; we do not know if these pathological changes are correlated with alterations in left ventricular mechanics. The aim was correlating the oxidative stress state with the left ventricular global longitudinal strain (GLS and the left ventricular end diastolic pressure (LVEDP. Twenty-five patients with essential hypertension and 25 controls paired by age and gender were studied. All of the participants were subjected to echocardiography and biochemical determination of oxidative stress markers. The hypertensive patients, compared with control subjects, had significantly (p<0.05 higher levels of oxidized proteins (5.03±1.05 versus 4.06±0.63 nmol/mg, lower levels of extracellular superoxide dismutase (EC-SOD activity (0.045±0.02 versus 0.082±0.02 U/mg, higher LVEDP (16.2±4.5 versus 11.3±1.6 mm Hg, and lower GLS (−12% versus −16%. Both groups had preserved ejection fraction and the results showed a positive correlation of oxidized proteins with GLS (r=0.386, p=0.006 and LVEDP (r=0.389, p=0.005; we also found a negative correlation of EC-SOD activity with GLS (r=-0.404, p=0.004 and LVEDP (r=-0.347, p=0.014.

  2. System Tb-Fe-O: thermodynamic properties of ternary oxides using solid-state electrochemical cells

    International Nuclear Information System (INIS)

    Rakshit, S.K.; Parida, S.C.; Dash, S.; Singh, Ziley; Prasad, R.; Venugopal, V.

    2003-01-01

    The standard molar Gibbs free energies of formation of TbFeO 3 (s) and Tb 3 Fe 5 O 12 (s) have been determined using solid-state electrochemical cell employing different solid electrolytes. The reversible emfs of the following solid-state electrochemical cells have been measured in the temperature range 1050≤T/K≤1250. Cell (I):(-)Pt/{TbFeO 3 (s)+Tb 2 O 3 (s)+Fe(s)}//YDT/CSZ//{Fe(s)+Fe 0.95 O(s)}/Pt(+))) (Cell (II):(-)Pt/{Fe(s)+Fe 0.95 O(s)}//CSZ//{TbFeO 3 (s)+Tb 3 Fe 5 O 12 (s)+Fe 3 O 4 (s)}/Pt(+) The oxygen chemical potentials corresponding to the three-phase equilibria involving the ternary oxides have been computed from the emf data. The standard molar Gibbs free energies of formation of solid TbFeO 3 and Tb 3 Fe 5 O 12 calculated by the least-squares regression analysis of the data obtained in the present study are given by {Δ f G compfn m (TbFeO 3 ,s)/(kJ·mol -1 )±3.2}=-1357.5+0.2531·(T/K); (1050≤T/K≤1548);))and({Δ f G compfn m (Tb 3 Fe 5 O 12 ,s)/(kJ·mol -1 )±3.5}=-4901.7+ 0.9997·(T/K); (1050≤T/K≤1250).)) The uncertainty estimates for Δ f G compfn m include the standard deviation in the emf and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagram and chemical potential diagrams were computed for the system Tb-Fe-O at T=1250 K

  3. Thermally-assisted Magma Emplacement Explains Restless Calderas.

    Science.gov (United States)

    Amoruso, Antonella; Crescentini, Luca; D'Antonio, Massimo; Acocella, Valerio

    2017-08-11

    Many calderas show repeated unrest over centuries. Though probably induced by magma, this unique behaviour is not understood and its dynamics remains elusive. To better understand these restless calderas, we interpret deformation data and build thermal models of Campi Flegrei caldera, Italy. Campi Flegrei experienced at least 4 major unrest episodes in the last decades. Our results indicate that the inflation and deflation of magmatic sources at the same location explain most deformation, at least since the build-up of the last 1538 AD eruption. However, such a repeated magma emplacement requires a persistently hot crust. Our thermal models show that this repeated emplacement was assisted by the thermal anomaly created by magma that was intruded at shallow depth ~3 ka before the last eruption. This may explain the persistence of the magmatic sources promoting the restless behaviour of the Campi Flegrei caldera; moreover, it explains the crystallization, re-melting and mixing among compositionally distinct magmas recorded in young volcanic rocks. Our model of thermally-assisted unrest may have a wider applicability, possibly explaining also the dynamics of other restless calderas.

  4. Automatic Compound Annotation from Mass Spectrometry Data Using MAGMa.

    NARCIS (Netherlands)

    Ridder, L.O.; Hooft, van der J.J.J.; Verhoeven, S.

    2014-01-01

    The MAGMa software for automatic annotation of mass spectrometry based fragmentation data was applied to 16 MS/MS datasets of the CASMI 2013 contest. Eight solutions were submitted in category 1 (molecular formula assignments) and twelve in category 2 (molecular structure assignment). The MS/MS

  5. Crystallization of Magma. CEGS Programs Publication Number 14.

    Science.gov (United States)

    Berry, R. W.

    Crystallization of Magma is one of a series of single-topic problem modules intended for use in undergraduate geology and earth science courses. Through problems and observations based on two sets of experiments, this module leads to an understanding of how an igneous rock can form from molten material. Environmental factors responsible for…

  6. Loki Patera as the Surface of a Magma Sea

    Science.gov (United States)

    Matson, D. L.; Davies, A. G.; Veeder, G. J.; Rathbun, J. A.; Johnson, T. V.

    2004-01-01

    Inspired by the finding of Schubert et al that Io's figure is consistent with a hydrostatic shape, we explore the consequences of modeling Loki Patera as the surface of a large magma sea. This model is attractive because of its sheer simplicity and its usefulness in interpreting and predicting observations. Here, we report on that work.

  7. Studi On Oxidation State Of U In Ba2NdUO6

    International Nuclear Information System (INIS)

    Firman Windarto, Hendri

    1996-01-01

    Ba 2 NdUO 6 is not of the important compounds that is formed from a solidification process for high level liquid waste using super high temperature method Ba 2 NdUO 6 has ordered perovskite structure. The objective of this study is to investigate oxidation state of U in Ba 2 NdUO 6 . The properties of Ba 2 NdUO 6 were observed by using Faraday-type torsion magnetometer and X-ray Photoelectron Spectrometer (XPS). The magnetic susceptibility measured in the temperature range of 4K to room temperature showed that the Ba 2 NdUO 6 is paramagnetism that obeys the Curie-Weiss law. The effective moment of Ba 2 NdUO 6 is 3.04 μB. The results of xPs spectrum showed that the peaks of U4f for Ba 2 NdUO 6 appeared exactly between binding energy of UO 2 and UO 3 . It can be concluded that Ba 2 NdUO 6 has binding energy peaks corresponding to pentavalent uranium

  8. Petrology of chromite in ureilites: Deconvolution of primary oxidation states and secondary reduction processes

    Science.gov (United States)

    Goodrich, Cyrena Anne; Harlow, George E.; Van Orman, James A.; Sutton, Stephen R.; Jercinovic, Michael J.; Mikouchi, Takashi

    2014-06-01

    Ureilites are ultramafic achondrites thought to be residues of partial melting on a carbon-rich asteroid. They show a trend of FeO-variation (olivine Fo from ∼74 to 95) that suggests variation in oxidation state. Whether this variation was established during high-temperature igneous processing on the ureilite parent body (UPB), or preserved from nebular precursors, is a subject of debate. The behavior of chromium in ureilites offers a way to assess redox conditions during their formation and address this issue, independent of Fo. We conducted a petrographic and mineral compositional study of occurrences of chromite (Cr-rich spinel) in ureilites, aimed at determining the origin of the chromite in each occurrence and using primary occurrences to constrain models of ureilite petrogenesis. Chromite was studied in LEW 88774 (Fo 74.2), NWA 766 (Fo 76.7), NWA 3109 (Fo 76.3), HaH 064 (Fo 77.5), LAP 03587 (Fo 74.9), CMS 04048 (Fo 76.4), LAP 02382 (Fo 78.6) and EET 96328 (Fo 85.2). Chromite occurs in LEW 88774 (∼5 vol.%), NWA 766 (event involved initial elevation of T (to 1300-1400 °C), followed by rapid decompression and drop in T (to exclusively in low-Fo samples supports the interpretation that the ureilite FeO-variation was established during igneous processing on the UPB.

  9. Waste management state-of-the-art review for mixed-oxide fuel fabrication facilities

    International Nuclear Information System (INIS)

    Woodsum, H.C.; Goodman, J.

    1977-11-01

    This report provides a state-of-the-art review of the waste management for mixed-oxide (MOX) fuel fabrication facilities. The intent of this report is to focus on those processes and regulatory issues which have a direct bearing on existing and anticipated future management of transuranic (TRU) wastes from a commercial MOX fuel fabrication faciity. Recent government agency actions are reviewed with regard to their impact on existing and projected waste management regulations; and it is concluded that acceleration in the development of regulations, standards, and criteria is one of the most important factors in the implementation of improved MOX plant waste management techniques. ERDA development programs pertaining to the management of TRU wastes have been reviewed and many promising methods for volume reduction of both solid and liquid wastes are discussed. For solid wastes, these methods include compaction, shredding and baling, combustion, acid digestion, and decontamination by electropolishing or by electrolytic treatment. For liquid wastes, treatment options include evaporation, drying, calcination, flocculation, ion exchange, filtration, reverse osmosis, combustion (of combustible organics), and bioprocessing. Based on this review, it is recommended that ERDA continue with its combustible solid waste volume reduction program and complete these development activities by 1979. Following this, a critical evaluation of solid waste volume reduction techniques should be made to select the most promising systems for a commercial MOX fuel facility

  10. Oxidation state of uranium in metamict and annealed zircon: near-infrared spectroscopic quantitative analysis

    CERN Document Server

    Zhang Ming; Ewing, R C

    2003-01-01

    Radiation and thermally induced changes in the oxidation state of uranium in metamict zircon have been systematically analysed, for the first time, using polarized near-infrared spectroscopy. The results showed that in damaged zircon U ions in crystalline domains exhibited relatively sharp, anisotropic signals from tetravalent and pentavalent U ions in crystalline domains (U sub c sub r sub y sub s sub t sub a sub l sup 4 sup + and U sub c sub r sub y sub s sub t sub a sub l sup 5 sup +). The linewidths and peak positions of the 4834 cm sup - sup 1 band (U sub c sub r sub y sub s sub t sub a sub l sup 4 sup + , E || c) and the 6668 cm sup - sup 1 band (U sub c sub r sub y sub s sub t sub a sub l sup 5 sup + , E perp. c) are a non-linear function of the self-radiation dose. They reach nearly constant values at doses greater than approx 3.5 x 10 sup 1 sup 8 alpha-events g sup - sup 1. Quantitative analysis of U sub c sub r sub y sub s sub t sub a sub l sup 4 sup + and U sub c sub r sub y sub s sub t sub a sub l...

  11. Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide

    Science.gov (United States)

    Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J.; Schlom, Darrell G.; Alem, Nasim; Gopalan, Venkatraman

    2016-01-01

    Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden–Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure. PMID:27578622

  12. Atomic scale imaging of competing polar states in a Ruddlesden-Popper layered oxide.

    Science.gov (United States)

    Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J; Schlom, Darrell G; Alem, Nasim; Gopalan, Venkatraman

    2016-08-31

    Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden-Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure.

  13. Carbonate-linked poly(ethylene oxide) polymer electrolytes towards high performance solid state lithium batteries

    International Nuclear Information System (INIS)

    He, Weisheng; Cui, Zili; Liu, Xiaochen; Cui, Yanyan; Chai, Jingchao; Zhou, Xinhong; Liu, Zhihong; Cui, Guanglei

    2017-01-01

    The classic poly(ethylene oxide) (PEO) based solid polymer electrolyte suffers from poor ionic conductivity of ambient temperature, low lithium ion transference number and relatively narrow electrochemical window (<4.0 V vs. Li + /Li). Herein, the carbonate-linked PEO solid polymer such as poly(diethylene glycol carbonate) (PDEC) and poly(triethylene glycol carbonate) (PTEC) were explored to find out the feasibility of resolving above issues. It was proven that the optimized ionic conductivity of PTEC based electrolyte reached up to 1.12 × 10 −5 S cm −1 at 25 °C with a decent lithium ion transference number of 0.39 and a wide electrochemical window about 4.5 V vs. Li + /Li. In addition, the PTEC based Li/LiFePO 4 cell could be reversibly charged and discharged at 0.05 C-rates at ambient temperature. Moreover, the higher voltage Li/LiFe 0.2 Mn 0.8 PO 4 cell (cutoff voltage 4.35 V) possessed considerable rate capability and excellent cycling performance even at ambient temperature. Therefore, these carbonate-linked PEO electrolytes were demonstrated to be fascinating candidates for the next generation solid state lithium batteries simultaneously with high energy and high safety.

  14. 3 and 4 oxidation state element solubilities in borosilicate glasses. Implement to actinides in nuclear glasses

    International Nuclear Information System (INIS)

    Cachia, J.N.

    2005-12-01

    In order to ensure optimal radionuclides containment, the knowledge of the actinide loading limits in nuclear waste glasses and also the comprehension of the solubilization mechanisms of these elements are essential. A first part of this manuscript deals with the study of the differences in solubility of the tri and tetravalent elements (actinides and surrogates) particularly in function of the melting temperature. The results obtained indicate that trivalent elements (La, Gd, Nd, Am, Cm) exhibit a higher solubility than tetravalent elements (Hf, Th, Pu). Consequently, it was planned to reduce plutonium at the oxidation state (III), the later being essentially tetravalent in borosilicate glasses. An innovating reduction process of multi-valent elements (cerium, plutonium) using silicon nitride has been developed in a second part of this work. Reduced plutonium-bearing glasses synthesized by Si 3 N 4 addition made it possible to double the plutonium solubility from 2 to 4 wt% at 1200 deg C. A structural approach to investigate the differences between tri and tetravalent elements was finally undertaken. These investigations were carried out by X-rays Absorption Spectroscopy (EXAFS) and NMR. Trivalent rare earth and actinide elements seem to behave as network modifiers while tetravalent elements rather present true intermediaries' behaviour. (author)

  15. 75 FR 28778 - Magma Flood Retarding Structure (FRS) Supplemental Watershed Plan, Pinal County, AZ

    Science.gov (United States)

    2010-05-24

    ... DEPARTMENT OF AGRICULTURE Natural Resources Conservation Service Magma Flood Retarding Structure... statement is not being prepared for the Magma Flood Retarding Structure (FRS) Supplemental Watershed Plan... rehabilitate the Magma FRS to provide for continued flood protection for a portion of the Town of Florence and...

  16. Mechanisms and timescales of generating eruptible rhyolitic magmas at Yellowstone caldera from zircon and sanidine geochronology and geochemistry

    Science.gov (United States)

    Stelten, Mark; Cooper, Kari M.; Vazquez, Jorge A.; Calvert, Andrew T.; Glessner, Justin G

    2015-01-01

    antecrystic zircons require a model where eruptible rhyolites are generated by extracting melt and zircons from a long-lived mush of immobile crystal-rich magma. In this process the larger sanidine crystals remain trapped in the locked crystal network. The extracted melts (plus antecrystic zircon) amalgamate into a liquid dominated (i.e., eruptible) magma body that is maintained as a physically distinct entity relative to the bulk of the long-lived crystal mush. Zircon surfaces and sanidines in each rhyolite crystallize after melt extraction/amalgamation and their ages constrain the residence time of eruptible magmas at Yellowstone. Residence times of the large volume rhyolites (~40 – 70 km3) are ≤ 1 kyr (conservatively < 6 kyr), which suggests that large volumes of rhyolite can be generated rapidly by extracting melt from a crystal mush. Because the lifespan of the crystal mush that sourced the Central Plateau Member rhyolites is two orders of magnitude longer than the residence time of eruptible magma bodies within the reservoir, it is apparent that the Yellowstone magma reservoir spends most of its time in a largely-crystalline (i.e., uneruptible) state, similar to the present-day magma reservoir, and that eruptible magma bodies are ephemeral features.

