Micro-XANES Measurements on Experimental Spinels and the Oxidation State of Vanadium in Spinel-Melt Pairs

NASA Technical Reports Server (NTRS)

Righter, K.; Sutton, S.R.; Newville, M.

2004-01-01

Spinel can be a significant host phase for V as well as other transition metals such as Ni and Co. However, vanadium has multiple oxidation states V(2+), V(3+), V(4+) or V(5+) at oxygen fugacities relevant to natural systems. We do know that D(V) spinel/melt is correlated with V and TiO2 content and fO2, but the uncertainty of the oxidation state under the range of natural conditions has made elusive a thorough understanding of D(V) spinel/melt. For example, V(3+) is likely to be stable in spinels, based on exchange with Al in experiments in the CaO-MgO-Al2O3-SiO2 system. On the other hand, it has been argued that V(4+) will be stable across the range of natural oxygen fugacities in nature. In order to gain a better understanding of D(V) spinel/melt we have equilibrated spinel-melt pairs at controlled oxygen fugacities, between HM to NNO, where V is present in the spinel at natural levels (approx. 300 ppm V). These spinel-melt pairs were analyzed using micro-XANES at the Advanced Photon Source at Argonne National Laboratory. The new results will be used together with spinel compositional data (Ti, V content) and oxygen fugacity, to unravel the effects of these variables on D(V) spinel/melt.

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

NASA Astrophysics Data System (ADS)

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 invoked to explain mantle oxygen fugacity, although implications for trace elements in the Earth's core and mantle are still being explored. [1] Ringwood, AE (1979) [2] Armstrong, K et al (2016) LPSC, 2580 [3] Armstrong, K et al (2017) ACCRETE workshop [4] Zhang, HL et al (2017) GCA, 204, 83 [5] Frost, DJ et al (2004) Nature, 428, 409 [6] Schaefer, L et al (2016) ApJ, 829, 63

Oxygen buffering of Kilauea volcanic gases and the oxygen fugacity of Kilauea basalt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gerlach, T.M.

1993-02-01

Volcanic gases collected during episode 1 of the Puu Oo eruption along the east rift zone of Kilauea Volcano, Hawaii, have uniform C-O-H-S-Cl-F compositions that are sharply depleted in CO[sub 2]. The CO[sub 2]-poor gases are typical of Type II volcanic gases (GERLACH and GRAEBER, 1985) and were emitted from evolved magma stored for a prolonged period of time in the east rift zone after releasing CO[sub 2]-rich gases during an earlier period of temporary residence in the summit magma chamber. The samples are remarkably free of contamination by atmospheric gases and meteoric water. Thermodynamic evaluation of the analytical datamore » shows that the episode 1 gases have equilibrium compositions appropriate for temperatures between 935 and 1032[degrees]C. Open- and closed-system equilibrium models of species distributions for the episode 1 gases show unequivocally that coexisting lavas buffered the gas oxygen fugacities during cooling. These models indicate that the F[sub o[sub 2

The effect of oxygen fugacity on the partitioning of nickel and cobalt between olivine, silicate melt, and metal

NASA Technical Reports Server (NTRS)

Ehlers, Karin; Grove, Timothy L.; Sisson, Thomas W.; Recca, Steven I.; Zervas, Deborah A.

1992-01-01

The effect of oxygen fugacity, f(O2), on the partitioning behavior of Ni and Co between olivine, silicate melt, and metal was investigated in the CaO-MgO-Al2O3-SiO2-FeO-Na2O system, an analogue of a chondrule composition from an ordinary chondrite. The conditions were 1350 C and 1 atm, with values of f(O2) varying between 10 exp -5.5 and 10 exp -12.6 atm (i.e., the f(O2) range relevant for crystal/liquid processes in terrestrial planets and meteorite parent bodies). Results of chemical analysis showed that the values of the Ni and Co partitioning coefficients begin to decrease at values of f(O2) that are about 3.9 log units below the nickel-nickel oxide and cobalt-cobalt oxide buffers, respectively, near the metal saturation for the chondrule analogue composition.

Ferric iron partitioning between plagioclase and silicate liquid: thermodynamics and petrological applications

NASA Astrophysics Data System (ADS)

Sugawara, Toru

2001-06-01

A series of Fe and Mg partition experiments between plagioclase and silicate liquid were performed in the system SiO2-Al2O3-Fe2O3-FeO-MgO-CaO-Na2O under oxygen fugacities from below the IW buffer up to that of air. A thermodynamic model of plagioclase solid solution for the (CaAl,NaSi,KSi)(Fe3+,Al3+)Si2O8-Ca(Fe2+,Mg)Si3O8 system is proposed and is calibrated by regression analysis based on new and previously reported experimental data of Fe and Mg partitioning between plagioclase and silicate liquid, and reported thermodynamic properties of end members, ternary feldspar and silicate liquid. Using the derived thermodynamic model, FeOt, MgO content and Mg/(Fet+Mg) in plagioclase can be predicted from liquid composition with standard deviations of +/-0.34 wt% (relative error =9%) and +/-0.08 wt% (14%) and +/-0.7 (8%) respectively. Calculated Fe3+-Al exchange chemical potentials of plagioclase, $μ { Fe{ 3 + } ( {Al} ){ - 1} }{ Pl} agree with those calculated using reported thermodynamic models for multicomponent spinel, μ { Fe{ 3 + } ( {Al} ){ - 1} }{ Sp} and clinopyroxene, μ { Fe{ 3 + } ( {Al} ){ - 1} }{ Cpx} $ . The FeOt content of plagioclase coexisting with spinel or clinopyroxene is affected by Fe3+/(Fe3++Al) and Mg/(Fe+Mg) of spinel or clinopyroxene and temperature, while it is independent of the anorthite content of plagioclase. Three oxygen barometers based on the proposed model are investigated. Although the oxygen fugacities predicted by the plagioclase-liquid oxygen barometer are scattered, this study found that plagioclase-spinel-clinopyroxene-oxygen and plagioclase-olivine-oxygen equilibria can be used as practical oxygen barometers. As a petrological application, prediction of plagioclase composition and fO2 are carried out for the Upper Zone of the Skaergaard intrusion. The estimated oxygen fugacities are well below QFM buffer and consistent with the estimation of oxidization states in previous studies.

Temperature and Oxygen Fugacity Constraints on CK and R Chondrites and Implications for Water and Oxidation in the Early Solar System

NASA Technical Reports Server (NTRS)

Righter, K.; Neff, K. E.

2007-01-01

Recent chondritic meteorite finds in Antarctica have included CB, CH, CK and R chondrites, the latter two of which are among the most oxidized materials found in meteorite collections. In this study we present petrographic and mineralogic data for a suite of CK and R chondrites, and compare to previous studies of CK and R, as well as some CV chondrites. In particular we focus on the opaque minerals magnetite, chromite, sulfides, and metal as well as unusual silicates hornblende, biotite, and plagioclase. Several mineral thermometers and oxy-barometers are utilized to calculate temperatures and oxygen fugacities for these unusual meteorites compared to other more common chondrite groups. R and CK chondrites show lower equilibrium temperatures than ordinary chondrites, even though they are at similar petrologic grades (e.g., thermal type 6). Oxygen fugacity calculated for CV and R chondrites ranges from values near the iron-wustite (IW) oxygen buffer to near the fayalite-magnetite-quartz (FMQ) buffer. In comparison, the fO2 recorded by ilmenite-magnetite pairs from CK chondrites are much higher, from FMQ+3.1 to FMQ+5.2. The latter values are the highest recorded for materials in meteorites, and place some constraints on the formation conditions of these magnetite-bearing chondrites. Differences between mineralogic and O isotopic compositions of CK and R chondrites suggest two different oxidation mechanisms, which may be due to high and low water: rock ratios during metamorphism, or to different fluid compositions, or both.

A New Spinel-Olivine Oxybarometer: Near-Liquidus Partitioning of V between Olivine-Melt, Spinel-Melt, and Spinel-Olivine in Martian Basalt Composition Y980459 as a Function of Oxygen Fugacity

NASA Technical Reports Server (NTRS)

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

2013-01-01

Our research on valence state partitioning began in 2005 with a review of Cr, Fe, Ti, and V partitioning among crystallographic sites in olivine, pyroxene, and spinel [1]. That paper was followed by several on QUE94201 melt composition and specifically on Cr, V, and Eu partitioning between pyroxene and melt [2-5]. This paper represents the continuation of our examination of the partitioning of multivalent V between olivine, spinel, and melt in martian olivine-phyric basalts of Y980459 composition [6, 7]. Here we introduce a new, potentially powerful oxybarometer, V partitioning between spinel and olivine, which can be used when no melt is preserved in the meteorite. The bulk composition of QUE94201 was ideal for our study of martian pyroxene-phyric basalts and specifically the partitioning between pyroxene-melt for Cr, V, and Eu. Likewise, bulk composition Y980459 is ideal for the study of martian olivine-phyric basalts and specifically for olivine-melt, spinel-melt, and spinel-olivine partitioning of V as a function of oxygen fugacity.

Oxygen fugacity control in piston-cylinder experiments: a re-evaluation

NASA Astrophysics Data System (ADS)

Jakobsson, Sigurdur; Blundy, Jon; Moore, Gordon

2014-06-01

Jakobsson (Contrib Miner Petrol 164(3):397-407, 2012) investigated a double capsule assembly for use in piston-cylinder experiments that would allow hydrous, high-temperature, and high-pressure experiments to be conducted under controlled oxygen fugacity conditions. Using a platinum outer capsule containing a metal oxide oxygen buffer (Ni-NiO or Co-CoO) and H2O, with an inner gold-palladium capsule containing hydrous melt, this study was able to compare the oxygen fugacity imposed by the outer capsule oxygen buffer with an oxygen fugacity estimated by the AuPdFe ternary system calibrated by Barr and Grove (Contrib Miner Petrol 160(5):631-643, 2010). H2O loss or gain, as well as iron loss to the capsule walls and carbon contamination, is often observed in piston-cylinder experiments and often go unexplained. Only a few have attempted to actually quantify various aspects of these changes (Brooker et al. in Am Miner 83(9-10):985-994, 1998; Truckenbrodt and Johannes in Am Miner 84:1333-1335, 1999). It was one of the goals of Jakobsson (Contrib Miner Petrol 164(3):397-407, 2012) to address these issues by using and testing the AuPdFe solution model of Barr and Grove (Contrib Miner Petrol 160(5):631-643, 2010), as well as to constrain the oxygen fugacity of the inner capsule. The oxygen fugacities of the analyzed melts were assumed to be equal to those of the solid Ni-NiO and Co-CoO buffers, which is incorrect since the melts are all undersaturated in H2O and the oxygen fugacities should therefore be lower than that of the buffer by 2 log.

Oxygen buffering of Kilauea volcanic gases and the oxygen fugacity of Kilauea basalt

USGS Publications Warehouse

Gerlach, T.M.

1993-01-01

Volcanic gases collected during episode 1 of the Puu Oo eruption along the east rift zone of Kilauea Volcano, Hawaii, have uniform C-O-H-S-Cl-F compositions that are sharply depleted in CO2. The CO2-poor gases are typical of Type II volcanic gases (gerlach and Graeber, 1985) and were emitted from evolved magma stored for a prolonged period of time in the east rift zone after releasing CO2-rich gases during an earlier period of temporary residence in the summit magma chamber. The samples are remarkably free of contamination by atmospheric gases and meteoric water. Thermodynamic evaluation of the analytical data shows that the episode 1 gases have equilibrium compositions appropriate for temperatures between 935 and 1032??C. Open- and closed-system equilibrium models of species distributions for the episode 1 gases show unequivocally that coexisting lavas buffered the gas oxygen fugacities during cooling. These models indicate that the fO2 buffering process occurs by transfer of oxygen from the major species in the gas phase (H2O, CO2, SO2) to the lava during cooling and that the transfer of oxygen also controls the fugacities of several minor and trace species (H2, CO, H2S, S2, Cl2, F2), in addition to O2 during cooling. Gas/lava exchanges of other components are apparently insignificant and exert little influence, compared to oxygen exchange, during cooling. Oxygen transfer during cooling is variable, presumably reflecting short-term fluctuations in gas flow rates. Higher flow rates restrict the time available for gas/lava oxygen transfer and result in gases with higher equilibrium temperatures. Lower flow rates favor fO2-constrained equilibration by oxygen transfer down to lower temperatures. Thus, the chemical equilibrium preserved in these gases is a heterogeneous equilibrium constrained by oxygen fugacity, and the equilibrium temperatures implied by the compositions of the gases reflect the temperatures at which gas/lava oxygen exchange ceased. This conclusion challenges the common assumption that volcanic gases are released from lava in a state of chemical equilibrium and then continue equilibrating homogeneously with falling temperature until reaction rates are unable to keep pace with cooling. No evidence is found, moreover, that certain gas species are kinetically more responsive and able to equilibrate down to lower temperatures than those of the last gas/lava oxygen exchange. Homogeneous reaction rates in the gas phase are apparently slow compared to the time it took for the gases to move from the last site of gas/lava equilibration to the site of collection. An earlier set of data for higher temperature CO2-rich Type I volcanic gases, which come from sustained summit lava lake eruptions supplied by magma that experienced substantially shorter periods of crustal storage, shows fO2 buffering by oxygen transfer up to 1185??C. Oxygen fugacity measurements in drill holes into ponded lava flows suggest that buffering by oxygen transfer may control the fO2 of residual gases down to several hundred degrees below the solidus in the early stages of cooling. Although the details of the fO2 buffering mechanisms for oxygen transfer are unknown, the fact that fO2 buffering is effective from molten to subsolidus conditions suggests that the reaction mechanisms must change with cooling as the reactants change from predominantly melt, to melt plus crystals, to glass plus crystals. Mass balance calculations suggest that redox reactions between the gas and ferrous/ferric iron in the lava are plausible mechanisms for the oxygen transfer and that the fO2 of the gases is buffered by sliding ferrous/ferric equilibria in the erupting lavas. Contrary to expectations based on models predicting the oxidation of basalt by H2 and CO escape during crustal storage, CO2-rich Type I gases and CO2-poor Type II gases have identical oxygen fugacities despite greatly different crustal storage and degassing histories. Volcanic gas data give a tightly co

Platinum catalytic effect on oxygen fugacity of CO 2H 2 gas mixtures measured with ZrO 2 oxygen sensor at 105 Pa from 1300 to 700°C

NASA Astrophysics Data System (ADS)

Miyamoto, M.; Mikouchi, T.

1996-08-01

The oxygen fugacity of CO 2H 2 gas mixtures were measured with a ZrO 2 oxygen sensor at high temperatures in a furnace. We confirmed that the oxygen fugacity values measured by the ZrO 2 cell are more reducing than those of the CO 2H 2 gas mixtures calculated by using JANAF data at temperatures below 1150°C as was previously reported by Huebner (1975). We successfully decreased the deviation of the measured oxygen-fugacity value from the calculated one down to temperature of 800°C by using a Pt catalyst. Our results suggest that the deviation is probably due to incomplete equilibration of the gases.

A Polygenetic Origin for some Oceanic Lithosphere: Evidence from Forearc, Continental Margin and Ophiolite Mantle Sequences

NASA Astrophysics Data System (ADS)

Pearce, J. A.; Parkinson, I. J.

2003-12-01

It is a common assumption that ophiolites and oceanic lithosphere attain their structures and compositions through partial melting of mantle in a single tectonic setting and with a simple petrogenetic relationship between all the units. There is, however, growing evidence that some oceanic lithosphere and ophiolite complexes contain a record of a polygenetic history of formation. This may be apparent in crustal units (complex lava stratigraphies or cross-cutting dykes and gabbros) but the best evidence is recorded in the chrome spinel compositions of residual mantle. Among the most effective plots is that of oxygen fugacity, calculated from accurately-determined ferric iron concentrations, against Cr-number. In the ocean basins, forearc peridotites from the Izu-Bonin Mariana, Tonga and South Sandwich systems may be of two types. In the first, both peridotites and dunites have similar oxygen fugacities and a small range in Cr-number. We interpret these as mongenetic. In the second, the peridotites have low oxygen fugacities and moderate Cr-number and trend towards dunites with high oxygen fugacities and high Cr-number. We interpret these as representing mid-ocean ridge mantle lithosphere, which existed prior to a subduction event and was subsequently invaded by subduction-related melts. The time-gap between the ridge and subduction events may be millions of years or, in the case of subduction initiation, represent a continuum. At passive continental margins, such as the Galicia margin, the origin may again be monogenetic or polygenetic. In the latter case, the mantle peridotites may exhibit a trend from low Cr-number to moderate Cr-number and decreasing oxygen fugacity. We interpret these as representing orogenic peridotite uplifted during an amagmatic extensional event and invaded by MORB magma during subsequent spreading. As with forearc peridotites, the time gap between these two events may be large or there be a continuum. A surprising number of ophiolites exhibit this polygenetic character, especially those which may be linked to subduction initiation (such as the northern Semail ophiolite, Pindos, Zambales) or to ocean opening (e.g. Western Mediterranean ophiolites, Othris, Lizard). And even in essentially monogenetic ophiolites, such as the Troodos Massif, there are subtle variations that may be related to ridge jumps or other local processes. These observations raise questions over the extent to which oceanic lithosphere really is the product of 100% extension or whether it may sometimes contain relics of a more complex history.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alderman, O. L. G.; Wilding, M. C.; Tamalonis, A.

Here, the local structure about Fe(II) and Fe(III) in silicate melts was investigated in-situ using iron K-edge X-ray absorption near-edge structure (XANES) spectroscopy. An aerodynamic levitation and laser heating system was used to allow access to high temperatures without contamination, and was combined with a chamber and gas mixing system to allow the iron oxidation state, Fe 3+/ΣFe, to be varied by systematic control of the atmospheric oxygen fugacity. Eleven alkali-free, mostly iron-rich and depolymerized base compositions were chosen for the experiments, including pure oxide FeO, olivines (Fe,Mg) 2SiO 4, pyroxenes (Fe,Mg)SiO 3, calcic FeO-CaSiO 3, and a calcium aluminosilicatemore » composition, where total iron content is denoted by FeO for convenience. Melt temperatures varied between 1410 and 2160 K and oxygen fugacities between FMQ – 2.3(3) to FMQ + 9.1(3) log units (uncertainties in parentheses) relative to the fayalite-magnetite-β-quartz (FMQ) buffer.« less

Experimental crystallization of chrome spinel in FAMOUS basalt 527-1-1

NASA Astrophysics Data System (ADS)

Fisk, Martin R.; Bence, A. E.

1980-06-01

FAMOUS basalt 527-1-1 (a high-Mg oceanic pillow basalt) has three generations of spinel which can be distinguished petrographically and chemically. The first generation (Group I) have reaction coronas and are high in Al 2O 3. The second generation (Group II) have no reaction coronas and are high in Cr 2O 3 and the third generation (Group III) are small, late-stage spinels with intermediate Al 2O 3 and Cr 2O 3. Experimental synthesis of spinels from fused rock powder of this basalt was carried out at temperatures of 1175-1270°C and oxygen fugacities of 10 -5.5 to 10 -10 atm at 1 atm pressure. Spinel is the liquidus phase at oxygen fugacities of 10 -8.5 atm and higher but it does not crystallize at any temperature at oxygen fugacities less than 10 -9.5. The composition of our spinels synthesized at 1230-1250°C and 10 -9 atm f O 2 are most similar to the high-Cr spinels (Group II) found in the rock. Spinels synthesized at 1200°C and 10 -8.5 atm O 2 are chemically similar to the Group III spinels in 527-1-1. We did not synthesize spinel at any temperature or oxygen fugacity that are similar to the high-Al (Group I) spinel found in 527-1-1. These results indicate that the high-Cr (Group II) spinel is the liquidus phase in 527-1-1 at low pressure and Group III spinel crystallize below the liquidus (˜1200°C) after eruption of the basalt on the sea floor. The high-Al spinel (Group I) could have crystallized at high pressure or from a magma enriched in Al and perhaps Mg compared to 527-1-1.

Influence of Silicate Melt Composition on Metal/Silicate Partitioning of W, Ge, Ga and Ni

NASA Technical Reports Server (NTRS)

Singletary, S. J.; Domanik, K.; Drake, M. J.

2005-01-01

The depletion of the siderophile elements in the Earth's upper mantle relative to the chondritic meteorites is a geochemical imprint of core segregation. Therefore, metal/silicate partition coefficients (Dm/s) for siderophile elements are essential to investigations of core formation when used in conjunction with the pattern of elemental abundances in the Earth's mantle. The partitioning of siderophile elements is controlled by temperature, pressure, oxygen fugacity, and by the compositions of the metal and silicate phases. Several recent studies have shown the importance of silicate melt composition on the partitioning of siderophile elements between silicate and metallic liquids. It has been demonstrated that many elements display increased solubility in less polymerized (mafic) melts. However, the importance of silicate melt composition was believed to be minor compared to the influence of oxygen fugacity until studies showed that melt composition is an important factor at high pressures and temperatures. It was found that melt composition is also important for partitioning of high valency siderophile elements. Atmospheric experiments were conducted, varying only silicate melt composition, to assess the importance of silicate melt composition for the partitioning of W, Co and Ga and found that the valence of the dissolving species plays an important role in determining the effect of composition on solubility. In this study, we extend the data set to higher pressures and investigate the role of silicate melt composition on the partitioning of the siderophile elements W, Ge, Ga and Ni between metallic and silicate liquid.

Magma Ocean Depth and Oxygen Fugacity in the Early Earth--Implications for Biochemistry.

PubMed

Righter, Kevin

2015-09-01

A large class of elements, referred to as the siderophile (iron-loving) elements, in the Earth's mantle can be explained by an early deep magma ocean on the early Earth in which the mantle equilibrated with metallic liquid (core liquid). This stage would have affected the distribution of some of the classic volatile elements that are also essential ingredients for life and biochemistry - H, C, S, and N. Estimates are made of the H, C, S, and N contents of Earth's early mantle after core formation, considering the effects of variable temperature, pressure, oxygen fugacity, and composition on their partitioning. Assessment is made of whether additional, exogenous, sources are required to explain the observed mantle concentrations, and areas are identified where additional data and experimentation would lead to an improved understanding of this phase of Earth's history.

The oxidation state of Hadean magmas and implications for early Earth's atmosphere.

PubMed

Trail, Dustin; Watson, E Bruce; Tailby, Nicholas D

2011-11-30

Magmatic outgassing of volatiles from Earth's interior probably played a critical part in determining the composition of the earliest atmosphere, more than 4,000 million years (Myr) ago. Given an elemental inventory of hydrogen, carbon, nitrogen, oxygen and sulphur, the identity of molecular species in gaseous volcanic emanations depends critically on the pressure (fugacity) of oxygen. Reduced melts having oxygen fugacities close to that defined by the iron-wüstite buffer would yield volatile species such as CH(4), H(2), H(2)S, NH(3) and CO, whereas melts close to the fayalite-magnetite-quartz buffer would be similar to present-day conditions and would be dominated by H(2)O, CO(2), SO(2) and N(2) (refs 1-4). Direct constraints on the oxidation state of terrestrial magmas before 3,850 Myr before present (that is, the Hadean eon) are tenuous because the rock record is sparse or absent. Samples from this earliest period of Earth's history are limited to igneous detrital zircons that pre-date the known rock record, with ages approaching ∼4,400 Myr (refs 5-8). Here we report a redox-sensitive calibration to determine the oxidation state of Hadean magmatic melts that is based on the incorporation of cerium into zircon crystals. We find that the melts have average oxygen fugacities that are consistent with an oxidation state defined by the fayalite-magnetite-quartz buffer, similar to present-day conditions. Moreover, selected Hadean zircons (having chemical characteristics consistent with crystallization specifically from mantle-derived melts) suggest oxygen fugacities similar to those of Archaean and present-day mantle-derived lavas as early as ∼4,350 Myr before present. These results suggest that outgassing of Earth's interior later than ∼200 Myr into the history of Solar System formation would not have resulted in a reducing atmosphere.

A seismologically consistent compositional model of Earth's core.

PubMed

Badro, James; Côté, Alexander S; Brodholt, John P

2014-05-27

Earth's core is less dense than iron, and therefore it must contain "light elements," such as S, Si, O, or C. We use ab initio molecular dynamics to calculate the density and bulk sound velocity in liquid metal alloys at the pressure and temperature conditions of Earth's outer core. We compare the velocity and density for any composition in the (Fe-Ni, C, O, Si, S) system to radial seismological models and find a range of compositional models that fit the seismological data. We find no oxygen-free composition that fits the seismological data, and therefore our results indicate that oxygen is always required in the outer core. An oxygen-rich core is a strong indication of high-pressure and high-temperature conditions of core differentiation in a deep magma ocean with an FeO concentration (oxygen fugacity) higher than that of the present-day mantle.

A seismologically consistent compositional model of Earth’s core

PubMed Central

Badro, James; Côté, Alexander S.; Brodholt, John P.

2014-01-01

Earth’s core is less dense than iron, and therefore it must contain “light elements,” such as S, Si, O, or C. We use ab initio molecular dynamics to calculate the density and bulk sound velocity in liquid metal alloys at the pressure and temperature conditions of Earth's outer core. We compare the velocity and density for any composition in the (Fe–Ni, C, O, Si, S) system to radial seismological models and find a range of compositional models that fit the seismological data. We find no oxygen-free composition that fits the seismological data, and therefore our results indicate that oxygen is always required in the outer core. An oxygen-rich core is a strong indication of high-pressure and high-temperature conditions of core differentiation in a deep magma ocean with an FeO concentration (oxygen fugacity) higher than that of the present-day mantle. PMID:24821817

Determination of Oxygen Fugacity using Olivine-Melt Equilibrium: Implications for the Redox States of Mid-Ocean Ridge Basalt, Ocean Island Basalt, and Island Arc Basalt Mantle Source Regions

NASA Astrophysics Data System (ADS)

Peterman, K. J.; Bryson, S.; Rilling-Hall, S.; Barton, M.

2017-12-01

In order to connect volcanic rocks to their mantle sources, it is essential to consider redox equilibria and their dependence on temperature, pressure, chemical composition, and oxygen fugacity. Oxygen fugacity (fO2) is an intensive variable that strongly affects the behavior of those elements in magmas that are sensitive to changes in redox state, such as Fe, and therefore Mg-Fe silicates, such as olivine. Since fO2 plays an important role in fractional crystallization, in principle it is possible to estimate fO2 from analyses of olivine in equilibrium with the melt. This research describes a new method based on this principle called the Olivine-Melt Equilibrium Method. The Fe3+ and Fe2+ contents of melt in equilibrium with olivine are calculated from the relationship of Gee and Sack (1988) that describes the partitioning of Mg and Fe2+ between olivine and melt. The Fe3+ and Fe2+ contents of the melt are then used to calculate the fO2 at which olivine and melt are in equilibrium using the model of Kress and Carmichael (1991) for the relationship between Fe3+/Fe2+ , fO2, T, P, and melt composition. We have calculated oxygen fugacities from published analyses of coexisting glass and olivine pairs in 1020 samples from three different tectonic settings. The results (expressed as ΔFMQ) for Mid-Ocean Ridge Basalts from the Mid-Atlantic Ridge (-1.55 ± 0.75), the East Pacific Rise (-0.65 ± 0.51), the Juan de Fuca Ridge (-0.77 ± 0.42), and the Galápagos Spreading Center (+0.08 ± 0.48) agree with results obtained using other methods and average -1.09 ± 0.89. Ocean Island Basalts from Iceland and the Galápagos Islands (ΔFMQ = -0.43 ± 0.71 and -0.33 ± 0.35 respectively) also yield values consistent with those obtained by other methods and fall in the same range as MORB. However, lavas from the Canary Islands are more oxidized than typical MORB and OIB, with values (average = +0.68 ± 0.52) approaching those for island arc magmas. We obtain ΔFMQ = +1.03 ± 0.52 for olivine-melt pairs from Sunda arc basalts. The results for MORB and OIB potentially provide evidence for redox heterogeneity in the mantle, possibly as the result of crustal recycling. However it is necessary to evaluate the possibility that fO2 changes during magma ascent before concluding that the oxygen fugacities of erupted magmas directly reflect those of the mantle source regions.

Iron K-edge X-ray absorption near-edge structure spectroscopy of aerodynamically levitated silicate melts and glasses

DOE PAGES

Alderman, O. L. G.; Wilding, M. C.; Tamalonis, A.; ...

2017-01-26

Here, the local structure about Fe(II) and Fe(III) in silicate melts was investigated in-situ using iron K-edge X-ray absorption near-edge structure (XANES) spectroscopy. An aerodynamic levitation and laser heating system was used to allow access to high temperatures without contamination, and was combined with a chamber and gas mixing system to allow the iron oxidation state, Fe 3+/ΣFe, to be varied by systematic control of the atmospheric oxygen fugacity. Eleven alkali-free, mostly iron-rich and depolymerized base compositions were chosen for the experiments, including pure oxide FeO, olivines (Fe,Mg) 2SiO 4, pyroxenes (Fe,Mg)SiO 3, calcic FeO-CaSiO 3, and a calcium aluminosilicatemore » composition, where total iron content is denoted by FeO for convenience. Melt temperatures varied between 1410 and 2160 K and oxygen fugacities between FMQ – 2.3(3) to FMQ + 9.1(3) log units (uncertainties in parentheses) relative to the fayalite-magnetite-β-quartz (FMQ) buffer.« less

Redox state of the Archean mantle: Evidence from V partitioning in 3.5-2.4 Ga komatiites

NASA Astrophysics Data System (ADS)

Nicklas, Robert W.; Puchtel, Igor S.; Ash, Richard D.

2018-02-01

Oxygen fugacity of the mantle is a crucial thermodynamic parameter that controls such fundamental processes as planetary differentiation, mantle melting, and possible core-mantle exchange. Constraining the evolution of the redox state of the mantle is of paramount importance for understanding the chemical evolution of major terrestrial reservoirs, including the core, mantle, and atmosphere. In order to evaluate the secular evolution of the redox state of the mantle, oxygen fugacities of six komatiite systems, ranging in age from 3.48 to 2.41 Ga, were determined using high-precision partitioning data of the redox-sensitive element vanadium between liquidus olivine, chromite and komatiitic melt. The calculated oxygen fugacities range from -0.11 ± 0.30 ΔFMQ log units in the 3.48 Ga Komati system to +0.43 ± 0.26 ΔFMQ log units in the 2.41 Ga Vetreny system. Although there is a slight hint in the data for an increase in the oxygen fugacity of the mantle between 3.48 and 2.41 Ga, these values generally overlap within their respective uncertainties; they are also largely within the range of oxygen fugacity estimates for modern MORB lavas of +0.60 ± 0.30 ΔFMQ log units that we obtained using the same technique. Our results are consistent with the previous findings that argued for little change in the mantle oxygen fugacity since the early Archean and indicate that the mantle had reached its nearly-present day redox state by at least 3.48 Ga.

Oxygen fugacity of mare basalts and the lunar mantle application of a new microscale oxybarometer based on the valence state of vanadium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shearer, C.K.; Karner, J.; Papike, J.J.

2004-05-25

Using the valence state of vanadium on a microscale in lunar volcanic glasses we have developed another approach to estimating the oxygen fugacity of mare basalts. The ability to estimate oxygen fugacities for mare basalts and to extend these observations to the lunar mantle is limited using bulk analysis techniques based on buffering assemblages or the valence state of iron. These limitations are due to reequilibration of mineral assemblages at subsolidus conditions, deviations of mineral compositions from thermodynamic ideality, size requirements, and the limits of the iron valence at very low fO{sub 2}. Still, these approaches have been helpful andmore » indicate that mare basalts crystallized at fO{sub 2} between the iron-wuestite buffer (IW) and the ilmenite breakdown reaction (ilmenite = rutile + iron). It has also been inferred from these estimates that the lunar mantle is also highly reduced lying at conditions below IW. Generally, these data cannot be used to determine if the mare basalts become increasingly reduced during transport from their mantle source and eruption at the lunar surface and if there are differences in fO{sub 2} among mare basalts or mantle sources. One promising approach to determining the fO2 of mare basalts is using the mean valence of vanadium (2+, 3+, 4+, 5+) determined on spots of a few micrometers in diameter using synchrotron x-ray absorption fine structure (XAFS) spectroscopy. The average valence state of V in basaltic glasses is a function of fO{sub 2}, temperature, V coordination, and melt composition. Here, we report the initial results of this approach applied to lunar pyroclastic glasses.« less

Correlation of cycles in Lava Lake motion and degassing at Erebus Volcano, Antarctica

NASA Astrophysics Data System (ADS)

Peters, Nial; Oppenheimer, Clive; Killingsworth, Drea Rae; Frechette, Jed; Kyle, Philip

2014-08-01

Several studies at Erebus volcano have recorded pulsatory behavior in many of the observable properties of its active lava lake. A strong correlation between the variations in surface speed of the lake and the composition of gas emitted has previously been noted. While previous studies have shown that the SO2 flux and the surface elevation exhibit pulsatory behavior with a similar period to that of the surface speed and gas composition, suggesting they are linked, a lack of overlap between the different measurements has prevented direct comparisons from being made. Using high time-resolution measurements of surface elevation, surface speed, gas composition, and SO2 flux, we demonstrate for the first time an unambiguous link between the cyclic behavior in each of these properties. We also show that the variation in gas composition may be explained by a subtle change in oxygen fugacity. The cycles are found to be in-phase with each other, with a small but consistent lag of 1-3 min between the peaks in surface elevation and surface speed. Explosive events are found to have no observable effect on the pulsatory behavior beyond the ˜5 min period required for lake refill. The close correspondences between the varying lake surface motion, gas flux and composition, and modeled oxygen fugacity suggest strong links between magma degassing, redox change, and the fluid dynamics of the shallow magmatic system.

Oxygen Fugacity in Large Metal Capsules

NASA Astrophysics Data System (ADS)

Faul, U.; Cline, C. J., II; Jackson, I.; Berry, A.

2016-12-01

During experiments with iron bearing silicates, equilibration between metal capsules and sample interior depends on diffusion of Fe if the capsule composition is not initially in equilibrium with the sample composition. For example, placing Pt or Ni capsules in contact with Fe-bearing olivine leads to Fe-loss from the olivine. In a fully equilibrated system the Fe contents of coexisting metal capsule and olivine reflect the oxygen fugacity (fO2) of the system. Experiments were conducted with olivine encapsulated or wrapped in four different metals (Fe, Ni70Fe30, Ni and Pt) to determine the fO2 in the cm-sized samples used for deformation and seismic property experiments. Small Pt particles mixed with olivine powder were used as fO2 sensors in the interior of the capsules. The results show an ordering of the fO2 in the interior that is consistent with the enclosing metals, i.e. the fO2 is lowest in a Fe capsule and highest in a Pt capsule. However, fO2 values in the more oxidizing metal capsules are substantially below their respective metal-oxide buffers. For example, solgel olivine encapsulated in Ni has an oxygen fugacity that is more than three orders of magnitude below Ni-NiO at 1200C and 0.3 GPa. The fO2 in a capsule interior is therefore to some extent self-buffering and only moderately influenced by the composition of the capsule. While the Pt particles in the interior are equilibrated, Fe gradients from the interior up to the Pt and Ni sample-capsule interfaces show that Fe loss into the capsules is diffusion limited. The fO2 at the interface also has implications for the water retention in unbuffered capsules. We infer that relatively high fO2 and hence fH2O observed adjacent to Pt capsules enables retention of water in these capsules, but the fO2 adjacent to Ni capsules is too low and water is lost.

The oxidation state of the mantle and the extraction of carbon from Earth's interior.

PubMed

Stagno, Vincenzo; Ojwang, Dickson O; McCammon, Catherine A; Frost, Daniel J

2013-01-03

Determining the oxygen fugacity of Earth's silicate mantle is of prime importance because it affects the speciation and mobility of volatile elements in the interior and has controlled the character of degassing species from the Earth since the planet's formation. Oxygen fugacities recorded by garnet-bearing peridotite xenoliths from Archaean lithosphere are of particular interest, because they provide constraints on the nature of volatile-bearing metasomatic fluids and melts active in the oldest mantle samples, including those in which diamonds are found. Here we report the results of experiments to test garnet oxythermobarometry equilibria under high-pressure conditions relevant to the deepest mantle xenoliths. We present a formulation for the most successful equilibrium and use it to determine an accurate picture of the oxygen fugacity through cratonic lithosphere. The oxygen fugacity of the deepest rocks is found to be at least one order of magnitude more oxidized than previously estimated. At depths where diamonds can form, the oxygen fugacity is not compatible with the stability of either carbonate- or methane-rich liquid but is instead compatible with a metasomatic liquid poor in carbonate and dominated by either water or silicate melt. The equilibrium also indicates that the relative oxygen fugacity of garnet-bearing rocks will increase with decreasing depth during adiabatic decompression. This implies that carbon in the asthenospheric mantle will be hosted as graphite or diamond but will be oxidized to produce carbonate melt through the reduction of Fe(3+) in silicate minerals during upwelling. The depth of carbonate melt formation will depend on the ratio of Fe(3+) to total iron in the bulk rock. This 'redox melting' relationship has important implications for the onset of geophysically detectable incipient melting and for the extraction of carbon dioxide from the mantle through decompressive melting.

Solubility of tungsten in a haplobasaltic melt as a function of temperature and oxygen fugacity

NASA Astrophysics Data System (ADS)

Ertel, W.; O'Neill, H. St. C.; Dingwell, D. B.; Spettel, B.

1996-04-01

The solubility of tungsten (W) in a haplobasaltic melt has been determined as a function of oxygen fugacity in the temperature range 1300-1500°C using the mechanically assisted equilibrium technique of Dingwell et al. (1994), and at 1600-1700°C by the wire loop method. Quenched samples were analysed for W by using ICP-AES as well as INAA, and sample major element compositions were checked by electron microprobe. W concentrations ranged from 20 ppm to 17 wt%, and the solution of WO 2 in the melt may be described by Henry's Law up to remarkably high concentrations (e.g., 14 wt% at 1500°C). W dissolves in the melt with a quadrivalent (4+) formal oxidation state over the entire range of oxygen fugacity and temperature investigated. The solubility of W decreases strongly with increasing temperature at constant oxygen fugacity. The solubility data have been used to calculate trace distribution coefficients for W between Fe-rich metal and silicate melt, using literature values for the activity coefficient of W in liquid Fe. Comparison of our data with the distribution coefficients for Mo calculated from the analogous Mo solubility data of Holzheid et al. (1994) shows that the ratio of the metal-silicate distribution coefficient DMomet/sil/ DWmet/sil remains very high (~10 3) at all T-fO 2 conditions. However, in the Earth's mantle, Mo is relatively more depleted than W only by a factor of three. The relative abundances of W and Mo in the Earth's mantle cannot, therefore, be explained by core formation from a homogeneously accreted Earth whatever the temperature at which metal/silicate equilibrium may have ocurred might have been. Their abundances may be quantitatively accounted for by a heterogeneous accretion model such as that of O'Neill (1991).

Crystallization Experiments of the Martian Meteorite QUE94201: Additional Constraints on Its Formation Condition

NASA Technical Reports Server (NTRS)

Koizumi, E.; McKay, G.; Mikouchi, T.; Le, L.; Schwandt, C.; Monkawa, A.; Miyamoto, M.

2002-01-01

We focused on the Al/Ti ratio in synthetic pyroxenes as a marker for the onset of plagioclase crystallization and discuss the effects of oxygen fugacity on the Kd(Fe/Mg)ol/gl in our experiments using the same composition of QUE94201. Additional information is contained in the original extended abstract.

Technical Update: Johnson Space Center system using a solid electrolytic cell in a remote location to measure oxygen fugacities in CO/CO2 controlled-atmosphere furnaces

NASA Technical Reports Server (NTRS)

Jurewicz, A. J. G.; Williams, R. J.; Le, L.; Wagstaff, J.; Lofgren, G.; Lanier, A.; Carter, W.; Roshko, A.

1993-01-01

Details are given for the design and application of a (one atmosphere) redox-control system. This system differs from that given in NASA Technical Memorandum 58234 in that it uses a single solid-electrolytic cell in a remote location to measure the oxygen fugacities of multiple CO/CO2 controlled-atmosphere furnaces. This remote measurement extends the range of sample-furnace conditions that can be measured using a solid-electrolytic cell, and cuts costs by extending the life of the sensors and by minimizing the number of sensors in use. The system consists of a reference furnace and an exhaust-gas manifold. The reference furnace is designed according to the redox control system of NASA Technical Memorandum 58234, and any number of CO/CO2 controlled-atmosphere furnaces can be attached to the exhaust-gas manifold. Using the manifold, the exhaust gas from individual CO/CO2 controlled atmosphere furnaces can be diverted through the reference furnace, where a solid-electrolyte cell is used to read the ambient oxygen fugacity. The oxygen fugacity measured in the reference furnace can then be used to calculate the oxygen fugacity in the individual CO/CO2 controlled-atmosphere furnace. A BASIC computer program was developed to expedite this calculation.

Magmatic oxygen fugacity estimated using zircon-melt partitioning of cerium

NASA Astrophysics Data System (ADS)

Smythe, Duane J.; Brenan, James M.

2016-11-01

Using a newly-calibrated relation for cerium redox equilibria in silicate melts (Smythe and Brenan, 2015), and an internally-consistent model for zircon-melt partitioning of Ce, we provide a method to estimate the prevailing redox conditions during crystallization of zircon-saturated magmas. With this approach, oxygen fugacities were calculated for samples from the Bishop tuff (USA), Toba tuff (Indonesia) and the Nain plutonic suite (Canada), which typically agree with independent estimates within one log unit or better. With the success of reproducing the fO2 of well-constrained igneous systems, we have applied our Ce-in-zircon oxygen barometer to estimating the redox state of Earth's earliest magmas. Using the composition of the Jack Hills Hadean zircons, combined with estimates of their parental magma composition, we determined the fO2 during zircon crystallization to be between FMQ -1.0 to +2.5 (where FMQ is the fayalite-magnetite-quartz buffer). Of the parental magmas considered, Archean tonalite-trondhjemite-granodiorite (TTG) compositions yield zircon-melt partitioning most similar to well-constrained modern suites (e.g., Sano et al., 2002). Although broadly consistent with previous redox estimates from the Jack Hills zircons, our results provide a more precise determination of fO2, narrowing the range for Hadean parental magmas by more than 8 orders of magnitude. Results suggest that relatively oxidized magmatic source regions, similar in oxidation state to that of 3.5 Ga komatiite suites, existed by ∼4.4 Ga.

Oxidation and evaporation of sulfur species at atmospheric entry of iron sulfide fine particles

NASA Astrophysics Data System (ADS)

Isobe, H.; Murozono, K.

2017-12-01

Micrometeorites have the most abundant flux in current accumulation of planetary materials to the Earth. Micrometeorites are heated and reacted with upper atmosphere at atmospheric entry. Evaporation of meteoritic materials, especially sulfur species, may have environmental effect at upper atmosphere (e.g. Court and Sephton, 2011; Tomkins et al., 2016). Troilite is typical FeS phase in chondritic meteorites. In this study, quick heating and cooling experiments of FeS reagent particles were carried out with a fine particles free falling apparatus with controlled gas flow (Isobe and Gondo, 2013). Starting material reagent is inhomogeneous mixture of troilite, iron oxide and iron metal. Oxygen fugacity was controlled to FMQ +1.5 log unit. Maximum temperature of the particles was higher than 1400°C for approximately 0.5 seconds. Run products with rounded shape and smooth surface show the particles were completely melted. Chemical compositions of particles analyzed on cross sections are generally well homogenized from inhomogeneous starting materials by complete melting. Molar ratios of Fe in melted regions are close to 0.5, while compositions of S and O are various. Varieties of S and O compositions show various degree of oxidation and evaporation of sulfur. Distribution of compositions of melted regions in Fe-S-O system is plotted in liquidus compositions of FeO and FeS saturated melt. Troilite in micrometeorite is melted and oxidized by atmospheric entry. Compositions of FeS melt in fine spherules are following Fe-S-O phase relations even in a few seconds. Molar ratios of Fe in melt are close to 0.5, while compositions of S and O are various. Varieties of S and O compositions show various degree of oxidation and evaporation of sulfur. Evaporation of sulfur from meteoritic materials in atmospheric entry heating may depend on oxygen fugacity of the upper atmosphere. Sulfur supply from meteoritic materials to atmosphere may be limited on planets with oxygen-free atmosphere.

Lunar and Planetary Science XXXV: Special Session: Oxygen in the Solar System, II

NASA Technical Reports Server (NTRS)

2004-01-01

The Special Session: Oxygen in the Solar System, II, included the following reports:Evolution of Oxygen Isotopes in the Solar Nebula; Disequilibrium Melting of Refractory Inclusions: A Mechanism for High-Temperature Oxygen; Isotope Exchange in the Solar Nebula; Oxygen Isotopic Compositions of the Al-rich Chondrules in the CR Carbonaceous Chondrites: Evidence for a Genetic Link to Ca-Al-rich Inclusions and for Oxygen Isotope Exchange During Chondrule Melting; Nebular Formation of Fayalitic Olivine: Ineffectiveness of Dust Enrichment; Water in Terrestrial Planets: Always an Oxidant?; Oxygen Barometry of Basaltic Glasses Based on Vanadium Valence Determination Using Synchrotron MicroXANES; A New Oxygen Barometer for Solar System Basaltic Glasses Based on Vanadium Valence; The Relationship Between Clinopyroxene Fe3+ Content and Oxygen Fugacity ; and Olivine-Silicate Melt Partitioning of Iridium.

Redox systematics of a magma ocean with variable pressure-temperature gradients and composition.

PubMed

Righter, K; Ghiorso, M S

2012-07-24

Oxygen fugacity in metal-bearing systems controls some fundamental aspects of the geochemistry of the early Earth, such as the FeO and siderophile trace element content of the mantle, volatile species that influence atmospheric composition, and conditions for organic compounds synthesis. Redox and metal-silicate equilibria in the early Earth are sensitive to oxygen fugacity (fO(2)), yet are poorly constrained in modeling and experimentation. High pressure and temperature experimentation and modeling in metal-silicate systems usually employs an approximation approach for estimating fO(2) that is based on the ratio of Fe and FeO [called "ΔIW (ratio)" hereafter]. We present a new approach that utilizes free energy and activity modeling of the equilibrium: Fe + SiO(2) + O(2) = Fe(2)SiO(4) to calculate absolute fO(2) and relative to the iron-wüstite (IW) buffer at pressure and temperature [ΔIW (P,T)]. This equilibrium is considered across a wide range of pressures and temperatures, including up to the liquidus temperature of peridotite (4,000 K at 50 GPa). Application of ΔIW (ratio) to metal-silicate experiments can be three or four orders of magnitude different from ΔIW (P,T) values calculated using free energy and activity modeling. We will also use this approach to consider the variation in oxygen fugacity in a magma ocean scenario for various thermal structures for the early Earth: hot liquidus gradient, 100 °C below the liquidus, hot and cool adiabatic gradients, and a cool subsolidus adiabat. The results are used to assess the effect of increasing P and T, changing silicate composition during accretion, and related to current models for accretion and core formation in the Earth. The fO(2) in a deep magma ocean scenario may become lower relative to the IW buffer at hotter and deeper conditions, which could include metal entrainment scenarios. Therefore, fO(2) may evolve from high to low fO(2) during Earth (and other differentiated bodies) accretion. Any modeling of core formation and metal-silicate equilibrium should take these effects into account.

Interpreting Assemblages with Titanite (Sphene): It Does not have to be Greek to You.

NASA Technical Reports Server (NTRS)

Xirouchakis, Dimitrios M.; Lindsley, Donald H.; McKay, Gordon A. (Technical Monitor)

2000-01-01

Assemblages with titanite, pyroxene(s), olivine, ilmenite, magnetite, and quartz can be used to constrain the intensive and compositional variables that operate during crystallization. Such assemblages are relatively rare in metamorphic rocks, but they are more common in igneous rocks and more frequently reported in plutonic than volcanic rocks. We used the program QUILF, enhanced with thermodynamic data for titanite, to compute stable reactions among titanite (CaTiOSiO4), Fe-Mg-Ti ilmenite and magnetite (hereafter ilmenite and magnetite), Ca-Mg-Fe pyroxenes and olivine, and quartz, and to evaluate some of the factors that control titanite stability. Calculations at 1, 3, and 6 Kbar and 650, 850, 1100 0 C, in the system CaO - MgO - FeO Fe2O3 - TiO2 - SiO2, suggest that the reactions: Augitc + Ilmenite = Titanite + Magnetite + Quartz and Augite + Ilmenite + Quartz = Titanite + Orthopyroxene, impose well defined fugacity of O2, alpha(sub SiO2), , and compositional restrictions to the assemblages: (1) Titanite + Magnetite + Quartz, (2) Titanite + Orthopyroxene, (3) Augite + Ilmenite, and consequently titanite stability. From our calculations in this system we can draw the following general conclusions: (1) The assemblage Titanite + Magnetite + Quartz is always a good indicator of relatively high fugacity of O2, and it is likely more common in relatively iron-rich bulk compositions and for decreasing temperature and pressure conditions. (2) At high temperatures (>= 650 C) titanite is not stable in quartz-saturated rocks that contain the assemblage Orthopyroxene + Augite + Ilmenite + Magnetite. (3) In quartz-saturated rocks the coexistence of titanite and magnetite with either orthopyroxene or olivine requires a confluence of conditions relating bulk composition, fugacity of O2, and slow cooling. Thus, such assemblages must be rare. (4) Regardless of T and fugacity of O2 conditions, and bulk-composition, titanite is not stable in quartz-absent rocks that contain Olivine + Orthopyroxene + Augite + Ilmenite + Magnetite. Decreasing temperature and pressure conditions appear to favor titanite crystallization, thus, it is not unsurprising that titanite is frequently observed in slowly cooled rocks, albeit, in association with amphibole. We argue that the titanite + amphibole association is likely favored by high water activity, regardless of oxygen fugacity. Because water activity increases during crystallization of a pluton, the association titanite + amphibole, and consequently titanite, is likely to be more common in plutonic rocks than in volcanic rocks.

High Pressure/Temperature Metal Silicate Partitioning of Tungsten

NASA Technical Reports Server (NTRS)

Shofner, G. A.; Danielson, L.; Righter, K.; Campbell, A. J.

2010-01-01

The behavior of chemical elements during metal/silicate segregation and their resulting distribution in Earth's mantle and core provide insight into core formation processes. Experimental determination of partition coefficients allows calculations of element distributions that can be compared to accepted values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Tungsten (W) is a moderately siderophile element and thus preferentially partitions into metal versus silicate under many planetary conditions. The partitioning behavior has been shown to vary with temperature, silicate composition, oxygen fugacity, and pressure. Most of the previous work on W partitioning has been conducted at 1-bar conditions or at relatively low pressures, i.e. <10 GPa, and in two cases at or near 20 GPa. According to those data, the stronger influences on the distribution coefficient of W are temperature, composition, and oxygen fugacity with a relatively slight influence in pressure. Predictions based on extrapolation of existing data and parameterizations suggest an increased pressured dependence on metal/ silicate partitioning of W at higher pressures 5. However, the dependence on pressure is not as well constrained as T, fO2, and silicate composition. This poses a problem because proposed equilibration pressures for core formation range from 27 to 50 GPa, falling well outside the experimental range, therefore requiring exptrapolation of a parametereized model. Higher pressure data are needed to improve our understanding of W partitioning at these more extreme conditions.

The Effect of Pressure on Iron Speciation in Silicate Melts at a Fixed Oxygen Fugacity: The Possibility of a Redox Profile Through a Terrestrial Magma Ocean

NASA Astrophysics Data System (ADS)

Armstrong, K.; Frost, D. J.; McCammon, C. A.; Rubie, D. C.; Boffa Ballaran, T.

2017-12-01

As terrestrial planets accreted, mantle silicates equilibrated with core-forming metallic iron, which would have imposed a mantle oxygen fugacity below the iron-wüstite oxygen buffer. Throughout Earth's history, however, the oxygen fugacity of at least the accessible portions of the upper mantle has been 4-5 orders of magnitude higher. The process that caused the rapid increase in the redox state of the mantle soon after core formation is unclear. Here we test the possibility that pressure stabilises ferric iron in silicate melts, as has been observed in silicate minerals. A deep magma ocean, which would have likely existed towards the end of accretion, could then develop a gradient in oxygen fugacity for a fixed ferric-ferrous ratio as a result of pressure. We have equilibrated an andesitic melt with a Ru-RuO2 buffer in a multianvil press between 5 and 24 GPa. Further experiments were performed on the same melt in equilibrium with iron metal. The recovered melts were then analysed using Mössbauer spectroscopy to determine the ferric/ferrous ratio. The results show that for the Ru-RuO2 buffer at lower pressures, the ferric iron content decreases with pressure, due to a positive volume change of the reaction FeO + 1/4O2 = FeO1.5. Ferric iron content also appears to be sensitive to water content at lower pressures. However, above 15 GPa this trend apparently reverses and the ferric iron content increases with pressure. This reversal in pressure dependence would drive the oxygen fugacity of a deep magma ocean with a fixed ferric/ferrous ratio down with increasing depth. This would create a redox gradient, where the magma ocean could potentially be in equilibrium with metallic iron at its base but more oxidised in its shallower regions. Crystallisation of this magma ocean could render an upper mantle oxygen fugacity similar to that in the Earth's accessible mantle today.

The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt

NASA Technical Reports Server (NTRS)

Pawley, Alison R.; Holloway, John R.; Mcmillan, Paul F.

1992-01-01

The solubility of CO2-CO fluids in a midocean ridge basalt have been measured at 1200 C, 500-1500 bar, and oxygen fugacities between NNO and NNO-4. In agreement with results of previous studies, the results reported here imply that, at least at low pressures, CO2 dissolves in basaltic melt only in the form of carbonate groups. The dissolution reaction is heterogeneous, with CO2 molecules in the fluid reacting directly with reactive oxygens in the melt to produce CO3(2-). CO, on the other hand, is insoluble, dissolving neither as carbon, molecular CO, nor CO3(2-). It is shown that, for a given pressure and temperature, the concentration of dissolved carbon-bearing species in basaltic melt in equilibrium with a carbon-oxygen fluid is proportional to the mole fraction of CO2 in the fluid, which is a function of fO2. At low pressures CO2 solubility is a linear function of CO2 fugacity at constant temperatures.

Electrochemically-Induced Redox Reactions in Basalt at High Pressure and Temperature: An Iron and Vanadium K-edge XANES Study

NASA Astrophysics Data System (ADS)

Kavner, A.; Walker, D.; Newville, M.; Sutton, S. R.

2005-12-01

An applied electric field across a silicate sample at high pressures and temperatures in a piston cylinder apparatus can generate a wide range of oxidation states of polyvalent cations within a single experiment. If two or more polyvalent cations are included, this technique can be used to cross-calibrate oxybarometers within a single experiment. The redox state of Fe and V within a partially melted basaltic silicate was manipulated in situ in a piston-cylinder experiment with a DC power supply providing a source and sink of electrons to the sample. A 1V electrical potential differential was applied across vanadium-doped and Fe-bearing synthetic basalt samples for 24 hrs. at 20 kbar and 1400°C in a specially-designed piston cylinder sample assembly. Three experiments were performed: a control sample with no applied voltage, one with bottom cathode and top anode, and a third with top cathode and bottom anode. Synchrotron-based x-ray absorption near edge structure (XANES) spectroscopy was used to provide spot analysis of iron and vanadium oxidation states with 5μm x 5μm spatial resolution throughout the recovered samples. Systematic spatial changes of increasing oxidation states of V and Fe were observed approaching the anode. The differences in oxidation states were mapped to a corresponding local effective oxygen fugacity by comparison and extension of a calibration of vanadium oxidation states as a function of controlled oxygen fugacity from a previous study (Sutton et al., 2005, GCA, vol. 69, pp. 2333-2348). The vanadium mapping indicates that a 1V potential drop across the sample induces effective oxygen fugacity perturbations in excess of ten orders of magnitude. The presence of both Fe and V within the same sample provides a wide range of oxygen fugacity cross-calibration in these recovered samples. A relationship between oxygen fugacity and electrochemical driving force is derived. The experimental results are in good agreement with the derived relationship between applied electrochemical potential difference (the 1V in this experiment), and corresponding calculated oxygen fugacity.

Partitioning of Ni, Co and V between Spinel-Structured Oxides and Silicate Melts: Importance of Spinel Composition

NASA Technical Reports Server (NTRS)

Righter, K.; Leeman, W. P.; Hervig, R. L.

2006-01-01

Partitioning of Ni, Co and V between Cr-rich spinels and basaltic melt has been studied experimentally between 1150 and 1325 C, and at controlled oxygen fugacity from the Co-CoO buffer to slightly above the hematite magnetite buffer. These new results, together with new Ni, Co and V analyses of experimental run products from Leeman [Leeman, W.P., 1974. Experimental determination of the partitioning of divalent cations between olivine and basaltic liquid, Pt. II. PhD thesis, Univ. Oregon, 231 - 337.], show that experimentally determined spinel melt partition coefficients (D) are dependent upon temperature (T), oxygen fugacity (fO2) and spinel composition. In particular, partition coefficients determined on doped systems are higher than those in natural (undoped) systems, perhaps due to changing activity coefficients over the composition range defined by the experimental data. Using our new results and published runs (n =85), we obtain a multilinear regression equation that predicts experimental D(V) values as a function of T, fO2, concentration of V in melt and spinel composition. This equation allows prediction of D(V) spinel/melt values for natural mafic liquids at relevant crystallization conditions. Similarly, D(Ni) and D(Co) values can be inferred from our experiments at redox conditions approaching the QFM buffer, temperatures of 1150 to 1250 C and spinel composition (early Cr-bearing and later Ti-magnetite) appropriate for basic magma differentiation. When coupled with major element modelling of liquid lines of descent, these values (D(Ni) sp/melt=10 and D(Co) sp/melt=5) closely reproduce the compositional variation observed in komatiite, mid-ocean ridge basalt (MORB), ocean island basalt (OIB) and basalt to rhyolite suites.

Platinum Partitioning at Low Oxygen Fugacity: Implications for Core Formation Processes

NASA Technical Reports Server (NTRS)

Medard, E.; Martin, A. M.; Righter, K.; Lanziroti, A.; Newville, M.

2016-01-01

Highly siderophile elements (HSE = Au, Re, and the Pt-group elements) are tracers of silicate / metal interactions during planetary processes. Since most core-formation models involve some state of equilibrium between liquid silicate and liquid metal, understanding the partioning of highly siderophile elements (HSE) between silicate and metallic melts is a key issue for models of core / mantle equilibria and for core formation scenarios. However, partitioning models for HSE are still inaccurate due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variable like temperature, pressure, and oxygen fugacity. In this abstract, we describe a self-consistent set of experiments aimed at determining the valence of platinum, one of the HSE, in silicate melts. This is a key information required to parameterize the evolution of platinum partitioning with oxygen fugacity.

Oxygen fugacities directly measured in magmatic gases.

PubMed

Sato, M; Wright, T L

1966-09-02

An electrochemical device was used to measure the fugacity of oxygen (fo(o2)) in holes drilled through the crust of Makaopuhi lava lake, Kilauea Volcano, Hawaii. Results obtained within 6 months of the lake formation show that log fo(o2) normally varies linearly with the reciprocal of the absolute temperature, and that chemical changes occurring in the cooling tholeiitic basalt are reflected in the fo(o2) values measured in the holes.

Mineral chemistry of Pangidi basalt flows from Andhra Pradesh

NASA Astrophysics Data System (ADS)

Nageswara Rao, P. V.; Swaroop, P. C.; Karimulla, Syed

2012-04-01

This paper elucidates the compositional studies on clinopyroxene, plagioclase, titaniferous magnetite and ilmenite of basalts of Pangidi area to understand the geothermometry and oxybarometry conditions. Petrographic evidence and anorthite content (up to 85%) of plagioclase and temperature estimates of clinopyroxene indicate that the clinopyroxene is crystallized later than or together with plagioclase. The higher An content indicates that the parent magma is tholeiitic composition. The equilibration temperatures of clinopyroxene (1110-1190°C) and titaniferous magnetite and ilmenite coexisting mineral phases (1063-1103°C) are almost similar in lower basalt flow and it is higher for clinopyroxene (900-1110°C) when compared to titaniferous magnetite and ilmenite coexisting mineral phases (748-898°C) in middle and upper basalt flows. From this it can be inferred that the clinopyroxene is crystallized earlier than Fe-Ti oxide phases reequilibration, which indicates that the clinopyroxene temperature is the approximate eruption temperature of the present lava flows. The wide range of temperatures (900-1190°C) attained by clinopyroxene may point out that the equilibration of clinopyroxene crystals initiated from depth till closer to the surface before the melt erupted. Pangidi basalts follow the QFM buffer curve which indicates the more evolved tholeiitic composition. This suggests the parent tholeiitic magma suffered limited fractionation at high temperature under increasing oxygen fugacity in lower basalt flow and more fractionation at medium to lower temperatures under decreasing oxygen fugacity conditions during cooling of middle and upper basalt flows. The variation of oxygen fugacity indicates the oxidizing conditions for lower basalt flow (9.48-10.3) and extremely reducing conditions for middle (12.1-15.5) and upper basalt (12.4-15.54) flows prevailed at the time of cooling. Temperature vs. (FeO+Fe2O3)/(FeO+Fe2O3 +MgO) data plots for present basalts suggested the lower basaltic flow is formed at higher temperatures while the middle and upper basalt flows at medium to lower temperatures. The lower basalt flow is represented by higher temperatures which shows high modal values of opaques and glass whereas the medium to lower temperatures of middle and upper flow are caused by vesicular nature which contain larger content of gases and humid to semi-arid conditions during cooling.

Preeruption conditions and timing of dacite-andesite magma mixing in the 2.2 ka eruption at Mount Rainier

NASA Astrophysics Data System (ADS)

Venezky, D. Y.; Rutherford, M. J.

1997-01-01

Analytical, field, and experimental evidence demonstrate that the Mount Rainier tephra layer C (2.2 ka) preserves a magma mixing event between an andesitic magma (whole rock SiO2 content of 57-60 wt %) and a dacitic magma (whole rock SiO2 content of 65±1 wt %). The end-member andesite (a mix of an injected and chamber andesite) and dacite can be characterized on the basis of the homogeneity of the matrix glass and phenocryst rim compositions. Many pumices, however, contain mixtures of the end-members. The end-member dacite contains a microlite-free matrix glass with 74-77 wt % SiO2, orthopyroxene rims of Mg57-64, clinopyroxene rims of Mg66-74, and plagioclase rim anorthite contents of An45-65. The temperature and oxygen fugacity, from Fe-Ti oxide compositions, are 930±10°C and 0.5-0.75 log units above NNO. The mixed andesite contains Mg73-84 orthopyroxene rims, Mg73-78 clinopyroxene rims, An78-84 plagioclase rims, and Mg67-74 amphibole rims. The temperature from Fe-Ti oxides, hornblendeplagioclase, and two-pyroxene geothermometry is 1060±15°C, and the oxygen fugacity is approximately one log unit above NNO for the injected andesite. The chamber andesite is estimated to be a magma with a ˜64-65 wt % SiO2 melt at 980°C and a NNO oxygen fugacity. We conclude that the andesitic and dacitic magmas are from separate magma storage regions (at >7 km and ˜2.4 km) due to differences in the bimodal whole rock, matrix glass, and phenocryst compositions and the presence or absence of stable hornblende. The time involved from the mixing event through the eruption is limited to a period of 4-5 days based on Fe-Ti oxide reequilibration, phenocryst growth rates, and hornblende breakdown. The eruption sequence is interpreted as having been initiated by an injection of the 1060±15°C andesitic magma into the ˜980°C (>7 km) andesite storage region. The mixed andesitic magma then intersected a shallow, ˜2.4 km, dacitic storage system on its way toward the surface. The eruption became more dacitic over time, and the final products some show evidence of partial reequilibration between the andesite and dacite.

Redox systematics of a magma ocean with variable pressure-temperature gradients and composition

PubMed Central

Righter, K.; Ghiorso, M. S.

2012-01-01

Oxygen fugacity in metal-bearing systems controls some fundamental aspects of the geochemistry of the early Earth, such as the FeO and siderophile trace element content of the mantle, volatile species that influence atmospheric composition, and conditions for organic compounds synthesis. Redox and metal-silicate equilibria in the early Earth are sensitive to oxygen fugacity (fO2), yet are poorly constrained in modeling and experimentation. High pressure and temperature experimentation and modeling in metal-silicate systems usually employs an approximation approach for estimating fO2 that is based on the ratio of Fe and FeO [called “ΔIW (ratio)” hereafter]. We present a new approach that utilizes free energy and activity modeling of the equilibrium: Fe + SiO2 + O2 = Fe2SiO4 to calculate absolute fO2 and relative to the iron-wüstite (IW) buffer at pressure and temperature [ΔIW (P,T)]. This equilibrium is considered across a wide range of pressures and temperatures, including up to the liquidus temperature of peridotite (4,000 K at 50 GPa). Application of ΔIW (ratio) to metal-silicate experiments can be three or four orders of magnitude different from ΔIW (P,T) values calculated using free energy and activity modeling. We will also use this approach to consider the variation in oxygen fugacity in a magma ocean scenario for various thermal structures for the early Earth: hot liquidus gradient, 100 °C below the liquidus, hot and cool adiabatic gradients, and a cool subsolidus adiabat. The results are used to assess the effect of increasing P and T, changing silicate composition during accretion, and related to current models for accretion and core formation in the Earth. The fO2 in a deep magma ocean scenario may become lower relative to the IW buffer at hotter and deeper conditions, which could include metal entrainment scenarios. Therefore, fO2 may evolve from high to low fO2 during Earth (and other differentiated bodies) accretion. Any modeling of core formation and metal-silicate equilibrium should take these effects into account. PMID:22778438

Oxygen and iron production by electrolytic smelting of lunar soil

NASA Technical Reports Server (NTRS)

Haskin, Larry A.

1989-01-01

Previous work has shown that Fe(sup 0) and O2 can be derived by electrolysis from silicate smelt of a composition typical of lunar soils (Lindstrom and Haskin 1979). In the present study, the goal is to refine further the conditions necessary to optimize production and to determine efficiencies of production (how much product is derived for a given current) and purity of products. These depend on several factors, including potential imposed between electrodes, configuration and surface area of the electrodes, composition of the electrolyzed silicate melt, and oxygen fugacity. Experiments were designed to measure the dependence on these variables of three parameters that must be known before production by electrolysis can be optimized. These parameters are: Limiting Current; Actual Current; and Efficiencies of Production.

An electrochemical series of redox couples in silicate melts - A review and applications to geochemistry

NASA Technical Reports Server (NTRS)

Schreiber, Henry D.

1987-01-01

An electrochemical series for redox couples in a glass-forming oxide melt is developed. This series is a quantitative numerical scale of reference reduction potentials of the redox couples in a silicate melt that is a model for basaltic magmas. The redox couples are ordered in terms of their reference reduction potentials; the order appears to be relatively independent of the exact melt composition and temperature. Thus, upon calibration to a desired composition, oxygen fugacity, and temperature, this electrochemical series can provide estimates of redox state proportions in basaltic magmas on different planetary bodies. The geochemical electrochemical series can also be used to understand the interrelationship of the redox state of the magma and the presence of volatile species such as oxygen, water, sulfur gases, and carbon gases.

Volatile Element Behavior During Melting and Vaporisation on Earth and Protoplanets.

NASA Astrophysics Data System (ADS)

Wood, B. J.; Norris, C. A.

2017-12-01

During accretion the Earth and many of the smaller bodies which were added to it, underwent periods of partial melting, vaporisation and re-condensation. This resulted in patterns of volatile element depletion relative to CI chondrite which are difficult to interpret. The behavior of moderately volatile elements (Pb, Cd, Zn,Cu, In,Tl etc) during these melting, vaporisation and condensation processes is usually approximated by the temperature of condensation from a gas of solar composition. Thus, Tl and In have low condensation temperatures and are regarded as the most volatile of this group. In order to test this volatility approximation we have studied the vaporisation behavior of 13 elements (Ag,Bi,Cd,Cr,Cu,Ga,Ge,In,Pb,Sb,Sn,Tl,Zn) from molten basalt at 1 atm pressure and oxygen fugacities between Ni-NiO and 2 log units below Fe-FeO. The relative volatilities of the elements turn out to be only weakly correlated with condensation temperature, indicating that the latter is a poor proxy for volatility on molten bodies. Cu, Zn and In for example all have similar volatility in the oxygen fugacity range of concern, despite the condensation temperature of Cu (1037K at 10-4bar) being 500K greater than that of In. The oxygen fugacity dependence of volatility indicates that the volatile species are, for all elements more reduced than the melt species. We addressed the differences between condensation temperature and relative volatility in 2 steps. Firstly we used metal-silicate partitioning experiments to estimate the activity coefficients of the trace element oxides in silicate melts. We then used available thermodynamic data to compute the vapor pressures of the stable species of these 13 elements over the silicate melt at oxygen fugacities ranging from Ni-NiO to about 6 log units below Fe-FeO, which approximates the solar gas. Thus we find that presence of Cl and S in the solar gas and the stable Cl and S species of In,Tl Ga Ge Cd and Sn are important contributing factors to volatility in the solar nebula. Our measured volatilities from silicate melt under reducing (S and Cl-absent) conditions are consistent with abundances in the silicate Earth, indicating that these moderately volatile elements were added to Earth in bodies which had undergone episodes of melting and vaporisation.

Oxygen stoichiometry, phase stability, and thermodynamic behavior of the lead-doped and lead-free Bi-2212 systems

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Hash, M.; Tani, B. S.; Maroni, V. A.

1996-02-01

Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made on lead-doped and lead-free Bi 2- zPb zSr 2Ca 1Cu 2O x superconducting ceramics in the temperature range ≈ 700-815°C by means of an oxygen-titration techique that employs an yttria-stabilized zirconia electrolyte. Equations for the variation of oxygen partial pressure with composition and temperature have been derived from our EMF measurements. Thermodynamic assessments of the partial molar quantities Δ overlineH(O 2) and Δ overlineS(O 2) for lead-doped Bi-2212 and lead-free Bi-2212 indicate that the solid-state decomposition of these bismuth cuprates at low oxygen partial pressure can be represented by the diphasic CuOCu 2O system.

Long-term geochemical surveillance of fumaroles at Showa-Shinzan dome, Usu volcano, Japan

USGS Publications Warehouse

Symonds, R.B.; Mizutani, Y.; Briggs, P.H.

1996-01-01

This study investigates 31 years of fumarole gas and condensate (trace elements) data from Showa-Shinzan, a dacitic dome-cryptodome complex that formed during the 1943-1945 eruption of Usu volcano. Forty-two gas samples were collected from the highest-temperature fumarole, named A-1, from 1954 (800??C) to 1985 (336??C), and from lower-temperature vents. Condensates were collected contemporaneously with the gas samples, and we reanalyzed ten of these samples, mostly from the A-1 vent, for 32 cations and three anions. Modeling using the thermochemical equilibrium program, SOLVGAS, shows that the gas samples are mild disequilibrium mixtures because they: (a) contain unequilibrated sedimentary CH4 and NH3; (b) have unequilibrated meteoric water; or (c) lost CO, either by air oxidation or by absorption by the sodium hydroxide sampling solution. SOLVGAS also enabled us to restore the samples by removing these disequilibrium effects, and to estimate their equilibrium oxygen fugacities and amounts of S2 and CH4. The restored compositions contain > 98% H2O with minor to trace amounts of CO2, H2, HCl, SO2, HF, H2S, CO, S2 and CH4. We used the restored gas and condensate data to test the hypotheses that these time-series compositional data from the dome's fumaroles provide: (1) sufficient major-gas data to analyze long-term degassing trends of the dome's magma-hydrothermal system without the influence of sampling or contamination effects; (2) independent oxygen fugacity-versus-temperature estimates of the Showa-Shinzan dacite; (3) the order of release of trace elements, especially metals, from magma; and (4) useful information for assessing volcanic hazards. The 1954-1985 restored A-1 gas compositions confirm the first hypothesis because they are sufficient to reveal three long-term degassing trends: (1) they became increasingly H2O-rich with time due to the progressive influx of meteoric water into the dome; (2) their C/S and S/Cl ratios decreased dramatically while their Cl/F ratios stayed roughly constant, indicating the progressive outgassing of less soluble components (F ??? Cl > S > C) from the magma reservoir; and (3) their H2O/H2, CO2/CO and H2S/SO2 ratios increased significantly in concert with equilibrium changes expected for the ??? 500??C temperature drop. When plotted against reciprocal temperature, the restored-gas log oxygen fugacities follow a tight linear trend from 800??C to NNO + 2.5 at ??? 400??C. This trend largely disproves the second hypothesis because the oxygen fugacities for the < 800??C restored gases can only be explained by mixing of hot magmatic gases with ??? 350??C steam from superheated meteoric water. But above 800??C this trend intersects the opposing linear trend for other Usu eruptive products, implying a log oxygen fugacity of -11.45 at 902??C for the Showa-Shinzan magma. The time-series trace-element data also disprove the third hypothesis because rock- and incrustation-particle contaminants in the condensates account for most of the trace-element variation. Nonetheless, highly volatile elements like B and As are relatively unaffected by this particle contamination, and they show similar time-series trends as Cl and F. Finally, except for infrequent sampling around the 1977 Usu eruption, the results generally confirm the fourth hypothesis, since the time-series trends for the major gases and selected trace elements indicate that, with time, the system cooled, degassed and was infiltrated by meteoric water, all of which are positive signs that volcanic activity declined over the 31-year history. This study also suggests that second boiling of shallow magma within and possibly beneath the cryptodome sustained magmatic degassing for at least 20 years after emplacement.

Stable Vanadium Isotopes as a Redox Proxy at High Temperatures?

NASA Astrophysics Data System (ADS)

Prytulak, J.; Sossi, P.; Halliday, A.; Plank, T. A.; Savage, P.; Woodhead, J. D.

2016-12-01

There is currently no consensus on the relative oxygen fugacity (fO2) of the mantle source of mid-ocean ridge basalts compared to the sub-arc mantle, the region that is central to the mediation of crust-mantle mass balances. Vanadium is a multivalent transition metal whose stable isotope fractionation may reflect oxygen fugacity (fO2). However, a direct link between V isotope composition and fO2 is currently far from convincingly demonstrated. Furthermore, differences in co-ordination environment also play a large role in causing stable isotope fractionation. Here we present V isotope measurements of two suites of co-genetic magmas from contrasting tectonic settings: the Mariana arc and Hekla volcano, Iceland. We use this data alongside the tightly constrained V isotope composition of MORB [1] to assess the effects of fO2 and crystal fractionation on stable vanadium isotopes. We show that, for a given MgO content, V isotopes are identical within analytical error between arc basalts from the Marianas, lavas from Hekla, and MORB. The most striking aspect of our igneous, high temperature V isotope data is the large isotope fractionation (on the order of 2 ‰) towards heavier values in magmatic suites from both Hekla and the Marianas with progressive differentiation. We use a self consistent model of fractionating cotectic phases in both igneous suites to match major, trace and V isotope data. Vanadium partition coefficients required for (titano)magnetite are significantly higher in Hekla (DVmag = 42) than Mariana lavas (DVmag = 32), consistent with a more oxidised source in the latter. Calculated Rayleigh fractionation factors are similar in both suites (Δ51Vmin-melt of -0.4 to -0.5‰) and strongly implicate co-ordination differences between oxides and melt are the dominant driving force for V isotope fractionation. Thus, although fO2likely has a second order effect on V isotopes, they are not a direct proxy for oxygen fugacity in magmatic systems. [1] Prytulak, et al. 2013. EPSL 365, 177-189

Workshop on Oxygen in Asteroids and Meteorites

NASA Technical Reports Server (NTRS)

2005-01-01

Contents include the following: Constraints on the detection of solar nebula's oxidation state through asteroid observation. Oxidation/Reduction Processes in Primitive Achondrites. Low-Temperature Chemical Processing on Asteroids. On the Formation Location of Asteroids and Meteorites. The Spectral Properties of Angritic Basalts. Correlation Between Chemical and Oxygen Isotopic Compositions in Chondrites. Effect of In-Situ Aqueous Alteration on Thermal Model Heat Budgets. Oxidation-Reduction in Meteorites: The Case of High-Ni Irons. Ureilite Atmospherics: Coming up for Air on a Parent Body. High Temperature Effects Including Oxygen Fugacity, in Pre-Planetary and Planetary Meteorites and Asteroids. Oxygen Isotopic Variation of Asteroidal Materials. High-Temperature Chemical Processing on Asteroids: An Oxygen Isotope Perspective. Oxygen Isotopes and Origin of Opaque Assemblages from the Ningqiang Carbonaceous Chondrite. Water Distribution in the Asteroid Belt. Comparative Planetary Mineralogy: V Systematics in Planetary Pyroxenes and fo 2 Estimates for Basalts from Vesta.