  17. Extensive, water-rich magma reservoir beneath southern Montserrat

    Science.gov (United States)

    Edmonds, M.; Kohn, S. C.; Hauri, E. H.; Humphreys, M. C. S.; Cassidy, M.

    2016-05-01

    South Soufrière Hills and Soufrière Hills volcanoes are 2 km apart at the southern end of the island of Montserrat, West Indies. Their magmas are distinct geochemically, despite these volcanoes having been active contemporaneously at 131-129 ka. We use the water content of pyroxenes and melt inclusion data to reconstruct the bulk water contents of magmas and their depth of storage prior to eruption. Pyroxenes contain up to 281 ppm H2O, with significant variability between crystals and from core to rim in individual crystals. The Al content of the enstatites from Soufrière Hills Volcano (SHV) is used to constrain melt-pyroxene partitioning for H2O. The SHV enstatite cores record melt water contents of 6-9 wt%. Pyroxene and melt inclusion water concentration pairs from South Soufriere Hills basalts independently constrain pyroxene-melt partitioning of water and produces a comparable range in melt water concentrations. Melt inclusions recorded in plagioclase and in pyroxene contain up to 6.3 wt% H2O. When combined with realistic melt CO2 contents, the depth of magma storage for both volcanoes ranges from 5 to 16 km. The data are consistent with a vertically protracted crystal mush in the upper crust beneath the southern part of Montserrat which contains heterogeneous bodies of eruptible magma. The high water contents of the magmas suggest that they contain a high proportion of exsolved fluids, which has implications for the rheology of the mush and timescales for mush reorganisation prior to eruption. A depletion in water in the outer 50-100 μm of a subset of pyroxenes from pumices from a Vulcanian explosion at Soufrière Hills in 2003 is consistent with diffusive loss of hydrogen during magma ascent over 5-13 h. These timescales are similar to the mean time periods between explosions in 1997 and in 2003, raising the possibility that the driving force for this repetitive explosive behaviour lies not in the shallow system, but in the deeper parts of a vertically

  18. Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

    Directory of Open Access Journals (Sweden)

    Elixabet Díaz-de-Cerio

    2016-05-01

    Full Text Available Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high. The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.

  19. Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States.

    Science.gov (United States)

    Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

    2016-05-11

    Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.

  20. Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

    Science.gov (United States)

    Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

    2016-01-01

    Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production. PMID:27187352

  1. The protonation state around TyrD/TyrD• in photosystem II is reflected in its biphasic oxidation kinetics.

    Science.gov (United States)

    Sjöholm, Johannes; Ho, Felix; Ahmadova, Nigar; Brinkert, Katharina; Hammarström, Leif; Mamedov, Fikret; Styring, Stenbjörn

    2017-02-01

    The tyrosine residue D2-Tyr160 (Tyr D ) in photosystem II (PSII) can be oxidized through charge equilibrium with the oxygen evolving complex in PSII. The kinetics of the electron transfer from Tyr D has been followed using time-resolved EPR spectroscopy after triggering the oxidation of pre-reduced Tyr D by a short laser flash. After its oxidation Tyr D is observed as a neutral radical (Tyr D • ) indicating that the oxidation is coupled to a deprotonation event. The redox state of Tyr D was reported to be determined by the two water positions identified in the crystal structure of PSII [Saito et al. (2013) Proc. Natl. Acad. Sci. USA 110, 7690]. To assess the mechanism of the proton coupled electron transfer of Tyr D the oxidation kinetics has been followed in the presence of deuterated buffers, thereby resolving the kinetic isotope effect (KIE) of Tyr D oxidation at different H/D concentrations. Two kinetic phases of Tyr D oxidation - the fast phase (msec-sec time range) and the slow phase (tens of seconds time range) were resolved as was previously reported [Vass and Styring (1991) Biochemistry 30, 830]. In the presence of deuterated buffers the kinetics was significantly slower compared to normal buffers. Furthermore, although the kinetics were faster at both high pH and pD values the observed KIE was found to be similar (~2.4) over the whole pL range investigated. We assign the fast and slow oxidation phases to two populations of PSII centers with different water positions, proximal and distal respectively, and discuss possible deprotonation events in the vicinity of Tyr D . Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Magma Reservoirs Feeding Giant Radiating Dike Swarms: Insights from Venus

    Science.gov (United States)

    Grosfils, E. B.; Ernst, R. E.

    2003-01-01

    Evidence of lateral dike propagation from shallow magma reservoirs is quite common on the terrestrial planets, and examination of the giant radiating dike swarm population on Venus continues to provide new insight into the way these complex magmatic systems form and evolve. For example, it is becoming clear that many swarms are an amalgamation of multiple discrete phases of dike intrusion. This is not surprising in and of itself, as on Earth there is clear evidence that formation of both magma reservoirs and individual giant radiating dikes often involves periodic magma injection. Similarly, giant radiating swarms on Earth can contain temporally discrete subswarms defined on the basis of geometry, crosscutting relationships, and geochemical or paleomagnetic signatures. The Venus data are important, however, because erosion, sedimentation, plate tectonic disruption, etc. on Earth have destroyed most giant radiating dike swarm's source regions, and thus we remain uncertain about the geometry and temporal evolution of the magma sources from which the dikes are fed. Are the reservoirs which feed the dikes large or small, and what are the implications for how the dikes themselves form? Does each subswarm originate from a single, periodically reactivated reservoir, or do subswarms emerge from multiple discrete geographic foci? If the latter, are these discrete foci located at the margins of a single large magma body, or do multiple smaller reservoirs define the character of the magmatic center as a whole? Similarly, does the locus of magmatic activity change with time, or are all the foci active simultaneously? Careful study of giant radiating dike swarms on Venus is yielding the data necessary to address these questions and constrain future modeling efforts. Here, using giant radiating dike swarms from the Nemesis Tessera (V14) and Carson (V43) quadrangles as examples, we illustrate some of the dike swarm focal region diversity observed on Venus and briefly explore some

  3. Seismic tremors and magma wagging during explosive volcanism.

    Science.gov (United States)

    Jellinek, A Mark; Bercovici, David

    2011-02-24

    Volcanic tremor is a ubiquitous feature of explosive eruptions. This oscillation persists for minutes to weeks and is characterized by a remarkably narrow band of frequencies from about 0.5 Hz to 7 Hz (refs 1-4). Before major eruptions, tremor can occur in concert with increased gas flux and related ground deformation. Volcanic tremor is thus of particular value for eruption forecasting. Most models for volcanic tremor rely on specific properties of the geometry, structure and constitution of volcanic conduits as well as the gas content of the erupting magma. Because neither the initial structure nor the evolution of the magma-conduit system will be the same from one volcano to the next, it is surprising that tremor characteristics are so consistent among different volcanoes. Indeed, this universality of tremor properties remains a major enigma. Here we employ the contemporary view that silicic magma rises in the conduit as a columnar plug surrounded by a highly vesicular annulus of sheared bubbles. We demonstrate that, for most geologically relevant conditions, the magma column will oscillate or 'wag' against the restoring 'gas-spring' force of the annulus at observed tremor frequencies. In contrast to previous models, the magma-wagging oscillation is relatively insensitive to the conduit structure and geometry, which explains the narrow band of tremor frequencies observed around the world. Moreover, the model predicts that as an eruption proceeds there will be an upward drift in both the maximum frequency and the total signal frequency bandwidth, the nature of which depends on the explosivity of the eruption, as is often observed.

  4. Mezcla de magmas en Vulcanello (Isla Vulcano, Italia

    Directory of Open Access Journals (Sweden)

    Aparicio, A.

    2008-06-01

    Full Text Available Volcanic activity in Vulcano starts about 350 ka ago and continues up to present day with the development of thre main episodes corresponding to the calderas of Piano and La Fossa, and Vulcanello. These cover a compositional range from rhyolitic to trachybasaltic rocks. This lithological diversity is produced by different petrogenetic processes such as fractional crystallization, assimilation coupled to fractional crystallization (AFC, mixing, etc.The eruption of Vulcanello area emitted trachyandesitic materials, including shoshonites and latites. A magma-mixing process is established between trachytes and shoshonites to origine latites. Trachytes and rhyolites are produced by fractional crystallization and by ACF processes (assimilation of sedimentary rocks from trachyandesitic magmas.La actividad volcánica de Isla Vulcano comienzó aproximadamente hace 350.000 años y continúa hasta la actualidad con el desarrollo de tres grandes episodios correspondientes a las caldera de Piano, caldera de Fossa y a Vulcanello, que han emitido piroclastos y coladas de composiciones muy variadas, desde riolitas a traquibasaltos. Esta variedad litológica ha sido relacionada con procesos petrogenéticos tan diversos como cristalización fraccionada, asimilación simultánea con cristalización (ACF, mezcla de magmas, etc.El episodio de Vulcanello emite rocas traquiandesíticas, con composiciones shoshoníticas y latíticas. Un proceso de mezcla de magmas es reconocido entre traquitas y shoshonitas para generar latitas. Traquitas y riolitas son producidas por procesos de cristalización fraccionada simple y por ACF con asimilación de rocas sedimentarias a partir de magmas traquiandesíticos.

  5. Rapid Synthesis of Lead Oxide Nanorods by One-step Solid-state Chemical Reaction at Room Temperature

    Institute of Scientific and Technical Information of China (English)

    CAO, Ya-Li(曹亚丽); JIA, Dian-Zeng(贾殿赠); LIU, Lang(刘浪); LUO, Jian-Min(骆建敏)

    2004-01-01

    A simple and facile method was reported to synthesize lead oxide nanorods. Nanorods of lead oxide were obtained directly from grinding solid metal salt and sodium hydroxide in agate mortar with the assistance of a suitable nonionic surfactant in only one step, which is different from the result of hydroxide in solution. The product has been characterized by XRD, TEM and SEM. The formation mechanism of rod-like morphology is discussed and the surfactant plays an important soft-template role in modifying the interface of solid-state reaction and according process of rod-formation.

  6. Investigation of electrochemical behaviour and structure of oxide films on Ni60Nb40 alloy in amorphous and crystalline states

    International Nuclear Information System (INIS)

    Tomashov, N.D.; Skvortsova, I.B.; Gorodetskij, A.E.; Bogomolov, D.B.

    1987-01-01

    Electrochemical properties of Ni 60 Nb 40 alloy in amorphous and crystalline states as well as structure of oxide films forming during anode polarization in electrolytes on the surface of this alloy in both its states are investigated. It is stated that increased passive ability of Ni 60 Nb 40 alloys in amorphous state and high efficiency of chlorine evolution (2 n NaCl+HCl up to pH=0) anode process in comparison with crystalline state are defined by increased homogeneity and uniformity of passive films forming on amorphous alloy and their increased electron conductivity, that is in direct dependence on different structure of passive films forming on alloys in amorphous and crystalline states

  7. Assigning Oxidation States to Organic Compounds via Predictions from X-Ray Photoelectron Spectroscopy: A Discussion of Approaches and Recommended Improvements

    Science.gov (United States)

    Gupta, Vipul; Ganegoda, Hasitha; Engelhard, Mark H.; Terry, Jeff; Linford, Matthew R.

    2014-01-01

    The traditional assignment of oxidation states to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation state of zero when bonded to carbon. Here, we show that X-ray photoelectron…

  8. Regional and temporal variability of melts during a Cordilleran magma pulse: Age and chemical evolution of the jurassic arc, eastern mojave desert, California

    Science.gov (United States)

    Barth, A.P.; Wooden, J.L.; Miller, David; Howard, Keith A.; Fox, Lydia; Schermer, Elizabeth R.; Jacobson, C.E.

    2017-01-01

    Intrusive rock sequences in the central and eastern Mojave Desert segment of the Jurassic Cordilleran arc of the western United States record regional and temporal variations in magmas generated during the second prominent pulse of Mesozoic continental arc magmatism. U/Pb zircon ages provide temporal control for describing variations in rock and zircon geochemistry that reflect differences in magma source components. These source signatures are discernible through mixing and fractionation processes associated with magma ascent and emplacement. The oldest well-dated Jurassic rocks defining initiation of the Jurassic pulse are a 183 Ma monzodiorite and a 181 Ma ignimbrite. Early to Middle Jurassic intrusive rocks comprising the main stage of magmatism include two high-K calc-alkalic groups: to the north, the deformed 183–172 Ma Fort Irwin sequence and contemporaneous rocks in the Granite and Clipper Mountains, and to the south, the 167–164 Ma Bullion sequence. A Late Jurassic suite of shoshonitic, alkali-calcic intrusive rocks, the Bristol Mountains sequence, ranges in age from 164 to 161 Ma and was emplaced as the pulse began to wane. Whole-rock and zircon trace-element geochemistry defines a compositionally coherent Jurassic arc with regional and secular variations in melt compositions. The arc evolved through the magma pulse by progressively greater input of old cratonic crust and lithospheric mantle into the arc magma system, synchronous with progressive regional crustal thickening.

  9. Thirteen million years of silicic magma production in Iceland: Links between petrogenesis and tectonic settings

    Science.gov (United States)

    Martin, E.; Sigmarsson, O.

    2010-04-01

    The origin of the Quaternary silicic rocks in Iceland is thought to be linked to the thermal state of the crust, which in turn depends on the regional tectonic settings. This simple model is tested here on rocks from the Miocene to present, both to suggest an internally consistent model for silicic magma formation in Iceland and to constrain the link between tectonic settings and silicic magma petrogenesis. New major and trace-element compositions together with O-, Sr- and Nd-isotope ratios have been obtained on silicic rocks from 19 volcanic systems ranging in age from 13 Ma to present. This allows us to trace the spatial and temporal evolution of both magma generation and the corresponding sources. Low δ18O (geothermal gradient. But later than 5.5 Ma they were produced in a flank zone environment by fractional crystallisation alone, probably due to decreasing geothermal gradient, of basalts derived from a mantle source with lower 143Nd/ 144Nd. This is in agreement with an eastwards rift-jump, from Snæfellsnes towards the present Reykjanes Rift Zone, between 7 and 5.5 Ma. In the South Iceland Volcanic Zone (SIVZ), the intermediate Nd-signature observed in silicic rocks from the Torfajökull central volcano reflects the transitional character of the basalts erupted at this propagating rift segment. Therefore, the abundant evolved rocks at this major silicic complex result from partial melting of the transitional alkaline basaltic crust (Iceland can, therefore, be used for deciphering past geodynamic settings characterized by rift- and off-rift zones resulting from interaction of a mantle plume and divergent plate boundaries.