Hydrogen and Ferric Iron in Mars Materials

NASA Technical Reports Server (NTRS)

Dyar, Melinda D.

2004-01-01

Knowledge of oxygen and hydrogen fugacity is of paramount importance in constraining phase equilibria and crystallization processes of melts, as well as understanding the partitioning of elements between the cope and silicate portions of terrestrial planets. H and Fe(3+) must both be analyzed in order to reconstruct hydrogen and oxygen fugacities on Mars. To date, SIMS data have elucidated D/H and H contents of hydrous phases in SNC meteorites, but until now anhydrous martian minerals have not been systematically examined for trace hydrogen. Ferric iron has been quantified using XANES in many martian phases, but integrated studies of both Fe(3+) and H on the same spots are really needed to address the H budget. Finally, the effects of shock on both Fe(3+) and H in hydrous and anhydrous phases must be quantified. Thus, the overall goal of this research was to understand the oxygen and hydrogen fugacities under which martian samples crystallized. In this research one-year project, we approached this problem by 1) characterizing Fe(3+) and H contents of SNC meteorites using both bulk (Mossbauer spectroscopy and uranium extraction, respectively) and microscale (synchrotron micro-XANES and SIMS) methods; 2) relating Fe(3+) and H contents of martian minerals to their oxygen and hydrogen fugacities through analysis of experimentally equilibrated phases (for pyroxene) and through study of volcanic rocks in which the oxygen and hydrogen fugacities can be independently constrained (for feldspar); and 3) studying the effects of shock processes on Fe(3+) and H contents of the phases of interest. Results have been used to assess quantitatively the distribution of H and Fe(3+) among phases in the martian interior, which will better constrain the geodynamic processes of the interior, as well as the overall hydrogen and water budgets on Mars. There were no inventions funded by this research.

A system using solid ceramic oxygen electrolyte cells to measure oxygen fugacities in gas-mixing systems

NASA Technical Reports Server (NTRS)

Williams, R. J.; Mullins, O.

1976-01-01

Details are given for the construction and operation of a 101.3 kN/sq m (1 atmosphere) redox control system. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a vertical quench, gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples. The system also contains the high input impedance electronics necessary for measurements, a simplified version of a gas mixing apparatus, and devices for experiments under controlled rates of change relative to temperature and redox state. The calibration and maintenance of the system are discussed.

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

NASA Technical Reports Server (NTRS)

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.

FirefOx Design Reference fO2 Sensor for Hot, Deep Atmospheres

NASA Astrophysics Data System (ADS)

Izenberg, N.; Papadakis, S.; Deglau, D.; Francomacaro, A. S.

2016-12-01

Understanding the composition of the lowest portion of Venus' atmosphere is critical to knowing the stable mineralogy of the rocks there. Oxygen gas is a critical trace component, with fugacity, or partial pressure, estimated in the range of 10-19 to 10-22 from early probe measurements down to 22km altitude (Pioneer Venus, Venera), chemical equilibrium measurements, and other modeling. "FirefOx" is a simple oxygen fugacity sensor with the express purpose of determining the partial pressure of oxygen in the lowest scale heights of the Venus atmosphere, and especially the lowest hundreds of meters; the surface atmosphere interface, where the atmosphere and surface move to thermodynamic equilibrium. Knowledge of the fO2 at the surface atmosphere interface is crucial to determining the stable mineralogy of surface materials (e.g. magnetite vs. hematite) and gas chemistry in the near-surface atmosphere FirefOx is a Metal/Metal Oxide oxygen fugacity sensor intended to be mounted on the outside of a Venus descent probe, with electronics housed inside a thermally controlled environment. The sole sensor capability is the precise, accurate detection of the partial pressure of oxygen gas (fO2) in the near-surface environment of Venus, at up to 95-bar pressure (predominantly CO2. Surface temperatures at mean planetary elevation are near 735 K, thus a required operational temperature range of 710-740 K covers a range of near-surface elevations. FirefOx system requirements are low ( 100-200 grams, mass, milliwatt power, several kilobytes total science data). A design reference sensor, composed of custom, Yittria-ZrO ceramic electrolyte, with an encapsulated Pd/PdO standard and patterned Pt electrodes has demonstrated scientifically useful signal-to-noise millivolt level potential at temperatures as low as 620 K, relatable to fO2 by a Nernst equation E = RT/4F ln(PO2/PrefO2) where E = open circuit potential across the sensor electrolyte, R = universal gas constant, T = temperature, F = Faraday constant, PrefO2 = reference oxygen pressure, and PO2 = unknown oxygen pressure of the outside environment. The FirefOx sensor shows promise for direct fO2 measurement on potential upcoming Venus in situ and other deep atmosphere probes.

Electrochemical measurements and thermodynamic calculations of redox equilibria in pallasite meteorites - Implications for the eucrite parent body

NASA Technical Reports Server (NTRS)

Righter, Kevin; Arculus, Richard J.; Paslick, Cassi; Delano, John W.

1990-01-01

The intrinsic oxygen fugacity (IOF) of olivine separates from the Salta, Springwater, and Eagle Station pallasites was measured between 850 and 1150 C using oxygen-specific solid zirconia electrolytes at 100,000 Pa. Thermodynamic calculations of redox equilibria involving equalibrium pallasite assemblages are in good agreement with the experimental results and provide a lower limit to pallasite redox stability; others involving disequilibrium assemblages, suggest that pallasites experienced localized, late-stage oxidation and reduction effects. Consideration of the redox buffer metal-olivine-orthopyroxene utilizing calculated Eucrite Parent Body (EPB) mantle phase compositions indicates that small redox gradients may have existed in the EPB. Such gradients may have produced strong compositional variation within the EPB. In addition, there is apparently significant redox heterogeneity in the source area of Eagle Station Trio pallasites and Bocaiuva iron meteorites.

Oxygen Fugacity at High Pressure: Equations of State of Metal-Oxide Pairs

NASA Technical Reports Server (NTRS)

Campbell A. J.; Danielson, L.; Righter, K.; Wang, Y.; Davidson, G.; Wang, Y.

2006-01-01

Oxygen fugacity (fO2) varies by orders of magnitude in nature, and can induce profound changes in the chemical state of a substance, and also in the chemical equilibrium of multicomponent systems. One prominent area in high pressure geochemistry, in which fO2 is widely recognized as a principal controlling factor, is that of metal-silicate partitioning of siderophile trace elements (e.g., [1]). Numerous experiments have shown that high pressures and temperatures can significantly affect metal/silicate partitioning of siderophile and moderately siderophile elements. Parameterization of these experimental results over P, T, X, and fO2 can allow the observed siderophile element composition of the mantle to be associated with particular thermodynamic conditions [2]. However, this is best done only if quantitative control exists over each thermodynamic variable relevant to the experiments. The fO2 values for many of these partitioning experiments were determined relative to a particular metal-oxide buffer (e.g., Fe-FeO (IW), Ni-NiO (NNO), Co-CoO, Re-ReO2 (RRO)), but the parameterization of all experimental results is weakened by the fact that the pressure-induced relative changes between these buffer systems are imprecisely known.

High temperature deformation of hot-pressed polycrystalline orthoenstatite. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Dehghan-Banadaki, A.

1983-01-01

Artificial hot pressed polycrystalline samples were prepared from purified powder of Bamble, Norway, orthoenstatite, (Mg0.86Fe0.14)SiO3. The uniaxial creep behavior of the polycrystalline orthoenstatite was studied over stress ranges of 10-180 MPa and temperatures of 1500-1700 K (0.82-0.93 T sub m) under two different oxygen fugacities, namely equilibrium (Mo-MoO2 buffer) and a reducing (graphite heating element) atmosphere, respectively. An intergranular glassy phase of different compositions with a cavitational creep deformation were observed. In the Mo-MoO2 buffer atmosphere with PO2 approx. 10 to the minus 11 power - 10 to the minus 13 power atmospheres, the results of an analytical electron microscopy analysis indicate that the glassy phases are richer in Ca and Al due to the residual impurities after hot pressing. In the reducing atmosphere with an oxygen fugacity of PO2 approx. 10 to the minus 3 power - 10 to the minus 25 power atmospheres, the results of analytical electron microscopy analysis indicate that the glassy phase is almost pure silica with the presence of free iron precipitate on grain facets and at triple junctions due to the reduction of bulk materials.

Calculation of Oxygen Fugacity in High Pressure Metal-Silicate Experiments and Comparison to Standard Approaches

NASA Technical Reports Server (NTRS)

Righter, K.; Ghiorso, M.

2009-01-01

Calculation of oxygen fugacity in high pressure and temperature experiments in metal-silicate systems is usually approximated by the ratio of Fe in the metal and FeO in the silicate melt: (Delta)IW=2*log(X(sub Fe)/X(sub FeO)), where IW is the iron-wustite reference oxygen buffer. Although this is a quick and easy calculation to make, it has been applied to a huge variety of metallic (Fe- Ni-S-C-O-Si systems) and silicate liquids (SiO2, Al2O3, TiO2, FeO, MgO, CaO, Na2O, K2O systems). This approach has surely led to values that have little meaning, yet are applied with great confidence, for example, to a terrestrial mantle at "IW-2". Although fO2 can be circumvented in some cases by consideration of Fe-M distribution coefficient, these do not eliminate the effects of alloy or silicate liquid compositional variation, or the specific chemical effects of S in the silicate liquid, for example. In order to address the issue of what the actual value of fO2 is in any given experiment, we have calculated fO2 from the equilibria 2Fe (metal) + SiO2 (liq) + O2 = Fe2SiO4 (liq).

Silicon in Mars' Core: A Prediction Based on Mars Model Using Nitrogen and Oxygen Isotopes in SNC Meteorites

NASA Technical Reports Server (NTRS)

Mohapatra, R. K.; Murty, S. V. S.

2002-01-01

Chemical and (oxygen) isotopic compositions of SNC meteorites have been used by a number of workers to infer the nature of precursor materials for the accretion of Mars. The idea that chondritic materials played a key role in the formation of Mars has been the central assumption in these works. Wanke and Dreibus have proposed a mixture of two types of chondritic materials, differing in oxygen fugacity but having CI type bulk chemical composition for the nonvolatile elements, for Mars' precursor. But a number of studies based on high pressure and temperature melting experiments do not favor a CI type bulk planet composition for Mars, as it predicts a bulk planet Fe/Si ratio much higher than that reported from the recent Pathfinder data. Oxygen forms the bulk of Mars (approximately 40% by wt.) and might provide clues to the type of materials that formed Mars. But models based on the oxygen isotopic compositions of SNC meteorites predict three different mixtures of precursor materials for Mars: 90% H + 10% CM, 85% H + 11% CV + 4% CI and 45% EH + 55% H. As each of these models has been shown to be consistent with the bulk geophysical properties (such as mean density, and moment of inertia factor) of Mars, the nature of the material that accreted to form Mars remains ambiguous.

Oxygen Fugacity of Mare Basalts and the Lunar Mantle Application of a New Microscale Oxybarometer Based on the Valence State of Vanadium

NASA Technical Reports Server (NTRS)

Shearer, C. K.; Karner, J.; Papike, J. J.; Sutton, S. R.

2004-01-01

The ability to estimate oxygen fugacities for mare basalts and to extend these observations to the lunar mantle is limited using bulk analysis techniques based on buffering assemblages or the valence state of iron. These limitations are due to reequilibration of mineral assemblages at subsolidus conditions, deviations of mineral compositions from thermodynamic ideality, size requirements, and the limits of the iron valence at very low fO2. Still, these approaches have been helpful and indicate that mare basalts crystallized at fO2 between the iron-w stite buffer (IW) and the ilmenite breakdown reaction (ilmenite = rutile + iron). It has also been inferred from these estimates that the lunar mantle is also highly reduced lying at conditions below IW. Generally, these data cannot be used to determine if the mare basalts become increasingly reduced during transport from their mantle source and eruption at the lunar surface and if there are differences in fO2 among mare basalts or mantle sources. One promising approach to determining the fO2 of mare basalts is using the mean valence of vanadium (2+, 3+, 4+, 5+) determined on spots of a few micrometers in diameter using synchrotron x-ray absorption fine structure (XAFS) spectroscopy. The average valence state of V in basaltic glasses is a function of fO2, temperature, V coordination, and melt composition. Here, we report the initial results of this approach applied to lunar pyroclastic glasses.

Constraints on oxygen fugacity within metal capsules

NASA Astrophysics Data System (ADS)

Faul, Ulrich H.; Cline, Christopher J., II; Berry, Andrew; Jackson, Ian; Garapić, Gordana

2018-06-01

Experiments were conducted with olivine encapsulated or wrapped in five different metals (Pt, Ni, Ni_{70}Fe_{30}, Fe, and Re) to determine the oxygen fugacity in the interior of large capsules used for deformation and seismic property experiments. Temperature (1200°C), pressure (300 MPa), and duration (24 h) were chosen to represent the most common conditions in these experiments. The oxygen fugacity was determined by analysing the Fe content of initially pure Pt particles that were mixed with the olivine powder prior to the experiments. Oxygen fugacities in the more oxidizing metal containers are substantially below their respective metal-oxide buffers, with the fO_2 of sol-gel olivine in Ni about 2.5 orders of magnitude below Ni-NiO. Analysis of olivine and metal blebs reveals three different length-, and hence diffusive time scales: (1) Fe loss to the capsule over ˜ 100 μ m, (2) fO_2 gradients at the sample-capsule interface up to 2 mm into the sample, and (3) constant interior fO_2 values with an ordering corresponding to the capsule material. The inferred diffusive processes are: Fe diffusion in olivine with a diffusivity ˜ 10^{-14} m^2/s, diffusion possibly of oxygen along grain boundaries with a diffusivity ˜ 10^{-12} m^2/s, and diffusion possibly involving pre-existing defects with a diffusivity ˜ 10^{-10} m^2/s. The latter, fast adjustment to changing fO_2 may consist of a rearrangement of pre-existing defects, representing a metastable equilibrium, analogous to decoration of pre-existing defects by hydrogen. Full adjustment to the external fO_2 requires atomic diffusion.

High pressure effects on the iron iron oxide and nickel nickel oxide oxygen fugacity buffers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Campbell, Andrew J; Danielson, Lisa; Righter, Kevin

The chemical potential of oxygen in natural and experimental samples is commonly reported relative to a specific oxygen fugacity (fO{sub 2}) buffer. These buffers are precisely known at 1 bar, but under high pressures corresponding to the conditions of the deep Earth, oxygen fugacity buffers are poorly calibrated. Reference (1 bar) fO{sub 2} buffers can be integrated to high pressure conditions by integrating the difference in volume between the solid phases, provided that their equations of state are known. In this work, the equations of state and volume difference between the metal-oxide pairs Fe-FeO and Ni-NiO were measured using synchrotronmore » X-ray diffraction in a multi-anvil press and laser heated diamond anvil cells. The results were used to construct high pressure fO{sub 2} buffer curves for these systems. The difference between the Fe-FeO and Ni-NiO buffers is observed to decrease significantly, by several log units, over 80 GPa. The results can be used to improve interpretation of high pressure experiments, specifically Fe-Ni exchange between metallic and oxide phases.« less

Peridotites and basalts reveal broad congruence between two independent records of mantle fO2 despite local redox heterogeneity

NASA Astrophysics Data System (ADS)

Birner, Suzanne K.; Cottrell, Elizabeth; Warren, Jessica M.; Kelley, Katherine A.; Davis, Fred A.

2018-07-01

The oxygen fugacity (fO2) of the oceanic upper mantle has fundamental implications for the production of magmas and evolution of the Earth's interior and exterior. Mid-ocean ridge basalts and peridotites sample the oceanic upper mantle, and retain a record of oxygen fugacity. While fO2 has been calculated for mid-ocean ridge basalts worldwide (>200 locations), ridge peridotites have been comparatively less well studied (33 samples from 11 locations), and never in the same geographic location as basalts. In order to determine whether peridotites and basalts from mid-ocean ridges record congruent information about the fO2 of the Earth's interior, we analyzed 31 basalts and 41 peridotites from the Oblique Segment of the Southwest Indian Ridge. By measuring basalts and peridotites from the same ridge segment, we can compare samples with maximally similar petrogenetic histories. We project the composition and oxygen fugacity of each lithology back to source conditions, and evaluate the effects of factors such as subsolidus diffusion in peridotites and fractional crystallization in basalts. We find that, on average, basalts and peridotites from the Oblique Segment both reflect a source mantle very near the quartz-fayalite-magnetite (QFM) buffer. However, peridotites record a significantly wider range of values (nearly 3 orders of magnitude in fO2), with a single dredge recording a range in fO2 greater than that previously reported for mid-ocean ridge peridotites worldwide. This suggests that mantle fO2 may be heterogeneous on relatively short length scales, and that this heterogeneity may be obscured within aggregated basalt melts. We further suggest that the global peridotite fO2 dataset may not provide a representative sample of average basalt-source mantle. Our study motivates further investigation of the fO2 recorded by ridge peridotites, as peridotites record information about the fO2 of the Earth's interior that cannot be gleaned from analysis of basalts alone.

Redox dependent behaviour of molybdenum during magmatic processes in the terrestrial and lunar mantle: Implications for the Mo/W of the bulk silicate Moon

NASA Astrophysics Data System (ADS)

Leitzke, F. P.; Fonseca, R. O. C.; Sprung, P.; Mallmann, G.; Lagos, M.; Michely, L. T.; Münker, C.

2017-09-01

We present results of high-temperature olivine-melt, pyroxene-melt and plagioclase-melt partitioning experiments aimed at investigating the redox transition of Mo in silicate systems. Data for a series of other minor and trace elements (Sc, Ba, Sr, Cr, REE, Y, HFSE, U, Th and W) were also acquired to constrain the incorporation of Mo in silicate minerals. All experiments were carried out in vertical tube furnaces at 1 bar and temperatures ranging from ca. 1220 to 1300 °C. Oxygen fugacity was controlled via CO-CO2 gas mixtures and varied systematically from 5.5 log units below to 1.9 log units above the fayalite-magnetite-quartz (FMQ) redox buffer thereby covering the range in oxygen fugacities of terrestrial and lunar basalt genesis. Molybdenum is shown to be volatile at oxygen fugacities above FMQ and that its compatibility in pyroxene and olivine increases three orders of magnitude towards the more reducing conditions covered in this study. The partitioning results show that Mo is dominantly tetravalent at redox conditions below FMQ-4 and dominantly hexavalent at redox conditions above FMQ. Given the differences in oxidation states of the terrestrial (oxidized) and lunar (reduced) mantles, molybdenum will behave significantly differently during basalt genesis in the Earth (i.e. highly incompatible; average DMoperidotite/melt ∼ 0.008) and Moon (i.e. moderately incompatible/compatible; average DMoperidotite/melt ∼ 0.6). Thus, it is expected that Mo will strongly fractionate from W during partial melting in the lunar mantle, given that W is broadly incompatible at FMQ-5. Moreover, the depletion of Mo and the Mo/W range in lunar samples can be reproduced by simply assuming a primitive Earth-like Mo/W for the bulk silicate Moon. Such a lunar composition is in striking agreement with the Moon being derived from the primitive terrestrial mantle after core formation on Earth.

The Northwest Africa 8159 martian meteorite: Expanding the martian sample suite to the early Amazonian

NASA Astrophysics Data System (ADS)

Herd, Christopher D. K.; Walton, Erin L.; Agee, Carl B.; Muttik, Nele; Ziegler, Karen; Shearer, Charles K.; Bell, Aaron S.; Santos, Alison R.; Burger, Paul V.; Simon, Justin I.; Tappa, Michael J.; McCubbin, Francis M.; Gattacceca, Jérôme; Lagroix, France; Sanborn, Matthew E.; Yin, Qing-Zhu; Cassata, William S.; Borg, Lars E.; Lindvall, Rachel E.; Kruijer, Thomas S.; Brennecka, Gregory A.; Kleine, Thorsten; Nishiizumi, Kunihiko; Caffee, Marc W.

2017-12-01

Northwest Africa (NWA) 8159 is an augite-rich shergottite, with a mineralogy dominated by Ca-, Fe-rich pyroxene, plagioclase, olivine, and magnetite. NWA 8159 crystallized from an evolved melt of basaltic composition under relatively rapid conditions of cooling, likely in a surface lava flow or shallow sill. Redox conditions experienced by the melt shifted from relatively oxidizing (with respect to known Martian lithologies, ∼QFM) on the liquidus to higher oxygen fugacity (∼QFM + 2) during crystallization of the groundmass, and under subsolidus conditions. This shift resulted in the production of orthopyroxene and magnetite replacing olivine phenocryst rims. NWA 8159 contains both crystalline and shock-amorphized plagioclase (An50-62), often observed within a single grain; based on known calibrations we bracket the peak shock pressure experienced by NWA 8159 to between 15 and 23 GPa. The bulk composition of NWA 8159 is depleted in LREE, as observed for Tissint and other depleted shergottites; however, NWA 8159 is distinct from all other martian lithologies in its bulk composition and oxygen fugacity. We obtain a Sm-Nd formation age of 2.37 ± 0.25 Ga for NWA 8159, which represents an interval in Mars geologic time which, until recently, was not represented in the other martian meteorite types. The bulk rock 147Sm/144Nd value of 0.37 ± 0.02 is consistent with it being derived directly from its source and the high initial ε143Nd value indicates this source was geochemically highly depleted. Cr, Nd, and W isotopic compositions further support a unique mantle source. While the rock shares similarities with the 2.4-Ga NWA 7635 meteorite, there are notable distinctions between the two meteorites that suggest differences in mantle source compositions and conditions of crystallization. Nevertheless, the two samples may be launch-paired. NWA 8159 expands the known basalt types, ages and mantle sources within the Mars sample suite to include a second igneous unit from the early Amazonian.

Graphite in the Bishop Tuff and its effect on postcaldera oxygen fugacity

USGS Publications Warehouse

Hildreth, Edward; Ryan-Davis, Juliet; Harlow, Benjamin

2017-01-01

Several cubic kilometers of Paleozoic graphite-bearing argillitic country rocks are present as lithic fragments in Bishop Tuff ignimbrite and fallout. The lithics were entrained by the 650 km3 of rhyolite magma that vented during the 5- to 6-day-long, caldera-forming eruption at Long Valley, California. The caldera is floored by a 350 km2 roof plate that collapsed during the eruption and consists in large part of the Paleozoic strata that provided the abundant hornfelsed metapelitic lithic clasts in the tuff. Graphite has been identified by Raman spectroscopy, electron-dispersive spectroscopy, and X-ray diffraction as an irregularly dispersed component in the small fraction of Bishop Tuff pumice that is dark-colored. Carbon concentration has been determined in pumice, lithics, and wall rocks. Values of δ13C range from –21‰ to –29‰ Vienna Peedee Belemnite (VPDB) for pumice, lithics, and argillitic wall rocks, reflecting the biogenic origin of the reduced carbon in oxygen-limited black Paleozoic marine mudrocks. Carbonate contents, measured separately, are negligible in fresh pumice and lithics. Microprobe analyses of titanomagnetite-ilmenite pairs show that oxygen-fugacity values of numerous batches of postcaldera Early Rhyolite (750–640 ka; ~100 km3) are up to one log unit more reduced than those of the temperature–oxygen fugacity (T-fO2) array of the Bishop Tuff (767 ka), despite similar major-element compositions and Fe-Ti–oxide temperature ranges. All of the many batches of Early Rhyolite, which erupted episodically over an interval of ~125,000 years, yield the reduced fO2 values, indicating that reaction with graphite lowered magmatic fO2 after the caldera-forming eruption but before the first eruption of Early Rhyolite. It is inferred that reaction of postcaldera rhyolite magma with the reduced carbon in a great mass of subsided roof rocks lowered its fO2. It is suggested that comparable effects could have attended caldera collapse of other magma chambers hosted in continental sedimentary rocks.

Chemistry of uranium in aluminophosphate glasses

NASA Technical Reports Server (NTRS)

Schreiber, H. D.; Balazs, G. B.; Williams, B. J.

1982-01-01

The U(VI)-U(V)-U(IV) redox equilibria are investigated in two sodium aluminophosphate base compositions at a variety of melt temperatures, imposed oxygen fugacities, and uranium contents. Results show that the higher redox states of uranium are quite soluble in the phosphate glasses, although U(IV) readily precipitates from the melts as UO2. In addition, comparisons of the uranium redox equilibria established in phosphate melts versus those in silicate melts shows that the coordination sites of the individual uranium species are generally the same in both solvent systems although they differ in detail.

Experimentally reproduced textures and mineral chemistries of high-titanium mare basalts

NASA Technical Reports Server (NTRS)

Usselman, T. M.; Lofgren, G. E.; Williams, R. J.; Donaldson, C. H.

1975-01-01

Many of the textures, morphologies, and mineral chemistries of the high-titanium mare basalts have been experimentally duplicated using single-stage cooling histories. Lunar high-titanium mare basalts are modeled in a 1 m thick gravitationally differentiating flow based on cooling rates, thermal models, and modal olivine contents. The low-pressure equilibrium phase relations of a synthetic high-titanium basalt composition were investigated as a function of oxygen fugacity, and petrographic criteria are developed for the recognition of phenocrysts which were present in the liquid at the time of eruption.

Partitioning of Oxygen During Core Formation on Earth and Mars

NASA Astrophysics Data System (ADS)

Rubie, D. C.; Gessmann, C. K.; Frost, D. J.

2003-12-01

Core formation on Earth and Mars involved the physical separation of Fe-Ni metal alloy from silicate, most likely in deep magma oceans. Although core-formation models explain many aspects of mantle geochemistry, they do not account for large differences between the compositions of the mantles of Earth ( ˜8 wt% FeO) and Mars ( ˜18 wt% FeO) or the much smaller mass fraction of the Martian core. Here we explain these differences using new experimental results on the solubility of oxygen in liquid Fe-Ni alloy, which we have determined at 5-23 GPa, 2100-2700 K and variable oxygen fugacities using a multianvil apparatus. Oxygen solubility increases with increasing temperature and oxygen fugacity and decreases with increasing pressure. Thus, along a high temperature adiabat (e.g. after formation of a deep magma ocean on Earth), oxygen solubility is high at depths up to about 2000 km but decreases strongly at greater depths where the effect of high pressure dominates. For modeling oxygen partitioning during core formation, we assume that Earth and Mars both accreted from oxidized chondritic material with a silicate fraction initially containing around 18 wt% FeO. In a terrestrial magma ocean, 1200-2000 km deep, high temperatures resulted in the extraction of FeO from the silicate magma ocean, due to the high solubility of oxygen in the segregating metal, leaving the mantle with its present FeO content of ˜8 wt%. Lower temperatures of a Martian magma ocean resulted in little or no extraction of FeO from the mantle, which thus remained unchanged at about 18 wt%. The mass fractions of segregated metal are consistent with the mass fraction of the Martian core being small relative to that of the Earth. FeO extracted from the Earth's magma ocean by segregating core-forming liquid may have contributed to chemical heterogeneities in the lowermost mantle, a FeO-rich D'' layer and the light element budget of the core.

Sulfur speciation in hydrous experimental glasses of varying oxidation state - Results from measured wavelength shifts of sulfur X-rays

NASA Technical Reports Server (NTRS)

Carroll, Michael R.; Rutherford, Malcolm J.

1988-01-01

The focusing geometry of an electron microprobe has been used to measure the wavelength shifts of sulfur X-rays from hydrous experimental melts synthesized at oxygen fugacities that range from near the iron-wustite buffer to the magnetite-hermatite buffer. It is found that the proportion of dissolved sulfur which is present as sulfate increases with increasing oxygen fugacity. It is noted that in natural melts that have equilibrated at or below fayalite-magnetite-quartz values of +1, sulfur is probably present mainly as S(2-).

Storage and interaction of compositionally heterogeneous magmas from the 1986 eruption of Augustine Volcano, Alaska

USGS Publications Warehouse

Roman, Diana C.; Cashman, Katharine V.; Gardner, Cynthia A.; Wallace, Paul J.; Donovan, John J.

2006-01-01

Compositional heterogeneity (56–64 wt% SiO2 whole-rock) in samples of tephra and lava from the 1986 eruption of Augustine Volcano, Alaska, raises questions about the physical nature of magma storage and interaction beneath this young and frequently active volcano. To determine conditions of magma storage and evolutionary histories of compositionally distinct magmas, we investigate physical and chemical characteristics of andesitic and dacitic magmas feeding the 1986 eruption. We calculate equilibrium temperatures and oxygen fugacities from Fe-Ti oxide compositions and find a continuous range in temperature from 877 to 947°C and high oxygen fugacities (ΔNNO=1–2) for all magmas. Melt inclusions in pyroxene phenocrysts analyzed by Fourier-transform infrared spectroscopy and electron probe microanalysis are dacitic to rhyolitic and have water contents ranging from <1 to ∼7 wt%. Matrix glass compositions are rhyolitic and remarkably similar (∼75.9–76.6 wt% SiO2) in all samples. All samples have ∼25% phenocrysts, but lower-silica samples have much higher microlite contents than higher-silica samples. Continuous ranges in temperature and whole-rock composition, as well as linear trends in Harker diagrams and disequilibrium mineral textures, indicate that the 1986 magmas are the product of mixing between dacitic magma and a hotter, more mafic magma. The dacitic endmember is probably residual magma from the previous (1976) eruption of Augustine, and we interpret the mafic endmember to have been intruded from depth. Mixing appears to have continued as magmas ascended towards the vent. We suggest that the physical structure of the magma storage system beneath Augustine contributed to the sustained compositional heterogeneity of this eruption, which is best explained by magma storage and interaction in a vertically extensive system of interconnected dikes rather than a single coherent magma chamber and/or conduit. The typically short repose period (∼10 years) between Augustine's recent eruptive pulses may also inhibit homogenization, as short repose periods and chemically heterogeneous magmas are observed at several volcanoes in the Cook Inlet region of Alaska.

Experimental Study of the Partitioning of Siderophile Elements in a Crystallizing Lunar Magma Ocean

NASA Technical Reports Server (NTRS)

Galenas, M.; Righter, K.; Danielson, L.; Pando, K.; Walker, R. J.

2012-01-01

The distributions of trace elements between the lunar interior and pristine crustal rocks were controlled by the composition of starting materials, lunar core formation, and crystallization of the lunar magma ocean (LMO) [1]. This study focuses on the partitioning of highly siderophile elements (HSE) including Re, Os, Ir, Ru, Pt, Rh, Pd and Au as well as the moderately siderophile elements Mo and W, and the lithophile elements of Hf and Sr. Our experiments also include Ga, which can be slightly siderophile, but is mostly considered to be chalcophile. Partitioning of these elements is not well known at the conditions of a crystallizing LMO. Previous studies of HSE partitioning in silicate systems have yielded highly variable results for differing oxygen fugacity (fO2) and pressure [2-4]. For example, under certain conditions Pt is compatible in clinopy-roxene [2] and Rh and Ru are compatible in olivine [3]. The silicate compositions used for these experiments were nominally basaltic. Ruthenium, Rh, and Pd are incompatible in plagioclase under these conditions[4]. However, this latter study was done at extremely oxidizing conditions and at atmospheric pressure, possibly limiting the applicability for consideration of conditions of a crystallizing LMO. In this study we address the effects of pressure and oxygen fugacity on the crystal/liquid partition coefficients of these trace elements. We are especially interested in the plagioclase/melt partition coefficients so that it may be possible to use reverse modeling to constrain the concentrations of these elements in the lunar mantle through their abundances in pristine crustal rocks.

Oxygen fugacity of gases and rocks from Momotombo Volcano, Nicaragua: Application to volcanological monitoring

NASA Astrophysics Data System (ADS)

Benhamou, G.; Allard, P.; Sabroux, J. C.; Vitter, G.; Dajlevic, D.; Creusot, A.

1988-12-01

The oxygen fugacity (fO2) and the fO2 versus T°C relationship of high-temperature (600°-860°C) gas emissions from Momotombo volcano, Nicaragua, was determined from both field electrochemical measurements (electrolytic cell assembly) and thermodynamic computations on gas samples collected between 1978 and 1985. It was then compared with the intrinsic fO2 of fresh and altered lavas from the last eruption (1905), as measured between 500° and 1100°C in laboratory. The electrochemical results show that the oxygen fugacity of Momotombo fumaroles, at equivalent temperature, is much higher than that of the fresh 1905 lava (˜FMQ buffer) and closer to that of their altered wall rocks (˜FMQ buffer). The equilibrium O2 fugacities calculated from the chemistry of gas samples confirm this pattern. However, they suggest that the gas mixtures preserve the (variable) memory of a higher thermal equilibrium achieved at depth, under temperature and fO2 conditions of up to 1050°C and 10-9.0 atm, respectively, which correspond to the cross over between the fO2-T gas and lava trends. These data thus support the idea that Momotombo volcanic gases, released in a period of increasing activity, escape from a shallow magma body before suffering a variable oxidation during their ascent through both unbuffered cooling and reactions with environmental fluids and rocks. This late oxidation is weaker at central fumaroles than at peripherical ones. While between 1978 and 1985 the temperature of the hottest fumarole increased from 750° to 865°-900°C, the equilibrium fO2 of the gas decreased by nearly one order of magnitude (at comparable equilibrium temperature). Such an evolution presumably reflects an increasing connection between the surface exhalations and the magma degassing at depth along with time. This work underlines the possibility of monitoring the processes of magma ascent and gas-magma separation within a volcano before an eruption by continuously recording the changes of both oxygen fugacity and temperature in hot fumaroles.

Partial pressures of oxygen, phosphorus and fluorine in some lunar lavas

NASA Technical Reports Server (NTRS)

Nash, W. P.; Hausel, W. D.

1973-01-01

Lunar sample 14310 is a feldspar-rich basalt which shows no evidence of shock deformation or recrystallization. Pyroxenes include Mg-rich orthopyroxene, pigeonite and augite; pyroxferroite occurs in the interstitial residuum. Plagioclase feldspars are zoned from An(96) to An(67), and variations in feldspar compositions do not necessarily indicate loss of Na during eruption of the lava. Opaque phases include ilmenite, ulvospinel, metallic iron, troilite, and schreibersite. Both whitlockite and apatite are present, and the interstitial residua contain baddeleyite, tranquillityite and barium-rich sanidine. Theoretical calculations provide estimates of partial pressures of oxygen, phosphorus, and fluorine in lunar magmas. In general, partial pressures of oxygen are restricted by the limiting assemblages of iron-wuestite and ilmenite-iron-rutile; phosphorus partial pressures are higher in lunar magmas than in terrestrial lavas. The occurrence of whitlockite indicates significantly lower fugacities of fluorine in lunar magmas than in terrestrial magmas.

Phase relations of a simulated lunar basalt as a function of oxygen fugacity, and their bearing on the petrogenesis of the Apollo 11 basalts

USGS Publications Warehouse

Tuthill, R.L.; Sato, M.

1970-01-01

A glass of Apollo 11 basalt composition crystallizing at 1 atm at low f{hook}02 showed the following crystallization sequence; ferropseudobrookite at 1210??C, olivine at 1200??C, ilmenite and plagioclase at 1140??C, clinopyroxene at 1113??C. Ferropseudobrookite and olivine have a reaction relation to the melt. This sequence agrees with that assumed on textural grounds for some Apollo 11 basalts. It also indicates that the Apollo 11 basalts cannot have been modified by low-pressure fractionation. ?? 1970.

Effect of Cooling Rate and Oxygen Fugacity on the Crystallization of the Queen Alexandra Range 94201 Martian Melt Composition

NASA Technical Reports Server (NTRS)

Koizumi, E.; Mikouchi, T.; McKay, G.; Schwandt, C.; Monkawa, A.; Miyamoto, M.

2002-01-01

Although many basaltic shergottites have been recently found in north African deserts, QUE94201 basaltic shergottite (QUE) is still important because of its particular mineralogical and petrological features. This meteorite is thought to represent its parent melt composition [1 -3] and to crystallize under most reduced condition in this group [1,4]. We performed experimental study by using the synthetic glass that has the same composition as the bulk of QUE. After homogenization for 48 hours at 1300 C, isothermal and cooling experiments were done under various conditions (e.g. temperature, cooling rates, and redox states). Our goals are (1) to verify that QUE really represents its parent melt composition, (2) to estimate a cooling rate of this meteorite, (3) to clarify the crystallization sequences of present minerals, and (4) to verity that this meteorite really crystallized under reduced condition.

The effect of oxygen fugacity on the rheological evolution of crystallizing basaltic melts

NASA Astrophysics Data System (ADS)

Kolzenburg, S.; Di Genova, D.; Giordano, D.; Hess, K. U.; Dingwell, D. B.

2018-04-01

Storage and transport of silicate melts in the Earth's crust and their emplacement on the planet's surface occur almost exclusively at sub-liquidus temperatures. At these conditions, the melts undergo crystallization under a wide range of cooling-rates, deformation-rates, and oxygen fugacities (fO2). Oxygen fugacity is known to influence the thermodynamics and kinetics of crystallization in magmas and lavas. Yet, its influence on sub-liquidus rheology remains largely uncharted. We present the first rheological characterization of crystallizing lavas along natural cooling paths and deformation-rates and at varying fO2. Specifically, we report on apparent viscosity measurements for two crystallizing magmatic suspensions 1) at log ⁡ fO2 of -9.15 (quartz-fayalite-magnetite buffer, QFM, -2.1) and 2) in air. These fugacities span a range of reduced to oxidized conditions pertinent to magma migration and lava emplacement. We find that: 1) crystallization at constant cooling-rates results in a quasi-exponential increase in the apparent viscosity of the magmatic suspensions until they achieve their rheological cut off temperature (Tcutoff), where the melt effectively solidifies 2) the rheological departure and Tcutoff increase with increasing fO2 and 3) increasing fO2 results in decreased crystallization-rates. Based on the experimental results and by comparison with previous rheological isothermal studies we propose a generalisation of the effect of fO2 on the dynamic rheological evolution of natural magmatic and volcanic suspensions. We further discuss the implications for magmatic transport in plumbing and storage systems (e.g. conduits, dikes and magma chambers) and during lava flow emplacement.

The Effects of Redox Reactions on Sulfur Isotopes in Sulfide Melts at 1200 °C: Implications for 34S Enrichment in Magmas

NASA Astrophysics Data System (ADS)

Sanderson, A. M.; Frank, M. R.; Dodd, J. P.; Walker, J. A.

2017-12-01

δ34S values of mantle derived melts in subduction zones can differ from mantle values. This is often attributed to assimilation of country rock or interaction with another S-bearing reservoir. We hypothesized that variations in oxygen fugacity, f(O2), and in sulfur's valence state, may impact a change in the measured δ34S value of sulfide melts. Two synthetic sulfide melts (SM5 & SM7) with a composition of the mono-sulfide solution (MSS; Fe51S37Ni5Cu7) were homogenized for 30, 60 and 90 minutes at an oxygen fugacity between the quartz-fayalite-magnetite (QFM) and iron-wüstite (IW) buffers. Samples were separated into aliquots and subjected to varying fO2 (atmospheric O2, nickel-nickel oxide (NNO), QFM, and IW) at 1200 °C. Equilibrium was established through reversals and as a function of time. The δ34S value of the starting material was measured to be +7.3 to 7.9 ‰ (VCDT). δ34S values from experiments are displayed here relative to the starting material used for that experiment (δ34Ssample - δ34Sstarting). Experiments conducted at log f(O2) of -11.74 (IW), -10.02, -8.3 (QFM), and -7.6 (NNO) were found to be +0.1, +0.6, +1.7, and +1.8 ‰, respectively. The measured average δ34S values were found to vary directly with the imposed oxygen fugacity. The enrichment in 34S relative to 32S is most likely related to changes in the sulfur redox state (from S2-) or sulfur volatilization. Our results suggest that volatilization or variations in a magma's oxidation state can produce measurable changes in δ34S and that those changes must be considered when using δ34S to evaluate possible external sulfur contributions. These results will likely inform discussions on the source of metals and sulfur in layered mafic intrusions (e.g. Bushveld Complex).

The Northwest Africa 8159 martian meteorite: Expanding the martian sample suite to the early Amazonian

DOE PAGES

Herd, Christopher D. K.; Walton, Erin L.; Agee, Carl B.; ...

2017-09-01

Northwest Africa (NWA) 8159 is an augite-rich shergottite, with a mineralogy dominated by Ca-, Fe-rich pyroxene, plagioclase, olivine, and magnetite. NWA 8159 crystallized from an evolved melt of basaltic composition under relatively rapid conditions of cooling, likely in a surface lava flow or shallow sill. Redox conditions experienced by the melt shifted from relatively oxidizing (with respect to known Martian lithologies, ~QFM) on the liquidus to higher oxygen fugacity (~QFM + 2) during crystallization of the groundmass, and under subsolidus conditions. This shift resulted in the production of orthopyroxene and magnetite replacing olivine phenocryst rims. NWA 8159 contains both crystallinemore » and shock-amorphized plagioclase (An 50–62), often observed within a single grain; based on known calibrations we bracket the peak shock pressure experienced by NWA 8159 to between 15 and 23 GPa. The bulk composition of NWA 8159 is depleted in LREE, as observed for Tissint and other depleted shergottites; however, NWA 8159 is distinct from all other martian lithologies in its bulk composition and oxygen fugacity. Here, we obtain a Sm-Nd formation age of 2.37 ± 0.25 Ga for NWA 8159, which represents an interval in Mars geologic time which, until recently, was not represented in the other martian meteorite types. The bulk rock 147Sm/ 144Nd value of 0.37 ± 0.02 is consistent with it being derived directly from its source and the high initial ε 143Nd value indicates this source was geochemically highly depleted. Cr, Nd, and W isotopic compositions further support a unique mantle source. While the rock shares similarities with the 2.4-Ga NWA 7635 meteorite, there are notable distinctions between the two meteorites that suggest differences in mantle source compositions and conditions of crystallization. Nevertheless, the two samples may be launch-paired. Finally, NWA 8159 expands the known basalt types, ages and mantle sources within the Mars sample suite to include a second igneous unit from the early Amazonian.« less

The Northwest Africa 8159 martian meteorite: Expanding the martian sample suite to the early Amazonian

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herd, Christopher D. K.; Walton, Erin L.; Agee, Carl B.

Northwest Africa (NWA) 8159 is an augite-rich shergottite, with a mineralogy dominated by Ca-, Fe-rich pyroxene, plagioclase, olivine, and magnetite. NWA 8159 crystallized from an evolved melt of basaltic composition under relatively rapid conditions of cooling, likely in a surface lava flow or shallow sill. Redox conditions experienced by the melt shifted from relatively oxidizing (with respect to known Martian lithologies, ~QFM) on the liquidus to higher oxygen fugacity (~QFM + 2) during crystallization of the groundmass, and under subsolidus conditions. This shift resulted in the production of orthopyroxene and magnetite replacing olivine phenocryst rims. NWA 8159 contains both crystallinemore » and shock-amorphized plagioclase (An 50–62), often observed within a single grain; based on known calibrations we bracket the peak shock pressure experienced by NWA 8159 to between 15 and 23 GPa. The bulk composition of NWA 8159 is depleted in LREE, as observed for Tissint and other depleted shergottites; however, NWA 8159 is distinct from all other martian lithologies in its bulk composition and oxygen fugacity. Here, we obtain a Sm-Nd formation age of 2.37 ± 0.25 Ga for NWA 8159, which represents an interval in Mars geologic time which, until recently, was not represented in the other martian meteorite types. The bulk rock 147Sm/ 144Nd value of 0.37 ± 0.02 is consistent with it being derived directly from its source and the high initial ε 143Nd value indicates this source was geochemically highly depleted. Cr, Nd, and W isotopic compositions further support a unique mantle source. While the rock shares similarities with the 2.4-Ga NWA 7635 meteorite, there are notable distinctions between the two meteorites that suggest differences in mantle source compositions and conditions of crystallization. Nevertheless, the two samples may be launch-paired. Finally, NWA 8159 expands the known basalt types, ages and mantle sources within the Mars sample suite to include a second igneous unit from the early Amazonian.« less

Diffusivities of Redox-Sensitive Elements in Basalt vs. Oxygen Fugacity Determined by LA-ICP-MS

NASA Technical Reports Server (NTRS)

Szumila, Ian; Danielson, Lisa; Trail, Dustin

2017-01-01

Several diffusion experiments were conducted in a piston cylinder device across a range of oxygen fugacities (FMQ-3 FMQ-1.2, FMQ+6) at 1 GPa and 1300 C. This was done to explore the effects of oxygen fugacity (fO2) on diffusivity of redox sensitive trace elements. This allows investigation of how these elements diffuse across the fO2 range encountered in different reservoirs on planets and moons in our solar system. The University of Rochester LA-ICP-MS system was used for analysis of samples. Analyses were conducted using an Agilent 7900 quadrupole mass spectrometer connected to a Photon Machines 193 nm G2 laser ablation (LA) system equipped with a HelEx 2-volume sample chamber. Spots used were 35 micrometers circles spaced at 65 micrometers intervals. Laser fluence was 7.81 J/cm^2 with a rep rate of 10 Hz. The iolite software package was used to reduce data collected from laser ablation analysis of experiments with Si-29 used as the internal standard isotope. Iolite's global fit module was used to simultaneously fit elements' diffusivities in each experiment while keeping the Matano interface constant. Elements analysed include V, Nb, W, Mo, La, Ce, Pr, Sm, Eu, Gd, Ta, and W. Figures

Developing V-Xanes Oxybarometry for Probing Materials Formed in Reducing Environments in the Early Solar Disk

NASA Technical Reports Server (NTRS)

Butterworth, A. L.; Gainsforth, Z.; Jilly-Rehak, C. E.; Righter, K.; Westphal, A. J.

2017-01-01

Vanadium exhibits four oxidation states (V(sup 2+), V(sup 3+), V(sup 4+) and V(sup 5+)) that have been shown to preferentially partition between melt phases dependent on redox conditions, spanning oxygen fugacity across more than 10 log units. We are developing synchrotron-based x-ray absorption spectroscopy of low-fugacity standards for the determination of V oxidation state in highly reducing conditions relevant to the early solar nebula.

Si and O partitioning between core metal and lower mantle minerals during core formation

NASA Astrophysics Data System (ADS)

Nakajima, Y.; Frost, D. J.; Rubie, D. C.

2010-12-01

In addition to Fe and Ni, the Earth’s core contains light alloying elements (e.g., H, C, O, Si, and/or S) in order to explain the 10% core density deficit (e.g., Birch, 1964, JGR). Experimental data on the partitioning behavior of siderophile elements such as Ni and Co between liquid Fe and mantle minerals indicate that equilibration between core-forming metal and a silicate magma ocean likely occurred at lower-mantle pressures (e.g., Li and Agee, 1996 Nature). If core-mantle differentiation has occurred under such conditions, significant quantities of O or Si could have entered the core. At these conditions the nature of the dominant light element in the core will depend strongly on the oxygen fugacity at which equilibration occurred. High pressure experiments were carried out at 25 GPa and 2400-2950 K using a Kawai-type multi-anvil apparatus in order to investigate the partitioning of Si and O between liquid Fe and (Mg,Fe)SiO3 perovskite (Pv), silicate melt, and (Mg,Fe)O ferropericlace (Fp). Starting materials consisting of metallic Fe (+-Si) and olivine (Fo70-95) were contained in single-crystal MgO capsules. Over the oxygen fugacity range IW-0.5 to -3, the Si molar partition coefficient D* (= [Si]metal /[Si]silicate) between metal and Pv increases linearly with decreasing oxygen fugacity at a fixed given temperature. The partition coefficient between metal and silicate melt is of a similar magnitude but is less dependent on the oxygen fugacity. The obtained oxygen distribution coefficient Kd (= [Fe]metal[O]metal /[FeO]Fp) is in agreement with that determined in the Fe-Fp binary system (Asahara et al., 2007 EPSL) below the silicate liquidus temperature. In contrast, a correlation between the O partitioning and Si concentration in Fe is observed above 2700 K where liquid metal coexists with silicate melt + Fp. With an increasing concentration of Si in the liquid metal, O partitioning into Fp is strongly enhanced. Five atomic% Si in the metal reduces the metal-silicate O partition coefficient by about 1 order magnitude. Near the base of a deep magma ocean where pressures exceed 20 GPa, liquid metal could have coexisted with silicate melt, Pv, and Fp. Our results show that Si would readily partitioned into core-forming metal from both perovskite and silicate liquid at a relevant oxygen fugacity (e.g., IW-2). Simultaneously, the Si solubility would hinder the dissolution of O in the liquid metal. This implies that the presence of Si in liquid metal must be included in models of O partitioning.

Measured oxygen fugacities of the Angra dos Reis achondrite as a function of temperature

USGS Publications Warehouse

Brett, R.; Stephen, Huebner J.; Sato, M.

1977-01-01

Measurements of the oxygen fugacity (f{hook}O2) as a function of temperature (T) were made on an interior bulk sample of the cumulate achondrite, Angra dos Reis. Data clustered between the f{hook}O2-T relationship of the iron-wu??stite assemblage and 1.2 log atm units above iron-wu??stite. Interpretation of the data indicates that, throughout most of the cooling history of the meteorite, f{hook}O2 values were defined by equilibria involving iron-bearing species at values close to the f{hook}O2 of the assemblage iron-wu??stite. Measured f{hook}O2 data are compatible with crystallization and cooling at pressures greater than 50 bars. ?? 1977.

Three FORTRAN programs for finite-difference solutions to binary diffusion in one and two phases with composition-and time-dependent diffusion coefficients

USGS Publications Warehouse

Sanford, R.F.

1982-01-01

Geological examples of binary diffusion are numerous. They are potential indicators of the duration and rates of geological processes. Analytical solutions to the diffusion equations generally do not allow for variable diffusion coefficients, changing boundary conditions, and impingement of diffusion fields. The three programs presented here are based on Crank-Nicholson finite-difference approximations, which can take into account these complicating factors. Program 1 describes the diffusion of a component into an initially homogeneous phase that has a constant surface composition. Specifically it is written for Fe-Mg exchange in olivine at oxygen fugacities appropriate for the lunar crust, but other components, phases, or fugacities may be substituted by changing the values of the diffusion coefficient. Program 2 simulates the growth of exsolution lamellae. Program 3 describes the growth of reaction rims. These two programs are written for pseudobinary Ca-(Mg, Fe) exchange in pyroxenes. In all three programs, the diffusion coefficients and boundary conditions can be varied systematically with time. To enable users to employ widely different numerical values for diffusion coefficients and diffusion distance, the grid spacing in the space dimension and the increment by which the grid spacing in the time dimension is increased at each time step are input constants that can be varied each time the programs are run to yield a solution of the desired accuracy. ?? 1982.

Miocene and early Pliocene epithermal gold-silver deposits in the northern Great Basin, western United States: Characteristics, distribution, and relationship to Magmatism

USGS Publications Warehouse

John, D.A.

2001-01-01

Numerous important Miocene and early Pliocene epithermal Au-Ag deposits are present in the northern Great Basin. Most deposits are spatially and temporally related to two magmatic assemblages: bimodal basalt-rhyolite and western andesite. These magmatic assemblages are petrogenetic suites that reflect variations in tectonic environment of magma generation. The bimodal assemblage is a K-rich tholeiitic series formed during continental rifting. Rocks in the bimodal assemblage consist mostly of basalt to andesite and rhyolite compositions that generally contain anhydrous and reduced mineral assemblages (e.g., quartz + fayalite rhyolites). Eruptive forms include mafic lava flows, dikes, cinder and/or spatter cones, shield volcanoes, silicic flows, domes, and ash-flow calderas. Fe-Ti oxide barometry indicates oxygen fugacities between the magnetite-wustite and fayalite-magnetite-quartz oxygen buffers for this magmatic assemblage. The western andesite assemblage is a high K calc-alkaline series that formed a continental-margin are related to subduction of oceanic crust beneath the western coast of North America. In the northern Great Basin, most of the western andesite assemblage was erupted in the Walker Lane belt, a zone of transtension and strike-slip faulting. The western andesite assemblage consists of stratovolcanoes, dome fields, and subvolcanic plutons, mostly of andesite and dacite composition. Biotite and hornblende phenocrysts are abundant in these rocks. Oxygen fugacities of the western andesite assemblage magmas were between the nickel-nickel oxide and hematite-magnetite buffers, about two to four orders of magnitude greater than magmas of the bimodal assemblage. Numerous low-sulfidation Au-Ag deposits in the bimodal assemblage include deposits in the Midas (Ken Snyder), Sleeper, DeLamar, Mule Canyon, Buckhorn, National, Hog Ranch, Ivanhoe, and Jarbidge districts; high-sulfidation gold and porphyry copper-gold deposits are absent. Both high- and low-sulfidation gold-silver and porphyry copper-gold deposits are affiliated with the western andesite assemblage and include the Comstock Lode, Tonopah, Goldfield, Aurora, Bodie, Paradise Peak, and Rawhide deposits. Low-sulfidation Au-Ag deposits in the bimodal assemblage formed under relatively low oxygen and sulfur fugacities and have generally low total base metal (Cu + Pb + Zn) contents, low Ag/Au ratios, and notably high selenide mineral contents compared to temporally equivalent low-sulfidation deposits in the western andesite assemblage. Petrologic studies suggest that these differences may reflect variations in the magmatic-tectonic settings of the associated magmatic assemblages-deposits in the western andesite assemblage formed from oxidized, water-rich, subduction-related calc-alkaline magmas, whereas deposits in the bimodal assemblage were associated with reduced, water-poor tholeiitic magmas derived from the lithospheric mantle during continental extension. The contrasting types and characteristics of epithermal deposits and their affinities with associated igneous rocks suggest that a genetic relationship is present between these Au-Ag deposits and their temporally associated magmatism, although available data do not prove this relationship for most low-sulfidation deposits.

Oxygen fugacity and piston cylinder capsule assemblies

NASA Astrophysics Data System (ADS)

Jakobsson, S.

2011-12-01

A double capsule assembly designed to control oxygen fugacity in piston cylinder experiments has been tested at 1200 °C and 10 kbar. The assembly consists of an outer Pt-capsule containing a solid buffer (Ni-NiO or Co-CoO plus H2O) and an inner AuPd-capsule containing the sample, H2O and a Pt-wire. To prevent direct contact with the buffer phases the AuPd-capsule is embedded in finely ground Al2O3 along with some coarser, fractured Al2O3 facilitating fluid inclusion formation. No water loss is observed in the sample even after 48 hrs but a slight increase in water content is observed in longer duration runs due to oxygen and hydrogen diffusion into the AuPd-capsule. Carbon from the furnace also diffuses through the outer Pt-capsule but reacts with H2O in the outer capsule to form CO2 and never reaches the inner capsule. Oxygen fugacity of runs in equilibrium with the Ni-NiO and Co-CoO buffers was measured by analyzing the Fe content of the Pt-wire in the sample1 and by analyzing Fe dissolved in the AuPd capsule2. The second method gives values that are in good agreement with established buffer whereas results from the first method are one half to one log units higher than the established values. References 1. E. Medard, C. A. McCammon, J. A. Barr, T. L. Grove, Am. Mineral. 93, 1838 (2008). 2. J. Barr, T. Grove, Contrib. Mineral. Petrol. 160, 631 (2010)

A review of the compositional variation of amphiboles in alkaline plutonic complexes

NASA Astrophysics Data System (ADS)

Mitchell, Roger H.

1990-12-01

Compositional data for amphiboles occurring in alkaline plutonic complexes are reviewed and a standard procedure for plotting these data in an isometric prism is proposed. The main compositional trend found in both oversaturated and undersaturated complexes of either miascitic or peralkaline affinity is referred to as the primary magmatic trend. Amphiboles range in composition from magnesian hastingsitic hornblende and ferro-edenitic hornblende through katophorite to ferro-richterite and arfvedsonite. Individual complexes differ with respect to the amphibole {Mg}/{Fe} and {Si}/{Al} ratio and the extent of Na-enrichment. Extensive or limited ranges in the composition of amphiboles may occur in a given complex. A subtrend found only in oversaturated complexes is from ferro-edenitic hornblende to ferro-actinolite. This trend termed the ferro-actinolitic subtrend is found only in low temperature non-peralkaline residua. Some aluminous nepheline syenites and associated alkali gabbros contain amphiboles which range in composition from kaersutite through ferroan pargasitic hornblende to hastingsite. This trend termed the primary miascitic magmatic trend is is one of decreasing {Mg}/{Fe}, at essentially constant {Si}/{Al} and Ca content. Na-enrichment does not occur. Amphiboles formed by reactions of preexisting phases with hydrothermal or deuteric fluids are termed the late stage reaction assemblage. Amphibole compositional trends from calcic through sodic-calcic to sodic amphiboles reflect decreasing temperature and oxygen fugacity at or below the QFM oxygen buffer. The compositional trends are of use in determining petrogenetic relationships between apparently consanguineous syenites.

Formation of orange hibonite, as inferred from some Allende inclusions

NASA Astrophysics Data System (ADS)

Simon, S. B.; Davis, A. M.; Grossman, L.

2001-03-01

We studied three fluffy Type A refractory inclusions from Allende that contain orange hibonite. The melilite in the present samples is very Al-rich, averaging Åk6, Åk14, and Åk12 in the three samples studied. Hibonite in two inclusions, unlike that in Murchison, has low rare earth element abundances of <10???CI in the other inclusion, the hibonite, melilite and perovskite have Group II-like patterns. The hibonite and melilite in all three inclusions studied have excess 26Mg consistent with (26Al/27Al)I =5???10-5. Much of the hibonite and some of the spinel in these inclusions is corroded. These phases are found enclosed in melilite, but based on bulk compositions and phase equilibria, hibonite should not be an early-crystallizing phase in these inclusions. We conclude that the hibonite and probably some of the spinel is relict. Reversely zoned melilite, rounded spinel and isotopically heavy Mg in the inclusions probably reflect reheating events that involved melting and evaporation. Alteration of the gehlenitic melilite gave rise to some rare phases, including corundum and nearly pure CaTs pyroxene. Studies have shown that blue hibonite contains Ti3+ while orange hibonite does not (Ihinger and Stolper, 1986; Beckett et al., 1988). Orange hibonite formed either under oxidizing conditions (such as at oxygen fugacities at least seven orders of magnitude greater than that of a solar gas at 1700K), or under conditions reducing enough (e. g., solar) that it contained Ti3+, which was later oxidized in situ. Although V and Ce oxides are volatile at the temperature and range of oxygen fugacities at which orange hibonite is known to be stable, we find that: a) the hibonite is V-rich (~1 wt % V2O3); and b) there are no negative Ce anomalies in Allende hibonite. This indicates that the hibonite did not form by condensation under oxidizing conditions. In addition, there are slight excesses of Ti + Si cations relative to Mg + Fe cations (up to 0.1 of 0.8 cations per 19 oxygen anions), probably reflecting the original presence of Ti3+. The results of this study strongly support the suggestion (Ihinger and Stolper, 1986) that Allende hibonite originally formed under reducing conditions and was later oxidized. Oxygen fugacities within ~2-3 orders of magnitude of that of a solar gas are implied; otherwise, strong Ce and V depletions would be observed.

Solubility of oxygen in liquid Fe at high pressure and consequences for the early differentiation of Earth and Mars

NASA Astrophysics Data System (ADS)

Rubie, D. C.; Gessmann, C. K.; Frost, D. J.

2003-04-01

Knowledge of the solubility of oxygen in liquid iron enables the partitioning of oxygen between metal and silicates and the oxidation state of residual silicates to be constrained during core formation in planetary bodies. We have determined oxygen solubility experimentally at 5--23 GPa, 2100--2700 K and oxygen fugacities 1--4 log units below the iron-wüstite buffer in samples of liquid Ni-Fe alloy contained in magnesiowüstite capsules using a multianvil apparatus. Results show that oxygen solubility increases with increasing temperature but decreases slightly with increasing pressure over the range of experimental conditions, at constant oxygen fugacity. Using an extrapolation of the results to higher pressures and temperatures, we have modeled the geochemical consequences of metal-silicate separation in magma oceans in order to explain the contrasting FeO contents of the mantles of Earth and Mars. We assume that both Earth and Mars accreted originally from material with a chondritic composition; because the initial oxidation state is uncertain, we vary this parameter by defining the initial oxygen content. Two metal-silicate fractionation models are considered: (1) Metal and silicate are allowed to equilibrate at fictive conditions that approximate the pressure and temperature at the base of a magma ocean. (2) The effect of settling Fe droplets in a magma ocean is determined using a simple polybaric metal-silicate fractionation model. We assume that the temperature at the base of a magma ocean is close to the peridotite liquidus. In the case of Earth, high temperatures in a magma ocean with a depth >1200 km would have resulted in significant quantities of oxygen dissolving in the liquid metal with the consequent extraction of FeO from the residual silicate. In contrast, on Mars, even if the magma ocean extended to the depth of the current core-mantle boundary, temperatures would not have been sufficiently high for oxygen solubility in liquid metal to be significant. The results show that Earth and Mars could have accreted from similar material, with an initial FeO content around 18 wt%. On Earth, oxygen was extracted from silicates by the segregating metal during core formation, leaving the mantle with its present FeO content of ˜8 wt%. On Mars, in contrast, the segregating metal extracted little or no oxygen and left the FeO content unaltered at ˜18 wt%. A consequence of this model is that oxygen should be an important light element in the Earth's core but not in the Martian core.

Diffusion of Redox-Sensitive Elements in Basalt at Different Oxygen Fugacities

NASA Technical Reports Server (NTRS)

Szumila, I.; Trail, D.; Danielson, L. R.

2017-01-01

The terrestrial planets and moons of our solar system have differentiated over a range of oxygen fugacity conditions. Basalts formed from magmas on the Earth cover a range of more oxidized states (from approximately IW (iron wustite) plus 2 to approximately FMQ (fayalite-magnetite-quartz) plus 3) than crustal rocks from Mars (IW to approximately IW plus 3), and basalts from the Moon are more reduced than both, ranging from IW to IW minus 2. The small body Vesta differentiated around IW minus 4. Characterization of redox sensitive elements' diffusivities will offer insight into behavior of these elements as a function of f (fugacity of) O2 for these planetary bodies. Here, we report a systematic study of the diffusion of redox-sensitive elements in basaltic melts with varying oxygen fugacities (fO2) for trace elements, V, Nb, W, Mo, La, Ce, Pr, Sm, Eu, Gd, Ta, and W. Since fO2 is an intensive variable that is different for the reservoirs of various planets and moons in our solar system, it is important to characterize how changes in redox states will affect diffusion. We conducted experiments in a piston cylinder device at 1300 degrees Centigrade and 1 gigapascal, at the University of Rochester and NASA Johnson Space Center. We buffered some experiments at Ru-RuO2 (FMQ plus 6.00), and conducted other experiments within either a graphite or Mo capsule, which corresponds to fO2s of either FMQ minus1.2, or FMQ minus 3.00, respectively. Characterizing the diffusivities of redox sensitive elements at different fO2s is important because some elements, like Eu, have varying valence states, such as Eu (sup 2 plus) and Eu (sup 3 plus). Differences in charge and ion radii may lead to differences in diffusivities within silicate melts. This could, lead to formation of a Eu anomaly by diffusion, the magnitude of which may be controlled by the fO2. Characterization of trace element diffusion is also important in understanding trace element fractionation. We found, during the course of our investigation, that not only did the diffusivities of the redox sensitive elements change with fO2, but that the diffusivities of all other analyzed elements also changed. This indicates that not only do changes in valence influence trace elements diffusivities but that the structure of melt may have changed with varying oxygen fugacity, probably due to changes in the speciation of the major element Fe.

Fe-Ti oxide geothermometry: thermodynamic formulation and the estimation of intensive variables in silicic magmas

NASA Astrophysics Data System (ADS)

Ghiorso, Mark S.; Sack, O.

1991-10-01

A new thermodynamic formulation of the Fe-Ti oxide geothermometer/oxygen barometer is developed. The method is based upon recently calibrated models for spinel solid solutions in the quinary system (Fe2+, Mg)(Al,Fe3+,Cr)2O4-(Fe2+, Mg)2TiO4 by Sack and Ghiorso, and rhombohedral oxides in the quaternary system (Fe2+,Mg,Mn)TiO3-Fe2O3 (this paper). The formulation is internally consistent with thermodynamic models for (Fe2+,Mg)-olivine and -orthopyroxene solid solutions and end-member thermodynamic properties tabulated by Berman. The constituent expressions account for compositional and temperature dependent cation ordering and reproduce miscibility gap features in all of the component binaries. The calibration does not account for the excess Gibbs energy resulting from compositional and temperature dependent magnetic ordering in either phase. This limits application of the method to assemblages that equilibrated at temperatures above 600° C. Practical implementation of the proposed geothermometer/oxygen barometer requires minimal use of projection algorthms in accommodating compositions of naturally occurring phases. The new formulation is applied to the estimation of temperature and oxygen fugacity in a wide variety of intermediate to silicic volcanic rocks. In combination with previous work on olivine and orthopyroxene thermodynamics, equilibration pressures are computed for a subset of these volcanics that contain the assemblage quartz, oxides and either ferromagnesian silicate. The calculated log10 f O 2- T relations are reflected in coexisting ferromagnesian mineral assemblages. Volcanics with the lowest relative oxygen fugacity (Δlog10 f O 2) are characterized by the assemblage olivine-quartz, those with slightly higher Δ log10 f O 2 s, by the assemblage orthopyroxene-quartz. The sequence proceeds with the necessary phases biotite-feldspar, then hornblende-quartz-clinopyroxene, and finally at the highest Δ log10 f O 2 s, sphene-quartz-clinopyroxene. Quantitative analysis of these trends, utilizing thermodynamic data for the constituent phases, establishes that, in most cases, the T-log10 f O 2value computed from the oxides is consistent with the compositions of coexisting silicate phases, indicating that phenocryst equilibrium was achieved prior to eruption. There is, however, considerable evidence of oxide-silicate disequilibrium in samples collected from more slowly cooled domes and obsidians. In addition, T-log10 f O 2trends from volcanic rocks that contain biotite and orthopyroxene are interpreted to imply a condition of Fe2+-Mg exchange disequilibrium between orthopyroxene and coexisting ferromagnesian silicates and melt. It is suspected that many biotite-feldspar-quartz-orthopyroxene bearing low temperature volcanic rocks inherit orthopyroxene xenocrysts which crystallized earlier in the cooling history of the magma body.

Chemical composition and the potential for proteomic transformation in cancer, hypoxia, and hyperosmotic stress

PubMed Central

2017-01-01

The changes of protein expression that are monitored in proteomic experiments are a type of biological transformation that also involves changes in chemical composition. Accompanying the myriad molecular-level interactions that underlie any proteomic transformation, there is an overall thermodynamic potential that is sensitive to microenvironmental conditions, including local oxidation and hydration potential. Here, up- and down-expressed proteins identified in 71 comparative proteomics studies were analyzed using the average oxidation state of carbon (ZC) and water demand per residue (\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{upgreek} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} }{}${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$\\end{document}n¯H2O), calculated using elemental abundances and stoichiometric reactions to form proteins from basis species. Experimental lowering of oxygen availability (hypoxia) or water activity (hyperosmotic stress) generally results in decreased ZC or \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{upgreek} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} }{}${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$\\end{document}n¯H2O of up-expressed compared to down-expressed proteins. This correspondence of chemical composition with experimental conditions provides evidence for attraction of the proteomes to a low-energy state. An opposite compositional change, toward higher average oxidation or hydration state, is found for proteomic transformations in colorectal and pancreatic cancer, and in two experiments for adipose-derived stem cells. Calculations of chemical affinity were used to estimate the thermodynamic potentials for proteomic transformations as a function of fugacity of O2 and activity of H2O, which serve as scales of oxidation and hydration potential. Diagrams summarizing the relative potential for formation of up- and down-expressed proteins have predicted equipotential lines that cluster around particular values of oxygen fugacity and water activity for similar datasets. The changes in chemical composition of proteomes are likely linked with reactions among other cellular molecules. A redox balance calculation indicates that an increase in the lipid to protein ratio in cancer cells by 20% over hypoxic cells would generate a large enough electron sink for oxidation of the cancer proteomes. The datasets and computer code used here are made available in a new R package, canprot. PMID:28603672

Opaque Assemblages in CK and CV Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Neff, K. E.; Righter, K.

2006-01-01

CK carbonaceous chondrites are the only group of carbonaceous chondrites that exhibit thermal metamorphism. As a result, CKs display features of metamorphism such as silicate darkening, recrystallization and shock veins. Calcium Aluminum Inclusions and Fe-Ni metal are rare. CV carbonaceous chondrites are unequilibrated and have two subgroups; oxidized and reduced. The CV and CK carbonaceous chondrite groups have been compared to each other often because of petrographic similarities, such as overlapping oxygen isotopic ratios. Scientists have suggested the two groups of carbonaceous chondrites formed from the same parent body and CKs are equilibrated CV chondrites [1, 2]. The oxidized CV group has been most closely related to CKs. This study examines the petrology and mineralogy of CKs and CVs focusing on opaque minerals found in the meteorites. Using the oxide, metal and sulfide assemblages, constraints can be placed on the temperature and oxygen fugacity at which the meteorites equilibrated. The temperature and oxygen fugacity of the CK and CV chondrites can be compared in order to help define their formation history.

Spectral chemistry of green glass-bearing 15426 regolith

NASA Technical Reports Server (NTRS)

Burns, R. G.; Dyar, M. D.

1983-01-01

The detection of appreciable concentrations of ferric iron in a synthetic green glass equilibrated at an oxygen fugacity of 10 to the -11th atm prompted a Moessbauer spectral study of pristine emerald-green glass spherules carefully handpicked from regolith sample 15426. No Fe(3+) ions were detected in this lunar sample or in a synthetic green glass simulant equilibrated at fO2 = 10 to the -14th atm, suggesting that the green glass clods in rock 15426 formed under conditions of correspondingly low oxygen fugacities. The Moessbauer spectra indicated the presence of olivine crystallites in the lunar emerald green glass spherules. Measurements of homogeneous and partially devitrified synthetic silicate glasses revealed that significant changes of coordination environment about Fe(2+) ions in the glass structure occur during crystallization of olivine crystals from the melt.

Chondrules and Opaque Phases in Unequilibrated R Chondrites: A Comprehensive Assessment of Their Formation

NASA Technical Reports Server (NTRS)

Miller, K. E.; Lauretta, D. S.; Connolly, H. C., Jr.; Berger, E. L.; Domanik, K.

2016-01-01

Equilibrated Rumuruti (R) chondrites record an oxygen fugacity between 0 and 3.5 log units below the fayalite-magnetite-quartz buffer, and a sulfur fugacity (fS2) 2 log units above the iron-troilite buffer. They are more than an order of magnitude more oxidized than the ordinary chondrites [1], and orders of magnitude more sulfidized than solar values. Although the R chondrites have the highest (delta)O-17 value of any meteorites, analyses of unequilibrated R chondrites indicate chondrule formation in an oxygen isotope reservoir similar to that of the ordinary chondrite chondrules. We present the relationship of the R chondrite parent body to pre-accretionary volatiles O and S based on our analyses of unequilibrated R chondrite material in two thin sections from the meteorite Mount Prestrud (PRE) 95404.

EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolery, T.J.

1992-09-14

EQ3NR is an aqueous solution speciation-solubility modeling code. It is part of the EQ3/6 software package for geochemical modeling. It computes the thermodynamic state of an aqueous solution by determining the distribution of chemical species, including simple ions, ion pairs, and complexes, using standard state thermodynamic data and various equations which describe the thermodynamic activity coefficients of these species. The input to the code describes the aqueous solution in terms of analytical data, including total (analytical) concentrations of dissolved components and such other parameters as the pH, pHCl, Eh, pe, and oxygen fugacity. The input may also include a desiredmore » electrical balancing adjustment and various constraints which impose equilibrium with special pure minerals, solid solution end-member components (of specified mole fractions), and gases (of specified fugacities). The code evaluates the degree of disequilibrium in terms of the saturation index (SI = 1og Q/K) and the thermodynamic affinity (A = {minus}2.303 RT log Q/K) for various reactions, such as mineral dissolution or oxidation-reduction in the aqueous solution itself. Individual values of Eh, pe, oxygen fugacity, and Ah (redox affinity) are computed for aqueous redox couples. Equilibrium fugacities are computed for gas species. The code is highly flexible in dealing with various parameters as either model inputs or outputs. The user can specify modification or substitution of equilibrium constants at run time by using options on the input file.« less

Interplay of crystal fractionation, sulfide saturation and oxygen fugacity on the iron isotope composition of arc lavas: An example from the Marianas

NASA Astrophysics Data System (ADS)

Williams, H. M.; Prytulak, J.; Woodhead, J. D.; Kelley, K. A.; Brounce, M.; Plank, T.

2018-04-01

Subduction zone systems are central to a multitude of processes from the evolution of the continental crust to the concentration of metals into economically viable deposits. The interplay between oxygen fugacity, sulfur saturation, fluid exsolution and fractionating mineral assemblages that gives rise to typical arc magma chemical signatures is, however, still poorly understood and novel geochemical approaches are required to make further progress. Here we examine a well-characterized suite of arc lavas from the Marianas (W. Pacific) for their stable Fe isotope composition. In agreement with previous work and mass balance considerations, contributions from sediments and/or fluids are shown to have negligible effect on Fe isotopes. Instead, we focus on disentangling processes occurring during basalt through dacite differentiation using a sample suite from the island of Anatahan. Anatahan whole rock Fe isotope compositions (δ57Fe) range from -0.05 ± 0.05 to 0.17 ± 0.03 (2 S.D.)‰. A fractionation model is constructed, where three distinct stages of differentiation are required to satisfy the combined major and trace element and isotopic observations. In particular, the sequestration of isotopically heavy Fe into magnetite and isotopically light Fe into sulfide melts yields important constraints. The data require that lavas are first undersaturated with respect to crystalline or molten sulfide, followed by the crystallisation of magnetite, which then triggers late sulfide saturation. The model demonstrates that the final stage of removal of liquid or crystalline sulfide can effectively sequester Cu (and presumably other chalcophiles) and that late stage exsolution of magmatic fluids or brines may not be required to do this, although these processes are not mutually exclusive. Finally, the new Fe isotope data are combined with previous Tl-Mo-V stable isotope determinations on the same samples. Importantly, the multi-valent transition metal stable isotope systems of Fe and V are decoupled by sulfide saturation, thus providing a potential tool to constrain its somewhat intractable timing. The observed decoupling of notionally redox-sensitive tracers underlines the caution required in the application of transition metal isotopes as direct redox proxies.

Pyrochlore-rich titanate ceramics for the immobilization of plutonium: redox effects on phase equilibria in cerium- and thorium- substituted analogs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryerson, F J; Ebbinghaus, B

2000-05-25

Three compositions representing plutonium-free analogs of a proposed Ca-Ti-Gd-Hf-U-PU oxide ceramic for the immobilization of plutonium were equilibrated at 1 atm, 1350 C over a range of oxygen fugacities between air and that equivalent to the iron-wuestite buffer. The cerium analog replaces Pu on a mole-per-mole basic with Ce; the thorium analog replaces Pu with Th. A third material has 10 wt% Al{sub 2}O{sub 3} added to the cerium analog to encourage the formation of a Hf-analog of, CaHfTi{sub 2}O{sub 7}, zirconolite, which is referred to as hafnolite. The predominant phase produced in each formulation under all conditions is pyrochlore,more » A{sub 2}T{sub 2}O{sub 7}, where the T site is filled by Ti, and Ca, the lanthanides, Hf, U and Pu are accommodated on the A-site. Other lanthanide and uranium-bearing phases encountered include brannerite (UTi{sub 2}O{sub 6}), hafnolite (CaHfTi{sub 2}O{sub 7}), perovskite (CaTiO{sub 3}) and a calcium-lanthanide aluminotitanate with nominal stoichiometry (Ca,Ln)Ti{sub 2}Al{sub 9}O{sub 19}, where Ln is a lanthanide. The phase compositions show progressive shifts with decreasing oxygen fugacity. All of the phases observed have previously been identified in titanate-based high-level radioactive waste ceramics and demonstrate the flexibility of these ceramics to variations in processing parameters. The main variation is an increase in the uranium concentrations of pyrochlore and brannerite which must be accommodated by variations in modal abundance. Pyrochlore compositions are consistent with existing spectroscopic data suggesting that uranium is predominantly pentavalent in samples synthesized in air. A simple model based on ideal stoichiometry suggests the U{sup +4}/{Sigma}U varies linearly with log fO{sub 2} and that all of the uranium is quadravalent at the iron-wuestite buffer.« less

Zoned Cr, Fe-spinel from the La Perouse layered gabbro, Fairweather Range, Alaska

USGS Publications Warehouse

Czamanske, G.K.; Himmelberg, G.R.; Goff, F.E.