  10. Ground surface deformation patterns, magma supply, and magma storage at Okmok volcano, Alaska, from InSAR analysis: 1. Intereruption deformation, 1997–2008

    Science.gov (United States)

    Lu, Zhong; Dzurisin, Daniel; Biggs, Juliet; Wicks, Charles; McNutt, Steve

    2010-01-01

    Starting soon after the 1997 eruption at Okmok volcano and continuing until the start of the 2008 eruption, magma accumulated in a storage zone centered ~3.5 km beneath the caldera floor at a rate that varied with time. A Mogi-type point pressure source or finite sphere with a radius of 1 km provides an adequate fit to the deformation field portrayed in time-sequential interferometric synthetic aperture radar images. From the end of the 1997 eruption through summer 2004, magma storage increased by 3.2–4.5 × 107 m3, which corresponds to 75–85% of the magma volume erupted in 1997. Thereafter, the average magma supply rate decreased such that by 10 July 2008, 2 days before the start of the 2008 eruption, magma storage had increased by 3.7–5.2 × 107 m3 or 85–100% of the 1997 eruption volume. We propose that the supply rate decreased in response to the diminishing pressure gradient between the shallow storage zone and a deeper magma source region. Eventually the effects of continuing magma supply and vesiculation of stored magma caused a critical pressure threshold to be exceeded, triggering the 2008 eruption. A similar pattern of initially rapid inflation followed by oscillatory but generally slowing inflation was observed prior to the 1997 eruption. In both cases, withdrawal of magma during the eruptions depressurized the shallow storage zone, causing significant volcano-wide subsidence and initiating a new intereruption deformation cycle.

  11. The expected greenhouse benefits from developing magma power at Long Valley, California

    International Nuclear Information System (INIS)

    Haraden, John.

    1995-01-01

    Magma power is the production of electricity from shallow magma bodies. Before magma becomes a practical source of power, many engineering problems must still be solved. When they are solved, the most likely site for the first magma power plant is Long Valley, California, USA. In this paper, we examine the greenhouse benefits from developing Long Valley. By generating magma power and by curtailing an equal amount of fossil power, we estimate the expected mass and the expected discounted value of reduced CO 2 emissions. For both measures, the expected benefits seem to be substantial. (author)

  12. Triplet-State Dissolved Organic Matter Quantum Yields and Lifetimes from Direct Observation of Aromatic Amine Oxidation.

    Science.gov (United States)

    Schmitt, Markus; Erickson, Paul R; McNeill, Kristopher

    2017-11-21

    Excited triplet state chromophoric dissolved organic matter ( 3 CDOM*) is a short-lived mixture of excited-state species that plays important roles in aquatic photochemical processes. Unlike the study of the triplet states of well-defined molecules, which are amenable to transient absorbance spectroscopy, the study of 3 CDOM* is hampered by it being a complex mixture and its low average intersystem crossing quantum yield (Φ ISC ). This study is an alternative approach to investigating 3 CDOM* using transient absorption laser spectroscopy. The radical cation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), formed through oxidation by 3 CDOM*, was directly observable by transient absorption spectroscopy and was used to probe basic photophysical properties of 3 CDOM*. Quenching and control experiments verified that TMPD •+ was formed from 3 CDOM* under anoxic conditions. Model triplet sensitizers with a wide range of excited triplet state reduction potentials and CDOM oxidized TMPD at near diffusion-controlled rates. This gives support to the idea that a large cross-section of 3 CDOM* moieties are able to oxidize TMPD and that the complex mixture of 3 CDOM* can be simplified to a single signal. Using the TMPD •+ transient, the natural triplet lifetime and Φ ISC for different DOM isolates and natural waters were quantified; values ranged from 12 to 26 μs and 4.1-7.8%, respectively.

  13. The Oxidation State of Fe in Glasses from the Galapagos Archipelago: Variable Oxygen Fugacity as a Function of Mantle Source

    Science.gov (United States)

    Peterson, M. E.; Kelley, K. A.; Cottrell, E.; Saal, A. E.; Kurz, M. D.

    2015-12-01

    The oxidation state of the mantle plays an intrinsic role in the magmatic evolution of the Earth. Here we present new μ-XANES measurements of Fe3+/ΣFe ratios (a proxy for ƒO2) in a suite of submarine glasses from the Galapagos Archipelago. Using previously presented major, trace, and volatile elements and isotopic data for 4 groups of glass that come from distinct mantle sources (depleted upper mantle, 2 recycled, and a primitive mantle source) we show that Fe3+/ΣFe ratios vary both with the influence of shallow level processes and with variations in mantle source. Fe3+/ΣFe ratios increase with differentiation (i.e. decreasing MgO), but show a large variation at a given MgO. Progressive degassing of sulfur accompanies decreasing Fe3+/ΣFe ratios, while assimilation of hydrothermally altered crust (as indicated by increasing Sr/Sr*) is shown to increase Fe3+/ΣFe ratios. After taking these processes into account, there is still variability in the Fe3+/ΣFe ratios of the isotopically distinct sample suites studied, yielding a magmatic ƒO2 that ranges from ΔQFM = +0.16 to +0.74 (error ITE = enriched Sr and Pb isotopes) shows evidence of mixing between oxidized and reduced sources (ITE oxidized end-member = 0.177). This suggests that mantle sources in the Galapagos that are thought to contain recycled components (i.e., WD and ITE groups) have distinct oxidation states. The high 3He/4He Fernandina samples (HHe group) are shown to be the most oxidized (ave. 0.175 ± 0.006). With C/3He ratios an order of magnitude greater than MORB this suggests that the primitive mantle is a more carbonated and oxidized source than the depleted upper mantle.

  14. Oxidation-state distribution of plutonium in surface and subsurface waters at Thule, northwest Greenland

    International Nuclear Information System (INIS)

    McMahon, C.A.; Leon Vintro, L.; Mitchell, P.I.; Dahlgaard, H.

    2000-01-01

    The speciation of plutonium in Arctic waters sampled on the northwest Greenland shelf in August 1997 is discussed in this paper. Specifically, we report the results of analyses carried out on seawater sampled (a) close to the Thule air base where, in 1968, a US military aircraft carrying four nuclear weapons crashed on sea ice, releasing kilogram quantities of plutonium to the snow pack and underlying seabed sediments, and (b) at a reference station (Upernavik) located ∼400 km to the south. The data show that most of the plutonium in the dissolved phase at Thule is in the form of Pu(V, VI) (mean: 68±6%; n=6), with little if any distinction apparent between surface and bottom waters. Further, the oxidation state distribution at stations close to the accident site is similar to that measured at Upernavik, remote from this site. It is also similar to the distribution observed in shelf waters at mid-latitudes, suggesting that the underlying processes controlling plutonium speciation are insensitive to temperature over the range 0-25 deg. C. Measurements using tangential-flow ultrafiltration indicate that virtually all of the plutonium (including the fraction in a reduced chemical form) is present as fully dissolved species. Most of this plutonium would seem to be of weapons fallout origin, as the mean 238 Pu/ 239,240 Pu activity ratio in the water column (dissolved phase) at Thule (0.06±0.02; n=10) is similar to the global fallout ratio at this latitude (∼0.04). Thus, there is little evidence of weapons-grade plutonium in the water column at Thule at the present time

  15. The changing face of lower tropospheric sulfur oxides in the United States

    Directory of Open Access Journals (Sweden)

    G. M. Hidy

    2016-12-01

    Full Text Available Abstract Sulfur oxides, sulfur dioxide and airborne sulfate, SOx, are short-lived species in the troposphere whose concentrations in air and precipitation have changed dramatically in association with fossil fuel combustion. The historic rise in concentration is coincident with the era of the so-called “Anthropocene.” Unlike concentrations of long-lived species such as carbon dioxide, atmospheric SOx in the United States (US peaked between 1970 and 2005 then declined. The rise and fall of SOx is traced by comparing national data on emission changes, ambient concentrations, and precipitation sulfate from prior to World War II to the present. Surface SOx concentrations and precipitation sulfate have decreased with emissions in most parts of the US after the late 1970s. Continued reduction toward a natural “background” condition has depended on aggressive management of anthropogenic emission sources. Annual average ambient concentrations of SO2 and SO4 have become more uniform across the US at levels of 1–3 ppbv and 0.3–3 µg/m3, respectively. Precipitation SO4 has a nominal concentration generally less than 0.5 mg/L. The effective lifetime of SOx in the troposphere is a few days. This duration limits the spatial extent of emission source influence of SOx to regional scales, wherein spatial gradients in species concentrations lead to variations in human exposure and impacts on vulnerable terrestrial and aquatic ecosystems. The effects of domestic emission reductions on SOx levels are moderated by intra- and intercontinental transport of SOx from Canada, Mexico, Asia and elsewhere. The trends in tropospheric SOx concentrations illustrate the results of more than a century of rising public awareness and action to progressively reduce a US environmental risk, accomplished with advances in energy production technology that have maintained economic well-being.

  16. Global analysis of genetic variation in human arsenic (+ 3 oxidation state) methyltransferase (AS3MT)

    International Nuclear Information System (INIS)

    Fujihara, Junko; Soejima, Mikiko; Yasuda, Toshihiro; Koda, Yoshiro; Agusa, Tetsuro; Kunito, Takashi; Tongu, Miki; Yamada, Takaya; Takeshita, Haruo

    2010-01-01

    Human arsenic (+ 3 oxidation state) methyltransferase (AS3MT) is known to catalyze the methylation of arsenite. The objective of this study was to investigate the diversity of the AS3MT gene at the global level. The distribution of 18 single nucleotide polymorphisms (SNPs) in AS3MT was performed in 827 individuals from 10 populations (Japanese, Korean, Chinese, Mongolian, Tibetans, Sri Lankan Tamils, Sri Lankan Sinhalese, Nepal Tamangs, Ovambo, and Ghanaian). In the African populations, the A allele in A6144T was not observed; the allele frequencies of C35587 were much lower than those in other populations; the allele frequencies of A37616 and C37950 were relatively higher than those in other populations. Among Asian populations, Mongolians showed a different genotype distribution pattern. A lower C3963 and T6144 frequencies were observed, and, in the C37616A and T37950C polymorphism, the Mongolian population showed higher A37616 and C37950 allele frequencies than other Asian populations, similarly to the African populations. A total of 66 haplotypes were observed in the Ovambo, 48, in the Ghanaian, 99, in the Japanese, 103, in the Korean, 103, in the South Chinese, 20, in the Sri Lankan Tamil, 12, in the Sri Lankan Sinhalese, 21, in the Nepal Tamang, 50, in the Tibetan, and 45, in the Mongolian populations. The D' values between the SNP pairs were extremely high in the Sri Lankan Sinhalese population. Relatively higher D' values were observed in Mongolian and Sri Lankan Tamil populations. Network analysis showed two clusters that may have different origins, African and Asians (Chinese and/or Japanese). The present study is the first to demonstrate the existence of genetic heterogeneity in a world wide distribution of 18 SNPs in AS3MT.

  17. Metabolomic profiles of arsenic (+3 oxidation state) methyltransferase knockout mice: Effect of sex and arsenic exposure

    Science.gov (United States)

    Huang, Madelyn C.; Douillet, Christelle; Su, Mingming; Zhou, Kejun; Wu, Tao; Chen, Wenlian; Galanko, Joseph A.; Drobná, Zuzana; Saunders, R. Jesse; Martin, Elizabeth; Fry, Rebecca C.; Jia, Wei; Stýblo, Miroslav

    2016-01-01

    Arsenic (+3 oxidation state) methyltransferase (As3mt) is the key enzyme in the pathway for methylation of inorganic arsenic (iAs). Altered As3mt expression and AS3MT polymorphism have been linked to changes in iAs metabolism and in susceptibility to iAs toxicity in laboratory models and in humans. As3mt-knockout mice have been used to study the association between iAs metabolism and adverse effects of iAs exposure. However, little is known about systemic changes in metabolism of these mice and how these changes lead to their increased susceptibility to iAs toxicity. Here, we compared plasma and urinary metabolomes of male and female wild-type (WT) and As3mt-KO (KO) C57BL6 mice and examined metabolomic shifts associated with iAs exposure in drinking water. Surprisingly, exposure to 1 ppm As elicited only small changes in the metabolite profiles of either WT or KO mice. In contrast, comparisons of KO mice with WT mice revealed significant differences in plasma and urinary metabolites associated with lipid (phosphatidylcholines, cytidine, acyl-carnitine), amino acid (hippuric acid, acetylglycine, urea), and carbohydrate (L-sorbose, galactonic acid, gluconic acid) metabolism. Notably, most of these differences were sex-specific. Sex-specific differences were also found between WT and KO mice in plasma triglyceride and lipoprotein cholesterol levels. Some of the differentially changed metabolites (phosphatidylcholines, carnosine, and sarcosine) are substrates or products of reactions catalyzed by other methyltransferases. These results suggest that As3mt KO alters major metabolic pathways in a sex-specific manner, independent of iAs treatment, and that As3mt may be involved in other cellular processes beyond iAs methylation. PMID:26883664

  18. Terrestrial magma ocean and core segregation in the earth

    Science.gov (United States)

    Ohtani, Eiji; Yurimoto, Naoyoshi

    1992-01-01

    According to the recent theories of formation of the earth, the outer layer of the proto-earth was molten and the terrestrial magma ocean was formed when its radius exceeded 3000 km. Core formation should have started in this magma ocean stage, since segregation of metallic iron occurs effectively by melting of the proto-earth. Therefore, interactions between magma, mantle minerals, and metallic iron in the magma ocean stage controlled the geochemistry of the mantle and core. We have studied the partitioning behaviors of elements into the silicate melt, high pressure minerals, and metallic iron under the deep upper mantle and lower mantle conditions. We employed the multi-anvil apparatus for preparing the equilibrating samples in the ranges from 16 to 27 GPa and 1700-2400 C. Both the electron probe microanalyzer (EPMA) and the Secondary Ion Mass spectrometer (SIMS) were used for analyzing the run products. We obtained the partition coefficients of various trace elements between majorite, Mg-perovskite, and liquid, and magnesiowustite, Mg-perovskite, and metallic iron. The examples of the partition coefficients of some key elements are summarized in figures, together with the previous data. We may be able to assess the origin of the mantle abundances of the elements such as transition metals by using the partitioning data obtained above. The mantle abundances of some transition metals expected by the core-mantle equilibrium under the lower mantle conditions cannot explain the observed abundance of some elements such as Mn and Ge in the mantle. Estimations of the densities of the ultrabasic magma Mg-perovskite at high pressure suggest existence of a density crossover in the deep lower mantle; flotation of Mg-perovskite occurs in the deep magma ocean under the lower mantle conditions. The observed depletion of some transition metals such as V, Cr, Mn, Fe, Co, and Ni in the mantle may be explained by the two stage process, the core-mantle equilibrium under the lower

  19. When Magma Meets Carbonate: Explosive Criminals of Climate Change?

    Science.gov (United States)

    Carter, L. B.