1976-01-01

Zoned spinel of unusual composition and morphology has been found in massive pyrrhotite-chalcopyrite-pent-landite ore from the La Perouse layered gabbro intrusion in the Fairweather Range, southeastern Alaska. The spinel grains show continuous zoning from cores with up to 53 wt.% Cr2O3 to rims with less than 11 wt.% Cr2O3. Their composition is exceptional because they contain less than 0.32 wt.% MgO and less than 0.10 wt.% Al2O3 and TiO2. Also notable are the concentrations of MnO and V2O3, which reach 4.73 and 4.50 wt.%, respectively, in the cores. The spinel is thought to have crystallized at low oxygen fugacity and at temperatures above 900??C, directly from a sulfide melt that separated by immiscibility from the gabbroic parental magma. ?? 1976.

Bulk flow strength of forsterite?enstatite composites as a function of forsterite content

NASA Astrophysics Data System (ADS)

Ji, Shaocheng; Wang, Zichao; Wirth, Richard

2001-11-01

Creep experiments have been conducted to investigate the effect of varying forsterite content ( VFo) on the bulk flow strength of dry forsterite-enstatite (Fo-En) aggregates in order to evaluate the applicability of existing theoretical models to two-phase rocks, as well as to understand the rheology of polyphase systems in general. The experiments were performed at temperatures of 1423-1593 K, stresses of 18-100 MPa, oxygen fugacities of 10 -14-10 -2.5 MPa and 0.1 MPa total pressure. The fine-grained (Fo: 10-17 μm; En: 14-31 μm) composites of various Fo volume fractions ( VFo=0, 0.2, 0.4, 0.5, 0.6, 0.8 and 1) were synthesized by isostatically hot-pressing in a gas-medium apparatus at 1523 and 350 MPa. Our experiments show that flow strength contrasts between Fo and En are in the range of 3-8 at the given experimental conditions, with Fo as the stronger phase. The measured stress exponent ( n) and activation energy ( Q) values of the Fo-En composites fall between those of the end-members. The n values show a nearly linear increase from 1.3 to 2.0, while the Q values display a non-linear increase from 472 to 584 kJ/mol with En volume fraction from 0 to 1.0. There is no clear dependence of creep rates on oxygen fugacity for the Fo-En composites. The mechanical data and TEM microstructural observations suggest no change in deformation mechanism of each phase when in the composites, compared to when in a single-phase aggregate, the En deformed mainly by dislocation creep while the Fo deformed by dislocation-accommodated diffusion creep for our grain sizes and experimental conditions. Comparisons between the measured composite strengths and various theoretical models indicate that none of the existing theoretical models can give a precise predication over the entire VFo range from 0 to 1. However, the theoretical models based on weak-phase supported structures (WPS) yield a good prediction for the flow strengths of the composites with VFo<0.4, while those based on strong-phase supported structures (SPS) are better for the composites with VFo>0.6. No model gives a good prediction for the bulk strength of two-phase composites in the transitional regime ( VFo=0.4-0.6). Applications of the WPS- and SPS-based models in the transitional regime result in under- and over-estimations for the composite flow strength, respectively. Thus, the effect of rock microstructure should be taken into consideration in modeling the bulk flow strengths of the crust and upper mantle using laboratory-determined flow laws of single-phase aggregates.

Acute and chronic environmental effects of clandestine methamphetamine waste.

PubMed

Kates, Lisa N; Knapp, Charles W; Keenan, Helen E

2014-09-15

The illicit manufacture of methamphetamine (MAP) produces substantial amounts of hazardous waste that is dumped illegally. This study presents the first environmental evaluation of waste produced from illicit MAP manufacture. Chemical oxygen demand (COD) was measured to assess immediate oxygen depletion effects. A mixture of five waste components (10mg/L/chemical) was found to have a COD (130 mg/L) higher than the European Union wastewater discharge regulations (125 mg/L). Two environmental partition coefficients, K(OW) and K(OC), were measured for several chemicals identified in MAP waste. Experimental values were input into a computer fugacity model (EPI Suite™) to estimate environmental fate. Experimental log K(OW) values ranged from -0.98 to 4.91, which were in accordance with computer estimated values. Experimental K(OC) values ranged from 11 to 72, which were much lower than the default computer values. The experimental fugacity model for discharge to water estimates that waste components will remain in the water compartment for 15 to 37 days. Using a combination of laboratory experimentation and computer modelling, the environmental fate of MAP waste products was estimated. While fugacity models using experimental and computational values were very similar, default computer models should not take the place of laboratory experimentation. Copyright © 2014 Elsevier B.V. All rights reserved.

57Fe Mössbauer spectroscopy of mineral assemblages in mantle spinel lherzolites from Cenozoic alkali basalt, eastern China: Petrological applications

NASA Astrophysics Data System (ADS)

Hao, Xi-Luo; Li, Yi-Liang

2013-01-01

Mineral assemblages in spinel lherzolite xenoliths from the Cenozoic alkali basalt of eastern China were analyzed by 57Fe Mössbauer spectroscopy for Fe3+/ΣFe and distribution of Fe2+/Fe3+ in non-equivalent crystal cites. Orthopyroxene, clinopyroxene and spinel have 0.08-0.13, 0.19-0.31 and 0.13-0.23 Fe3+/ΣFe, respectively. The cation-exchange equilibrium temperatures, Fe3+ partition coefficient and oxygen fugacity of the upper mantle peridotites were calculated. The equilibrium temperatures are between 1103 K and 1405 K consistent with those reported elsewhere. The oxygen fugacities of spinel lherzolites calculated with olivine-orthopyroxene-spinel (ΔlogƒO2 from - 1.1 to 0) and clinopyroxene-olivine-orthopyroxene oxybarometers (ΔlogƒO2 from - 2.0 to 0.7) are consistent with previously reported upper mantle values.

Facilitating atmosphere oxidation through mantle convection

NASA Astrophysics Data System (ADS)

Lee, K. K. M.; Gu, T.; Creasy, N.; Li, M.; McCammon, C. A.; Girard, J.

2017-12-01

Earth's mantle connects the surface with the deep interior through convection, and the evolution of its redox state will affect the distribution of siderophile elements, recycling of refractory isotopes, and the oxidation state of the atmosphere through volcanic outgassing. While the rise of oxygen in the atmosphere, i.e., the Great Oxidation Event (GOE) occurred 2.4 billion years ago (Ga), multiple lines of evidence point to oxygen production in the atmosphere well before 2.4 Ga. In contrast to the fluctuations of atmospheric oxygen, vanadium in Archean mantle lithosphere suggests that the mantle redox state has been constant for 3.5 Ga. Indeed, the connection between the redox state of the deep Earth and the atmosphere is enigmatic as is the effect of redox state on mantle dynamics. Here we show a redox-induced density contrast affects mantle convection and may potentially cause the oxidation of the upper mantle. We compressed two synthetic enstatite chondritic samples with identical bulk compositions but formed under different oxygen fugacities (fO2) to lower mantle pressures and temperatures and find Al2O3 forms its own phase separate from the dominant bridgmanite phase in the more reduced composition, in contrast to a more Al-rich, bridgmanite-dominated assemblage for a more oxidized starting composition. As a result, the reduced material is 1-1.5% denser than the oxidized material. Subsequent experiments on other plausible mantle compositions, which differ only in redox state of the starting glass materials, show similar results: distinct mineral assemblages and density contrasts up to 4%. Our geodynamic simulations suggest that such a density contrast causes a rapid ascent and accumulation of oxidized material in the upper mantle, with descent of the denser reduced material to the core-mantle boundary. The resulting heterogeneous redox conditions in Earth's interior may have contributed to the large low-shear velocity provinces in the lower mantle and the rise of oxygen in Earth's atmosphere.

The electrum-tarnish method for the determination of the fugacity of sulfur in laboratory sulfide systems

USGS Publications Warehouse

Barton, P.B.; Toulmin, P.

1964-01-01

A new method for the determination of the fugacity of sulfur in laboratory systems consists of visual observation of the development and decomposition of a sulfide tarnish phase on silver-gold alloy (electrum) of precisely known composition. The alloy system is calibrated against pure sulfur. The method has the following advantages: simple apparatus; ability to cover a large range of fugacity of S2; ability to cover a large temperature range by permitting runs of long duration; ability to tolerate other components in the gas phase; and ease of recovery of the quenched charges for determinations of phases and compositions. Results obtained by the electrum-tarnish method are in satisfactory agreement with those obtained by other workers for the fs2 vs. T curves for the assemblage Ni(1-x)S + NiS2. The electrum-tarnish method shows promise for investigating many other reactions. Univariant reactions studied by this method can be represented as lines forming a genetic grid in terms of the environmental parameters fs2 and T, The slopes of such lines can yield valuable thermodynamic data for the phases involved, but activity coefficients must be known for phases of variable composition. ?? 1964.

Experimental petrology and origin of rocks from the Descartes Highlands

NASA Technical Reports Server (NTRS)

Walker, D.; Longhi, J.; Grove, T. L.; Stolper, E.; Hays, J. F.

1973-01-01

Petrographic studies of Apollo 16 samples indicate that rocks 62295 and 68415 are crystallization products of highly aluminous melts. 60025 is a shocked, crushed and partially annealed plagioclase cumulate. 60315 is a recrystallized noritic breccia of disputed origin. 60335 is a feldspathic basalt filled with xenoliths and xenocrysts of anorthosite, breccia, and anorthite. The Fe/(Fe+Mg) of plagioclase appears to be a relative crystallization index. Low pressure melting experiments with controlled Po2 indicate that the igneous samples crystallized at oxygen fugacities well below the Fe/FeO buffer. Crystallization experiments at various pressures suggest that the 62295 and 68415 compositions were produced by partial or complete melting of lunar crustal materials, and not by partial melting of the deep lunar interior.

Aubrite and Impact Melt Enstatite Chondrite Meteorites as Potential Analogs to Mercury

NASA Technical Reports Server (NTRS)

Wilbur, Z. E.; Udry, A.; Mccubbin, Francis M.; McCubbin, F. M.; Combs, L. M.; Rahib, R. R.; McCoy, C.; McCoy, T. J.

2018-01-01

The MESSENGER (MErcury Sur-face, Space ENvironment, GEochemistry and Ranging) orbiter measured the Mercurian surface abundances of key rock-forming elements to help us better understand the planet's surface and bulk geochemistry. A major discovery is that the Mercurian surface and interior are characterized by an extremely low oxygen fugacity (ƒO2; Iron-Wüstite (IW) -7.3 to IW-2.6. This is supported by low Fe and high S abundances on the surface. This low ƒO2 causes a different elemental partioning from what is observed on Earth. Using surface composition, it was shown that the Mercurian surface mainly consists of normative plagioclase, pyroxene, olivine, and exotic sulfides, such as niningerite ((Mg,Mn, Fe)S) and oldhamite (CaS).

Chemical complexity and source of the White River Ash, Alaska and Yukon

USGS Publications Warehouse

Preece, S.J.; McGimsey, Robert G.; Westgate, J.A.; Pearce, N.J.G.; Hartmann, W.K.; Perkins, W.T.

2014-01-01

The White River Ash, a prominent stratigraphic marker bed in Alaska (USA) and Yukon (Canada), consists of multiple compositional units belonging to two geochemical groups. The compositional units are characterized using multiple criteria, with combined glass and ilmenite compositions being the best discriminators. Two compositional units compose the northern group (WRA-Na and WRA-Nb), and two units are present in the eastern group (WRA-Ea and the younger, WRA-Eb). In the proximal area, the ca. 1900 yr B.P. (Lerbekmo et al., 1975) WRA-Na displays reverse zoning in the glass phase and systematic changes in ilmenite composition and estimated oxygen fugacity from the base to the top of the unit. The eruption probably tapped different magma batches or bodies within the magma reservoir with limited mixing or mingling between them. The 1147 cal yr B.P. (calibrated years, approximately equivalent to calendric years) (Clague et al., 1995) WRA-Ea eruption is only weakly zoned, but pumices with different glass compositions are present, along with gray and white intermingled glass in individual pumice clasts, indicating the presence of multiple magmatic bodies or layers. All White River Ash products are high-silica adakites and are sourced from the Mount Churchill magmatic system.

Ferric Iron Production in Magma Oceans and Evolution of Mantle Oxidation State

NASA Astrophysics Data System (ADS)

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

2018-05-01

Self-oxidation of the magma ocean by ferric iron production at high pressure may explain the mantle oxidation state of the Earth. Partitioning during fractional crystallization can further increase the mantle oxygen fugacity during solidification.

Untangling the History of Oceanic Peridotites Using Spinel Oxybarometry

NASA Astrophysics Data System (ADS)

Birner, S.; Warren, J. M.; Cottrell, E.; Davis, F. A.

2014-12-01

Comprehensive knowledge of the oxygen fugacity of the upper mantle is critical to understanding the processes associated with melt production, interaction, and extraction. Thus, it is important to understand how fO2 changes during a peridotite's thermal and petrologic history in the asthenospheric and lithospheric mantle, as metamorphic subsolidus reequilibration can result in changes to recorded fO2. A case study of Tongan forearc peridotites highlights the heterogeneity seen in mantle peridotites. We analyzed two dredges located 250 km apart along the trench: one dredge ranges in fO2 from 0.5 to 1 log unit above the QFM buffer, similar to analyses of supra-subduction zone xenoliths (e.g. Brandon and Draper, 1996; Wood and Virgo, 1989) while the other dredge ranges from QFM-0.75 to QFM+0.25 and exhibits high spinel Cr# (ranging from 0.45 to 0.75). Systematics between fO2, Ti concentration, olivine forsterite content, and Cr# within each dredge allow us to differentiate between the effects of melt extraction, melt interaction, and cooling. Because the spinel oxybarometry equation is dependent on temperature, it is important to be able to accurately determine the temperature recorded by peridotites. Though many geothermometers are available for mantle rocks, we assert that geothermometers based on Fe-Mg exchange between olivine and spinel are the most applicable to fO2 calculations, because the oxygen fugacity recorded by a mantle assemblage is primarily controlled by this exchange. Additionally, preliminary analyses of diffusion profiles across olivine-spinel grain boundaries provide insight into the cooling of peridotite in the oceanic lithosphere and its effects on oxygen fugacity. Mg-Fe exchange between olivine and spinel is controlled by the distribution coefficient, KD, which is dependent on both temperature and the proportion of Cr to other trivalent cations in spinel. We see an increase in olivine forsterite content towards the olivine-spinel interface, consistent with an increase in KD as cooling occurs. Limited data indicate that while spinel Cr# decreases as the interface is approached, no change is seen in spinel Fe3+/ΣFe ratios. As a result, the increased Fo# in olivine dominates the oxybarometry equation, resulting in higher oxygen fugacity values near the interface as cooling occurs.

OH in Rutile: an Oxygen and Water Barometer

NASA Astrophysics Data System (ADS)

Johnson, E. A.; Manning, C. E.; Antignano, A.; Tropper, P.

2005-12-01

Dehydration of the subducting lithosphere induces oxidation and partial melting in the mantle wedge above subduction zones, and storage of water in the form of hydroxyl in high-pressure mineral phases may be an important mechanism for transfer of water to the mantle. It is therefore important to quantify water content of fluids and oxygen fugacity in subduction zones, but these variables can be difficult to measure or infer in many rocks. This study investigates the possibility of determining oxygen fugacity or water activity based on OH concentration measurements in rutile. The solubility of OH in pure rutile has been determined using rutile grains from aqueous fluid solubility experiments (Tropper and Manning 2005, Am Min, 90, 502). In pure rutile, H+ is stoichiometrically incorporated into the structure via reduction of Ti4+ to Ti3+, resulting in a change in color from pale yellow to deep blue. Synthetic rutile crystals were equilibrated in pure H2O or a H2O-NaCl solution at 1-2 GPa and 600-1100°C. The runs were unbuffered with respect to oxygen fugacity but were close to the NNO buffer (Newton and Manning 2005, J Petr, 46, 701). Rutile OH concentrations were determined using FTIR spectroscopy and the calibration of Maldener (2001, Min Pet, 71, 21). At a constant pressure of 1 GPa, OH concentrations of rutile in equilibrium with pure H2O increase exponentially from 600 to 1100°C. The data are fit with the equation [OH] = 17.7exp(4.00×10-3T) (R=0.998), where [OH] is in ppm H2O wt. and T is in °C. Increasing pressure from 1 to 2 GPa at 1100°C results in an increase in OH solubility from 1540 to 2220 ppm H2O. OH solubility in rutile decreases from 2220 to 1290 ppm H2O by lowering the water activity of the fluid from 1 to 0.49 at P = 2 GPa and T = 1100°C. Using the solubility data and the exchange reaction, Ti3+O(OH) + O2 = Ti4+O2 + <

Effect of fO2 on phase relationship in basaltic andesites during magmatic differentiation: Control of fO2 and sulphur speciation in piston cylinder experiments.

NASA Astrophysics Data System (ADS)

Matjuschkin, Vladimir; Tattitch, Brian; Blundy, Jonathan D.; Skora, Susanne

2014-05-01

Within the mantle wedge above subduction zones, oxidation reaction take place by interaction of reduced mantle rocks with more oxidized, hydrous fluids, which can cause a local drop of the solidus, resulting in partial melting (2,6,7). The resultant melts are more oxidized that their ocean floor counterparts, which has implications for their subsequent differentiation paths, the speciation of multivalent elements and the solubility and transport of chemical compounds in magmatic systems (1,4,5). We present a series of sulphur-doped high-pressure experiments conducted to investigate the effect of oxygen fugacity on phase relationships and the behaviour of sulphur in silicate melts. Natural aphyric andesite (FM37) erupted from Laguna del Maule volcano, Chile (3) was selected as a starting composition. Experiments were carried out at 5kbar, 950-1150° C and variable oxygen fugacity conditions. New experiments buffered at Co-CoO and Ni-NiO buffer conditions have been performed using a new "MTB capsule design" developed in order to accurately control fO2 by means of a double capsule containing metal-oxide buffers and a pyrex sleeve to minimise H2 diffusion. This new design constrains oxygen fugacity to within ±0.1-0.2logfO2 units of the target value. Before conducting these experiments, the assemblage was tested multiple times at 10kbar, 1000° C over 24-48 hours and demonstrated consistent, accurate fO2 control. Analyses of the preliminary experimental run products, from a related Chilean basaltic andesite starting composition, demonstrate a clear effect of fO2 on phase relationships and the proportion of melt generated during experiments. Under oxidized conditions, as temperature decreased from 1150° C to 1050° C, the amount of melt decreased from 100% to ~80%, due to the formation of orthopyroxene, anhydrite and plagioclase. In contrast, in reduced runs the system remains nearly liquid (~5% crystals) down to 950° C due to the change in sulphur speciation and onset of orthopyroxene precipitation at much lower temperatures. The change in temperature from 1150 to 950° C resulted in a drop in S content from ~2500ppm to ~1000ppm in the melt for oxidized experiments, whereas S slightly increased from ~3000 to ~3500ppm in the reduced experiments. Quantitative control over fO2 will allow for more precise determination of phase relations and control of sulphur specification, offering a possibility of detailed reconstruction of metals enrichment in silicate melts. Cited references: [1] Botcharnikov et al. (2011) Nature 4:217-230, [2] Foley (2011) J Petrol 52:1363-1391, [3] Frey et al. (1984) CMP 88:133-149, [4] Jenner et al. (2010) J Petrol 51:2445-2464, [5] Jugo et al. (2010) GCA 74:5926-5938, [6] Rohrbach et al. (2007) Nature 449:456-458, [7] Taylor and Green (1988) Nature 332:349-352

Oxygen deficient Ti oxides (natural magnéli phases) from mudstone xenoliths with native iron from Disko, central West Greenland

NASA Astrophysics Data System (ADS)

Pedersen, A. K.; Rønsbo, J. G.

1987-05-01

Mudstone xenoliths in a strongly reduced andesitic subaquatic breccia with native iron from the Asuk Member on Disko contain Ti oxides which are oxygen deficient relative to rutile. Ore microscopy reveals that the mudstone xenoliths contain former clastic oxide grains which have equilibrated to blue Ti oxides and grey aluminous Ti oxides. They also contain still immature coal fragments in a glassy matrix with native iron. The blue oxides are compositionally similar to magnéli phases TinO2n-1 within the range n=4 to 7, and several grains contain more than one natural magnéli phase. Two other phases found are 1) pale orange blebs in magnéli phases with a composition approaching Al1Ti{1/3+}Ti{2/4+}O7 (AlTi phase B) and 2) grey oxide rims on magnéli phases or independent grains of the compositional series Al2-x(Ti{0.5/4+}(Mg,Fe)0.5)xTi{n-2/4+}O2n-1 with n mostly between 7 and 10 (AlTi phase A). The natural magnéli phases equilibrated at oxygen fugacities 4 to 5 log units below the Fe-W oxygen buffer at igneous temperatures and represent the most reduced high-temperature environment yet recorded among native iron bearing rocks from Disko. The extremely reducing conditions were met in rocks where coal fragments were still in a state of degassing hydrocarbon components at the time of quenching. Field geology and carbon barometry indicate equilibration at pressures of less than 10 bars.

Viscosity of carbonate-rich melts under different oxygen fugacity conditions

NASA Astrophysics Data System (ADS)

Di Genova, Danilo; Hess, Kai-Uwe; Cimarelli, Corrado; Dingwell, Donald B.

2015-04-01

Viscosity is a fundamental property of many materials and its changes affects the fluid dynamics of natural system as well as industrial processes. The mobility of carbonatitic melts, which are carbonate-rich and very fluid melts, has attracted renewed interest in both earth science and industry. In fact, these melts are considered the main transport agent of carbon from the mantle to the crust and may be intimately linked to the generation of kimberlites. At the same time lithium, potassium and sodium carbonate are used as electrolytes in molten carbonate fuel cells which operate at high temperatures (~650° C) for the production of electricity without CO2 emissions. Accurate measurement of the transport property (i.e. viscosity) of carbonatitic melts is a priority in order to understand the carbonatite mobility and reaction rates. Additionally, obtaining accurate viscosity measurements of such low viscosity melts is however an experimental challenge due to volatility, very low torques and chemical melt instability in the viscometer. To overcome these limitations we have customized a Modular Compact Rheometer (MCR 502 from Anton Paar) ad hoc equipped with 2 narrow gap concentric-cylinder geometries of steel and Pt-Au. The rheometer is characterized by an air-bearing-supported synchronous motor with torque ranging between 0.01 μNm and 230 mNm (resolution of 0.1 nNm), achieving very low viscosity measurements in the order of mPa s, temperatures up to 1000° C and shear rates ranging between 1 and 100 sec-1. These experimental conditions well match the temperature-viscosity-shear rate window relevant for carbonate melts. Here we present the calibration of the rheometer and the results of a rheological characterization study on a series of very low viscous synthetic and natural carbonatitic melts at different oxygen fugacity (air and CO2 saturated atmosphere). Viscosity measurements on carbonate melts have been performed in the temperature range between ~650 and 1000° C. Measured values range between ~2 and 20 mPa sec. The results point out that the viscosity of synthetic samples is inversely related to the cations radius, being Li2CO3 melt the more viscous. Viscosity measurements on natural samples (carbonatitic lava from Lengai volcano, Tanzania), reveal a higher viscosity (~1000 mPa s) and a dramatic higher activation energy than the synthetic samples. Our results have been compared with literature data in order to determine the effect of chemical composition and oxygen fugacity conditions on the liquid viscosity of carbonatitic melts.

Fe3+ partitioning during basalt differentiation on Mars: insights into the oxygen fugacity of the shergottite mantle source(s).

NASA Astrophysics Data System (ADS)

Medard, E.; Martin, A. M.; Collinet, M.; Righter, K.; Grove, T. L.; Newville, M.; Lanzirotti, A.

2014-12-01

The partitioning of Fe3+ between silicate melts and minerals is a key parameter to understand magmatic processes, as it is directly linked to oxygen fugacity (fO2). fO2 is, a priori, not a constant during magmatic processes, and its evolution depends on the compatibility of Fe3+. We have experimentally determined the partition coefficients of Fe3+ between augite, pigeonite, and silicate melt, and use them to constrain the fO2of the martian mantle and of differentiated martian basalts. A series of experiments on various martian basaltic compositions were performed under controlled fO2 in one-atmosphere gas-mixing furnaces. Fe3+/Fetotal ratios in silicate melts and pyroxenes were determined using synchrotron Fe K-edge XANES on the 13 IDE beamline at APS (Argonne). Fe3+ mineral/melt partition coefficients (DFe3+) for augite and pigeonite were obtained with a relative uncertainty of 10-15 %. Both are constant over a wide range of oxygen fugacity (FMQ-2.5 to FMQ+2.0). DFe3+ for augite and pigeonite are broadly consistent with previous data by [1], but DFe3+ for augite is significantly higher (by a factor of 2) than the indirect determinations of [2]. Since augites in [2] are extremely poor in iron compared to ours (0.18 wt% vs 13 wt% FeO), this strongly suggests that DFe3+ varies with Mg#, indicating that Fe3+is more compatible than previously thought in terrestrial mantle pyroxenes (3 wt% FeO) as well. Crystallization paths for shergottite parental melts have been calculated using the MELTS software, combined with our partition coefficients. fO2 in the residual melts is calculated from the models of [3] and [4]. It stays relatively constant at high temperatures, but increases very strongly during the latest stages of crystallization. These results explain the large range of fO2 determined in enriched shergottites. In order to estimate the fO2 of the martian mantle, only the highest temperature phases in the most primitive martian samples should be used. The most primitive shergottites record a mantle fO2 around FMQ-2.5, consistent with the lowest fO2estimated for surface basalts [5]. [1] McCanta et al. (2004) Am Min 89:1685-1693; [2] Mallmann and O'Neill (2009) J Petrol 50:1765-1794; [3] Righter et al. (2013) Am Min 98:616-628; [4] Kress and Carmichael (1991) CMP 108:82-92; [5] Schmidt ME et al. (2014) EPSL 384:198-208.

Formation of Si-Al-Mg-Ca-rich zoned magnetite in an end-Permian phreatomagmatic pipe in the Tunguska Basin, East Siberia

NASA Astrophysics Data System (ADS)

Neumann, Else-Ragnhild; Svensen, Henrik H.; Polozov, Alexander G.; Hammer, Øyvind

2017-12-01

Magma-sediment interactions in the evaporite-rich Tunguska Basin resulted in the formation of numerous phreatomagmatic pipes during emplacement of the Siberian Traps. The pipes contain magnetite-apatite deposits with copper and celestine mineralization. We have performed a detailed petrographic and geochemical study of magnetite from long cores drilled through three pipe breccia structures near Bratsk, East Siberia. The magnetite samples are zoned and rich in Si (≤5.3 wt% SiO2), Ca, Al, and Mg. They exhibit four textural types: (1) massive ore in veins, (2) coating on breccia clasts, (3) replacement ore, and (4) reworked ore at the crater base. The textural types have different chemical characteristics. "Breccia coating" magnetite has relatively low Mg content relative to Si, as compared to the other groups, and appears to have formed at lower oxygen fugacity. Time series analyses of MgO variations in microprobe transects across Si-bearing magnetite in massive ore indicate that oscillatory zoning in the massive ore was controlled by an internal self-organized process. We suggest that hydrothermal Fe-rich brines were supplied from basalt-sediment interaction zones in the evaporite-rich sedimentary basin, leading to magnetite ore deposition in the pipes. Hydrothermal fluid composition appears to be controlled by proximity to dolerite fragments, temperature, and oxygen fugacity. Magnetite from the pipes has attributes of iron oxide-apatite deposits (e.g., textures, oscillatory zoning, association with apatite, and high Si content) but has higher Mg and Ca content and different mineral assemblages. These features are similar to magnetite found in skarn deposits. We conclude that the Siberian Traps-related pipe magnetite deposit gives insight into the metamorphic and hydrothermal effects following magma emplacement in a sedimentary basin.

Experimental Constraints on the Stability of Clinopyroxene (+) Magnesite in Iron Bearing Planetary Mantles: Implications for Nakhlite Formation

NASA Technical Reports Server (NTRS)

Martin, Audrey M.; Righter, Kevin

2010-01-01

Carbon is present in various forms in the Earth s upper mantle (carbonate- or diamond-bearing mantle xenoliths, carbonatite magmas, CO2 emissions from volcanoes...). Moreover, there is enough carbon in chondritic material to stabilize carbonates into the mantles of Mars or Venus as well as in the Earth. However, the interactions with iron have to be constrained, because Fe is commonly thought to buffer oxygen fugacity into planetary mantles. [1] and [2] show evidences of the stability of clinopyroxene Ca(Mg,Fe)Si2O6 + magnesite (Mg,Fe)CO3 in the Earth s mantle around 6GPa (about 180km). The stability of oxidized forms of carbon (like magnesite) depends on the oxygen fugacity of the system. In the Earth s mantle, the maximum carbon content is 10000 ppm [3]. The fO2 parameter varies vertically as a function of pressure, but also laterally because of geodynamic processes like subduction. Thus, carbonates, graphite, diamond, C-rich gases and melts are all stable forms of carbon in the Earth s mantle. [4] show that the fO2 variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. [5] inferred from thermodynamic calculations that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond). After [6], a metasomatizing agent like a CO2-rich melt may infiltrate the mantle source of nakhlites. However, according to [7] and [8], the FeO wt% value in the Martian bulk mantle is more than twice that of the Earth s mantle (KLB-1 composition by [9]). As iron and carbon are two elements with various oxidation states, Fe/C interaction mechanisms must be considered.

Graphite solubility and co-vesiculation in basalt-like melts at one-ATM

NASA Technical Reports Server (NTRS)

Colson, R. O.

1993-01-01

The identity and source of the vapor phase that caused lunar lava-fountaining and vesiculation in lunar basalts continues to be of interest because of its implications for the composition and state of the lunar interior and because of its implications for lunar resources. In light of the apparent near-absence of H2O on the Moon, it has been suggested that the vapor phase may be CO2-CO. This premise is supported by the presence of carbon on the surface of volcanic glass beads. However, although the rapid exsolution of CO2 from a melt during decompression may be consistent with firefountaining, it fails to provide a satisfying explanation for vesiculation in mare basalt where exsolution of the gas phase would more reasonably be related to cooling/crystallization at low pressure rather than decompression from high pressure. Also, geochemical trends in lunar volcanic glasses suggest that their source has an oxygen fugacity more reducing than the iron-wustite buffer, an oxygen fugacity that is inconsistent with presence of dissolved CO2-CO at depth. The results of experiments in which a vesicular 'basalt' is produced from a melt equilibrated with graphite and pure CO gas at one atmosphere pressure are reported. The vesiculation is apparently related to exsolution of CO or a CO species during cooling of the melt or growth of quench crystals. Additionally, particulate carbon dispersed through the quenched sample suggests that elemental carbon is either in solution in the melt prior to quenching or tends to go into suspension perhaps as colloid-like particles. These two observations may provide insight into the nature of fire-fountaining and vesiculation on the Moon.

Formation of unequilibrated R chondrite chondrules and opaque phases

NASA Astrophysics Data System (ADS)

Miller, K. E.; Lauretta, D. S.; Connolly, H. C.; Berger, E. L.; Nagashima, K.; Domanik, K.

2017-07-01

Sulfide assemblages are commonly found in chondritic meteorites as small inclusions in the matrix or in association with chondrules. These assemblages are widely hypothesized to form through pre-accretionary corrosion of metal by H2S gas or through parent body processes. We report here on two unequilibrated R chondrite samples that contain large, chondrule-sized sulfide nodules in the matrix. Both samples are from Mount Prestrud (PRE) 95404. Chemical maps and spot and broad-beam electron microprobe analyses (EMPA) were used to assess the distribution, stoichiometry, and bulk composition of sulfide nodules and silicate chondrules in the clasts. Oxygen isotope data were collected via secondary ion mass spectrometry (SIMS) to assess the relationship of chondrules to other chondrite groups. Scanning electron microscopy (SEM), focused ion beam (FIB), and transmission electron microscopy (TEM) analyses were used to assess fine-scale features and identify crystal structures in sulfide assemblages. Thermodynamic models were used to assess the temperature, sulfur fugacity (fS2), total pressure, dust-to-gas ratio, and oxygen fugacity (fO2) conditions during sulfide nodule and chondrule formation. The unequilibrated clasts include a mixture of type I and type II chondrules, as well as non-porphyritic chondrules. Chondrule oxygen isotopes overlap with ordinary-chondrite chondrules. Sulfide nodules average 200 μm in diameter, have rounded shapes, and are primarily composed of pyrrhotite, pentlandite, and magnetite. Some are deformed around chondrules in a petrologic relationship similar in appearance to compound chondrules. Both nodules and sulfides in chondrules include phosphate inclusions and Cu-rich lamellae, which suggests a genetic relationship between sulfides in chondrules and in the matrix. Ni/Co ratios for matrix and chondrule sulfides are solar, while Fe and Ni are non-solar and inversely related. We hypothesize that sulfide nodules formed via pre-accretionary melt processes. During chondrule formation, precursors composed of a mixture of silicate and sulfide material were heated to form immiscible melt droplets, which separated and cooled to form Si-rich chondrules and S-rich nodules. Sulfide melt was stabilized by a high total pressure (∼1 atm) in a dust- or ice-enriched environment. Heating of this material contributed to a high fS2 (2 × 10-3 atm at 1138 °C), and high fO2 (IW - 1 to IW - 4), in an environment with peak temperatures between 1539 °C and 1750 °C. Oxygen isotopic compositions in this region were similar to those recorded by the LL-chondrite chondrules.

Oxygen Fugacity Variation From Mantle Transition Zone To Ocean Ridges Recorded By In Situ Diamond-Bearing Peridotite Of Indus Ophiolite

NASA Astrophysics Data System (ADS)

Das, S.; Basu, A. R.

2017-12-01

Our recently discovered transition zone ( 410 - 660 Km) -derived peridotites in the Indus Ophiolite, Ladakh Himalaya [1] provide a unique opportunity to study changes in oxygen fugacity from shallow mantle beneath ocean ridges to mantle transition zone. We found in situ diamond, graphite pseudomorphs after diamond crystals, hydrocarbon (C - H) and hydrogen (H2) fluid inclusions in ultra-high pressure (UHP) peridotites that occur in the mantle - section of the Indus ophiolite and sourced from the mantle transition zone [2]. Diamond occurs as octahedral inclusion in orthoenstatite of one of these peridotites. The graphite pseudomorphs after diamond crystals and primary hydrocarbon (C-H), and hydrogen (H2) fluids are included in olivine of this rock. Hydrocarbon fluids are also present as inclusions in high pressure clinoenstatite (> 8 GPa). The association of primary hydrocarbon and hydrogen fluid inclusions in the UHP peridotites suggest that their source-environment was highly reduced at the base of the upper mantle. We suggest that during mantle upwelling beneath Neo Tethyan spreading center, the hydrocarbon fluid was oxidized and precipitated diamond. The smaller diamonds converted to graphite at shallower depth due to size, high temperature and elevated oxygen fugacity. This process explains how deep mantle upwelling can oxidize reduced fluid carried from the transition zone to produce H2O - CO2. The H2O - CO2 fluids induce deep melting in the source of the mid oceanic ridge basalts (MORB) that create the oceanic crust. References: [1] Das S, Mukherjee B K, Basu A R, Sen K, Geol Soc London, Sp 412, 271 - 286; 2015. [2] Das S, Basu A R, Mukherjee B K, Geology 45 (8), 755 - 758; 2017.

Formation of ore minerals in metamorphic rocks of the German continental deep drilling site (KTB)

NASA Astrophysics Data System (ADS)

Kontny, A.; Friedrich, G.; Behr, H. J.; de Wall, H.; Horn, E. E.; Möller, P.; Zulauf, G.

1997-08-01

The German Continental Deep Drilling Program (KTB) drilled a 9.1 km deep profile through amphibolite facies metamorphic rocks and reached in situ temperatures of 265°C. Each lithologic unit is characterized by typical ore mineral assemblages related to the regional metamorphic conditions. Paragneisses contain pyrrhotite + rutile + ilmenite ± graphite, metabasic units bear ilmenite + rutile + pyrrhotite ± pyrite, and additionally, the so-called variegated units yield pyrrhotite + titanite assemblages. In the latter unit, magnetite + ilmenite + rutile + titanite assemblages related to the lower amphibolite facies breakdown of ilmenite-hematite solid solution also occur locally. Retrograde hydrothermal mineralization which commenced during Upper Carboniferous times is characterized by the following geochemical conditions: (1) low saline Na-K-Mg-Cl fluids with sulfur and oxygen fugacities at the pyrite-pyrrhotite buffer and temperatures of 400-500°C, (2) fluids with CO2, CH4±N2, andpH, Eh, sulfur, and oxygen fugacity in the stability field of graphite + pyrite at temperatures of 280-350° and (3) moderate to high saline Ca-Na-Cl fluids with CH4+ N2; sulfur and oxygen fugacity are in the stability field of pyrrhotite at temperatures <300°C. The latter environment is confirmed by in situ conditions found at the bottom of the deep drilling. Monoclinic, ferrimagnetic pyrrhotite is the main carrier of magnetization which disappears below about 8.6 km, corresponding to in situ temperatures of about 250°C. Below this depth, hexagonal antiferromagnetic pyrrhotite with a Curie temperature of 260°C is the stable phase. Temperature-dependent transformation of pyrrhotite and the reaching of its Curie isotherm within the Earth crust are one of the striking results of the KTB deep drilling project.

The Mineralogical Record of Oxygen Fugacity Variation and Alteration in Northwest Africa 8159: Evidence for Interaction Between a Mantle Derived Martian Basalt and a Crustal Component(s)

NASA Technical Reports Server (NTRS)

Shearer, Charles K.; Burger, Paul V.; Bell, Aaron S.; McCubbin, Francis M.; Agee, Carl; Simon, Justin I.; Papike, James J.

2015-01-01

A prominent geochemical feature of basaltic magmatism on Mars is the large range in initial Sr isotopic ratios (approx. 0.702 - 0.724) and initial epsilon-Nd values (approx. -10 to greater than +50). Within this range, the shergottites fall into three discreet subgroups. These subgroups have distinct bulk rock REE patterns, mineral chemistries (i.e. phosphate REE patterns, Ni, Co, V in olivine), oxygen fugacity of crystallization, and stable isotopes, such as O. In contrast, nakhlites and chassignites have depleted epsilon-Nd values (greater than or equal to +15), have REE patterns that are light REE enriched, and appear to have crystallized near the FMQ buffer. The characteristics of these various martian basalts have been linked to different reservoirs in the martian crust and mantle, and their interactions during the petrogenesis of these magmas. These observations pose interesting interpretive challenges to our understanding of the conditions of the martian mantle (e.g. oxygen fugacity) and the interaction of mantle derived magmas with the martian crust and surface. Martian meteorite NWA 8159 is a unique fine-grained augite basalt derived from a highly depleted mantle source as reflected in its initial epsilon-Nd value, contains a pronounced light REE depleted pattern, and crystallized presumably under very oxidizing conditions. Although considerably older than both shergottites and nahklites, it has been petrogenetically linked to both styles of martian magmatism. These unique characteristics of NWA 8159 may provide an additional perspective for deciphering the petrogenesis of martian basalts and the nature of the crust of Mars.

Experimental testing of olivine-melt equilibrium models at high temperatures

NASA Astrophysics Data System (ADS)

Krasheninnikov, S. P.; Sobolev, A. V.; Batanova, V. G.; Kargaltsev, A. A.; Borisov, A. A.

2017-08-01

Data are presented on the equilibrium compositions of olivine and melts in the products of 101 experiments performed at 1300-1600°C, atmospheric pressure, and controlled oxygen fugacity by means of new equipment at the Vernadsky Institute. It was shown that the available models of the olivine-melt equilibrium describe with insufficient adequacy the natural systems at temperatures over 1400°C. The most adequate is the model by Ford et al. (1983). However, this model overestimates systematically the equilibrium temperature with underestimating by 20-40°C at 1450-1600°C. These data point to the need for developing a new, improved quantitative model of the olivine-melt equilibrium for high-temperature magnesian melts, as well as to the possibility of these studies on the basis of the equipment presented.

Comparative Planetary Mineralogy: Co, Ni Systematics in Chromite from Planetary Basalts

NASA Technical Reports Server (NTRS)

Karner, J. M.; Shearer, C. K.; Papike, J. J.; Righter,K.

2005-01-01

Spinel is a minor but important phase in planetary basalts because its variable composition often reflects basalt petrogenesis. For example, complicated zoning trends in spinel can give clues to melt evolution [1], and V concentrations in chromite lend insight into magma oxygen fugacity (fO2) conditions [2]. Nickel and Co are two elements that are commonly used as a measure of melt fractionation, and their partitioning between olivine and melt is fairly well understood. Less clear is their partitioning into spinel, although [3] has explored Ni and Co systematics in experimental charges. This study documents Ni and Co behavior in early crystallizing spinel (chromite) from several planetary basalts in an attempt to compare our results with [3], and also gain insight into basalt evolution on the three planets.

Mutual interactions of redox couples via electron exchange in silicate melts - Models for geochemical melt systems

NASA Technical Reports Server (NTRS)

Schreiber, Henry D.; Merkel, Robert C., Jr.; Schreiber, V. Lea; Balazs, G. Bryan

1987-01-01

The mutual interactions via electron exchange of redox couples in glass-forming melts were investigated both theoretically and experimentally. A thermodynamic approach for considering the mutual interactions leads to conclusion that the degree of mutual interaction in the melt should be proportional in part to the difference in relative reduction potentials of the interacting redox couples. Experimental studies verify this conclusion for numerous redox couples in several composition/temperature/oxygen fugacity regimes. Geochemical systems simultaneously possess many potentially multivalent elements; the stabilized redox states in the resulting magmas can be explained in part by mutual interactions and by redox buffering through the central Fe(III)- Fe(II) couples in the melts. The significance of these results for basaltic magmas of the earth, moon, and meteorites is addressed.

Electrical conductivity structure of the mantle derived from inversion of geomagnetic observatory data: implications for lateral variations in temperature, composition and water content.

NASA Astrophysics Data System (ADS)

Munch, Federico; Grayver, Alexander; Khan, Amir; Kuvshinov, Alexey

2017-04-01

As most of Earth's interior remains geochemically unsampled, geophysical techniques based on seismology, geodesy, gravimetry, and electromagnetic studies play prominent roles because of their ability to sense structure at depth. Although seismic tomography maps show a variety of structures, separating thermal and compositional contributions from seismic velocities alone still remains a challenging task. Alternatively, as electrical conductivity is sensitive to temperature, chemical composition, oxygen fugacity, water content, and the presence of melt, it can serve for determining chemistry, mineralogy, and physical structure of the deep mantle. In this work we estimate and invert local C-responses (period range 3-100 days) for a number of worldwide geomagnetic observatories to map lateral variations of electrical conductivity in Earth's mantle (400-1600 km depth). The obtained conductivity profiles are interpreted in terms of basalt fraction in a basalt-harzburgite mixture, temperature structure, and water content variations. Interpretation is based on a self-consistent thermodynamic calculation of mineral phase equilibria, electrical conductivity databases, and probabilistic inverse methods.

Water and the oxidation state of subduction zone magmas.

PubMed

Kelley, Katherine A; Cottrell, Elizabeth

2009-07-31

Mantle oxygen fugacity exerts a primary control on mass exchange between Earth's surface and interior at subduction zones, but the major factors controlling mantle oxygen fugacity (such as volatiles and phase assemblages) and how tectonic cycles drive its secular evolution are still debated. We present integrated measurements of redox-sensitive ratios of oxidized iron to total iron (Fe3+/SigmaFe), determined with Fe K-edge micro-x-ray absorption near-edge structure spectroscopy, and pre-eruptive magmatic H2O contents of a global sampling of primitive undegassed basaltic glasses and melt inclusions covering a range of plate tectonic settings. Magmatic Fe3+/SigmaFe ratios increase toward subduction zones (at ridges, 0.13 to 0.17; at back arcs, 0.15 to 0.19; and at arcs, 0.18 to 0.32) and correlate linearly with H2O content and element tracers of slab-derived fluids. These observations indicate a direct link between mass transfer from the subducted plate and oxidation of the mantle wedge.

Gold-bearing hedenbergite skarns from the SW contact of the Andorra granite (Central Pyrenees, Spain)

NASA Astrophysics Data System (ADS)

Soler, A.; Ayora, C.; Cardellach, E.; Delgado, J.

1990-12-01

Several varieties of skarn outcrop have been found to develop along the contact between the Andorra granite and the Devonian limestones. The skarns contain variable amounts of gold ranging up to 5 g/t, always associated with sulphides. The sulphides in the skarn include arsenopyrite and pyrrhotite with lesser amounts of chalcopyrite, galena, sphalerite and Bi-minerals. Geothermometric and geobarometric data indicate the skarns formed at about 2 kbar and temperatures ranging from 500 ° to 350 °C from CO2-free polysaline brines at a slightly acidic pH and oxygen fugacity which decreases with time from the pyrite-pyrrhotite-magnetite towards the QFM buffer. Available data on gold solubility suggest that sufficient quantities of gold to form an ore deposit could have been transported as AuCl{2/-}at the high temperatures and salinities under which the skarns formed. Both gold deposition and sulphide precipitation could have occurred due to a decrease in temperature and/or oxygen fugacity.

Ti(3+) in meteoritic and synthetic hibonite

NASA Technical Reports Server (NTRS)

Beckett, John R.; Stolper, Edward; Live, David; Tsay, Fun-Dow; Grossman, Lawrence

1988-01-01

This paper describes the first direct determination (performed by electron spin resonance spectroscopy) of Ti(3+) in hibonite from inclusion SH-7 of the Murchison C2 chondrite and in synthetic hibonites of four compositions, three of which corresponded to the compositions of blue hibonites and one to that of an orange hibonite. The Ti(3+) concentration in the hibonite from SH-7 was found to range from 0.35 to 0.44 percent, while the Ti(3+) contents in three synthetic blue hibonites ranged from 0.02 to 0.64 percent. Orange hibonite contained no Ti(3+), supporting an earlier conclusion that the orange-to-blue transition is associated with the presence of Ti(3+). At constant temperature and oxygen fugacity, the Ti(3+)/Ti(4+) ratio in synthetic hibonites was found to increase with decreasing V, but was not strongly dependent on bulk Ti. Fe and Cr contents did not have a significant effect on the amount of Ti(3+).

Ti(3+) in meteoritic and synthetic hibonite

NASA Astrophysics Data System (ADS)

Beckett, John R.; Live, David; Tsay, Fun-Dow; Grossman, Lawrence; Stolper, Edward

1988-06-01

This paper describes the first direct determination (performed by electron spin resonance spectroscopy) of Ti(3+) in hibonite from inclusion SH-7 of the Murchison C2 chondrite and in synthetic hibonites of four compositions, three of which corresponded to the compositions of blue hibonites and one to that of an orange hibonite. The Ti(3+) concentration in the hibonite from SH-7 was found to range from 0.35 to 0.44 percent, while the Ti(3+) contents in three synthetic blue hibonites ranged from 0.02 to 0.64 percent. Orange hibonite contained no Ti(3+), supporting an earlier conclusion that the orange-to-blue transition is associated with the presence of Ti(3+). At constant temperature and oxygen fugacity, the Ti(3+)/Ti(4+) ratio in synthetic hibonites was found to increase with decreasing V, but was not strongly dependent on bulk Ti. Fe and Cr contents did not have a significant effect on the amount of Ti(3+).

Workshop on Parent-Body and Nebular Modification of Chondritic Materials

NASA Technical Reports Server (NTRS)

Zolensky, M. E. (Editor); Krot, A. N. (Editor); Scott, E. R. D. (Editor)

1997-01-01

Topics considered include: thermal Metamorphosed Antarctic CM and CI Carbonaceous Chondrites in Japanese Collections, and Transformation Processes of Phyllosilicates; use of Oxygen Isotopes to Constrain the Nebular and Asteroidal Modification of Chondritic Materials; effect of Revised Nebular Water Distribution on Enstatite Chondrite Formation; interstellar Hydroxyls in Meteoritic Chondrules: Implications for the Origin of Water in the Inner Solar System; theoretical Models and Experimental Studies of Gas-Grain Chemistry in the Solar Nebula; chemical Alteration of Chondrules on Parent Bodies; thermal Quenching of Silicate Grains in Protostellar Sources; an Experimental Study of Magnetite Formation in the Solar Nebula; the Kaidun Meteorite: Evidence for Pre- and Postaccretionary Aqueous Alteration; a Transmission Electron Microscope Study of the Matrix Mineralogy of the Leoville CV3 (Reduced-Group) Carbonaceous Chondrite: Nebular and Parent-Body Features; rubidium-Strontium Isotopic Systematic of Chondrules from the Antarctic CV Chondrites Yamato 86751 and Yamato 86009: Additional Evidence for Late Parent-Body Modification; oxygen-Fugacity Indicators in Carbonaceous Chondrites: Parent-Body Alteration or High-Temperature Nebular Oxidation; thermodynamic Modeling of Aqueous Alteration in CV Chondrites; asteroidal Modification of C and O Chondrites: Myths and Models; oxygen Fugacity in the Solar Nebular; and the History of Metal and Sulfides in Chondrites.

Solubility of C-O-H volatiles in graphite-saturated martian basalts and application to martian atmospheric evolution

NASA Astrophysics Data System (ADS)

Stanley, B. D.; Hirschmann, M. M.; Withers, A. C.

2012-12-01

The modern martian atmosphere is thin, leading to surface conditions too cold to support liquid water. Yet, there is evidence of liquid surface water early in martian history that is commonly thought to require a thick CO2 atmosphere. Our previous work follows the analysis developed by Holloway and co-workers (Holloway et al. 1992; Holloway 1998), which predicts a linear relationship between CO2 and oxygen fugacity (fO2) in graphite-saturated silicate melts. At low oxygen fugacity, the solubility of CO2 in silicate melts is therefore very low. Such low calculated solubilities under reducing conditions lead to small fluxes of CO2 associated with martian magmatism, and therefore production of a thick volcanogenic CO2 atmosphere could require a prohibitively large volume of mantle-derived magma. The key assumption in these previous calculations is that the carbonate ion is the chief soluble C-O-H species. The results of the calculations would not be affected appreciably if molecular CO2, rather than carbonate ion, were an important species, but could be entirely different if there were other appreciable C-species such as CO, carbonyl (C=O) complexes, carbide (Si-C), or CH4. Clearly, graphite-saturated experiments are required to explore how much volcanogenic C may be degassed by reduced martian lavas. A series of piston-cylinder experiments were performed on synthetic martian starting materials over a range of oxygen fugacities (IW+2.3 to IW-0.9), and at pressures of 1-3 GPa and temperatures of 1340-1600 °C in Pt-graphite double capsules. CO2 contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and range from 0.0026-0.50 wt%. CO2 solubilities change by one order of magnitude with an order of magnitude change in oxygen fugacity, as predicted by previous work. Secondary ion mass spectrometry (SIMS) determinations of C contents in glasses range from 0.0131-0.2626 wt%. C contents determined by SIMS are consistently higher than CO2 contents determined by FTIR. This difference, termed excess C, is attributed to the presence of other reduced C-species, such as carbonyls and amides (which have C=O and N-H bonds), detected using FTIR in reduced graphite-saturated martian basalts. An atmosphere produced by degassing of magmas similar to this study would be richer in C-O-H species than previously modeled using only CO2 and could create a much warmer climate that stabilizes liquid water on the ancient martian surface.

The effect of water activity and oxygen fugacity on the phase relations and oxidation state of Fe in parental ferrobasaltic magma of Skaergaard

NASA Astrophysics Data System (ADS)

Botcharnikov, R.; Koepke, J.; Holtz, F.; McCammon, C.

2003-04-01

Phase relations and differentiation in the ferrobasaltic (FeO*=13wt%) system "SC1", an assumed parental liquid of the Skaergaard layered intrusion, have been investigated experimentally at dry conditions (1 atm) [1, 2]. However, the Skaergaard magma is believed to contain water. The present study investigates the role of water and fO2 on the phase relations and differentiation of the "SC1" ferrobasaltic system. The crystallization experiments have been performed in an internally heated pressure vessel equipped with a rapid quench facility and Shaw-membrane to determine the prevailing oxygen fugacity within the sample capsule [3]. To prevent the Fe-loss into the capsule material and ensure the desired conditions inside the capsule, the AuPd capsules were presaturated with iron and starting glasses were preequilibrated at the expected fO2 of the run. Water activity was varied by changing the H2O/CO2 ratio in the fluid phase. The first results of the experiments at P=200 MPa, T=1200-1000°C, various oxygen fugacities (logfO2=FMQ+4 to FMQ-1) and water activities (0 to 1) show that water influences not only the liquidus temperatures and temperature interval of mineral crystallization but also the sequence of crystallizing minerals; when compared with the dry system. Since water solubility strongly depends on pressure in the pressure range of 200-300 MPa, corresponding to the storage conditions of Skaergaard magma, the aH2O of hydrous magma may change significantly as a result of convection. Thus, convection has the potential to produce significant differences in stability and proportions of the prevailing minerals. This, in turn, may contribute to the formation of complex layering of the Skaergaard intrusion. The Moessbauer analysis of the quenched glasses shows that the Fe3+ / Sum Fe ratio of the silicate melt is a positive function of the water activity and has a linear dependence on water mole fraction in the system at 1200°C. The decrease of Fe3+ / Sum Fe ratio of the water-bearing melt with decreasing oxygen fugacity is more pronounced than that calculated for dry melts after [4]. [1] Toplis MJ &Carroll MR, J. Petrol., 36, 1137-1170, 1995. [2] Lattard D &Partsch GM, Eur. J. Mineral., 13, 467-478, 2001. [3] Berndt J et al., Am. Mineral., 87, 1717-1726, 2002. [4] Kress VC &Carmichael ISE, Contr.Min.Petrol., 108, 82-92, 1991.

The Origin of Refractory Minerals in Comet 81P/Wild 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chi, M; Ishii, H A; Simon, S B

2008-11-20

Refractory Ti-bearing minerals in the calcium-, aluminium-rich inclusion (CAI) Inti, recovered from the comet 81P/Wild 2 sample, were examined using analytical (scanning) transmission electron microscopy (STEM) methods including imaging, nanodiffraction, energy dispersive spectroscopy (EDX) and electron energy loss spectroscopy (EELS). Inti fassaite (Ca(Mg,Ti,Al)(Si,Al){sub 2}O{sub 6}) was found to have a Ti{sup 3+}/Ti{sup 4+} ratio of 2.0 {+-} 0.2, consistent with fassaite in other solar system CAIs. The oxygen fugacity (log f{sub O{sub 2}}) of formation estimated from this ratio, assuming equilibration among phases at 1509K, is -19.4 {+-} 1.3. This value is near the canonical solar nebula value (-18.1 {+-}more » 0.3) and in close agreement with that reported for fassaite-bearing Allende CAIs (-19.8 {+-} 0.9) by other researchers using the same assumptions. Nanocrystals of osbornite (Ti(V)N), 2-40 nm in diameter, are embedded as inclusions within anorthite, spinel and diopside in Inti. Vanadium is heterogeneously distributed within some osbornite crystals. Compositions range from pure TiN to Ti{sub 0.36}V{sub 0.64}N. The possible presence of oxide and carbide in solid solution with the osbornite was evaluated. The osbornite may contain O but does not contain C. The presence of osbornite, likely a refractory early condensate, together with the other refractory minerals in Inti, indicates that the parent comet contains solids that condensed closer to the proto-sun than the distance at which the parent comet itself accreted. The estimated oxygen fugacity and the reported isotopic and chemical compositions are consistent with Inti originating in the inner solar system as opposed to it being a surviving CAI from an extrasolar source. These results provide insight for evaluating the validity of models of radial mass transport dynamics in the early solar system. The oxidation environments inferred for the Inti mineral assemblage are inconsistent with an X-wind formation scenario. In contrast, radial mixing models allowing accretion of components from different heliocentric distances can satisfy the observations from the cometary CAI Inti.« less

Core formation conditons in planetesimals: constraints from isotope fractionation experiments.

NASA Astrophysics Data System (ADS)

Guignard, J.; Quitté, G.; Toplis, M. J.; Poitrasson, F.

2016-12-01

Planetesimals are small objects (10 to 1000 km) early accreted in the history of the solar system which show a wide variety of thermal history due to the initial amount of radiogenic elements [1] (26Al and 60Fe), from a simple metamorphism to a complete metal-silicate differentiation. Moreover, isotope compositions of siderophile element, e.g. Fe, Ni, and W in meteorites spread on a range that can be attributed to the process of core-mantle segregation. We therefore performed isotope fractionation experiments of nickel and tungsten between metal and silicate in a gas-mixing (CO-CO2) vertical furnace, at different temperatures (from 1270°C to 1600°C), oxygen fugacity (from IW+2 to IW-6) and annealing times (from 20 minutes to 48 hours). The starting silicate is an anorthite-diopside eutectic composition glass, synthesize from the respective oxides. The starting metal is either a nickel or tungsten wire according to the element to study. After each experiment, metal and silicate are mechanically separated and digested in acids. Nickel and Tungsten separation have been made according to the methods developed by [2] and [3] and isotopes measurements have been made using a high resolution MC-ICP-MS (Neptune; Thermofisher©). Results show evidence for a strong kinetic isotope fractionation during the first annealing times with a faster diffusion of lightest isotopes than heaviest. Similar mechanism has been already highlighted for iron isotope fractionation between silicate and metal [4]. Chemical and isotopic equilibrium is also reached in our experiments but the time required dependent on the conditions of temperature and oxygen fugacity. Therefore, at equilibrium, metal-silicate isotope fractionation has also been quantified as well its temperature dependence. These experimental data can be used in order to bring new constraints on the metal silicate segregation in the planetesimals early accreted. [1] Lee T., et al., GRL, 3, 41-44 (1976) [2] Quitté G., and Oberli F., JAAS, 21, 1249-1255 (2006) [3] Breton T., and Quitté G., JAAS, 29, 2284-2293 (2014) [4] Roskosz M., et al., EPSL, 248, 851-867 (2006)

Subsolidus cooling of mid-ocean ridge peridotites and implications for the oxygen fugacity of the oceanic upper mantle

NASA Astrophysics Data System (ADS)

Birner, S.; Davis, F. A.; Cottrell, E.; Warren, J. M.; Kelley, K. A.

2017-12-01

Peridotites dredged from mid-ocean ridges provide a window into the chemistry of Earth's upper mantle. At equilibrium, mineral assemblages within peridotite record intrinsic properties, including oxygen fugacity (fO2). During cooling below the solidus, however, reactions affect the chemical compositions and modal abundances of minerals, directly affecting the fO2 recorded by these mineral assemblages. The slow kinetics of subsolidus diffusion also prevent full re-equilibration of peridotite during cooling, and different reactions have different closure temperatures. As a result, peridotites measured at the surface record neither equilibrium nor asthenospheric conditions. In order to quantify the effect of subsolidus diffusion on fO2, we analyzed minerals from abyssal peridotites dredged from the Southwest Indian Ridge (SWIR), which we then used as a basis for modeling potential subsolidus reactions. We first examined exchange reactions where no modal changes occur. We considered both Fe-Mg exchange between olivine and spinel [1] and Al-Cr exchange between orthopyroxene and spinel [2], and combined these models with spinel oxybarometry [3] to determine the effect of these reactions on fO2. Our results indicate that as peridotites cool from 1300°C to 900°C, these exchange processes together increase recorded fO2 by 0.3 log units relative to the approach in which compositional changes are not considered. Some reactions additionally change mineral modal abundances during cooling, in particular the Tschermak exchange in orthopyroxene [2], which consumes olivine and Al-rich orthopyroxene and produces spinel and Al-poor orthopyroxene as temperature decreases. Depending on partitioning of Fe3+ between phases, this reaction may dilute the concentration of Fe3+ in spinel and decrease recorded fO2 as temperature decreases. Preliminary results suggest that the magnitude of this effect is strongly sensitive to both initial spinel mode and partitioning of Fe3+ between orthopyroxene and spinel. Finally, we compare the fO2 recorded by SWIR peridotites to the fO2 recorded by basalts, projected to source conditions. [1] Li et al., 1995; [2] Voigt and von der Handt, 2011; [3] Davis et al., 2017

An experimental study of Fe-Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

NASA Astrophysics Data System (ADS)

Zhang, Zhou; von der Handt, Anette; Hirschmann, Marc M.

2018-03-01

The behavior of nickel in the Earth's mantle is controlled by sulfide melt-olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe-Ni composition of molten sulfide in the Earth's upper mantle via sulfide melt-olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt X_{{{Ni}}}^{{{Sulfide}}}={{Ni}}/{{Ni+{Fe}}} (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of {f_{{{O}2}}} on Fe-Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31-46, 1995), "zero time" experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0 ± 1.0 log units more reduced than the fayalite-magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ - 1 or more oxidized (suite 4). For the reduced (suites 1-3) experiments, Fe-Ni distribution coefficients K_{{D}}{}={(X_{{{Ni}}}^{{{sulfide}}}/X_{{{Fe}}}^{{{sulfide}}})}/{(X_{{{Ni}}^{{{olivine}}}/X_{{{Fe}}}^{{{olivine}}})}} are small, averaging 10.0 ± 5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K D (21.1-25.2). Compared to previous determinations at 100 kPa, values of K D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peridotite indicates that compositions are intermediate in composition (X_{{{Ni}}}^{{{sulfide}}} 0.4-0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6-0.7) at depths near 80-120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (X_{{{Ni}}}^{{{sulfide}}} 0.28) > 140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.

Olivine-Orthopyroxene Equilibrium in Metal-rich Systems: Applications to Achondrites and Equilibrated Chondrites

NASA Technical Reports Server (NTRS)

Lauretta, D. S.; Benedix, G. K.; McCoy, T. J.

2003-01-01

Olivine and orthopyroxene are major minerals in every type of stony meteorite. The majority of achondritic meteorites and silicate-bearing iron meteorites have experienced high temperatures. If these temperatures persisted for an extended period of time then the iron contents of olivine and orthopyroxene should be in equilibrium. In their study of ungrouped clasts and chondritic meteorites, suggested that the equilibrium compositions of olivine and orthopyroxene should fall on a mixing line between LL chondrites and aubrites. Here we show that this is not necessarily the case and that a range of FeO contents in olivine and orthopyroxene can be in equilibrium with each other. The key parameters that determine the equilibrium Fe content in these minerals are temperature, oxygen fugacity (fO2), and silica activity (aSiO2).

Melting phase relations in the Fe-S and Fe-S-O systems at core conditions in small terrestrial bodies

NASA Astrophysics Data System (ADS)

Pommier, Anne; Laurenz, Vera; Davies, Christopher J.; Frost, Daniel J.

2018-05-01

We report an experimental investigation of phase equilibria in the Fe-S and Fe-S-O systems. Experiments were performed at high temperatures (1400-1850 °C) and high pressures (14 and 20 GPa) using a multi-anvil apparatus. The results of this study are used to understand the effect of sulfur and oxygen on core dynamics in small terrestrial bodies. We observe that the formation of solid FeO grains occurs at the Fe-S liquid - Fe solid interface at high temperature ( > 1400 °C at 20 GPa). Oxygen fugacities calculated for each O-bearing sample show that redox conditions vary from ΔIW = -0.65 to 0. Considering the relative density of each phase and existing evolutionary models of terrestrial cores, we apply our experimental results to the cores of Mars and Ganymede. We suggest that the presence of FeO in small terrestrial bodies tends to contribute to outer-core compositional stratification. Depending on the redox and thermal history of the planet, FeO may also help form a transitional redox zone at the core-mantle boundary.

Experimental Study into the Partitioning Behavior of Fluorine, Chlorine, Hydroxyl, and Sulfur (S2-) Between Apatite and a Synthetic Kreep Basalt Melt

NASA Technical Reports Server (NTRS)

Turner, Amber; Vander Kaaden, Kathleen; McCubbin, Francis; Danielson, Lisa R.

2017-01-01

The mineral apatite (Ca5 (PO4)3(F, Cl, OH)) is known for its ability to constrain the petrogenesis of the rock in which it is hosted and for its ubiquity throughout the Solar System, as it is found in lunar, martian, and terrestrial rocks alike (McCubbin et. al, 2015). The abundance of volatile elements, and for this particular study, the elevated abundance of sulfur (S2-) in high-Al basalt samples bearing apatite, could provide more insight for inquiries posed about the behavior of volatiles in lunar and martian magmatic systems (Boyce et. al, 2010). Oxygen fugacity will be an important parameter for these experiments, as the Moon, Mars, and Earth have different redox states (Herd, 2008). The objective of this experimental endeavor is to determine apatite-melt partition coefficients for the volatile elements (F-, Cl-, OH-, S2-) that make up the X-site (i.e., the typically monovalent anion site) in the mineral apatite in a lunar melt composition under lunar oxygen fugacity conditions approx.1-2 log units below the iron-wüstite buffer). All experiments will be conducted at NASA, Johnson Space Center in the High Pressure Experimental Petrology Laboratory. In order to conduct apatite-melt partition experiments with oxygen fugacity as an additional parameter, we will create a synthetic mix of the lunar KREEP basalt 15386, a sample retrieved during Apollo 15 that is believed to represent an indigenous volcanic melt derived from the lunar interior (Rhodes, J.M et. al, 2006). Other geochemically significant elements including C, Co, Ni, Mo, and rare earth elements will be included in the mix at trace abundances in order to assess their partitioning behavior without effecting the overall behavior of the system. The synthetic mix will then be loaded into a piston cylinder, an apparatus used to simulate high-pressure/high-temperature conditions of planetary interiors, and exposed to 0.5 GPa of pressure, the pressure observed in the upper mantle of the Moon, and heated to the melting temperature of the materials. To make sure crystals grow large enough for the necessary analyses, the sample will be kept at the crystallization temperature for 8 hours. This extended run time should also allow the sample to achieve a steady state which is necessary to accurately assess the partitioning of these elements between apatite and melt. The results from this experimental study will allow us to determine the fate of F-, Cl-, OH-, and S2- during the magmatic evolution of the Moon.

Apollo 15 green glass - Compositional distribution and petrogenesis

NASA Technical Reports Server (NTRS)

Steele, Alison M.; Colson, Russell O.; Korotev, Randy L.; Haskin, Larry A.

1992-01-01

We have characterized a comprehensive suite of individual green-glass beads from Apollo 15 soil to determine interelement behavior and to constrain petrogenetic relationships. We analyzed 365 particles for trace elements by instrumental neutron activation analysis and analyzed 52 of them, selected to cover the compositional ranges observed for trace elements, for major elements by electron microprobe analysis. We confirm the observation of Delano (1979) that the beads comprise discrete compositional groups, although two of the groups he defined are further split on the basis of trace-element compositions. Each of the resulting seven groups has distinct average rare-earth abundances. The coherence between major- and trace-element data was masked in previous studies by imprecision, correlated error, and nonrepresentative sampling of the different groups. Most of the compositional characteristics of the green glasses can be explained by a model for batch equilibrium melting of a nearly homogeneous, ultramafic source region, when the complicating effects of high pressure and low oxygen fugacity are taken into account. The previously puzzling behavior of Ni and Co as apparently incompatible elements may arise from partial reduction of those elements to the zero oxidation state, resulting in low mineral/melt partition coefficients. The model also offers explanations for why the green glasses form boomerang-shaped trends on many two-element variation diagrams and why certain compositions (Groups A and D) are more abundant than glasses with other compositions.

The redox potential of boron nitride and implications for its use as a crucible material in experimental petrology

NASA Technical Reports Server (NTRS)

Wendlandt, R. F.; Huebner, J. S.; Harrison, W. J.

1982-01-01

The suitability of boron nitride for use as a crucible material in silicate and oxygen-bearing metal sulfide systems has been investigated. Boron nitride is unsatisfactory for use with many silicate systems because its presence in combination with a source of oxygen establishes the oxygen fugacity at values below that of the assemblage quartz + fayalite + iron, reducing transition metal ions such as Ni(2+) and Fe(2+) to the metallic state. B2O3, resulting from the oxidation of BN, acts as a flux to promote formation of melt.

Control and monitoring of oxygen fugacity in piston cylinder experiments

NASA Astrophysics Data System (ADS)

Matjuschkin, Vladimir; Brooker, Richard A.; Tattitch, Brian; Blundy, Jon D.; Stamper, Charlotte C.

2015-01-01

We present a newly developed capsule design that resolves some common problems associated with the monitoring and control of oxygen fugacity ( fO2) in high-pressure piston cylinder experiments. The new fO2 control assembly consists of an AuPd outer capsule enclosing two inner capsules: one of AuPd capsule containing the experimental charge (including some water), and the other of Pt containing a solid oxygen buffer plus water. The inner capsules are separated by crushable alumina. The outer capsule is surrounded by a Pyrex sleeve to simultaneously minimise hydrogen loss from the cell and carbon infiltration from the graphite furnace. Controlled fO2 experiments using this cell design were carried out at 1.0 GPa and 1,000 °C. We used NiPd, CoPd and (Ni, Mg)O fO2 sensors, whose pressure sensitivity is well calibrated, to monitor the redox states achieved in experiments buffered by Re-ReO2, Ni-NiO and Co-CoO, respectively. Results for the fO2 sensors are in good agreement with the intended fO2 established by the buffer, demonstrating excellent control for durations of 24-48 h, with uncertainties less than ± 0.3 log bar units of fO2.

Using Vanadium in Spinel as a Sensor of Oxygen Fugacity in Meteorites: Applications to Mars, Vesta, and Other Asteroids

NASA Technical Reports Server (NTRS)

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

2009-01-01

Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or constrained such as FeTi oxides, olivine-opx-spinel, or some other oxybarometer [1]. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these samples is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in natural meteorite samples. Because the V pre-edge peak intensity and energy in chromites varies with fO2 (Fig. 1) [2], and this has been calibrated over a large fO 2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints.

Highly oxidising fluids generated during serpentinite breakdown in subduction zones.

PubMed

Debret, B; Sverjensky, D A

2017-09-04

Subduction zones facilitate chemical exchanges between Earth's deep interior and volcanism that affects habitability of the surface environment. Lavas erupted at subduction zones are oxidized and release volatile species. These features may reflect a modification of the oxidation state of the sub-arc mantle by hydrous, oxidizing sulfate and/or carbonate-bearing fluids derived from subducting slabs. But the reason that the fluids are oxidizing has been unclear. Here we use theoretical chemical mass transfer calculations to predict the redox state of fluids generated during serpentinite dehydration. Specifically, the breakdown of antigorite to olivine, enstatite, and chlorite generates fluids with high oxygen fugacities, close to the hematite-magnetite buffer, that can contain significant amounts of sulfate. The migration of these fluids from the slab to the mantle wedge could therefore provide the oxidized source for the genesis of primary arc magmas that release gases to the atmosphere during volcanism. Our results also show that the evolution of oxygen fugacity in serpentinite during subduction is sensitive to the amount of sulfides and potentially metal alloys in bulk rock, possibly producing redox heterogeneities in subducting slabs.

Thermometers and thermobarometers in granitic systems

USGS Publications Warehouse

Anderson, J.L.; Barth, A.P.; Wooden, J.L.; Mazdab, F.; ,

2008-01-01

The ability to determine the thermal and barometric history during crystallization and emplacement of granitic plutons has been enhanced by several new calibrations applicable to granitic mineral assemblages. Other existing calibrations for granitic plutons have continued to be popular and fairly robust. Recent advances include the trace element thermometers Ti-in-quartz, Ti-in-zircon, and Zr-in-sphene (titanite), which need to be further evaluated on the roles of reduced activities due to lack of a saturating phase, the effect of pressure dependence (particularly for the Ti-in-zircon thermometer), and how resistive these thermometers are to subsolidus reequilibration. As zircon and sphene are also hosts to radiogenic isotopes, these minerals potentially also provide new insights into the temperature - time history of magmas. When used in conjunction with pressure-sensitive mineral equilibria in the same rocks, a complete assessment of the P-T-t (pressure-temperature-time) path is possible given that the mineralogy of plutons can reflect crystallization over a range of pressure and temperature during ascent and emplacement and that many intrusions are now seen as forming over several millions of years during the protracted history of batholith construction. Accessory mineral saturation thermometers, such as those for zircon, apatite, and allanite, provide a different and powerful perspective, specifically that of the temperature of the onset of crystallization of these minerals, which can allow an estimate of the range of temperature between the liquidus and solidus of a given pluton. In assessment of the depth of crystallization and emplacement of granitic plutons, the Al-in-hornblende remains popular for metaluminous granites when appropriately corrected for temperature. For peraluminous granites, potential new calibrations exist for the assemblages bearing garnet, biotite, plagioclase, muscovite, and quartz. Other thermometers, based on oxygen abundance, and including Fe-Ti oxides, pyroxene, fayalitic olivine, quartz, sphene, and/or biotite, some of which have been recently revised, can provide additional information on temperature and oxygen fugacity. Oxygen fugacity can range over several orders of magnitude in different magmatic systems and can have profound influence on the mineralogy and mineral compositions in granitic magmas. It also forms the foundation of the popular magnetite- versus ilmenite-series granite classification. Copyright ?? Mineralogical Society of America.

FeO2 and FeOOH under deep lower-mantle conditions and Earth's oxygen-hydrogen cycles.

PubMed

Hu, Qingyang; Kim, Duck Young; Yang, Wenge; Yang, Liuxiang; Meng, Yue; Zhang, Li; Mao, Ho-Kwang

2016-06-09

The distribution, accumulation and circulation of oxygen and hydrogen in Earth's interior dictate the geochemical evolution of the hydrosphere, atmosphere and biosphere. The oxygen-rich atmosphere and iron-rich core represent two end-members of the oxygen-iron (O-Fe) system, overlapping with the entire pressure-temperature-composition range of the planet. The extreme pressure and temperature conditions of the deep interior alter the oxidation states, spin states and phase stabilities of iron oxides, creating new stoichiometries, such as Fe4O5 (ref. 5) and Fe5O6 (ref. 6). Such interactions between O and Fe dictate Earth's formation, the separation of the core and mantle, and the evolution of the atmosphere. Iron, in its multiple oxidation states, controls the oxygen fugacity and oxygen budget, with hydrogen having a key role in the reaction of Fe and O (causing iron to rust in humid air). Here we use first-principles calculations and experiments to identify a highly stable, pyrite-structured iron oxide (FeO2) at 76 gigapascals and 1,800 kelvin that holds an excessive amount of oxygen. We show that the mineral goethite, FeOOH, which exists ubiquitously as 'rust' and is concentrated in bog iron ore, decomposes under the deep lower-mantle conditions to form FeO2 and release H2. The reaction could cause accumulation of the heavy FeO2-bearing patches in the deep lower mantle, upward migration of hydrogen, and separation of the oxygen and hydrogen cycles. This process provides an alternative interpretation for the origin of seismic and geochemical anomalies in the deep lower mantle, as well as a sporadic O2 source for the Great Oxidation Event over two billion years ago that created the present oxygen-rich atmosphere.

The chemical composition of the cores of the terrestrial planets and the moon

NASA Technical Reports Server (NTRS)

Kuskov, O. L.; Khitarov, N. I.

1977-01-01

Using models of the quasi-chemical theory of solutions, the activity coefficients of silicon are calculated in the melts Fe-Si, Ni-Si, and Fe-Ni-Si. The calculated free energies of solution of liquid nickel and silicon in liquid iron in the interval 0 to 1400 kbar and 1500 to 4000 K, shows that Fe-Ni-Si alloy is stable under the conditions of the outer core of the earth and the cores of the terrestrial planets. The oxidation-reduction conditions are studied, and the fugacity of oxygen in the mantles of the planets and at the core-mantle boundary are calculated. The mechanism of reduction of silicon is analyzed over a broad interval of p and T. The interaction between the matter of the core and mantle is studied, resulting in the extraction of silicon from the mantle and its solution in the material of the core. It is concluded that silicon can enter into the composition of the outer core of the earth and Venus, but probably does not enter into the composition of the cores of Mercury, Mars, and the moon, if in fact the latter possesses one.

Discovery Of Low Oxygen Fugacity (fo2) Mineral And Fluid Phases In Lower Mantle -Derived Early Pulse Of The Deccan Flood Basalts

NASA Astrophysics Data System (ADS)

Basu, A. R.; Das, S.

2017-12-01

Estimation of Earth's lower mantle mineralogy and oxygen fugacity are principally based on indirect geophysical and experimental studies. According to these studies, the mantle becomes increasingly reducing from upper to lower mantle due to the distribution of ferric (Fe3+) and ferrous (Fe2+) iron in perovskite, the dominant mineral phase in the lower mantle. However, the natural occurrence of low oxygen fugacity (fO2), lower mantle mineral and fluid phases are rare, except some for discrete inclusions in superdeep diamonds. In this study, we document that some rocks associated with plume volcanism, such as the Deccan flood basalt volcanic province, preserve the lower mantle mineral phases. We document here unusual primary texture - bearing minerals in olivine-clinopyroxene bearing picrite intrusives associated with the Deccan Traps. The olivine and clinopyroxene of these rocks have high 3He/4He ratio (R/RA 14) as well as Nd, Sr and Pb isotopes identical to those of the Réunion plume, clearly indicating their lower mantle - derivation. These rocks are the initial pulse at 68Ma of the Deccan Trap eruption [1]. Presence of unusual exsolved lamella and rectangular, vermicular intergrowths of diopside and magnetite in olivine indicate a precursory phase with higher Fe3+. The diopside part in rectangular intergrowth show presence of hydrocarbon. Trails of small graphitic carbon crystals are also present both in the cores of these olivine and diopside. We suggest that the hydrocarbons are derived from the lower mantle having much lesser fO2 than the upper mantle. This study unequivocally indicates that direct lower mantle mineralogical signature, including their fo2 can be obtained from early pulse of plume volcanism. References: [1] Basu A R, Renne P R, Dasgupta D K, Teichmann F, Poreda R J, Science 261, 902 - 906; 1993.

Redox variations in Mauna Kea lavas, the oxygen fugacity of the Hawaiian plume, and the role of volcanic gases in Earth’s oxygenation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brounce, Maryjo; Stolper, Edward; Eiler, John

The behavior of C, H, and S in the solid Earth depends on their oxidation states, which are related to oxygen fugacity (fO2). Volcanic degassing is a source of these elements to Earth’s surface; therefore, variations in mantle fO2 may influence the fO2 at Earth’s surface. However, degassing can impact magmatic fO2 before or during eruption, potentially obscuring relationships between the fO2 of the solid Earth and of emitted gases and their impact on surface fO2. We show that low-pressure degassing resulted in reduction of the fO2 of Mauna Kea magmas by more than an order of magnitude. The leastmore » degassed magmas from Mauna Kea are more oxidized than midocean ridge basalt (MORB) magmas, suggesting that the upper mantle sources of Hawaiian magmas have higher fO2 than MORB sources. One explanation for this difference is recycling of material from the oxidized surface to the deep mantle, which is then returned to the surface as a component of buoyant plumes. It has been proposed that a decreasing pressure of volcanic eruptions led to the oxygenation of the atmosphere. Extension of our findings via modeling of degassing trends suggests that a decrease in eruption pressure would not produce this effect. If degassing of basalts were responsible for the rise in oxygen, it requires that Archean magmas had at least two orders of magnitude lower fO2 than modern magmas. Estimates of fO2 of Archean magmas are not this low, arguing for alternative explanations for the oxygenation of the atmosphere.« less

Redox variations in Mauna Kea lavas, the oxygen fugacity of the Hawaiian plume, and the role of volcanic gases in Earth's oxygenation.

PubMed

Brounce, Maryjo; Stolper, Edward; Eiler, John

2017-08-22

The behavior of C, H, and S in the solid Earth depends on their oxidation states, which are related to oxygen fugacity ( f O 2 ). Volcanic degassing is a source of these elements to Earth's surface; therefore, variations in mantle f O 2 may influence the f O 2 at Earth's surface. However, degassing can impact magmatic f O 2 before or during eruption, potentially obscuring relationships between the f O 2 of the solid Earth and of emitted gases and their impact on surface f O 2 We show that low-pressure degassing resulted in reduction of the f O 2 of Mauna Kea magmas by more than an order of magnitude. The least degassed magmas from Mauna Kea are more oxidized than midocean ridge basalt (MORB) magmas, suggesting that the upper mantle sources of Hawaiian magmas have higher f O 2 than MORB sources. One explanation for this difference is recycling of material from the oxidized surface to the deep mantle, which is then returned to the surface as a component of buoyant plumes. It has been proposed that a decreasing pressure of volcanic eruptions led to the oxygenation of the atmosphere. Extension of our findings via modeling of degassing trends suggests that a decrease in eruption pressure would not produce this effect. If degassing of basalts were responsible for the rise in oxygen, it requires that Archean magmas had at least two orders of magnitude lower f O 2 than modern magmas. Estimates of f O 2 of Archean magmas are not this low, arguing for alternative explanations for the oxygenation of the atmosphere.

Redox variations in Mauna Kea lavas, the oxygen fugacity of the Hawaiian plume, and the role of volcanic gases in Earth’s oxygenation

PubMed Central

Stolper, Edward; Eiler, John

2017-01-01

The behavior of C, H, and S in the solid Earth depends on their oxidation states, which are related to oxygen fugacity (fO2). Volcanic degassing is a source of these elements to Earth’s surface; therefore, variations in mantle fO2 may influence the fO2 at Earth’s surface. However, degassing can impact magmatic fO2 before or during eruption, potentially obscuring relationships between the fO2 of the solid Earth and of emitted gases and their impact on surface fO2. We show that low-pressure degassing resulted in reduction of the fO2 of Mauna Kea magmas by more than an order of magnitude. The least degassed magmas from Mauna Kea are more oxidized than midocean ridge basalt (MORB) magmas, suggesting that the upper mantle sources of Hawaiian magmas have higher fO2 than MORB sources. One explanation for this difference is recycling of material from the oxidized surface to the deep mantle, which is then returned to the surface as a component of buoyant plumes. It has been proposed that a decreasing pressure of volcanic eruptions led to the oxygenation of the atmosphere. Extension of our findings via modeling of degassing trends suggests that a decrease in eruption pressure would not produce this effect. If degassing of basalts were responsible for the rise in oxygen, it requires that Archean magmas had at least two orders of magnitude lower fO2 than modern magmas. Estimates of fO2 of Archean magmas are not this low, arguing for alternative explanations for the oxygenation of the atmosphere. PMID:28784788

Redox variations in Mauna Kea lavas, the oxygen fugacity of the Hawaiian plume, and the role of volcanic gases in Earth's oxygenation

NASA Astrophysics Data System (ADS)

Brounce, Maryjo; Stolper, Edward; Eiler, John

2017-08-01

The behavior of C, H, and S in the solid Earth depends on their oxidation states, which are related to oxygen fugacity (fO2). Volcanic degassing is a source of these elements to Earth’s surface; therefore, variations in mantle fO2 may influence the fO2 at Earth’s surface. However, degassing can impact magmatic fO2 before or during eruption, potentially obscuring relationships between the fO2 of the solid Earth and of emitted gases and their impact on surface fO2. We show that low-pressure degassing resulted in reduction of the fO2 of Mauna Kea magmas by more than an order of magnitude. The least degassed magmas from Mauna Kea are more oxidized than midocean ridge basalt (MORB) magmas, suggesting that the upper mantle sources of Hawaiian magmas have higher fO2 than MORB sources. One explanation for this difference is recycling of material from the oxidized surface to the deep mantle, which is then returned to the surface as a component of buoyant plumes. It has been proposed that a decreasing pressure of volcanic eruptions led to the oxygenation of the atmosphere. Extension of our findings via modeling of degassing trends suggests that a decrease in eruption pressure would not produce this effect. If degassing of basalts were responsible for the rise in oxygen, it requires that Archean magmas had at least two orders of magnitude lower fO2 than modern magmas. Estimates of fO2 of Archean magmas are not this low, arguing for alternative explanations for the oxygenation of the atmosphere.

JSC systems using solid ceramic oxygen electrolyte cells to measure oxygen fugacites in gas-mixing systems

NASA Technical Reports Server (NTRS)

Williams, R. J.; Mullins, O.

1981-01-01

Details are given for the construction and operation of a 101.3 KN/sq meter (1 atmosphere) redox control system. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a vertical quench gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples, a simplified version of a gas mixing apparatus, and devices for experiments under controlled rates of change of temperature. A thermogravimetric analysis system employing these techniques of redox control and measurement is also described. The calibration and maintenance of the system are discussed.

Decoding magma plumbing and geochemical evolution beneath the Lastarria volcanic complex (Northern Chile)-Evidence for multiple magma storage regions

NASA Astrophysics Data System (ADS)

Stechern, André; Just, Tobias; Holtz, François; Blume-Oeste, Magdalena; Namur, Olivier

2017-05-01

The petrology of quaternary andesites and dacites from Lastarria volcano was investigated to reconstruct the magma plumbing and storage conditions beneath the volcano. The mineral phase compositions and whole-rock major and trace element compositions were used to constrain temperature, pressure and possible mechanisms for magma differentiation. The applied thermobarometric models include two-pyroxene thermobarometry, plagioclase-melt thermometry, amphibole composition thermobarometry, and Fe-Ti oxide thermo-oxybarometry. The overall temperature estimation is in the range 840 °C to 1060 °C. Calculated oxygen fugacity ranges between NNO to NNO + 1. Results of the geo-barometric calculations reveal multiple magma storage regions, with a distinct storage level in the uppermost crust ( 6.5-8 km depth), a broad zone at mid-crustal levels ( 10-18 km depth), and a likely deeper zone at intermediate to lower crustal levels (> 20 km depth). The highest temperatures in the range 940-1040 °C are recorded in minerals stored in the mid-crustal levels ( 10-18 km depth). The whole-rock compositions clearly indicate that magma mixing is the main parameter controlling the general differentiation trends. Complex zoning patterns and textures in the plagioclase phenocrysts confirm reheating and remobilization processes due to magma replenishment.

Apatite-Melt Partitioning of Volatiles in Basaltic Systems: Implications for Determining Volatile Abundances in Planetary Bodies from Apatite

NASA Technical Reports Server (NTRS)

McCubbin, F. M.

2017-01-01

Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials, and due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources [i.e., 1]. Experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in basaltic systems [e.g., 2- 3], reporting that apatite-melt partitioning of volatiles is best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, exchange coefficients may vary as a function of temperature, pressure, melt composition, and/or oxygen fugacity. Furthermore, exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite [3]. In these regions of ternary space, we anticipate that crystal chemistry could influence partitioning behavior. Consequently, we conducted experiments to investigate the effect of apatite crystal chemistry on apatite-melt partitioning of F, Cl, and OH.

Solubility of Sulfur in Shergottitic Silicate Melts Up to 0.8 GPA: Implications for S Contents of Shergottites

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K.M.; Danielson, L.

2009-01-01

Shergottites have high S contents (1300 to 4600 ppm; [1]), but it is unclear if they are sulfide saturated or under-saturated. This issue has fundamental implications for determining the long term S budget of the martian surface and atmosphere (from mantle degassing), as well as evolution of the highly siderophile elements (HSE) Au, Pd, Pt, Re, Rh, Ru, Ir, and Os, since concentrations of the latter are controlled by sulfide stability. Resolution of sulfide saturation depends upon temperature, pressure, oxygen fugacity (and FeO), and magma composition [2]. Expressions derived from experimental studies allow prediction of S contents, though so far they are not calibrated for shergottitic liquids [3-5]. We have carried out new experiments designed to test current S saturation models, and then show that existing calibrations are not suitable for high FeO and low Al2O3 compositions characteristic of shergottitic liquids. The new results show that existing models underpredict S contents of sulfide saturated shergottitic liquids by a factor of 2.

Ultra-oxidized rocks in subduction mélanges? Decoupling between oxygen fugacity and oxygen availability in a Mn-rich metasomatic environment

NASA Astrophysics Data System (ADS)

Tumiati, Simone; Godard, Gaston; Martin, Silvana; Malaspina, Nadia; Poli, Stefano

2015-06-01

The manganese ore of Praborna (Italian Western Alps) is embedded within a metasedimentary sequence belonging to a subduction mélange equilibrated at high-pressure (HP) conditions (ca. 2 GPa) during the Alpine orogenesis. The pervasive veining of the ore and the growth of "pegmatoid" HP minerals suggest that these Mn-rich rocks strongly interacted with slab-derived fluids during HP metamorphism. These rocks are in textural and chemical equilibrium with the veins and in contact with sulphide- and magnetite-bearing metabasites at the bottom of the sequence. They contain braunite (Mn2+Mn3+6SiO12), quartz, pyroxmangite (Mn2+SiO3), and minor hematite, omphacite, piemontite and spessartine-rich garnet. Sulphides are absent in the Mn-rich rocks, whereas sulphates (barite, celestine) occur together with As- and Sb-oxides and silicates. This rock association provides an excellent natural laboratory to constrain the redox conditions in subducting oceanic slab mélanges at HP and fluid-present conditions. Similarly to Fe-bearing minerals, Mn oxides and silicates can be regarded as natural redox-sensors. A thermodynamic dataset for these Mn-bearing minerals is built, using literature data as well as new thermal expansion parameters for braunite aud pyrolusite, derived from experiments. Based on this dataset and the observed assemblages at Praborna, thermodynamic calculations show that these mélange rocks are characterised by ultra-oxidized conditions (∆FMQ up to + 12.7) if the chemical potential of oxygen (or the oxygen fugacity fO2) is accounted for. On the other hand, if the molar quantity of oxygen is used as the independent state variable to quantify the bulk oxidation state, the ore appears only moderately oxidized and comparable to typical subduction-slab mafic eclogites. Such an apparent contradiction may happen in rock systems whenever oxygen is improperly considered as a perfectly mobile component. In the Earth's mantle, redox reactions take place mainly between solid oxides and silicates, because O2 is a negligible species in the fluid phase. Therefore, the description of the redox conditions of most petrological systems requires the introduction of an extensive variable, namely the oxygen molar quantity (nO2). As a consequence, the oxygen chemical potential, and thus fO2, becomes a dependent state variable, not univocally indicative of the redox conditions of the entire rock column of a subduction zone, from the dehydrating oceanic crust to the overlying mantle wedge. On a more general basis, the comparison of fO2 retrieved from different bulk compositions and different phase assemblages is sometimes challenging and should be undertaken with care. From the study of mélange rocks at Praborna, the distribution of oxygen at subduction zones could be modelled as an oxidation gradient, grading from a maximum in the subducted altered oceanic crust to a minimum in the overlying peridotites of the mantle hanging-wall.

BurnMan: Towards a multidisciplinary toolkit for reproducible deep Earth science

NASA Astrophysics Data System (ADS)

Myhill, R.; Cottaar, S.; Heister, T.; Rose, I.; Unterborn, C. T.; Dannberg, J.; Martin-Short, R.

2016-12-01

BurnMan (www.burnman.org) is an open-source toolbox to compute thermodynamic and thermoelastic properties as a function of pressure and temperature using published mineral physical parameters and equations-of-state. The framework is user-friendly, written in Python, and modular, allowing the user to implement their own equations of state, endmember and solution model libraries, geotherms, and averaging schemes. Here we introduce various new modules, which can be used to: Fit thermodynamic variables to data from high pressure static and shock wave experiments, Calculate equilibrium assemblages given a bulk composition, pressure and temperature, Calculate chemical potentials and oxygen fugacities for given assemblages Compute 3D synthetic seismic models using output from geodynamic models and compare these results with global seismic tomographic models, Create input files for synthetic seismogram codes. Users can contribute scripts that reproduce the results from peer-reviewed articles and practical demonstrations (e.g. Cottaar et al., 2014).

The solubility of gold in silicate melts: First results

NASA Technical Reports Server (NTRS)

Borisov, A.; Palme, H.; Spettel, B.

1993-01-01

The effects of oxygen fugacity and temperature on the solubility of Au in silicate melts were determined. Pd-Au alloys were equilibrated with silicate of anorthite-diopside eutectic composition at different T-fO2 conditions. The behavior of Au was found to be similar to that of Pd reported recently. Au solubilities for alloys with 30 to 40 at. percent Au decrease at 1400 C from 12 ppm in air to 160 ppb at a log fO2 = -8.7. The slope of the log(Me-solubility) vs. log(fO2) curve is close to 1/4 for Au and the simultaneously determined Pd suggesting a formal valence of Au and Pd of 1+. Near the IW buffer Pd and Au solubilities become even less dependent on fO2 perhaps reflecting the presence of some metallic Au and Pd.

Crystallization conditions of porphyritic high-K calc-alkaline granitoids in the extreme northeastern Borborema Province, NE Brazil, and geodynamic implications

NASA Astrophysics Data System (ADS)

Campos, Benedita Cleide Souza; Vilalva, Frederico Castro Jobim; Nascimento, Marcos Antônio Leite do; Galindo, Antônio Carlos

2016-10-01

An integrated textural and chemical study on amphibole, biotite, plagioclase, titanite, epidote, and magnetite was conducted in order to estimate crystallization conditions, along with possible geodynamic implications, for six Ediacaran porphyritic high-K calc-alkaline granite plutons (Monte das Gameleiras, Barcelona, Acari, Caraúbas, Tourão, and Catolé do Rocha) intrusive into Archean to Paleoproterozoic rocks of the São José do Campestre (SJCD) and Rio Piranhas-Seridó (RPSD) domains, northern Borborema Province. The studied rocks include mainly porphyritic leucocratic monzogranites, as well as quartz-monzonites and granodiorites. Textures are marked by K-feldspar megacrysts (5-15 cm long) in a fine-to medium-grained matrix composed of quartz, plagioclase, amphibole, biotite, as well as titanite, epidote, Fesbnd Ti oxides, allanite, apatite, and zircon as accessory minerals. Amphibole, biotite and titanite share similar compositional variations defined by increasing Al and Fe, and decreasing Mg contents from the plutons emplaced into the SJCP (Monte das Gameleiras and Barcelona) towards those in the RPSD (Acari, Caraúbas, Tourão, and Catolé do Rocha). Estimated intensive crystallization parameters reveal a weak westward range of increasing depth of emplacement, pressure and temperature in the study area. The SJCD plutons (to the east) crystallized at shallower crustal depths (14-21 km), under slightly lower pressure (3.8-5.5 kbar) and temperature (701-718 °C) intervals, and high to moderate oxygen fugacity conditions (+0.8 < ΔFQM < +2.0). On the other hand, the RPSD plutons (to the west) were emplaced at slightly deeper depths (18-23 km), under higher, yet variable pressures (4.8-6.2 kbar), temperatures (723-776 °C), and moderate to low oxygen fugacity conditions (-1.0 < ΔFQM < +1.8). These results reinforce the contrasts between the tectono-strutuctural domains of São José do Campestre and Rio Piranhas-Seridó in the northern Borborema Province.

Two-Oxide Disequilibrium: A New Geospeedometer Based on Diffusion in Ilmenite

NASA Astrophysics Data System (ADS)

Williams, K. B.; Krawczynski, M. J.; Van Orman, J. A.

2016-12-01

Diffusion-annealing experiments were conducted in a 0.5" piston cylinder apparatus to investigate diffusivity of Fe2+, Mg2+, and Mn2+ in ilmenite solid solutions between 800ºC and 1000ºC. Polycrystalline ilmenite (FeTiO3) was juxtaposed against either an oriented geikielite (MgTiO3) single crystal or polycrystalline Mn-bearing (5 mol% Mn) ilmenite, in a "diffusion-couple" geometry. Geikielite single crystals were synthesized at Los Alamos National Laboratory, cut into 1 mm edge-length cubes, and polished either perpendicular or parallel to the c-axis. Polycrystalline ilmenite starting materials were synthesized by mixing high purity reagent-grade oxides (FeO, MnO, and TiO2) and sintering in a piston cylinder apparatus, then cut into wafers and polished. Experimental run products were analyzed by electron microprobe at Washington University in St. Louis. Microprobe analyses were obtained perpendicularly across the diffusion interface for each experiment. Experimental diffusion profiles create smooth curves that, when fit with an error function, define Fe-Mg and Fe-Mn interdiffusion coefficients in ilmenite. The diffusion coefficients do not appear compositionally dependent, but do show significant anisotropy. Preliminary results suggest diffusion activation energies are lower in ilmenite than in titanomagnetite [1]. Ilmenite-titanomagnetite equilibria define pre-eruptive temperatures and oxygen fugacities. However, oxides often exist out of equilibrium [2]. We use the cation diffusion data for ilmenite and existing data on titanomagnetite to establish two-oxide disequilibrium as a geospeedometer. Our data constrain oxide-oxide re-equilibration timescales at Mt. Unzen to months, consistent with estimates from zoned, single crystals of magnetite [3,4]. Future experiments will examine the effect of oxygen fugacity on diffusivity in ilmenite solid solutions. References:[1] Van Orman & Crispin (2010) RiMG 72, 757-825.[2] Bacon & Hirschmann (1988) Am. Min. 73, 57-61.[3] Nakamura (1995) Geology 23, 807-810.[4] Venezky & Rutherford (1999) J. Volc. Geo. Res. 89, 213-230.

In situ major and trace element analysis of amphiboles in quartz monzodiorite porphyry from the Tonglvshan Cu-Fe (Au) deposit, Hubei Province, China: insights into magma evolution and related mineralization

NASA Astrophysics Data System (ADS)

Duan, Deng-Fei; Jiang, Shao-Yong

2017-05-01

The Tonglvshan deposit is the largest Cu-Fe (Au) skarn deposit in the Edong district, which is located in the westernmost part of the Middle and Lower Yangtze River metallogenic belt, China. In this study, we performed a detailed in situ analysis of major and trace elements in amphiboles from the ore-related Tonglvshan quartz monzodiorite porphyry using electron microprobe (EMPA) analysis and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Two distinct populations of amphiboles, which can be distinguished by their aluminum content, are found in the quartz monzodiorite porphyry. The low-aluminum (Low-Al) amphiboles are subhedral or anhedral and formed at 46.3-73.5 MPa and 713-763 °C. In contrast, the high-aluminum (High-Al) amphiboles are euhedral and formed at 88-165 MPa and 778-854 °C. Some euhedral amphiboles are partially or completely replaced by Low-Al amphibole. The compositions of parental melts in equilibrium with the High-Al amphibole ( Melt 1) and Low-Al amphibole ( Melt 2) were computed by applying solid/liquid partition coefficients. This modeling shows that magma in equilibrium with High-Al amphibole ( Melt 1) underwent 40% fractional crystallization of amphibole, plagioclase and apatite at a depth of 5 km to evolve to magma in equilibrium with Low-Al amphibole ( Melt 2). Copper enrichment occurred in the magma after undergoing fractional crystallization. The magma had a high oxygen fugacity, increasing from NNO + 1 ( Melt 1) through NNO + 2 to HM ( Melt 2), which could have prevented the loss of Cu (and possibly Au) to sulfide minerals during crystallization. Finally, the evolved magma intruded to shallower depths, where it presumably exsolved aqueous ore-forming fluids. Therefore, the large Cu-Fe-Au reserves of the Tonglvshan deposit can likely be attributed to a combination of controlling factors, including high oxygen fugacity, fractional crystallization, fluid exsolution, and a shallow emplacement depth.

The role of water in generating Fe-depletion and the calc-alkaline trend

NASA Astrophysics Data System (ADS)

Zimmer, M. M.; Plank, T.

2006-12-01

Describing a magmatic suite as calc-alkaline (CA) or tholeiitic (TH) is a first order characterization, but existing classification schemes (AFM ternary plots and FeO*/MgO vs. SiO2) may convolute magmatic processes and can result in contradictory classification. The salient feature of TH vs. CA evolution is the extent of Fe enrichment or depletion in the magma. A plot of FeO* vs. MgO provides the most straightforward way to quantify Fe enrichment and to develop models for its origin. We present a new quantitative classification utilizing the FeO*-MgO plot, the tholeiitic index (THI) = Fe3-5/Fe8 (Fe3-5=average FeO* at 3-5 wt% MgO; Fe8=FeO* at 8 wt% MgO). THI of 1.2 indicates 20% FeO* enrichment from a magma's starting composition at Fe8, while THI of 0.8 indicates 20% depletion in FeO*. A magmatic suite is CA if THI is <1, and TH if THI is >1. Arcs range from 0.6 to 1.1, back arc basins from 1.1-1.3, and MORBs are \\ge1.6. This classification allows comparison of magmatic evolution on a global basis, regardless of starting composition, and is useful for quantitative comparison to liquid line of descent models. Hypotheses for generating CA magmas include high water contents, high pressure of crystallization, high oxygen fugacity, and high Mg# andesitic starting compositions. In order to test the control of H2O, we compare the THI to average magmatic water contents from undegassed melt inclusions and glasses (S>1000 ppm or CO2>50 ppm) from twenty-eight arc volcanoes and back arc basins, including new water contents from seven Aleutian volcanoes. The resulting negative correlation (R2=0.8) between water concentration and THI (with end-members at 0.8 wt% H2O, THI =1.3 and 6.1 wt% H2O, THI = 0.6) suggests water plays a fundamental role in generating the CA fractionation trend. MORB data plot off the trend at a higher THI, possibly related to lower oxygen fugacity during melting and/or crystallization. Models using the pMelts program are consistent with experimentally- and observationally-demonstrated effects of water on suppression of plagioclase and early formation of oxides relative to silicates during magma fractionation, and the resulting FeO* depletion with respect to decreasing MgO.

Applying the Ce-in-zircon oxygen geobarometer to diverse silicic magmatic systems

NASA Astrophysics Data System (ADS)

Claiborne, L. L.; Miller, C. F.

2012-12-01

Zircon provides information on age, temperature, and composition of the magma from which it grew. In systems such as Mount St. Helens, where zircon is not coeval with the rest of the crystal cargo, it provides the only accessible record of the extended history of the magmatic system, including cycles of intrusion, crystallization and rejuvenation beneath an active volcano (Claiborne et al., 2010). The rare earth elements, which are present in measureable quantities in zircon, provide information about the composition of the magma from which zircon grew. Unique among the generally trivalent rare earth elements, cerium can exist as either trivalent or tetravalent, depending on the oxidation state of the magma. The tetravalent ion is highly compatible in zircon, in the site that usually hosts tetravalent zirconium, and so the amount of Cerium in zircon relative (relative to what would be expected of trivalent Ce) depends the oxidation state of the magma from which it grew. Trail et al. (2011) proposed a calibration based on experimental data that uses the Ce anomaly in zircon as a direct proxy for magma oxidation (fugacity), describing the relationship between Ce in zircon and magma oxygen fugacity as ln(Ce/Ce*)D = (0.1156±0.0050)xln(fO2)+(13860±708)/T-(6.125±0.484). For systems like Mount St. Helens, where the major minerals record only events in the hundreds to thousands of years leading to eruption, (including the Fe-Ti oxides traditionally relied upon for records of oxidation state of the magmas), this presents a novel approach for understanding more extended histories of oxidation of magmas in the tens and hundreds of thousands of years of magmatism at a volcanic center. This calibration also promises to help us better constrain conditions of crystallization in intrusive portions of volcanic systems, as well as plutonic bodes. We apply this new oxygen geobarometer to natural volcanic and plutonic zircons from a variety of tectonic settings, and compare to existing indicators of oxidation state for each system, as available. Zircons included this study are from Mount St. Helens (ΔNNO +1.5 log units; Smith, 1984), the Peach Spring Tuff and Spirit Mountain Batholith (sphene-bearing, silicic, Miocene-aged rocks from the Colorado River Extensional Corridor), Alid Volcano in Eritrea, and rhyolites and granites from Iceland. Median log fO2 for these systems, calculated from the Cerium anomaly in zircons following Trail et al. (2011) using temperatures from Ti-in-zircon thermometry (Ferry and Watson, 2007) are as follows: Alid -12 bars (ΔNNO +3 log units) at 750 degrees C; Iceland -11 bars (ΔNNO +3 log units) at 800 degrees C; Mount St. Helens -8.6 bars (ΔNNO +6 log units) at 750 degrees C; Peach Spring Tuff -3.4 (ΔNNO +10 log units) at 830 degrees C. While ubiquitous sphene in the Spirit Mountain granites suggest relatively high fO2, calculations based on the cerium anomaly in zircon suggest median log fO2 of >0 at 770 degrees C, which is certainly erroneous. While median values for our natural zircons are, for the most part, above expected fugacities for each system when compared with other indicators, and extreme values for each system are almost certainly erroneous, many are within expected values for terrestrial magmas and they vary relative to one another as might be expected given the magma types and tectonic settings.

Petrology of Anomalous Eucrites

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Peng, Z. X.; Ross, D. K.

2015-01-01

Most mafic achondrites can be broadly categorized as being "eucritic", that is, they are composed of a ferroan low-Ca clinopyroxene, high-Ca plagioclase and a silica phase. They are petrologically distinct from angritic basalts, which are composed of high-Ca, Al-Ti-rich clinopyroxene, Carich olivine, nearly pure anorthite and kirschsteinite, or from what might be called brachinitic basalts, which are composed of ferroan orthopyroxene and high-Ca clinopyroxene, intermediate-Ca plagioclase and ferroan olivine. Because of their similar mineralogy and composition, eucrite-like mafic achondrites formed on compositionally similar asteroids under similar conditions of temperature, pressure and oxygen fugacity. Some of them have distinctive isotopic compositions and petrologic characteristics that demonstrate formation on asteroids different from the parent of the HED clan (e.g., Ibitira, Northwest Africa (NWA) 011). Others show smaller oxygen isotopic distinctions but are otherwise petrologically and compositionally indistinguishable from basaltic eucrites (e.g., Pasamonte, Pecora Escarpment (PCA) 91007). The degree of uniformity in delta O-17 of eucrites and diogenites is one piece of evidence considered to favor of a magma-ocean scenario for their petrogenesis. Given that the O isotopic differences separating Pasamonte and PCA 91007 from other eucrites are small, and that there is an absence of other distinguishing characteristics, a legitimate question is: Did the HED parent asteroid fail to homogenize via a magma-ocean stage, thus explaining outliers like Pasamonte? We are initiating a program of study of anomalous eucrite-like achondrites as one part of our effort to seek a resolution of this issue. Here we present preliminary petrologic information on Asuka (A-) 881394, Elephant Moraine (EET) 87520 and EET 87542. We will have studied several more by conference time.

A solid ceramic electrolyte system for measuring redox conditions in high temperature gas mixing studies

NASA Technical Reports Server (NTRS)

Williams, R. J.

1972-01-01

The details of the construction and operation of a gas mixing furnace are presented. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a standard vertical-quench, gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples. The system also contains the highinput impedance electronics necessary for measurements and a simplified version of standard gas mixing apparatus. The calibration and maintenance of the system are discussed.

Estimating Values of H2O-ACTIVITIES in the Mantle Using Amphibole Equilibria

NASA Astrophysics Data System (ADS)

Lamb, W. M.; Hunt, L. E.

2017-12-01

Determining values of H2O activity (aH2O) for mantle rocks will yield a better understanding of those mantle processes that are controlled, in part, by the availability of H2O (e.g., melting and deformation). The H contents of the upper mantle can be estimated from amount of H contained in nominally anhydrous minerals (NAMs). However, for many common NAMs, the relation between aH2O and H content is not well known, and certain NAMs may be prone to retrograde H loss. The activities of H2O and other fluids species (e.g., CO2) may be estimated using mineral equilibria. Equilibria involving amphibole can, for example, be used to estimate values of aH2O and hydrogen fugacity (ƒH2). Spinel equilibria can be applied to estimate values of oxygen fugacity (ƒO2) that, when combined with ƒH2, will provide a second estimate of aH2O. We have characterized mineral chemistries in 11 amphibole-bearing peridotite xenoliths from the southwestern U.S.A. The compositions of co-existing pyroxenes ± garnet yield P-T conditions of ≈ 1.1 GPa, and 880 to 980˚C, and application of dehydration equilibria yields values of aH2O ranging from 0.04 to 0.19. The compositions of coexisting spinel + olivine + opx yield DlogƒO2(FMQ) of -0.2 to +0.9. Values of ƒH2, estimated using amphibole dehydrogenation equilibria (6 to 91 bars) were combined with values of ƒO2 to estimate aH2O in nine samples (≈ 0.02 to 0.12). The difference between these two values of aH2O, estimated using dehydration equilibria versus ƒH2 + ƒO2, is generally < 0.1, suggesting that the amphiboles experienced little or no retrograde H-loss. All samples equilibrated at low values of aH2O, and these values may be used to predict NAM H-contents. For example, according to Gaetani et al. (2014, Cont. Min. Pet., p. 965), the concentration of H in olivine is a function of P, T, the fugacities of H2O and O2, and olivine composition. Their relation yields relatively low predicted H-contents of 10 to 28 wt. ppm for olivine in our samples. These results suggest that if P, T, and bulk composition are appropriate to stabilize amphibole in the mantle, this mineral may act to consume much of the available H and equilibrate at low values of aH2O. The NAMs in these rocks will have relatively low H-contents and, if these NAMs control the rheology the rock, this portion of the mantle will have a relatively high viscosity.

Degassing of reduced carbon from planetary basalts.

PubMed

Wetzel, Diane T; Rutherford, Malcolm J; Jacobsen, Steven D; Hauri, Erik H; Saal, Alberto E

2013-05-14

Degassing of planetary interiors through surface volcanism plays an important role in the evolution of planetary bodies and atmospheres. On Earth, carbon dioxide and water are the primary volatile species in magmas. However, little is known about the speciation and degassing of carbon in magmas formed on other planets (i.e., Moon, Mars, Mercury), where the mantle oxidation state [oxygen fugacity (fO2)] is different from that of the Earth. Using experiments on a lunar basalt composition, we confirm that carbon dissolves as carbonate at an fO2 higher than -0.55 relative to the iron wustite oxygen buffer (IW-0.55), whereas at a lower fO2, we discover that carbon is present mainly as iron pentacarbonyl and in smaller amounts as methane in the melt. The transition of carbon speciation in mantle-derived melts at fO2 less than IW-0.55 is associated with a decrease in carbon solubility by a factor of 2. Thus, the fO2 controls carbon speciation and solubility in mantle-derived melts even more than previous data indicate, and the degassing of reduced carbon from Fe-rich basalts on planetary bodies would produce methane-bearing, CO-rich early atmospheres with a strong greenhouse potential.

V Xanes in Spinels as an Oxy-Barometer in Meteorites with Implications for Redox Variations in the Inner Solar System

NASA Technical Reports Server (NTRS)

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

2015-01-01

The variation of oxygen fugacity within inner solar system materials spans a range of nearly 15 orders of magnitude. Igneous and metamorphic rocks commonly contain a mineral assemblage that allows oxygen fugacity to be calculated or con-strained such as FeTi oxides, olivine-opx-spinel, or some other oxy-barometer. Some rocks, however, contain a limited mineral assemblage and do not provide constraints on fO2 using mineral equilibria. Good examples of the latter are orthopyroxenites or dunites, such as diogenites, ALH 84001, chassignites, or brachinites. In fact it is no surprise that the fO2 of many of these achondrites is not well known, other than being "reduced" and below the metal saturation value. In order to bridge this gap in our understanding, we have initiated a study of V in chromites in achondrite. Because the V pre-edge peak intensity and energy in chromites varies with fO2, and this has been calibrated over a large fO2 range, we can apply this relation to rocks for which we otherwise have no fO2 constraints.

The partitioning of sulfur between multicomponent aqueous fluids and felsic melts

NASA Astrophysics Data System (ADS)

Binder, Bernd; Wenzel, Thomas; Keppler, Hans

2018-02-01

Sulfur partitioning between melt and fluid phase largely controls the environmental impact of volcanic eruptions. Fluid/melt partitioning data also provide the physical basis for interpreting changes in volcanic gas compositions that are used in eruption forecasts. To better constrain some variables that control the behavior of sulfur in felsic systems, in particular the interaction between different volatiles, we studied the partitioning of sulfur between aqueous fluids and haplogranitic melts at 200 MPa and 750-850 °C as a function of oxygen fugacity (Ni-NiO or Re-ReO2 buffer), melt composition (Al/(Na + K) ratio), and fluid composition (NaCl and CO2 content). The data confirm a first-order influence of oxygen fugacity on the partitioning of sulfur. Under "reducing conditions" (Ni-NiO buffer), D fluid/melt is nearly one order of magnitude larger (323 ± 14 for a metaluminous melt) than under "oxidizing conditions" (Re-ReO2 buffer; 74 ± 5 for a metaluminous melt). This effect is likely related to a major change in sulfur speciation in both melt and fluid. Raman spectra of the quenched fluids show the presence of H2S and HS- under reducing conditions and of SO4 2- and HSO4 - under oxidizing conditions, while SO2 is undetectable. The latter observation suggests that already at the Re-ReO2 buffer, sulfur in the fluid is almost completely in the S6+ state and, therefore, more oxidized than expected according to current models. CO2 in the fluid (up to x CO2 = 0.3) has no effect on the fluid/melt partitioning of sulfur, neither under oxidizing nor under reducing conditions. However, the effect of NaCl depends on redox state. While at oxidizing conditions, D fluid/melt is independent of x NaCl, the fluid/melt partition coefficient strongly decreases with NaCl content under reducing conditions, probably due to a change from H2S to NaSH as dominant sulfur species in the fluid. A decrease of D fluid/melt with alkali content in the melt is observed over the entire compositional range under reducing conditions, while it is prominent only between the peraluminous and metaluminous composition in oxidizing experiments. Overall, the experimental results suggest that for typical oxidized, silicic to intermediate subduction zone magmas, the degassing of sulfur is not influenced by the presence of other volatiles, while under reducing conditions, strong interactions with chlorine are observed. If the sulfur oxidation state is preserved during an explosive eruption, a large fraction of the sulfur released from oxidized magmas may be in the S6+ state and may remain undetected by conventional methods that only measure SO2. Accordingly, the sulfur yield and the possible climatic impact of some eruptions may be severely underestimated.

Statistical Constraints from Siderophile Elements on Earth's Accretion, Differentiation, and Initial Core Stratification

NASA Astrophysics Data System (ADS)

O'Rourke, J. G.; Stevenson, D. J.

2015-12-01

Abundances of siderophile elements in the primitive mantle constrain the conditions of Earth's core/mantle differentiation. Core growth occurred as Earth accreted from collisions between planetesimals and larger embryos of unknown original provenance, so geochemistry is directly related to the overall dynamics of Solar System formation. Recent studies claim that only certain conditions of equilibration (pressure, temperature, and oxygen fugacity) during core formation can reproduce the available data. Typical analyses, however, only consider the effects of varying a few out of tens of free parameters in continuous core formation models. Here we describe the Markov chain Monte Carlo method, which simultaneously incorporates the large uncertainties on Earth's composition and the parameterizations that describe elemental partitioning between metal and silicate. This Bayesian technique is vastly more computationally efficient than a simple grid search and is well suited to models of planetary accretion that involve a plethora of variables. In contrast to previous work, we find that analyses of siderophile elements alone cannot yield a unique scenario for Earth's accretion. Our models predict a wide range of possible light element contents for the core, encompassing all combinations permitted by seismology and mineral physics. Specifically, we are agnostic between silicon and oxygen as the dominant light element, and the addition of carbon or sulfur is also permissible but not well constrained. Redox conditions may have remained roughly constant during Earth's accretion or relatively oxygen-rich material could have been incorporated before reduced embryos. Pressures and temperatures of equilibration, likewise, may only increase slowly throughout accretion. Therefore, we do not necessarily expect a thick (>500 km), compositionally stratified layer that is stable against convection to develop at the top of the core of Earth (or, by analogy, Venus). A thinner stable layer might inhibit the initialization of the dynamo.

Geochemistry, mineralogy, and petrology of boninitic and komatiitic rocks on the mercurian surface: Insights into the mercurian mantle

NASA Astrophysics Data System (ADS)

Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Nittler, Larry R.; Peplowski, Patrick N.; Weider, Shoshana Z.; Frank, Elizabeth A.; McCoy, Timothy J.

2017-03-01

Orbital data from the MESSENGER mission to Mercury have facilitated a new view of the planet's structure, chemical makeup, and diverse surface, and have confirmed Mercury's status as a geochemical endmember among the terrestrial planets. In this work, the most recent results from MESSENGER's X-Ray Spectrometer, Gamma-Ray Spectrometer, and Neutron Spectrometer have been used to identify nine distinct geochemical regions on Mercury. Using a variation on the classical CIPW normative mineralogy calculation, elemental composition data is used to constrain the potential mineralogy of Mercury's surface; the calculated silicate mineralogy is dominated by plagioclase, pyroxene (both orthopyroxene and clinopyroxene), and olivine, with lesser amounts of quartz. The range in surface compositions indicate that the rocks on the surface of Mercury are diverse and vary from komatiitic to boninitic. The high abundance of alkalis on Mercury's surface results in several of the nine regions being classified as alkali-rich komatiites and/or boninites. In addition, Mercury's surface terranes span a wide range of SiO2 values that encompass crustal compositions that are more silica-rich than geochemical terranes on the Moon, Mars, and Vesta, but the range is similar to that of Earth. Although the composition of Mercury's surface appears to be chemically evolved, the high SiO2 content is a primitive feature and a direct result of the planet's low oxygen fugacity.

Petrogenesis and provenance of ungrouped achondrite Northwest Africa 7325 from petrology, trace elements, oxygen, chromium and titanium isotopes, and mid-IR spectroscopy

NASA Astrophysics Data System (ADS)

Goodrich, Cyrena A.; Kita, Noriko T.; Yin, Qing-Zhu; Sanborn, Matthew E.; Williams, Curtis D.; Nakashima, Daisuke; Lane, Melissa D.; Boyle, Shannon

2017-04-01

Northwest Africa (NWA) 7325 is an ungrouped achondrite that has recently been recognized as a sample of ancient differentiated crust from either Mercury or a previously unknown asteroid. In this work we augment data from previous investigations on petrography and mineral compositions, mid-IR spectroscopy, and oxygen isotope compositions of NWA 7325, and add constraints from Cr and Ti isotope compositions on the provenance of its parent body. In addition, we identify and discuss notable similarities between NWA 7325 and clasts of a rare xenolithic lithology found in polymict ureilites. NWA 7325 has a medium grained, protogranular to poikilitic texture, and consists of 10-15 vol.% Mg-rich olivine (Fo 98), 25-30 vol.% diopside (Wo 45, Mg# 98), 55-60 vol.% Ca-rich plagioclase (An 90), and trace Cr-rich sulfide and Fe,Ni metal. We interpret this meteorite to be a cumulate that crystallized at ⩾1200 °C and very low oxygen fugacity (similar to the most reduced ureilites) from a refractory, incompatible element-depleted melt. Modeling of trace elements in plagioclase suggests that this melt formed by fractional melting or multi-stage igneous evolution. A subsequent event (likely impact) resulted in plagioclase being substantially remelted, reacting with a small amount of pyroxene, and recrystallizing with a distinctive texture. The bulk oxygen isotope composition of NWA 7325 plots in the range of ureilites on the CCAM line, and also on a mass-dependent fractionation line extended from acapulcoites. The ε54Cr and ε50Ti values of NWA 7325 exhibit deficits relative to terrestrial composition, as do ordinary chondrites and most achondrites. Its ε54Cr value is distinct from that of any analyzed ureilite, but is not resolved from that of acapulcoites (as represented by Acapulco). In terms of all these properties, NWA 7325 is unlike any known achondrite. However, a rare population of clasts found in polymict ureilites ("the magnesian anorthitic lithology") are strikingly similar to NWA 7325 in mineralogy and mineral compositions, oxygen isotope compositions, and internal textures in plagioclase. These clasts are probably xenolithic in polymict ureilites, and could be pieces of NWA 7325-like meteorites. Using constraints from chromium, titanium and oxygen isotopes, we discuss two possible models for the provenance of the NWA 7325 parent body: (1) accretion in the inner solar system from a reservoir similar to that of acapulcoites in Δ17O, ε54Cr and ε50Ti; or (2) early (<1 Ma after CAI formation) accretion in the outer solar system (beyond the snow line), before 54Cr and 50Ti anomalies were introduced to this region of the solar system. The mid-IR emission spectrum of NWA 7325 obtained in this work matches its modal mineralogy, and so can be compared with spectra of new meteorites or asteroids/planets to help identify similar materials and/or the parent body of NWA 7325.

The redox state of the mantle during and just after core formation.

PubMed

Frost, D J; Mann, U; Asahara, Y; Rubie, D C

2008-11-28

Siderophile elements are depleted in the Earth's mantle, relative to chondritic meteorites, as a result of equilibration with core-forming Fe-rich metal. Measurements of metal-silicate partition coefficients show that mantle depletions of slightly siderophile elements (e.g. Cr, V) must have occurred at more reducing conditions than those inferred from the current mantle FeO content. This implies that the oxidation state (i.e. FeO content) of the mantle increased with time as accretion proceeded. The oxygen fugacity of the present-day upper mantle is several orders of magnitude higher than the level imposed by equilibrium with core-forming Fe metal. This results from an increase in the Fe2O3 content of the mantle that probably occurred in the first 1Ga of the Earth's history. Here we explore fractionation mechanisms that could have caused mantle FeO and Fe2O3 contents to increase while the oxidation state of accreting material remained constant (homogeneous accretion). Using measured metal-silicate partition coefficients for O and Si, we have modelled core-mantle equilibration in a magma ocean that became progressively deeper as accretion proceeded. The model indicates that the mantle would have become gradually oxidized as a result of Si entering the core. However, the increase in mantle FeO content and oxygen fugacity is limited by the fact that O also partitions into the core at high temperatures, which lowers the FeO content of the mantle. (Mg,Fe)(Al,Si)O3 perovskite, the dominant lower mantle mineral, has a strong affinity for Fe2O3 even in the presence of metallic Fe. As the upper mantle would have been poor in Fe2O3 during core formation, FeO would have disproportionated to produce Fe2O3 (in perovskite) and Fe metal. Loss of some disproportionated Fe metal to the core would have enriched the remaining mantle in Fe2O3 and, if the entire mantle was then homogenized, the oxygen fugacity of the upper mantle would have been raised to its present-day level.

Electrical conductivity of San Carlos olivine along [100] under oxygen- and pyroxene-buffered conditions and implications for defect equilibria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wanamaker, B.J.; Duba, A.G.

1993-01-10

The electrical conductivity along [100] of single crystal San Carlos olivine was measured as a function of temperature between 1100[degrees] and 1200[degrees]C and oxygen fugacity between 10[sup [minus]6] and 10[sup +0.5] Pa (at 1200[degrees]C), and either with (pyroxene-buffered) or without (self-buffered) an added natural pyroxene buffer from a San Carlos Iherzolite. Under these temperature and fO[sub 2] conditions, electrical conduction in the self-buffered sample is attributed to polarons (Fe[sup [sm bullet

Oxygen Fugacity of Abyssal Peridotites Along the Gakkel Ridge

NASA Astrophysics Data System (ADS)

Said, M.; Birner, S.; Cottrell, E.

2015-12-01

The oxygen budget of the Earth's mantle is important in understanding how our planet evolves chemically over time. The Gakkel Ridge is the world's slowest spreading ridge [1], and exposes peridotites along its axis that record the activity of oxygen in the upper mantle. Our samples comprise relatively fertile lherzolites and harzburgites (Cr#=0.13-0.17, 3.1-8.3% modal cpx [2]) as well as refractory harzburgites (Cr#=0.43-0.55, 0.2-1.0% modal cpx [2]). Using spinel peridotite oxygen barometry [3], we calculated the oxygen fugacity (fO2) of a suite of 10 peridotites from the Gakkel Ridge in order to investigate how melt processes affect the oxygen budget of the Earth's interior. We show that the low-Cr# lherzolites and harzburgites range from -0.1 to +0.6 log units relative to the QFM buffer, consistent with the global abyssal peridotite array, whereas high-Cr# refractory harzburgites have low fO2 values, ranging from -0.7 to -2.7 log units below QFM, with the most refractory samples falling significantly lower than the global array. Because D'Errico et al. (submitted) interprets the refractory samples as recording ancient melt extraction, the low fO2 recorded by these samples may originate in the geologic past, perhaps even in a different tectonic setting. While LREE enrichment in the refractory harzburgites [2] provides evidence for refertilization by an infiltrating melt that could have recently imprinted reducing conditions, we see no corresponding increase in TiO2 content in the spinels, which weakens this hypothesis. Further research on additional refractory harzburgites is needed to constrain whether the reduced nature of these samples is telling us something about the effect of extreme melt extraction on fO2 at ridges, or whether these samples record a unique history that obscures processes operating at ridges today. [1] Coakley and Cochran, EPSL (1998), [2] D'Errico et al., submitted, [3] Bryndzia and Wood, American Journal of Science (1990)

Effect of iron content on the creep behavior of Olivine: 2. Hydrous conditions

NASA Astrophysics Data System (ADS)

Zhao, Yong-Hong; Zimmerman, Mark E.; Kohlstedt, David L.

2018-05-01

We have undertaken an experimental investigation of the effect of iron content on the viscosity of Fe-Mg olivine aggregates deformed under hydrous conditions in order to provide a basis for comparing convection models for the mantle of Earth with those for the more iron-rich mantle of Mars. Fine-grained samples of Fe-bearing olivine with fayalite contents, Fax, of x = 100, 75, 50, 30 and 10 were deformed in triaxial compressive creep primarily in the dislocation creep regime under water-saturated conditions at temperatures of 1273 to 1473 K and a confining pressure of 300 MPa. Nickel sleeves around the samples of Fa10, Fa30 and Fa50 set the oxygen fugacity at the Ni:NiO buffer and thus the water fugacity at ≲300 MPa, while Fe sleeves around samples of Fa75 and Fa100 set the oxygen fugacity at the Fe:FeO buffer and thus the water fugacity at ≲200 MPa. Samples were deformed in triaxial compression to a maximum strain of 0.2 at differential stresses from 10 to 300 MPa and strain rates from 10-7 to 10-3 s-1. In the dislocation creep field at a given temperature, the viscosity of samples of Fa50 is a factor of ∼10 smaller than the viscosity of samples of Fa30, while the viscosity of samples of Fa30 is a factor of ∼10 smaller than that of samples of Fa10. Our experimental results can be described by the flow law ε˙disl =Cdisl(σ/μ) ndisl XFa pdisl exp(-(Qdisl0 +αdislXFa)/RT) fH2Omdisl with Cdisl = 99.7 MPa-5/4 s-1, ndisl = 3.7, pdisl = 0.5, Qdisl0 = 510 kJ/mol, αdisl = -120 kJ/mol, and mdisl = 5/4. This flow law indicates that the viscosity of olivine of a specific Fe:Mg ratio is a factor of ∼10 smaller than its counterpart deformed under anhydrous conditions. In a hydrous environment at the same thermodynamic conditions, the viscosity of the more Fe-rich mantle (∼Fa19) of Mars is a factor of ∼5 lower than that of the mantle (∼Fa8) of Earth.

The ungrouped chondrite El Médano 301 and its comparison with other reduced ordinary chondrites

NASA Astrophysics Data System (ADS)

Pourkhorsandi, Hamed; Gattacceca, Jérôme; Devouard, Bertrand; D'Orazio, Massimo; Rochette, Pierre; Beck, Pierre; Sonzogni, Corinne; Valenzuela, Millarca

2017-12-01

El Médano 301 (EM 301) is an ungrouped chondrite with overall texture and trace-element distribution similar to those of ordinary chondrites (OCs), but with silicate (olivine and low-Ca pyroxene) compositions that are more reduced than those in OCs, with average olivine and low-Ca pyroxene of Fa3.9±0.3 and Fs12.8±4.9, respectively. These values are far lower than the values for OCs and even for chondrites designed as ;reduced; chondrites. Low-Ca pyroxene is the dominant mineral phase and shows zoning with higher MgO contents along the crystal rims and cracks (reverse zoning). The Co content of kamacite is also much lower than the concentrations observed in OCs (below detection limit of 0.18 wt% versus 0.44-37 wt%). Oxygen isotopic composition is Δ17O = +0.79,+0.78‰ and slightly different from that of OCs. The lower modal olivine/pyroxene ratio, different Infrared (IR) spectra, lower Co content of kamacite, lower mean FeO contents of olivine and pyroxene, different kamacite texture, and different oxygen-isotopic composition show that EM 301 does not belong to a known OC group. EM 301 shows similarities with chondritic clasts in Cumberland Falls aubrite, and with Northwest Africa 7135 (NWA 7135) and Acfer 370 ungrouped chondrites. However, dissimilar to NWA 7135 and the clasts, it does not contain highly reduced mineral phases like daubréelite. Our observations suggest the formation of EM 301 in a nebular region compositionally similar to OCs but with a different redox state, with oxygen fugacity (ƒO2) in this region lower than that of OCs and higher than that of enstatite chondrites condensation region. A second, possibly nebular, phase of reduction by the production of reducing gas phases (e.g., C-rich) could be responsible for the subsequent reduction of the primary material and the occurrence of reverse zoning in the low-Ca pyroxene and lower average Fa/Fs ratio. Based on the IR spectra of EM 301 we suggest the possibility that the parent body of this chondrite was a V-type asteroid.

Zircon U-Pb geochronology and Sr-Nd-Pb-Hf isotopic constraints on the timing and origin of Mesozoic granitoids hosting the Mo deposits in northern Xilamulun district, NE China

NASA Astrophysics Data System (ADS)

Shu, Qihai; Lai, Yong; Zhou, Yitao; Xu, Jiajia; Wu, Huaying

2015-12-01

Located in the east section of the Central Asian orogen in northeastern China, the Xilamulun district comprises several newly discovered molybdenum deposits, primarily of porphyry type and Mesozoic ages. This district is divided by the Xilamulun fault into the southern and the northern parts. In this paper, we present new zircon U-Pb dating, trace elements and Hf isotope, and/or whole rock Sr-Nd-Pb isotopic results for the host granitoids from three Mo deposits (Yangchang, Haisugou and Shabutai) in northern Xilamulun. Our aim is to constrain the age and petrogenesis of these intrusions and their implications for Mo mineralization. Zircon U-Pb LA-ICP-MS dating shows that the monzogranites from the Shabutai and Yangchang deposits formed at 138.4 ± 1.5 and 137.4 ± 2.1 Ma, respectively, which is identical to the molybdenite Re-Os ages and coeval well with the other Mo deposits in this region, thereby indicating an Early Cretaceous magmatism and Mo mineralization event. Zircon Ce/Nd ratios from the mineralized intrusions are significantly higher than the barren granites, implying that the mineralization-related magmas are characterized by higher oxygen fugacity. These mineralized intrusions share similar zircon in-situ Hf and whole rock Sr-Nd isotopic compositions, with slightly negative to positive εHf(t) ranging from - 0.8 to + 10.0, restricted εNd(t) values from - 3.7 to + 1.6 but a little variable (87Sr/86Sr)i ratios between 0.7021 and 0.7074, indicative of formation from primary magmas generated from a dominantly juvenile lower crust source derived from depleted mantle, despite diverse consequent processes (e.g., magma mixing, fractional crystallization and crustal contamination) during their evolution. The Pb isotopes (whole rock) also show a narrow range of initial compositions, with (206Pb/204Pb)i = 18.03-18.88, (207Pb/204Pb)i = 15.48-15.58 and (208Pb/204Pb)i = 37.72-38.28, in agreement with Sr-Nd-Hf isotopes reflecting the dominance of a mantle component. An integration of geochronological and isotopic data points to three stages of Mo mineralization events (i.e., Triassic, Late Jurassic, and Early Cretaceous) associated with magmas generated from three different source regions in the Xilamulun district, NE China. The variation in the origin of the magmas from which the porphyry Mo systems were generated suggests that the formation of Mo deposit lies not in the composition of magma sources. Other factors, including high magma oxygen fugacity, may have taken a fundamental role in Mo enrichment and subsequent mineralization.

Radioactive nuclear waste stabilization - Aspects of solid-state molecular engineering and applied geochemistry

NASA Technical Reports Server (NTRS)

Haggerty, S. E.

1983-01-01

Stabilization techniques for the storage of radioactive wastes are surveyed, with emphasis on immobilization in a primary barrier of synthetic rock. The composition, half-life, and thermal-emission characteristics of the wastes are shown to require thermally stable immobilization enduring at least 100,000 years. Glass materials are determined to be incapable of withstanding the expected conditions, average temperatures of 100-500 C for the first 100 years. The geological-time stability of crystalline materials, ceramics or synthetic rocks, is examined in detail by comparing their components with similar naturally occurring minerals, especially those containing the same radioactive elements. The high-temperature environment over the first 100 years is seen as stabilizing, since it can recrystallize radiation-induced metamicts. The synthetic-rock stabilization technique is found to be essentially feasible, and improvements are suggested, including the substitution of nepheline with freudenbergite and priderite for alkaline-waste stabilization, the maintenance of low oxygen fugacity, and the dilution of the synthetic-rock pellets into an inert medium.

Mineralogy, Petrology and Oxygen Fugacity of the LaPaz Icefield Lunar Basaltic Meteorites and the Origin of Evolved Lunar Basalts

NASA Technical Reports Server (NTRS)

Collins, S. J.; Righter, K.; Brandon, A. D.

2005-01-01

LAP 02205 is a 1.2 kg lunar mare basalt meteorite found in the Lap Paz ice field of Antarctica in 2002 [1]. Four similar meteorites were also found within the same region [1] and all five have a combined mass of 1.9 kg (LAP 02224, LAP 02226, LAP 02436 and LAP 03632, hereafter called the LAP meteorites). The LAP meteorites all contain a similar texture, mineral assemblage, and composition. A lunar origin for these samples comes from O isotopic data for LAP 02205 [1], Fe/Mn ratios of pyroxenes [1-5], and the presence of distinct lunar mineralogy such as Fe metal and baddeleyite. The LAP meteorites may represent an area of the Moon, which has never been sampled by Apollo missions, or by other lunar meteorites. The data from this study will be used to compare the LAP meteorites to Apollo mare basalts and lunar basaltic meteorites, and will ultimately help to constrain their origin.

Geochemical differences of magnetite from the Algoma- and Superior- type banded iron formations based on in situ LA-ICP-MS analysis

NASA Astrophysics Data System (ADS)

Moon, I.; Lee, I.; Park, J. W.; Yang, X.

2017-12-01

Precambrian banded iron formations (BIFs) have been highly attractive study issues for decades about their genesis. Recently, more detailed geochemical studies have been conducted on mineral chemistry of magnetite using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Magnetite geochemistry enables us to constrain the physicochemical controlling factors for abundance of trace elements in magnetite and understand depositional environment of BIFs. In this study, we provide results of magnetite trace elemental features from two representative types of BIFs which are Algoma- and Superior- type BIF in the world, with aims to understand systematic differences in magnetite compositions between Algoma- and Superior- type BIF. The magnetites are divided into two groups according to their Al, Mn, Ti, V, and Ni concentration. The magnetites from the Algoma-type BIFs are more enriched in trace elements than those from the Superior-type. The geochemical differences are caused by difference precipitation condition including oxygen fugacity, temperature and fluid source.

Degassing of reduced carbon from planetary basalts

PubMed Central

Wetzel, Diane T.; Rutherford, Malcolm J.; Jacobsen, Steven D.; Hauri, Erik H.; Saal, Alberto E.

2013-01-01

Degassing of planetary interiors through surface volcanism plays an important role in the evolution of planetary bodies and atmospheres. On Earth, carbon dioxide and water are the primary volatile species in magmas. However, little is known about the speciation and degassing of carbon in magmas formed on other planets (i.e., Moon, Mars, Mercury), where the mantle oxidation state [oxygen fugacity (fO2)] is different from that of the Earth. Using experiments on a lunar basalt composition, we confirm that carbon dissolves as carbonate at an fO2 higher than -0.55 relative to the iron wustite oxygen buffer (IW-0.55), whereas at a lower fO2, we discover that carbon is present mainly as iron pentacarbonyl and in smaller amounts as methane in the melt. The transition of carbon speciation in mantle-derived melts at fO2 less than IW-0.55 is associated with a decrease in carbon solubility by a factor of 2. Thus, the fO2 controls carbon speciation and solubility in mantle-derived melts even more than previous data indicate, and the degassing of reduced carbon from Fe-rich basalts on planetary bodies would produce methane-bearing, CO-rich early atmospheres with a strong greenhouse potential. PMID:23569260

Mineralogy and Chemistry of Continental-like Calc-alkaline Plutons on Adak Island in the Oceanic Aleutian arc: Emplacement and Implications for the Eocene History of the Arc

NASA Astrophysics Data System (ADS)

Kay, S. M.; Citron, G. P.; Kay, R. W.; Jicha, B. R.

2016-12-01

The mineralogy and chemistry of the 15 km wide latest Eocene/Oligocene (34.6-30.9 Ma) Hidden Bay and Miocene (14.2-13.7 Ma) Kagalaska calc-alkaline plutons on Adak and Kagalaska Islands in the central Aleutian arc provide insight into the arc's Tertiary evolution. The plutons intrude the moderately light REE-enriched tholeiitic basaltic to mafic andesites of the Eocene Finger Bay Formation. The Hidden Bay pluton largely consists of mid to high-K amphibole-bearing cumulate diorite (53-55% SiO2) and granodiorite (57-64% & 61-64% SiO2) with lesser amounts of gabbro (50-52%), leucogranodiorite (67-69% SiO2) and aplite (76-77% SiO2). REE patterns indicate important fractionation of amphibole and plagioclase with pyroxene and olivine present in mafic units and orthopyroxene, biotite, quartz and K-feldspar in silicic units. Quartz, K-feldspar and biotite occur in interstices in most units. Plagioclase cores are mostly from AN40-60 with K-feldspar at OR95-OR98. Fractionation of homogeneous gabbros with high-Al basalt compositions (51% SiO2) best explains the chemistry and mineralogy of the Hidden Bay pluton. The presence of pargasitic amphibole in medium to course grained diorite cumulates indicates fractionation at 12-14 km at 950-1000°C with 5.5% H2O and a NNO oxygen fugacity. Two pyroxene, Mg hornblende and Ti-Zr zircon thermometers for granodiorite and late crystallized areas record temperatures of 850-750°C at 3.5- 4.5 % H2O and a NNO+2 oxygen fugacity. The Kagalaska pluton differs in being more calc-alkaline (alkali-rich), more bimodal in being dominated by amphibole-bearing gabbro and granodiorite/ leucogranodiorite (63-68% SiO2) and in requiring more amphibole fractionation. Both plutons have compositions approaching continental crust and characteristics that are similar to plutons intruded into continental crust. Differences with the Finger Bay Volcanic are best explained by thickening of the crust to near modern thicknesses ( 35-38 km) by the time of pluton emplacement. Residual garnet in the source required by REE patterns in some samples as well as depleted isotopic signatures are best explained by oceanic crust removed by forearc subduction erosion entering the mantle wedge as magmatism waned and the arc migrated northward after the emplacement of the plutons.

CO2 content of andesitic melts at graphite-saturated upper mantle conditions with implications for redox state of oceanic basalt source regions and remobilization of reduced carbon from subducted eclogite

NASA Astrophysics Data System (ADS)

Eguchi, James; Dasgupta, Rajdeep

2017-03-01

We have performed experiments to determine the effects of pressure, temperature and oxygen fugacity on the CO2 contents in nominally anhydrous andesitic melts at graphite saturation. The andesite composition was specifically chosen to match a low-degree partial melt composition that is generated from MORB-like eclogite in the convective, oceanic upper mantle. Experiments were performed at 1-3 GPa, 1375-1550 °C, and fO2 of FMQ -3.2 to FMQ -2.3 and the resulting experimental glasses were analyzed for CO2 and H2O contents using FTIR and SIMS. Experimental results were used to develop a thermodynamic model to predict CO2 content of nominally anhydrous andesitic melts at graphite saturation. Fitting of experimental data returned thermodynamic parameters for dissolution of CO2 as molecular CO2: ln( K 0) = -21.79 ± 0.04, Δ V 0 = 32.91 ± 0.65 cm3mol-1, Δ H 0 = 107 ± 21 kJ mol-1, and dissolution of CO2 as CO3 2-: ln (K 0 ) = -21.38 ± 0.08, Δ V 0 = 30.66 ± 1.33 cm3 mol-1, Δ H 0 = 42 ± 37 kJ mol-1, where K 0 is the equilibrium constant at some reference pressure and temperature, Δ V 0 is the volume change of reaction, and Δ H 0 is the enthalpy change of reaction. The thermodynamic model was used along with trace element partition coefficients to calculate the CO2 contents and CO2/Nb ratios resulting from the mixing of a depleted MORB and the partial melt of a graphite-saturated eclogite. Comparison with natural MORB and OIB data suggests that the CO2 contents and CO2/Nb ratios of CO2-enriched oceanic basalts cannot be produced by mixing with partial melts of graphite-saturated eclogite. Instead, they must be produced by melting of a source containing carbonate. This result places a lower bound on the oxygen fugacity for the source region of these CO2-enriched basalts, and suggests that fO2 measurements made on cratonic xenoliths may not be applicable to the convecting upper mantle. CO2-depleted basalts, on the other hand, are consistent with mixing between depleted MORB and partial melts of a graphite-saturated eclogite. Furthermore, calculations suggest that eclogite can remain saturated in graphite in the convecting upper mantle, acting as a reservoir for C.

The P-T-fO 2 stability of deerite, Fe{12/2+}Fe{6/3+}[Si12O40](OH)10

NASA Astrophysics Data System (ADS)

Lattard, Dominique; Le Breton, Nicole

1994-02-01

New equilibrium experiments have been performed in the 20 27 kbar range to determine the upper thermal stability limit of endmember deerite, Fe{12/2+}Fe{6/3+}[Si12O40](OH)10. In this pressure range, the maximum thermal stability limit is represented by the oxygen-conserving reaction: deerite(De)=9 ferrosilite(Fs)+3 magnetite(Mag)+3 quartz(Qtz)+5 H2O(W) (1). Under the oxygen fugacities of the Ni-NiO buffer the breakdown-reduction reaction: De=12 Fs+2 Mag+5 W+1/2 O2 (10) takes place at lower temperatures (e.g. ΔT=63° at 27 kbar). The experimental brackets can be fitted using thermodynamic data for ferrosilite, magnetite and quartz from Berman (1988) and the following 1 bar, 298 K data for deerite (per gfw): Vo=55.74 J.bar-1, So=1670 J.K-1, ΔH{f/o}=-18334 kJ, α=2.5x10-5K-1, β=-0.18x10-5 bar-1. Using these data in conjunction with literature data on coesite, grunerite, minnesotaite, and greenalite, the P-T stability field of endmember deerite has been calculated for P s= P H 2O. This field is limited by 6 univariant oxygenconserving dehydration curves, from which three have positive d P/d T slopes, the other three negative slopes. The lower pressure end of the stability field of endmember deerite is thus located at an invariant point at 250±70°C and 10+-1.5 kbar. Deerite rich in the endmember can thus appear only in environments with geothermal gradients lower than 10°C/km and at pressures higher than about 10 kbar, which is in agreement with 4 out of 5 independent P-T estimates for known occurrences. The presence of such deerite places good constraints on minimum pressure and maximum temperature conditions. From log f O 2- T diagrams constructed with the same data base at different pressures, it appears that endmember deerite is, at temperatures near those of its upper stability limit, stable only over a narrow range of oxygen fugacities within the magnetite field. With decreasing temperatures, deerite becomes stable towards slightly higher oxygen fugacities but reaches the hematite field only at temperatures more than 200°C lower than the upper stability limit. This practically precludes the coexistence deerite-hematite with near-endmember deerite in natural environments.

Redox state of earth's upper mantle from kimberlitic ilmenites

NASA Technical Reports Server (NTRS)

Haggerty, S. E.; Tompkins, L. A.

1983-01-01

Temperatures and oxygen fugacities are reported on discrete ilmenite nodules in kimberlites from West Africa which demonstrate that the source region in the upper mantle is moderately oxidized, consistent with other nodule suites in kimberlites from southern Africa and the United States. A model is presented for a variety of tectonic settings, proposing that the upper mantle is profiled in redox potential, oxidized in the fertile asthenosphere but reduced in the depleted lithosphere.

Europium anomaly in plagioclase feldspar - Experimental results and semiquantitative model.

NASA Technical Reports Server (NTRS)

Weill, D. F.; Drake, M. J.

1973-01-01

The partition of europium between plagioclase feldspar and magmatic liquid is considered in terms of the distribution coefficients for divalent and trivalent europium. A model equation is derived giving the europium anomaly in plagioclase as a function of temperature and oxygen fugacity. The model explains europium anomalies in plagioclase synthesized under controlled laboratory conditions as well as the variations of the anomaly observed in natural terrestrial and extraterrestrial igneous rocks.

Europium anomaly in plagioclase feldspar: experimental results and semiquantitative model.

PubMed

Weill, D F; Drake, M J

1973-06-08

The partition of europium between plagioclase feldspar and magmatic liquid is considered in terms of the distribution coefficients for divalent and trivalent europium. A model equation is derived giving the europium anomaly in plagioclase as a function of temperature and oxygen fugacity. The model explains europium anomalies in plagioclase synthesized under controlled laboratory conditions as well as the variations of the anomaly observed in natural terrestrial and extraterrestrial igneous rocks.

Experimental Behavior of Sulfur Under Primitive Planetary Differentiation Processes, the Sulfide Formations in Enstatite Meteorites and Implications for Mercury.

NASA Technical Reports Server (NTRS)

Malavergne, V.; Brunet, F.; Righter, K.; Zanda, B.; Avril, C.; Borensztajn, S.; Berthet, S.

2012-01-01

Enstatite meteorites are the most reduced naturally-occuring materials of the solar system. The cubic monosulfide series with the general formula (Mg,Mn,Ca,Fe)S are common phases in these meteorite groups. The importance of such minerals, their formation, composition and textural relationships for understanding the genesis of enstatite chondrites (EC) and aubrites, has long been recognized (e.g. [1]). However, the mechanisms of formation of these sulfides is still not well constrained certainly because of possible multiple ways to produce them. We propose to simulate different models of formation in order to check their mineralogical, chemical and textural relevancies. The solubility of sulfur in silicate melts is of primary interest for planetary mantles, particularly for the Earth and Mercury. Indeed, these two planets could have formed, at least partly, from EC materials (e.g. [2, 3, 4]). The sulfur content in silicate melts depends on the melt composition but also on pressure (P), temperature (T) and oxygen fugacity fO2. Unfortunately, there is no model of general validity in a wide range of P-T-fO2-composition which describes precisely the evolution of sulfur content in silicate melts, even if the main trends are now known. The second goal of this study is to constrain the sulfur content in silicate melts under reducing conditions and different temperatures.

Petrology of peridotite xenoliths from the Miocene alkaline basalt from Baegryeong Island

NASA Astrophysics Data System (ADS)

Park, G. Y.; Kim, E.; Yang, K.

2017-12-01

Peridotite xenoliths occurring in late Miocene intraplate alkaline basalt from Baegryeong Island, west-northern part of the Korean peninsula, are mainly anhydrous spinel lherzolites. Their textures and chemical compositions give a deep insight for upper mantle. This study presents the results of modal, major composition of minerals and trace composition of clinopyroxene. The xenoliths display coarse grained protogranular through inequigranular to cumulate textures, grading into each other. They often show well-developed annealed textures and contain left-over olivine grains within orthopyroxene, suggesting that they went through static(±dynamic) recrystallization. The constituent minerals are compositionally homogeneous and appear to be equilibrated. The xenoliths are characterized by the high Mg#[=100×Mg/(Mg+Fetotal) atomic ratio] of olivine, orthopyroxene and clinopyroxene (89-93) and the Cr#[=100×Cr/(Cr+Al) atomic ratio] of spinel (9-15). The calculated equilibrium temperatures and oxygen fugacities resulted in 920-1070°C and ΔfO2 (QFM) = -1.5 -0.5, respectively. Clinopyroxenes of the xenoliths are mostly enriched in incompatible trace elements, exhibiting three types of REE patterns such as LREE-depleted, LREE-enriched and a enrichment in La over Ce, and depletion in high field strength elements(HFSE; Nb-Ta, Zr-Hf, Ti). From these trace element signatures, we thus propose the Baegryeong peridotite xenoliths represent residues left after early melt extraction, which was subsequently subjected to different degrees of modal/cryptic metasomatism by residual slab-derived, silica- and LREE-enriched fluids (or melts).

Volcanism on Mars controlled by early oxidation of the upper mantle

NASA Astrophysics Data System (ADS)

Tuff, J.; Wade, J.; Wood, B. J.

2013-06-01

Detailed information about the chemical composition and evolution of Mars has been derived principally from the SNC (shergottite-nakhlite-chassignite) meteorites, which are genetically related igneous rocks of Martian origin. They are chemically and texturally similar to terrestrial basalts and cumulates, except that they have higher concentrations of iron and volatile elements such as phosphorus and chlorine and lower concentrations of nickel and other chalcophile (sulphur-loving) elements. Most Martian meteorites have relatively young crystallization ages (1.4 billion years to 180 million years ago) and are considered to be derived from young, lightly cratered volcanic regions, such as the Tharsis plateau. Surface rocks from the Gusev crater analysed by the Spirit rover are much older (about 3.7 billion years old) and exhibit marked compositional differences from the meteorites. Although also basaltic in composition, the surface rocks are richer in nickel and sulphur and have lower manganese/iron ratios than the meteorites. This has led to doubts that Mars can be described adequately using the `SNC model'. Here we show, however, that the differences between the compositions of meteorites and surface rocks can be explained by differences in the oxygen fugacity during melting of the same sulphur-rich mantle. This ties the sources of Martian meteorites to those of the surface rocks through an early (>3.7 billion years ago) oxidation of the uppermost mantle that had less influence on the deeper regions, which produce the more recent volcanic rocks.

V, Cr, and Mn in the Earth, Moon, EPB, and SPB and the origin of the Moon: Experimental studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Drake, M.J.; Capobianco, C.J.; Newsom, H.E.

1989-08-01

The abundances of V, Cr, and Mn inferred for the mantles of the Earth and Moon decrease in that order and are similar, but are distinct from those inferred for the mantles of the Eucrite Parent Body (EPB) and Shergottite Parent Body (SPB). This similarity between Earth and Moon has been used to suggest that the Moon is derived substantially or entirely from Earth mantle material following terrestrial core formation. To test this hypothesis, the authors have determined the partitioning of V, Cr, and Mn between solid iron metal, S-rich metallic liquid, and synthetic basaltic silicate liquid at 1,260{degree}C andmore » one bar pressure. The sequence of compatibility in the metallic phases is Cr > V > Mn at high oxygen fugacity and V > Cr > Mn at low oxygen fugacities. Solubilities in liquid metal always exceed solubilities in solid metal. These partition coefficients suggest that the abundances of V, Cr, and Mn do not reflect core formation in the Earth. Rather, they are consistent with the relative volatilities of these elements. The similarity in the depletion patterns of V, Cr, and Mn inferred for the mantles of the Earth and Moon is a necessary, but not sufficient, condition for the Moon to have been derived wholly or in part from the Earth's mantle.« less

Oxygen stoichiometry, phase stability, and thermodynamic behavior of the lead-doped Bi-2223 and Ag/Bi-2223 systems

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Hash, M.; Tani, B. S.; Luo, J. S.; Maroni, V. A.

1995-02-01

Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made in the lead-doped Bi-2223 superconducting system in the temperature range 700-815°C by means of an oxygen titration technique that employs an yttria-stabilized zirconia electrolyte. The results of our studies indicate that processing or annealing lead-doped Bi-2223 at temperatures ranging from 750 to 815°C and at oxygen partial pressures ranging from ∼ 0.02 to 0.2 atm should preserve Bi-2223 as essentially single-phase material. Thermodynamic assessments of the partial molar quantities ΔS¯( O2) andΔH¯( O2) indicate that the plateau regions in the plot of oxygen partial pressure versus oxygen stoichiometry ( x) can be represented by the diphasic CuOCu 2O system. In accord with the EMF measurements, it was found that lead-doped Bi-2223 in a silver sheath is stable at 815°C for oxygen partial pressures between 0.02 and 0.13 atm.

A thermodynamic study of pyrite and pyrrhotite

USGS Publications Warehouse

Toulmin, P.; Barton, P.B.

1964-01-01

Through the use of the electrum-tarnish method the following equation has been found to interrelate the composition of pyrrhotite, fugacity of sulfur, and temperature: In this equation fs2 is the fugacity of sulfur relative to the ideal diatomic gas at 1 atm, N is the mol fraction of FeS in pyrrhotite (in the system FeS-S2), and T the absolute temperature. The experimental uncertainty in the equation is 0-003 in N. The activity of FeS (aFeS) in pyrrhotite relative to the pure substance at the temperature of consideration follows from the above equation by virtue of the Gibbs-Duhem relation; it is given by:. The electrum-tarnish method has permitted us to determine the fs2 vs. T curve for the univariant assemblage pyrrhotite-pyrite-vapor from 743 to 325??C. Our determinations of the composition of pyrrhotite are in excellent agreement with the results of Arnold. The activity of FeS in pyrite-saturated pyrrhotite is very different from unity, a fact that greatly influences the interpretation of some other phase equilibrium studies involving pyrrhotite and their application to sulfide mineral assemblages, but has little effect on the more general calculations of composition of hydrothermal or magmatic fluids. Pressure effects calculated from available volumetric data on the phases are small. ?? 1964.