    2017-12-01

    The natural carbon cycle is a key component of global climate change. Identifying and quantifying all processes in the cycle is essential to determine the effects of human greenhouse gas contributions and make future predictions. Volcanoes are the main natural source of carbon dioxide to the atmosphere [1]. In settings where carbonate rocks underlie the edifice, they can be consumed by magma passing through, which can release extra CO2, potentially explaining the extremely high emissions at Mount Etna in Italy [2-4]. We conduct laboratory experiments, mimicking conditions in the crust, to study how different carbonate rocks interact with hot magmas at pressure, and determine the amount of CO2 generated. We find that some types of magma can raise volcanic gas output and cause more explosive and dangerous eruptions [5-6]. Others are more likely to release hot fluids to the surrounding rocks, releasing CO2 by skarnification, which leaves economically important ores like in the western US [3,7] but can weaken the subsurface, potentially leading to landslides. Gas can also be released on the flanks of a volcano or in regions lacking an active volcano, due to the breakdown of certain carbonate rocks by heat [7], seen as bubbling springs in Yellowstone [8]. Our experiments indicate that if dolostone, not limestone, surrounds a magma chamber, over half the CO2 that was locked in the crust can escape even at lower temperatures a distance away. These processes are perhaps pertinent to why the Earth's climate was warm >50 million years ago, when more magma-carbonate interaction likely occurred than today [3] and thus contributed several times the current volcanic output [4] to the atmosphere. As significant parts of the long-term carbon cycle, it is necessary to include magma-carbonate reactions when considering climate changes before taking into account human input. [1] Aiuppa et al 2017 ESciRev (168) 24-47; [2] Ganino and Arndt 2009 Geol (37) 323-326; [3] Lee et al. 2013

  20. Determination of Pu Oxidation states in the HCl Media Using with UV-Visible Absorption Spectroscopic Techniques

    International Nuclear Information System (INIS)

    Lee, Myung Ho; Suh, Mu Yeol; Park, Kyoung Kyun; Park, Yeong Jae; Kim, Won Ho

    2006-01-01

    The spectroscopic characteristics of Pu (III, IV, V, VI) in the HCl media were investigated by measuring Pu oxidation states using a UV-Vis-NIR spectrophotometer (400-1200 nm) after adjusting Pu oxidation states with oxidation/reduction reagents. Pu in stock solution was reduced to Pu(III) with NH 2 OH · HCl, and oxidized to Pu(IV) and Pu(VI) with NaNO 2 and HCIO 4 , respectively. Also, Pu(V) was adjusted in the Pu(VI) solution with NH 2 OH · HCl. The major absorption peaks of Pu (IV) and Pu(III) were measured in the 470 nm and 600 nm, respectively. The major absorption peaks of Pu (VI) and Pu(V) were measured in the 830 nm and 1135 nm, respectively. There was not found to be significant changes of UV-V is absorption spectra for Pu(III), Pu(IV) and Pu(VI) with aging time, except that an unstable Pu(V) immediately reduced to Pu(III).

  1. V6O13 films by control of the oxidation state from aqueous precursor to crystalline phase.

    Science.gov (United States)

    Peys, Nick; Ling, Yun; Dewulf, Daan; Gielis, Sven; De Dobbelaere, Christopher; Cuypers, Daniel; Adriaensens, Peter; Van Doorslaer, Sabine; De Gendt, Stefan; Hardy, An; Van Bael, Marlies K

    2013-01-28

    An aqueous deposition process for V(6)O(13) films is developed whereby the vanadium oxidation state is continuously controlled throughout the entire process. In the precursor stage, a controlled wet chemical reduction of the vanadium(V) source with oxalic acid is achieved and monitored by (51)Vanadium Nuclear Magnetic Resonance ((51)V-NMR) and Ultraviolet-Visible (UV-Vis) spectroscopy. The resulting vanadium(IV) species in the aqueous solution are identified as mononuclear citrato-oxovanadate(IV) complexes by Electron Paramagnetic Resonance (EPR) and Fourier Transform Infra-Red (FTIR) spectroscopy. This precursor is successfully employed for the deposition of uniform, thin films. The optimal deposition and annealing conditions for the formation of crystalline V(6)O(13), including the control of the vanadium oxidation state, are determined through an elaborate study of processing temperature and O(2) partial pressure. To ensure a sub 100 nm adjustable film thickness, a non-oxidative intermediate thermal treatment is carried out at the end of each deposition cycle, allowing maximal precursor decomposition while still avoiding V(IV) oxidation. The resulting surface hydrophilicity, indispensable for the homogeneous deposition of the next layer, is explained by an increased surface roughness and the increased availability of surface vanadyl groups. Crystalline V(6)O(13) with a preferential (002) orientation is obtained after a post deposition annealing in a 0.1% O(2) ambient for thin films with a thickness of 20 nm.

  2. Advances in high-resolution synchrotron micro-XANES for constraining the redox evolution of terrestrial and extraterrestrial magma

    Science.gov (United States)

    Lanzirotti, A.; Sutton, S. R.; Dyar, M. D.; McCanta, M. C.; Head, E.

    2017-12-01

    Quantifying the redox evolution of geological materials is of fundamental importance for understanding the evolution of the Earth and terrestrial planets. Microfocused, synchrotron X-ray Absorption Spectroscopy (XAS) provides direct, in-situ analyses of the valence state for elements that can be used as proxies for oxygen fugacity (Fe, V, Cr, Ti, S, Eu, and Ce). Such proxies span the entire fO2 range of solar system evolution, covering at least 16 log units. Recent technical improvements at the Advanced Photon Source 13-ID-E microspectroscopy beamline have improved the energy, spatial resolution and detection sensitivity for XAS. The application of multiple valence state oxybarometers to individual mineral grains is valuable as demonstrated in a study of Ti, V and Cr valence in olivine and pyroxene of the ungrouped achondrite NWA 7325 [1], results which yielded a very reduced fO2 estimate of IW-3 and suggested a likely origin of NWA 7325 in a parent body with similar redox conditions to the ureilite parent body. Simultaneously, we have made advances using multivariate prediction models to more precisely measure ever-smaller variations in elemental valence [2]. Applied to V XAS spectra in glasses, we have developed an MVA calibration model that directly relates the measured spectra to predicted fO2, improving the precision in calculating fO2 with more robust error analysis. These machine learning based algorithms also allow for XAS to be collected in an imaging modality to spatially map elemental redox states within samples. For example for imaging changes in Fe oxidation state in natural lunar picritic glasses [3] that may be related to magmatic degassing. This presentation highlights recent examples of this research at 13-ID-E, including application of Fe, S and V valence state oxybarometers in the analysis of terrestrial volcanic glasses and melt inclusions for looking at long term evolution of oxygen fugacity of magmas. [1] Sutton S. et al. (2017) GCA, 211, 115

  3. A Semi-Analytical Extraction Method for Interface and Bulk Density of States in Metal Oxide Thin-Film Transistors.

    Science.gov (United States)

    Chen, Weifeng; Wu, Weijing; Zhou, Lei; Xu, Miao; Wang, Lei; Ning, Honglong; Peng, Junbiao

    2018-03-11

    A semi-analytical extraction method of interface and bulk density of states (DOS) is proposed by using the low-frequency capacitance-voltage characteristics and current-voltage characteristics of indium zinc oxide thin-film transistors (IZO TFTs). In this work, an exponential potential distribution along the depth direction of the active layer is assumed and confirmed by numerical solution of Poisson's equation followed by device simulation. The interface DOS is obtained as a superposition of constant deep states and exponential tail states. Moreover, it is shown that the bulk DOS may be represented by the superposition of exponential deep states and exponential tail states. The extracted values of bulk DOS and interface DOS are further verified by comparing the measured transfer and output characteristics of IZO TFTs with the simulation results by a 2D device simulator ATLAS (Silvaco). As a result, the proposed extraction method may be useful for diagnosing and characterising metal oxide TFTs since it is fast to extract interface and bulk density of states (DOS) simultaneously.

  4. A Semi-Analytical Extraction Method for Interface and Bulk Density of States in Metal Oxide Thin-Film Transistors

    Directory of Open Access Journals (Sweden)

    Weifeng Chen

    2018-03-01

    Full Text Available A semi-analytical extraction method of interface and bulk density of states (DOS is proposed by using the low-frequency capacitance–voltage characteristics and current–voltage characteristics of indium zinc oxide thin-film transistors (IZO TFTs. In this work, an exponential potential distribution along the depth direction of the active layer is assumed and confirmed by numerical solution of Poisson’s equation followed by device simulation. The interface DOS is obtained as a superposition of constant deep states and exponential tail states. Moreover, it is shown that the bulk DOS may be represented by the superposition of exponential deep states and exponential tail states. The extracted values of bulk DOS and interface DOS are further verified by comparing the measured transfer and output characteristics of IZO TFTs with the simulation results by a 2D device simulator ATLAS (Silvaco. As a result, the proposed extraction method may be useful for diagnosing and characterising metal oxide TFTs since it is fast to extract interface and bulk density of states (DOS simultaneously.

  5. Non steady-state model for dry oxidation of nuclear wastes metallic containers in long term interim storage conditions

    International Nuclear Information System (INIS)

    Bertrand, Nathalie; Desgranges, Clara; Poquillon, Dominique; Monceau, Daniel

    2006-01-01

    oxidation tests. In a second step, in order to increase the reliability of the long term extrapolations from basic models, a non-steady state numerical model able to take into account several elementary steps is built. The aim is to get a more reliable tool to describe mechanisms that control oxide scale growth in this specific low temperature range. The paper has the following contains: Experimental results; Growth kinetics; Scale morphology; A basic model for kinetics of oxidation; Conclusion of the experimental study; EKINOX: Estimation KINetics OXidation: an advanced model; General description; Equations in the model; Results; Future developments; Conclusion. To summarize, the basic model consists in some extrapolations of available experimental data in the temperature range of interest following simple analytical laws deduced from classical oxidation theories. This leads to a very small oxide scale and thus to the loss of very small amounts of metal even for extrapolations to over 100 years. However, the reliability of this kind of basic models is very poor since it is based on the assumption that a single elementary process controls the oxidation rate. Indeed in the temperature range concerned by long term interim deposit of waste containers, several mechanisms can control the oxidation rate. A numerical model able to take in consideration several growth mechanisms is now in progress. At this stage of development, the originality of the proposed advanced model consists in explicitly calculating the vacancy profiles and treating these as non-conservative species. It is based on an original numerical treatment to correctly and easily describe elimination of vacancies at the metal/oxide interface and thus relative motion between the substrate lattice and the oxide one, even for non-stationary states. It can treat Wagner's model but without the quasi-steady state 'hypothesis or also take into account a partial control of the oxidation process by interfacial reaction. In

  6. Storage, Ascent, and Release of Silicic Magma in Caldera-forming Eruptions

    Science.gov (United States)

    Myers, Madison Logan

    The mechanisms and timescales associated with the triggering of caldera-forming eruptions remain ambiguous and poorly constrained. Do such eruptions start vigorously, then escalate, or can there be episodicity? Are they triggered through internal processes (e.g. recharge, buoyancy), or can external modulations play an important role? Key to answering these questions is the ability to reconstruct the state of the magma body immediately prior to eruption. My dissertation research seeks to answer these questions through detailed investigation of four voluminous caldera-forming eruptions: (1) 650 km3, 0.767 Ma Bishop Tuff, Long Valley, (2) 530 km3, 25.4 ka Oruanui eruption, Taupo, (3) 2,500 km3, 2.08 Ma Huckleberry Ridge Tuff, Yellowstone and (4) 250 km3, 26.91 Ma Cebolla Creek Tuff, Colorado. The main techniques I applied integrated glass geochemistry (major, trace and volatile), diffusion modeling, and detailed field sampling. In chapters two, three, and four these methods are applied to the initial fall deposits of three supereruptions (Bishop, Oruanui and Huckleberry Ridge) that preserve field-evidence for different opening behaviors. These behaviors range from continuous deposition of fall deposits and ignimbrite (Bishop), to repetitive start/stop behavior, with time breaks between eruptive episodes on the order of weeks to months (Oruanui, Huckleberry Ridge). To reconstruct the timescales of opening activity and relate this to conduit processes, I used two methods that exploit diffusion of volatiles through minerals and melt, providing estimates for the rate at which magmas ascended to the surface. This knowledge is then integrated with the pre-eruptive configuration of the magma body, based on melt inclusion chemistry, to interpret what triggered these systems into unrest. Finally, in chapter five I take a different approach by integrating geochemical data for melt inclusions and phenocryst minerals to test whether the mechanism of heat and volatile recharge

  7. Towards a comprehensive classification of igneous rocks and magmas

    Science.gov (United States)

    Middlemost, Eric A. K.

    1991-08-01

    The IUGS Subcommission on the Systematics of Igneous Rocks has recently published an excellent book on the classification of these rocks. This event has shifted the vexed question of classification towards the top of the agenda in igneous petrology. Over the years the Subcommission has used many different criteria to establish the positions of the boundaries between the various common igneous rocks. It now has to adopt a holistic approach and develop a comprehensive, coherent classification that is purged of all the minor anomalies that arise between the various classifications that it has approved. It is appreciated that the Subcommission's classification was never intended to have any genetic implications; however, it is suggested that an ideal classification should he presented in such a way that it is able to group rocks into an order that directs attention to petrogenetic relationships between individual rocks and larger groups of rocks. Unfortunately, many of the Subcommission's definitions are Earth chauvinistic; for example, igneous rocks are defined as being those rocks that solidified from a molten state either within or on the surface of the Earth. Nowhere in the book is it acknowledged that during the past 20 years, while the Subcommission has been framing its many recommendations, a whole new science of planetary petrology has subsumed classical petrology. In any new edition of the book, the Subcommission should acknowledge that rocks are essentially the solid materials of which planets, natural satellites and other broadly similar cosmic bodies are made. The Subcommission should also explicitly recognise that igneous rocks can be divided into either a main sequence of essentially common rocks or a number of supplementary clans of special rocks that evolved outside the main sequence. It is hoped that in the near future the Subcommission will rescind its recommendation that the TAS classification should be regarded as an adjunct to its more traditional

  8. Monitoring the State of the Magmatic Structures of Elbrus Volcano Based on Observation of Lithosphere Strains

    International Nuclear Information System (INIS)

    Milyukov, Vadim; Myasnikov, Andrey; Mironov, Alexey

    2008-01-01

    An analysis of crustal strain recorded by the Baksan laser interferometer revealed a shallow magma chamber in the structure of Elbrus Volcano (The Northern Caucasus, Russia). The analysis is based on estimation of parameters of magmatic structures resonant modes excited by teleseismic signals. The resonance parameters we have found were interpreted in the framework of contemporary models of magma resonators. The depth and dimension of the magma chamber, as well as the properties of the magma fluid were estimated. It was suggested the changing the magma state due to rising the intrachamber pressure

  9. Segregating gas from melt: an experimental study of the Ostwald ripening of vapor bubbles in magmas

    Science.gov (United States)

    Lautze, Nicole C.; Sisson, Thomas W.; Mangan, Margaret T.; Grove, Timothy L.