Explosive volcanism and the graphite-oxygen fugacity buffer on the parent asteroid(s) of the ureilite meteorites

NASA Technical Reports Server (NTRS)

Warren, Paul H.; Kallemeyn, Gregory W.

1992-01-01

A new model of the production of the uniformly low plagioclase and Al contents of ureilites is proposed. It is argued that those contents are consequences of widespread explosive volcanism during the evolution of the parent asteroid(s). It is noted that the great abundance of graphite on the ureilite asteroid(s) made them ideal sites for explosive volcanism driven by oxidation of graphite in partial melts ascending within the asteroid(s).

A More Reduced Mantle Source for Enriched Shergottites; Insights from the Olivine-Phyric Shergottite Lar 06319

NASA Technical Reports Server (NTRS)

Peslier, A. H.; Hnatyshin, D.; Herd, C. D. K.; Walton, E. L.; Brandon, A. D.; Lapen, T. J.; Shafer, J.

2010-01-01

A detailed petrographic study of melt inclusions and Cr-Fe-Ti oxides of LAR 06319 leads to two main conclusions: 1) this enriched oxidized olivine- phyric shergottite represents nearly continuous crystallization of a basaltic shergottite melt, 2) the melt became more oxidized during differentiation. The first crystallized mineral assemblages record the oxygen fugacity which is closest to that of the melt s mantle source, and which is lower than generally attributed to the enriched shergottite group.

Lunar and Planetary Science XXXVI, Part II

NASA Technical Reports Server (NTRS)

2005-01-01

Some topics covered: Implications of internal fragmentation on the structure of comets; Atmospheric excitation of mars polar motion; Dunite viscosity dependence on oxygen fugacity; Cross profile and volume analysis of bahram valles on mars; Calculations of the fluxes of 10-250 kV lunar leakage gamma rays; Alluvian fans on mars; Investigating the sources of the apollo 14 high-Al mare basalts; Relationship of coronae, regional plains and rift zones on venus; and Chemical differentiation and internal structure of europa and callisto.

Element migration of pyrites during ductile deformation of the Yuleken porphyry Cu deposit (NW-China)

USGS Publications Warehouse

Hong, Tao; Xu, Xing-Wang; Gao, Jun; Peters, Stephen; Li, Jilei; Cao, Mingjian; Xiang, Peng; Wu, Chu; You, Jun

2017-01-01

The strongly deformed Yuleken porphyry Cu deposit (YPCD) occurs in the Kalaxiangar porphyry Cu belt (KPCB), which occupies the central area of the Central Asian Orogenic Belt (CAOB) between the Sawu’er island arc and the Altay Terrane in northern Xinjiang. The YPCD is one of several typical subduction-related deposits in the KPCB, which has undergone syn-collisional and post-collisional metallogenic overprinting. The YPCD is characterized by three pyrite-forming stages, namely a hydrothermal stage A (Py I), a syn-ductile deformation stage B (Py II) characterized by Cu-Au enrichment, and a fracture-filling stage C (Py III). In this study, we conducted systematic petrographic and geochemical studies of pyrites and coexist biotite, which formed during different stages, in order to constrain the physicochemical conditions of the ore formation. Euhedral, fragmented Py I has low Pb and high Te and Se concentration and Ni contents are low with Co/Ni ratios mostly between 1 and 10 (average 9.00). Py I is further characterized by enrichments of Bi, As, Ni, Cu, Te and Se in the core relative to the rim domains. Anhedral round Py II has moderate Co and Ni contents with high Co/Ni ratios >10 (average 95.2), and average contents of 46.5 ppm Pb and 5.80 ppm Te. Py II is further characterized by decreasing Bi, Cu, Pb, Zn, Ag, Te, Mo, Sb and Au contents from the rim to the core domains. Annealed Py III has the lowest Co content of all pyrite types with Co/Ni ratios mostly <0.1 (average 1.33). Furthermore, Py III has average contents of 3.31 ppm Pb, 1.33 ppm Te and 94.6 ppm Se. In addition, Fe does not correlate with Cu and S in the Py I and Py III, while Py II displays a negative correlation between Fe and Cu as well as a positive correlation between Fe and S. Therefore, pyrites which formed during different tectonic regimes also have different chemical compositions. Biotite geothermometer and oxygen fugacity estimates display increasing temperatures and oxygen fugacities from stage A to stage B, while temperature and oxygen fugacities decrease from stage B to stage C. The Co/Ni ratio of pyrite depends discriminates between the different mineralizing stages in the Yuleken porphyry copper deposit: Py II, associated with the deformation stage B and Cu-enrichment, shows higher Co/Ni ratios and enrichments of Pb, Zn, Mo, Te and Sb than the pyrites formed during the other two stages. The Co/Ni ratio of pyrite can not only apply to discriminate the submarine exhalative, magmatic or sedimentary origins for ore deposits but also can distinguish different ore-forming stages in a single porphyry Cu deposit. Thus, Co/Ni ratio of pyrites may act as an important exploration tool to distinguish pyrites from Cu-rich versus barren area. Furthermore, the distribution of Cu, Mo, Pb, Au, Bi, Sb and Zn in the variably deformed pyrite is proportional to the extent of deformation of the pyrites, indicating in accordance with variable physicochemical conditions different element migration behavior during the different stages of deformation and, thus, mineralisation.

Vapor pressure and vapor fractionation of silicate melts of tektite composition

USGS Publications Warehouse

Walter, Louis S.; Carron, M.K.

1964-01-01

The total vapor pressure of Philippine tektite melts of approximately 70 per cent silica has been determined at temperatures ranging from 1500 to 2100??C. This pressure is 190 ?? 40 mm Hg at 1500??C, 450 ?? 50 mm at 1800??C and 850 ?? 70 mm at 2100?? C. Determinations were made by visually observing the temperature at which bubbles began to form at a constant low ambient pressure. By varying the ambient pressure, a boiling point curve was constructed. This curve differs from the equilibrium vapor pressure curve due to surface tension effects. This difference was evaluated by determining the equilibrium bubble size in the melt and calculating the pressure due to surface tension, assuming the latter to be 380 dyn/cm. The relative volatility from tektite melts of the oxides of Na, K, Fe, Al and Si has been determined as a function of temperature, total pressure arid roughly, of oxygen fugacity. The volatility of SiO2 is decreased and that of Na2O and K2O is increased in an oxygen-poor environment. Preliminary results indicate that volatilization at 2100??C under atmospheric pressure caused little or no change in the percentage Na2O and K2O. The ratio Fe3 Fe2 of the tektite is increased in ambient air at a pressure of 9 ?? 10-4 mm Hg (= 106.5 atm O2, partial pressure) at 2000??C. This suggests that tektites were formed either at lower oxygen pressures or that they are a product of incomplete oxidation of parent material with a still lower ferricferrous ratio. ?? 1964.

Core formation in the shergottite parent body and comparison with the earth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Treiman, A.H.; Jones, J.H.; Drake, M.J.

1987-03-30

The mantle of the shergottite parent body (SPB) is depleted relative to the bulk SPB in siderophile and chalcophile elements; these elements are inferred to reside in the SPB's core. Our chemical model of these depletions rests on a physically plausible process of segregation of partially molten metal form partially molten silicates as the SPB grows and is heated above silicate and metallic solidi during accretion. Metallic and silicate phases equilibrate at low pressures as new material is accreted to the SPB surface. Later movement of the metallic phases to the planet's center is so rapid that high-pressure equilibration ismore » insignificant. Partitioning of siderophile and chalcophile elements among solid and liquid metal and silicate determines their abundances in the SPB mantle. Using partition coefficients and the SPB mantle composition determined in earlier studies, we model the abundances of Ag, Au, Co, Ga, Mo, Ni, P, Re, S, and W with free parameters being oxygen fugacity, proportion of solid metal formed, proportion of metallic liquid formed, and proportion of silicate that is molten.« less

Water and the Interior Structure of Terrestrial Planets and Icy Bodies

NASA Astrophysics Data System (ADS)

Monteux, J.; Golabek, G. J.; Rubie, D. C.; Tobie, G.; Young, E. D.

2018-02-01

Water content and the internal evolution of terrestrial planets and icy bodies are closely linked. The distribution of water in planetary systems is controlled by the temperature structure in the protoplanetary disk and dynamics and migration of planetesimals and planetary embryos. This results in the formation of planetesimals and planetary embryos with a great variety of compositions, water contents and degrees of oxidation. The internal evolution and especially the formation time of planetesimals relative to the timescale of radiogenic heating by short-lived 26Al decay may govern the amount of hydrous silicates and leftover rock-ice mixtures available in the late stages of their evolution. In turn, water content may affect the early internal evolution of the planetesimals and in particular metal-silicate separation processes. Moreover, water content may contribute to an increase of oxygen fugacity and thus affect the concentrations of siderophile elements within the silicate reservoirs of Solar System objects. Finally, the water content strongly influences the differentiation rate of the icy moons, controls their internal evolution and governs the alteration processes occurring in their deep interiors.

Core formation in the shergottite parent body and comparison with the earth

NASA Technical Reports Server (NTRS)

Treiman, Allan H.; Jones, John H.; Drake, Michael J.

1987-01-01

Abundances of elements in shergottite, nakhlite, and Chassigny meteorites which originated on a single planet, the shergottite parent body (SPB), were examined with the aim of elucidating the chemical conditions of metal separation and core formation in the SPB and of testing present models of planetary core formation. Using partition coefficients and the SPB mantle composition determined in earlier studies, the abundances of Ag, Au, Co, Ga, Mo, Ni, P, Re, S, and W were modeled, with free parameters being oxygen fugacity, proportion of solid metal formed, proportion of metallic liquid formed, and proportion of silicate that is molten. It is shown that the abundances of all elements (except Mo) could be reproduced using models with these four free parameters. In contrast to the SPB, an equivalent model used to predict element abundances in the earth's mantle was shown by Jones and Drake (1986) to be inadequate; there is at present no hypothesis capable of quantitatively reproducing the elemental abundances of the earth's mantle. The contrast suggests that these two terrestrial planets (assuming that the SPB is Mars) may have accreted or differentiated differently.

Sulfur and oxygen isotopic systematics of the 1982 eruptions of El Chichón Volcano, Chiapas, Mexico

USGS Publications Warehouse

Rye, R.O.; Luhr, J.F.; Wasserman, M.D.

1984-01-01

Thermometers based on sulfur and oxygen isotopic compositions of anhydrite, pyrrhotite, titanomagnetite, and plagioclase crystals from fresh pumices of the 1982 eruptions of El Chichón Volcano indicate a pre-eruption temperature of 810 ± 40°C, confirming textural evidence that the anhydrite precipitated directly from the melt. The isotopic composition of sulfate leached from fresh ashfall samples shows it to be a mixture of anhydrite microphenocrysts and adsorbed sulfate derived from oxidized sulfur (SO2) in the eruption plume. The leachate data show no evidence for rapid oxidation of significant amounts of H2S in the eruption cloud even though the fugacity ratio of H2S/SO2 in the gas phase of the magma was >400. This may indicate kinetic inhibition of H2S to SO2 conversion in the eruption cloud. Prior to eruption, the magma contained an estimated 2.6 wt. % sulfur (as SO3). The estimated δ 34S of the bulk magma is 5.8‰. Such a high value may reflect assimilation of 34S-enriched evaporites or the prior loss of 34S-depleted H2S to a fluid or gas phase during formation of a small prophyry-type hydrothermal system or ore deposit. In either case, the original magma must have been very sulfur rich. It is likely that the initial high sulfur content of the magma and at least some of its 34S enrichment reflects involvement of subducted volcanogenic massive sulfides deposits during Benioff-zone partial melting. Isotopic data on mineralized, accidental lithic fragments support the possible development of a porphyry-type system at El Chichón.

Iron isotopes in ancient and modern komatiites: Evidence in support of an oxidised mantle from Archean to present

NASA Astrophysics Data System (ADS)

Hibbert, K. E. J.; Williams, H. M.; Kerr, A. C.; Puchtel, I. S.

2012-03-01

The mantle of the modern Earth is relatively oxidised compared to the initially reducing conditions inferred for core formation. The timing of the oxidation of the mantle is not conclusively resolved but has important implications for the timing of the development of the hydrosphere and atmosphere. In order to examine the timing of this oxidation event, we present iron isotope data from three exceptionally well preserved komatiite localities, Belingwe (2.7 Ga), Vetreny (2.4 Ga) and Gorgona (0.089 Ga). Measurements of Fe isotope compositions of whole-rock samples are complemented by the analysis of olivine, spinel and pyroxene separates. Bulk-rock and olivine Fe isotope compositions (δ57Fe) define clear linear correlations with indicators of magmatic differentiation (Mg#, Cr#). The mean Fe isotope compositions of the 2.7-2.4 Ga and 0.089 Ga samples are statistically distinct and this difference can be explained by greater extent of partial melting represented by the older samples and higher mantle ambient temperatures in the Archean and early Proterozoic relative to the present day. Significantly, samples of all ages define continuous positive linear correlations between bulk rock δ57Fe and V/Sc and δ57Fe and V, and between V/Sc and V with TiO2, providing evidence for the incompatible behaviour of V (relative to Sc) and of isotopically heavy Fe. Partial melting models calculated using partition coefficients for V at oxygen fugacities (fO2s) of 0 and + 1 relative to the fayalite-magnetite-quartz buffer (FMQ) best match the data arrays, which are defined by all samples, from late Archean to Tertiary. These data, therefore, provide evidence for komatiite generation under moderately oxidising conditions since the late Archean, and argue against a change in mantle fO2 concomitant with atmospheric oxygenation at ~ 2.4 Ga.

Redox processes in subducting oceanic crust recorded by sulfide-bearing high-pressure rocks and veins (SW Tianshan, China)

NASA Astrophysics Data System (ADS)

Li, Ji-Lei; Gao, Jun; Klemd, Reiner; John, Timm; Wang, Xin-Shui

2016-09-01

The oxidized nature of the sub-arc mantle and hence arc magmas is generally interpreted as a result of the migration of subduction-related oxidizing fluids or melts from the descending slab into the mantle wedge. This is of particular importance seeing that the oxidization state of sub-arc magmas seems to play a key role in the formations of arc-related ore deposits. However, direct constraints on the redox state of subducted oceanic crust are sparse. Here, we provide a detailed petrological investigation on sulfide- and oxide-bearing eclogites, blueschists, micaschists, eclogite-facies and retrograde veins from the Akeyazi high-pressure (HP) terrane (NW China) in order to gain insight into the redox processes recorded in a subducting oceanic slab. Sulfides in these rocks are mainly pyrite and minor pyrrhotite, chalcopyrite, bornite, molybdenite, sphalerite and chalcocite, including exsolution textures of bornite-chalcopyrite intergrowth. Magnetite, ilmenite and pyrite occur as inclusions in garnet, whereas sulfides are dominant in the matrix. Large pyrite grains in the matrix contain inclusions of garnet, omphacite and other HP index minerals. However, magnetite replacing pyrite textures are commonly observed in the retrograded samples. The eclogite-facies and retrograde veins display two fluid events, which are characterized by an early sulfide-bearing and a later magnetite-bearing mineral assemblage, respectively. Textural and petrological evidences show that the sulfides were mainly formed during HP metamorphism. Mineral assemblage transitions reveal that the relative oxygen fugacity of subducted oceanic crust decreases slightly with increasing depths. However, according to oxygen mass balance calculations, based on the oxygen molar quantities ( nO2), the redox conditions remain constant during HP metamorphism. At shallow levels (<60 km) in the subduction channel, interaction with oxidized fluid seems to have caused an increase of the oxygen fugacity and the oxidation state of exhuming HP rocks. This study suggests that oxygen components are not released in significant amounts during HP metamorphism of subducted oceanic crust and, thus, cannot be responsible for oxidizing the mantle wedge and increasing the oxidation state of sub-arc mantle melts.

Hydrothermal stability of adenine under controlled fugacities of N2, CO2 and H2.

PubMed

Franiatte, Michael; Richard, Laurent; Elie, Marcel; Nguyen-Trung, Chinh; Perfetti, Erwan; LaRowe, Douglas E

2008-04-01

An experimental study has been carried out on the stability of adenine (one of the five nucleic acid bases) under hydrothermal conditions. The experiments were performed in sealed autoclaves at 300 degrees C under fugacities of CO(2), N(2) and H(2) supposedly representative of those in marine hydrothermal systems on the early Earth. The composition of the gas phase was obtained from the degradation of oxalic acid, sodium nitrite and ammonium chloride, and the oxidation of metallic iron. The results of the experiments indicate that after 200 h, adenine is still present in detectable concentration in the aqueous phase. In fact, the concentration of adenine does not seem to be decreasing after approximately 24 h, which suggests that an equilibrium state may have been established with the inorganic constituents of the hydrothermal fluid. Such a conclusion is corroborated by independent thermodynamic calculations.

Melting of the Primitive Mercurian Mantle, Insights into the Origin of Its Surface Composition

NASA Technical Reports Server (NTRS)

Boujibar, A.; Righter, K.; Rapp, J. F.; Ross, D. K.; Pando, K. M.; Danielson, L. R.; Fontaine, E.

2016-01-01

Recent findings of the MESSENGER mission on Mercury have brought new evidence for its reducing nature, widespread volcanism and surface compositional heteregeneity. MESSENGER also provided major elemental ratios of its surface that can be used to infer large-scale differentiation processes and the thermal history of the planet. Mercury is known as being very reduced, with very low Fe-content and high S and alkali contents on its surface. Its bulk composition is therefore likely close to EH enstatite chondrites. In order to elucidate the origin of the chemical diversity of Mercury's surface, we determined the melting properties of EH enstatite chondrites, at pressures between 1 bar and 3 GPa and oxygen fugacity of IW-3 to IW-5, using piston-cylinder experiments, combined with a previous study on EH4 melting at 1 bar. We found that the presence of Ca-rich sulfide melts induces significant decrease of Ca-content in silicate melts at low pressure and low degree of melting (F). Also at pressures lower than 3 GPa, the SiO2-content decreases with F, while it increases at 3 GPa. This is likely due to the chemical composition of the bulk silicate which has a (Mg+Fe+Ca)/Si ratio very close to 1 and to the change from incongruent to congruent melting of enstatite. We then tested whether the various chemical compositions of Mercury's surface can result from mixing between two melting products of EH chondrites. We found that the majority of the geochemical provinces of Mercury's surface can be explained by mixing of two melts, with the exception of the High-Al plains that require an Al-rich source. Our findings indicate that Mercury's surface could have been produced by polybaric melting of a relatively primitive mantle.

Comparative Planetary Mineralogy: V/(Cr+Al) Systematics in Chromites as an Indicator of Relative Oxygen Fugacity

NASA Technical Reports Server (NTRS)

Papike, J. J.; Kamer, J. M.; Shearer, C. K.

2004-01-01

As our contribution to the new "Oxygen in the Solar System" initiative of the Lunar and Planetary Institute and the NASA Cosmochemistry Program, we have been developing oxygen barometers based largely on behavior of V which can occur in four valence states V2+, V3+, V4+, and V5+, and record at least 8 orders of magnitude of fO2. Our first efforts in measuring these valence proportions were by XANES techniques in basaltic glasses from Earth, Moon, and Mars. We now address the behavior of V valence states in chromite in basalts from Earth, Moon, and Mars. We have been looking for a "V in chromite oxybarometer" that works with data collected by the electron microprobe and thus is readily accessible to a large segment of the planetary materials community. This paper describes very early results that will be refined over the next two years.

Fugacity of H2O from 0° to 350°C at the liquid-vapor equilibrium and at 1 atmosphere

USGS Publications Warehouse

Hass, John L.

1970-01-01

The fugacity and fugacity coefficient of H2O at the liquid-vapor equilibrium, the fugacity and the Gibbs free energy of formation of H2O at 1 atm (1.01325 bars) total pressure have been calculated from published data on the physical and thermodynamic properties of H2O and are presented at ten-degree intervals from 0° to 350°C.

Metal/Silicate Partitioning of W, Ge, Ga and Ni: Dependence on Silicate Melt Composition

NASA Astrophysics Data System (ADS)

Singletary, S.; Drake, M. J.

2004-12-01

Metal/silicate partition coefficients (Dm/s) for siderophile elements are essential to investigations of core formation when used in conjunction with the pattern of elemental abundances in the Earth's mantle (Drake and Righter, 2002; Jones and Drake, 1986; Righter et al. 1997). The partitioning of siderophile elements is controlled by temperature, pressure, oxygen fugacity, and by the compositions of the metal and silicate phases. In this work, we investigate the role of silicate melt composition on the partitioning of the siderophile elements W, Ge, Ga and Ni between metallic and silicate liquid. Experiments were performed in the Experimental Geochemistry Laboratory at the University of Arizona utilizing a non-end loaded piston cylinder apparatus with a barium carbonate pressure medium. Starting materials were created by combining the mafic and silicic compositions of Jaeger and Drake (2000) with Fe powder (~25 wt% of the total mixture) to achieve metal saturation. Small amounts of W, Ge, Ga2O3 and NiO powder (less than 2 wt% each) were also added to the starting compositions. The experiments were contained in a graphite capsule and performed with temperature and pressure fixed at 1400ºC and 1.5 GPa. Experimental run products were analyzed with the University of Arizona Cameca SX50 electron microprobe with four wavelength dispersive spectrometers and a PAP ZAF correction program. All experiments in our set are saturated with metal and silicate liquid, indicating that oxygen fugacity is below IW. Several of the runs also contain a gallium-rich spinel as an additional saturating phase. Quench phases are also present in the silicate liquid in all runs. The experimentally produced liquids have nbo/t values (calculated using the method of Mills, 1993) that range from 1.10 to 2.97. These values are higher than those calculated for the liquids in the Jaeger and Drake (2000) study. The higher nbo/t values are due to uptake of Fe by the melt. The initial silicate composition contained no FeO, however the experimentally produced silicate liquids contained from 15 to 26 wt % FeO. We find that W is incompatible over the range of compositions used in this study. However, W compatibility increases as melts become more silicic, with D(W) = 0.0005 at nbo/t = 2.97 and D(W) = 0.09 at nbo/t = 1.1. The slope of the best fit line for the W data when plotted in nbo/t vs Log D space is -1.22 and close to the value of -1.34 found by Jaeger and Drake (2000). Ge is compatible at all compositions and follows a similar pattern to that of W becoming more compatible with decreasing nbo/t (D(Ge)= 14 at nbo/t = 2.97 and D(Ge) = 100 at nbo/t = 1.1). Ni and Ga display essentially flat slopes within the error of our analysis, with D(Ni) = 395 at nbo/t = 2.97 and D(Ni) = 870 at nbo/t 1.10 and D(Ga) = 0.08 at nbo/t = 2.97 and D(Ga) = 0.02 at nbo/t = 1.1. A second series of experiments is in progress to verify these data and extend the study to lower values of nbo/t. References: Drake, M.J. and Righter, K. (2002) Nature, v. 416, 39-44; Jones, J.H. and Drake, M.J. (1986) Nature, v. 323, 470-471; Righter, K., et al. (1997) Physics Earth and Planet. Int., v. 100, 115-134; Jaeger, W.L. and Drake, M.J. (2000) Geo. Cosmo. Acta, v. 64, 3887-3895; Mills, K.C. (1993) ISIJ International, v. 33, 148-155.

Assessment of the air-soil partitioning of polycyclic aromatic hydrocarbons in a paddy field using a modified fugacity sampler.

PubMed

Wang, Yan; Luo, Chunling; Wang, Shaorui; Liu, Junwen; Pan, Suhong; Li, Jun; Ming, Lili; Zhang, Gan; Li, Xiangdong

2015-01-06

Rice, one of the most widely cultivated crops, has received great attention in contaminant uptake from soil and air, especially for the special approaches used for its cultivation. The dry-wet alternation method can influence the air-soil partitioning of semivolatile organic compounds (SVOCs) in the paddy ecosystem. Here, we modified a fugacity sampler to investigate the air-surface in situ partitioning of ubiquitous polycyclic aromatic hydrocarbons (PAHs) at different growth stages in a suburban paddy field in South China. The canopy of rice can form a closed space, which acts like a chamber that can force the air under the canopy to equilibrate with the field surface. When we compared the fugacities calculated using a fugacity model of the partition coefficients to the measured fugacities, we observed similar trends in the variation, but significantly different values between different growing stages, especially during the flooding stages. However, the measured and calculated fugacity fractions were comparable when uncertainties in our calculations were considered, with the exception of the high molecular weight (HMW) PAHs. The measured fugacity fractions suggested that the HMW PAHs were also closed to equilibrium between the paddy field and atmosphere. The modified fugacity sampler provided a novel way of accurately determining the in situ air-soil partitioning of SVOCs in a wet paddy field.

Electrical properties of granite with implications for the lower crust.

USGS Publications Warehouse

Olhoeft, G.R.

1981-01-01

The electrical properties of granite appear to be dominantly controlled by the amount of free water in the granite and by temperature. Minor contributions to the electrical properties are provided by hydrostatic and lithostatic pressure, structurally bound water, oxygen fugacity, and other parameters. The effect of sulphur fugacity may be important but is experimentally unconfirmed. In addition to changing the magnitude of electrical properties, the amount and chemistry of water in granite significantly changes the temperature dependence of the electrical properties. With increasing temperature, changes in water content retain large, but lessened, effects on electrical properties. Near room temperature, a monolayer of water will decrease the electrical resistivity by an order of magnitude. Several weight-percent water may decrease the electrical resistivity by as much as nine orders of magnitude and decrease the thermal activation energy by a factor of five. At elevated temperatures just below granitic melting, a few weight-percent water may still decrease the resistivity by as much as 3 orders of magnitude and the activation energy by a factor of two.-Author

Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

NASA Technical Reports Server (NTRS)

Srinivasan, P.; McCubbin, F. M.; Rahman, Z.; Keller, L. P.; Agee, C. B.

2016-01-01

CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approximately 576-867 degrees Centigrade. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Me-tallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120-degree triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3 plus, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

Noble Metal Arsenides and Gold Inclusions in Northwest Africa 8186

NASA Technical Reports Server (NTRS)

Srinivasan, P.; McCubbin, F. M.; Rahman, Z.; Keller, L. P.; Agee, C. B.

2016-01-01

CK carbonaceous chondrites are a highly thermally altered group of carbonaceous chondrites, experiencing temperatures ranging between approx.576-867 C. Additionally, the mineralogy of the CK chondrites record the highest overall oxygen fugacity of all chondrites, above the fayalite-magnetite-quartz (FMQ) buffer. Metallic Fe-Ni is extremely rare in CK chondrites, but magnetite and Fe,Ni sulfides are commonly observed. Noble metal-rich inclusions have previously been found in some magnetite and sulfide grains. These arsenides, tellurides, and sulfides, which contain varying amounts of Pt, Ru, Os, Te, As, Ir, and S, are thought to form either by condensation from a solar gas, or by exsolution during metamorphism on the chondritic parent body. Northwest Africa (NWA) 8186 is a highly metamorphosed CK chondrite. This meteorite is predominately composed of NiO-rich forsteritic olivine (Fo65), with lesser amounts of plagioclase (An52), augite (Fs11Wo49), magnetite (with exsolved titanomagnetite, hercynite, and titanohematite), monosulfide solid solution (with exsolved pentlandite), and the phosphate minerals Cl-apatite and merrillite. This meteorite contains coarse-grained, homogeneous silicates, and has 120deg triple junctions between mineral phases, which indicates a high degree of thermal metamorphism. The presence of NiO-rich olivine, oxides phases all bearing Fe3+, and the absence of metal, are consistent with an oxygen fugacity above the FMQ buffer. We also observed noble metal-rich phases within sulfide grains in NWA 8186, which are the primary focus of the present study.

Oxygen fugacity profile of the oceanic upper mantle and the depth of redox melting beneath ridges

NASA Astrophysics Data System (ADS)

Davis, F. A.; Cottrell, E.

2014-12-01

Oxygen fugacity (fO2) of a mantle mineral assemblage, controlled primarily by Fe redox chemistry, sets the depth of the diamond to carbonated melt reaction (DCO3). Near-surface fO2 recorded by primitive MORB glasses and abyssal peridotites anchor the fO2 profile of the mantle at depth. If the fO2-depth relationship of the mantle is known, then the depth of the DCO3 can be predicted. Alternatively, if the DCO3 can be detected geophysically, then its depth can be used to infer physical and chemical characteristics of upwelling mantle. We present an expanded version of a model of the fO2-depth profile of adiabatically upwelling mantle first presented by Stagno et al. (2013), kindly provided by D. Frost. The model uses a chemical mass balance and empirical fits to experimental data to calculate compositions and modes of mantle minerals at specified P, T, and bulk Fe3+/ƩFe. We added P and T dependences to the partitioning of Al and Ca to better simulate the mineralogical changes in peridotite at depth and included majorite component in garnet to increase the depth range of the model. We calculate fO2 from the mineral assemblages using the grt-ol-opx oxybarometer (Stagno et al., 2013). The onset of carbonated melting occurs at the intersection of a Fe3+/ƩFe isopleth with the DCO3. Upwelling mantle is tied to the DCO3 until all native C is oxidized to form carbonated melts by reduction of Fe3+ to Fe2+. The depth of intersection of a parcel of mantle with the DCO3 is a function of bulk Fe3+/ƩFe, potential temperature, and bulk composition. We predict that fertile mantle (PUM) along a 1400 °C adiabat, with 50 ppm bulk C, and Fe3+/ƩFe = 0.05 after C oxidation begins redox melting at a depth of 250 km. The model contextualizes observations of MORB redox chemistry. Because fertile peridotite is richer in Al2O3, the Fe2O3-bearing components of garnet are diluted leading to lower fO2 at a given depth compared to refractory mantle under the same conditions. This may indicate that the negativecorrelation observed between enrichment and fO2 at ridges (Cottrell and Kelley, 2013) is a consequence of the increased fertility of remixing recycled crust into the mantle. Addition of reduced C to the mantle during subduction can also explain this observation. Geophysical detection of the depth of the DCO3 may resolve these hypotheses.

Pink manganian phengite in a high P/ T meta-conglomerate from northern Syros (Cyclades, Greece)

NASA Astrophysics Data System (ADS)

Altherr, Rainer; Soder, Christian; Panienka, Sandra; Peters, Daniel; Meyer, Hans-Peter

2013-11-01

A new occurrence of Mn-rich rocks was discovered within the high-pressure/low-temperature metamorphic rocks on the Palos peninsula of Syros (Greece). Near the summit of Mount Príonas, a meta-conglomerate consists of calcite (~63 wt%), pink manganian phengite, blue-purple manganian aegirine-jadeite, microcline, albite and quartz. In addition, it contains abundant braunite-rich aggregates (up to ~1.5 cm in diameter) that include hollandite [(Ba0.98-1.02K<0.01Na<0.02Ca<0.03) (Mn{1.02-1.52/3+}Fe{0.38-0.88/3+}Ti0.29-0.92Mn{5.11-5.76/4+})O16], barite and manganian hematite. Due to metamorphic recrystallization and deformation, the contacts between clasts and matrix are blurred and most clasts have lost their identity. In back-scattered electron images, many aegirine-jadeite grains appear patchy and show variable jadeite contents (Jd10-67). These pyroxenes occur in contact with either quartz or albite. Manganian phengite (3.41-3.49 Si per 11 oxygen anions) is of the 3T type and contains 1.4-2.2 wt% of Mn2O3. At the known P- T conditions of high-pressure metamorphism on Syros (~1.4 GPa/ 470 °C), the mineral sub-assemblage braunite + quartz + calcite (former aragonite) suggests high oxygen fugacities relative to the HM buffer (+7 ≤ ΔfO2 ≤ + 17) and relatively high CO2 fugacities. The exact origin of the conglomerate is not known, but it is assumed that the Fe-Mn-rich and the calcite-rich particles originated from different sources. Braunite has rather low contents of Cu (~0.19 wt%) and the concentrations of Co, Ni and Zn are less than 0.09 wt%. Hollandite shows even lower concentrations of these elements. Furthermore, the bulk-rock compositions of two samples are characterized by low contents of Cu, Co and Ni, suggesting a hydrothermal origin of the manganese ore. Most likely, these Fe-Mn-Si oxyhydroxide deposits consisted of ferrihydrite, todorokite, birnessite, amorphous silica (opal-A) and nontronite. Al/(Al + Fe + Mn) ratios of 0.355 and 0.600 suggest the presence of an aluminosilicate detrital component.

A novel method for high-pressure annealing experiments in a water-rich environment: hydrogen solubility and speciation in natural, gem-quality diopside

NASA Astrophysics Data System (ADS)

Bromiley, G. D.; Keppler, H.; Bromiley, F. A.; Jacobsen, S. D.

2003-04-01

Previous experimental invesitgations on the incorporation of structurally-bound hydrogen in nominally anhydrous minerals have either involved synthesis experiments or annealing of natural samples under hydrothermal conditions. For investigation of hydrogen incorporation using FTIR, large, good quality crystals are required. Because of experimental difficulties, synthesis experiments are limited to the investigation of end-member systems. Annealing experiments may be used to investigate chemically more complex systems. However, in previous investigations problems have arisen due to reaction of samples with chemical buffers and fluids at elevated pressures and temperatures, and run times have been limited to less than 48 hours, raising questions regarding attainment of equilbrium. In the present study, a novel method for conducting long duration (100 s of hours) annealing experiments to investigate hydrogen incorporation in samples at high-pressure has been developed. The method relies on the use of a semi-permeable platinum membrane, which protects the sample during the experiment. Samples, cut into 1×2×3 mm blocks, are surrounded by a thin platinum jacket, which is "shrink-wrapped" around the samples. The samples are then loaded into larger Pt10%Rh capsules with a buffer mixture of the same composition as the Cr-diopside, a large amount of excess water, excess silica and a Ni-NiO buffer to control oxygen fugacity. At elevated pressures and temperatures, hydrogen can diffuse freely through the platinum membrane, but the samples are protected from reaction with the surrounding buffer material and fluid. Capsules are loaded into a specially designed low-friction NaCl cells for use in piston-cylinder apparatus. Samples are recovered completely intact and crack-free. Several experiments have been performed at 1.5 GPa, with increasing run duration, to demonstrate the attainment of equilibrium hydrogen contents in the sample. Experiments have been performed at pressures from 0.5 to 4.0 GPa, 1000 to 1100^oC, with run times of several hundred hours. The effects of increasing pressure and oxygen fugacity on hydeogen solubility, and hydrogen speciation in the diopside have been fully characterised using polarised FTIR spectoscopy. The high-quality of recovered samples means that further investigations on the effects of increasing water contents on other physical properties in the samples should be possible.

Thermodynamic and nonstoichiometric behavior of the lead-doped Bi-2223 system

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Hash, M.; Tani, B. S.; Luo, J. S.; Maroni, V. A.

1994-12-01

Electromotive force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made in the lead-doped Bi-2223 superconducting system in the temperature range 700-815°C by means of an oxygen titration technique. The results of our studies indicate that processing or annealing lead-doped Bi-2223 at temperatures ranging from 700 to 815°C and at oxygen partial pressures ranging from ∼0.02 to 0.2 atm should tend to preserve Bi-2223 as essentially single-phase material. Thermodynamic assessments of partial molar quantities indicate that the plateau regions can be represented by the diphasic CuOCu 2O system. In accord with the EMF measurements, it was found that lead-doped Bi-2223 in a silver sheath is stable at 815°C for oxygen partial pressures between 0.02 and 0.13 atm. Long-duration post anneals of silver-clad Bi-2223 filaments at 825°C and an oxygen partial pressure of 0.075 atm eliminated Bi-2212 intergrowths with a concomitant increase in the superconducting transition sharpness.

Effects of hydrogen fugacity and confining pressure on the interdiffusion rate of NaSi-CaAl in plagioclase

NASA Astrophysics Data System (ADS)

Yund, Richard A.; Snow, Eleanour

1989-08-01

Average? values for NaSi-CaAl interdiffusion in the compositional interval from An0 to An26 have been determined at 1000°C by the method of lamellar homogenization. At 1500 MPa confining pressure (P), ? increases 1 order of magnitude (5.0×10-21 to 4.0×10-20 m2/s) for 4 orders of magnitude increase in hydrogen fugacity (0.029, Mn3O4-Mn2O3 buffer, to 197 MPa, FeO-Fe3O4 buffer). At constant hydrogen fugacity (fH2), ? increases rapidly at low pressure and becomes nearly independent of P above 1000 MPa. (For fH2 = 0.1 MPa, ? = 2.8 × 10-22 m2/s at P = 0.1 MPa, 5.0 × 10-21 at P = 500, 1.3×10-20 at P = 1000, and 1.4×10-20 at P = 1500). The dependence of ? on increasing pressure, when a hydrogen-related species is present, is believed to be due to an increase in the concentration of the structural defect associated with increase in the hydrogen impurity. In most crustal igneous rocks, which are internally buffered near quartz-fayalite-magnetite, the dependence of ? on fH2 is relatively minor compared to the effect of confining pressure.

Lunar and Planetary Science XXXV: Viewing the Lunar Interior Through Titanium-Colored Glasses

NASA Technical Reports Server (NTRS)

2004-01-01

The session"Viewing the Lunar Interior Through Titanium-Colored Glasses" included the following reports:Consequences of High Crystallinity for the Evolution of the Lunar Magma Ocean: Trapped Plagioclase; Low Abundances of Highly Siderophile Elements in the Lunar Mantle: Evidence for Prolonged Late Accretion; Fast Anorthite Dissolution Rates in Lunar Picritic Melts: Petrologic Implications; Searching the Moon for Aluminous Mare Basalts Using Compositional Remote-Sensing Constraints II: Detailed analysis of ROIs; Origin of Lunar High Titanium Ultramafic Glasses: A Hybridized Source?; Ilmenite Solubility in Lunar Basalts as a Function of Temperature and Pressure: Implications for Petrogenesis; Garnet in the Lunar Mantle: Further Evidence from Volcanic Glasses; Preliminary High Pressure Phase Relations of Apollo 15 Green C Glass: Assessment of the Role of Garnet; Oxygen Fugacity of Mare Basalts and the Lunar Mantle. Application of a New Microscale Oxybarometer Based on the Valence State of Vanadium; A Model for the Origin of the Dark Ring at Orientale Basin; Petrology and Geochemistry of LAP 02 205: A New Low-Ti Mare-Basalt Meteorite; Thorium and Samarium in Lunar Pyroclastic Glasses: Insights into the Composition of the Lunar Mantle and Basaltic Magmatism on the Moon; and Eu2+ and REE3+ Diffusion in Enstatite, Diopside, Anorthite, and a Silicate Melt: A Database for Understanding Kinetic Fractionation of REE in the Lunar Mantle and Crust.

Stability of hydrocarbon systems at thermobaric conditions corresponding to depth down to 50 km

NASA Astrophysics Data System (ADS)

Kutcherov, V.; Kolesnikov, A.; Mukhina, E.; Serovaiskii, A.

2017-12-01

Most of the theoretical models show that crude oil stability is limited by the depth of 6-8 km (`oil window'). Commercial discovery of crude oil deposits on the depth more than 10 km in the different petroleum basins worldwide casts doubt on the validity of the above-mentioned theoretical calculations. Therefore, the question at which depth complex hydrocarbon systems could be stable is important not only from fundamental research point of view but has a great practical application. To answer this question a hydrocarbon mixture was investigated under thermobaric conditions corresponding to the conditions of the Earth's lower crust. Experiments were conducted by means of Raman Mössbauer spectroscopy. The results obtained show that the complex hydrocarbon systems could be stable and remain their qualitative and quantitative composition at temperature 320-450 °C and pressure 0.7-1.4 GPa. The oxidizing resistance of hydrocarbon system was tested in the modelled the Earth's crust surrounding. The hydrocarbon system stability at the presence of Fe2O3 strongly confirms that the Earth's crust oxygen fugacity does not influence on petroleum composition. The data obtained broaden our knowledge about the possible range of depths for crude oil and natural gas deposits in the Earth's crust and give us the possibility to revise the depth of petroleum deposits occurrence.

Fusion of acid oxides for potentially radiation-resistant waste forms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herrick, C.C.; Penneman, R.A.

1983-02-01

Skull melting of groups VA and VB acid oxides with alkali metal oxides and urania leads to compounds with a good ability to retain radionuclides and establishes immunity to radiation damage. Substitution of neptunium and plutonium for uranium should not diminish these desirable properties. For hexavalent transplutonic elements, even at high oxygen fugacities and oxide activities, acid character losses and the reducing nature of radiation suggest the lower valences (III and IV) will be the stable states. Plutonium becomes the pivotal radionuclide when valence stability in a radiation field is considered.

A compositional tipping point governing the mobilization and eruption style of rhyolitic magma

NASA Astrophysics Data System (ADS)

di Genova, D.; Kolzenburg, S.; Wiesmaier, S.; Dallanave, E.; Neuville, D. R.; Hess, K. U.; Dingwell, D. B.

2017-12-01

The most viscous volcanic melts and the largest explosive eruptions on our planet consist of calcalkaline rhyolites. These eruptions have the potential to influence global climate. The eruptive products are commonly very crystal-poor and highly degassed, yet the magma is mostly stored as crystal mushes containing small amounts of interstitial melt with elevated water content. It is unclear how magma mushes are mobilized to create large batches of eruptible crystal-free magma. Further, rhyolitic eruptions can switch repeatedly between effusive and explosive eruption styles and this transition is difficult to attribute to the rheological effects of water content or crystallinity. Here we measure the viscosity of a series of melts spanning the compositional range of the Yellowstone volcanic system and find that in a narrow compositional zone, melt viscosity increases by up to two orders of magnitude. These viscosity variations are not predicted by current viscosity models and result from melt structure reorganization, as confirmed by Raman spectroscopy. We identify a critical compositional tipping point, independently documented in the global geochemical record of rhyolites, at which rhyolitic melts fluidize or stiffen and that clearly separates effusive from explosive deposits worldwide. This correlation between melt structure, viscosity and eruptive behaviour holds despite the variable water content and other parameters, such as temperature, that are inherent in natural eruptions. Thermodynamic modelling demonstrates how the observed subtle compositional changes that result in fluidization or stiffening of the melt can be induced by crystal growth from the melt or variation in oxygen fugacity. However, the rheological effects of water and crystal content alone cannot explain the correlation between composition and eruptive style. We conclude that the composition of calcalkaline rhyolites is decisive in determining the mobilization and eruption dynamics of Earth’s largest volcanic systems, resulting in a better understanding of how the melt structure controls volcanic processes.

A compositional tipping point governing the mobilization and eruption style of rhyolitic magma.

PubMed

Di Genova, D; Kolzenburg, S; Wiesmaier, S; Dallanave, E; Neuville, D R; Hess, K U; Dingwell, D B

2017-12-13

The most viscous volcanic melts and the largest explosive eruptions on our planet consist of calcalkaline rhyolites. These eruptions have the potential to influence global climate. The eruptive products are commonly very crystal-poor and highly degassed, yet the magma is mostly stored as crystal mushes containing small amounts of interstitial melt with elevated water content. It is unclear how magma mushes are mobilized to create large batches of eruptible crystal-free magma. Further, rhyolitic eruptions can switch repeatedly between effusive and explosive eruption styles and this transition is difficult to attribute to the rheological effects of water content or crystallinity. Here we measure the viscosity of a series of melts spanning the compositional range of the Yellowstone volcanic system and find that in a narrow compositional zone, melt viscosity increases by up to two orders of magnitude. These viscosity variations are not predicted by current viscosity models and result from melt structure reorganization, as confirmed by Raman spectroscopy. We identify a critical compositional tipping point, independently documented in the global geochemical record of rhyolites, at which rhyolitic melts fluidize or stiffen and that clearly separates effusive from explosive deposits worldwide. This correlation between melt structure, viscosity and eruptive behaviour holds despite the variable water content and other parameters, such as temperature, that are inherent in natural eruptions. Thermodynamic modelling demonstrates how the observed subtle compositional changes that result in fluidization or stiffening of the melt can be induced by crystal growth from the melt or variation in oxygen fugacity. However, the rheological effects of water and crystal content alone cannot explain the correlation between composition and eruptive style. We conclude that the composition of calcalkaline rhyolites is decisive in determining the mobilization and eruption dynamics of Earth's largest volcanic systems, resulting in a better understanding of how the melt structure controls volcanic processes.

Utilizing Polymer-Coated Vials to Illustrate the Fugacity and Bioavailability of Chlorinated Pesticide Residues in Contaminated Soils

ERIC Educational Resources Information Center

Andrade, Natasha A.; McConnell, Laura L.; Torrents, Alba; Hapeman, Cathleen J.

2013-01-01

Fugacity and bioavailability can be used to facilitate students' understanding of potential environmental risks associated with toxic chemicals and, therefore, should be incorporated in environmental chemistry and science laboratories. Although the concept of concentration is easy to grasp, fugacity and bioavailability can be challenging…

Making Mercury's Core with Light Elements

NASA Technical Reports Server (NTRS)

Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Ross, D. Kent

2016-01-01

Recent results obtained from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging spacecraft showed the surface of Mercury has low FeO abundances (less than 2 wt%) and high S abundances (approximately 4 wt%), suggesting the oxygen fugacity of Mercury's surface materials is somewhere between 3 to 7 log10 units below the IW buffer. The highly reducing nature of Mercury has resulted in a relatively thin mantle and a large core that has the potential to exhibit an exotic composition in comparison to the other terrestrial planets. This exotic composition may extend to include light elements (e.g., Si, C, S). Furthermore, has argued for a possible primary floatation crust on Mercury composed of graphite, which may require a core that is C-saturated. In order to investigate mercurian core compositions, we conducted piston cylinder experiments at 1 GPa, from 1300 C to 1700 C, using a range of starting compositions consisting of various Si-Fe metal mixtures (Si5Fe95, Si10Fe90, Si22Fe78, and Si35Fe65). All metals were loaded into graphite capsules used to ensure C-saturation during the duration of each experimental run. Our experiments show that Fe-Si metallic alloys exclude carbon relative to more Fe-rich metal. This exclusion of carbon commences within the range of 5 to 10 wt% Si. These results indicate that if Mercury has a Si-rich core (having more than approximately 5 wt% silicon), it would have saturated in carbon at low C abundances allowing for the possible formation of a graphite floatation crust as suggested by. These results have important implications for the thermal and magmatic evolution of Mercury.

Analyzing the dependence of oxygen incorporation current density on overpotential and oxygen partial pressure in mixed conducting oxide electrodes.

PubMed

Guan, Zixuan; Chen, Di; Chueh, William C

2017-08-30

The oxygen incorporation reaction, which involves the transformation of an oxygen gas molecule to two lattice oxygen ions in a mixed ionic and electronic conducting solid, is a ubiquitous and fundamental reaction in solid-state electrochemistry. To understand the reaction pathway and to identify the rate-determining step, near-equilibrium measurements have been employed to quantify the exchange coefficients as a function of oxygen partial pressure and temperature. However, because the exchange coefficient contains contributions from both forward and reverse reaction rate constants and depends on both oxygen partial pressure and oxygen fugacity in the solid, unique and definitive mechanistic assessment has been challenging. In this work, we derive a current density equation as a function of both oxygen partial pressure and overpotential, and consider both near and far from equilibrium limits. Rather than considering specific reaction pathways, we generalize the multi-step oxygen incorporation reaction into the rate-determining step, preceding and following quasi-equilibrium steps, and consider the number of oxygen ions and electrons involved in each. By evaluating the dependence of current density on oxygen partial pressure and overpotential separately, one obtains the reaction orders for oxygen gas molecules and for solid-state species in the electrode. We simulated the oxygen incorporation current density-overpotential curves for praseodymium-doped ceria for various candidate rate-determining steps. This work highlights a promising method for studying the exchange kinetics far away from equilibrium.

Isotopic-Geochemical Features of Zircon and Its Significance for Reconstructing the Geological History of Paleoarchean Granulites in the Ukrainian Shield

NASA Astrophysics Data System (ADS)

Lobach-Zhuchenko, S. B.; Kaulina, T. V.; Lokhov, K. I.; Egorova, Yu. S.; Skublov, S. G.; Galankina, O. L.; Antonov, A. V.

2017-12-01

This paper presents the results of a complex study (morphology of grains, internal texture in cathodoluminescence and backscattered electrons, microprobe analysis, Lu-Hf data) of five groups (generations) of zircon crystals differing in age and separated from the same granulite sample pertaining to the Bug River Complex of the Ukrainian Shield. The data show that the oldest zircon crystals of the first group (3.74 Ga in age) are xenogenic and initially crystallized from a granitic melt; zircon of the second group (3.66 Ga) formed from a mafic melt contaminated by felsic country rocks. The third group (3.59 Ga) is represented by zircons that formed about 100 Ma later than the second group under conditions of granulite-facies metamorphism and with the participation of fluid-saturated anatectic melt. Two Paleoproterozoic zircon groups ( 2.5 and 2.1 Ga) also formed under granulite-facies conditions; to a certain extent, their structure and composition were controlled by fluid. The geochemistry of all zircon generations provides evidence for their crystallization in the continental crust, but from the sources differing in the contribution of mantle-derived material and in oxygen fugacity.

Carbon and nitrogen speciation in nitrogen-rich C-O-H-N fluids at 5.5-7.8 GPa

NASA Astrophysics Data System (ADS)

Sokol, Alexander G.; Palyanov, Yury N.; Tomilenko, Anatoly A.; Bul'bak, Taras A.; Palyanova, Galina A.

2017-02-01

Carbon and nitrogen speciation has been studied in high-pressure experiments in the C-O-H-N and C-O-H-N-Fe3C systems at 5.5 to 7.8 GPa and 1100 to 1500 °C using a split-sphere multi-anvil apparatus. Oxygen fugacity in the samples was either buffered by the Mo-MoO2 (MMO) and Fe-FeO (IW) equilibria using a double-capsule technique or left unbuffered. fO2 varied from 2 log units below to +4 log units above the iron-wüstite oxygen buffer (IW) depending on water contents in the charges and buffering. Ultra-reduced fluids contained NH3 as the dominant species, but its concentration was slightly lower, while CH4 was higher at higher temperatures. As oxygen fugacity and temperature increased to fO2 0.7 log units above IW and T ≥ 1400 °C, N2 became the predominant nitrogen species; the dominance among carbon species changed from CH4 and C2-C5 alkanes to oxygenated hydrocarbons and higher alkanes. It has been found out for the first time that the N2-rich fluid lacks methane at fO2 4 log units above IW but may bear a few percent of C2H6, C3H8, and C15-C18 alkanes and within one percent of alcohols, aldehydes, ketones, carboxylic acids, and furans. Thus, the NH3 enrichment of fluids and the nitrogen storage capacity of silicates at depths ∼200 km are expected to be the greatest in cold (1100-1200 °C) and reduced continental lithospheric mantle. In a hotter lithosphere of ∼1400 °C, the concentrations of NH3 and N2 in fluids are similar, and the nitrogen storage capacity of silicates should be relatively low. The stability of some higher alkanes and oxygenated hydrocarbons in nitrogen-rich fluids near the enstatite-magnesite-olivine-diamond/graphite (EMOG/D) equilibrium suggest that these carbon species, together with N2, can survive at the redox barrier, where silicate or silicate-carbonate melts capture them and entrain to shallow mantle.

Partitioning of rare earth elements between hibonite and melt and implications for nebular condensation of the rare earth elements

NASA Technical Reports Server (NTRS)

Drake, Michael J.; Boynton, William V.

1988-01-01

The effect of oxygen fugacity on the partitioning of REEs between hibonite and silicate melt is investigated in hibonite-growth experiments at 1470 C. The experimental procedures and apparatus are described, and the results are presented in extensive tables and graphs and characterized in detail. The absolute activity coefficients in hibonite are estimated as 330 for La, 1200 for Eu(3+), and 24,000 for Yb. It is inferred that ideal solution behavior cannot be assumed when calculating REE condensation temperatures for (Ca, Al)-rich inclusions in carbonaceous chondrites.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, H. L.; Hirschmann, M. M.; Cottrell, E.

Experiments establishing the effect of pressure on the Fe 3+/ΣFe ratio of andesitic silicate melts buffered by coexisting Ru and RuO 2 were performed from 100 kPa to 7 GPa and 1400–1750 °C. Fe 3+/ΣFe ratios were determined by room temperature Mössbauer spectroscopy, but corrected for the effects of recoilless fraction. Fe 3+/ΣFe ratios in quenched glasses decrease with increasing pressure consistent with previous results between 100 kPa and 3 GPa (O’Neill et al., 2006), but show only small pressure effects above 5 GPa. Ratios also decrease with increasing temperature. Mössbauer hyperfine parameters indicate mean coordination of Fe 3+ ionsmore » of ~5 in glasses, with no dependence on the pressure from which the glasses were quenched, but show an increase with pressure in mean coordination of Fe 2+ ions, from ~5 to ~6. XANES spectra on these glasses show variations in pre-edge intensities and centroid positions that are systematic with Fe 3+/ΣFe, but are displaced from those established from otherwise identical andesitic glasses quenched at 100 kPa (Zhang et al., 2016). These systematics permit construction of a new XANES calibration curve relating pre-edge sub-peak intensities to Fe 3+/ΣFe applicable to high pressure glasses. Consistent with interpretations of the Mössbauer hyperfine parameters, XANES pre-edge peak features in high pressure glasses are owing chiefly to the effects of pressure on the coordination of Fe 2+ ions from ~5.5 to ~6, with negligible effects evident for Fe 3+ ions. We use the new data to construct a thermodynamic model relating the effects of oxygen fugacity and pressure on Fe 3+/ΣFe. We apply this model to calculate variations in oxygen fugacity in isochemical (constant Fe 3+/ΣFe) columns of magma representative of magma oceans, in which fO2 is fixed at the base by equilibration with molten Fe. These calculations indicate that oxygen fugacities at the surface of shallow magma oceans are more reduced than at depth. For magma oceans in which the pressure at the base is near 5 GPa, as may be appropriate for Mercury and the Moon, conditions at the surface are ~1.5 log unit more reduced at the surface than at their base. If the results calibrated up to pressures of 7 GPa can be extrapolated to higher pressures appropriate for magma oceans on larger terrestrial planets such as Mars or Earth, then conditions at the surface are ~2 or 2.5 log units more reduced at the surface than at the base, respectively. Thus, atmospheres overlying shallow magma oceans should be highly reduced and rich in H 2 and CO.« less

Origin of EL3 chondrites: Evidence for variable C/O ratios during their course of formation—A state of the art scrutiny

NASA Astrophysics Data System (ADS)

El Goresy, A.; Lin, Y.; Miyahara, M.; Gannoun, A.; Boyet, M.; Ohtani, E.; Gillet, P.; Trieloff, M.; Simionovici, A.; Feng, L.; Lemelle, L.

2017-05-01

Mineral inventories of enstatite chondrites; (EH and EL) are strictly dictated by combined parameters mainly very low dual oxygen (fO2) and sulfur (fS2) fugacities. They are best preserved in the Almahata Sitta MS-17, MS-177 fragments, and the ALHA 77295 and MAC 88136 Antarctic meteorites. These conditions induce a stark change of the geochemical behavior of nominally lithophile elements to chalcophile or even siderophile and changes in the elemental partitioning thus leading to formation of unusual mineral assemblages with high abundance of exotic sulfide species and enrichment in the metallic alloys, for example, silicides and phosphides. Origin and mode of formation of these exotic chondrites, and their parental source regions could be best scrutinized by multitask research experiments of the most primitive members covering mineralogical, petrological, cosmochemical, and indispensably short-lived isotopic chronology. The magnitude of temperature and pressure prevailed during their formation in their source regions could eventually be reasonably estimated: pre- and postaccretionary could eventually be deduced. The dual low fugacities are regulated by the carbon to oxygen ratios estimated to be >0.83 and <1.03. These parameters not only induce unusual geochemical behavior of the elements inverting many nominally lithophile elements to chalcophile or even siderophile or anthracophile. Structure and mineral inventories in EL3 and EH3 chondrites are fundamentally different. Yet EH3 and EL3 members store crucial information relevant to eventual source regions and importantly possible variation in C/O ratio in the course of their evolution. EL3 and EH3 chondrites contain trichotomous lithologies (1) chondrules and their fragments, (2) polygonal enstatite-dominated objects, and (3) multiphase metal-rich nodules. Mineralogical and cosmochemical inventories of lithologies in the same EL3 indicate not only similarities (REE inventory and anomalies in oldhamite) but also distinct differences (sinoite-enstatite-graphite relationship). Oldhamite in chondrules and polygonal fragments in EL3 depict negative Eu anomaly attesting a common cosmochemical source. Metal-dominated nodules in both EL3 and EH3 are conglomerates of metal clasts and sulfide fragments in EH3 and concentrically zoned C-bearing metal micropebbles (≥25 μm ≤50 μm) in EL3 thus manifesting a frozen in unique primordial accretionary metal texture and composition. Sinoite-enstatite-diopside-graphite textures reveal a nucleation and growth strongly suggestive of fluctuating C/O ratio during their nucleation and growth in the source regions. Mineral inventories, sulfide phase relations, sinoite-enstatite-graphite intergrowth, carbon and nitrogen isotopic compositions of graphite, spatial nitrogen abundance in graphite in metal nodules, and last but not least 129I/129Xe and 53Mn/53Cr systematics negate any previously suggested melting episode, pre-accretionary or dynamic, in parental asteroids.

Inclusions in diamonds constrain thermo-chemical conditions during Mesozoic metasomatism of the Kaapvaal cratonic mantle

NASA Astrophysics Data System (ADS)

Weiss, Yaakov; Navon, Oded; Goldstein, Steven L.; Harris, Jeff W.

2018-06-01

Fluid/melt inclusions in diamonds, which were encapsulated during a metasomatic event and over a short period of time, are isolated from their surrounding mantle, offering the opportunity to constrain changes in the sub-continental lithospheric mantle (SCLM) that occurred during individual thermo-chemical events, as well as the composition of the fluids involved and their sources. We have analyzed a suite of 8 microinclusion-bearing diamonds from the Group I De Beers Pool kimberlites, South Africa, using FTIR, EPMA and LA-ICP-MS. Seven of the diamonds trapped incompatible-element-enriched saline high density fluids (HDFs), carry peridotitic mineral microinclusions, and substitutional nitrogen almost exclusively in A-centers. This low-aggregation state of nitrogen indicates a short mantle residence times and/or low mantle ambient temperature for these diamonds. A short residence time is favored because, elevated thermal conditions prevailed in the South African lithosphere during and following the Karoo flood basalt volcanism at ∼180 Ma, thus the saline metasomatism must have occurred close to the time of kimberlite eruptions at ∼85 Ma. Another diamond encapsulated incompatible-element-enriched silicic HDFs and has 25% of its nitrogen content residing in B-centers, implying formation during an earlier and different metasomatic event that likely relates to the Karoo magmatism at ca. 180 Ma. Thermometry of mineral microinclusions in the diamonds carrying saline HDFs, based on Mg-Fe exchange between garnet-orthopyroxene (Opx)/clinopyroxene (Cpx)/olivine and the Opx-Cpx thermometer, yield temperatures between 875-1080 °C at 5 GPa. These temperatures overlap with conditions recorded by touching inclusion pairs in diamonds from the De Beers Pool kimberlites, which represent the mantle ambient conditions just before eruption, and are altogether lower by 150-250 °C compared to P-T gradients recorded by peridotite xenoliths from the same locality. Oxygen fugacity (fO2) differs as well. The fO2 calculated for the saline HDF compositions (Δlog ⁡ fO 2 (FMQ) = - 2.47 to -1.34) are higher by about a log unit compared with that recorded by xenoliths at 4-7 GPa. We conclude that enriched saline HDFs mediated the metasomatism that preceded Group I kimberlite eruptions in the southwestern Kaapvaal craton, and that their 'cold and oxidized' nature reflects their derivation from a deep subducting slab. This event had little impact on the temperature and redox state of the Kaapvaal lithosphere as a reservoir, however, it likely affected its properties along limited metasomatized veins and their wall rock. To reconcile the temperature and oxygen fugacity discrepancy between inclusions in diamonds and xenoliths, we argue that xenoliths did not equilibrate during the last saline metasomatic event or kimberlite eruption. Thus the P-T- fO2 gradients they record express pre-existing lithospheric conditions that were likely established during the last major thermal event in the Kaapvaal craton (i.e. the Karoo magmatism at ca. 180 Ma).

Copper and Gold Partitioning Between Brine and Vapor as a Function of Reduced Sulfur

NASA Astrophysics Data System (ADS)

Ehlich, J. J.; Frank, M. R.; Bodnar, R. J.

2017-12-01

This study examined Cu and Au partitioning between sulfur-rich vapors (v) and brines (b) at conditions representative of porphyry ore deposits. Experiments were conducted at 700 °C and 100 MPa, with oxygen fugacity, f(O2), buffered by either Ni-NiO or MnO-Mn3O4. Sulfur fugacity, f(S2), was buffered by pyrrhotite + chalcopyrite or bornite + pyrrhotite + chalcopyrite mineral assemblages between log -5.6 and log 0.6. The fugacities of H2S and SO2 were calculated using the known values of fO2 and fS2. In each experiment, a gold capsule was loaded with a sulfide assemblage, a quartz core to trap fluid inclusions, and a 5 wt.% NaCl-equivalent aqueous solution containing NaCl, KCl and HCl with molar NaCl:KCl and NaCl:HCl ratios of 1 and 100, respectively. Coexisting low salinity (v) and high salinity (b) inclusions were trapped in the quartz and their salinities were estimated using microthermometry, and verified against expected salinities from the NaCl-H2O system. Na, K, Fe, Cu, and Au concentrations from 73 b and 39 v fluid inclusions were determined using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Nernst-style partition coefficients between b and v for a given element (Dxb/v) were determined as a function of O2, S2, H2S, and SO2 fugacities. DCub/v ranged from 2.8 to 6.6 and increased with increasing f(O2), decreased with increasing f(S2), and decreased with increasing f(H2S). Gold partition coefficients ranged from 4.6 to 8.5, with DAub/v increasing with increasing f(O2), decreasing with increasing f(S2), and decreasing with increasing f(H2S). The absolute concentrations of Cu and Au increased in both the b and v phases with increasing f(H2S), but the increase was proportionally greater in v than b. Cu and Au partitioned into b relative to v at all conditions, but Dxb/v decreased slightly with decreasing O2 or increasing S2 fugacity. Dxb/v for Cu and Au appear most strongly linked to H2S, consistently decreasing with increasing f(H2S), but our data suggest that Cu and Au prefer chloride-complexes in porphyry systems (Dxb/v always >1). Reduced sulfur species may become increasingly important ligands in the porphyry-epithermal transition, in particularly high f(H2S) systems, or in systems dominated by a low salinity supercritical fluid or vapor.

Thermodynamic controls on element partitioning between titanomagnetite and andesitic-dacitic silicate melts

NASA Astrophysics Data System (ADS)

Sievwright, R. H.; Wilkinson, J. J.; O'Neill, H. St. C.; Berry, A. J.

2017-08-01

Titanomagnetite-melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity ( fO2) and temperature ( T) in an andesitic-dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite-melt partitioning of the divalent cations (Mg2+, Mn2+, Co2+, Ni2+, Zn2+) and Cu2+/Cu+ with increasing fO2 between 0.2 and 3.7 log units above the fayalite-magnetite-quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral-melt partitioning of divalent cations, a more rigorous justification of magnetite-melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO2 implies a reciprocal relationship between a(Fe2+O) and a(Fe3+O1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite-melt partitioning of divalent cations with fO2 in magnetite-rich spinel. As a result of this, titanomagnetite-melt partitioning of divalent cations is indirectly sensitive to changes in fO2 in silicic, but less so in mafic bulk systems.

Calculation of the relative metastabilities of proteins using the CHNOSZ software package

PubMed Central

Dick, Jeffrey M

2008-01-01

Background Proteins of various compositions are required by organisms inhabiting different environments. The energetic demands for protein formation are a function of the compositions of proteins as well as geochemical variables including temperature, pressure, oxygen fugacity and pH. The purpose of this study was to explore the dependence of metastable equilibrium states of protein systems on changes in the geochemical variables. Results A software package called CHNOSZ implementing the revised Helgeson-Kirkham-Flowers (HKF) equations of state and group additivity for ionized unfolded aqueous proteins was developed. The program can be used to calculate standard molal Gibbs energies and other thermodynamic properties of reactions and to make chemical speciation and predominance diagrams that represent the metastable equilibrium distributions of proteins. The approach takes account of the chemical affinities of reactions in open systems characterized by the chemical potentials of basis species. The thermodynamic database included with the package permits application of the software to mineral and other inorganic systems as well as systems of proteins or other biomolecules. Conclusion Metastable equilibrium activity diagrams were generated for model cell-surface proteins from archaea and bacteria adapted to growth in environments that differ in temperature and chemical conditions. The predicted metastable equilibrium distributions of the proteins can be compared with the optimal growth temperatures of the organisms and with geochemical variables. The results suggest that a thermodynamic assessment of protein metastability may be useful for integrating bio- and geochemical observations. PMID:18834534

Partitioning of Moderately Siderophile Elements Among Olivine, Silicate Melt, and Sulfide Melt: Constraints on Core Formation in the Earth and Mars

NASA Technical Reports Server (NTRS)

Gaetani, Glenn A.; Grove, Timothy L.

1997-01-01

This study investigates the effects of Variations in the fugacities of oxygen and sulfur on the partitioning of first series transition metals (V, Cr, Mn, Fe, Co, Ni. and Cu) and W among coexisting sulfide melt, silicate melt, and olivine. Experiments were performed at 1 atm pressure, 1350 C, with the fugacities of oxygen and sulfur controlled by mixing CO2, CO, and SO2 gases. Starting compositions consisted of a CaO-MgO-Al2O3-SiO2-FeO-Na2O analog for a barred olivine chondrule from an ordinary chondrite and a synthetic komatiite. The f(sub O2)/f(sub S2), conditions ranged from log of f(sub O2) = -7.9 to - 10.6, with log of f(sub S2) values ranging from - 1.0 to -2.5. Our experimental results demonstrate that the f(sub O2)/f(sub S2) dependencies of sulfide melt/silicate melt partition coefficients for the first series transition metals arc proportional to their valence states. The f(sub O2)/f(sub S2) dependencies for the partitioning of Fe, Co, Ni, and Cu are weaker than predicted on the basis of their valence states. Variations in conditions have no significant effect on olivine/melt partitioning other than those resulting from f(sub O2)-induced changes in the valence state of a given element. The strong f(sub O2)/f(sub S2) dependence for the olivine/silicate melt partitioning of V is attributable to a change of valence state, from 4+ to 3+, with decreasing f(sub O2). Our experimentally determined partition coefficients are used to develop models for the segregation of sulfide and metal from the silicate portion of the early Earth and the Shergottite parent body (Mars). We find that the influence of S is not sufficient to explain the overabundance of siderophile and chalcophile elements that remained in the mantle of the Earth following core formation. Important constraints on core formation in Mars are provided by our experimental determination of the partitioning of Cu between silicate and sulfide melts. When combined with existing estimates for siderophile element abundances in the Martian mantle and a mass balance constraint from Fe, the experiments allow a determination of the mass of the Martian core (approx. 17 to 22 wt% of the planet) and its S content (approx.0.4 wt%). These modeling results indicate that Mars is depleted in S, and that its core is solid.

Fluid inclusion geothermometry

USGS Publications Warehouse

Cunningham, C.G.

1977-01-01

Fluid inclusions trapped within crystals either during growth or at a later time provide many clues to the histories of rocks and ores. Estimates of fluid-inclusion homogenization temperature and density can be obtained using a petrographic microscope with thin sections, and they can be refined using heating and freezing stages. Fluid inclusion studies, used in conjunction with paragenetic studies, can provide direct data on the time and space variations of parameters such as temperature, pressure, density, and composition of fluids in geologic environments. Changes in these parameters directly affect the fugacity, composition, and pH of fluids, thus directly influencing localization of ore metals. ?? 1977 Ferdinand Enke Verlag Stuttgart.

The thermodynamic properties of pyrrhotite and pyrite: A re-evaluation

NASA Astrophysics Data System (ADS)

Barker, W. W.; Parks, T. C.

1986-10-01

On a plot of log sulfur activity versus inverse absolute temperature, the variation in published pyrite/pyrrhotite curves below 500°C is larger than expected from the precision of the measurements. The precise data by RAU (1976) fall between interpretations by SCOTT and BARNES (1971) and by TOULMIN and BARTON (1964) and are recommended. Scott and Barnes calibrated sulfur fugacities in the system Fe-Zn-S, against the data of Toulmin and Barton, but this involved a double extrapolation of empirical relationships, to and from a region where fugacities in pyrrhotite are unmeasured. Regular-solution models offer no improvement. An apparent interruption in the properties of the high-temperature pyrrhotite solid solution, at the composition Fe 7S 8 ( POWELL, 1983) is probably due to the inclusion of metastable microdomains of monoclinic pyrrhotite in some of Rau's experimental runs, rather than to an equilibrium change of structure. Hence, the uncertainties of extrapolation are unlikely to account for the displacement of the pyrite/pyrrhotite curve of Scott and Barnes. There may be a systematic error in the composition of pyrrhotite inferred by Scott and Barnes from X-ray lattice spacings, due to the effects of preparation-dependent ordering. Other influences on pyrrhotite thermodynamics are discussed. There is a maximum in the pyrrhotite fundamental unit-cell parameter, "a," as composition is changed. This maximum shifts towards the Fe-rich boundary of pyrrhotite as temperature is increased, so it suggests a contribution from intrinsic defects, even at low temperatures. The thermodynamic effects of pressure need recalculating to suit these unit-cell data.

Petrology of iron-rich magmatic segregations associated with strongly peraluminous trondhjemite in the Cornucopia stock, northeastern Oregon

NASA Astrophysics Data System (ADS)

Johnson, K.; Barnes, C. G.; Browning, J. M.; Karlsson, H. R.

The Middle Cretaceous Cornucopia stock in the Blue Mountains of northeastern Oregon is a small composite intrusion consisting of hornblende biotite tonalite, biotite trondhjemite, and three cordierite two mica trondhjemite units. Unusual magnetite + biotite-rich tonalitic rocks are associated with the Crater Lake cordierite trondhjemite, the youngest of the intrusions. Oxide-rich tonalites are characterized by high Fe ( 47-68 wt% total Fe as FeO), low SiO2 (<36 wt%), and enrichments in HFSE and REE (La(N)=361-903). Oxide-rich tonalites appear in a variety of forms, including composite dikes and sheets, in which they are associated with leucocratic tonalite. Leucotonalite is lower in SiO2 (60-72 wt%) than Crater Lake trondhjemite, and generally has ΣREE contents and Eu anomalies intermediate between the oxide-rich tonalite and Crater Lake compositions. Oxide-rich tonalites crosscut, and are crosscut by, shear zones in the host trondhjemite, indicating their emplacement late in the pluton's crystallization history. Granitic dikes crosscut the composite dikes in all localities. Geochemical considerations and sedimentary-like structures, such as load casts and bedding of magnetite-rich assemblages in the composite dikes and sheets, are suggestive of crystal settling from an Fe-rich parental magma. The Fe-rich liquid parental to the oxide-rich tonalite-leucotonalite pairs formed by extensive, in-situ, plagioclase + quartz-dominated crystallization of strongly peraluminous trondhjemite. Early magnetite saturation in the trondhjemite was suppressed, either because the parental trondhjemitic magma had a lower initial total Fe content or because it had a lower ferric-ferrous ratio, possibly reflecting a lower oxygen fugacity. Accumulation of magnetite from Fe-rich residual magma is a viable mechanism for the concentration of iron, and the subsequent formation of Fe-rich rocks, in calcic siliceous intrusions. Apparently, Fe-enrichment can occur locally in calcic magmas, and is not restricted to rocks of mafic tholeiitic or anorthositic affinity.

Petrology of iron-rich magmatic segregations associated with strongly peraluminous trondhjemite in the Cornucopia stock, northeastern Oregon

NASA Astrophysics Data System (ADS)

Johnson, K.; Barnes, C. G.; Browning, J. M.; Karlsson, H. R.

2001-11-01

The Middle Cretaceous Cornucopia stock in the Blue Mountains of northeastern Oregon is a small composite intrusion consisting of hornblende biotite tonalite, biotite trondhjemite, and three cordierite two mica trondhjemite units. Unusual magnetite + biotite-rich tonalitic rocks are associated with the Crater Lake cordierite trondhjemite, the youngest of the intrusions. Oxide-rich tonalites are characterized by high Fe ( 47-68 wt% total Fe as FeO), low SiO2 (<36 wt%), and enrichments in HFSE and REE (La(N)=361-903). Oxide-rich tonalites appear in a variety of forms, including composite dikes and sheets, in which they are associated with leucocratic tonalite. Leucotonalite is lower in SiO2 (60-72 wt%) than Crater Lake trondhjemite, and generally has ΣREE contents and Eu anomalies intermediate between the oxide-rich tonalite and Crater Lake compositions. Oxide-rich tonalites crosscut, and are crosscut by, shear zones in the host trondhjemite, indicating their emplacement late in the pluton's crystallization history. Granitic dikes crosscut the composite dikes in all localities. Geochemical considerations and sedimentary-like structures, such as load casts and bedding of magnetite-rich assemblages in the composite dikes and sheets, are suggestive of crystal settling from an Fe-rich parental magma. The Fe-rich liquid parental to the oxide-rich tonalite-leucotonalite pairs formed by extensive, in-situ, plagioclase + quartz-dominated crystallization of strongly peraluminous trondhjemite. Early magnetite saturation in the trondhjemite was suppressed, either because the parental trondhjemitic magma had a lower initial total Fe content or because it had a lower ferric-ferrous ratio, possibly reflecting a lower oxygen fugacity. Accumulation of magnetite from Fe-rich residual magma is a viable mechanism for the concentration of iron, and the subsequent formation of Fe-rich rocks, in calcic siliceous intrusions. Apparently, Fe-enrichment can occur locally in calcic magmas, and is not restricted to rocks of mafic tholeiitic or anorthositic affinity.

Upper mantle fluids evolution, diamond formation, and mantle metasomatism

NASA Astrophysics Data System (ADS)

Huang, F.; Sverjensky, D. A.

2017-12-01

During mantle metasomatism, fluid-rock interactions in the mantle modify wall-rock compositions. Previous studies usually either investigated mineral compositions in xenoliths and xenocrysts brought up by magmas, or examined fluid compositions preserved in fluid inclusions in diamonds. However, a key study of Panda diamonds analysed both mineral and fluid inclusions in the diamonds [1] which we used to develop a quantitative characterization of mantle metasomatic processes. In the present study, we used an extended Deep Earth Water model [2] to simulate fluid-rock interactions at upper mantle conditions, and examine the fluids and mineral assemblages together simultaneously. Three types of end-member fluids in the Panda diamond fluid inclusions include saline, rich in Na+K+Cl; silicic, rich in Si+Al; and carbonatitic, rich in Ca+Mg+Fe [1, 3]. We used the carbonatitic end-member to represent fluid from a subducting slab reacting with an excess of peridotite + some saline fluid in the host environment. During simultaneous fluid mixing and reaction with the host rock, the logfO2 increased by about 1.6 units, and the pH increased by 0.7 units. The final minerals were olivine, garnet and diamond. The Mg# of olivine decreased from 0.92 to 0.85. Garnet precipitated at an early stage, and its Mg# also decreased with reaction progress, in agreement with the solid inclusions in the Panda diamonds. Phlogopite precipitated as an intermediate mineral and then disappeared. The aqueous Ca, Mg, Fe, Si and Al concentrations all increased, while Na, K, and Cl concentrations decreased during the reaction, consistent with trends in the fluid inclusion compositions. Our study demonstrates that fluids coming from subducting slabs could trigger mantle metasomatism, influence the compositions of sub-lithospherc cratonic mantle, precipitate diamonds, and change the oxygen fugacity and pH of the upper mantle fluids. [1] Tomlinson et al. EPSL (2006); [2] Sverjensky, DA et al., GCA (2014), Huang, F, Ph. D. thesis, Johns Hopkins University, (2017); [3] Shirey et al., Rev. Mineral. Geochem. (2013)

Expanding the REE Partitioning Database for Lunar Materials

NASA Technical Reports Server (NTRS)

Rapp, Jennifer F.; Draper, David S.