    2011-01-01

    Diffusive coarsening (Ostwald ripening) of H2O and H2O-CO2 bubbles in rhyolite and basaltic andesite melts was studied with elevated temperature–pressure experiments to investigate the rates and time spans over which vapor bubbles may enlarge and attain sufficient buoyancy to segregate in magmatic systems. Bubble growth and segregation are also considered in terms of classical steady-state and transient (non-steady-state) ripening theory. Experimental results are consistent with diffusive coarsening as the dominant mechanism of bubble growth. Ripening is faster in experiments saturated with pure H2O than in those with a CO2-rich mixed vapor probably due to faster diffusion of H2O than CO2 through the melt. None of the experimental series followed the time1/3 increase in mean bubble radius and time-1 decrease in bubble number density predicted by classical steady-state ripening theory. Instead, products are interpreted as resulting from transient regime ripening. Application of transient regime theory suggests that bubbly magmas may require from days to 100 years to reach steady-state ripening conditions. Experimental results, as well as theory for steady-state ripening of bubbles that are immobile or undergoing buoyant ascent, indicate that diffusive coarsening efficiently eliminates micron-sized bubbles and would produce mm-sized bubbles in 102–104 years in crustal magma bodies. Once bubbles attain mm-sizes, their calculated ascent rates are sufficient that they could transit multiple kilometers over hundreds to thousands of years through mafic and silicic melt, respectively. These results show that diffusive coarsening can facilitate transfer of volatiles through, and from, magmatic systems by creating bubbles sufficiently large for rapid ascent.

  10. Solid-phase extraction of plutonium in various oxidation states from simulated groundwater using N-benzoylphenylhydroxylamine

    International Nuclear Information System (INIS)

    Perevalov, S.A.; Malofeeva, G.I.; Kuzovkina, E.V.; Spivakov, B.Ya.

    2013-01-01

    Solid-phase extraction of plutonium in different individual and mixed oxidation states from simulated groundwater (pH 8.5) was studied. The extraction of plutonium species was carried out in a dynamic mode using DIAPAK C16 cartridges modified by N-benzoylphenylhydroxylamine (BPHA). It was shown that the extent of recovery depends on the oxidation state of plutonium. The extraction of Pu(IV) was at the level of 98-99% regardless of the volume and flow-rate of the sample solution. Pu(V) was extracted by 90-95% and 75-80% from 10- and 100-mL aliquots of the samples, respectively, whereas the extraction of Pu(VI) did not exceed 45-50%. An equimolar mixture of Pu(IV), Pu(V), and Pu(VI) was extracted by 74%. The distribution coefficients (K d ) and kinetic exchange capacities (S) of plutonium in various oxidation states were measured. It was found that during the sorption process, Pu(V) was reduced to Pu(IV) by 80-90% after an hour-long contact with the solid phase. Pu(VI) is reduced to Pu(V) by 34% and to Pu(IV) by 55%. In the case of mixed-valent solution of plutonium, only Pu(V) and Pu(IV) were found in the effluents. (author)

  11. Homoleptic Ce(III) and Ce(IV) Nitroxide Complexes: Significant Stabilization of the 4+ Oxidation State

    Energy Technology Data Exchange (ETDEWEB)

    Bogart, Justin A.; Lewis, Andrew J.; Medling, Scott A.; Piro, Nicholas A.; Carroll, Patrick J.; Booth, Corwin H.; Schelter, Eric J.

    2014-06-25

    Electrochemical experiments performed on the complex Ce-IV[2-((BuNO)-Bu-t)py](4), where [2-((BuNO)-Bu-t)py](-) = N-tert-butyl-N-2-pyridylnitroxide, indicate a 2.51 V stabilization of the 4+ oxidation state of Ce compared to [(Bu4N)-Bu-n](2)[Ce(NO3)(6)] in acetonitrile and a 2.95 V stabilization compared to the standard potential for the ion under aqueous conditions. Density functional theory calculations suggest that this preference for the higher oxidation state is a result of the tetrakis(nitroxide) ligand framework at the Ce cation, which allows for effective electron donation into, and partial covalent overlap with, vacant 4f orbitals with delta symmetry. The results speak to the behavior of CeO2 and related solid solutions in oxygen uptake and transport applications, in particular an inherent local character of bonding that stabilizes the 4+ oxidation state. The results indicate a cerium(IV) complex that has been stabilized to an unprecedented degree through tuning of its ligand-field environment.

  12. High-Pressure Reactivity of Kr and F2—Stabilization of Krypton in the +4 Oxidation State

    Directory of Open Access Journals (Sweden)

    Dominik Kurzydłowski

    2017-10-01

    Full Text Available Since the synthesis of the first krypton compound, several other Kr-bearing connections have been obtained. However, in all of them krypton adopts the +2 oxidation state, in contrast to xenon which forms numerous compounds with an oxidation state as high as +8. Motivated by the possibility of thermodynamic stabilization of exotic compounds with the use of high pressure (exceeding 1 GPa = 10 kbar, we present here theoretical investigations into the chemistry of krypton and fluorine at such large compression. In particular we focus on krypton tetrafluoride, KrF4, a molecular crystal in which krypton forms short covalent bonds with neighboring fluorine atoms thus adopting the +4 oxidation state. We find that this hitherto unknown compound can be stabilized at pressures below 50 GPa. Our results indicate also that, at larger compressions, a multitude of other KrmFn fluorides should be stable, among them KrF which exhibits covalent Kr–Kr bonds. Our results set the stage for future high-pressure synthesis of novel krypton compounds.

  13. Degassing during magma ascent in the Mule Creek vent (USA)

    Science.gov (United States)

    Stasiuk, M.V.; Barclay, J.; Carroll, M.R.; Jaupart, Claude; Ratte, J.C.; Sparks, R.S.J.; Tait, S.R.

    1996-01-01

    The structures and textures of the rhyolite in the Mule Creek vent (New Mexico, USA) indicate mechanisms by which volatiles escape from silicic magma during eruption. The vent outcrop is a 300-m-high canyon wall comprising a section through the top of a feeder conduit, vent and the base of an extrusive lava dome. Field relations show that eruption began with an explosive phase and ended with lava extrusion. Analyses of glass inclusions in quartz phenocrysts from the lava indicate that the magma had a pre-eruptive dissolved water content of 2.5-3.0 wt% and, during eruption, the magma would have been water-saturated over the vertical extent of the present outcrop. However, the vesicularity of the rhyolite is substantially lower than that predicted from closed-system models of vesiculation under equilibrium conditions. At a given elevation in the vent, the volume fraction of primary vesicles in the rhyolite increases from zero close to the vent margin to values of 20-40 vol.% in the central part. In the centre the vesicularity increases upward from approximately 20 vol.% at 300 m below the canyon rim to approximately 40 vol.% at 200 m, above which it shows little increase. To account for the discrepancy between observed vesicularity and measured water content, we conclude that gas escaped during ascent, probably beginning at depths greater than exposed, by flow through the vesicular magma. Gas escape was most efficient near the vent margin, and we postulate that this is due both to the slow ascent of magma there, giving the most time for gas to escape, and to shear, favouring bubble coalescence. Such shear-related permeability in erupting magma is supported by the preserved distribution of textures and vesicularity in the rhyolite: Vesicles are flattened and overlapping near the dense margins and become progressively more isolated and less deformed toward the porous centre. Local zones have textures which suggest the coalescence of bubbles to form permeable

  14. Finite automata over magmas: models and some applications in Cryptography

    Directory of Open Access Journals (Sweden)

    Volodymyr V. Skobelev

    2018-05-01

    Full Text Available In the paper the families of finite semi-automata and reversible finite Mealy and Moore automata over finite magmas are defined and analyzed in detail. On the base of these models it is established that the set of finite quasigroups is the most acceptable subset of the set of finite magmas at resolving model problems in Cryptography, such as design of iterated hash functions and stream ciphers. Defined families of finite semi-automata and reversible finite automata over finite $T$-quasigroups are investigated in detail. It is established that in this case models time and space complexity for simulation of the functioning during one instant of automaton time can be much lower than in general case.

  15. A magma ocean and the Earth's internal water budget

    Science.gov (United States)

    Ahrens, Thomas J.

    1992-01-01

    There are lines of evidence which relate bounds on the primordial water content of the Earth's mantle to a magma ocean and the accompanying Earth accretion process. We assume initially (before a magma ocean could form) that as the Earth accreted, it grew from volatile- (H2O, CO2, NH3, CH4, SO2, plus noble) gas-rich planetesimals, which accreted to form an initial 'primitive accretion core' (PAC). The PAC retained the initial complement of planetesimal gaseous components. Shock wave experiments in which both solid, and more recently, the gaseous components of materials such as serpentine and the Murchison meteorite have demonstrated that planetesimal infall velocities of less than 0.5 km/sec, induce shock pressures of less than 0.5 GPa and result in virtually complete retention of planetary gases.

  16. Evidence of a global magma ocean in Io's interior.

    Science.gov (United States)

    Khurana, Krishan K; Jia, Xianzhe; Kivelson, Margaret G; Nimmo, Francis; Schubert, Gerald; Russell, Christopher T

    2011-06-03

    Extensive volcanism and high-temperature lavas hint at a global magma reservoir in Io, but no direct evidence has been available. We exploited Jupiter's rotating magnetic field as a sounding signal and show that the magnetometer data collected by the Galileo spacecraft near Io provide evidence of electromagnetic induction from a global conducting layer. We demonstrate that a completely solid mantle provides insufficient response to explain the magnetometer observations, but a global subsurface magma layer with a thickness of over 50 kilometers and a rock melt fraction of 20% or more is fully consistent with the observations. We also place a stronger upper limit of about 110 nanoteslas (surface equatorial field) on the dynamo dipolar field generated inside Io.

  17. Effects of Vanadium Ions in Different Oxidation States on Myosin ATPase Extracted from the Solitary Ascidian, Halocynthia roretzi (Drasche) : Biochemistry

    OpenAIRE

    HITOSHI, MICHIBATA; YUTAKA, ZENKO; KENJI, YAMADA; MASATO, HASEGAWA; TATSURO, TERADA; TAKAHARU, NUMAKUANI; Biological Institute, Faculty of Science, Toyama University; Biological Institute, Faculty of Science, Toyama University; Biological Institute, Faculty of Science, Toyama University; Biological Institute, Faculty of Science, Toyama University; Department of Chemistry, Toyama College of Technology; Marine Biological Station, Tohoku University

    1989-01-01

    Some ascidians are known to accumulate vanadium ion within their tissues by 10^6-fold as that in sea water and store the metal ion in its reduced tetravalent and/or trivalent states. It is also well known that phosphoenzymes are inhibited by pentavalent vanadium ion over a range of 10nM to 1mM. In the present experiment we have therefore examined the effects of vanadium ions in different oxidation states on the activity of myosin ATPase extracted from the mantle of the ascidian, Halocynthia r...

  18. Current emission trends for nitrogen oxides, sulfur dioxide, and volatile organic compounds by month and state: Methodology and results

    International Nuclear Information System (INIS)

    Kohout, E.J.; Miller, D.J.; Nieves, L.A.; Rothman, D.S.; Saricks, C.L.; Stodolsky, F.; Hanson, D.A.

    1990-08-01

    This report presents estimates of monthly sulfur dioxide (SO 2 ), nitrogen oxides (NO x ), and nonmethane voltatile organic compound (VOC) emissions by sector, region, and state in the contiguous United States for the years 1975 through 1988. This work has been funded as part of the National Acid Precipitation Assessment Program's Emissions and Controls Task Group by the US Department of Energy (DOE) Office of Fossil Energy (FE). The DOE project officer is Edward C. Trexler, DOE/FE Office of Planning and Environment

  19. Plutonium uptake by the green alga Scenedesmus obliquus (Turp) Kutz, as a function of isotope and oxidation state

    Energy Technology Data Exchange (ETDEWEB)

    Tkacik, M.F.

    1977-01-01

    This study was designed to determine the effect of plutonium chemical valence state on the availability of small concentrations of /sup 238/Pu and /sup 239/Pu to algae. The uptake experiments involved the green alga Scenedesmus obliquus, grown in batch cultures. Plutonium concentrations accumulated by this alga were linearly related to plutonium concentrations. There was no significant difference (rho = 0.05) in algal plutonium accumulations, on a mass basis, of either /sup 238/Pu or /sup 239/Pu in either Pu/sup +4/ or Pu/sup +6/ oxidation state at the concentrations studied.

  20. Plutonium uptake by the green alga Scenedesmus obliquus (Turp) Kutz, as a function of isotope and oxidation state

    International Nuclear Information System (INIS)

    Tkacik, M.F.

    1977-01-01

    This study was designed to determine the effect of plutonium chemical valence state on the availability of small concentrations of 238 Pu and 239 Pu to algae. The uptake experiments involved the green alga Scenedesmus obliquus, grown in batch cultures. Plutonium concentrations accumulated by this alga were linearly related to plutonium concentrations. There was no significant difference (rho = 0.05) in algal plutonium accumulations, on a mass basis, of either 238 Pu or 239 Pu in either Pu +4 or Pu +6 oxidation state at the concentrations studied

  1. Thermally-assisted Magma Emplacement Explains Restless Calderas

    Science.gov (United States)

    Amoruso, A.; Crescentini, L.; D'Antonio, M.; Acocella, V.

    2017-12-01

    Many calderas show repeated unrest over centuries. Though probably induced by magma, this unique behaviour is not understood and its dynamics remains elusive. To better understand these restless calderas, we interpret deformation data and build thermal models of Campi Flegrei, Italy, which is the best-known, yet most dangerous calderas, lying to the west of Naples and restless since the 1950s at least.Our elaboration of the geodetic data indicates that the inflation and deflation of magmatic sources at the same location explain most deformation, at least since the build-up of the last 1538 AD eruption. However, such a repeated magma emplacement requires a persistently hot crust.Our thermal models show that the repeated emplacement was assisted by the thermal anomaly created by magma that was intruded at shallow depth 3 ka before the last eruption and, in turn, contributed to maintain the thermal anomaly itself. This may explain the persistence of the magmatic sources promoting the restless behaviour of the Campi Flegrei caldera; moreover, it explains the crystallization, re-melting and mixing among compositionally distinct magmas recorded in young volcanic rocks.Available information at other calderas highlights similarities to Campi Flegrei, in the pattern and cause of unrest. All monitored restless calderas have either geodetically (Yellowstone, Aira Iwo-Jima, Askja, Fernandina and, partly, Long Valley) or geophysically (Rabaul, Okmok) detected sill-like intrusions inducing repeated unrest. Some calderas (Yellowstone, Long Valley) also show stable deformation pattern, where inflation insists on and mimics the resurgence uplift. The common existence of sill-like sources, also responsible for stable deformation patterns, in restless calderas suggests close similarities to Campi Flegrei. This suggests a wider applicability of our model of thermally-assisted sill emplacement, to be tested by future studies to better understand not only the dynamics of restless

  2. MAGMA: generalized gene-set analysis of GWAS data.

    Science.gov (United States)

    de Leeuw, Christiaan A; Mooij, Joris M; Heskes, Tom; Posthuma, Danielle

    2015-04-01

    By aggregating data for complex traits in a biologically meaningful way, gene and gene-set analysis constitute a valuable addition to single-marker analysis. However, although various methods for gene and gene-set analysis currently exist, they generally suffer from a number of issues. Statistical power for most methods is strongly affected by linkage disequilibrium between markers, multi-marker associations are often hard to detect, and the reliance on permutation to compute p-values tends to make the analysis computationally very expensive. To address these issues we have developed MAGMA, a novel tool for gene and gene-set analysis. The gene analysis is based on a multiple regression model, to provide better statistical performance. The gene-set analysis is built as a separate layer around the gene analysis for additional flexibility. This gene-set analysis also uses a regression structure to allow generalization to analysis of continuous properties of genes and simultaneous analysis of multiple gene sets and other gene properties. Simulations and an analysis of Crohn's Disease data are used to evaluate the performance of MAGMA and to compare it to a number of other gene and gene-set analysis tools. The results show that MAGMA has significantly more power than other tools for both the gene and the gene-set analysis, identifying more genes and gene sets associated with Crohn's Disease while maintaining a correct type 1 error rate. Moreover, the MAGMA analysis of the Crohn's Disease data was found to be considerably faster as well.

  3. The chlorine isotope fingerprint of the lunar magma ocean.

    Science.gov (United States)

    Boyce, Jeremy W; Treiman, Allan H; Guan, Yunbin; Ma, Chi; Eiler, John M; Gross, Juliane; Greenwood, James P; Stolper, Edward M

    2015-09-01

    The Moon contains chlorine that is isotopically unlike that of any other body yet studied in the Solar System, an observation that has been interpreted to support traditional models of the formation of a nominally hydrogen-free ("dry") Moon. We have analyzed abundances and isotopic compositions of Cl and H in lunar mare basalts, and find little evidence that anhydrous lava outgassing was important in generating chlorine isotope anomalies, because (37)Cl/(35)Cl ratios are not related to Cl abundance, H abundance, or D/H ratios in a manner consistent with the lava-outgassing hypothesis. Instead, (37)Cl/(35)Cl correlates positively with Cl abundance in apatite, as well as with whole-rock Th abundances and La/Lu ratios, suggesting that the high (37)Cl/(35)Cl in lunar basalts is inherited from urKREEP, the last dregs of the lunar magma ocean. These new data suggest that the high chlorine isotope ratios of lunar basalts result not from the degassing of their lavas but from degassing of the lunar magma ocean early in the Moon's history. Chlorine isotope variability is therefore an indicator of planetary magma ocean degassing, an important stage in the formation of terrestrial planets.

  4. Isotopic abundances relevant to the identification of magma sources

    International Nuclear Information System (INIS)

    O'Nions, R.K.

    1984-01-01

    The behaviour of natural radiogenic isotope tracers in the Earth that have lithophile and atmophile geochemical affinity is reviewed. The isotope tracer signature of oceanic and continental crust may in favourable circumstances by sufficiently distinct from that of the mantle to render a contribution from these sources resolvable within the isotopic composition of the magma. Components derived from the sedimentary and altered basaltic portion of oceanic crust are recognized in some island arc magmas from their Sr, Nd and Pb isotopic signatures. The rare-gas isotope tracers (He, Ar, Xe in particular) are not readily recycled into the mantle and thus provide the basis of an approach that is complementary to that based on the lithophile tracers. In particular, a small mantle-derived helium component may be readily recognized in the presence of a predominant radiogenic component generated in the continents. The importance of assessing the mass balance of these interactions rather than merely a qualitative recognition is emphasized. The question of the relative, contribution of continental-oceanic crust and mantle to magma sources is an essential part of the problem of generation and evolution of continental crust. An approach to this problem through consideration of the isotopic composition of sediments is briefly discussed. (author)

  5. Parental magmas of Mare Fecunditatis - Evidence from pristine glasses

    International Nuclear Information System (INIS)

    Jin, Y.; Taylor, L.A.

    1990-01-01

    Results are presented on the petrography and electron microprobe analyses of 14 discrete glass beads from the Luna 16 core sample (21036,15) from Mare Fecunditatis regolith, that were previously characterized as representing pristine glasses. Compared to Apollo pristine glasses analyzed by Delano (1986), the Luna 16 pristine glasses have higher CaO and Al2O3 contents but lower MgO and Ni. On the basis of their contents of MgO, FeO, Al2O3, and CaO, these pristine glasses could be divided into two groups, A and B. It is suggested that at least two parental magmas are needed to explain the chemical variations among these glasses. The Group B glasses appear to represent primitive parental magma that evolved by olivine fractionation to the compositions of the Luna 16 aluminous mare basalts, whereas the Group A volcanic glasses may represent an unusual new basalt magma type that contains a high plagioclase component. 14 refs

  6. Automatic Compound Annotation from Mass Spectrometry Data Using MAGMa.

    Science.gov (United States)

    Ridder, Lars; van der Hooft, Justin J J; Verhoeven, Stefan

    2014-01-01

    The MAGMa software for automatic annotation of mass spectrometry based fragmentation data was applied to 16 MS/MS datasets of the CASMI 2013 contest. Eight solutions were submitted in category 1 (molecular formula assignments) and twelve in category 2 (molecular structure assignment). The MS/MS peaks of each challenge were matched with in silico generated substructures of candidate molecules from PubChem, resulting in penalty scores that were used for candidate ranking. In 6 of the 12 submitted solutions in category 2, the correct chemical structure obtained the best score, whereas 3 molecules were ranked outside the top 5. All top ranked molecular formulas submitted in category 1 were correct. In addition, we present MAGMa results generated retrospectively for the remaining challenges. Successful application of the MAGMa algorithm required inclusion of the relevant candidate molecules, application of the appropriate mass tolerance and a sufficient degree of in silico fragmentation of the candidate molecules. Furthermore, the effect of the exhaustiveness of the candidate lists and limitations of substructure based scoring are discussed.

  7. Concentration variance decay during magma mixing: a volcanic chronometer.

    Science.gov (United States)

    Perugini, Diego; De Campos, Cristina P; Petrelli, Maurizio; Dingwell, Donald B

    2015-09-21

    The mixing of magmas is a common phenomenon in explosive eruptions. Concentration variance is a useful metric of this process and its decay (CVD) with time is an inevitable consequence during the progress of magma mixing. In order to calibrate this petrological/volcanological clock we have performed a time-series of high temperature experiments of magma mixing. The results of these experiments demonstrate that compositional variance decays exponentially with time. With this calibration the CVD rate (CVD-R) becomes a new geochronometer for the time lapse from initiation of mixing to eruption. The resultant novel technique is fully independent of the typically unknown advective history of mixing - a notorious uncertainty which plagues the application of many diffusional analyses of magmatic history. Using the calibrated CVD-R technique we have obtained mingling-to-eruption times for three explosive volcanic eruptions from Campi Flegrei (Italy) in the range of tens of minutes. These in turn imply ascent velocities of 5-8 meters per second. We anticipate the routine application of the CVD-R geochronometer to the eruptive products of active volcanoes in future in order to constrain typical "mixing to eruption" time lapses such that monitoring activities can be targeted at relevant timescales and signals during volcanic unrest.

  8. Shock compression of strongly correlated oxides: A liquid-regime equation of state for cerium(IV) oxide

    Science.gov (United States)

    Weck, Philippe F.; Cochrane, Kyle R.; Root, Seth; Lane, J. Matthew D.; Shulenburger, Luke; Carpenter, John H.; Sjostrom, Travis; Mattsson, Thomas R.; Vogler, Tracy J.

    2018-03-01

    The shock Hugoniot for full-density and porous CeO2 was investigated in the liquid regime using ab initio molecular dynamics (AIMD) simulations with Erpenbeck's approach based on the Rankine-Hugoniot jump conditions. The phase space was sampled by carrying out NVT simulations for isotherms between 6000 and 100 000 K and densities ranging from ρ =2.5 to 20 g /cm3 . The impact of on-site Coulomb interaction corrections +U on the equation of state (EOS) obtained from AIMD simulations was assessed by direct comparison with results from standard density functional theory simulations. Classical molecular dynamics (CMD) simulations were also performed to model atomic-scale shock compression of larger porous CeO2 models. Results from AIMD and CMD compression simulations compare favorably with Z-machine shock data to 525 GPa and gas-gun data to 109 GPa for porous CeO2 samples. Using results from AIMD simulations, an accurate liquid-regime Mie-Grüneisen EOS was built for CeO2. In addition, a revised multiphase SESAME-type EOS was constrained using AIMD results and experimental data generated in this work. This study demonstrates the necessity of acquiring data in the porous regime to increase the reliability of existing analytical EOS models.

  9. Making mushy magma chambers in the lower continental crust: Cold storage and compositional bimodality

    Science.gov (United States)

    Jackson, Matthew; Blundy, Jon; Sparks, Steve

    2017-04-01

    Increasing geological and geophysical evidence suggests that crustal magma reservoirs are normally low melt fraction 'mushes' rather than high melt fraction 'magma chambers'. Yet high melt fractions must form within these mush reservoirs to explain the observed flow and eruption of low crystallinity magmas. In many models, crystallinity is linked directly to temperature, with higher temperature corresponding to lower crystallinity (higher melt fraction). However, increasing temperature yields less evolved (silicic) melt composition for a given starting material. If mobile, low crystallinity magmas require high temperature, it is difficult to explain how they can have evolved composition. Here we use numerical modelling to show that reactive melt flow in a porous and permeable mush reservoir formed by the intrusion of numerous basaltic sills into the lower continental crust produces magma in high melt fraction (> 0.5) layers akin to conventional magma chambers. These magma-chamber-like layers contain evolved (silicic) melt compositions and form at low (close to solidus) temperatures near the top of the mush reservoir. Evolved magma is therefore kept in 'cold storage' at low temperature, but also at low crystallinity so the magma is mobile and can leave the mush reservoir. Buoyancy-driven reactive flow and accumulation of melt in the mush reservoir controls the temperature and composition of magma that can leave the reservoir. The modelling also shows that processes in lower crustal mush reservoirs produce mobile magmas that contain melt of either silicic or mafic composition. Intermediate melt compositions are present but are not within mobile magmas. Silicic melt compositions are found at high melt fraction within the magma-chamber like layers near the top of the mush reservoir. Mafic melt compositions are found at high melt fraction within the cooling sills. Melt elsewhere in the reservoir has intermediate composition, but remains trapped in the reservoir because

  10. Oxygen isotope study of the Long Valley magma system, California: isotope thermometry and convection in large silicic magma bodies

    Science.gov (United States)

    Bindeman, Ilya; Valley, John

    2002-07-01

    Products of voluminous pyroclastic eruptions with eruptive draw-down of several kilometers provide a snap-shot view of batholith-scale magma chambers, and quench pre-eruptive isotopic fractionations (i.e., temperatures) between minerals. We report analyses of oxygen isotope ratio in individual quartz phenocrysts and concentrates of magnetite, pyroxene, and zircon from individual pumice clasts of ignimbrite and fall units of caldera-forming 0.76 Ma Bishop Tuff (BT), pre-caldera Glass Mountain (2.1-0.78 Ma), and post-caldera rhyolites (0.65-0.04 Ma) to characterize the long-lived, batholith-scale magma chamber beneath Long Valley Caldera in California. Values of δ18O show a subtle 1‰ decrease from the oldest Glass Mountain lavas to the youngest post-caldera rhyolites. Older Glass Mountain lavas exhibit larger ( 1‰) variability of δ18O(quartz). The youngest domes of Glass Mountain are similar to BT in δ18O(quartz) values and reflect convective homogenization during formation of BT magma chamber surrounded by extremely heterogeneous country rocks (ranging from 2 to +29‰). Oxygen isotope thermometry of BT confirms a temperature gradient between "Late" (815 °C) and "Early" (715 °C) BT. The δ18O(quartz) values of "Early" and "Late" BT are +8.33 and 8.21‰, consistent with a constant δ18O(melt)=7.8+/-0.1‰ and 100 °C temperature difference. Zircon-melt saturation equilibria gives a similar temperature range. Values of δ18O(quartz) for different stratigraphic units of BT, and in pumice clasts ranging in pre-eruptive depths from 6 to 11 km (based on melt inclusions), and document vertical and lateral homogeneity of δ18O(melt). Worldwide, five other large-volume rhyolites, Lava Creek, Lower Bandelier, Fish Canyon, Cerro Galan, and Toba, exhibit equal δ18O(melt) values of earlier and later erupted portions in each of the these climactic caldera-forming eruptions. We interpret the large-scale δ18O homogeneity of BT and other large magma chambers as evidence

  11. Buffered and unbuffered dike emplacement on Earth and Venus - Implications for magma reservoir size, depth, and rate of magma replenishment

    Science.gov (United States)

    Parfitt, E. A.; Head, J. W., III

    1993-01-01

    Models of the emplacement of lateral dikes from magma chambers under constant (buffered) driving pressure conditions and declining (unbuffered) driving pressure conditions indicate that the two pressure scenarios lead to distinctly different styles of dike emplacement. In the unbuffered case, the lengths and widths of laterally emplaced dikes will be severely limited and the dike lengths will be highly dependent on chamber size; this dependence suggests that average dike length can be used to infer the dimensions of the source magma reservoir. On Earth, the characteristics of many mafic-dike swarms suggest that they were emplaced in buffered conditions (e.g., the Mackenzie dike swarm in Canada and some dikes within the Scottish Tertiary). On Venus, the distinctive radial fractures and graben surrounding circular to oval features and edifices on many size scales and extending for hundreds to over a thousand km are candidates for dike emplacement in buffered conditions.

  12. Magmatic sulphides in Quaternary Ecuadorian arc magmas

    Science.gov (United States)

    Georgatou, Ariadni; Chiaradia, Massimo; Rezeau, Hervé; Wälle, Markus

    2018-01-01

    New petrographic and geochemical data on magmatic sulphide inclusions (MSIs) are presented and discussed for 15 Quaternary volcanic centers of the Ecuadorian frontal, main and back volcanic arc. MSIs occur mostly in Fe-Ti oxides (magnetite and/or magnetite-ilmenite pair) and to a lesser extent in silicate minerals (amphibole, plagioclase, and pyroxene). MSIs are present in all volcanic centers ranging in composition from basalt to dacite (SiO2 = 50-67 wt.%), indicating that sulphide saturation occurs at various stages of magmatic evolution and independently from the volcano location along the volcanic arc. MSIs also occur in dioritic, gabbroic and hornblenditic magmatic enclaves of the volcanic rocks. MSIs display variable sizes (1-30 μm) and shapes (globular, ellipsoidal, angular, irregular) and occur mostly as polymineralic inclusions composed of Fe-rich and Cu-poor (pyrrhotite) and Cu-rich (mostly chalcopyrite) phases. Aerial sulphide relative abundances range from 0.3 to 7 ppm in volcanic host rocks and from 13 to 24 ppm in magmatic enclaves. Electron microprobe analyses of MSIs indicate maximum metal contents of Cu = 65.7 wt.%, Fe = 65.2 wt.%, Ni = 10.1 wt.% for those hosted in the volcanic rocks and of Cu = 57.7 wt.%, Fe = 60.9 wt.%, Ni = 5.1 wt.%, for those hosted in magmatic enclaves. Relationships of the sulphide chemistry to the host whole rock chemistry show that with magmatic differentiation (e.g., increasing SiO2) the Cu and Ni content of sulphides decrease whereas the Fe and S contents increase. The opposite behavior is observed with the increase of Cu in the whole rock, because the latter is anti-correlated with the SiO2 whole rock content. Laser ablation ICP-MS analyses of MSIs returned maximum values of PGEs and noble metals of Pd = 30 ppm, Rh = 8.1 ppm, Ag = 92.8 ppm and Au = 0.6 ppm and Pd = 43 ppm, Rh = 22.6 ppm, Ag = 89 ppm and Au = 1 ppm for those hosted in volcanic rocks and magmatic enclaves, respectively. These PGE contents display a

  13. Geochemical evidences of magma dynamics at Campi Flegrei (Italy)

    Science.gov (United States)

    Caliro, S.; Chiodini, G.; Paonita, A.