2014-01-01

Positive europium anomalies are ubiquitous in the plagioclase-rich rocks of the lunar highlands, and complementary negative Eu anomalies are found in most lunar basalts. This is taken as evidence of a large-scale differentation event, with crystallization of a global-scale lunar magma ocean (LMO) resulting in a plagioclase flotation crust and a mafic lunar interior from which mare basalts were later derived. However, the extent of the Eu anomaly in lunar rocks is variable. Some plagioclase grains in a lunar impact rock (60635) have been reported to display a negative Eu anomaly, or in some cases single grains display both positive and neagtive anomalies. Cathodoluminescence images reveal that some crystals have a negative anomaly in the core and positive at the rim, or vice versa, and the negative anomalies are not associated with crystal overgrowths. Oxygen fugacity is known to affect Eu partitioning into plagioclase, as under low fO2 conditions Eu can be divalent, and has an ionic radius similar to Ca2+ - significant in lunar samples where plagioclase compositions are predominantly anorthitic. However, there are very few experimental studies of rare earth element (REE) partitioning in plagioclase relevant to lunar magmatism, with only two plagioclase DEu measurements from experiments using lunar materials, and little data in low fO2 conditions relevant to the Moon. We report on REE partitioning experiments on lunar compositions. We investigate two lunar basaltic compositions, high-alumina basalt 14072 and impact melt breccia 60635. These samples span a large range of lunar surface bulk compositions. The experiments are carried out at variable fO2 in 1 bar gas mixing furnaces, and REE are analysed by and LA-ICP-MS. Our results not only greatly expand the existing plagioclase DREE database for lunar compositions, but also investigate the significance of fO2 in Eu partitioning, and in the interpretation of Eu anomalies in lunar materials.

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

NASA Astrophysics Data System (ADS)

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 < 10%) of the difference between Fe3+/∑Fe ratios determined by micro-colorimety and XANES can be attributed to the Mössbauer-based XANES calibration. The difference must instead derive from a bias between micro-colorimetry performed on experimental vs. natural basalts. 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.

Arsenic-enriched Cu-Ni-PGE Mineralization in Wetlegs, Duluth Complex, St. Louis County, Minnesota, USA

NASA Astrophysics Data System (ADS)

Raič, Sara; Mogessie, Aberra; Benkó, Zsolt; Molnár, Ferenc; Hauck, Steven; Severson, Mark

2014-05-01

The magmatic sulfide ore deposit Wetlegs is found within the troctolitic Partridge River Intrusion (PRI) of the 1.1 Ga Duluth Complex. It is of great interest, due to its highly mineralized zones containing Cu-Ni-Fe-Sulfides, platinum-group minerals (PGM) and arsenic-enriched ores. Sulfides appear as disseminated patches of primary pyrrhotite, chalcopyrite, Co-rich pentlandite and cubanite within a plagioclase, olivine and pyroxene matrix. Ores associated with hydrous silicate phases are secondary chalcopyrite, arsenic-enriched minerals, PGMs like sperrylite, stibiopalladinite and other precious minerals such as clausthalite, parkerite and electrum. Based on textural relationships, mineral compositions and sulfur isotopic studies, a paragenetic sequence of ore genesis in Wetlegs could be reconstructed starting with the formation of composite sulfides such as pyrrhotite, chalcopyrite, Co-enriched pentlandite and cubanite (at increased sulfur fugacity), defined as the Sulfide Stage. The Arsenide Stage is characterized by increased arsenic fugacity and a strong drop in sulfur fugacity with the following succession of precipitated minerals: 1) Monoarsenides (nickeline) found as remnants in diarsenides. 2) Diarsenides comprising members of the rammelsbergite - safflorite - loellingite solid-solution series (RSLss) and minerals of the rammelsbergite - loellingite solid-solutions series (RLss). Their crystallization temperature is between 550 and 625°C, estimated with solvus lines postulated by ROSEBOOM (1963) and GERVILLA & RØNSBO (1992) in the system CoAs2 - NiAs2 - FeAs2. This is subsequently followed by an Arsenide/Sulfide Stage which marks the formation of sulfarsenides of the cobaltite - gersdorffite solid-solution series at increased sulfur fugacity (drop in arsenic fugacity). Sulfarsenides display a clear cobalt trend from core to rim, and formed around 650°C with a decrease in temperature to ~ 500°C, documented by cobalt enriched rims, based on the solvus lines form HEM & MAKOVICKY (2004) and HEM (2006) in the system CoAsS - NiAsS - FeAsS. The presence of arsenides, sulfarsenides and graphite in footwall rocks may suggest the metasedimentary Virginia Formation as a potential source of As, Sb, and C. These elements were remobilized by hydrothermal fluids and introduced in the crystallizing magma to form arsenic-enriched Cu-Ni-PGE mineralization within the basal ultramafic rocks. δ34S of sulfides from representative samples of Wetlegs vary between 2.04 and 22.80 ‰. This suggests the involvement of crustal materials in addition to the magmatic source of sulfur in the Cu-Ni-PGE mineralization, as documented in previous studies (MOGESSIE & STUMPFL, 1992). We acknowledge financial support by the Austrian Research Fund (P23157-N21) to A. Mogessie GERVILLA, F. & RØNSBO, J. (1992): Neues Jahrb. Mineral., Monatsh. 13, pp. 193-206. HEM, S. R. (2006): Chem. Geol. 225, pp. 291-303. HEM. S. R. & MAKOVICKY, E. (2004): Canadian Mineralogist, v. 42, pp. 63-86. MOGESSIE, A. & STUMPLF, E. F. (1992): Australian Journal of Earth Sciences, v. 39, pp. 315-325. ROSEBOOM, E. H. (1963): American Mineralogist, v. 48, pp. 271-299.

Valence State Partitioning of Cr and V Between Olivine-Melt and Pyroxene-Melt in Experimental Basalts of a Eucritic Composition

NASA Technical Reports Server (NTRS)

Karner, J. M.; Jones, J. H.; Le, L.

2017-01-01

The partitioning of multivalent elements in basaltic systems can elucidate the oxygen fugacity (fO2) conditions under which basalts formed on planetary bodies (Earth, Moon, Mars, asteroids). Chromium and V are minor and trace elements in basaltic melts, partition into several minerals that crystallize from basaltic melts, exist in multiple valence states at differing fO2 conditions, and can therefore be used as oxybarometers for basaltic melts. Chromium is mostly 3+ in terrestrial basaltic melts at relatively high fO2 values (= IW+3.5), and mostly 2+ in melts at low fO2 values (= IW-1), such as those on the Moon and some asteroids. At intermediate fO2s, (i.e., IW-1 to IW+3.5), basaltic melts contain both Cr3+ and Cr2+. Vanadium in basaltic melts is mostly 4+ at high fO2, mostly 3+ at low fO2, and a mix of V3+ and V4+ at intermediate fO2 con-ditions. Understanding the partitioning of Cr and V into silicate phases with changing fO2 is therefore critical to the employment of Cr and V oxybarometers. In this abstract we examine the equilibrium partitioning of Cr and V between olivine/melt and pyroxene/melt in experimental charges of a eucritic composition produced at differing fO2 conditions. This study will add to the experimental data on DCr and DV (i.e., olivine/melt, pyroxene/melt) at differing fO2, and in turn these D values will be used to assess the fO2 of eucrite basalts and perhaps other compositionally similar planetary basalts.

Valence State Partitioning of V between Pyroxene and Melt for Martian Melt Compositions Y 980459 and QUE 94201: The Effect of Pyroxene Composition and Crystal Structure

NASA Technical Reports Server (NTRS)

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

2014-01-01

A spiked (with REE, V, Sc) martian basalt Y980459 composition was used to synthesize olivine, spinel, and pyroxene at 1200 C at 5 oxygen fugacities: IW-1, IW, IW+1, IW+2, and QFM. The high spike levels for REE were used for two specific reasons. First, we wanted to be able to analyze REE by both electron microprobe and ion probe. Second, we wanted the most important "Others" components, (i.e., those outside the pyroxene quadrilateral such as Al, Cr3+, Fe3+, REE3+, V3+, V4+, etc.) to be REE3+Mg (Si,Al)2O6. At the doped levels we used, the most important "Others" component is REE3+ in the M2 site coupled with Al in the tetrahedral site. The goal of this paper is to explain the significant increase in the value of D(sub V)(sup pyroxene/melt) with increased Wo content of the pyroxene. We compare augite (Wo approx. 33), pigeonite (Wo approx. 13) and orthopyroxene (Wo approx 3.8). We also show olivine for comparison. The crystal chemical factors which account for this remarkable increase of DV with Wo are twofold. First, with Ca in the M2 site (as in diopside, CaMgSi2O6) the site is large and 8-coordinated while Mg in the M2 site (as in enstatite, Mg2Si2O6) the site is smaller and 6- coordinated. Second, tetrahedral Al in the pyroxene chains provides charge balance and makes the M2 site larger and more compliant for the introduction of REE.

Oxygen Buffering in High Pressure Solid Media Assemblies: New Approach Enabling Study of fO2 from IW-4 to IW+4.5

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K. M.; Ross, D. K.; Butterworth, A. L.; Gainsforth, Z.; Jilly-Rehak, C. E.; Westphal, A. J.

2017-01-01

Oxygen fugacity is an intensive parameter that controls some fundamental chemical and physical properties in planetary materials. In terrestrial magmas high fO2 promotes magnetite stability and low fO2 causes Fe-enrichment due to magnetite suppression. In lunar and asteroidal basalts, low fO2 can allow metal to be stable. Experimental studies will therefore be most useful if they are done at a specific and relevant fO2 for the samples under consideration. Control of fO2 in the solid media apparatus (piston cylinder multi-anvil) has relied on either sliding sensors or graphite capsule buffering, which are of limited application to the wide range of fO2 recorded in planetary or astromaterials. Here we describe a new approach that allows fO2 to be specified across a wide range of values relevant to natural samples.

The Abandoned E-Waste Recycling Site Continued to Act As a Significant Source of Polychlorinated Biphenyls: An in Situ Assessment Using Fugacity Samplers.

PubMed

Wang, Yan; Luo, Chunling; Wang, Shaorui; Cheng, Zhineng; Li, Jun; Zhang, Gan

2016-08-16

The recycling of e-waste has attracted significant attention due to emissions of polychlorinated biphenyls (PCBs) and other contaminants into the environment. We measured PCB concentrations in surface soils, air equilibrated with the soil, and air at 1.5-m height using a fugacity sampler in an abandoned electronic waste (e-waste) recycling site in South China. The total concentrations of PCBs in the soils were 39.8-940 ng/g, whereas the concentrations in air equilibrated with the soil and air at 1.5 m height were 487-8280 pg/m(3) and 287-7380 pg/m(3), respectively. The PCB concentrations displayed seasonal variation; they were higher in winter in the soils and higher in summer in the air, indicating that the emission of PCBs from the soil was enhanced during hot seasons for the relatively high temperature or additional sources, especially for low-chlorinated PCBs. We compared two methods (traditional fugacity model and fugacity sampler) for assessing the soil-air partition coefficients (Ksa) and the fugacity fractions of PCBs. The results suggested that the fugacity sampler provided more instructive and practical estimation on Ksa values and trends in air-soil exchange, especially for low-chlorinated PCBs. The abandoned e-waste burning site still acted as a significant source of PCBs many years after the prohibition on open burning.

Semi-empirical estimation of organic compound fugacity ratios at environmentally relevant system temperatures.

PubMed

van Noort, Paul C M

2009-06-01

Fugacity ratios of organic compounds are used to calculate (subcooled) liquid properties, such as solubility or vapour pressure, from solid properties and vice versa. They can be calculated from the entropy of fusion, the melting temperature, and heat capacity data for the solid and the liquid. For many organic compounds, values for the fusion entropy are lacking. Heat capacity data are even scarcer. In the present study, semi-empirical compound class specific equations were derived to estimate fugacity ratios from molecular weight and melting temperature for polycyclic aromatic hydrocarbons and polychlorinated benzenes, biphenyls, dibenzo[p]dioxins and dibenzofurans. These equations estimate fugacity ratios with an average standard error of about 0.05 log units. In addition, for compounds with known fusion entropy values, a general semi-empirical correction equation based on molecular weight and melting temperature was derived for estimation of the contribution of heat capacity differences to the fugacity ratio. This equation estimates the heat capacity contribution correction factor with an average standard error of 0.02 log units for polycyclic aromatic hydrocarbons, polychlorinated benzenes, biphenyls, dibenzo[p]dioxins and dibenzofurans.

Partitioning of carbon between Fe-rich alloy melt and silicate melt in a magma ocean - Implications for the abundance and origin of volatiles in Earth, Mars, and the Moon

NASA Astrophysics Data System (ADS)

Chi, Han; Dasgupta, Rajdeep; Duncan, Megan S.; Shimizu, Nobumichi

2014-08-01

The budget and origin of carbon in Earth and other terrestrial planets are debated and one of the key unknowns is the fate of carbon during early planetary processes including accretion, core formation, and magma ocean (MO) crystallization. Here we determine, experimentally, the solubility of carbon in coexisting Fe-Ni alloy melt and basaltic silicate melt in shallow MO conditions, i.e., at 1-3 GPa, 1500-1800 °C. Oxygen fugacity of the experiments, estimated based on Fe (in metallic alloy melt)-FeO (in silicate melt) equilibrium, varied between ∼IW-0.4 and IW-1.0, where IW refers to the oxygen fugacity imposed by the coexistence of iron and wüstite. Four different starting mixes, each with 7:3 silicate:metal mass ratio and silicate melt NBO/T (estimated proportion of non-bridging oxygen with respect to tetrahedral cations; NBO/T=2×/total OT -4, where T = Si + Ti + Al + Cr + P) ranging from 0.81 to 1.54 were studied. Concentrations of carbon in the alloy melt were determined using electron microprobe whereas carbon contents of quenched basaltic glasses were determined using secondary ionization mass spectrometry (SIMS). Identification of carbon and hydrogen-bearing species in silicate glasses was performed using Raman and Fourier Transformed Infrared (FTIR) spectroscopy. Our results show that carbon in the metallic melt varies between 4.4 wt.% and 7.4 wt.% and increases with increasing temperature and modestly with increasing pressure but decreases with increasing Ni content of the alloy melt. Carbon concentration in the silicate melts, on the other hand, varies from 11 ± 1 ppm to 111 ± 7 ppm and is negatively correlated with pressure but positively correlated with temperature, the NBO/T, the oxygen fugacity and the water content of the silicate melts. Raman and FTIR results show that at our experimental conditions, carbon in silicate melt is dissolved both as hydrogenated species and CO32-. The calculated carbon partition coefficient DCmetal/silicate varies from 510 ± 53 to 5369 ± 217 and varies systematically as a function of P, T, fO2, water content, the composition of the silicate melt (expressed using NBO/T), and Ni content of alloy melt (XNi). The range of DCmetal/silicate measured in our study with carbonated and hydrogenated carbon species in silicate melt is similar to that reported in the literature for experiments where carbonyl complexes are the chief carbon species in silicate melts. A parameterization was derived using the data from this and existing studies such as lnDCmetal/silicate=a/T+b·P/T+c·ln(fO2)+d·(NBO/T)+e·ln(1-XNi)+f where a = -33,510, b = 1357, c = -0.596, d = -1.182, e = 4.15, f = 13.38, the temperature is in Kelvin, and the pressure is in gigapascal. Using this parameterization and the estimated conditions for the base of the MOs, the average DCmetal/silicate value for Earth, Mars, and the Moon can be predicted. The deep MO of Earth is predicted to cause the strongest depletion of its silicate carbon budget, closely followed by Mars with intermediate depth MO, and then the Moon with a shallow MO. We predict that the lunar mantle carbon budget, similar to that of the Earth’s present-day upper mantle, might have been set by equilibrium core-mantle fractionation in MO; whereas for Earth, later processes such as ingassing from a proto-atmosphere and late-stage accretion of volatile-rich material was necessary for delivery of carbon and other volatiles. Finally, the comparison of our measured and predicted value of DCmetal/silicate for terrestrial MO with similar constraints on DNmetal/silicate from the literature suggests that the apparent depletion of nitrogen relative to carbon for the bulk silicate Earth and the Earth’s upper mantle is unlikely to be caused by preferential partitioning of nitrogen to alloy melt during core formation.

Onset of phase separation in the double perovskite oxide La2MnNiO6

NASA Astrophysics Data System (ADS)

Spurgeon, Steven R.; Sushko, Peter V.; Devaraj, Arun; Du, Yingge; Droubay, Timothy; Chambers, Scott A.

2018-04-01

Identification of kinetic and thermodynamic factors that control crystal nucleation and growth represents a central challenge in materials synthesis. Here we report that apparently defect-free growth of La2MnNiO6 (LMNO) thin films supported on SrTiO3 (STO) proceeds up to 1-5 nm, after which it is disrupted by precipitation of NiO phases. Local geometric phase analysis and ensemble-averaged x-ray reciprocal space mapping show no change in the film strain away from the interface, indicating that mechanisms other than strain relaxation induce the formation of the NiO phases. Ab initio simulations suggest that the electrostatic potential build-up associated with the polarity mismatch at the film-substrate interface promotes the formation of oxygen vacancies with increasing thickness. In turn, oxygen deficiency promotes the formation of Ni-rich regions, which points to the built-in potential as an additional factor that contributes to the NiO precipitation mechanisms. These results suggest that the precipitate-free region could be extended further by either incorporating dopants that suppress the built-in potential or by increasing the oxygen fugacity in order to suppress the formation of oxygen vacancies.

Northwest Africa 5298: A Basaltic Shergottite

NASA Technical Reports Server (NTRS)

Hui, Hejiu; Peslier, Anne; Lapen, Thomas J.; Brandon, Alan; Shafer, John

2009-01-01

NWA 5298 is a single 445 g meteorite found near Bir Gandouz, Morocco in March 2008 [1]. This rock has a brown exterior weathered surface instead of a fusion crust and the interior is composed of green mineral grains with interstitial dark patches containing small vesicles and shock melts [1]. This meteorite is classified as a basaltic shergottite [2]. A petrologic study of this Martian meteorite is being carried out with electron microprobe analysis and soon trace element analyses by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Oxygen fugacity is calculated from Fe-Ti oxides pairs in the sample. The data from this study constrains the petrogenesis of basaltic shergottites.

Substitution and diffusion of Cr 2+ and Cr 3+ in synthetic forsterite and natural olivine at 1200–1500 °C and 1 bar

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jollands, M. C.; O'Neill, H. St. C.; Van Orman, J.

The diffusion and substitution mechanisms of Cr in forsterite were studied as a function of crystallographic orientation and the chemical potentials of all four components in the system MgO-SiO2-Cr-O. Oxygen fugacity (fO2) was varied over 15.4 log units at 1400 °C and was fixed at the iron-wüstite equilibrium for a temperature series (1200–1500 °C). The valence state changes of Cr along some diffusion profiles was also investigated using X-ray absorption near edge structure spectroscopy.

Distinct Chlorine Isotopic Reservoirs on Mars: Implications for Character, Extent and Relative Timing of Crustal Interaction with Mantle-Derived Magmas, Evolution of the Martian Atmosphere, and the Building Blocks of an Early Mars

NASA Technical Reports Server (NTRS)

Shearer, C. K.; Messenger, S.; Sharp, Z. D.; Burger, P. V.; Nguyen, N.; McCubbin, F. M.

2017-01-01

The style, magnitude, timing, and mixing components involved in the interaction between mantle derived Martian magmas and Martian crust have long been a point of debate. Understanding this process is fundamental to deciphering the composition of the Martian crust and its interaction with the atmosphere, the compositional diversity and oxygen fugacity variations in the Martian mantle, the bulk composition of Mars and the materials from which it accreted, and the noble gas composition of Mars and the Sun. Recent studies of the chlorine isotopic composition of Martian meteorites imply that although the variation in delta (sup 37) Cl is limited (total range of approximately14 per mille), there appears to be distinct signatures for the Martian crust and mantle. However, there are potential issues with this interpretation. New Cl isotope data from the SAM (Sample Analysis at Mars) instrument on the Mars Science Lab indicate a very wide range of Cl isotopic compositions on the Martian surface. Recent measurements by [10] duplicated the results of [7,8], but placed them within the context of SAM surface data. In addition, Martian meteorite Chassigny contains trapped noble gases with isotopic ratios similar to solar abundance, and has long been considered a pristine, mantle derived sample. However, previous studies of apatite in Chassigny indicate that crustal fluids have interacted with regions interstitial to the cumulus olivine. The initial Cl isotope measurements of apatite in Chassigny suggest an addition of crustal component to this lithology, apparently contradicting the rare gas data. Here, we examine the Cl isotopic composition of multiple generations and textures of apatite in Chassigny to extricate the crustal and mantle components in this meteorite and to reveal the style and timing of the addition of crustal components to mantle-derived magmas. These data reveal distinct Martian Cl sources whose signatures have their origins linked to both the early Solar System and the evolving Martian atmosphere.

The Role of Carbon in Exotic Crust Formation on Mercury

NASA Technical Reports Server (NTRS)

Vander Kaaden, Kathleen E.; McCubbin, Francis M.

2018-01-01

The terrestrial planets that comprise our inner Solar System, including the Moon, are all rocky bodies that have differentiated into a crust, mantle, and core. Furthermore, all of these bodies have undergone various igneous processes since their time of primary crust formation. These processes have resurfaced each of these bodies, at least in part, resulting in the production of a secondary crust, to which Mercury is no exception. From its first flyby encounter with Mercury on January 14, 2008, the MErcury Surface, Space ENvironment, GEochemistry and Ranging (MESSENGER) spacecraft collected data on the structure, chemical makeup, and density of the planet among other important characteristics. The X-Ray Spectrometer on board MESSENGER measured elevated abundances of sulfur and low abundances of iron, suggesting the planets oxygen fugacity (fO2) is several log10 units below the Iron-Wustite buffer. Similar to the role of other volatiles (e.g. sulfur) on highly reducing planetary bodies, carbon is expected to behave differently in an oxygen starved environment than it does in an oxygen enriched environment (e.g., Earth).

Cr, Mn, and Ca distributions for olivine in angritic systems: Constraints on the origins of Cr-rich and Ca-poor core olivine in angrite LEW87051

NASA Technical Reports Server (NTRS)

Mikouchi, T.; Mckay, G.; Le, L.

1994-01-01

Angrite meteorites are a type of basaltic achondrites that are noted for their very old cyrstallization ages (4.55 b.y.) and unusual chemical and mineralogical properties. In spite of great interest, only four angrites have been found. LEW87051 is the smallest one which weighs 0.6 g. It is a porphyritic rock with coarse subhedral to euhedral olivines set in a fine-grained groundmass which clearly represents a crystallized melt. The largest uncertainty about the petrogenesis of LEW87051 is the relationship between the large olivine crystals and the groundmass. Prinz et al. suggests that olivines are xenocrysts, while McKay et al. proposed a fractional cyrstallization model based on experimental studies. However, the crystals have Cr-rich and Ca-poor cores which do not match experimental olivines. Although Jurewicz and McKay tried to explaine the zoning of the rim by diffusion, some features are not explained. There also exists a definite composition boundary of Fe(2+) and MnO between the core and the rim. To clarify the origin of these olivines, we have performed experiments using LEW87051 analogs to measure the effects of oxygen fugacity on distribution coefficients of various elements in an angritic system.

Geochronology and petrogenesis of the Qibaoshan Cu-polymetallic deposit, northeastern Hunan Province: Implications for the metal source and metallogenic evolution of the intracontinental Qinhang Cu-polymetallic belt, South China

NASA Astrophysics Data System (ADS)

Yuan, Shunda; Mao, Jingwen; Zhao, Panlao; Yuan, Yabin

2018-03-01

The recently recognized Qinhang metallogenic belt (QHMB) is an economically important intracontinental Mesozoic porphyry-skarn Cu-polymetallic metallogenic belt in South China. However, the origin of the ore-bearing magma and the major factors controlling the different metal assemblages in the QHMB are still unclear. The Qibaoshan deposit is a large Cu-Au-Pb-Zn-Ag-Fe deposit located at the juncture between the northern and central parts of the QHMB. In this study, new zircon U-Pb ages, Hf-O isotopic data, molybdenite Re-Os ages, and whole-rock geochemical data are combined to constrain the timing of the mineralization and the origin and petrogenesis of the ore-bearing porphyry in the Qibaoshan deposit. The ages obtained from both zircon U-Pb and molybdenite Re-Os dating fall in the Late Jurassic (between 152.7 and 148.3 Ma), revealing that this deposit is significantly younger than previously estimated (227-184 Ma). The Qibaoshan ore-bearing quartz porphyry shows variable negative zircon εHf(t) values (-14.8 to -5.5), high δ18O values (8.4 to 10.8‰), and high Mg# values (69.1 to 73.0), indicating that it formed via the partial melting of ancient crust triggered by the injection of mantle-derived magma. Zircon Hf-O isotopic modeling of the mixing of two extreme endmembers indicates that the magmatic source comprised 70-80% reworked ancient crustal components and 20-30% depleted mantle components. Based on comparisons with other ore-bearing porphyries in the QHMB, a magmatic source dominated by crust-derived material and relatively low oxygen fugacities (ΔFMQ -1.8 to ΔFMQ +0.8) was responsible for the high (Pb + Zn)/Cu ratio in the Qibaoshan deposit, and the Pb, Zn and Ag were mainly derived from the reworked ancient crust. Although four analyses of inherited Neoproterozoic zircons ( 800 Ma) have variable positive εHf(t) values (0.72 to 11.21), indicating that Neoproterozoic juvenile crust was involved in the formation of the Qibaoshan ore-bearing quartz porphyry, the relatively low oxygen fugacities (ΔFMQ -1.2 to ΔFMQ +0.4) of the parent magma of these inherited zircons suggest that this parent magma could not have provided significant metallic Cu for mineralization in the Qibaoshan Cu-polymetallic deposit. Therefore, the metallic Cu in the Qibaoshan Cu-polymetallic deposit was probably provided by the injection of the mantle-derived magma. Because ore-forming magmas with relatively low oxygen fugacities have low Au solubility, the large Au mineralization in the Qibaoshan deposit may be related to high background values of Au in this area. Our data, integrated with regional petrogeochemical data, indicate that the magmatic source exerted a first-order control on the different metal assemblages in the deposits in the QHMB.

An evolving magmatic-hydrothermal system in the formation of the Mesozoic Meishan magnetite-apatite deposit in the Ningwu volcanic basin, eastern China

NASA Astrophysics Data System (ADS)

Liu, Wen-Hao; Jiang, Man-Rong; Zhang, Xiao-Jun; Xia, Yan; Algeo, Thomas J.; Li, Huan

2018-06-01

The Meishan iron deposit contains 338 Mt of iron-ore reserves at 39% Fe and represents the largest magnetite-apatite deposit in the Ningwu Basin of eastern China. Controversy has long existed about whether this deposit had a hydrothermal or iron-oxide melt origin. Iron mineralization is genetically related to plutons that are composed of gabbro-diorite, which were emplaced at 130 ± 1 Ma. These rocks have SiO2 contents of 51.72-54.60 wt%, Na2O contents of 3.47-4.04 wt%, K2O contents of 2.02-2.69 wt%, and K2O/Na2O ratios of 0.51-0.73. These rocks are enriched in LILEs and LREEs and depleted in Nb, Ta, and Ti, which indicates that the magma originated through partial melting of an enriched lithospheric mantle source in a subduction environment. A pattern of decreasing initial Sr isotopic ratios and increasing εNd(t) values with time in Early Cretaceous magmatic rocks of the Ningwu Basin may indicate incorporation of increasing proportions of asthenospheric mantle material into the source magma, which is consistent with the processes of lithospheric thinning and asthenospheric upwelling in eastern China related to Mesozoic subduction of the Paleo-Pacific Plate. Two stages of magnetite are found in the gabbro-diorite: (1) early-crystallized magnetite as euhedral-subhedral crystals in larger clinopyroxene crystals, and (2) later-crystallized magnetite and accompanying ilmenite grains in the voids between plagioclase and clinopyroxene crystals. The formation of magnetite before clinopyroxene, combined with the results of Fe-Ti oxide geothermometry and analysis of magnetite V content, indicates that the oxygen fugacity of the source magma was greater than ΔFMQ +2.2 at an early stage (>640 °C) but decreased to ΔFMQ -2.66 as abundant magnetite crystallized at a later stage (∼489 °C). The early crystallization of magnetite at a high oxygen fugacity does not support a Fenner evolution trend for the primitive magma and diminishes the likelihood of liquid immiscibility, which could have generated an iron-rich melt, and is thus inconsistent with an iron-oxide melt origin for the Meishan iron deposit. The δ34S values of pyrite (6.6-15.1‰) and anhydrite (15.6-16.9‰) in the deposit and the occurrence of evaporites under the volcanic rocks likely indicate that the iron ores and alteration rocks of the Meishan deposit were formed by the circulation of fluids of evaporitic origin driven by heat from the hypabyssal gabbro-diorite intrusives. In the late magmatic stage, oxygen fugacity decreased to a reducing range, triggering the reduction of sulfate to reduced sulfur and leading to local gold and pyrite mineralization.

Chicxulub ejecta at the Cretaceous-Paleogene (K-P) boundary in Northeastern Mexico

NASA Astrophysics Data System (ADS)

Schulte, Peter; Kontny, Agnes

2005-04-01

The combined petrological and rock magnetic study of the Cretaceous-Paleogene (K-P) boundary in northeastern Mexico revealed compositionally and texturally complex Chicxulub ejecta deposits. The predominant silicic ejecta components are Fe-Mg-rich chlorite and Si-Al-K-rich glass spherules with carbonate inclusions and schlieren. Besides these silica phases, the most prominent ejecta component is carbonate. Carbonate occurs as lithic clasts, accretionary lapilli, melt globules (often with quench textures), and as microspar. The composition of the spherules provides evidence for a range of target rocks of mafic to intermediate composition, presumably situated in the northwestern sector of the Chicxulub impact structure. The abundance of carbonate ejecta suggests that this area received ejecta mainly from shallow, carbonate-rich lithologies. Rare µm-sized metallic and sulfidic Ni-Co-rich inclusions in the spherules indicate a possible contamination by meteoritic material. This complex composition underlines the similarities of ejecta in NE Mexico to Chicxulub ejecta from K-P sections worldwide. Although the ejecta display a great variability, the magnetic susceptibility, remanence, and hysteresis properties of the ejecta deposits are fairly homogeneous, with dominantly paramagnetic susceptibilities and a weak ferromagnetic contribution from hematite and goethite. The absence of spinels and the ubiquitous presence of hematite and goethite points to high oxygen fugacity during the impact process. The microfacies and internal texture of the ejecta deposits show welding and fusing of components, as well as evidence for liquid immiscibility between silicic and carbonate melts. No evidence for binary mixing of ejecta phases was found. Therefore, Chicxulub ejecta in NE Mexico probably derived from less energetic parts of the ejecta curtain. However, welding features of ejecta particles and enclosed marl clasts and/or benthic foraminifera from a siliciclastic environment suggest interaction of the - still hot - ! ejecta curtain with northern Mexican shelf sediments. In addition, an initial ground surge-like ejecta-dispersion mode seems possible.

Mass dependent fractionation of stable chromium isotopes in mare basalts: Implications for the formation and the differentiation of the Moon

NASA Astrophysics Data System (ADS)

Bonnand, Pierre; Parkinson, Ian J.; Anand, Mahesh

2016-02-01

We present the first stable chromium isotopic data from mare basalts in order to investigate the similarity between the Moon and the Earth's mantle. A double spike technique coupled with MC-ICP-MS measurements was used to analyse 19 mare basalts, comprising high-Ti, low-Ti and KREEP-rich varieties. Chromium isotope ratios (δ53Cr) for mare basalts are positively correlated with indices of magmatic differentiation such as Mg# and Cr concentration which suggests that Cr isotopes were fractionated during magmatic differentiation. Modelling of the results provides evidence that spinel and pyroxene are the main phases controlling the Cr isotopic composition during fractional crystallisation. The most evolved samples have the lightest isotopic compositions, complemented by cumulates that are isotopically heavy. Two hypotheses are proposed to explain this fractionation: (i) equilibrium fractionation where heavy isotopes are preferentially incorporated into the spinel lattice and (ii) a difference in isotopic composition between Cr2+ and Cr3+ in the melt. However, both processes require magmatic temperatures below 1200 °C for appreciable Cr3+ to be present at the low oxygen fugacities found in the Moon (IW -1 to -2 log units). There is no isotopic difference between the most primitive high-Ti, low-Ti and KREEP basalts, which suggest that the sources of these basalts were homogeneous in terms of stable Cr isotopes. The least differentiated sample in our sample set is the low-Ti basalt 12016, characterised by a Cr isotopic composition of -0.222 ± 0.025‰, which is within error of the current BSE value (-0.124 ± 0.101‰). The similarity between the mantles of the Moon and Earth is consistent with a terrestrial origin for a major fraction of the lunar Cr. This similarity also suggests that Cr isotopes were not fractionated by core formation on the Moon.

Examining the Possibility of Carbon as a Light Element in the Core of Mercury

NASA Technical Reports Server (NTRS)

Vander Kaaden, Kathleen; McCubbin, Francis M.; Turner, Amber; Ross, D. Kent

2017-01-01

Results from the MErcury Surface, Space ENvironment, GEochemistry and Ranging (MESSENGER) spacecraft have shown elevated abundances of C on the surface of Mercury. Peplowski et al. used GRS data from MESSENGER to show an average northern hemisphere abundance of C on the planet of 0 to 4.1 wt% C at the three-sigma detection limit. Confirmation of C on the planet prompts many questions regarding the role of C during the differentiation and evolution of Mercury. The elevated abundances of both S and C on Mercury's surface, coupled with the low abundances of iron, suggest that the oxygen fugacity of the planet is several log10 units below the Iron-Wustite buffer. These observations spark questions about the bulk composition of Mercury's core. This experimental study seeks to understand the impact of C as a light element on potential mercurian core compositions. In order to address this question, experiments were conducted at 1 GPa and a variety of temperatures (700 - 1500 C) on metal compositions ranging from Si5Fe95 to Si22Fe78, possibly representative of the mercurian core. All starting metals were completely enclosed in a graphite capsule to ensure C saturation at a given set of run conditions. All elements, including C, were analyzed using electron probe microanalysis. Precautions were taken to ensure accurate measurements of C with this technique including using the LDE2 crystal, the cold finger on the microprobe to minimize contamination and increase the vacuum, and an instrument with no oil based pumps. Based on the superliquidus experimental results in the present study, as Fe-rich cores become more Si-rich, the C content of that core composition will decrease. Furthermore, although C concentration at graphite saturation (CCGS) varies from a liquid to a solid, temperature does not seem to play a substantial role in CCGS, at least at 1 GPa.

Magnesioferrite from the Cretaceous-Tertiary boundary, Caravaca, Spain

USGS Publications Warehouse

Bohor, B.F.; Foord, E.E.; Ganapathy, R.

1986-01-01

Magnesioferrite grading toward magnetite has been identified as a very small but meaningful constituent of the basal iron-rich portion of the Cretaceous-Tertiary (K-T) boundary clay at the Barranco del Gredero section, Caravaca, Spain. This spinel-type phase and others of the spinel group, found in K-T boundary clays at many widely separated sites, have been proposed as representing unaltered remnants of ejecta deposited from an earth-girdling dust cloud formed from the impact of an asteroid or other large bolide at the end of the Cretaceous period. The magnesioferrite occurs as euhedral, frequently skeletal, micron-sized octahedral crystals. The magnesioferrite contains 29 ?? 11 ppb Ir, which accounts for only part of the Ir anomaly at this K-T boundary layer (52 ?? 1 ppb Ir). Major element analyses of the magnesioferrite show variable compositions. Some minor solid solution exists toward hercynite-spinel and chromite-magnesiochromite. A trevorite-nichromite (NiFe2O4NiCr2O4) component is also present. The analyses are very similar to those reported for sites at Furlo and Petriccio, Umbria, Italy. On the basis of the morphology and general composition of the magnesioferrite grains, rapid crystallization at high temperature is indicated, most likely directly from a vapor phase and in an environment of moderate oxygen fugacity. Elemental similarity with metallic alloy injected into rocks beneath two known impact craters suggests that part of the magnesioferrite may be derived from the vaporized chondritic bolide itself, or from the mantle; there is no supporting evidence for its derivation from crustal target rocks. ?? 1986.

Gas chemistry and thermometry of the Cerro Prieto, Mexico, geothermal field

USGS Publications Warehouse

Nehring, N.L.; D'Amore, F.

1984-01-01

Gas compositions of Cerro Prieto wells in 1977 reflected strong boiling in the reservoir around wells M-20 and M-25. This boiling zone appeared to be collapsing in 1982 when a number of wells in this area of the field were shut-in. In 1977 and 1982, gas compositions also showed boiling zones corresponding to faults H and L postulated by Halfman et al. (1982). Four gas geothermometers were applied, based on reservoir equilibria and calculated fugacities. The Fisher - Tropsch reaction predicted high temperatures and appeared to re-equilibrate slowly, whereas the H2S reaction predicted low temperatures and appeared to re-equilibrate rapidly. Hydrogen and NH3 reactions were intermediate. Like gas compositions, the geothermometers reflected reservoir processes, such as boiling. Surface gas compositions are related to well compositions, but contain large concentrations of N2 originating from air dissolved in groundwater. The groundwater appears to originate in the east and flow over the production field before mixing with reservoir gases near the surface. ?? 1984.

Experimental determination of activities in FeTiO3-MnTiO3 ilmenite solid solution by redox reversals

NASA Astrophysics Data System (ADS)

Feenstra, A.; Peters, Tjerk

1996-12-01

Solid solutions of (Fe,Mn)TiO3 were synthesized, mostly at 0.10 XMn intervals, at 1 bar, 900°C and log f O 2 = 17.50. Analysis by EMP indicate an ideal stoichiometry for the Fe-Mn ilmenites with (Fe+Mn) = Ti = 1.000 when normalized to 3 oxygens. Their unit cell volume increases linearly with XMn. The composition of Fe-Mn ilmenite coexisting with metallic Fe and rutile was reversed at 1 bar, 700 900°C and fixed f O 2 in a gas-mixing furnace. Oxygen fugacity was controlled by mixing CO2 and H2 gas and was continuously monitored with an yttrium-stabilized zirconia electrolyte. Solution properties of Fe-Mn ilmenite were derived from the experimental data by mathematical programming (Engi and Feenstra, in preparation) including notably the results of Fe-Mn exchange experiments between ilmenite and garnet (Feenstra and Engi, submitted) and anchoring the standard state properties to the updated thermodynamic dataset of Berman and Aranovich (1996). The thermodynamic analysis resulted in positive deviations from ideality for (Fe,Mn)TiO3 ilmenite, which is well described by an asymmetric Margules model with WH FeFeMn = 9.703 and WH FeMnMn = 23.234 kJ/mol, WS FeFeMn = 19.65 and WS FeMnMn = 22.06 J/(K·mol). The excess free energy for Fe-Mn ilmenite derived from the redox reversals is larger than in the symmetric ilmenite model (WG FeMn = +2.2 kJ/mol) determined by O'Neill et al. from emf measurements on the assemblage iron-rutile-(Fe,Mn)ilmenite.

Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

NASA Astrophysics Data System (ADS)

Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

2018-03-01

Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T < 1422 K for rhodium sesquioxide and T < 1815 K for ruthenium dioxide), the formed oxides are relatively stable. On the other hand, at high temperatures (T > 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

Metal-rich meteorites from the aubrite parent body

NASA Technical Reports Server (NTRS)

Casanova, I.; Mccoy, T. J.; Keil, K.

1993-01-01

Three metal-rich meteorites - Mt. Egerton, Horse Creek, and LEW 88055 - were studied and it is suggested that they formed in the aubrite parent body. LEW 85369 and 88631 may also have a common origin, but these rocks have not yet been studied in detail. This body was probably heated to about 1600 C by a very strong heat source. While molten, metal agglomerated into sizeable nodules which never segregated efficiently to form a core, but were trapped in the silicate mantle. Different clasts and lithologies in aubrites solidified and cooled under local equilibrium conditions of oxygen fugacity, and with different thermal histories. Impacts mixed clasts from throughout the parent body, creating the typical aubrite breccias.

Fugacity ratio estimations for high-melting rigid aromatic compounds.

PubMed

Van Noort, Paul C M

2004-07-01

Prediction of the environmental fate of organic compounds requires knowledge of their tendency to stay in the gas and water phase. Vapor pressure and aqueous solubility are commonly used descriptors for these processes. Depending on the type of distribution process, values for either the pure solid state or the (subcooled) liquid state have to be used. Values for the (subcooled) liquid state can be calculated from those for the solid state, and vice versa, using the fugacity ratio. Fugacity ratios are usually calculated from the entropy of fusion and the melting point. For polycyclic aromatic hydrocarbons, chlorobenzenes, chlorodibenzofuranes, and chlorodibenzo(p)dioxins, fugacity ratios calculated using experimental entropies of fusion were systematically less than those obtained from a thermodynamically more rigorous approach using heat capacity data. The deviation was more than 1 order of magnitude at the highest melting point. The use of a universal value for the entropy of fusion of 56 J/molK resulted in either over or underestimation by up to more than 1 order of magnitude. A simple correction factor, based on the melting point only, was derived. This correction factor allowed the fugacity ratios to be estimated from experimental entropies of fusion and melting point with an accuracy better than 0.1-0.2 log units. Copyright 2004 Elsevier Ltd.

Onset of phase separation in the double perovskite oxide La 2 MnNiO 6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spurgeon, Steven R.; Sushko, Peter V.; Devaraj, Arun

2018-04-01

Identification of kinetic and thermodynamic factors that control crystal nucleation and growth represents a central challenge in materials synthesis. Here we report that apparently defect-free growth of La2MnNiO6 (LMNO) thin films supported on SrTiO3 (STO) proceeds up to 1–5 nm, after which it is disrupted by precipitation of NiO phases. Local geometric phase analysis and ensemble-averaged x-ray reciprocal space mapping show no change in the film strain away from the interface, indicating that mechanisms other than strain relaxation induce the formation of the NiO phases. Ab initio simulations suggest that the electrostatic potential build-up associated with the polarity mismatch atmore » the film-substrate interface promotes the formation of oxygen vacancies with increasing thickness. In turn, oxygen deficiency promotes the formation of Ni-rich regions, which points to the built-in potential as an additional factor that contributes to the NiO precipitation mechanisms. These results suggest that the precipitate-free region could be extended further by either incorporating dopants that suppress the built-in potential or by increasing the oxygen fugacity in order to suppress the formation of oxygen vacancies.« less

Calc-silicate mineralization in active geothermal systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bird, D.K.; Schiffman, P.; Elders, W.A.

The detailed study of calc-silicate mineral zones and coexisting phase relations in the Cerro Prieto geothermal system were used as examples for thermodynamic evaluation of phase relations among minerals of variable composition and to calculate the chemical characteristics of hydrothermal solutions compatible with the observed calc-silicate assemblages. In general there is a close correlation between calculated and observed fluid compositions. Calculated fugacities of O{sub 2} at about 320{degrees}C in the Cerro Prieto geothermal system are about five orders of magnitude less than that at the nearby Salton Sea geothermal system. This observation is consistent with the occurrence of Fe{sup 3+}more » rich epidotes in the latter system and the presence of prehnite at Cerro Prieto.« less

Experimental evidence for Mo isotope fractionation between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Burkhardt, Christoph; Schmidt, Max W.; Bourdon, Bernard; Kleine, Thorsten

2013-10-01

Stable isotope fractionation of siderophile elements may inform on the conditions and chemical consequences of core-mantle differentiation in planetary objects. The extent to which Mo isotopes fractionate during such metal-silicate segregation, however, is so far unexplored. We have therefore investigated equilibrium fractionation of Mo isotopes between liquid metal and liquid silicate to evaluate the potential of Mo isotopes as a new tool to study core formation. We have performed experiments at 1400 and 1600 °C in a centrifuging piston cylinder. Tin was used to lower the melting temperature of the Fe-based metal alloys to <1400 °C, while variable Fe-oxide contents were used to vary oxygen fugacity in graphite and MgO capsules. Isotopic analyses were performed using a double spike technique. In experiments performed at 1400 °C, the 98Mo/95Mo ratio of silicate is 0.19±0.03‰ (95% confidence interval) heavier than that of metal. This fractionation is not significantly affected by the presence or absence of carbon. Molybdenum isotope fractionation is furthermore independent of oxygen fugacity in the range IW -1.79 to IW +0.47, which are plausible values for core formation. Experiments at 1600 °C show that, at equilibrium, the 98Mo/95Mo ratio of silicate is 0.12±0.02‰ heavier than that of metal and that the presence or absence of Sn does not affect this fractionation. Equilibrium Mo isotope fractionation between liquid metal and liquid silicate as a function of temperature can therefore be described as ΔMoMetal-Silicate98/95=-4.70(±0.59)×105/T2. Our experiments show that Mo isotope fractionation may be resolvable up to metal-silicate equilibration temperatures of about 2500 °C, rendering Mo isotopes a novel tool to investigate the conditions of core formation in objects ranging from planetesimals to Earth sized bodies.

Experimental determination of Pb partitioning between sulfide melt and basalt melt as a function of P, T and X

NASA Astrophysics Data System (ADS)

Hart, Stanley R.; Gaetani, Glenn A.

2016-07-01

We have measured the partition coefficient of Pb (KdPb) between FeS melt and basalt melt at temperatures of 1250-1523 °C, pressures of 1.0-3.5 GPa and oxygen fugacities at iron-wustite and wustite-magnetite. The total observed range of KdPb is 4.0-66.6, with a strong negative dependence on pressure and a strong negative dependence on FeO of the silicate melt (Fe+2 only). The FeO control was constrained over a wide range of FeO (4.2-39.5%). We found that the effect of oxygen fugacity can be subsumed under the FeO control parameter. Prior work has established the lack of a significant effect of temperature (Kiseeva and Wood, 2015; Li and Audétat, 2015). Our data are parameterized as: KdPb = 4.8 + (512 - 119*P in GPa)*(1/FeO - 0.021). We also measured a single value of KdPb between clinopyroxene and basalt melt at 2.0 GPa of 0.020 ± 0.001. This experimental data supports the ;natural; partitioning of Pb measured on sulfide globules in MORB (Patten et al., 2013), but not the low KdPb of ∼3 inferred from sulfides in abyssal peridotites by Warren and Shirey (2012). It also quantitatively affirms the modeling of Hart and Gaetani (2006) with respect to using sulfide to buffer the canonical Nd/Pb ratio for MORB and OIB (Hofmann, 2003). For the low FeO and pressure of segregation typical of MORB, KdPb ∼ 45, and the Nd/Pb ratio of erupted basalts will be the same as the Nd/Pb ratio of the mantle source. The remaining puzzle is why MORB and OIB have the same Nd/Pb when they clearly have different FeO and pressure of melt segregation.

Oxidation of shallow conduit magma: Insight from μ-XANES analysis on volcanic ash particle

NASA Astrophysics Data System (ADS)

Miwa, T.; Ishibashi, H.; Iguchi, M.

2014-12-01

Redox state of magma is important to understand dynamics of volcanic eruptions because magma properties such as composition of degassed volatiles, stability field of minerals, and rheology of magma depend on redox state. To evaluate redox state of magma, Fe3+/ΣFe ratio [= Fe3+/( Fe3++ Fe2+)] of volcanic glass has been measured non-destructively by Fe-K edge μ-XANES (micro X-ray Absorption Near Edge Structure) spectroscopy (e.g., Cottrell and Kelly, 2011). We performed textural, compositional, and Fe-K edge μ-XANES analyses on volcanic ash to infer oxidation process of magma at shallow conduit during eruption at Bromo Volcano, Indonesia. The volcanic ash particles were collected in 24th March 2011 by real-time sampling from ongoing activity. The activity was characterized by strombolian eruption showing magma head ascended to near the ground surface. The ash sample contains two type of volcanic glasses named as Brown and Black glasses (BrG and BlG), based on their color. Textual analysis shows microlite crystallinities are same in the two type of glasses, ranging from 0 to 3 vol.%. EPMA analyses show that all of the glasses have almost identical andesitic composition with SiO2 = 60 wt.%. In contrast, Fe-K edge μ-XANES spectra with the analytical method by Ishibashi et al. (in prep) demonstrate that BrG (Fe3+/ΣFe = 0.20-0.26) is more oxidized than BlG (Fe3+/ΣFe = 0.32-0.60). From combination of the glass composition, the measured Fe3+/ΣFe ratio and 1060 degree C of temperature (Kress and Carmichael, 1991), the oxygen fugacities are estimated to be NNO and NNO+4 for BrG and BlG, respectively. The volcanic glasses preserve syn-eruptive physicochemical conditions by rapid quenching due to their small size ranging from 125 to 250 μm. Our results demonstrate that BrG and BlG magmas are textually and chemically identical but their redox conditions are different at the eruption. The oxidation of magma can be caused by following two processes; 1) diffusive transport of oxygen, and 2) dissociation reaction of hydrogen from magma head. The two processes should be easy to occur in shallower region of the conduit. Therefore we suggest BlG magma existed in shallower part of the conduit than BrG magma. The K-edge μ-XANES analysis can be strong tool for understanding on degassing and ascent process of magma at shallow conduit.

Utilizing polymer-coated vials to illustrate the fugacity and bioavailability of chlorinated pesticide residues in contaminated soils

USDA-ARS?s Scientific Manuscript database

Fugacity and bioavailability concepts can be challenging topics to communicate effectively in the timeframe of an academic laboratory course setting. In this experiment, students observe partitioning of the residues over time into an artificial biological matrix. The three compounds utilized are o...

Fe and S redox states during serpentinite dehydration in subduction settings

NASA Astrophysics Data System (ADS)

Merkulova, Margarita; Munoz, Manuel; Vidal, Olivier; Brunet, Fabrice

2016-04-01

Serpentinite rocks formed by hydrothermal alteration of oceanic peridotites compose ~70% of the oceanic crust (Hacker et al., 2003), which later sinks into subduction zone and experiences metamorphic reactions. Serpentinites carry ~12 wt.% H2O and thereby introduces large amount of water in the upper mantle during dehydration in subduction (Ulmer and Trommsdorff, 1995). In addition, serpentinites are known to contain such minerals as magnetite Fe3O4 and pyrite FeS2 in the amounts of ~5 wt.% (Debret et al., 2014) and 1.5 wt.% (Alt et al., 2013), respectively. During metamorphic reactions speciations of Fe and S are tended to change and affect oxygen fugacity. In turn, oxygen fugacity influences the mobility of fluid mobile elements and metals (Pokrovski and Dubrovinsky 2011). We characterized Fe and S speciation and amount of released water during serpentinite dehydration at different temperature and pressure intervals along a subduction zone. We performed three sets of experiments using piston-cylinder apparatus. Three different starting materials composed of powdered mineral mixtures were used: Fe(III)-antigorite (atg), atg + magnetite, atg + pyrite. Experimental runs were performed at 2 GPa, between 400 and 900°C. Experimental products were first characterized by X-ray diffraction and electron microprobe. Speciation of Fe and S were characterized by X-ray absorption spectroscopy (XANES) at iron and sulfur K-edges. In addition, thermodynamic modeling was applied in this work with constrained thermodynamical data for Fe-bearing antigorite. The results demonstrate the continuous dehydration of serpentinites with the main water releasing domain between 670 and 700°C, which is happening due to breakdown of antigorite. Fe K-edge XANES measurements show that the amount of ferric iron dramatically decreases between 550-650°C, leading to a release of free oxygen in the system. As a result, we show that the first fluids released from the slab dehydration most likely present highly oxidizing properties. At higher P-T conditions, higher amounts of water are released with minor oxygen release. In addition, sulfur is shown to be progressively reduced at temperature 450-500°C due to pyrite to pyrrhotite transition. The reaction of pyrite reduction was observed to happen with sequestration of Fe from silicates and a release of oxygen. Effectively, the presence of sulphides in serpentinites contribute additional oxygen to the fluid, whereas the release of S may be negligible. The detailed study of the evolution of redox conditions during serpentinite dehydration in subduction zones will help constraining, 1) the behavior and mobility, from slab to the upper mantle, of elements of economical interest, as well as 2) the global geochemical cycling of elements. References: 1. Hacker et al. (2003) J. Geophys. Res. 108, article number 2029. 2. Ulmer & Trommsdorff (1995) Science 268, 858-861. 3. Debret et al. (2014) EPSL 400, 206-218. 4. Alt et al. (2013) Lithos 178, 40-54. 5. Pokrovski & Dubrovinsky (2011) Science 331, 1052-1056.

Relationships between oxygen fugacity and metasomatism in the Kaapvaal subcratonic mantle, represented by garnet peridotite xenoliths in the Wesselton kimberlite, South Africa

NASA Astrophysics Data System (ADS)

Hanger, Brendan J.; Yaxley, Gregory M.; Berry, Andrew J.; Kamenetsky, Vadim S.

2015-01-01

A suite of 12 peridotite xenoliths from the Wesselton kimberlite was studied and found to sample the subcratonic lithospheric mantle over a pressure range from 3.6 to 4.7 GPa and a temperature range of 880 to 1120 °C. Major, minor and trace element compositions indicate that both metasomatised and un-metasomatised samples are present over this pressure range. Fe3 +/∑ Fe in garnet from four xenoliths was determined using Fe K-edge XANES spectroscopy, enabling the redox state of the sampled subcratonic mantle to be determined for three garnet bearing samples. ΔlogfO2[FMQ] varied from 0 to - 3.3 over the sampled pressure interval, with the un-metasomatised samples falling within the global trend of decreasing ΔlogfO2[FMQ] with increasing depth. Superimposed on this was an oxidation trend, at higher pressures (≥ 4.5 GPa), with ΔlogfO2 increasing by 1.5 to 2 units in the metasomatically enriched samples, indicating a clear link between metasomatism and oxidation. One potential source of this oxidation is a carbonated silicate melt, which will increase in carbonate content as ΔlogfO2 increases. Mantle minerals affected by such a melt have the potential to shift from the field of diamond stability into that of carbonate, threatening the stability of diamond.

Redox-influenced seismic properties of upper-mantle olivine

NASA Astrophysics Data System (ADS)

Cline, C. J., II; Faul, U. H.; David, E. C.; Berry, A. J.; Jackson, I.

2018-03-01

Lateral variations of seismic wave speeds and attenuation (dissipation of strain energy) in the Earth’s upper mantle have the potential to map key characteristics such as temperature, major-element composition, melt fraction and water content. The inversion of these data into meaningful representations of physical properties requires a robust understanding of the micromechanical processes that affect the propagation of seismic waves. Structurally bound water (hydroxyl) is believed to affect seismic properties but this has yet to be experimentally quantified. Here we present a comprehensive low-frequency forced-oscillation assessment of the seismic properties of olivine as a function of water content within the under-saturated regime that is relevant to the Earth’s interior. Our results demonstrate that wave speeds and attenuation are in fact strikingly insensitive to water content. Rather, the redox conditions imposed by the choice of metal sleeving, and the associated defect chemistry, appear to have a substantial influence on the seismic properties. These findings suggest that elevated water contents are not responsible for low-velocity or high-attenuation structures in the upper mantle. Instead, the high attenuation observed in hydrous and oxidized regions of the upper mantle (such as above subduction zones) may reflect the prevailing oxygen fugacity. In addition, these data provide no support for the hypothesis whereby a sharp lithosphere–asthenosphere boundary is explained by enhanced grain boundary sliding in the presence of water.

Evolution of Indarch (EH4 Chondrite) at 1 GPa and High Temperature

NASA Technical Reports Server (NTRS)

Berthet, S.; Malavergne, V.; Righter, K.

2008-01-01

The chondritic meteorites are materials that are as old as the solar system itself characterized by variations in bulk chemical and oxidation state, and have long been considered possible building blocks that accreted to form the terrestrial inner planets. Enstatite chondrites contain nearly FeO free enstatite, silicon-rich kamacite and various sulfides indicating formation under highly reducing conditions. These materials could have participated in the formation of the Earth. However, "fingerprinting" of meteoritic materials has shown that no known meteoritic class corresponds to a hypothetical bulk Earth composition in every aspect. To derive constraints on early accretion and differentiation processes and possibly resolve the debate on the formation of the Earth, it is required to study experimentally a variety of chondritic materials and investigate their melting relations and elemental partitioning behavior at variable pressure (P), temperature (T) and oxygen fugacities (fO2). Variations in fO2 can indeed change chemical features and phase equilibria dramatically. The P-T phase diagrams of peridotites and carbonaceous chondrites have been extensively studied experimentally up to pressures and temperatures corresponding to the transition zone and lower mantle. Even though partial melting experiments have been conducted at ambient pressure on the enstatite chondrite Indarch, enstatite meteorites have never been experimentally investigated at high PT. The following investigation focuses on the effect of the fO2 on the phase relations of Indarch, an EH4 chondrite.

Water sensitivity of the seismic properties of upper-mantle olivine

NASA Astrophysics Data System (ADS)

Cline, Christopher; David, Emmanuel; Faul, Ulrich; Berry, Andrew; Jackson, Ian

2017-04-01

The wave speeds and attenuation of seismic waves in the upper mantle are expected to be strongly influenced by the defect chemistry of olivine grain interiors and the associated chemical complexity of grain-boundary regions. Changes in chemical environment (oxygen fugacity and/or water fugacity) can impose different defect chemistries, including the creation and retention of hydrous defects, and therefore can directly influence anelastic relaxation involving stress-induced migration of lattice defects and/or grain-boundary sliding. Here we report the first low-frequency experimental study of the seismic properties of olivine under water-undersaturated conditions. Three synthetic sol-gel derived olivine (Fo90) specimens were fabricated by hot-pressing in welded Pt capsules with various concentrations of hydroxyl, chemically bound as doubly protonated Si vacancies, charge balanced by substitution of Ti on a neighboring M-site (i.e., the Ti-clinohumite-like defect). Hydroxyl contents, determined following the subsequent mechanical testing within Pt sleeves, increased systematically with the amount of added Ti-dopant. Added Ti concentrations ranged between 176 and 802 atom ppm Ti/Si, resulting in concentrations of bound hydrogen in the three samples ranging between 330 and 1150 atom ppm H/Si. Each hot-pressed specimen was precision ground and then sleeved in Pt for mechanical testing in forced torsional oscillation under water-undersaturated conditions. Forced-oscillation tests were conducted at seismic periods of 1 - 1000 s and 200 MPa confining pressure during slow staged cooling from 1200 to 25°C. Each Ti-doped specimen showed mechanical behavior of the high-temperature background type involving monotonically increasing dissipation and decreasing shear modulus with increasing oscillation period and increasing temperature. Comparison of the mechanical data acquired in these water-undersaturated conditions with a similarly tested, but dry, Ti-bearing specimen (enclosed within an Ni-Fe sleeve under more reducing conditions) shows a marked contrast. The OH-bearing specimens exhibit much lower shear moduli (by as much as 80%) and higher levels of dissipation (by as much as 0.5 log units in Q-1), but also limited sensitivity of the seismic properties to the total water content among the hydrated specimens in the series. These results indicate that the higher oxygen and water fugacities prevailing within Pt-sleeved specimens result in lower shear moduli and higher dissipation under water-undersaturated conditions - presumably attributable to contrasting defect populations and/or grain boundary chemistries. Clarification of the relative roles of grain-boundary sliding and any additional intragranular relaxation under increased fH2O and fO2 thus offers the prospect of an improved understanding of the seismological signature of more oxidized/hydrous portions of the Earth's upper mantle, such as subduction zone environments.

Implications of a reducing and warm (not hot) Archaean ambient mantle for ancient element cycles

NASA Astrophysics Data System (ADS)

Aulbach, Sonja

2016-04-01

There is considerable uncertainty regarding the oxygen partial pressure (fO2) and potential temperature (TP) of the ambient convecting mantle throughout Earth's history. Rare Archaean eclogite suites have elemental and isotopic compositions indicative of formation of crustal protoliths in oceanic spreading ridges, hence unaffected by continental sources. These include some eclogite xenoliths derived from cratonic mantle lithosphere and orogenic eclogites marking the exhumation of oceanic crust at Pacific-type margins. Their compositions may retain a memory of the thermal and redox state of the Archaean convecting mantle sources that gave rise to their low-pressure protoliths. Archaean eclogites have TiO2-REE relationships consistent with fractional crystallisation of olivine±plagioclase and cpx during formation of picritic protoliths from a melt that separated from a garnet-free peridotite source, implying intersection of the solidus at ≤2.5 to 3.0 GPa [1]. Low melt fractions (<0.25) inferred from samples with the least fractionated (lowest TiO2) protoliths further argue against deep intersection of the mantle solidus. This suggests a moderately elevated TP ~ 1420-1470 degrees C (lower than some estimates for the ambient convecting mantle at that time [2]), which would support an early onset of plate tectonics [3] and emergence of continents [4], heralding a transition to modern chemical cycles. Moderate TP further indicates that deep recycling of carbon and water, though reduced compared to today, may have been possible in the Archaean [5,6]. Carefully screened eclogites have V/Sc (reflecting the redox state of the ambient mantle during protolith formation [7]) corresponding to ΔFMQ corrected to 1 GPa as low as -1.7 at 3 Ga [1]. Such low oxygen fugacities have consequences for the location of the peridotite solidus and for the types of melts generated during redox melting [5,8]. They also modulate the redox state of volatiles liberated at oceanic spreading ridges [7] in the Archaean, with implications for the composition and oxygenation of the palaeo-atmosphere. Subsequent subduction of such reducing oceanic crust must have also affected the cycling of volatile elements (soluble instead of molecular species [9]) and of redox-sensitive ore-forming metals [10] during metamorphic dehydration and melting reactions. [1] Aulbach&Viljoen (2015) Earth Planet Sci Lett 431; [2] Herzberg et al. (2010) Earth Planet Sci Lett 292; [3] Sizova et al. (2010) Lithos 116; [4] Rey&Coltice (2008) Geology 36; [5] Dasgupta (2013) RIMG 75; [6] Magni et al. (2014) G3 15; [7] Li&Lee (2004) EPSL 228; [8] Stagno et al. (2013) Nature 493; [9] Sverjensky et al. (2014) Nat Geosci 7; [10] Evans & Tomkins (2011) Earth Planet Sci Lett 308.

Experimental study of trace element partitioning between enstatite and melt in enstatite chondrites at low oxygen fugacities and 5 GPa

NASA Astrophysics Data System (ADS)

Cartier, Camille; Hammouda, Tahar; Doucelance, Régis; Boyet, Maud; Devidal, Jean-Luc; Moine, Bertrand

2014-04-01

In order to investigate the influence of very reducing conditions, we report enstatite-melt trace element partition coefficients (D) obtained on enstatite chondrite material at 5 GPa and under oxygen fugacities (fO2) ranging between 0.8 and 8.2 log units below the iron-wustite (IW) buffer. Experiments were conducted in a multianvil apparatus between 1580 and 1850 °C, using doped (Sc, V, REE, HFSE, U, Th) starting materials. We used a two-site lattice strain model and a Monte-Carlo-type approach to model experimentally determined partition coefficient data. The model can fit our partitioning data, i.e. trace elements repartition in enstatite, which provides evidence for the attainment of equilibrium in our experiments. The precision on the lattice strain model parameters obtained from modelling does not enable determination of the influence of intensive parameters on crystal chemical partitioning, within our range of conditions (fO2, P, T, composition). We document the effect of variable oxygen fugacity on the partitioning of multivalent elements. Cr and V, which are trivalent in the pyroxene at around IW - 1 are reduced to 2+ state with increasingly reducing conditions, thus affecting their partition coefficients. In our range of redox conditions Ti is always present as a mixture between 4+ and 3+ states. However the Ti3+-Ti4+ ratio increases strongly with increasingly reducing conditions. Moreover in highly reducing conditions, Nb and Ta, that usually are pentavalent in magmatic systems, appear to be reduced to lower valence species, which may be Nb2+ and Ta3+. We propose a new proxy for fO2 based on D(Cr)/D(V). Our new data extend the redox range covered by previous studies and allows this proxy to be used in the whole range of redox conditions of the solar system objects. We selected trace-element literature data of six chondrules on the criterion of their equilibrium. Applying the proxy to opx-matrix systems, we estimated that three type I chondrules have equilibrated at IW - 7 ± 1, one type I chondrule at IW - 4 ± 1, and two type II chondrules at IW + 3 ± 1. This first accurate estimation of enstatite-melt fO2 for type I chondrules is very close to CAI values. Find the best-fit for trivalent elements. We set the r0M1 (3+) range to 0.55-0.75 Å, based on visual observations of the datapoints. For the other variables we have set boundary values beyond which the solutions would be unacceptable. For example, r0M2 (3+) has to be larger than r0M1 (3+). Finally we restricted the D0 range as follow: 0.2 r0(3+) > r0(4+) (see van Westrenen et al., 2000, for explanation), together with visual observation of our experimental data. D0 ranges: 1 < D0M1(2+) < 100; D0M2 (3+) < D0M2(2+) < 100 ; 0.01 < D0M1(4+) < 0.1 ; 0.0001 < D0M2(4+) < 0.01. These ranges are based on visual observation of our experimental data.

Reduced chromium in olivine grains from lunar basalt 15555 - X-ray Absorption Near Edge Structure (XANES)

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Jones, K. W.; Gordon, B.; Rivers, M. L.; Bajt, S.; Smith, J. V.

1993-01-01

The oxidation state of Cr in 200-micron regions within individual lunar olivine and pyroxene grains from lunar basalt 15555 was inferred using X-ray Absorption Near Edge Structure (XANES). Reference materials had previously been studied by optical absorption spectroscopy and included Cr-bearing borosilicate glasses synthesized under controlled oxygen fugacity and Cr-doped olivines. The energy dependence of XANES spectral features defined by these reference materials indicated that Cr is predominantly divalent in the lunar olivine and trivalent in the pyroxene. These results, coupled with the apparent f(02)-independence of partitioning coefficients for Cr into olivine, imply that the source magma was dominated by divalent Cr at the time of olivine crystallization.

Core-Mantle Partitioning of Volatile Siderophile Elements and the Origin of Volatile Elements in the Earth

NASA Technical Reports Server (NTRS)

Nickodem, K.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

2012-01-01

There are currently several hypotheses on the origin of volatile siderophile elements in the Earth. One hypothesis is that they were added during Earth s accretion and core formation and mobilized into the metallic core [1], others claim multiple stage origin [2], while some hypothesize that volatiles were added after the core already formed [3]. Several volatile siderophile elements are depleted in Earth s mantle relative to the chondrites, something which continues to puzzle many scientists. This depletion is likely due to a combination of volatility and core formation. The Earth s core is composed of Fe and some lighter constituents, although the abundances of these lighter elements are unknown [4]. Si is one of these potential light elements [5] although few studies have analyzed the effect of Si on metal-silicate partitioning, in particular the volatile elements. As, In, Ge, and Sb are trace volatile siderophile elements which are depleted in the mantle but have yet to be extensively studied. The metal-silicate partition coefficients of these elements will be measured to determine the effect of Si. Partition coefficients depend on temperature, pressure, oxygen fugacity, and metal and silicate composition and can constrain the concentrations of volatile, siderophile elements found in the mantle. Reported here are the results from 13 experiments examining the partitioning of As, In, Ge, and Sb between metallic and silicate liquid. These experiments will examine the effect of temperature, and metal-composition (i.e., Si content) on these elements in or-der to gain a greater understanding of the core-mantle separation which occurred during the Earth s early stages. The data can then be applied to the origin of volatile elements in the Earth.

New Martian Meteorite Is One of the Most Oxidized Found to Date

NASA Technical Reports Server (NTRS)

Hui, Hejiu; Peslier, Anne; Lapen, Thomas J.; Shafer, John T.; Brandon, Alan D.; Irving, Anthony J.

2014-01-01

As of 2013, about 60 meteorites from the planet Mars have been found and are being studied. Each time a new Martian meteorite is found, a wealth of new information comes forward about the red planet. The most abundant type of Martian meteorite is a shergottite; its lithologies are broadly similar to those of Earth basalts and gabbros; i.e., crustal igneous rocks. The entire suite of shergottites is characterized by a range of trace element, isotopic ratio, and oxygen fugacity values that mainly reflect compositional variations of the Martian mantle from which these magmas came. A newly found shergottite, NWA 5298, was the focus of a study performed by scientists within the Astromaterials Research and Exploration Science (ARES) Directorate at the Johnson Space Center (JSC) in 2012. This sample was found in Morocco in 2008. Major element analyses were performed in the electron microprobe (EMP) laboratory of ARES at JSC, while the trace elements were measured at the University of Houston by laser inductively coupled plasma mass spectrometry (ICPMS). A detailed analysis of this stone revealed that this meteorite is a crystallized magma that comes from the enriched end of the shergottite spectrum; i.e., trace element enriched and oxidized. Its oxidation comes in part from its mantle source and from oxidation during the magma ascent. It represents a pristine magma that did not mix with any other magma or see crystal accumulation or crustal contamination on its way up to the Martian surface. NWA 5298 is therefore a direct, albeit evolved, melt from the Martian mantle and, for its lithology (basaltic shergottite), it represents the oxidized end of the shergottite suite. It is thus a unique sample that has provided an end-member composition for Martian magmas.

Investigating the Formation of Mars Recurring Slope Lineae through Laboratory Experiments

NASA Astrophysics Data System (ADS)

Cantillo, D. C.; Hibbitts, C.; Wing, B. R.; Mushkin, A.; Stockstill-Cahill, K.; Viviano-Beck, C. E.

2017-12-01

The presence of low-albedo streaks on crater slopes, Recurring Slope Lineae (RSLs), may be evidence for present-day intermittent and repeated flow of water or brine on the surface of Mars. RSLs grow, fade, and can grow again seasonally as surface temperatures change [e.g. 1,2]. Although distinguishable by being darker than the surrounding terrain, they have no diagnostic absorption features [3] with the exception of a ferric feature that may be related to grain size [4] and the notable discovery of hydrated perchlorates at the base of one set of RSLs [5]. To explore liquid-based hypotheses for the formation of RSLs, we have constructed an environmental chamber that can simulate Martian surface conditions. The development of this chamber follows upon the successful completion of preliminary tests under a terrestrial atmosphere [6] to prove the optical design and subsequently under Mars pressure to verify the technical approach [7]. The Mars Analog Reflectance Spectroscopy (MARS) chamber is capable of exposing soils to brines from underneath, simulating possible subsurface wetting that could result in RSL formation. While maintaining Mars pressure and similar oxygen fugacity, the chamber will also allow the collection of spectra from 0.4 to 2.4 microns. Various brine compositions can be investigated, including solutions of iron chlorides. These unique salts can lower the soil albedo without inducing a spectral absorption feature, whereas other salts brighten the surface after drying or retain significant water [8]. Another possible darkening mechanism is also being explored within the MARS chamber. Experiments have shown that evaporation of liquid from palagonitic soils under Mars pressure create ubiquitous grain scale cavities within the surface [7]. This micro-roughness increases shadowing and darkens the surface, indicating it may be a process of darkening that is independent of brine composition.

Bulk rock and mineral chemistries and ascent rates of high-K calc-alkalic epidote-bearing magmas, Northeastern Brazil

NASA Astrophysics Data System (ADS)

Brasilino, R. G.; Sial, A. N.; Ferreira, V. P.; Pimentel, M. M.

2011-12-01

A manifestation of the Pan-African-Brasiliano orogeny (700-550 Ma) in northeastern Brazil was the emplacement of widespread Neoproterozoic granitoids in diverse tectonic terranes. Among these plutons are the magmatic epidote-bearing Conceição das Creoulas, Caldeirão Encantado, Murici, and Boqueirão plutons, located close to the boundary between the Alto Pajeú and Cachoeirinha-Salgueiro terranes. The plutons are high-K calc-alkalic granodiorites to monzogranites, with tabular K-feldspar megacrysts. Pistacite [atomic Fe+ 3/(Fe3++ Al)] in epidote in these granitoids ranges from 21 to 27%. High oxygen fugacity (log fO2 - 19 to - 13) and the preservation of epidote suggest that the magma was oxidized. Al-in-hornblende barometry indicates hornblende solidification between 6 and 8 kbar, at 620 to 780 °C according to the hornblende-plagioclase thermometer. Zircon saturation thermometry attests to a near-liquidus temperature range from 794 to 853 °C. Partial corrosion of magmatic epidote in these four plutons occurred during an interval of no more than 10-30 years, which corresponds to maximum magma ascent rates of 650-1000 m/year. Diking, associated with regional shearing, probably facilitated rapid transport of granitic magma through hot continental crust at peak metamorphism, and permitted survival of epidote that was out of equilibrium at the low pressure of final emplacement. Similarities between mineralogical composition, chemistry, and isotopic compositions (εNd(0.60Ga) between - 2 and - 5,TDM from 1.2 to 1.3 Ga, δ18O values > 10‰, V-SMOW) of these four plutons and Neoproterozoic magmatic epidote-bearing plutons elsewhere in northeastern Brazil, argue for similar metabasaltic/mafic sources that had previously experienced low-temperature alteration.

Component geochronology in the polyphase ca. 3920 Ma Acasta Gneiss

USGS Publications Warehouse

Mojzsis, Stephen J.; Cates, Nicole L.; Caro, Guillaume; Trail, Dustin; Abramov, Oleg; Guitreau, Martin; Blichert-Toft, Janne; Hopkins, Michelle D.; Bleeker, Wouter

2014-01-01

The oldest compiled U–Pb zircon ages for the Acasta Gneiss Complex in the Northwest Territories of Canada span about 4050–3850 Ma; yet older ca. 4200 Ma xenocrystic U–Pb zircon ages have also been reported for this terrane. The AGC expresses at least 25 km2 of outcrop exposure, but only a small subset of this has been documented in the detail required to investigate a complex history and resolve disputes over emplacement ages. To better understand this history, we combined new ion microprobe235,238U–207,206Pb zircon geochronology with whole-rock and zircon rare earth element compositions ([REE]zirc), Ti-in-zircon thermometry (Tixln) and 147Sm–143Nd geochronology for an individual subdivided ∼60 cm2 slab of Acasta banded gneiss comprising five separate lithologic components. Results were compared to other variably deformed granitoid-gneisses and plagioclase-hornblende rocks from elsewhere in the AGC. We show that different gneissic components carry distinct [Th/U]zirc vs. Tixln and [REE]zirc signatures correlative with different zircon U–Pb age populations and WR compositions, but not with 147Sm–143Nd isotope systematics. Modeled  [REE] from lattice-strain theory reconciles only the ca. 3920 Ma zircons with the oldest component that also preserves strong positive Eu∗ anomalies. Magmas which gave rise to the somewhat older (inherited) ca. 4020 Ma AGC zircon age population formed at ∼IW (iron–wüstite) to

Geochemistry and tectonic setting of the Golabad granitoid complex (SW Nain, Iran)

NASA Astrophysics Data System (ADS)

Mansouri Esfahani, Mahin; Khalili, Mahmoud; Alaminia, Zahra

2018-03-01

The Oligo-Miocene Golabad granitoid complex intrusive into the Eocene volcanic rocks occurs in the Urumieh-Dokhtar Magmatic Arc (UDMA) in Iran. According to microscopic and chemical studies, the granitoid complex consists of three different rock types: 1) plutonic rocks comprising diorite, quartz diorite, granodiorite and granite; 2) volcanic rocks composed of basalt, andesite basalt, ± pyroxene bearing andesite and rhyolite, and 3) pyroclastic rocks. The main mineral constituents of these rocks are mostly plagioclase (oligoclase and andesine), quartz, K-feldspar, amphibole (magnesio-hornblende and actinolite-hornblende) and Mg-biotite. In addition, apatite, titanite, zircon, and opaque minerals are common accessory minerals. The studied enclaves are classified as mafic micro-granular enclaves (MME) with monzodiorite compositions. Geochemically, the rocks in this study represent medium to high-K calc-alkaline series, metaluminous and I-type nature. Plotting, the chemical composition of plagioclase on the An-Ab-Or ternary diagram, the temperature of crystallization is estimated to range from 700 to 900 °C at a pressure of 4.5 Kbar. High TiO2 values of biotites from the Golabad granitoid complex suggest magmatic origin and the crystallization temperature is estimated to range from 700 to 750 °C. The amphiboles according to their chemical analysis, are classified as igneous amphiboles generated in high oxygen fugacity conditions. The chemical data of the amphiboles and biotites pointed out to the I- type nature of the Golabad granitoid complex emplaced in an active continental margin subduction setting. The amphibole crystallization pressure was estimated by Al in amphibole varies from 1.09 to 2.28 Kbar. Using the calculated pressure the depth of the formation of the Golabad granitoid complex estimated from 4 to 9 Km.

Magmatic processes that generated the rhyolite of Glass Mountain, Medicine Lake volcano, N. California

USGS Publications Warehouse

Grove, T.L.; Donnelly-Nolan, J. M.; Housh, T.