    2014-05-01

    Campi Flegrei caldera, within the Neapolitan area of Italy, is potentially one of the most dangerous volcanoes in the world, and during the last decade it has shown clear signs of reactivation, marked by the onset of uplift and changes in the geochemistry of gas emissions. We describe a 30-year-long data set of the CO2-He-Ar-N2 compositions of fumarolic emissions from La Solfatara crater, which is located in the center of the caldera. The data display continuous decreases in both the N2/He and N2/CO2 ratios since 1985, paralleled by an increase in He/CO2. These variations cannot be explained by either processes of boiling/condensation in the local hydrothermal system or with changes in the mixing proportions between a magmatic vapor and hydrothermal fluids. We applied the magma degassing model of Nuccio and Paonita (2001, Earth Planet. Sci. Lett. 193, 467-481) using the most recent inert-gas solubilities in order to interpret these peculiar features in accordance with petrologic constraints derived from the ranges of the melt compositions and reservoir pressures at Campi Flegrei. The model simulations for mafic melts (trachybasalt and shoshonite) show a remarkably good agreement with the measured data. Both decompressive degassing of an ascending magma and mixing between magmatic fluids exsolved at various levels along the ascent path can explain the long-term geochemical changes. Recalling that (i) a sill-like reservoir of gases at a depth of 3-4 km seems to be the main source of ground inflation and (ii) there is petrologic and geophysical evidence for a reservoir of magma at about 8 km below Campi Flegrei, we suggest that the most-intense episodes of inflation occur when the gas supply to the sill-like reservoir comes from the 8 km-deep magma, although fluids exsolved by magma bodies at shallower depths also contribute to the gas budget. Our work highlights that, in caldera systems where the presence of hydrothermal aquifers commonly masks the magmatic signature

  14. Computer Simulation To Assess The Feasibility Of Coring Magma

    Science.gov (United States)

    Su, J.; Eichelberger, J. C.

    2017-12-01

    Lava lakes on Kilauea Volcano, Hawaii have been successfully cored many times, often with nearly complete recovery and at temperatures exceeding 1100oC. Water exiting nozzles on the diamond core bit face quenches melt to glass just ahead of the advancing bit. The bit readily cuts a clean annulus and the core, fully quenched lava, passes smoothly into the core barrel. The core remains intact after recovery, even when there are comparable amounts of glass and crystals with different coefficients of thermal expansion. The unique resulting data reveal the rate and sequence of crystal growth in cooling basaltic lava and the continuous liquid line of descent as a function of temperature from basalt to rhyolite. Now that magma bodies, rather than lava pooled at the surface, have been penetrated by geothermal drilling, the question arises as to whether similar coring could be conducted at depth, providing fundamentally new insights into behavior of magma. This situation is considerably more complex because the coring would be conducted at depths exceeding 2 km and drilling fluid pressures of 20 MPa or more. Criteria that must be satisfied include: 1) melt is quenched ahead of the bit and the core itself must be quenched before it enters the barrel; 2) circulating drilling fluid must keep the temperature of the coring assembling cooled to within operational limits; 3) the drilling fluid column must nowhere exceed the local boiling point. A fluid flow simulation was conducted to estimate the process parameters necessary to maintain workable temperatures during the coring operation. SolidWorks Flow Simulation was used to estimate the effect of process parameters on the temperature distribution of the magma immediately surrounding the borehole and of drilling fluid within the bottom-hole assembly (BHA). A solid model of the BHA was created in SolidWorks to capture the flow behavior around the BHA components. Process parameters used in the model include the fluid properties and

  15. Signatures of Quantized Energy States in Solution-Processed Ultrathin Layers of Metal-Oxide Semiconductors and Their Devices

    KAUST Repository

    Labram, John G.

    2015-02-13

    Physical phenomena such as energy quantization have to-date been overlooked in solution-processed inorganic semiconducting layers, owing to heterogeneity in layer thickness uniformity unlike some of their vacuum-deposited counterparts. Recent reports of the growth of uniform, ultrathin (<5 nm) metal-oxide semiconductors from solution, however, have potentially opened the door to such phenomena manifesting themselves. Here, a theoretical framework is developed for energy quantization in inorganic semiconductor layers with appreciable surface roughness, as compared to the mean layer thickness, and present experimental evidence of the existence of quantized energy states in spin-cast layers of zinc oxide (ZnO). As-grown ZnO layers are found to be remarkably continuous and uniform with controllable thicknesses in the range 2-24 nm and exhibit a characteristic widening of the energy bandgap with reducing thickness in agreement with theoretical predictions. Using sequentially spin-cast layers of ZnO as the bulk semiconductor and quantum well materials, and gallium oxide or organic self-assembled monolayers as the barrier materials, two terminal electronic devices are demonstrated, the current-voltage characteristics of which resemble closely those of double-barrier resonant-tunneling diodes. As-fabricated all-oxide/hybrid devices exhibit a characteristic negative-differential conductance region with peak-to-valley ratios in the range 2-7.

  16. Eruptive dynamics during magma decompression: a laboratory approach

    Science.gov (United States)

    Spina, L.; Cimarelli, C.; Scheu, B.; Wadsworth, F.; Dingwell, D. B.

    2013-12-01

    A variety of eruptive styles characterizes the activity of a given volcano. Indeed, eruptive styles can range from effusive phenomena to explosive eruptions, with related implications for hazard management. Rapid changes in eruptive style can occur during an ongoing eruption. These changes are, amongst other, related to variations in the magma ascent rate, a key parameter affecting the eruptive style. Ascent rate is in turn dependent on several factors such as the pressure in the magma chamber, the physical properties of the magma and the rate at which these properties change. According to the high number of involved parameters, laboratory decompression experiments are the best way to achieve quantitative information on the interplay of each of those factors and the related impact on the eruption style, i.e. by analyzing the flow and deformation behavior of the transparent volatile-bearing analogue fluid. We carried out decompression experiments following different decompression paths and using silicone oil as an analogue for the melt, with which we can simulate a range of melt viscosity values. For a set of experiments we added rigid particles to simulate the presence of crystals in the magma. The pure liquid or suspension was mounted into a transparent autoclave and pressurized to different final pressures. Then the sample was saturated with argon for a fixed amount of time. The decompression path consists of a slow decompression from the initial pressure to the atmospheric condition. Alternatively, samples were decompressed almost instantaneously, after established steps of slow decompression. The decompression path was monitored with pressure transducers and a high-speed video camera. Image analysis of the videos gives quantitative information on the bubble distribution with respect to depth in the liquid, pressure and time of nucleation and on their characteristics and behavior during the ongoing magma ascent. Furthermore, we also monitored the evolution of

  17. Electrocatalytic oxidation of methanol by the [Ru3O(OAc6(py2(CH3OH]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

    Directory of Open Access Journals (Sweden)

    Henrique E. Toma

    2010-01-01

    Full Text Available The [Ru3O(Ac6(py2(CH3OH]+ cluster provides an effective electrocatalytic species for the oxidation of methanol under mild conditions. This complex exhibits characteristic electrochemical waves at -1.02, 0.15 and 1.18 V, associated with the Ru3III,II,II/Ru3III,III,II/Ru 3III,III,III /Ru3IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two RuIV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

  18. Control of anode supported SOFCs (solid oxide fuel cells): Part I. mathematical modeling and state estimation within one cell

    International Nuclear Information System (INIS)

    Amedi, Hamid Reza; Bazooyar, Bahamin; Pishvaie, Mahmoud Reza

    2015-01-01

    In this paper, a 3-dimensional mathematical model for one cell of an anode-supported SOFC (solid oxide fuel cells) is presented. The model is derived from the partial differential equations representing the conservation laws of ionic and electronic charges, mass, energy, and momentum. The model is implemented to fully characterize the steady state operation of the cell with countercurrent flow pattern of fuel and air. The model is also used for the comparison of countercurrent with concurrent flow patterns in terms of thermal stress (temperature distribution) and quality of operation (current density). Results reveal that the steady-state cell performance curve and output of simulations qualitatively match experimental data of the literature. Results also demonstrate that countercurrent flow pattern leads to an even distribution of temperature, more uniform current density along the cell and thus is more enduring and superior to the concurrent flow pattern. Afterward, the thorough 3-dimensional model is used for state estimation instead of a real cell. To estimate states, the model is simplified and changed to a 1-dimensional model along flow streams. This simplified model includes uncertainty (because of simplifying assumptions of the model), noise, and disturbance (because of measurements). The behaviors of extended and ensemble Kalman filter as an observer are evaluated in terms of estimating the states and filtering the noises. Results demonstrate that, like extended Kalman filter, ensemble Kalman filter properly estimates the states with 20 sets. - Highlights: • A 3-dimensional model for one cell of SOFC (solid oxide fuel cells) is presented. • Higher voltages and thermal stress in countercurrent than concurrent flow pattern. • State estimation of the cell is examined by ensemble and extended Kalman filters. • Ensemble with 20 sets is as good as extended Kalman filter.

  19. Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

    Science.gov (United States)

    Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

    2017-10-04

    We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10 -3 S cm -1 ) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g -1 at 0.1 A g -1 ), better rate capability (64% capacity retention until 20 A g -1 ), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg -1 at 1 A g -1 ) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

  20. State of dog's metabolism in the remote period after the oxide tritium influence

    International Nuclear Information System (INIS)

    Kalistratova, V.S.; Tishchenko, G.S.; Bortnik, L.A.; Nisimov, P.G.; Romanova, I.B.

    2000-01-01

    Influence of tritium oxide on the metabolism by some indices of lipid metabolism (common lipids, β-lipoproteins, cholesterin), protein metabolism (cholinesterase) and carbohydrate metabolism (blood sugar) was studied. It was established that the introduction into organism of tritium oxide in the quantities, which could form lethal and sublethal doses of internal radiation, provoked the main changes of values of mentioned indices of metabolism. The character of metabolism changes in the remote period allows to judge about the development of sclerosis processes which can be the result of radiation-stipulated acceleration of organism aging [ru

  1. Enhanced catalytic hydrogenation activity of Ni/reduced graphene oxide nanocomposite prepared by a solid-state method

    Science.gov (United States)

    Li, Yizhao; Cao, Yali; Jia, Dianzeng

    2018-01-01

    A simple solid-state method has been applied to synthesize Ni/reduced graphene oxide (Ni/rGO) nanocomposite under ambient condition. Ni nanoparticles with size of 10-30 nm supported on reduced graphene oxide (rGO) nanosheets are obtained through one-pot solid-state co-reduction among nickel chloride, graphene oxide, and sodium borohydride. The Ni/rGO nanohybrid shows enhanced catalytic activity toward the reduction of p-nitrophenol (PNP) into p-aminophenol compared with Ni nanoparticles. The results of kinetic research display that the pseudo-first-order rate constant for hydrogenation reaction of PNP with Ni/rGO nanocomposite is 7.66 × 10-3 s-1, which is higher than that of Ni nanoparticles (4.48 × 10-3 s-1). It also presents superior turnover frequency (TOF, 5.36 h-1) and lower activation energy ( E a, 29.65 kJ mol-1) in the hydrogenation of PNP with Ni/rGO nanocomposite. Furthermore, composite catalyst can be magnetically separated and reused for five cycles. The large surface area and high electron transfer property of rGO support are beneficial for good catalytic performance of Ni/rGO nanocomposite. Our study demonstrates a simple approach to fabricate metal-rGO heterogeneous nanostructures with advanced functions.

  2. The PROTEUS Experiment: Active Source Seismic Imaging of the Crustal Magma Plumbing Structure of the Santorini Arc Volcano

    Science.gov (United States)

    Hooft, E. E. E.; Morgan, J. V.; Nomikou, P.; Toomey, D. R.; Papazachos, C. V.; Warner, M.; Heath, B.; Christopoulou, M. E.; Lampridou, D.; Kementzetzidou, D.

    2016-12-01

    The goal of the PROTEUS seismic experiment (Plumbing Reservoirs Of The Earth Under Santorini) is to examine the entire crustal magma plumbing system beneath a continental arc volcano and determine the magma geometry and connections throughout the crust. These physical parameters control magma migration, storage, and eruption and inform the question of how physical and chemical processing of magma at arc volcanoes forms the andesitic rock compositions that dominate the lower continental crust. These physical parameters are also important to understand volcanic-tectonic interactions and geohazards. Santorini is ideal for these goals because the continental crust has been thinned by extension and so the deep magmatic system is more accessible, also it is geologically well studied. Since the volcano is a semi-submerged, it was possible to collect a unique 3D marine-land active source seismic dataset. During the PROTEUS experiment in November-December of 2015, we recorded 14,300 marine sound sources from the US R/V Langseth on 89 OBSIP short period ocean bottom seismometers and 60 German and 5 Greek land seismometers. The experiment was designed for high-density spatial sampling of the seismic wavefield to allow us to apply two state-of-the-art 3D inversion methods: travel time tomography and full waveform inversion. A preliminary travel time tomography model of the upper crustal seismic velocity structure of the volcano and surrounding region is presented in an accompanying poster. We also made marine geophysical maps of the seafloor using multi-beam bathymetry and of the gravity and magnetic fields. The new seafloor map reveals the detailed structure of the major fault system between Santorini and Amorgos, of associated landslides, and of newly discovered volcanic features. The PROTEUS project will provide new insights into the structure of the whole crustal magmatic system of a continental arc volcano and its evolution within the surrounding tectonic setting.

  3. Noble gas solubility in silicate melts:a review of experimentation and theory, and implications regarding magma degassing processes

    Directory of Open Access Journals (Sweden)

    A. Paonita

    2005-06-01

    Full Text Available Noble gas solubility in silicate melts and glasses has gained a crucial role in Earth Sciences investigations and in the studies of non-crystalline materials on a micro to a macro-scale. Due to their special geochemical features, noble gases are in fact ideal tracers of magma degassing. Their inert nature also allows them to be used to probe the structure of silicate melts. Owing to the development of modern high pressure and temperature technologies, a large number of experimental investigations have been performed on this subject in recent times. This paper reviews the related literature, and tries to define our present state of knowledge, the problems encountered in the experimental procedures and the theoretical questions which remain unresolved. Throughout the manuscript I will also try to show how the thermodynamic and structural interpretations of the growing experimental dataset are greatly improving our understanding of the dissolution mechanisms, although there are still several points under discussion. Our improved capability of predicting noble gas solubilities in conditions closer to those found in magma has allowed scientists to develop quantitative models of magma degassing, which provide constraints on a number of questions of geological impact. Despite these recent improvements, noble gas solubility in more complex systems involving the main volatiles in magmas, is poorly known and a lot of work must be done. Expertise from other fields would be extremely valuable to upcoming research, thus focus should be placed on the structural aspects and the practical and commercial interests of the study of noble gas solubility.

  4. The state-of-the-art and prospects of the oxidation titration method for the determination of uranium in geological samples

    International Nuclear Information System (INIS)

    Sun Jiayan

    1986-01-01

    The state-of-the-art of the oxidation titration method for the determination of uranium in geological samples is reviewed in some respects such as the prereduction of U(VI), oxidation of U(IV) and the detection of the end-point. Comments are also made on the prospects of further improvements of this method

  5. Magma viscosity estimation based on analysis of erupted products. Potential assessment for large-scale pyroclastic eruptions

    International Nuclear Information System (INIS)

    Takeuchi, Shingo

    2010-01-01

    After the formulation of guidelines for volcanic hazards in site evaluation for nuclear installations (e.g. JEAG4625-2009), it is required to establish appropriate methods to assess potential of large-scale pyroclastic eruptions at long-dormant volcanoes, which is one of the most hazardous volcanic phenomena on the safety of the installations. In considering the volcanic dormancy, magma eruptability is an important concept. The magma eruptability is dominantly controlled by magma viscosity, which can be estimated from petrological analysis of erupted materials. Therefore, viscosity estimation of magmas erupted in past eruptions should provide important information to assess future activities at hazardous volcanoes. In order to show the importance of magma viscosity in the concept of magma eruptability, this report overviews dike propagation processes from a magma chamber and nature of magma viscosity. Magma viscosity at pre-eruptive conditions of magma chambers were compiled based on previous petrological studies on past eruptions in Japan. There are only 16 examples of eruptions at 9 volcanoes satisfying data requirement for magma viscosity estimation. Estimated magma viscosities range from 10 2 to 10 7 Pa·s for basaltic to rhyolitic magmas. Most of examples fall below dike propagation limit of magma viscosity (ca. 10 6 Pa·s) estimated based on a dike propagation model. Highly viscous magmas (ca. 10 7 Pa·s) than the dike propagation limit are considered to lose eruptability which is the ability to form dikes and initiate eruptions. However, in some cases, small precursory eruptions of less viscous magmas commonly occurred just before climactic eruptions of the highly viscous magmas, suggesting that the precursory dike propagation by the less viscous magmas induced the following eruptions of highly viscous magmas (ca. 10 7 Pa·s). (author)

  6. Example of uranium(IV) insertion within a macrocyclic crown ether with coexistence of the metal in two oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Bombieri, G; De Paoli, G [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Immirzi, A

    1978-01-01

    Reaction of UCl/sub 4/ with 18-crown-6 in tetrahydrofuran yields (UCl/sub 4/)/sub 3/ (18-crown-6)/sub 2/ which on recrystallization in nitromethane, gives a partially oxidized and hydrolyzed product whose structure has been investigated by X-ray diffraction. The compound crystallizes in the orthorhombic system. The cell contains eight UCl/sub 3//sup +/ cations each inserted within a crown molecule and four (UO/sub 2/Cl/sub 3/(OH)(H/sub 2/O))/sup 2 -/anions having a pentagonal bipyramidal structure. Four solvated nitromethane molecules are also present. The compound represents one of the very few examples in which uranium exists in two oxidation states, and the first example in which its insertion within a crown macrocycle has been proved by an X-ray diffraction study.

  7. Remote mixed oxide fabrication facility development. Volume 2. State-of-the-art review of remote maintenance system technology

    International Nuclear Information System (INIS)

    Horgos, R.M.; Masch, M.L.

    1979-06-01

    This report provides a state-of-the-art review of remote systems technology, which includes manipulators, process connectors, vision systems and specialized process systems. A proposed mixed oxide fuel fabrication facility was reviewed and evaluated for identification of major remote maintenance and repair tasks. The technological areas were evaluated on the basis of their suitability or applicability for remote maintenance and repair of a proposed fully remote operating mixed oxide fuel fabrication facility. A technological base exists from which the design criteria for a reliable, remote operating facility can be established. Commercially available systems and components, along with those remote technologies now in development, will require modifications to adapt them to specific plant designs and requirements

  8. Electrochemistry and time dependent DFT study of a (vinylenedithio)-TTF derivative in different oxidation states

    NARCIS (Netherlands)

    Halpin, Yvonne; Schulz, Martin; Brooks, Andrew C.; Browne, Wesley R.; Wallis, John D.; Gonzalez, Leticia; Day, Peter; Vos, Johannes G.

    2013-01-01

    The electrochemical and spectroelectrochemical properties of a bis-pyrid-4-yl functionalised vinylenedithio-TFF derivative, 1, in solution are reported. The compound was immobilised on a Pt electrode and the resulting layers formed were investigated using electrochemical techniques. Two oxidation

  9. The state of permanganate with relation to in situ chemical oxidation

    International Nuclear Information System (INIS)

    Veronda, Brenda; Dingens, Matthew

    2007-01-01

    In Situ Chemical Oxidation (ISCO) with permanganate had its beginnings over 10 years ago. Since that time, many sites have been successfully treated for organic compounds including chlorinated ethenes (perchloroethylene, trichloroethylene, etc.) phenols, explosives such as RDX, and many other organics. The successful application of ISCO with permanganate requires the integration of many site-specific factors into the remedial design. ISCO with permanganate is an effective technology, not only for its oxidative properties and persistence, but also for its application flexibility to remediate soil and groundwater. The merits of any type of treatment technology can be assessed in terms of effectiveness, ease of use, reaction rate, and cost. The use of permanganate for in situ chemical oxidation results in the complete mineralization of TCE and PCE and can result in treatment levels below detection limits. Permanganate is a single component oxidizer, which is easily handled, mixed and distributed to the subsurface. Permanganate is also inexpensive to design and implement as compared to other technologies. This presentation will provide a general overview of the application and safety aspects of ISCO with permanganate. This paper will discuss the advantages and limitations of this technology, typical cost ranges, site evaluation and application technologies. (authors)

  10. Influence of Structure and Charge State on the Mechanism of CO Oxidation on Gold Clusters

    Science.gov (United States)

    Johnson, Grant; Burgel, Christian; Reilly, Nelly; Mitric, Roland; Kimble, Michele; Tyo, Eric; Castleman, A. W.; Bonacic-Koutecky, Vlasta

    2008-05-01

    Gas-phase reactivity experiments and high level theoretical calculations have been employed to study the interaction of both positively and negatively charged gold oxide clusters with carbon monoxide (CO). We demonstrate that for negatively charged clusters CO is oxidized to CO2 by an Eley-Ridel-like (ER-) mechanism involving the attack of CO on oxygen rather than gold. In contrast, for positively charged clusters, the oxidation reaction may also occur by a Langmuir-Hinshelwood-like (LH-) mechanism involving the initial binding of CO to a gold atom followed by subsequent migration to an oxygen site. The LH mechanism is made possible through the large energy gain associated with the adsorption of two CO molecules onto cationic gold clusters. Structure-reactivity relationships are also established which demonstrate that terminally bound oxygen atoms are the most active sites for CO oxidation. Bridge bonded oxygen atoms and molecularly bound O2 units are shown to be inert. We also establish an inverse relationship between the binding energy of CO to gold clusters and the energy of the clusters lowest unoccupied molecular orbital (LUMO).

  11. Petrologic testament to changes in shallow magma storage and transport during 30+ years of recharge and eruption at Kīlauea Volcano, Hawai‘i: Chapter 8

    Science.gov (United States)

    Thornber, Carl R.; Orr, Tim R.; Heliker, Christina; Hoblitt, Richard P.; Carey, Rebecca; Cayol, Valérie; Poland, Michael P.; Weis, Dominique

    2015-01-01

    Petrologic monitoring of Kīlauea Volcano from January 1983 to October 2013 has yielded an extensive record of glass, phenocryst, melt inclusion, and bulk-lava chemistry from well-quenched lava. When correlated with 30+ years of geophysical and geologic monitoring, petrologic details testify to physical maturation of summit-to-rift magma plumbing associated with sporadic intrusion and prolonged magmatic overpressurization. Changes through time in bulk-lava major- and trace-element compositions, along with glass thermometry, record shifts in the dynamic balance of fractionation, mixing, and assimilation processes inherent to magma storage and transport during near-continuous recharge and eruption. Phenocryst composition, morphology, and texture, along with the sulfur content of melt inclusions, constrain coupled changes in eruption behavior and geochemistry to processes occurring in the shallow magmatic system. For the first 17 years of eruption, magma was steadily tapped from a summit reservoir at 1–4 km depth and circulating between 1180 and 1200°C. Furthermore, magma cooled another 30°C while flowing through the 18 km long rift conduit, before erupting olivine-spinel-phyric lava at temperatures of 1150–1170°C in a pattern linked with edifice deformation, vent formation, eruptive vigor, and presumably the flux of magma into and out of the summit reservoir. During 2000–2001, a fundamental change in steady state eruption petrology to that of relatively low-temperature, low-MgO, olivine(-spinel)-clinopyroxene-plagioclase-phryic lava points to a physical transformation of the shallow volcano plumbing uprift of the vent. Preeruptive comagmatic mixing between hotter and cooler magma is documented by resorption, overgrowth, and compositional zonation in a mixed population of phenocrysts grown at higher and lower temperatures. Large variations of sulfur (50 to >1000 ppm) in melt inclusions within individual phenocrysts and among phenocrysts in most samples

  12. A study of relaxation mechanisms in the A{sup 2}{Sigma}{sup +} state of nitric oxide by time resolved double resonant polarization spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Stampanoni-Panariello, A; Bombach, R; Hemmerling, B; Hubschmid, W [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Double resonant polarization labeling spectroscopy is applied to detect nitric oxide in flames and to characterize rotational energy transfer and orientation changing collisions in its first excited electronic state. (author) 4 figs., 3 refs.

  13. The Earth’s mantle before convection: Effects of magma oceans and the Moon (Invited)

    Science.gov (United States)

    Elkins-Tanton, L. T.; Smrekar, S. E.; Tobie, G.

    2009-12-01

    thick solid lid and diminished the likelihood of mantle remixing. Second, on an Earth-sized planet a magma ocean would solidify to produce very dense near-surface solids that also contain the bulk of the water held in the solid state, and the bulk of the incompatible elements. During gravitationally-driven overturn shallow, dense, damp solids carry their water as they sink into the perovskite stability zone and transform the bulk of their mineralogy into perovskite. The last solids that form near the surface exceed the likely water saturation levels of perovskite and will be forced to dewater as they cross the boundary into the lower mantle, leaving water behind in a rapid flux as the dense material sinks. This event will form a kind of “water catastrophe,” and would have the potential to partially melt the upper mantle, to produce a damp asthensosphere, and indeed to encourage convection. These results imply that planets in which perovskite is stable, that is, planets that are larger than Mars, are perhaps more likely to have an early initiation of plate tectonics, and that larger planets may have more violent and near-surface mantle volatile releases during any overturn event.

  14. A detailed study on the transition from the blocked to the superparamagnetic state of reduction-precipitated iron oxide nanoparticles

    International Nuclear Information System (INIS)

    Witte, K.; Bodnar, W.; Mix, T.; Schell, N.; Fulda, G.; Woodcock, T.G.; Burkel, E.

    2016-01-01

    Magnetic iron oxide nanoparticles were prepared by salt-assisted solid-state chemical precipitation method with alternating fractions of the ferric iron content. The physical properties of the precipitated nanoparticles mainly consisting of magnetite were investigated by means of transmission electron microscopy, high energy X-ray diffraction, vibrating sample magnetometry and Mössbauer spectroscopy. With particle sizes ranging from 16.3 nm to 2.1 nm, a gradual transition from the blocked state to the superparamagnetic state was observed. The transition was described as a dependence of the ferric iron content used during the precipitation. Composition, mean particle size, coercivity, saturation polarisation, as well as hyperfine interaction parameters and their evolution were studied systematically over the whole series of iron oxide nanoparticles. - Highlights: • Study of superparamagnetic transition of magnetite varying ferric iron content. • Coercivity is mainly influenced by the particle size. • Saturation polarisation influenced by the goethite content and the particle size. • Number of vacancies tend to increase with increasing ferric iron content. • Fe 3 O 4 B-sites are stronger effected by the reduction of particle size than A-sites.

  15. All-solid-state flexible microsupercapacitors based on reduced graphene oxide/multi-walled carbon nanotube composite electrodes

    Science.gov (United States)

    Mao, Xiling; Xu, Jianhua; He, Xin; Yang, Wenyao; Yang, Yajie; Xu, Lu; Zhao, Yuetao; Zhou, Yujiu

    2018-03-01

    All-solid-state flexible microsupercapacitors have been intensely investigated in order to meet the rapidly growing demands for portable microelectronic devices. Herein, we demonstrate a facile, readily scalable and cost-effective laser induction process for preparing reduced graphene oxide/multi-walled carbon nanotube composite, which can be used as the interdigital electrodes in microsupercapacitors. The obtained composite exhibits high volumetric capacitance about 49.35 F cm-3, which is nearly 5 times higher than that of the pristine reduced graphene oxide film in aqueous 1.0 M H2SO4 solution (measured at a current density of 5 A cm-3 in a three-electrode testing). Additionally, an all-solid-state flexible microsupercapacitor employing these composite electrodes with PVA/H3PO4 gel electrolyte delivers high volumetric energy density of 6.47 mWh cm-3 at 10 mW cm-3 under the current density of 20 mA cm-3 as well as achieve excellent cycling stability retaining 88.6% of its initial value and outstanding coulombic efficiency after 10,000 cycles. Furthermore, the microsupercapacitors array connected in series/parallel can be easily adjusted to achieve the demands in practical applications. Therefore, this work brings a promising new candidate of prepare technologies for all-solid-state flexible microsupercapacitors as miniaturized power sources used in the portable and wearable electronics.

  16. Effect of charged deep states in hydrogenated amorphous silicon on the behavior of iron oxides nanoparticles deposited on its surface

    International Nuclear Information System (INIS)

    Gmucova, Katarina; Weis, Martin; Nadazdy, Vojtech; Capek, Ignac; Satka, Alexander; Chitu, Livia; Cirak, Julius; Majkova, Eva

    2008-01-01

    Langmuir-Blodgett technique has been used for the deposition of ordered two-dimensional arrays of iron oxides (Fe 3 O 4 /Fe 2 O 3 ) nanoparticles onto the photovoltaic hydrogenated amorphous silicon (a-Si:H) thin film. Electric field at the a-Si:H/iron oxides nanoparticles interface was directly in the electrochemical cell modified by light soaking and bias voltage (negative or positive) pretreatment resulting in the change of the dominant type of charged deep states in the a-Si:H layer. Induced reversible changes in the nanoparticle redox behavior have been observed. We suggest two possible explanations of the data obtained, both of them are needed to describe measured electrochemical signals. The first one consists in the electrocatalytical effect caused by the defect states (negatively or positively charged) in the a-Si:H layer. The second one consists in the possibility to manipulate the nanoparticle cores in the prepared structure immersed in aqueous solution via the laser irradiation under specific bias voltage. In this case, the nanoparticle cores are assumed to be covered with surface clusters of heterovalent complexes created onto the surface regions with prevailing ferrous or ferric valency. Immersed in the high viscosity surrounding composed of the wet organic nanoparticle envelope these cores are able to perform a field-assisted pivotal motion. The local electric field induced by the deep states in the a-Si:H layer stabilizes their 'orientation ordering' in an energetically favourable position