1997-01-01

Glass Mountain consists of a 1 km3, compositionally zoned rhyolite to dacite glass flow containing magmatic inclusions and xenoliths of underlying shallow crust. Mixing of magmas produced by fractional crystallization of andesite and crustal melting generated the rhyolite of Glass Mountain. Melting experiments were carried out on basaltic andesite and andesite magmatic inclusions at 100, 150 and 200 MPa, H2O-saturated with oxygen fugacity controlled at the nickel-nickel oxide buffer to provide evidence of the role of fractional crystallization in the origin of the rhyolite of Glass Mountain. Isotopic evidence indicates that the crustal component assimilated at Glass Mountain constitutes at least 55 to 60% of the mass of erupted rhyolite. A large volume of mafic andesite (2 to 2.5 km3) periodically replenished the magma reservoir(s) beneath Glass Mountain, underwent extensive fractional crystallization and provided the heat necessary to melt the crust. The crystalline residues of fractionation as well as residual liquids expelled from the cumulate residues are preserved as magmatic inclusions and indicate that this fractionation process occurred at two distinct depths. The presence and composition of amphibole in magmatic inclusions preserve evidence for crystallization of the andesite at pressures of at least 200 MPa (6 km depth) under near H2O-saturated conditions. Mineralogical evidence preserved in olivine-plagioclase and olivine-plagioclase-high-Ca clinopyroxene-bearing magmatic inclusions indicates that crystallization under near H2O-saturated conditions also occurred at pressures of 100 MPa (3 km depth) or less. Petrologic, isotopic and geochemical evidence indicate that the andesite underwent fractional crystallization to form the differentiated melts but had no chemical interaction with the melted crustal component. Heat released by the fractionation process was responsible for heating and melting the crust.

Fe-Ti-Cr-Oxides in Martian Meteorite EETA79001 Studied by Point-counting Procedure Using Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Wang, Alian; Kuebler, Karla E.; Jolliff, Bradley L.; Haskin, Larry A.

2003-01-01

Fe-Ti-Cr-Oxide minerals contain much information about rock petrogenesis and alteration. Among the most important in the petrology of common intrusive and extrusive rocks are those of the FeO-TiO2-Cr2O3 compositional system chromite, ulv spinel-magnetite, and ilmenite-hematite. These minerals retain memories of oxygen fugacity. Their exsolution into companion mineral pairs give constraints on formation temperature and cooling rate. Laser Raman spectroscopy is anticipated to be a powerful technique for characterization of materials on the surface of Mars. A Mars Microbeam Raman Spectrometer (MMRS) is under development. It combines a micro sized laser beam and an automatic point-counting mechanism, and so can detect minor minerals or weak Raman-scattering phases such as Fe- Ti-Cr-oxides in mixtures (rocks & soils), and provide information on grain size and mineral mode. Most Fe-Ti-Cr-oxides produce weaker Raman signals than those from oxyanionic minerals, e.g. carbonates, sulfates, phosphates, and silicates, partly because most of them are intrinsically weaker Raman scatters, and partly because their dark colors limit the penetration depth of the excitation laser beam (visible wavelength) and of the Raman radiation produced. The purpose of this study is to show how well the Fe-Ti-Cr-oxides can be characterized by on-surface planetary exploration using Raman spectroscopy. We studied the basic Raman features of common examples of these minerals using well-characterized individual mineral grains. The knowledge gained was then used to study the Fe-Ti-Cr-oxides in Martian meteorite EETA79001, especially effects of compositional and structural variations on their Raman features.

Un-Earth-like interiors of the Earth-like planets

NASA Astrophysics Data System (ADS)

Shim, S. H. D.; Nisr, C.; Pagano, M.; Chen, H.; Ko, B.; Noble, S.; Leinenweber, K. D.; Young, P.; Desch, S. J.

2015-12-01

A number of exoplanets have been described as "Earth-like" planets (or even exo-earths) based on the mass-radius relations. Yet, significant variations have been documented in elemental abundances of planet-hosting stars, which will result in very different structures and processes in the interiors of rocky exoplanets. Recent data suggest that the Mg/Si ratio can be as small as less than 1 and as large as more than 2, opening the possibilities for the upper mantles to be dominated by pyroxene and olivine, respectively, and the lower mantles to be dominated by bridgmanite and ferropericlase, respectively. The changes in mineralogy will alter key properties, such as discontinuity structures (and therefore scale of mantle mixing), viscosity, and volatiles storage, of the mantle. Partial melting of such mantles would result in different compositions of the crusts, affecting the tectonics. However, the prediction should be made carefully because oxygen fugacity and contents of volatiles can change the mineralogy even for the same bulk composition. In extremely reducing proto-planetary disks, carbides will form instead of oxides and silicates, and become main constituents of planets in the system. Because carbides have high thermal conductivity and low thermal expansivity, internal heat transport of such planets may be dominated by conduction and mantle mixing would be much more limited than that of the Earth. However, the behaviors and properties of carbides need to be understood better at high pressure and high temperature. Some rocky exoplanets may have very thick layers of water and other icy materials. Interactions between ice (or fluid) and rock at extreme conditions would be the key to understand dynamics and habitability of such exoplanets.

The impact of degassing on the oxidation state of basaltic magmas: A case study of Kīlauea volcano

NASA Astrophysics Data System (ADS)

Moussallam, Yves; Edmonds, Marie; Scaillet, Bruno; Peters, Nial; Gennaro, Emanuela; Sides, Issy; Oppenheimer, Clive

2016-09-01

Volcanic emissions link the oxidation state of the Earth's mantle to the composition of the atmosphere. Whether the oxidation state of an ascending magma follows a redox buffer - hence preserving mantle conditions - or deviates as a consequence of degassing remains under debate. Thus, further progress is required before erupted basalts can be used to infer the redox state of the upper mantle or the composition of their co-emitted gases to the atmosphere. Here we present the results of X-ray absorption near-edge structure (XANES) spectroscopy at the iron K-edge carried out for a series of melt inclusions and matrix glasses from ejecta associated with three eruptions of Kīlauea volcano (Hawai'i). We show that the oxidation state of these melts is strongly correlated with their volatile content, particularly in respect of water and sulfur contents. We argue that sulfur degassing has played a major role in the observed reduction of iron in the melt, while the degassing of H2O and CO2 appears to have had a negligible effect on the melt oxidation state under the conditions investigated. Using gas-melt equilibrium degassing models, we relate the oxidation state of the melt to the composition of the gases emitted at Kīlauea. Our measurements and modelling yield a lower constraint on the oxygen fugacity of the mantle source beneath Kīlauea volcano, which we infer to be near the nickel nickel-oxide (NNO) buffer. Our findings should be widely applicable to other basaltic systems and we predict that the oxidation state of the mantle underneath most hotspot volcanoes is more oxidised than that of the associated lavas. We also suggest that whether the oxidation states of a basalt (in particular MORB) reflects that of its source, is primarily determined by the extent of sulfur degassing.

Abrupt transition from fractional crystallization to magma mixing at Gorely volcano (Kamchatka) after caldera collapse

NASA Astrophysics Data System (ADS)

Gavrilenko, Maxim; Ozerov, Alexey; Kyle, Philip R.; Carr, Michael J.; Nikulin, Alex; Vidito, Christopher; Danyushevsky, Leonid

2016-07-01

A series of large caldera-forming eruptions (361-38 ka) transformed Gorely volcano, southern Kamchatka Peninsula, from a shield-type system dominated by fractional crystallization processes to a composite volcanic center, exhibiting geochemical evidence of magma mixing. Old Gorely, an early shield volcano (700-361 ka), was followed by Young Gorely eruptions. Calc-alkaline high magnesium basalt to rhyolite lavas have been erupted from Gorely volcano since the Pleistocene. Fractional crystallization dominated evolution of the Old Gorely magmas, whereas magma mixing is more prominent in the Young Gorely eruptive products. The role of recharge-evacuation processes in Gorely magma evolution is negligible (a closed magmatic system); however, crustal rock assimilation plays a significant role for the evolved magmas. Most Gorely magmas differentiate in a shallow magmatic system at pressures up to 300 MPa, ˜3 wt% H2O, and oxygen fugacity of ˜QFM + 1.5 log units. Magma temperatures of 1123-1218 °C were measured using aluminum distribution between olivine and spinel in Old and Young Gorely basalts. The crystallization sequence of major minerals for Old Gorely was as follows: olivine and spinel (Ol + Sp) for mafic compositions (more than 5 wt% of MgO); clinopyroxene and plagioclase crystallized at ˜5 wt% of MgO (Ol + Cpx + Plag) and magnetite at ˜3.5 wt% of MgO (Ol + Cpx + Plag + Mt). We show that the shallow magma chamber evolution of Old Gorely occurs under conditions of decompression and degassing. We find that the caldera-forming eruption(s) modified the magma plumbing geometry. This led to a change in the dominant magma evolution process from fractional crystallization to magma mixing. We further suggest that disruption of the magma chamber and accompanying change in differentiation process have the potential to transform a shield volcanic system to that of composite cone on a global scale.

Experimental investigation of the partitioning of phosphorus between metal and silicate phases - Implications for the earth, moon and eucrite parent body

NASA Technical Reports Server (NTRS)

Newsom, H. E.; Drake, M. J.

1983-01-01

An experimental study is reported of the partitioning of Phosphorus between solid metal and basaltic silicate liquid as a function of temperature and oxygen fugacity and of the implications for the earth, moon and eucrite parent body (EPB). The relationship established between the partition coefficient and the fugacity is given at 1190 C by log D(P) = -1.12 log fO2 - 15.95 and by log D(P) = -1.53 log fO2 17.73 at 1300 C. The partition coefficient D(P) was determined, and it is found to be consistent with a valence state of 5 for P in the molten silicate. Using the determined coefficient the low P/La ratios of the earth, moon, and eucrites relative to C1 chondrites can be explained. The lowering of the P/La ratio in the eucrites relative to Cl chondrite by a factor of 40 can be explained by partitioning P into 20-25 wt% sulfur-bearing metallic liquid corresponding to 5-25% of the total metal plus silicate system. The low P/La and W/La ratios in the moon may be explained by the partitioning of P and W into metal during formation of a small core by separation of liquid metal from silicate at low degrees of partial melting of the silicates. These observations are consistent with independent formation of the moon and the earth.

Use of Physicochemical Parameters to Assess the Environmental Fate of Organic Pollutants: The Fugacity Model

ERIC Educational Resources Information Center

Domenech, Xavier; Ayllon, Jose Antonio; Peral, Jose

2006-01-01

The environmental fate and behavior of different organic pollutants based on the qualitative analysis of thermodynamic and kinetic data is presented. The Fugacity model allows the use of different partition constants in an easy way, to determine the distribution of chemical between different phases in equilibrium of an environmental system.

A Graphical Representation for the Fugacity of a Pure Substance

ERIC Educational Resources Information Center

Book, Neil L.; Sitton, Oliver C.

2010-01-01

The thermodynamic equations used to define and compute the fugacity of a pure substance are depicted as processes on a semi-logarithmic plot of pressure vs. molar Gibbs energy (PG diagram) with isotherms for the substance behaving as an ideal gas superimposed. The PG diagram clearly demonstrates the physical basis for the definitions and the…

Fugacity and concentration gradients in a gravity field

NASA Technical Reports Server (NTRS)

May, C. E.

1986-01-01

Equations are reviewed which show that at equilibrium fugacity and concentration gradients can exist in gravitational fields. At equilibrium, the logarithm of the ratio of the fugacities of a species at two different locations in a gravitational field is proportional to the difference in the heights of the two locations and the molecular weight of the species. An analogous relation holds for the concentration ratios in a multicomponent system. The ratio is calculated for a variety of examples. The kinetics for the general process are derived, and the time required to approach equilibrium is calculated for several systems. The following special topics are discussed: ionic solutions, polymers, multiphase systems, hydrostatic pressure, osmotic pressure, and solubility gradients in a gravity field.

Carbon Solubility in Silicon-Iron-Bearing Metals during Core Formation on Mercury

NASA Technical Reports Server (NTRS)

Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Ross, D. Kent; Rapp, Jennifer F.; Danielson, Lisa R.; Keller, Lindsay P.; Righter, Kevin

2016-01-01

Recent results obtained from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft showed the surface of Mercury has high S abundances (approximately 4 wt%) and low Iron(II) Oxide abundances (less than 2 wt%). Based on these extreme values, the oxygen fugacity of Mercury's surface materials was estimated to be approximately 3 to 7 log(sub 10) units below the IW buffer (Delta IW-3 to Delta IW-7). This highly reducing nature of the planet has resulted in a large core and relatively thin mantle, extending to only approximately 420 km depth (corresponding to a core-mantle boundary pressure of approximately 4-7 GPa) within the planet. Furthermore, MESSENGER results have suggested the presence of carbon on the surface of the planet. Previous experimental results from have also suggested the possibility of a primary floatation crust on Mercury composed of graphite, produced after a global magma ocean event. With these exotic conditions of this compositional end-member planet, it begs the question, what is the core composition of Mercury? Although no definitive conclusion has been reached, previous studies have made advances towards answering this question. Riner et al. and Chen et al. looked at iron sulfide systems and implemented various crystallization and layered core scenarios to try and determine the composition and structure of Mercury's core. Malavergne et al. examined core crystallization scenarios in the presence of sulfur and silicon. Hauck et al. used the most recent geophysical constraints from the MESSENGER spacecraft to model the internal structure of Mercury, including the core, in a iron-sulfur-silicon system. More recently, Chabot et al. conducted a series of metal-silicate partitioning experiments in a iron-sulfur-silicon system. These results showed the core of Mercury has the potential to contain more than 15 wt% silicon. However, with the newest results from MESSENGER's low altitude campaign, carbon is another potential light element that could be incorporated into Mercury's core. The goal of this study is to determine the carbon concentration at graphite saturation in various silicon-iron bearing metals relevant to possible mercurian core compositions. Future experiments will include the addition of sulfur into these metals.

Ocean Surface Carbon Dioxide Fugacity Observed from Space

NASA Technical Reports Server (NTRS)

Liu, W. Timothy; Xie, Xiaosu

2014-01-01

We have developed and validated a statistical model to estimate the fugacity (or partial pressure) of carbon dioxide (CO2) at sea surface (pCO2sea) from space-based observations of sea surface temperature (SST), chlorophyll, and salinity. More than a quarter million in situ measurements coincident with satellite data were compiled to train and validate the model. We have produced and made accessible 9 years (2002-2010) of the pCO2sea at 0.5 degree resolutions daily over the global ocean. The results help to identify uncertainties in current JPL Carbon Monitoring System (CMS) model-based and bottom-up estimates over the ocean. The utility of the data to reveal multi-year and regional variability of the fugacity in relation to prevalent oceanic parameters is demonstrated.

Iron Redox Systematics of Shergottites and Martian Magmas

NASA Technical Reports Server (NTRS)

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.

Experimental Determination of Spinel/Melt, Olivine/Melt, and Pyroxene/Melt Partition Coefficients for Re, Ru, Pd, Au, and Pt

NASA Technical Reports Server (NTRS)

Righter, K.; Campbell, A. J.; Humayun, M.

2003-01-01

Experimental studies have identified spinels as important hosts phases for many of the highly siderophile elements (HSE). Yet experimental studies involving chromite or Cr-rich spinel have been lacking. Experimental studies of partitioning of HSEs between silicate, oxides and silicate melt are plagued by low solubilities and the presence of small metallic nuggets at oxygen fugacities relevant to magmas, which interfere with analysis of the phases of interest. We have circumvented these problems in two ways: 1) performing experiments at oxidized conditions, which are still relevant to natural systems but in which nuggets are not observed, and 2) analysis of run products with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), allowing a combination of high sensitivity and good spatial resolution.

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

NASA Astrophysics Data System (ADS)

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 (<5%), fresh, glassy obsidian samples with their post-eruptive (post-degassing) Fe2+ concentrations. Near-liquidus co-precipitation of two Fe-Ti oxides allows the pre-eruptive oxygen fugacity and temperature to be calculated in each rhyolite using the oxygen barometer and thermometer of Ghiorso and Evans (2008). Temperatures range from 793 (± 19) to 939 (± 15) °C, and ΔNNO values (log10fO2 of sample - log10fO2 of Ni-NiO buffer) range from -0.4 to +1.4. These ΔNNO values allow the ferric-ferrous ratio in the liquid to be calculated, using the experimental calibration of Kress and Carmichael (1991), which relates melt composition (not including dissolved water), oxygen fugacity and temperature to melt ferric-ferrous ratios. With temperature known, the plagioclase-liquid hygrometer of Lange et al. (2009) was applied and maximum melt water concentrations range from 4.2 to 7.5 wt%. Both the oxidation state and water concentration are known prior to eruption, at the time of phenocryst growth. After eruption, the rhyolites lost nearly all of their 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 rhyolite magmas, which requires that dissolved water has no resolvable affect on the activity ratio of the iron oxide components in melt.

Waiting for O2

NASA Astrophysics Data System (ADS)

Zahnle, K. J.; Catling, D. C.; Claire, M.

2011-12-01

Oxygenic photosynthesis appears to be a necessary condition for the creation of an oxygen-rich atmosphere like Earth's. But available geological and geochemical evidence suggests that oxygenic photosynthesis appeared hundreds of millions of years before the oxygen-rich atmosphere was fully established. The interregnum implies that at least one other necessary condition for O2 had to be met. Here we argue that the second condition was the irreversible oxidation of the surface and crust by hydrogen escape. This is the same cause as it is for other planets with oxidized surfaces, such as Mars. The link between hydrogen escape and oxygen is direct because the primary process in oxygenic photosynthesis is splitting H2O into hydrogen and O2. Gradual oxidation of the surface and crust eventually brought Earth to a tipping point where free O2 became more stable than competing reduced gases such as CH4; or put another way, the system evolved to the point where surface oxidation under a reducing atmosphere could not keep pace with hydrogen escape. Because hydrogen escape is no faster than other geological processes that govern the long-term redox budget of the atmosphere, the approach to oxygen's final triumph would have been fitful and punctuated by episodes of oxygenation, as the record suggests was the case. The duration of the interregnum was determined by the rate of hydrogen escape and by the size of the reduced reservoir that needed to be oxidized before O2 became favored. If hydrogen escape was responsible for O2, it may be possible to account for the rough constancy of del 13C as a rough constancy of the H2/CO2 ratio in volcanic gases that follows from the constancy of the mantle's oxygen fugacity and a rough constancy in the H2O/CO2 ratio in subducted materials.

Recognizing subtle evidence for silicic magma derivation from petrochemically-similar arc crust: Isotopic and chemical evidence for the bimodal volcanic series of Gorely Volcanic Center, Kamchatka, Russia

NASA Astrophysics Data System (ADS)

Seligman, A. N.; Bindeman, I. N.; Ellis, B. S.; Ponomareva, V.; Leonov, V.

2012-12-01

The Kamchatka Peninsula is home to some of the most prolific subduction related volcanic activity in the world. Gorely caldera and its central volcano are located in the rear of its currently active Eastern Volcanic Front. Recent work determined the presence of explosive ignimbrite eruptions sourced from Gorely volcano during the Pleistocene. We studied 32 eruptive units, including tephrochronologically-dated Holocene tephra, stratigraphically-arranged ignimbrites, as well as pre- and post-caldera lavas. We analyzed oxygen isotope ratios of pyroxene and plagioclase grains by laser fluorination, and major and trace element compositions of whole rocks. In addition, we determined 87Sr/86Sr and 143Nd/144Nd ratios of caldera-forming ignimbrite eruptions. Chemical compositions show that Gorely eruptive units range from basalt to basaltic andesite in the "Pra-Gorely" stages prior to caldera formation and the modern Gorely stages forming its current edifice. In contrast, eruptive material from earlier ignimbrites exposed at Opasny Ravine consists primarily of dacite. Whole rock analyses for Gorely indicate that silicic rocks and ignimbrites volumetrically dominate all other products, forming separate bimodal peaks in our SiO2-frequency diagram. In addition, trace element concentrations and ratios define two trends, one for more silicic and another for more mafic material. δ18Omelt values range from a low of 4.85 up to 6.22‰, where the lowest value was found in the last caldera forming eruption, suggesting incorporation of hydrothermally-altered material from earlier eruptions. 87Sr/86Sr and 143Nd/144Nd ratios range from 0.70328 to 0.70351 and from 0.51303 to 0.51309 respectively, with higher and more diverse values being characteristic of earlier ignimbrite units; again suggesting incorporation of surrounding crustal material. In contrast to these results, MELTS modeling using a variety of likely primitive basalts from Gorely shows it is possible to obtain silicic chemical compositions near the evolved ignimbrite compositions, strictly through 70-80% fractional crystallization at 1-2 kbars and NNO oxygen fugacity. The combination of light δ18O values as well as elevated 87Sr/86Sr and low 143Nd/144Nd values, in addition to the volumetric excess of silicic rocks suggest assimilation of the older and petrochemically-similar country-rocks (Karymshina volcano and/or the underlying Akhomten Massif). This research can be utilized for studies of other volcanoes at "long-term centers", underscoring the importance of using both isotopes and modeling of fractional crystallization to determine silicic magma derivation through coupled shallow crustal assimilation of similar older material and fractional crystallization.

Carbon isotopic composition and origin of SiC from kimberlites of Yakutia, Russia

NASA Astrophysics Data System (ADS)

Mathez, E. A.; Fogel, R. A.; Hutcheon, I. D.; Marshintsev, V. K.

1995-02-01

The stability of moissanite (SiC) has been computed for upper mantle conditions using the internally optimized thermodynamic dataset for the MgSiO compounds of Fei et al. (1990). The computations consider the effects of pressure and temperature on the elastic properties of phases involved in the reactions. The maximum stability of moissanite throughout the upper mantle is typically five to six orders of magnitude lower in oxygen fugacity ( fO2) than the Fe metal-wüstite oxygen buffer at equivalent temperature and pressure, in agreement with previous calculations. Under conditions of SiC stability, silicates will be Fe-free, Fe metal will contain substantial amounts of Si but little C in solution, and Mg-rich sulfides will be stable. Moissanite from the heavy mineral concentrate of the Mir and Aikhal kimberlite pipes, Yakutia, has been studied. Moissanite crystals are gemmy and vary in color from a characteristic blue-green to pale green to nearly colorless to blue-black. Most exhibit crystallographic faces and are in the size range 0.5 to 1 mm in long dimension. Their compositions include small quantities of Fe, which is ubiquitous, Al, Ca, V, Cr, and Mn, all of which may be present in concentrations > 100 ppmwt. Mineral inclusions are present in some crystals. Silicon metal is the most common; inclusions of ferrosilicite (Fe 3Si 7), FeTi silicides, REE silicate, and sinoite (Si 2N 2O) have also been observed. The carbon isotopic compositions of individual moissanite grains have been determined by ion microprobe. The nine analyzed crystals from Aikhal and fourteen from Mir are characterized by a narrow range in δ 13C values of -22 to -29‰; the majority of crystals fall within a more restricted range of -24 to -27‰. Two grains were analyzed for N and found to have a δ 15N of +9.7 ± 4.0 and +5.6 ± 2.0‰. Five mechanisms for the formation of moissanite are considered. Moissanite may be a relict of a reduced, primordial Earth and now present only as a trace phase in an otherwise oxidized mantle. Alternatively, there may be present-day global regions of the Earth that are both highly reduced and characterized by light carbon isotopic compositions. Although these possiblities cannot be disproved, they are not supported by observations. Two other possibilities, namely that moissanite stability extends to more oxidized conditions at pressures of the lower mantle or that it may form metastably, cannot be evaluated with present knowledge. The possibility most consistent with, although not proven by, the isotopic data is that moissanite formed by metamorphism of reduced, carbonaceous sediments during subduction.

Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation.

NASA Technical Reports Server (NTRS)

King, C.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

2010-01-01

Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

A re-assessment of the oxidation state of iron in MORB glasses

NASA Astrophysics Data System (ADS)

Berry, Andrew J.; Stewart, Glen A.; O'Neill, Hugh St. C.; Mallmann, Guilherme; Mosselmans, J. Fred W.

2018-02-01

The oxidation state of Fe, Fe/+3 ΣFe (where ΣFe =Fe2+ +Fe3+), in glass samples of mid-ocean ridge basalt (MORB), from a wide range of localities, was determined by XANES spectroscopy to be 0.10(2) (n = 42). This value is lower than that reported previously by XANES, 0.16 (1) (n = 103), but consistent with the most recent value determined by redox titrations, 0.11 (2) (n = 104), all for similar sets of samples. We attribute the anomalously high XANES value of 0.16 to a calibration error resulting from the interpretation of Mössbauer spectra and the resulting Fe/+3 ΣFe values of the standards. Our alternative interpretation removes the problem of resolving Fe/+3 ΣFe values <∼0.1 in basaltic glasses, produces isomer shift and quadrupole splitting values for Fe3+ that are independent of Fe3+/ΣFe (as is the case for Fe2+), and gives Fe/+3 ΣFe values that are consistent with the thermodynamically expected dependence on oxygen fugacity (fO2). Fe/+3Fe2+ is related to fO2 for our synthetic MORB composition by the temperature independent expression ΔQFM = 4 log ⁡ (Fe3+ /Fe2+) + 4.23 (5), where ΔQFM is the fO2 in log units relative to the quartz-fayalite-magnetite buffer. The average fO2 of natural MORB was estimated to be QFM+0.1.

Late Cretaceous transition from subduction to collision along the Bangong-Nujiang Tethys: New volcanic constraints from central Tibet

NASA Astrophysics Data System (ADS)

Liu, De-Liang; Shi, Ren-Deng; Ding, Lin; Zou, Hai-Bo

2018-01-01

This study deals with arc-type and subsequent bimodal volcanic rocks interbedded with (late) Cretaceous sedimentary formations near Gaize, central Tibet that shed new light on the Tethyan evolution along the Bangong-Nujiang suture. Unit I consists of trachyandesites interbedded with fine-grained sandstone, slate, and limestone. Zircon dating on a trachyandesite sample yields a 206Pb/238U age of 99 ± 1 Ma. The trachyandesites are characterized by strong enrichment in LILE but depletion in HFSE, low zircon saturation temperatures (TZr = 642-727 °C), and high oxygen fugacity (Δ FMQ = - 0.67-0.73), indicating their arc affinities. Unit II comprises a bimodal basalt-rhyolite suite interbedded with coarse-grained sandstone and conglomerate. Zircon dating on two rhyolitic samples yield 206Pb/238U ages of 97.1-87.0 Ma. In contrast with Unit I trachyandesites, Unit II basalts and rhyolites exhibit OIB-like trace element patterns, high temperatures (T = 1298-1379 °C for basalts, TZr = 855-930 °C for rhyolites), and low oxygen fugacity (Δ FMQ = - 3.37 - 0.43), suggesting that Unit II bimodal volcanic rocks probably formed in an extensional setting. The Sr-Nd isotopes of both Unit I (87Sr/86Sri = 0.7052-0.7074, εNd(t) = - 2.21-1.02) and Unit II (87Sr/86Sri = 0.7057-0.7098, εNd(t) = - 3.22-0.88) rocks are similar to mantle-wedge-derived volcanic rocks within the southern Qiangtang block. The parental magma of Unit I trachyandesites was formed by fluid induced melting of the mantle wedge above the subducted Bangong-Nujiang Tethyan slab, and contaminated by crustal materials during MASH process within a deep crustal hot zone; and Unit II bimodal volcanic rocks were derived by melting of upwelling asthenosphere and a mildly metasomatized mantle wedge during the Lhasa-Qiangtang collision. We propose that the transition from the Bangong-Nujiang Tethyan subduction to the Lhasa-Qiangtang collision occurred during the Late Cretaceous in central Tibet.

Anoxic atmospheres on Mars driven by volcanism: Implications for past environments and life

NASA Astrophysics Data System (ADS)

Sholes, Steven F.; Smith, Megan L.; Claire, Mark W.; Zahnle, Kevin J.; Catling, David C.

2017-07-01

Mars today has no active volcanism and its atmosphere is oxidizing, dominated by the photochemistry of CO2 and H2O. Mars experienced widespread volcanism in the past and volcanic emissions should have included reducing gases, such as H2 and CO, as well as sulfur-bearing gases. Using a one-dimensional photochemical model, we consider whether plausible volcanic gas fluxes could have switched the redox-state of the past martian atmosphere to reducing conditions. In our model, the total quantity and proportions of volcanic gases depend on the water content, outgassing pressure, and oxygen fugacity of the source melt. We find that, with reasonable melt parameters, the past martian atmosphere (∼3.5 Gyr to present) could have easily reached reducing and anoxic conditions with modest levels of volcanism, >0.14 km3 yr-1, which are well within the range of estimates from thermal evolution models or photogeological studies. Counter-intuitively we also find that more reducing melts with lower oxygen fugacity require greater amounts of volcanism to switch a paleo-atmosphere from oxidizing to reducing. The reason is that sulfur is more stable in such melts and lower absolute fluxes of sulfur-bearing gases more than compensate for increases in the proportions of H2 and CO. These results imply that ancient Mars should have experienced periods with anoxic and reducing atmospheres even through the mid-Amazonian whenever volcanic outgassing was sustained at sufficient levels. Reducing anoxic conditions are potentially conducive to the synthesis of prebiotic organic compounds, such as amino acids, and are therefore relevant to the possibility of life on Mars. Also, anoxic reducing conditions should have influenced the type of minerals that were formed on the surface or deposited from the atmosphere. We suggest looking for elemental polysulfur (S8) as a signature of past reducing atmospheres. Finally, our models allow us to estimate the amount of volcanically sourced atmospheric sulfate deposited over Mars' history, approximately ∼106-109 Tmol, with a spread depending on assumed outgassing rate history and magmatic source conditions.

Advances in high-resolution synchrotron micro-XANES for constraining the redox evolution of terrestrial and extraterrestrial magma

NASA Astrophysics Data System (ADS)

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, 115-132. [2] Dyar M. D et al. (2016) Amer. Mineral., 101, 744-748. [3] McCanta et al. (2017) Icarus, 285, 95-102.

Zircon and cassiterite U-Pb ages, petrogeochemistry and metallogenesis of Sn deposits in the Sibao area, northern Guangxi: constraints on the neoproterozoic granitic magmatism and related Sn mineralization in the western Jiangnan Orogen, South China

NASA Astrophysics Data System (ADS)

Chen, Lei; Wang, Zongqi; Yan, Zhen; Gong, Jianghua; Ma, Shouxian

2018-01-01

A number of Sn deposits associated with Neoproterozoic granites are located in the western Jiangnan Orogen of northern Guangxi. The distribution of Sn mineralization is controlled by faults occurring within and around the Neoproterozoic granites. The hydrothermal alteration and mineralization of these Sn deposits exhibit zoning from the granite to the wall rock. The laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb ages of the cassiterite and zircon from ore-bearing granite in the Menggongshan Sn deposit are 829 ± 19 Ma and 822 ± 4 Ma, respectively, indicating that the Sn mineralization and granites formed in the Neoproterozoic and can considered to be products of coeval magmatic and hydrothermal activities. The ore-bearing granite and Neoproterozoic granites in northern Guangxi are high-K, calc-alkaline, peraluminous, S-type granites that are depleted in Nb, Ti, Sr and Ba and highly enriched in Rb, U and Pb. All the granites show steep fractionated light rare earth element (LREE) and flat heavy rare earth element (HREE) patterns, with strongly negative Eu anomalies. The ɛHf(t) values of the ore-bearing granite vary from - 9.0 to - 1.7, with an average value of - 4.1. Additionally, the ore-bearing granite exhibits low oxygen fugacity values. The magmatic source experienced partial melting during their evolution, and the source was dominated by recycled heterogeneous continental crustal materials. Our evidence confirms that the Neoproterozoic granites in northern Guangxi formed in a collisional tectonic setting. The collision between the Cathaysia and Yangtze blocks or between the Sibao arc (Jiangnan arc) and the Yangtze Block caused asthenospheric upwelling, leading to partial melting and recycling of the crust, forming the peraluminous S-type granites in the Neoproterozoic. The Sn mineralization has a close genetic relationship with the Neoproterozoic granite. The highly differentiated, peraluminous, B-enriched, crustally derived Neoproterozoic granites provided the heat source and ore-forming material for the Sn mineralization. Furthermore, the low oxygen fugacity of these Neoproterozoic granites also favoured the Sn mineralization.

Nuclear Waste Package Mockups: A Study of In-situ Redox State

NASA Astrophysics Data System (ADS)

Helean, K.; Anderson, B.; Brady, P. V.

2006-05-01

The Yucca Mountain Repository (YMR), located in southern Nevada, is to be the first facility in the U.S. for the permanent disposal of high-level radioactive waste and spent nuclear fuels. Total system performance assessment(TSPA) has indicated that among the major radionuclides contributing to dose are Np, Tc, and I. These three radionuclides are mobile in most geochemical settings, and therefore sequestering them within the repository horizon is a priority for the Yucca Mountain Project (YMP). Corroding steel may offset radionuclide transport processes within the proposed waste packages at YMR by retaining radionuclides, creating locally reducing conditions, and reducing porosity. Ferrous iron has been shown to reduce UO22+ to UO2s, and some ferrous iron-bearing ion-exchange materials have been shown to adsorb radionuclides and heavy metals. Locally reducing conditions may lead to the reduction and subsequent immobilization of problematic dissolved species such as TcO4-, NpO2+, and UO22+ and can also inhibit corrosion of spent nuclear fuel. Water occluded during corrosion produces bulky corrosion products, and consequently less porosity is available for water and radionuclide transport. The focus of this study is on the nature of Yucca Mountain waste package corrosion products and their effects on local redox conditions, radionuclide transport, and porosity. In order to measure in-situ redox, six small-scale (1:40) waste package mockups were constructed using A516 and 316 stainless steel, the same materials as the proposed Yucca Mountain waste packages. The mockups are periodically injected with a simulated groundwater and the accumulated effluent and corrosion products are evaluated for their Fe(II)/Fe(III) content and mineralogy. Oxygen fugacities are then calculated and, thus, in-situ redox conditions are determined. Early results indicate that corrosion products are largely amorphous Fe-oxyhydroxides, goethite and magnetite. That information together with the measured Fe(II)/Fe(III) ratios in the mockup effluent constrain the oxygen fugacity to approximately 10-38 atm, many orders of magnitude below ambient. These results and their impact on radionuclide migration from YMR will be discussed.

Nuclear Planetology: Constraining the Driving Force in Wegener's Continental Drift Theory

NASA Astrophysics Data System (ADS)

Roller, G.

2015-12-01

Nuclear planetology [1] is a new research field, which aims at deciphering the nuclear physics processes responsible for the evolution of ultra-substellar objects and the driving force in Wegener's continental drift theory by means of Re-Os nuclear geochronometry [2]. Terrestrial Re/Os ratios observed within diamond sulphide inclusions [3], compatible with lunar r-process production ratios of Th/U≈1≈Au/Ir [4], drop from ≈0.8 to 0.2-0.05 for nucleogeochronometric ages between 2.3 Ga and 1.4 Ga [5]. It has therefore been argued [5,6] that the Re/Os fractionation is related to a change in oxygen fugacity due to the physics/chemistry of Earth's core after a possibly Fermi-pressure controlled core collapse [4]. Here, Pd/Ru, Pd/Pt, Pd/Ir, Pd/Os, Ru/Ir, Ru/Os, Pt/Ir or Pt/Os ratios from 24 published H chondrite components [7] are connected to their respective nucleogeochronometric ages to constrain an extended fossil fractionation record over 800 Ma. The following ranges are obtained: 0.06-1.04 (Pd/Ru), 0.06-0.79 (Pd/Pt), 0.06-1.76 (Pd/Os), 0.07-1.94 (Pd/Ir), 1.08-1.99 (Ru/Ir), 0.83-2.41 (Pt/Os), 0.82-2.64 (Pt/Ir). Comparing the Re/Os fractionation pattern of the diamond sulphide inclusions with these results and considering that Re is readily oxidized even at ultra-low oxygen fugacity, it may be concluded that (i) extremely reducing conditions within Earth's core basically preserve any unfractionated r-process element ratio until today; and (ii) nuclear/quantum physics processes leading to the observed ratios and fractionation pattern are ultimately the driving force in Wegener's continental drift theory. [1] Roller (2015), Abstract T34B-0407, AGU Spring Meeting. [2] Roller (2015), Geophys. Res. Abstr. 17, EGU2015-17. [3] Smit et al. (2010), GCA 74, 3292. [4] Roller (2015), Abstract #5041, 78th Ann. Met. Soc. Meeting. [5] Roller (2015), Geophys. Res. Abstr. 17, EGU2015-2399. [6] Roller (2015), Abstract PG34A-0283, AGU Spring Meeting. [7] Horan et al. (2009), GCA 73, 6984.

Phase relations in the system Fe-Si determined in an internally-resistive heated DAC

NASA Astrophysics Data System (ADS)

Komabayashi, T.; Antonangeli, D.; Morard, G.; Sinmyo, R.; Mezouar, N.

2015-12-01

It is believed that the iron-rich Earth's core contains some amounts of light elements on the basis of the density deficit of 7 % compared to pure iron. The identification of the kinds and amounts of the light elements in the core places constraints on the origin, formation, and evolution of the Earth because dissolution of light elements into an iron-rich core should place important constraints on the thermodynamic conditions (pressure (P), temperature (T), and oxygen fugacity) of the equilibration between liquid silicate and liquid iron during the core formation. Among potential light elements, silicon has been attracting attentions because it is abundant in the mantle, partitioned into both solid and liquid irons, and very sensitive to the oxygen fugacity. An important phase relation in iron alloy is a transition between the face-centred cubic (FCC) structure and hexagonal close-packed (HCP) structure. This boundary is a key to infer the stable structure in the inner core and is used to derive thermodynamic properties of the phases (Komabayashi, 2014). In the Fe-Si system, previous reports were based on experiments in laser-heated diamond anvil cells (DAC), which might have included large termperature uncertainties. We have revisited this boundary in the system Fe-Si using an internally resistive-heated DAC combined with synchrotron X-ray diffraction at the beamline ID27, ESRF. The internally-heated DAC (Komabayashi et al., 2009; 2012) provides much more stable heating than the laser-heated DAC and much higher temperature than externally resistive-heated DAC, which enables us to place tight constraints on the P-T locations of the boundaries. Also because the minimum measurable temperature is as low as 1000 K due to the stable electric heating, the internal heating is able to examine the low temperature phase stability which was not studied by the previous studies. We will report the P-T locations of the boundaries and evaluate the effect of Si on the phase relation of Earth's core materials. References Komabayashi, J. Geophys. Res., 119, 2014; Komabayashi et al., Earth Planet. Sci. Lett. 282, 2009; Komabayashi et al., Phys. Chem. Mineral 39, 2012.

Thermal state, oxygen fugacity and COH fluid speciation in cratonic lithospheric mantle: New data on peridotite xenoliths from the Udachnaya kimberlite, Siberia

NASA Astrophysics Data System (ADS)

Goncharov, A. G.; Ionov, D. A.; Doucet, L. S.; Pokhilenko, L. N.

2012-12-01

Oxygen fugacity (fO2) and temperature variations in a complete lithospheric mantle section (70-220 km) of the central Siberian craton are estimated based on 42 peridotite xenoliths in the Udachnaya kimberlite. Pressure and temperature (P-T) estimates for the 70-140 km depth range closely follow the 40 mW/m2 model conductive geotherm but show a bimodal distribution at greater depths. A subset of coarse garnet peridotites at 145-180 km plots near the "cold" 35 mW/m2 geotherm whereas the majority of coarse and sheared rocks at ≥145 km scatter between the 40 and 45 mW/m2 geotherms. This P-T profile may reflect a perturbation of an initially "cold" lithospheric mantle through a combination of (1) magmatic under-plating close to the crust-mantle boundary and (2) intrusion of melts/fluids in the lower lithosphere accompanied by shearing. fO2 values estimated from Fe3+/∑Fe in spinel and/or garnet obtained by Mössbauer spectroscopy decrease from +1 to -4 Δlog fO2 (FMQ) from the top to the bottom of the lithospheric mantle (˜0.25 log units per 10 km) due to pressure effects on Fe2+-Fe3+ equilibria in garnet. Garnet peridotites from Udachnaya appear to be more oxidized than those from the Kaapvaal craton but show fO2 distribution with depth similar to those in the Slave craton. Published fO2 estimates for Udachnaya xenoliths based on C-O-H fluid speciation in inclusions in minerals from gas chromatography are similar to our results at ≤120 km, but are 1-2 orders of magnitude higher for the deeper mantle, possibly due to uncertainties of fO2 estimates based on experimental calibrations at ≤3.5 GPa. Sheared peridotites containing garnets with u-shaped, sinusoidal and humped REE patterns are usually more oxidized than Yb, Lu-rich, melt-equilibrated garnets, which show a continuous decrease from heavy to light REE. This further indicates that mantle redox state may be related to sources and modes of metasomatism.

Geochronology and trace element geochemistry of titanite in the Machangqing Cu-Mo-dominated polymetallic deposit, Yunnan Province, southwest China

NASA Astrophysics Data System (ADS)

Fu, Yu; Sun, Xiaoming; Hollings, Pete; Li, Dengfeng; Yang, Tianjian

2018-06-01

The Machangqing Cu-Mo-dominated polymetallic deposit is a porphyry-skarn-epithermal Cu-Mo (-Au) metallogenic system located in the middle part of the Jinshajiang-Ailaoshan alkaline porphyry metallogenic belt. The skarn mineralization of the Machangqing deposit mainly occurs along the contacts between the alkalic porphyry intrusions and the surrounding Lower Ordovician Xiangyang Formation rocks. We present LA-ICP-MS U-Pb ages and trace element data for titanite from the Machangqing deposit in order to investigate the origin of this deposit. Based on mineral textures and assemblages, two types of titanite are recognized in Machangqing: magmatic titanite (Type I) from the granite porphyry and hydrothermal titanite from the mineralized skarn. The coarse-grained magmatic titanite is euhedral and occurs as discrete grains in the interstices of feldspar, quartz and biotite, whereas fine- to medium-grained hydrothermal titanite crystals (Type II) are euhedral to subhedral and occur in association with skarn minerals such as garnet, pyroxene and magnetite. Magmatic titanite has lower FeO, Al2O3, F and Nb/Ta but higher TiO2, Th/U, HFSEs and Lu/Hf than hydrothermal titanite. The magmatic titanite has higher LREE/HREE ratios and total REE contents with stronger negative Eu anomalies than its mineralized skarn counterpart. Trace elemental characteristics of hydrothermal titanite in Machangqing are consistent with relatively low F contents and oxygen fugacities when compared to the neighboring Beiya gold-dominated polymetallic deposit in the same metallogenic belt. The weighted average 206Pb/238U age of 34.3 ± 1.2 Ma of hydrothermal titanite is within error but slightly younger than the age of magmatic titanite (37.5 ± 4.1 Ma), indicating that the skarn mineralization followed the emplacement of the granite porphyry and was broadly coeval with the porphyry mineralization. The porphyry and skarn types of mineralization at Machangqing were formed from the same metallogenic system. Different ore-forming conditions, such as oxygen fugacities and F contents, might be responsible for different metal enrichments at the Machangqing and Beiya deposits.

Intrinsic oxygen fugacity measurements on seven chondrites, a pallasite, and a tektite and the redox state of meteorite parent bodies

USGS Publications Warehouse

Brett, R.; Sato, M.

1984-01-01

Intrinsic oxygen-fugacity (fO2) measurements were made on five ordinary chondrites, a carbonaceous chondrite, an enstatite chondrite, a pallasite, and a tektite. Results are of the form of linear log fO2 - 1 T plots. Except for the enstatite chondrite, measured results agree well with calculated estimates by others. The tektite produced fO2 values well below the range measured for terrestrial and lunar rocks. The lowpressure atmospheric regime that is reported to follow large terrestrial explosions, coupled with a very high temperature, could produce glass with fO2 in the range measured. The meteorite Salta (pallasite) has low fO2 and lies close to Hvittis (E6). Unlike the other samples, results for Salta do not parallel the iron-wu??stite buffer, but are close to the fayalite-quartz-iron buffer in slope. Minor reduction by graphite appears to have taken place during metamorphism of ordinary chondrites. fO2 values of unequilibrated chondrites show large scatter during early heating suggesting that the constituent phases were exposed to a range of fO2 conditions. The samples equilibrated with respect to fO2 in relatively short time on heating. Equilibration with respect to fO2 in ordinary chondrites takes place between grades 3 and 4 of metamorphism. Application of P - T - fO2 relations in the system C-CO-CO2 indicates that the ordinary chondrites were metamorphosed at pressures of 3-20 bars, as it appears that they lay on the graphite surface. A steep positive thermal gradient in a meteorite parent body lying at the graphite surface will produce thin reduced exterior, an oxidized near-surface layer, and an interior that is increasingly reduced with depth; a shallow thermal gradient will produce the reverse. A body heated by accretion on the outside will have a reduced exterior and oxidized interior. Meteorites from the same parent body clearly are not required to have similar redox states. ?? 1984.

Mapping out the QCD phase transition in multiparticle production

NASA Astrophysics Data System (ADS)

Kabana, Sonja; Minkowski, Peter

2001-04-01

We analyse multiparticle production in a thermal framework for seven central nucleus + nucleus collisions, e+ + e- annihilation into hadrons on the Z resonance and four hadronic reactions p + p and p + pbar with partial centrality selection), with centre of mass energies ranging from √(s) = 2.6 GeV (per nucleon pair) to 1.8 TeV. Thermodynamic parameters at chemical freeze-out (temperature and baryon and strangeness fugacities) are obtained from appropriate fits, generally improving in quality for reactions subjected to centrality cuts. All systems with non-vanishing fugacities are extrapolated along trajectories of equal energy density, density and entropy density to zero fugacities. The so-obtained temperatures extrapolated to zero fugacities as a function of initial energy density ɛin universally show a strong rise followed by a saturating limit of Tlim = 155 +/- 6 +/- 20 MeV. We interpret this behaviour as mapping out the boundary between quark gluon plasma and hadronic phases. The ratio of strange antiquarks to light ones as a function of the initial energy density ɛin shows the same behaviour as the temperature, saturating at a value of 0.365 +/- 0.033 +/- 0.07. No distinctive feature of `strangeness enhancement' is seen for heavy ion collisions relative to hadronic and leptonic reactions, when compared at the same initial energy density.

Ultra-reduced phases in Apollo 16 regolith: Combined field emission electron probe microanalysis and atom probe tomography of submicron Fe-Si grains in Apollo 16 sample 61500

NASA Astrophysics Data System (ADS)

Gopon, Phillip; Spicuzza, Michael J.; Kelly, Thomas F.; Reinhard, David; Prosa, Ty J.; Fournelle, John

2017-09-01

The lunar regolith contains a variety of chemically reduced phases of interest to planetary scientists and the most common, metallic iron, is generally ascribed to space weathering processes (Lucey et al. ). Reports of silicon metal and iron silicides, phases indicative of extremely reducing conditions, in lunar samples are rare (Anand et al. ; Spicuzza et al. ). Additional examples of Fe-silicides have been identified in a survey of particles from Apollo 16 sample 61501,22. Herein is demonstrated the utility of low keV electron probe microanalysis (EPMA), using the Fe Ll X-ray line, to analyze these submicron phases, and the necessity of accounting for carbon contamination. We document four Fe-Si and Si0 minerals in lunar regolith return material. The new Fe-Si samples have a composition close to (Fe,Ni)3Si, whereas those associated with Si0 are close to FeSi2 and Fe3Si7. Atom probe tomography of (Fe,Ni)3Si shows trace levels of C (60 ppma and nanodomains enriched in C, Ni, P, Cr, and Sr). These reduced minerals require orders of magnitude lower oxygen fugacity and more reducing conditions than required to form Fe0. Documenting the similarities and differences in these samples is important to constrain their formation processes. These phases potentially formed at high temperatures resulting from a meteorite impact. Whether carbon played a role in achieving the lower oxygen fugacities—and there is evidence of nearby carbonaceous chondritic material—it remains to be proven that carbon was the necessary component for the unique existence of these Si0 and iron silicide minerals.

Tetrahedrally Coordinated Fe3+ in Silicate Glasses: A Mossbauer, Iron K-edge XANES and Raman Spectroscopies Study

NASA Astrophysics Data System (ADS)

Cochain, B.; Neuville, D. R.; McCammon, C.; Henderson, G. S.; de Ligny, D.; Pinet, O.; Richet, P.

2009-05-01

In natural or industrial glasses, iron is the most abundant transition metal. A good knowledge of its redox equilibrium is important to better understand the chemical and structural evolution of magmas (crystallization, viscosity), and also to optimize vitrification processes and properties of iron-bearing glasses. To study the role of iron in silicate glasses and melts, we have used in a consistent manner the Mössbauer, iron K-edge XANES and Raman spectroscopies to investigate several series of silicate glasses as a function of redox state. The samples were selected to cover a wide composition range and to investigate the interactions of iron with two network forming cations, namely, Al3+ and B3+. The glasses investigated were synthesized at high temperature under various conditions of oxygen fugacity to achieve different redox ratios for each composition. Therefore, the iron redox state was varied from the most oxidized to the most reduced. Iron redox ratios were first determined by wet chemical analysis and in some cases by room temperature Mossbauer spectroscopy. This experimental method was also used to determine the local structure of iron of some of the investigated glasses. These results where compared to iron K-edge XANES/EXAFS spectroscopy results, which lead to the iron redox state and indicate that Fe2+ is in octahedral coordination whereas Fe3+ is in tetrahedral coordination. In addition, Raman spectroscopy gave us information on the network polymerization of glasses. Clearly changes in Raman spectra are visible with the evolution of iron redox ratio. For a given composition, we observed systematically, in the 800-1200 cm-1 envelope, which is sensitive to the environment of tetrahedrally coordinated cations, the growth of a band with the iron content and the oxidation state of the sample. The peak area of this band, which we attribute to vibrational modes involving tetrahedrally coordinated Fe3+, increases with the oxidation of the sample. This evolution leads us to establish a calibration procedure for a given composition. Calibration curves can be followed to investigate in situ kinetics of redox reactions. We present here results on the role of iron and its interactions with the silicate network for several compositions as pyroxene based glasses and iron bearing alkali alumino-borosilicate glasses.

Experimental Constraints on the Partitioning Behavior of F, Cl, and OH Between Apatite and Basaltic Melt

NASA Technical Reports Server (NTRS)

McCubbin, Francis M.; Barnes, Jessica J.; Vander Kaaden, Kathleen E.; Boyce, Jeremy W.; Ustunisik, Gokce; Whitson, Eric S.

2017-01-01

The mineral apatite is present in a wide range of planetary materials. The presence of volatiles (F, Cl, and OH) within its crystal structure (X-site) have motivated numerous studies to investigate the partitioning behavior of F, Cl, and OH between apatite and silicate melt with the end goal of using apatite to constrain the volatile contents of planetary magmas and mantle sources. A number of recent experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in magmatic systems. Apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, the partitioning behavior is likely to change as a function of temperature, pressure, oxygen fugacity, apatite composition, and melt composition. In the present study, we have conducted experiments to assess the partitioning behavior of F, Cl, and OH between apatite and silicate melt over a pressure range of 0-6 gigapascals, a temperature range of 950-1500 degrees Centigrade, and a wide range of apatite ternary compositions. All of the experiments were conducted between iron-wustite oxidation potentials IW minus 1 and IW plus 2 in a basaltic melt composition. The experimental run products were analyzed by a combination of electron probe microanalysis and secondary ion mass spectrometry (NanoSIMS). Temperature, apatite crystal chemistry, and pressure all play important roles in the partitioning behavior of F, Cl, and OH between apatite and silicate melt. In portions of apatite ternary space that undergo ideal mixing of F, Cl, and OH, exchange coefficients remain constant at constant temperature and pressure. However, exchange coefficients vary at constant temperature (T) and pressure (P) in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. The variation in exchange coefficients exhibited by apatite that does not undergo ideal mixing far exceeds the variations induced by changes in temperature (T) or pressure (P) . In regions where apatite undergoes ideal mixing of F, Cl, and OH, temperature has a stronger effect than pressure on the partitioning behavior, but both are important. Furthermore, fluorine becomes less compatible in apatite with increasing pressure and temperature. We are still in the process of analyzing our experimental run products, but we plan to quantify the effects of P and T on apatite-melt partitioning of F, Cl, and OH.

Hydrothermal reequilibration of igneous magnetite in altered granitic plutons and its implications for magnetite classification schemes: Insights from the Handan-Xingtai iron district, North China Craton

NASA Astrophysics Data System (ADS)

Wen, Guang; Li, Jian-Wei; Hofstra, Albert H.; Koenig, Alan E.; Lowers, Heather A.; Adams, David

2017-09-01

Magnetite is a common mineral in igneous rocks and has been used as an important petrogenetic indicator as its compositions and textures reflect changing physiochemical parameters such as temperature, oxygen fugacity and melt compositions. In upper crustal settings, igneous rocks are often altered by hydrothermal fluids such that the original textures and compositions of igneous magnetite may be partly or completely obliterated, posing interpretive problems in petrological and geochemical studies. In this paper, we present textural and compositional data of magnetite from variably albitized granitoid rocks in the Handan-Xingtai district, North China Craton to characterize the hydrothermal reequilibration of igneous magnetite. Four types of magnetite have been identified in the samples studied: pristine igneous magnetite (type 1), reequilibrated porous magnetite (type 2), reequilibrated nonporous magnetite (type 3), and hydrothermal magnetite (type 4). Pristine igneous magnetite contains abundant well-developed ilmenite exsolution lamellae that are largely replaced by titanite during subsequent hydrothermal alteration. The titanite has a larger molar volume than its precursor ilmenite and thus causes micro-fractures in the host magnetite grains, facilitating dissolution and reprecipitation of magnetite. During sodic alteration, the igneous magnetite is extensively replaced by type 2 and type 3 magnetite via fluid-induced dissolution and reprecipitation. Porous type 2 magnetite is the initial replacement product of igneous magnetite and is subsequently replaced by the nonoporous type 3 variety as its surface area is reduced and compositional equilibrium with the altering fluid is achieved. Hydrothermal type 4 magnetite is generally euhedral and lacks exsolution lamellae and porosity, and is interpreted to precipitate directly from the ore-forming fluids. Hydrothermal reequilibration of igneous magnetite has led to progressive chemical purification, during which trace elements such as Ti, Al, Mg, Zn, and Cr contents decrease dramatically (up to 2-3 orders of magnitude different), coupled with significant increase in iron concentrations from less than 64 wt.% to higher than 70 wt.%. Results presented here show that magnetite is much more susceptible to textural and compositional reequilibration than previously thought. The reequilibrated magnetite has geochemical patterns that may be distinctively different from its precursor, making existing discrimination plots questionable when applied to genetic interpretation. Based on textural characterization and high-resolution in situ compositional analyses, we propose that the Fe versus V/Ti diagram can be more confidently used to discriminate between pristine igneous magnetite, reequilibrated magnetite, and hydrothermal magnetite.

A fugacity-based indoor residential pesticide fate model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bennett, Deborah H.; Furtaw, Edward J.; McKone, Thomas E.

Dermal and non-dietary pathways are potentially significant exposure pathways to pesticides used in residences. Exposure pathways include dermal contact with residues on surfaces, ingestion from hand- and object-to-mouth activities, and absorption of pesticides into food. A limited amount of data has been collected on pesticide concentrations in various residential compartments following an application. But models are needed to interpret this data and make predictions about other pesticides based on chemical properties. In this paper, we propose a mass-balance compartment model based on fugacity principles. We include air (both gas phase and aerosols), carpet, smooth flooring, and walls as model compartments.more » Pesticide concentrations on furniture and toys, and in food, are being added to the model as data becomes available. We determine the compartmental fugacity capacity and mass transfer-rate coefficient for wallboard as an example. We also present the framework and equations needed for a dynamic mass-balance model.« less

Optical absorption and radiative heat transport in olivine at high temperature

NASA Technical Reports Server (NTRS)

Shankland, T. J.; Nitsan, U.; Duba, A. G.

1979-01-01

Results are presented of measurements of the optical absorption spectra (300-8000 nm) of olivine as a function of temperature (300-1700 K) under conditions of controlled and known oxygen fugacity within the stability field of the samples. The absorption spectra are used to calculate the temperature-dependent radiative transfer coefficient of olivine and to numerically study the accuracy of the method. The present absorption measurements in olivine under oxidizing conditions known to be within the olivine stability field indicate that the effective radiative conductivity K(R) is lower than that obtained in previous studies under different experimental conditions. The lower value of K(R) makes it more likely that some of the earth's internal heat is removed by convection and less likely that thermal models involving conduction and radiation alone will satisfactorily explain thermal conditions in the earth's mantle.

A system for conducting igneous petrology experiments under controlled redox conditions in reduced gravity

NASA Technical Reports Server (NTRS)

Williams, Richard J.

1987-01-01

The Space Shuttle and the planned Space Station will permit experimentation under conditions of reduced gravitational acceleration offering experimental petrologists the opportunity to study crystal growth, element distribution, and phase chemistry. In particular the confounding effects of macro and micro scale buoyancy-induced convection and crystal settling or flotation can be greatly reduced over those observed in experiments in the terrestrial laboratory. Also, for experiments in which detailed replication of the environment is important, the access to reduced gravity will permit a more complete simulation of processes that may have occurred on asteroids or in free space. A technique that was developed to control, measure, and manipulate oxygen fugacities with small quantities of gas which are recirculated over the sample. This system could be adaptable to reduced gravity space experiments requiring redox control.

Apatite/Melt Partitioning Experiments Reveal Redox Sensitivity to Cr, V, Mn, Ni, Eu, W, Th, and U

NASA Technical Reports Server (NTRS)

Righter, K.; Yang, S.; Humayun, M.

2016-01-01

Apatite is a common mineral in terrestrial, planetary, and asteroidal materials. It is commonly used for geochronology (U-Pb), sensing volatiles (H, F, Cl, S), and can concentrate rare earth elements (REE) during magmatic fractionation and in general. Some recent studies have shown that some kinds of phosphate may fractionate Hf and W and that Mn may be redox sensitive. Experimental studies have focused on REE and other lithophile elements and at simplified or not specified oxygen fugacities. There is a dearth of partitioning data for chalcophile, siderophile and other elements between apatite and melt. Here we carry out several experiments at variable fO2 to study the partitioning of a broad range of trace elements. We compare to existing data and then focus on several elements that exhibit redox dependent partitioning behavior.

Fayal dans l'Atlantique et Rapa dans le Pacifique: deux séries faiblement alcalines évoluant sous conditions anhydres

NASA Astrophysics Data System (ADS)

Brousse, R.; Bizouard, H.; Metrich, N.

1981-09-01

Though in two different geodynamic sites, the Isles of Fayal (Azores, North Atlantic) and Rapa (Australes, Pacific) show large similitudes. The two series differentiated under dry conditions by a process of crystal fractionation with low oxygen fugacity. Olivine is present in both series and evolves from Fo83 to Fo5 (Rapa) and from Fo77 to Fo22 (Fayal). The two series present some features of the tholeiitic series, even though their high contents in incompatible elements (K2O, TiO2, etc.) and normative Ne (0.30 in basalt) would assimilate them to alkaline series. These apparent conflicting datas are explained by an anhydrous melting (<15%) under high pressure (>15kb) of an undepleted pyrolitic mantle, according to a recent proposal by Jaques and Green (1980).

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

NASA Astrophysics Data System (ADS)

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 determined S apatite-melt partitioning coefficient debatable. Upon calibration over a range of geologically relevant T-P-X-fO2-fS2, S-in-apatite can serve as a powerful oxybarometer to quantify fO2.

Exsolution of Iron-Titanium Oxides in Magnetite in Miller Range (MIL) 03346 Nakhlite: Evidence for Post Crystallization Reduction in the Nakhlite Cumulate Pile

NASA Technical Reports Server (NTRS)

Righter, Kevin; Keller, L. P.; Rahman, Z.; Christoffersen, R.

2012-01-01

MIL 03346 is one of the most mesostasis-rich nakhlites [1] and thought to have equilibrated at oxygen fugacities near the fayalite-magnetite-quartz oxygen (FMQ) buffer ([2,3]). Studies of FeTi oxides in nakhlites have led to additional constraints on their equilibration temperatures and fO2s [4,5,6,7]. Comparison of these results to fO2s calculated for shergottites indicates that nakhlites are among the most oxidized samples from the martian meteorite suite [2]. The mesostasis of MIL 03346 contains skeletal titanomagnetite. Several scientists noticed several years ago (e.g. [8]) that this titanomagnetite contains very fine oxidation-driven exsolution lamellae (Figure 1). However, the lamellae are so small that they cannot be characterized by electron microprobe analysis (EMPA). Here we select several areas for focused ion beam (FIB) extraction, prepare transmission electron microscopy (TEM) foils, and identify and analyze the lamellae using TEM at the Johnson Space Center (JSC). The resulting analyses are combined with previous work on nakhlites to interpret the thermal and oxidation history of this meteorite group.

Fluid-absent metamorphism in the Adirondacks

NASA Technical Reports Server (NTRS)

Valley, J. W.

1986-01-01

Results on late Proterozoic metamorphism of granulite in the Adirondacks are presented. There more than 20,000 sq km of rock are at granulite facies. Low water fugacites are implied by orthopyroxene bearing assemblages and by stability of k'spar-plag-quartz assemblages. After mentioning the popular concept of infiltration of carbon dioxide into Precambrian rocks and attendent generation of granulite facies assemblages, several features of Adirondack rocks pertinent to carbon dioxide and water during their metamorphism are summarized: wollastonite occurs in the western lowlands; contact metamorphism by anorthosite preceeding granulite metamorphism is indicated by oxygen isotopes. Oxygen fugacity lies below that of the QFM buffer; total P sub water + P sub carbon dioxide determined from monticellite bearing assemblages are much less than P sub total (7 to 7.6 kb). These and other features indicate close spatial association of high- and low-P sub carbon dioxide assemblages and that a vapor phase was not present during metamorphism. Thus Adirondack rocks were not infiltrated by carbon dioxide vapor. Their metamorphism, at 625 to 775 C, occurred either when the protoliths were relatively dry or after dessication occurred by removal of a partial melt phase.

A petrologic, thermodynamic and experimental study of brachinites: Partial melt residues of an R chondrite-like precursor

NASA Astrophysics Data System (ADS)

Gardner-Vandy, Kathryn G.; Lauretta, Dante S.; McCoy, Timothy J.

2013-12-01

The primitive achondrites provide a window into the initial melting of asteroids in the early solar system. The brachinites are olivine-dominated meteorites with a recrystallized texture that we and others interpret as evidence of partial melting and melt removal on the brachinite parent body. We present a petrologic, thermodynamic and experimental study of the brachinites to evaluate the conditions under which they formed and test our hypothesis that the precursor material to the brachinites was FeO-rich compared to the precursors of other primitive achondrites. Petrologic analysis of six brachinites (Brachina, Allan Hills (ALH) 84025, Hughes 026, Elephant Moraine (EET) 99402, Northwest Africa (NWA) 3151, and NWA 4969) and one brachinite-like achondrite (NWA 5400) shows that they are meteorites with recrystallized texture that are enriched in olivine (⩾80 vol.%) and depleted in other minerals with respect to a chondritic mineralogy. Silicates in the brachinites are FeO-rich (Fa32-36). Brachinite-like achondrite Northwest Africa 5400 is similar in mineralogy and texture to the brachinites but with a slightly lower FeO-content (Fa30). Thermodynamic calculations yield equilibration temperatures above the Fe,Ni-FeS cotectic temperature (∼950 °C) for all meteorites studied here and temperatures above the silicate eutectic (∼1050 °C) for all but two. Brachina formed at an fO2 of ∼IW, and the other brachinites and NWA 5400 formed at ∼IW - 1. All the meteorites show great evidence of formation by partial melting having approximately chondritic to depleted chondritic mineralogies, equilibrated mineral compositions, and recrystallized textures, and having reached temperatures above that required for melt generation. In an attempt to simulate the formation of the brachinite meteorites, we performed one-atmosphere, gas-mixing partial melting experiments of R4 chondrite LaPaz Ice Field 03639. Experiments at 1250 °C and an oxygen fugacity of IW - 1 produce residual phases that are within the mineralogy and mineral compositions of the brachinites. These experiments provide further evidence for the formation of brachinites as a result of partial melting of a chondritic precursor similar in mineralogy and mineral compositions to the R chondrites.

Magmatic processes revealed by anorthoclase textures and trace element modeling: The case of the Lajes Ignimbrite eruption (Terceira Island, Azores)

NASA Astrophysics Data System (ADS)

D'Oriano, Claudia; Landi, Patrizia; Pimentel, Adriano; Zanon, Vittorio

2017-11-01

The Lajes Ignimbrite on Terceira Island (Azores) records the last major pyroclastic density current-forming eruption of Pico Alto Volcano that occurred ca. 21 kyrs ago. This comenditic trachyte ignimbrite contains up to 30 vol% of crystals, mostly anorthoclase. Geochemical investigation of the products collected throughout two key outcrops reveals that major element compositions are poorly variable, whereas trace elements show significant variability, pointing to the presence of a zoned magma reservoir. Thermometry and oxygen fugacity estimations yielded pre-eruptive temperatures of 850-900 °C and ΔNNO from - 2.4 to - 1.8. Melt-alkali-feldspar hygrometer indicates magmatic H2O contents ranging from 5.8 wt% in the upper part of the reservoir to 3.6 wt% at the bottom, indicating that the magma reservoir (confined at 4 km depth) was mainly water-undersaturated before the eruption, except for the topmost portion. Two types of anorthoclase crystals were identified. Type 1 crystals show reverse to oscillatory zoning with An contents of 0.4-2.1 mol% and Ba of 200-2000 ppm. They formed in the middle/upper portion of the reservoir, where fractional crystallization processes dominated. Type 2 crystals, mainly present in the less evolved products, are characterized by patchy-zoned cores with large dissolution pockets surrounded by thick oscillatory-zoned rims and show a wide compositional range (An of 0.5-4.7 mol% and Ba of 142-4824 ppm). Their zoning patterns, together with whole-rock and glass compositions of the juvenile clasts, are consistent with the involvement of an anorthoclase-bearing cumulate from the bottom of the reservoir that underwent partial melting. Crystal dissolution was likely induced by the presence of a heat source at depth, without any mass transfer to the eruptible magma, as suggested by the lack of petrographic and chemical evidences of mixing between the resident comenditic trachyte and a mafic/intermediate magma. Thermal instability generated convective plumes that were responsible for the admittance of crystals from the cumulate level into the intermediate portions of the magma reservoir and possibly acted as trigger of the explosive eruption.

Phase equilibria constraints on the chemical and physical evolution of the campanian ignimbrite

USGS Publications Warehouse

Fowler, S.J.; Spera, F.J.; Bohrson, W.A.; Belkin, H.E.; de Vivo, B.

2007-01-01

The Campanian Ignimbrite is a > 200 km3 trachyte-phonolite pyroclastic deposit that erupted at 39.3 ?? 0.1 ka within the Campi Flegrei west of Naples, Italy. Here we test the hypothesis that Campanian Ignimbrite magma was derived by isobaric crystal fractionation of a parental basaltic trachyandesitic melt that reacted and came into local equilibrium with small amounts (5-10 wt%) of crustal rock (skarns and foid-syenites) during crystallization. Comparison of observed crystal and magma compositions with results of phase equilibria assimilation-fractionation simulations (MELTS) is generally very good. Oxygen fugacity was approximately buffered along QFM+1 (where QFM is the quartz-fayalite-magnetite buffer) during isobaric fractionation at 0.15 GPa (???6 km depth). The parental melt, reconstructed from melt inclusion and host clinopyroxene compositions, is found to be basaltic trachyandesite liquid (51.1 wt% SiO2, 9.3 wt% MgO, 3 wt% H2O). A significant feature of phase equilibria simulations is the existence of a pseudo-invariant temperature, ???883??C, at which the fraction of melt remaining in the system decreases abruptly from ???0.5 to < 0.1. Crystallization at the pseudo-invariant point leads to abrupt changes in the composition, properties (density, dissolved water content), and physical state (viscosity, volume fraction fluid) of melt and magma. A dramatic decrease in melt viscosity (from 1700 Pa s to ???200 Pa s), coupled with a change in the volume fraction of water in magma (from ??? 0.1 to 0.8) and a dramatic decrease in melt and magma density acted as a destabilizing eruption trigger. Thermal models suggest a timescale of ??? 200 kyr from the beginning of fractionation until eruption, leading to an apparent rate of evolved magma generation of about 10-3 km3/year. In situ crystallization and crystal settling in density-stratified regions, as well as in convectively mixed, less evolved subjacent magma, operate rapidly enough to match this apparent volumetric rate of evolved magma production. ?? Copyright 2007 Oxford University Press.

Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions.

PubMed

Bennett, Neil R; Brenan, James M; Fei, Yingwei

2015-06-13

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied.

An experimental study of ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite: a strong dependence on H2O in the melt

NASA Astrophysics Data System (ADS)

Waters, Laura E.; Lange, Rebecca A.

2017-06-01

The effect of temperature, pressure, and dissolved H2O in the melt on the Fe2+-Mg exchange coefficient between orthopyroxene and rhyolite melt was investigated with a series of H2O fluid-saturated phase-equilibrium experiments. Experiments were conducted in a rapid-quench cold-seal pressure vessel over a temperature and pressure range of 785-850 °C and 80-185 MPa, respectively. Oxygen fugacity was buffered with the solid Ni-NiO assemblage in a double-capsule assembly. These experiments, when combined with H2O-undersaturated experiments in the literature, show that ^{{{{Fe}}^{2 + } {-}{{Mg}}}} K_{{D}} between orthopyroxene and rhyolite liquid increases strongly (from 0.23 to 0.54) as a function of dissolved water in the melt (from 2.7 to 5.6 wt%). There is no detectable effect of temperature or pressure over an interval of 65 °C and 100 MPa, respectively, on the Fe2+-Mg exchange coefficient values. The data show that Fe-rich orthopyroxene is favored at high water contents, whereas Mg-rich orthopyroxene crystallizes at low water contents. It is proposed that the effect of dissolved water in the melt on the composition of orthopyroxene is analogous to its effect on the composition of plagioclase. In the latter case, dissolved hydroxyl groups preferentially complex with Na+ relative to Ca2+, which reduces the activity of the albite component, leading to a more anorthite-rich (calcic) plagioclase. Similarly, it is proposed that dissolved hydroxyl groups preferentially complex with Mg2+ relative to Fe2+, thus lowering the activity of the enstatite component, leading to a more Fe-rich orthopyroxene at high water contents in the melt. The experimental results presented in this study show that reversely zoned pyroxene (i.e., Mg-rich rims) in silicic magmas may be a result of H2O degassing and not necessarily the result of mixing with a more mafic magma.

Pliocene-Quaternary basalts from the Harrat Tufail, western Saudi Arabia: Recycling of ancient oceanic slabs and generation of alkaline intra-plate magma

NASA Astrophysics Data System (ADS)

Bakhsh, Rami A.

2015-12-01

Harrat Tufail represents a Caenozoic basalt suite at the western margin of the Arabian plate. This rift-related suite includes voluminous Quaternary non-vesicular basalt (with fragments of earlier Pliocene vesicular flow) that forms a cap sheet over Miocene rhyolite and minor vesicular basalt. The contact between rhyolite and the basaltic cap is erosional with remarkable denudations indicating long time gap between the felsic and mafic eruptions. The geochemical data prove alkaline, sodic and low-Ti nature of the olivine basalt cap sheet. The combined whole-rock and mineral spot analyses by the electron microprobe (EMPA) suggest magma generation from low degree of partial melting (∼5%) from spinel- and garnet-lherzolite mantle source. Derivation from a mantle source is supported by low Na content in clinopyroxene (ferroan diopside) whereas high Mg content in ilmenite is an evidence of fractional crystallization trajectory. Accordingly, the Pliocene basaltic cap of Harrat Tufail is a product of mantle melt that originates by recycling in the asthenosphere during subduction of ancient oceanic slab(s). The whole-rock chemistry suggests an ancient ocean island basaltic slab (OIB) whereas the EMPA of Al-rich spinel inclusions in olivine phenocrysts are in favour of a mid-ocean ridge basaltic source (MORB). Calculations of oxygen fugacity based on the composition of co-existing Fe-Ti oxide suggest fluctuation from highly to moderately oxidizing conditions with propagation of crystallization (log10 fO2 from -22.09 to -12.50). Clinopyroxene composition and pressure calculation indicates low-pressure (0.4-2 kbar). Cores of olivine phenocrysts formed at highest temperature (1086-1151 °C) whereas the rims and olivine micro-phenocrysts formed at 712-9-796 °C which is contemporaneous to formation of clinopyroxene at 611-782 °C. Fe-Ti oxides crystallized over a long range (652-992 °C) where it started to form at outer peripheries of olivine phenocrysts and as interstitial phase with clinopyroxene.

Investigating the subsurface connection beneath Cerro Negro volcano and the El Hoyo Complex, Nicaragua

NASA Astrophysics Data System (ADS)

Venugopal, Swetha; Moune, Séverine; Williams-Jones, Glyn

2016-10-01

Cerro Negro, the youngest volcano along the Central American Volcanic Belt (CAVB), is a polygenetic cinder cone with relatively frequent basaltic eruptions. The neighbouring El Hoyo complex, of which Las Pilas is the dominant edifice, is a much larger and older complex with milder and less frequent eruptions. Previous studies have suggested a deep link beneath these two closely spaced volcanoes (McKnight, 1995; MacQueen, 2013). Melt inclusions were collected from various tephra samples in order to determine whether a connection exists and to delineate the features of this link. Major, volatile, and trace elemental compositions reveal a distinct geochemical continuum with Cerro Negro defining the primitive endmember and El Hoyo representing the evolved endmember. Magmatic conditions at the time of melt inclusion entrapment were estimated with major and volatile contents: 2.4 kbar and 1170 °C for Cerro Negro melts and 1.3 kbar and 1130 °C for El Hoyo melts with an overall oxygen fugacity at the NNO buffer. Trace element contents are distinct and suggest Cerro Negro magmas fractionally crystallise while El Hoyo magmas are a mix between primitive Cerro Negro melts and residual and evolved El Hoyo magma. Modelling of end member compositions with alphaMELTS confirms the unique nature of El Hoyo magmas as resulting from incremental mixing between Cerro Negro and residual evolved magma at 4 km depth. Combining all available literature data, this study presents a model of the interconnected subsurface plumbing system. This model considers the modern day analogue of the Lemptégy cinder cones in Massif Central, France and incorporates structurally controlled dykes. The main implications of this study are the classification of Cerro Negro as the newest conduit within the El Hoyo Complex as well as the potential re-activation of the El Hoyo edifice.

Complex Diffusion Mechanisms for Li in Feldspar: Re-thinking Li-in-Plag Geospeedometry

NASA Astrophysics Data System (ADS)

Holycross, M.; Watson, E. B.

2017-12-01

In recent years, the lithium isotope system has been applied to model processes in a wide variety of terrestrial environments. In igneous settings, Li diffusion gradients have been frequently used to time heating episodes. Lithium partitioning behavior during decompression or cooling events drives Li transfer between phases, but the extent of Li exchange may be limited by its diffusion rate in geologic materials. Lithium is an exceptionally fast diffuser in silicate media, making it uniquely suited to record short-lived volcanic phenomena. The Li-in-plagioclase geospeedometer is often used to time explosive eruptions by applying laboratory-calibrated Li diffusion coefficients to model concentration profiles in magmatic feldspar samples. To quantify Li transport in natural scenarios, experimental measurements are needed that account for changing temperature and oxygen fugacity as well as different feldspar compositions and crystallographic orientation. Ambient pressure experiments were run at RPI to diffuse Li from a powdered spodumene source into polished sanidine, albite, oligoclase or anorthite crystals over the temperature range 500-950 ºC. The resulting 7Li concentration gradients developed in the mineral specimens were evaluated using laser ablation ICP-MS. The new data show that Li diffusion in all feldspar compositions simultaneously operates by both a "fast" and "slow" diffusion mechanism. Fast path diffusivities are similar to those found by Giletti and Shanahan [1997] for Li diffusion in plagioclase and are typically 10 to 20 times greater than slow path diffusivities. Lithium concentration gradients in the feldspar experiments plot in the shape of two superimposed error function curves with the slow diffusion regime in the near-surface of the crystal. Lithium diffusion is most sluggish in sanidine and is significantly faster in the plagioclase feldspars. It is still unclear what diffusion mechanism operates in nature, but the new measurements may impact how Li-in-plagioclase geospeedometry is used to time igneous processes. Giletti, B.J., and T.M. Shanahan (1997) Alkali diffusion in plagioclase feldspar, Chem. Geol., 139, 3-20

Partitioning of Cu between mafic minerals, Fe-Ti oxides and intermediate to felsic melts

NASA Astrophysics Data System (ADS)

Liu, Xingcheng; Xiong, Xiaolin; Audétat, Andreas; Li, Yuan

2015-02-01

This study used improved capsule technique i.e., Pt95Cu05 or Au95Cu05 alloy capsules as Cu sources to determine Cu partitioning between mafic minerals, Fe-Ti oxides and intermediate to felsic melts at 0.5-2.5 GPa, 950-1100 °C and various oxygen fugacities (fO2). In combination with the data from the mafic composition systems, the results demonstrate that Cu is generally highly incompatible in mafic minerals and moderately incompatible to compatible in Fe-Ti oxides. The general order of mineral/melt Cu partition coefficients (DCu) is garnet (0.01-0.06) ⩽ olivine (0.04-0.20) ≈ opx (0.04-0.24) ≈ amphibole (0.04-0.20) ⩽ cpx (0.04-0.45) ⩽ magnetite, titanomagnetite and Cr-spinel (0.18-1.83). The variations in DCu depend mainly on temperature, fO2 or mineral composition. In general, DCu for olivine (and perhaps opx) increases with decreasing temperature and increasing fO2. DCu increases for cpx with Na+ (pfu) in cpx, for magnetite and Cr-spinel with Fe3+ (pfu) in these phases and for titanomagnetite with Ti4+ (pfu) in this phase. The large number of DCu data (99 pairs) serves as a foundation for quantitatively understanding the behavior of Cu during magmatic processes. The generation of intermediate to felsic magmas via fractional crystallization or partial melting of mafic rocks (magmas) at deep levels of crust involves removal of or leaving assemblages of mafic minerals + Fe-Ti oxides ± sulfides. With our DCu data on mafic minerals and Fe-Ti oxides, DCubulk values around 0.2 were obtained for the sulfide-free assemblages. Cu will thus be concentrated efficiently in the derived melts during these two processes if sulfides are absent or negligible, explaining that high fO2 and sulfide-destabilization are favorable to formation of the porphyry Cu system.

Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions

PubMed Central

Bennett, Neil R.; Brenan, James M.; Fei, Yingwei

2015-01-01

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied. PMID:26132380

Experimental constraints on Earth's core formation

NASA Astrophysics Data System (ADS)

Bouhifd, Mohamed Ali

2017-04-01

The Earth contains a Fe-rich metallic core that segregated from the primitive silicate mantle very early in its 4.5 billion year history. One major consequence of this segregation is the depletion of the Earth's mantle from the siderophile elements "high core affinity" relative to primitive solar system abundances. The way in which siderophile elements partition between metal and silicate depends strongly on pressure (P), temperature (T), oxygen fugacity (fO2) and chemical compositions of both metal and silicate phases. In the present presentation, I will discuss the experimental results of metal-silicate partitioning of Ni and Co that show a marked change with increasing pressure (e.g. Bouhifd and Jephcoat, 2011; Siebert et al., 2012; Fischer et al., 2015 for the most recent studies). This behavior coincides with a change in the coordination of silicon (in a basaltic melt composition) from 4-fold coordination under ambient conditions to 6-fold coordination at about 35 GPa, indicating that melt compressibility may controls siderophile-element partitioning (Sanloup et al., 2013). I will also discuss the impact of Earth's core formation on "lithophile" elements such as Sm, Nd, Ta and Nb (e.g. Bouhifd et al. 2015; Cartier et al., 2014), as well as the impact of sulphur on the behavior of various elements during core formation (e.g. Boujibar et al., 2014; Wohlers and Wood, 2015). By combining the metal-silicate partitioning data from siderophile, lithophile and chalcophile elements I will present and discuss the most plausible conditions for Earth's core formation. References Bouhifd and Jephcoat (2011) EPSL, 307, 341-348. Bouhifd et al. (2015) EPSL 413, 158-166. Boujibar et al. (2014) EPSL 391, 42-54. Cartier et al. (2014) Nature Geoscience, 7, 573-576. Fischer et al. (2015) GCA 167, 177-194. Sanloup et al. (2013) Nature, 503, 104-107. Siebert et al. (2012) EPSL 321-322, 189-197. Wohlers and Wood (2015) Nature 520, 337-340.

The influence of water and redox conditions on the seismic properties of olivine

NASA Astrophysics Data System (ADS)

Cline, C. J., II; Jackson, I.; Faul, U.; David, E. C.; Berry, A.

2017-12-01

Eight polycrystalline olivine specimens of both synthetic (solution-gelation derived) and natural (San Carlos) origins were fabricated by hot-pressing at 1200°C and 300 MPa. Amongst these specimens, six contained varying concentrations of Ti, allowing control of hydroxyl (or `water') content through the creation of the energetically favored Ti-clinohumite-like defect (doubly protonated Si vacancy associated with a Ti/Mg substitution). Along with a Ti-free Fo90 specimen, these materials have Ti contents ranging between 0 and 802 atom ppm Ti/Si and associated chemically bound `water' contents between 0 and 1150 atom ppm H/Si, along with molecular water concentrations between 0 and 245 atom ppm H/Si. Each hot-pressed specimen was then subsequently wrapped in Pt, Ni or NiFe foil to control oxygen fugacity (fO2), and interrogated under water-undersaturated conditions via forced torsional oscillation. Testing was conducted at seismic periods of 1 - 1000 s and 200 MPa confining pressure during slow staged cooling from 1200 to 25°C. All specimens, regardless of water content or metal sleeving, exhibit high temperature background behavior, involving monotonically increasing levels of dissipation and concomitantly decreasing shear modulus with increasing oscillation period and increasing temperature. Our experimental results demonstrate unambiguously that water content (and water fugacity) has a negligible effect on the measured seismic properties olivine. Rather, a relationship between the prevailing redox conditions set by the metal sleeving and the magnitude of anelastic relaxation was observed. These results suggest that low velocity and high attenuation anomalies in the upper mantle are not due to elevated water contents. Instead, in oxidized and hydrous regions above subducting slabs and perhaps in the oceanic asthenosphere, high attenuation may reflect elevated fO2 conditions.

Calc-Alkaline Liquid Lines of Descent Produced Under Oxidizing Conditions: An Experimental and Petrologic Study of Basaltic Tephras from the Western Aleutians, AK

NASA Astrophysics Data System (ADS)

Waters, L. E.; Cottrell, E.; Kelley, K. A.; Coombs, M. L.

2017-12-01

Buldir, a volcano in the western Aleutian Arc, features eruptive products that form one of the most strongly calc-alkaline compositional trends observed in modern island arcs. Previous studies of Buldir and nearby submarine dredge samples suggest that Buldir's mineral phases and isotopic signatures may be introduced through mixing of two distinct magmas and/or melts, as no experimental study has been able to create a liquid line of descent (LLD) as calc-alkaline as Buldir's whole rock trend. To further test this hypothesis, we present new experimental results and petrographic analysis of tephras from the 2015 field season of the GeoPRISMS shared platform. Tephras (51.4-54.8 wt% SiO2) have a phenocryst assemblage of olivine + plagioclase + cpx + spinel ± hornblende (hbl). In natural samples, plagioclase comprises most of the crystal volume, followed by either olivine or hornblende. In samples that contain abundant hbl (Hbl Mg#=65-80), olivine and plagioclase span a range of compositions from Fo72-86 and An60-93, respectively. In samples without hbl, olivines are more forsteritic (Fo79-90), and plagioclase is less calcic (An65-83). Spinel is ubiquitous; with Cr- rich spinel inclusions in olivine and hbl, and magnetite in the groundmass. Our petrologic observations do not require magma mixing. To determine whether these observations could be consistent with the LLD of a single parental liquid, we conducted a series of phase equilibrium experiments at 100 MPa in a rapid-quench cold-seal (MHC) apparatus on the most primitive natural lava from Buldir (9.34 wt% MgO). Experiments were equilibrated in noble metal capsules pre-saturated with Fe, and buffered at Re-ReO2 under water-saturated conditions. Spinel [(Mg80, Fe2+20)(Fe3+52, Cr83, Al66)O4] is the liquidus phase, followed by olivine, then plagioclase, then cpx, and lastly, hbl. Once cpx and hbl saturate, spinel composition shifts to magnetite. Experimental run products demonstrate that all mineral phases observed in the tephras are plausible phenocrysts. Experimental glass compositions demonstrate that the strongly calc-alkaline trend observed at Buldir can be produced through crystallization of a parental liquid under water-saturated conditions at relatively high oxygen fugacity, where the effect of high fO2 is to stabilize spinel as a liquidus phase.

An abrupt change in the magmatic source of rhyolite volcanism in Long Valley, CA recorded by pre-eruptive oxygen fugacities of the Early Rhyolites (Obsidians): evidence of transition from subduction-modified lithosphere to asthenosphere

NASA Astrophysics Data System (ADS)

Waters, L.; Lange, R. A.

2016-12-01

Detailed mapping of the Long Valley (CA) region (Hildreth, 2004) reveals that the eruption of the Late Bishop Tuff (LBT) is followed by eruption of the Early Rhyolites (ER), which are obsidian lavas. The obsidians are paradoxical, as they erupted effusively, contain multiple phases (some of which vary in composition), and yet, they are crystal-poor. The obsidians are saturated in ≥7 phases (plagioclase + orthopyroxene + ilmenite + titanomagnetite + biotite + apatite + zircon ± pyrrhotite). Plagioclase and orthopyroxene crystals have rounded edges accompanying euhedral margins, and large (>200µm) ilmenites have swallow-tail growth. Plagioclase and orthopyroxene span a compositional range between An20-45 and En43-58, respectively, and phase equilibrium experiments confirm that these are phenocrysts, despite their complex textures. Pre-eruptive temperatures and fO2 values are calculated applying Fe-Ti oxide thermometry to all possible oxide pairs and range from 724-861°C and ΔNNO -0.3 to -0.9, respectively. Application of the plagioclase hygrometer to crystals in ER obsidians reveals pre-eruptive H2O contents of 3-5wt%. We propose that mineral compositions and textures within the ER obsidians record rapid growth due to degassing-induced crystallization of a superheated melt. Superheating is required to explain the origin of the ER lavas as it eliminates nucleation sites, requiring crystallization to occur on nuclei that form during degassing enabling effusive eruption of crystal-poor lavas. The ER obsidians differ from the LBT in their crystallinities (<5% vs. >12%), phenocryst phases (e.g., sanidine is absent in ER obsidians), plagioclase compositions (An20-45 vs. An20-29), and fO2 values (ΔNNO < -0.3 vs. +0.5), which suggests that the ER lavas may not be derived from the LBT reservoir. Rather, we hypothesize that the ER phenocryst assemblage, reduced fO2 values, and requirement for superheating can be explained if the obsidians formed as partial melts of a mixed lithology, consisting of pre-existing crust and an additional component with low fO2. We propose that the reduced component in the ER source is aesthenospheric basalt, which suggests that a transition in mantle source, from subduction-modified lithosphere to asthenosphere, has occurred beneath Long Valley.

Initial H2O content and conditions of parent magma origin for Gorely volcano (Southern Kamchatka) estimated by trace element thermobarometry

NASA Astrophysics Data System (ADS)

Nazarova, D. P.; Portnyagin, M. V.; Krasheninnikov, S. P.; Mironov, N. L.; Sobolev, A. V.

2017-01-01

The formation conditions of the parental magmas of Gorely volcano, which is located behind a volcanic front in Southern Kamchatka, have been evaluated using the modern methods of micro-element thermobarometry. These magmas contained 1.7 ± 0.8 (2σ) wt % of H2O, the majority (82%) of which has been lost from inclusions. They crystallized at 1121 ± 17°C and an oxygen fugacity of ΔQFM 1.2 ± 0.2, and could have been produced by about 11% melting of an enriched MORB source (E-DMM) at a temperature of about 1270°C, and a pressure of about 1.5 GPa. A distinctive feature of Gorely volcano, compared with frontal volcanoes of Kamchatka, is the unusually high temperature (925 ± 20°C) of formation of the subduction component corresponding to the region of existence of water-bearing melts.

Low hydrogen contents in the cores of terrestrial planets.

PubMed

Clesi, Vincent; Bouhifd, Mohamed Ali; Bolfan-Casanova, Nathalie; Manthilake, Geeth; Schiavi, Federica; Raepsaet, Caroline; Bureau, Hélène; Khodja, Hicham; Andrault, Denis

2018-03-01

Hydrogen has been thought to be an important light element in Earth's core due to possible siderophile behavior during core-mantle segregation. We reproduced planetary differentiation conditions using hydrogen contents of 450 to 1500 parts per million (ppm) in the silicate phase, pressures of 5 to 20 GPa, oxygen fugacity varying within IW-3.7 and IW-0.2 (0.2 to 3.7 log units lower than iron-wüstite buffer), and Fe alloys typical of planetary cores. We report hydrogen metal-silicate partition coefficients of ~2 × 10 -1 , up to two orders of magnitude lower than reported previously, and indicative of lithophile behavior. Our results imply H contents of ~60 ppm in the Earth and Martian cores. A simple water budget suggests that 90% of the water initially present in planetary building blocks was lost during planetary accretion. The retained water segregated preferentially into planetary mantles.

Octahedral cation partitioning in Mg,Fe2+-olivine. Mössbauer spectroscopic study of synthetic (Mg0.5 Fe2+ 0.5)2SiO4 (Fa50)

NASA Astrophysics Data System (ADS)

Morozov, Mikhail; Brinkmann, Christian; Grodzicki, Michael; Lottermoser, Werner; Tippelt, Gerold; Amthauer, Georg; Kroll, Herbert

2005-11-01

The high-temperature partitioning of Fe2+ and Mg between the two non-equivalent octahedral M1 and M2 sites in synthetic olivine (Fa50) was studied by Mössbauer spectroscopy. Powder samples have been equilibrated in annealing experiments performed under reducing oxygen fugacity at temperatures between 500 and 800°C followed by rapid quenching in order to prevent redistribution of cations. M-site ordering with Fe2+ preferring M1, Mg preferring M2 sites increases continuously with rising equilibrium temperature. K D values increase from 1.21 at 500°C to 1.48 at 750°C. The results are consistent with both room temperature as well as in situ high temperature single crystal X-ray diffraction experiments of Heinemann et al. [8, 9].

Microscopic iron metal on glass and minerals - A tool for studying regolith maturity

NASA Technical Reports Server (NTRS)

Allen, C. C.; Morris, R. V.; Lauer, H. V., Jr.; Mckay, D. S.

1993-01-01

A novel method of producing mixtures of glass or minerals with iron metal is presented. A portion of the Fe(2+) in basaltic glass and minerals can be reduced to metal in a few hours at 1100 C and an oxygen fugacity well below the iron-wustite buffer. Part of the iron metals forms rounded submicrometer blebs on the surfaces and in some cases within the grains. A concentration of such blebs equivalent to 20-30 percent of a grain's surface area can totally dominate the reflectance spectra of basaltic glass, pyroxene, and olivine. The production of optically opaque iron metal blebs, combined with the decline in Fe(2+), affects the glass and mineral reflectance spectra in three ways: by lowering the overall reflectivity, reducing the spectral contrast of absorption features, and producing a continuum with a general rise in reflectivity toward longer wavelengths.

Geology and genesis of the Baid al Jimalah tungsten deposit, Kingdom of Saudi Arabia

USGS Publications Warehouse

Kamilli, R.J.; Cole, J.C.; Elliott, J.E.; Criss, R.E.

1993-01-01

The Baid ad Jimalah tungsten deposit in Saudi Arabia consists predominantly of swarms of steeply dipping, subparallel, tungsten-bearing quartz veins and of less abundant, smaller stockwork veins. It is spatially, temporally, and genetically associated with a 569 Ma, highly differentiated, porphyritic, two-feldspar granite that intrudes Late Proterozoic immature sandstones. Baid al Jimalah is similar in character and origin to Phanerozoic tungsten-tin greisen deposits throughout the world, especially the Hemerdon deposit in Devon, England. It is also analogous to Climax-type molybdenum deposits, which contain virtually identical mineral assemblages, but with the relative proportions of molybdenum and tungsten mineralization reversed, primarily owing to differences in oxygen fugacity. This similarity in mineralization styles and fluid histories indicates that metallogenic processes in granite-related deposits in the late Precambrian were similar to those seen in the Phanerozoic. -from Authors

Third Bose fugacity coefficient in one dimension, as a function of asymptotic quantities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amaya-Tapia, A., E-mail: jano@fis.unam.mx; Larsen, S.Y.; Lassaut, M.

2011-02-15

In one of the very few exact quantum mechanical calculations of fugacity coefficients, [L.R. Dodd, A.M. Gibbs. J. Math. Phys. 15 (1974) 41] obtained b{sub 2} and b{sub 3} for a one dimensional Bose gas, subject to repulsive delta-function interactions, by direct integration of the wave functions. For b{sub 2}, we have shown [A. Amaya-Tapia, S.Y. Larsen, M. Lassaut. Mol. Phys. 103 (2005) 1301-1306. < (arXiv:physics/0405150)>] that Dodd and Gibbs' result can be obtained from a phase shift formalism, if one also includes the contribution of oscillating terms, usually contributing only in one dimension. Now, we develop an exact expressionmore » for b{sub 3}-b{sub 3}{sup 0} (where b{sub 3}{sup 0} is the free particle fugacity coefficient) in terms of sums and differences of three-body eigenphase shifts. Further, we show that if we obtain these eigenphase shifts in a Distorted-Born approximation, then, to first order, we reproduce the leading low temperature behaviour, obtained from an expansion of the twofold integral of Dodd and Gibbs. The contributions of the oscillating terms cancel. The formalism that we propose is not limited to one dimension, but seeks to provide a general method to obtain virial coefficients, fugacity coefficients, in terms of asymptotic quantities. The exact one dimensional results allow us to confirm the validity of our approach in this domain.« less

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

NASA Astrophysics Data System (ADS)

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.

The Effects of Oxygen Fugacity on the Crystallization Sequence and Cr Partitioning of an Analog Y-98 Liquid

NASA Technical Reports Server (NTRS)

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

2013-01-01

Interpreting the relationship between "enriched" olivine-phyric shergottites (e.g. NWA 1068/1110) and the "enriched" pyroxene-plagioclase shergottites (e.g. Shergotty, Los Angeles) is problematic. Symes et al. [1] and Shearer et al. [2]) proposed that the basaltic magma that crystallized to produce olivine-phyric shergottite NWA 1068/1110 could produce pyroxene-plagioclase shergottites with additional fractional crystallization. However, additional observations indicate that the relationship among the enriched shergottites may be more complex [1-3]. For example, Herd [3] concluded that some portion of the olivine megacrysts in this meteorite was xenocrystic in origin, seemingly derived from more reduced basaltic liquids. This conclusion may imply that a variety of complex processes such as magma mixing, entrainment, and assimilation may play important roles in the petrologic history of these meteorites. It is therefore possible that these processes have obscured the petrogenetic linkages between the enriched olivine-phyric shergottites and the pyroxene-plagioclase shergottites. As a first order step in attempting to unravel these petrologic complexities, this study focuses upon exploring the effect of fO2 on the crystallization history for an analog primitive shergottite liquid composition (Y98). Results from this work will provide a basis for reconstructing the record of fO2 in shergottites, its effect on both mineral chemistries and valence state partitioning, and a means for examining the role of crystallization on the petrologic linkages between olivine-phyric and pyroxene-plagioclase shergottites. A companion abstract [4] explores the behavior of V over this range of fO2.

Metal/Silicate Partitioning at High Pressures and Temperatures

NASA Technical Reports Server (NTRS)

Shofner, G.; Campbell, A.; Danielson, L.; Righter, K.; Rahman, Z.

2010-01-01

The behavior of siderophile elements during metal-silicate segregation, and their resulting distributions provide insight into core formation processes. Determination of partition coefficients allows the calculation of element distributions that can be compared to established values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Moderately siderophile elements, including W, are particularly useful in constraining core formation conditions because they are sensitive to variations in T, P, oxygen fugacity (fO2), and silicate composition. To constrain the effect of pressure on W metal/silicate partitioning, we performed experiments at high pressures and temperatures using a multi anvil press (MAP) at NASA Johnson Space Center and laser-heated diamond anvil cells (LHDAC) at the University of Maryland. Starting materials consisted of natural peridotite mixed with Fe and W metals. Pressure conditions in the MAP experiments ranged from 10 to 16 GPa at 2400 K. Pressures in the LHDAC experiments ranged from 26 to 58 GPa, and peak temperatures ranged up to 5000 K. LHDAC experimental run products were sectioned by focused ion beam (FIB) at NASA JSC. Run products were analyzed by electron microprobe using wavelength dispersive spectroscopy. Liquid metal/liquid silicate partition coefficients for W were calculated from element abundances determined by microprobe analyses, and corrected to a common fO2 condition of IW-2 assuming +4 valence for W. Within analytical uncertainties, W partitioning shows a flat trend with increasing pressure from 10 to 16 GPa. At higher pressures, W becomes more siderophile, with an increase in partition coefficient of approximately 0.5 log units.

Partitioning of U, Th and K Between Metal, Sulfide and Silicate, Insights into the Volatile-Content of Mercury

NASA Technical Reports Server (NTRS)

Habermann, M.; Boujibar, A.; Righter, K.; Danielson, L.; Rapp, J.; Righter, M.; Pando, K.; Ross, D. K.; Andreasen, R.; Chidester, B.

2016-01-01

During the early stages of the Solar System formation, especially during the T-Tauri phase, the Sun emitted strong solar winds, which are thought to have expelled a portion of the volatile elements from the inner solar system. It is therefore usually believed that the volatile depletion of a planet is correlated with its proximity to the Sun. This trend was supported by the K/Th and K/U ratios of Venus, the Earth, and Mars. Prior to the MESSENGER mission, it was expected that Mercury is the most volatile-depleted planet. However, the Gamma Ray Spectrometer of MESSENGER spacecraft revealed elevated K/U and K/Th ratios for the surface of Mercury, much higher than previous expectations. It is possible that the K/Th and K/U ratios on the surface are not a reliable gauge of the bulk volatile content of Mercury. Mercury is enriched in sulfur and is the most reduced of the terrestrial planets, with oxygen fugacity (fO2) between IW-6.3 and IW-2.6 log units. At these particular compositions, U, Th and K behave differently and can become more siderophile or chalcophile. If significant amounts of U and Th are sequestered in the core, the apparent K/U and K/Th ratios measured on the surface may not represent the volatile budget of the whole planet. An accurate determination of the partitioning of these elements between silicate, metal, and sulfide phases under Mercurian conditions is therefore essential to better constrain Mercury's volatile content and assess planetary formation models.

Oxygen Compatibility Testing of Composite Materials

NASA Technical Reports Server (NTRS)

Engel, Carl D.; Watkins, Casey N.

2006-01-01

Composite materials offer significant weight-saving potential for aerospace applications in propellant and oxidizer tanks. This application for oxygen tanks presents the challenge of being oxygen compatible in addition to complying with the other required material characteristics. This effort reports on the testing procedures and data obtained in examining and selecting potential composite materials for oxygen tank usage. Impact testing of composites has shown that most of these materials initiate a combustion event when impacted at 72 ft-lbf in the presence of liquid oxygen, though testing has also shown substantial variability in reaction sensitivities to impact. Data for screening of 14 potential composites using the Bruceton method is given herein and shows that the 50-percent reaction frequencies range from 17 to 67 ft-lbf. The pressure and temperature rises for several composite materials were recorded to compare the energy releases as functions of the combustion reactions with their respective reaction probabilities. The test data presented are primarily for a test pressure of 300 psia in liquid oxygen. The impact screening process is compared with oxygen index and autogenous ignition test data for both the composite and the basic resin. The usefulness of these supplemental tests in helping select the most oxygen compatible materials is explored. The propensity for mechanical impact ignition of the composite compared with the resin alone is also examined. Since an ignition-free composite material at the peak impact energy of 72 ft-lbf has not been identified, composite reactivity must be characterized over the impact energy level and operating pressure ranges to provide data for hazard analyses in selecting the best potential material for liquid tank usage.

Oxygen inhibition layer of composite resins: effects of layer thickness and surface layer treatment on the interlayer bond strength.

PubMed

Bijelic-Donova, Jasmina; Garoushi, Sufyan; Lassila, Lippo V J; Vallittu, Pekka K

2015-02-01

An oxygen inhibition layer develops on surfaces exposed to air during polymerization of particulate filling composite. This study assessed the thickness of the oxygen inhibition layer of short-fiber-reinforced composite in comparison with conventional particulate filling composites. The effect of an oxygen inhibition layer on the shear bond strength of incrementally placed particulate filling composite layers was also evaluated. Four different restorative composites were selected: everX Posterior (a short-fiber-reinforced composite), Z250, SupremeXT, and Silorane. All composites were evaluated regarding the thickness of the oxygen inhibition layer and for shear bond strength. An equal amount of each composite was polymerized in air between two glass plates and the thickness of the oxygen inhibition layer was measured using a stereomicroscope. Cylindrical-shaped specimens were prepared for measurement of shear bond strength by placing incrementally two layers of the same composite material. Before applying the second composite layer, the first increment's bonding site was treated as follows: grinding with 1,000-grit silicon-carbide (SiC) abrasive paper, or treatment with ethanol or with water-spray. The inhibition depth was lowest (11.6 μm) for water-sprayed Silorane and greatest (22.9 μm) for the water-sprayed short-fiber-reinforced composite. The shear bond strength ranged from 5.8 MPa (ground Silorane) to 36.4 MPa (water-sprayed SupremeXT). The presence of an oxygen inhibition layer enhanced the interlayer shear bond strength of all investigated materials, but its absence resulted in cohesive and mixed failures only with the short-fiber-reinforced composite. Thus, more durable adhesion with short-fiber-reinforced composite is expected. © 2014 Eur J Oral Sci.

Is the Neoproterozoic oxygen burst a supercontinent legacy?

NASA Astrophysics Data System (ADS)

Macouin, Melina; Roques, Damien; Rousse, Sonia; Ganne, Jerome; Denele, Yoann; Trindade, Ricardo

2015-09-01

The Neoproterozoic (1000-542 Myr ago) witnessed the dawn of Earth as we know it with modern-style plate tectonics, high levels of O2 in atmosphere and oceans and a thriving fauna. Yet, the processes leading to the fully oxygenation of the external envelopes, its exact timing and its link with the inner workings of the planet remain poorly understood. In some ways, it is a "chicken and egg" question: did the Neoproterozoic Oxygenation Event (NOE) cause life blooming, low-latitudes glaciations and perturbations in geochemical cycles or is it a consequence of these phenomena? Here, we suggest that the NOE may have been triggered by multi-million years oxic volcanic emissions along a protracted period at the end of the Neoproterozoic when continents were assembled in the Rodinia supercontinent. We report a very oxidized magma source at the upper mantle beneath a ring of subducting margins around Rodinia, and detail here the evidence at the margin of the Arabian shield. We investigate the 780 Ma Biotite and Pink granites and associated rocks of the Socotra Island with rock magnetic and petrographic methods. Magnetic susceptibility and isothermal remanent magnetization acquisitions show that, in these granites, both magnetite and hematite are present. Hematite subdivides magnetite grains into small grains. Magnetite and hematite are found to be primary, and formed at the early magmatic evolution of the granite at very high oxygen fugacity. Massive degassing of these oxidized magmas would reduce the sink for oxygen, and consequently contribute to its rise in the atmosphere with a net O2 flux of at least 2.25 x 107 Tmol. Our conceptual model provides a deep Earth link to the NOE and implies the oxygenation burst has occurred earlier than previously envisaged, paving the way for later changes in the outer envelopes of the planet epitomized on the extreme Neoproterozoic glaciations and the appearance of the first animals.

Alteration of Al-rich inclusions inside amoeboid olivine aggregates in the Allende meteorite

NASA Technical Reports Server (NTRS)

Hashimoto, Akihiko; Grossman, Lawrence

1987-01-01

The primary phases of Al-rich inclusions in amoeboid olivine aggregates have undergone alteration reactions with the solar nebular gas. The simplest interpretation of the present observations is that melilite was the first primary phase to disappear with falling temperature, and was replaced by grossular + anorthite + feldspathoids, followed by fassaite; spinel was the last phase to be altered. Thermodynamic calculations suggest that Na-rich phlogopite could have formed at about 470 K and chlorite at about 328 K at a water fugacity of 0.000001, which is that of a gas of solar composition in this temperature range. The olivine around Al-rich inclusions is not serpentized, indicating the cessation of gas-solid equilibrium above 274 K.

Copper systematics during mantle melting and crustal differentiation in arcs: implications for S and Pb budgets of the continental crust

NASA Astrophysics Data System (ADS)

Lee, C.; Chin, E. J.; Dasgupta, R.; Luffi, P. I.; Le Roux, V.

2010-12-01

During mid-ocean ridge melting, Cu behaves like Sc and is therefore moderately incompatible, as evidenced by the twofold increase in Cu content in MORBs compared to the mantle. However, Cu content in the continental crust is comparable to that of the mantle, implying that during continental crust formation, Cu becomes effectively compatible. Cu is one of the only elements that exhibits Jekyll and Hyde behavior. This switch to being compatible is consistent with the observation that for the majority of arc magmas (as well as MORBs), Cu decreases with increasing SiO2 and decreasing MgO. Using natural samples, we infer new partition coefficients that indicate Cu is incompatible in olivine, pyroxenes, amphiboles, and biotite. The only mineral to exert significant control on Cu partitioning is sulfide. Cu behaves incompatibly during mantle melting because the modal abundance of sulfides relative to silicate minerals is extremely low. The monotonic decrease in Cu in most differentiating arc magmas requires sulfide saturation. In addition, the similar abundances of Cu in many primitive arc magmas compared to MORBs suggests that mantle melting in both environments occurs not only at sulfide saturation but without the need for excess Cu (or S). In a few cases, however, primitive arc magmas begin with high Cu or show increases in Cu with differentiation, which most likely requires unusually high oxygen fugacities in the source or magmatic evolution towards high oxygen fugacity. Such cases may be important for the origin of Cu porphyry deposits, but are generally rare. Because of the close link between Cu and sulfide during magma differentiation, Cu can be used as a proxy for the pre-degassed S content of arc magmas. The S content of continental crust, like many volatile elements, is basically unconstrained, but it can be inferred from Cu, which is much better constrained. Finally, the fact that the continental crust is highly depleted in Cu implies that there is a missing reservoir rich in Cu and by necessity sulfide. Cumulate xenoliths in arc settings fit this persona. Delamination of these cumulates, embedded with sulfides, will have profound implications for the Pb isotopic evolution of the mantle by linking the Pb paradox to continent formation.

Concentration and Mobility of Electrically-Conducting Defects in Olivine

NASA Astrophysics Data System (ADS)

Constable, S.; Roberts, J.; Duba, A.

2002-12-01

We have collected measurements of electrical conductivity and thermopower as a function of temperature and oxygen fugacity (f O2) on a sample of San Quintin dunite (95% olivine), and measurements of electrical conductivity equilibration after changes in f O2 on Mt.Porndon lherzolite (65% olivine). Both data sets have been analysed using nonlinear parameter inversion of mathematical models relating conductivity, thermopower, and diffusion kinetics to temperature, f O2, time, and defect concentration and mobility. From the dunite thermopower/conductivity data we are able to estimate the concentration and mobilities of electrically conducting defects. Our model allows electrons, small polarons (Fe+++ on Fe++ sites), and magnesium vacancies (V'' Mg) to contribute to conduction, but only polarons and V'' Mg are required by our data. Polarons dominate conduction below 1300°~C; at this temperature conduction, is equal for the two defects at all f O2 tested. Thermopower measurements allow us to estimate defect concentration independently from mobility, and so we can back out polaron mobility as 12.2x 10-6 exp(-1.05~eV/kT) m2V-1s-1 and magnesium vacancy mobility as 2.72x 10-6 exp(-1.09~eV/kT) m2V-1s-1. Electrical conductivity of the lherzolite, measured as a function of time after changes in the oxygen fugacity of the surrounding CO2/CO atmosphere, is used to infer the diffusivity of the point defects associated with the oxidation reactions. An observed f O2 dependence in the time constants associated with equilibration implies two species of fixed diffusivity, each with f O2-dependent concentrations. Although the rate-limiting step may not necessarily be associated with conducting defects, when time constants are converted to mobilities, the magnitudes and activation energies agree extremely well with the model presented above for the dunite, after one free parameter (effective grain size) is fit at a plausible 1.6~mm diameter. Not only does this study represent one of the few direct measurements of polaron mobility, but the very good agreement between two independent measurement techniques (thermopower versus equilibration kinetics) and two independent samples (dunite versus lherzolite) provides some level of confidence in the results. We are currently extending these modeling techniques to study olivine defect mobility anisotropy.

Monazite, iron oxide and barite exsolutions in apatite aggregates from CCSD drillhole eclogites and their geological implications

NASA Astrophysics Data System (ADS)

Sun, Xiaoming; Tang, Qian; Sun, Weidong; Xu, Li; Zhai, Wei; Liang, Jinlong; Liang, Yeheng; Shen, Kun; Zhang, Zeming; Zhou, Bing; Wang, Fangyue

2007-06-01

We have identified abundant exsolutions in apatite aggregates from eclogitic drillhole samples of the Chinese Continental Scientific Drilling (CCSD) project. Electron microscope and laser Raman spectroscopy analyses show that the apatite is fluorapatite, whereas exsolutions that can be classified into four types: (A) platy to rhombic monazite exsolutions; (B) needle-like hematite exsolutions; (C) irregular magnetite and hematite intergrowths; and (D) needle-like strontian barite exsolutions. The widths and lengths of type A monazite exsolutions range from about 6-10 μm (mostly 6 μm) and about 50-75 μm, respectively. Type B exsolutions are parallel with the C axis of apatite, with widths ranging from 0.5 to 2 μm, with most around 1.5 μm, and lengths that vary dramatically from 6 to 50 μm. Type C exsolutions are also parallel with the C axis of apatite, with lengths of ˜30-150 μm and widths of ˜10 to 50 μm. Type D strontian barite exsolutions coexist mostly with type B hematite exsolutions, with widths of about 9 μm and lengths of about 60-70 μm. Exsolutions of types B, C and D have never been reported in apatites before. Most of the exsolutions are parallel with the C axis of apatite, implying that they were probably exsolved at roughly the same time. Dating by the chemical Th-U-total Pb isochron method (CHIME) yields an U-Pb isochron age of 202 ± 28 Ma for monazite exsolutions, suggesting that these exsolutions were formed during recrystallization and retrograde metamorphism of the exhumed ultrahigh pressure (UHP) rocks. Quartz veins hosting apatite aggregates were probably formed slightly earlier than 202 Ma. Abundant hematite exsolutions, as well as coexistence of magnetite/hematite and barite/hematite in the apatite, suggest that the oxygen fugacity of apatite aggregates is well above the sulfide-sulfur oxide buffer (SSO). Given that quartz veins host these apatite aggregates, they were probably deposited from SiO 2-rich hydrous fluids formed during retrogression of the subducted slab. Such SiO 2-rich hydrous fluids may act as an oxidizing agent, a feasible explanation for the high oxygen fugacity in convergent margin systems.

The differentiation process of the I-type granitoids in southwest Japan and New South Wares in Australia

NASA Astrophysics Data System (ADS)

Kawakatsu, K.; Iwamoto, Y.; Ebisu, S.; Hasegawa, M.; Hiraiwa, N.; Kawakatsu, T.; Kitano, A.; Masuta, T.; Ootsubo, H.; Wakazono, R.

2013-12-01

Cretaceous-Paleogene Granitoids in the inner zone of southwest Japan have been divided into two series: the magnetite series that is distributed mainly in the San-in belt and the ilmenite series that is distributed mainly in San-yo belt. For 8 years, we have been investigating the two series to clear their processes of magmatic differentiation. Recently, we discovered oscillatory zoned structure, exsolution lamellae of amphibole, and relics of pyroxene left in the core of amphibole from Harima granodiorite, Nunobiki granodiorite (San-yo belt) and Daito-Yokota quartz diorite (San-in belt). The amphibole that has microstructure coexists with magnetite, ilmenite and pyrrhotite. We compared the two series for crystallization and re-equilibrium by ion substitution using the microstructure of the amphibole as 'time measure' during the differentitation process of acidic magma. While magnetites and ilmenites coexist with the core of the amphiboles, the oxygen fugacity of the San-yo belt magma was low until the later stage of magmatic differentiation where H2S from the Earth's crust mixed with it. In the subsolidus process, hydrothermal solutions circulated. On the other hand, the oxygen fugacity of the San-in belt magma began to rise in the early stage of magmatic differentiation. In the later stage, mafic magma was contaminated with SO2. The rims of amphiboles coexist with pyrrhotites in both of belts. Furthermore, the re-equilibrium of minerals underwent progressive oxidation and hydrothermal fluid circulated actively in the subsolidus process. Bingie Bingie Point at New South Wares (Eurobodalla National Park) is a peninsula about a meter around. The plutonic rocks were formed in the Devonian period and belong to the magnetite series. They are classified I-type granitoids such as those found in the inner zone of southwest Japan. They have only trace amounts of oxide minerals and pyrrhotite. The amphiboles of the granitoids have oscillatory zoned structures at pale green rims. The structures are formed by the fluid circulations of intruded granodiorite magma. The relic pyroxene is left in the core of amphibole. These minerals were crystallized under stable conditions and the microstructures were developed in the amphiboles under the subsolidus conditions. These researches contribute to clarifying magmatic differentiation and are the foundation of understanding the exchange of substances in magmatic activity.

The effects of nickel and sulphur on the core-mantle partitioning of oxygen in Earth and Mars

NASA Astrophysics Data System (ADS)

Tsuno, Kyusei; Frost, Daniel J.; Rubie, David C.

2011-03-01

Constraints on the partitioning of oxygen between silicates, oxides, and metallic liquids are important for determining the amount of oxygen that may have entered the cores of terrestrial planets and to identify likely reactions at the core-mantle boundary. Several previous studies have examined oxygen partitioning between liquid Fe metal and ferropericlase, however, the cores of terrestrial planets also contain nickel and most likely sulphur. We have performed experiments to examine the effects of both nickel and sulphur on the partitioning of oxygen between ferropericlase and liquid Fe alloy up to pressures of 24.5 GPa in the temperature range 2430-2750 K using a multianvil press. The results show that at a fixed oxygen fugacity the proportion of oxygen that partitions into liquid metal will decrease by approximately 1-2 mol% on the addition of 10-20 mol% nickel to the liquid. The addition of around 30 mol% sulphur will, on the other hand, increase the metal oxygen content by approximately 10 mol%. Experiments to examine the combined effects of both nickel and sulphur, show a decrease in the effect of nickel on oxygen partitioning as the sulphur content of the metal increases. We expand an existing thermodynamic model for the partitioning of oxygen at high pressures and temperatures to include the effects of nickel and sulphur by fitting these experimental data, with further constraints provided by existing phase equilibria studies at similar conditions in the Fe-S and Fe-O-S systems. Plausible terrestrial core sulphur contents have little effect on oxygen partitioning. When our model is extrapolated to conditions of the present day terrestrial core-mantle boundary, the presence of nickel is found to lower the oxygen content of the outer core that is in equilibrium with the expected mantle ferropericlase FeO content, by approximately 1 weight %, in comparison to nickel free calculations. In agreement with nickel-free experiments, this implies that the Earth's outer core is undersaturated in oxygen with respect to plausible mantle FeO contents, which will result in either the depletion of FeO from the base of the mantle or cause the development of an outer core layer that is enriched in oxygen. The oxygen content of the more sulphur-rich Martian core would be in the range 2-4 wt.% if it is in equilibrium with the FeO-rich Martian mantle.

Thermal Demagnetization of Mare Basalts 10017 and 10020

NASA Astrophysics Data System (ADS)

Suavet, C. R.; Weiss, B. P.; Grove, T. L.

2012-12-01

Paleomagnetic studies of lunar rocks 76535 (Garrick-Bethell et al., 2009), 10020 (Shea et al., 2012) and 10017 (Suavet et al., 2012) have shown that the Moon had an active dynamo field at 4.2 Ga, 3.7 Ga, and 3.6 Ga, respectively. These studies were carried out using alternating field (AF) demagnetization, which has the advantage to avoid sample alteration by heating, but the paleointensity is only constrained within a factor of 3-5 due to uncertainties on the calibration factor between thermoremanent magnetization (TRM) and anhysteretic remanent magnetization (ARM). Thermal demagnetization is expected to give better estimates of the paleofields. Thellier-Thellier paleointensity experiments on 10017 under reducing atmosphere (Sugiura et al., 1978) and in vacuum (Hoffman et al., 1979) were attempted in the past. Almost full demagnetization was observed after heating from 200 to 300°C, which was interpreted as alteration of magnetic carriers, or interaction effects between troilite and kamacite (Pearce et al., 1976). For both experiments, the oxygen fugacity was poorly constrained due to methodological flaws: no oxygen was introduced in the system and further reduction of the rocks could not be mitigated. We designed a controlled atmosphere apparatus to conduct thermal demagnetization in a mixture of H2 and CO2. Gas mixtures were calibrated by exploring the stability of iron, magnetite, and wustite at temperatures in the range of 300-800°C. We thermally demagnetized the natural remanent magnetization (NRM) of subsamples of 10017 and 10020 in a gas mixture with an oxygen fugacity ~1 log unit below the iron-wustite buffer (Sato et al., 1973). After heating from 200 to 250°C, the magnetization was reduced to 10% of the NRM for 10017, and 20% of the NRM for 10020, and the magnetization directions became unstable. A subsample of 10020 was given a 0.1 mT ARM, and thermally demagnetized up to 250°C: the magnetization was reduced to 38% of the ARM and the direction became unstable. The fact that the NRM and the ARM have similar behavior upon heating confirms that the magnetization is a TRM. We compared the AF demagnetization of a 0.1 mT ARM before and after heating a subsample of 10017 up to 250°C: there was no change in the coercivity spectrum, which shows that the demagnetization was not due to alteration of the magnetic carriers. The thermal demagnetization of a subsample of 10017 with a saturation isothermal magnetization (SIRM) does not show a Curie point at 250°C. Therefore, the low-temperature demagnetization of mare basalts 10017 and 10020 is real. It could be caused by a defect magnetization of troilite, interaction between troilite and kamacite, presence of cohenite, or an unknown phenomenon.

Characteristics of trophic transfer of polychlorinated biphenyls in marine organisms in Incheon North Harbor, Korea.

PubMed

Kim, Seung Kyu; Lee, Dong Soo; Oh, Jae Ryong

2002-04-01

The trophic transfer of polychlorinated biphenyls (PCBs) was characterized for zooplankton (primarily Paracalanus spp. and Acartia spp.), pacific oyster (Crassostrea gigas), shore crab (Hemigrapsus penicillatus), and goby (Acanthogobius hasta) in the aquatic system of Incheon North Harbor, Korea. The congener pattern in the species was clearly divided by the main PCB uptake route. Compared with zooplankton and oyster, the fraction of heavier homologues increased in crab and goby that take PCBs from food. Linear relationships were observed between log (fugacity in lipid/fugacity in seawater) and log Kow for all the species. For zooplankton and oyster, such an observation should not be regarded as a true absence of superhydrophobicity, because establishment of equilibrium with seawater was not evident. For crab and goby, the absence of superhydrophobicity was evidenced by the trophic transfer factor that continuously increased with Kow up to 10(7.8). These results suggest that superhydrophobicity might be species specific. The trophic transfer factors and the fugacity levels in the lipid phase indicated that bioaccumulation in crab and goby advanced beyond the level in equilibrium with seawater in the harbor basin.

VOLATILECALC: A silicate melt-H2O-CO2 solution model written in Visual Basic for excel

USGS Publications Warehouse

Newman, S.; Lowenstern, J. B.

2002-01-01

We present solution models for the rhyolite-H2O-CO2 and basalt-H2O-CO2 systems at magmatic temperatures and pressures below ~ 5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within MicrosoftR Excel (Office'98 and 2000). The series of macros, entitled VOLATILECALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H2O and CO2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H2O and CO2 vapors at magmatic temperatures. The basalt-H2O-CO2 macros in VOLATILECALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar. ?? 2002 Elsevier Science Ltd. All rights reserved.

V OLATILEC ALC: a silicate melt-H 2O-CO 2 solution model written in Visual Basic for excel

NASA Astrophysics Data System (ADS)

Newman, Sally; Lowenstern, Jacob B.

2002-06-01

We present solution models for the rhyolite-H 2O-CO 2 and basalt-H 2O-CO 2 systems at magmatic temperatures and pressures below ˜5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within Microsoft ® Excel (Office'98 and 2000). The series of macros, entitled V OLATILEC ALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H 2O and CO 2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H 2O and CO 2 vapors at magmatic temperatures. The basalt-H 2O-CO 2 macros in V OLATILEC ALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar.

Oxygen Isotopic Analyses of Water Extracted from the Martian Meteorite NWA 7034

NASA Astrophysics Data System (ADS)

Nunn, M.; Agee, C. B.; Thiemens, M. H.

2012-12-01

Introduction: The NWA 7034 meteorite has been identified as Martian, but it is distinct from the Shergottite-Nakhlite-Chassignite (SNC) grouping of meteorites in its petrology (it is the only known Martian basaltic breccia) and bulk silicate oxygen isotopic composition (Δ17O = 0.56 ± 0.06 ‰, where Δ17O = δ17O - 0.528 x δ18O, compared to the average SNC Δ17O ≈ 0.3 ‰) [e.g., 1-2]. We report here measurements of the oxygen isotopic composition of water extracted from NWA 7034 by stepwise heating. Methods: A piece (~1.2g) of NWA 7034 was pumped to vacuum until outgassing had stopped before heating to 50, 150, 320, 500, and 1000°C. The sample was maintained at each temperature step for at least one hour while collecting evolved volatiles in a liquid nitrogen cold trap. Water was selectively converted to molecular oxygen, the oxygen isotopic composition of which was then measured on a double collecting isotope ratio mass spectrometer. Results: Our stepwise heating experiments indicate NWA 7034 contains 3330ppm water, and this water has an average oxygen isotopic composition of Δ17O = 0.330 ± 0.011‰. The oxygen isotopic composition of water in NWA 7034 is unlike that of the silicates from which it is extracted (Δ17O = 0.56 ± 0.06 ‰) but is comparable to the average SNC silicate composition (Δ17O ≈ 0.3 ‰). However, there is no consensus on the oxygen isotopic composition of water in SNCs because aliquots of water extracted from different samples (separate pieces of a single meteorite or from different meteorites) have different oxygen isotopic compositions [3]. Furthermore, carbonates and sulfates extracted from SNCs also possess distinct oxygen isotopic compositions [4]. The variation in oxygen isotopic composition among these phases most likely results from the existence of isotopically distinct oxygen reservoirs on Mars that were not equilibrated. On Earth, interaction of ozone (O3) and carbon dioxide (CO2) leads to a mass independent oxygen isotopic composition of atmospheric CO2 [5]. This anomaly is transferred by exchange from CO2 to water and subsequently to secondary minerals. The much larger CO2 to water ratio on Mars could allow this process to introduce a measurable oxygen isotopic anomaly to sulfates, carbonates, and water. The magnitude and variability of this anomaly would depend on the formation mechanism of the species (particularly the source of oxygen), as is consistent with measurements to date of phases in SNCs. References: [1] Franchi, I.A., et al. (1999) MAPS 34, 657-661. [2] Rumble, D. and Irving, A.J. (2009) LPSC XXXX, #2293 [3] Karlsson, H.R., et al. (1992) Science 255, 1409-1411. [4] Farquhar, J. and Thiemens, M.H. (2000) J. Geophys. Res. 105, 11991-11997. [5] Yung, Y.L., et al. (1991) Geophys. Res. Lett. 18, 13-16.

Seasonality of Oxygen isotope composition in cow (Bos taurus) hair and its model interpretation

NASA Astrophysics Data System (ADS)

Chen, Guo; Schnyder, Hans; Auerswald, Karl

2017-04-01

Oxygen isotopes in animal and human tissues are expected to be good recorders of geographical origin and migration histories based on the isotopic relationship between hair oxygen and annual precipitation and the well-known spatial pattern of oxygen isotope composition in meteoric water. However, seasonal variation of oxygen isotope composition may diminish the origin information in the tissues. Here the seasonality of oxygen isotope composition in tail hair was investigated in a domestic suckler cow (Bos taurus) that underwent different ambient conditions, physiological states, and keeping and feeding strategies during five years. A detailed mechanistic model involving in ambient conditions, soil properties and animal physiology was built to explain this variation. The measured oxygen isotope composition in hair was significantly related (p<0.05) to the isotope composition in meteoric water in a regression analysis. Modelling suggested that this relation was only partly derived from the direct influence of feed moisture. Ambient conditions (temperature, moisture) did not only influence the isotopic signal of precipitation but also affected the animal itself (drinking water demand, transcutaneous vapor etc.). The clear temporal variation thus resulted from complex interactions with multiple influences. The twofold influence of ambient conditions via the feed and via the animal itself is advantageous for tracing the geographic origin because the oxygen isotope composition is then less influenced by variations in moisture uptake; however, it is unfavorable for indicating the production system, e.g. to distinguish between milk produced from fresh grass or from silage.

Fluid inclusion and stable isotope (O, H, C, and S) constraints on the genesis of the Serrinha gold deposit, Gurupi Belt, northern Brazil

NASA Astrophysics Data System (ADS)

Klein, Evandro L.; Harris, Chris; Renac, Christophe; Giret, André; Moura, Candido A. V.; Fuzikawa, Kazuo

2006-05-01

The Serrinha gold deposit of the Gurupi Belt, northern Brazil, belongs to the class of orogenic gold deposits. The deposit is hosted in highly strained graphitic schist belonging to a Paleoproterozoic (˜2,160 Ma) metavolcano-sedimentary sequence. The ore-zones are up to 11 m thick, parallel to the regional NW-SE schistosity, and characterized by quartz-carbonate-sulfide veinlets and minor disseminations. Textural and structural data indicate that mineralization was syn- to late-tectonic and postmetamorphic. Fluid inclusion studies identified early CO2 (CH4-N2) and CO2 (CH4-N2)-H2O-NaCl inclusions that show highly variable phase ratios, CO2 homogenization, and total homogenization temperatures both to liquid and vapor, interpreted as the product of fluid immiscibility under fluctuating pressure conditions, more or less associated with postentrapment modifications. The ore-bearing fluid typically has 18-33mol% of CO2, up to 4mol% of N2, and less than 2mol% of CH4 and displays moderate to high densities with salinity around 4.5wt% NaCl equiv. Mineralization occurred around 310 to 335°C and 1.3 to 3.0 kbar, based on fluid inclusion homogenization temperatures and oxygen isotope thermometry with estimated oxygen fugacity indicating relatively reduced conditions. Stable isotope data on quartz, carbonate, and fluid inclusions suggest that veins formed from fluids with δ18OH2O and δDH2O (310-335°C) values of +6.2 to +8.4‰ and -19 to -80‰, respectively, which might be metamorphic and/or magmatic and/or mantle-derived. The carbon isotope composition (δ13C) varies from -14.2 to -15.7‰ in carbonates; it is -17.6‰ in fluid inclusion CO2 and -23.6‰ in graphite from the host rock. The δ34S values of pyrite are -2.6 to -7.9‰. The strongly to moderately negative carbon isotope composition of the carbonates and inclusion fluid CO2 reflects variable contribution of organic carbon to an originally heavier fluid (magmatic, metamorphic, or mantle-derived) at the site of deposition and sulfur isotopes indicate some oxidation of the originally reduced fluid. The deposition of gold is interpreted to have occurred mainly in response to phase separation and fluid-rock interactions such as CO2 removal and desulfidation reactions that provoked variations in the fluid pH and redox conditions.

Oxygen Isotope Measurements of a Rare Murchison Type A CAI and Its Rim

NASA Technical Reports Server (NTRS)

Matzel, J. E. P.; Simon, J. I.; Hutcheon, I. D.; Jacobsen, B.; Simon, S. B.; Grossman, L.

2013-01-01

Ca-, Al-rich inclusions (CAIs) from CV chondrites commonly show oxygen isotope heterogeneity among different mineral phases within individual inclusions reflecting the complex history of CAIs in both the solar nebula and/or parent bodies. The degree of isotopic exchange is typically mineral-specific, yielding O-16-rich spinel, hibonite and pyroxene and O-16-depleted melilite and anorthite. Recent work demonstrated large and systematic variations in oxygen isotope composition within the margin and Wark-Lovering rim of an Allende Type A CAI. These variations suggest that some CV CAIs formed from several oxygen reservoirs and may reflect transport between distinct regions of the solar nebula or varying gas composition near the proto-Sun. Oxygen isotope compositions of CAIs from other, less-altered chondrites show less intra-CAI variability and 16O-rich compositions. The record of intra-CAI oxygen isotope variability in CM chondrites, which commonly show evidence for low-temperature aqueous alteration, is less clear, in part because the most common CAIs found in CM chondrites are mineralogically simple (hibonite +/- spinel or spinel +/- pyroxene) and are composed of minerals less susceptible to O-isotopic exchange. No measurements of the oxygen isotope compositions of rims on CAIs in CM chondrites have been reported. Here, we present oxygen isotope data from a rare, Type A CAI from the Murchison meteorite, MUM-1. The data were collected from melilite, hibonite, perovskite and spinel in a traverse into the interior of the CAI and from pyroxene, melilite, anorthite, and spinel in the Wark-Lovering rim. Our objectives were to (1) document any evidence for intra-CAI oxygen isotope variability; (2) determine the isotopic composition of the rim minerals and compare their composition(s) to the CAI interior; and (3) compare the MUM-1 data to oxygen isotope zoning profiles measured from CAIs in other chondrites.

Fahlore and Sphalerite from the Darasun Gold Deposit in the Eastern Transbaikal Region, Russia: I. Mineral Assemblages and Intergrowths, Chemical Composition, and Its Evolution

NASA Astrophysics Data System (ADS)

Lyubimtseva, N. G.; Bortnikov, N. S.; Borisovsky, S. E.; Prokofiev, V. Yu.; Vikent'eva, O. V.

2018-03-01

The mineral assemblages, mode of occurrence, and chemical compositions of coexisting fahlore and sphalerite from the Darasun gold deposit have been described. Three generations of fahlore and three generations of sphalerite have been recognized. The FeS content in sphalerite coexisting with fahlore ranges from 0.8 to 9.4 mol %. The complete solid solution series Fe-tetrahedrite-Zn-tetrahedrite-Fe-tennantite-Zn-tennantite reflected in Sb/(Sb + As) and Fe/(Fe + Zn) ratios ranging from 0 to 0.97 and from 0.07 to 1.00, respectively, with a predominant negative relationship between these ratios has been identified for the first time at the deposit. Stepped, oscillatory, and combined stepped-oscillatory growth zonings within fahlore grains and heterogeneous aggregates of fahlore have been found. Fahlore is enriched in As with respect to Sb, and Zn-tetrahedrite is followed by Fe- and Zn-tennantite from early to late generation; Zn-tetrahedrite is followed by Fe-tennantite in zoned grains and overgrown rims; sphalerite crystallized at decreased temperature and sulfur fugacity. The evolution of the chemical composition of fahlores was caused by the evolving temperature, fluid salinity, and conditions of metal migration.

Lipid Extraction and the Fugacity of Stable Isotope Values

NASA Astrophysics Data System (ADS)

Padula, V.; Causey, D.; Wolf, N.; Welker, J. M.

2013-12-01

Stable isotope analysis of blood, feathers, and other tissues are often used to infer migration patterns, diet composition and trophic status of seabirds. Tissues contain variable amounts of lipids that are depleted in the heavy carbon isotope (13C) and may introduce a bias in these values. There is evidence that lipid extraction may affect other stable isotope ratios, such as δ15N. Consequently, correction factors need to be applied to appropriately interpret δ13C and δ15N values for individual species and tissue type. In this study, we collected seven species of seabirds from the Near Islands, the western most group of islands in the Aleutian Island archipelago. We sampled kidney, liver, heart and muscle samples from each bird and after freeze drying, individual tissue samples were divided into two subsamples. We left one subsample unaltered and extracted lipids from the other subsample using a 2:1 chloroform-methanol solution. We found that the change in δ13C values after lipid extraction (Δδ13C) varied widely among categories (eg., species, tissue type) from 0 - 4 ‰, while Δδ15N values ranged from 0 to 2‰. Notably, within category variation was nonsignificant and the Δδ values were linear against the covariant C:N ratio of the isotopic data, which allows us to use arithmetic corrections for categorical values. Our data strongly indicate that the effects of lipid extraction on stable isotopic values, while linear within category, vary widely by species, tissue, geographic area, year of collection, and isotope. Fugacity is usually employed as a thermodynamic quantity related to the chemical potential or activity that characterizes the escaping tendency from a phase (eg. Mackay & Paterson 1982). Here we use fugacity in the earlier, broader sense of fleeting, transitory, or instable states (eg., S. Johnson 1751), and its measure may be approximated by the higher order variance of Δδ13C and Δδ15N among data categories. Clearly, understanding the nature of variation and the physiological processes responsible for stable isotope values from biological tissues are critical for their interpretation. Change in carbon and nitrogen stable isotopes (ΔδC13, Δδ15N) after lipid extraction for Tufted Puffins (Fratercula cirrhata) collected July 2010 at Attu Island, Aleutians.

Generation of highly N-type, defect passivated transition metal oxides using plasma fluorine insertion

DOEpatents

Baker, L. Robert; Seo, Hyungtak; Hervier, Antoine; Somorjai, Gabor A.

2016-04-12

A new composition of matter is disclosed wherein oxygen vacancies in a semiconducting transition metal oxide such as titanium dioxide are filled with a halogen such as Fluorine, whereby the conductivity of the composition is greatly enhanced, while at the same time the chemical stability of the composition is greatly improved. Stoichiometric titanium dioxide having less than 3 % oxygen vacancies is subject to fluorine insertion such that oxygen vacancies are filled, limited amounts of fluorine replace additional oxygen atoms and fluorine interstitially inserts into the body of the TiO.sub.2 composition.

Box-modeling of bone and tooth phosphate oxygen isotope compositions as a function of environmental and physiological parameters.

PubMed

Langlois, C; Simon, L; Lécuyer, Ch

2003-12-01

A time-dependent box model is developed to calculate oxygen isotope compositions of bone phosphate as a function of environmental and physiological parameters. Input and output oxygen fluxes related to body water and bone reservoirs are scaled to the body mass. The oxygen fluxes are evaluated by stoichiometric scaling to the calcium accretion and resorption rates, assuming a pure hydroxylapatite composition for the bone and tooth mineral. The model shows how the diet composition, body mass, ambient relative humidity and temperature may control the oxygen isotope composition of bone phosphate. The model also computes how bones and teeth record short-term variations in relative humidity, air temperature and delta18O of drinking water, depending on body mass. The documented diversity of oxygen isotope fractionation equations for vertebrates is accounted for by our model when for each specimen the physiological and diet parameters are adjusted in the living range of environmental conditions.

Effects of oxygen plasma treatment on domestic aramid fiber III reinforced bismaleimide composite interfacial properties

NASA Astrophysics Data System (ADS)

Shi, Chen; Wang, Jing; Chen, Ping; Feng, Jiayue; Cui, Jinyuan; Yang, Faze

2017-12-01

Domestic Aramid Fiber III (DAF III) was modified by oxygen plasma treatment. The fiber surface characteristics was observed by Scanning Electron Microscopy. The results showed that oxygen plasma treatment changed surface morphologies. The effects of oxygen plasma treatment on DAF III reinforced bismaleimides (BMI) composite bending and interfacial properties were investigated, respectively. The ILSS value increased from 49.3 MPa to 56.0 MPa (by 13.5%) after oxygen plasma treatment. The bending strength changed a little. Furthermore, the composite rupture mode changed from interfacial rupture to fiber or resin bulk rupture.

The effect of copper on the estimation of sulfur fugacity from the composition of pyrrhotite: an experimental evaluation

NASA Astrophysics Data System (ADS)

Mengason, M. J.; Piccoli, P. M.; Candela, P. A.

2009-12-01

Sulfur fugacity is a critical intensive variable, important to the study of volcanic and plutonic rocks, and experimental systems. In a pioneering study, Toulmin and Barton (1964; GCA 28, 641) derived an equation, based on experimental data, for the relationship between fS2, temperature, and the composition of pyrrhotite (po), a common magmatic sulfide. The binary po solid solution (FeS-S2) was the object of their study; however, po frequently contains in excess of 1 wt. % Cu, and therefore further work has been required to account for the effect of additional phase components in po on the estimation of fS2 by this technique. In order to have consistent results from both Cu-free, and Cu-bearing po, one must properly formulate the Cu-bearing phase component of the po. Toward this end, we have designed a novel series of experiments that allow us to evaluate the relationship between the composition of Cu-Fe sulfides and fS2. Results of these experiments have been used to develop a simple method for the determination of the fS2 from Cu-bearing po and the equations of Toulmin and Barton. The experiments were performed in evacuated sealed silica tubes. Starting materials included pairs of separated reference (Cu-free), and Cu-bearing po in the presence of a common S2 gas phase (and therefore the same fS2). Experiments consisted of silica tubes loaded with mixtures of synthetic po and bornite separated by ~ 1mm thick silica discs, creating vertically stacked chambers. The chambers prevent contact of the separate condensed phase charges, but allow for gas transfer. Samples were heated in a vertical quench furnace at 1050°C for 16 to 24 hours followed by 5 days at 1000°C, concluding with a drop quench into a water bath. The experiments spanned 4 log units (bar) fS2 and the Cu-bearing po had Cu concentrations that ranged from 4.5 to 7.3 wt. %. The data were processed using three methods for incorporating Cu into the calculation, with effectiveness evaluated by deviations in calculated fugacity between pairs of Cu-bearing and Cu-free po. In method 1, the Cu concentration was omitted from the calculation and XFeS (FeS-S2) alone was input into the equation of Toulmin and Barton. In method 2, ideal mixing was assumed and the sum of XCuS + XFeS (FeS-CuS-S2) was substituted for XFeS in the equation of Toulmin and Barton. In method 3, XCuS0.5+ XFeS (FeS-CuS0.5-S2) was substituted for XFeS. Method 1 resulted in overestimates ranging from 1.1 to 1.6 log units fS2; method 2 resulted in underestimates ranging from 0.4 to 1.7; and method 3 performed best, with deviations ranging from -0.02 to 0.4. The results of these experiments suggest that incorporating Cu into the model of Toulmin and Barton as CuS0.5 is appropriate in producing accurate estimates of fS2 in igneous and experimental systems.

On the habitability of a stagnant-lid Earth

NASA Astrophysics Data System (ADS)

Tosi, Nicola; Stracke, Barbara; Godolt, Mareike; Ruedas, Thomas; Grenfell, John Lee; Höning, Dennis; Nikolaou, Athanasia; Plesa, Ana-Catalina; Breuer, Doris; Spohn, Tilman

2016-04-01

Whether plate tectonics is a recurrent feature of terrestrial bodies orbiting other stars or is unique to the Earth is unknown. The stagnant-lid may rather be the most common tectonic mode through which terrestrial bodies operate. Here we model the thermal history of the mantle, the outgassing evolution of H2O and CO2, and the resulting climate of a hypothetical planet with the same mass, radius, and composition as the Earth, but lacking plate tectonics. We employ a 1-D model of parameterized stagnant-lid convection to simulate the evolution of melt generation, crust production, and volatile extraction over a timespan of 4.5 Gyr, focusing on the effects of three key mantle parameters: the initial temperature, which controls the overall volume of partial melt produced; the initial water content, which affects the mantle rheology and solidus temperature; and the oxygen fugacity, which is employed in a model of redox melting to determine the amount of carbon stored in partial melts. We assume that the planet lost its primordial atmosphere and use the H2O and CO2 outgassed from the interior to build up a secondary atmosphere over time. Furthermore, we assume that the planet may possess an Earth-like ocean. We calculate the atmospheric pressure based on the solubility of H2O and CO2 in basaltic magmas at the evolving surface pressure conditions. We then employ a 1-D radiative-convective, cloud-free stationary atmospheric model to calculate the resulting atmospheric temperature, pressure and water content, and the corresponding boundaries of the habitable zone (HZ) accounting for the evolution of the Sun's luminosity with time but neglecting escape processes. The interior evolution is characterized by a large initial production of partial melt accompanied by the formation of crust that rapidly grows until its thickness matches that of the stagnant lid so that the convecting sublithospheric mantle prevents further crustal growth. Even for initial water concentrations in excess of thousands of ppm, the high solubility of water in surface magmas limits the maximal partial pressure of atmospheric H2O to a few tens of bars, which places de facto an upper bound on the amount of water that can be delivered to the surface and atmosphere from the interior. The relatively low solubility of CO2 causes instead most of the carbon contained in surface melts to be outgassed. As a consequence, the partial pressure of atmospheric CO2 is largely controlled by the redox state of the mantle, with values that range from a few up to tens of bars for oxygen fugacities between the iron-wüstite buffer and one log-unit above it. At 1 AU and for most cases, liquid water on the surface is possible, hence the planets considered would be regarded as habitable although the atmospheric temperature may be well above the temperature limits for terrestrial life. The inner edge of the HZ depends on the amount of outgassed H2O and is located further away from the star if no initial water ocean is assumed. The outer edge of the HZ is controlled by the amount of outgassed CO2, hence by the assumed redox state of the mantle and its initial temperature.

Modeling the influence of climate change on the mass balance of polychlorinated biphenyls in the Adriatic Sea.

PubMed

Lamon, Lara; MacLeod, Matthew; Marcomini, Antonio; Hungerbühler, Konrad

2012-05-01

Climate forcing is forecasted to influence the Adriatic Sea region in a variety of ways, including increasing temperature, and affecting wind speeds, marine currents, precipitation and water salinity. The Adriatic Sea is intensively developed with agriculture, industry, and port activities that introduce pollutants to the environment. Here, we developed and applied a Level III fugacity model for the Adriatic Sea to estimate the current mass balance of polychlorinated biphenyls in the Sea, and to examine the effects of a climate change scenario on the distribution of these pollutants. The model's performance was evaluated for three PCB congeners against measured concentrations in the region using environmental parameters estimated from the 20th century climate scenario described in the Special Report on Emission Scenarios (SRES) by the IPCC, and using Monte Carlo uncertainty analysis. We find that modeled fugacities of PCBs in air, water and sediment of the Adriatic are in good agreement with observations. The model indicates that PCBs in the Adriatic Sea are closely coupled with the atmosphere, which acts as a net source to the water column. We used model experiments to assess the influence of changes in temperature, wind speed, precipitation, marine currents, particulate organic carbon and air inflow concentrations forecast in the IPCC A1B climate change scenario on the mass balance of PCBs in the Sea. Assuming an identical PCBs' emission profile (e.g. use pattern, treatment/disposal of stockpiles, mode of entry), modeled fugacities of PCBs in the Adriatic Sea under the A1B climate scenario are higher because higher temperatures reduce the fugacity capacity of air, water and sediments, and because diffusive sources to the air are stronger. Copyright © 2012 Elsevier Ltd. All rights reserved.

Biochar production method and composition therefrom

DOEpatents

Lee, James W; Buchanan, III, Archibald C; Evans, Barbara R; Kidder, Michelle K

2014-04-29

The invention is directed to a method for producing an oxygenated biochar material possessing a cation-exchanging property, wherein a biochar source is reacted with one or more oxygenating compounds in such a manner that the biochar source homogeneously acquires oxygen-containing cation-exchanging groups in an incomplete combustion process. The invention is also directed to oxygenated biochar compositions and soil formulations containing the oxygenated biochar material.

Biochar production method and composition therefrom

DOEpatents

Lee, James W.; Buchanan, III, Archibald C.; Evans, Barbara R.; Kidder, Michelle K.

2013-03-19

The invention is directed to a method for producing an oxygenated biochar material possessing a cation-exchanging property, wherein a biochar source is reacted with one or more oxygenating compounds in such a manner that the biochar source homogeneously acquires oxygen-containing cation-exchanging groups in an incomplete combustion process. The invention is also directed to oxygenated biochar compositions and soil formulations containing the oxygenated biochar material.

Perovskite/Carbon Composites: Applications in Oxygen Electrocatalysis.

PubMed

Zhu, Yinlong; Zhou, Wei; Shao, Zongping

2017-03-01

Oxygen electrocatalysis, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), plays an extremely important role in oxygen-based renewable-energy technologies such as rechargeable metal-air batteries, regenerative fuel cells and water splitting. Perovskite oxides have recently attracted increasing interest and hold great promise as efficient ORR and OER catalysts to replace noble-metal-based catalysts, owing to their high intrinsic catalytic activity, abundant variety, low cost, and rich resources. The introduction of perovskite-carbon interfaces by forming perovskite/carbon composites may bring a synergistic effect between the two phases, thus benefiting the oxygen electrocatalysis. This review provides a comprehensive overview of recent advances in perovskite/carbon composites for oxygen electrocatalysis in alkaline media, aiming to provide insights into the key parameters that influence the ORR/OER performance of the composites, including the physical/chemical properties and morphologies of the perovskites, the multiple roles of carbon, the synthetic method and the synergistic effect. A special emphasis is placed on the origin of the synergistic effect associated with the interfacial interaction between the perovskite and the carbon phases for enhanced ORR/OER performance. Finally, the existing challenges and the future directions for the synthesis and development of more efficient oxygen catalysts based on perovskite/carbon composites are proposed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The solubility of platinum in silicate melt under reducing conditions: Results from experiments without metal inclusions

NASA Astrophysics Data System (ADS)

Bennett, N. R.; Brenan, J. M.; Koga, K. T.

2014-05-01

The solubility of Pt in silicate melt was investigated at conditions of 2073-2573 K, 2 GPa and ˜IW -1.5 to +3.5. These are the first measurements of Pt solubility under conditions more reducing than the iron-wüstite buffer (IW) which are demonstrably free from contamination by metal-inclusions. Pt solubility increases with increasing temperature and decreasing oxygen fugacity. The ability of carbon to enhance Pt solubility under reducing conditions (3500 K. Under these conditions however, the estimated Pt/Os ratio is ˜40,000 times higher than that estimated for the PUM (Brandon et al., 2006). Instead, the PUM composition is generated most readily by metal-silicate equilibrium at more modest temperatures (˜3100 K), followed by a late accretion of chondritic material subsequent to core formation.

XANES and Mg isotopic analyses of spinels in Ca-Al-rich inclusions: Evidence for formation under oxidizing conditions

NASA Astrophysics Data System (ADS)

Paque, J. M.; Sutton, S. R.; Simon, S. B.; Beckett, J. R.; Burnett, D. S.; Grossman, L.; Yurimoto, H.; Itoh, S.; Connolly, H. C.

2013-10-01

Ti valence measurements in MgAl2O4 spinel from calcium-aluminum-rich inclusions (CAIs) by X-ray absorption near-edge structure (XANES) spectroscopy show that many spinels have predominantly tetravalent Ti, regardless of host phases. The average spinel in Allende type B1 inclusion TS34 has 87% Ti+4. Most spinels in fluffy type A (FTA) inclusions also have high Ti valence. In contrast, the rims of some spinels in TS34 and spinel grain cores in two Vigarano type B inclusions have larger amounts of trivalent titanium. Spinels from TS34 have approximately equal amounts of divalent and trivalent vanadium. Based on experiments conducted on CAI-like compositions over a range of redox conditions, both clinopyroxene and spinel should be Ti+3-rich if they equilibrated with CAI liquids under near-solar oxygen fugacities. In igneous inclusions, the seeming paradox of high-valence spinels coexisting with low-valence clinopyroxene can be explained either by transient oxidizing conditions accompanying low-pressure evaporation or by equilibration of spinel with relict Ti+4-rich phases (e.g., perovskite) prior to or during melting. Ion probe analyses of large spinel grains in TS34 show that they are enriched in heavy Mg, with an average Δ25Mg of 4.25 ± 0.028‰, consistent with formation of the spinel from an evaporating liquid. Δ25Mg shows small, but significant, variation, both within individual spinels and between spinel and adjacent melilite hosts. The Δ25Mg data are most simply explained by the low-pressure evaporation model, but this model has difficulty explaining the high Ti+4 concentrations in spinel.

Metamorphic ore remobilization in the Hällefors district, Bergslagen, Sweden: constraints from mineralogical and small-scale sulphur isotope studies

NASA Astrophysics Data System (ADS)

Wagner, Thomas; Jonsson, Erik; Boyce, Adrian J.

2005-07-01

The marble- and metavolcanic-hosted Pb Zn (Ag Sb As) deposits of the Hällefors district, located in the Palaeoproterozoic Bergslagen ore province, south central Sweden, comprise both stratabound sulphides and discordant, Ag-rich sulphide sulphosalt veins. The complex sulphide sulphosalt assemblages of the Alfrida-Jan Olof mines at Hällefors were investigated by a combination of ore microscopy, electron-microprobe analysis, and in situ laser sulphur isotope analysis. The massive ore is characterized by positive and homogeneous δ34S (+1.4‰ to +2.7‰ V-CDT), whereas vein-hosted sulphides and sulphosalts exhibit similar, but generally less positive to slightly negative δ34S (-0.6‰ to +2.0‰). Comparison of the observed ore mineral assemblages with calculated phase equilibria in the system Fe As S O H and isotopic fractionation as a function of temperature, oxygen fugacity and pH indicates that the vein-type mineralization was formed from relatively reduced and rather alkaline hydrothermal fluids. At these reduced conditions, fractionation of δ34S via changes of fO2 is insignificant, and thus the isotopic signatures of the vein minerals directly reflect the composition of the sulphur source. We therefore conclude that the vein-type ore essentially inherited the sulphur isotope signature from the pre-existing massive sulphides via metamorphic remobilization at approximately 300 400°C and 2 3 kbar. Scales of remobilization observable are on the order of about 5 mm to 30 cm. Overall, the sulphide sulphosalt assemblages from the Alfrida-Jan Olof mines exhibit δ34S values which are comparable to a majority of metasupracrustal-hosted deposits in the Bergslagen province, thereby suggesting a common origin from ca. 1.90 1.88 Ga volcanic-hydrothermal processes.

Fluid evolution and ore genesis of the Dalingshang deposit, Dahutang W-Cu ore field, northern Jiangxi Province, South China

NASA Astrophysics Data System (ADS)

Peng, Ning-Jun; Jiang, Shao-Yong; Xiong, Suo-Fei; Pi, Dao-Hui

2018-02-01

The Dalingshang W-Cu deposit is located in the North section of the Dahutang ore field, northern Jiangxi Province, South China. Vein- and breccia-style tungsten-copper mineralization is genetically associated with Mesozoic S-type granitic rocks. Infrared and conventional microthermometric studies of both gangue and ore minerals show that the homogenization temperatures for primary fluid inclusions in wolframite ( 340 °C) are similar to those in scheelite ( 330 °C), but about 40 °C higher than those of apatite ( 300 °C) and generally 70 °C higher than those in coexisting quartz ( 270 °C). Laser Raman analysis identifies CH4 and N2 without CO2 in fluid inclusions in scheelite and coexisting quartz, while fluid inclusions in quartz of the sulfide stage have variable CO2 content. The ore-forming fluids overall are characterized by high- to medium-temperature, low-salinity, CH4, N2, and/or CO2-bearing aqueous fluids. Chalcopyrite, muscovite, and sphalerite are the most abundant solids recognized in fluid inclusions from different ores. The H-O-S-Pb isotope compositions favor a dominantly magmatic origin for ores and fluids, while some depleted δ34S values (- 14.4 to - 0.9‰) of sulfides from the sulfide stage are most likely produced by an increase of oxygen fugacity, possibly caused by inflow of oxidized meteoric waters. The microthermometric data also indicate that a simple cooling process formed early scheelite and wolframite. However, increasing involvement of meteoric waters and fluid mixing may trigger a successive deposition of base metal sulfides. Fluid-rock interaction was critical for scheelite mineralization as indicated by in-situ LA-ICP-MS analysis of trace elements in scheelite.

Iron-carbonate interaction at Earth's core-mantle boundary

NASA Astrophysics Data System (ADS)

Dorfman, S. M.; Badro, J.; Nabiei, F.; Prakapenka, V.; Gillet, P.

2015-12-01

Carbon storage and flux in the deep Earth are moderated by oxygen fugacity and interactions with iron-bearing phases. The amount of carbon stored in Earth's mantle versus the core depends on carbon-iron chemistry at the core-mantle boundary. Oxidized carbonates subducted from Earth's surface to the lowermost mantle may encounter reduced Fe0 metal from disproportionation of Fe2+ in lower mantle silicates or mixing with the core. To understand the fate of carbonates in the lowermost mantle, we have performed experiments on sandwiches of single-crystal (Ca0.6Mg0.4)CO3 dolomite and Fe foil in the laser-heated diamond anvil cell at lower mantle conditions of 49-110 GPa and 1800-2500 K. Syntheses were conducted with in situ synchrotron X-ray diffraction to identify phase assemblages. After quench to ambient conditions, samples were sectioned with a focused Ga+ ion beam for composition analysis with transmission electron microscopy. At the centers of the heated spots, iron melted and reacted completely with the carbonate to form magnesiowüstite, iron carbide, diamond, magnesium-rich carbonate and calcium carbonate. In samples heated at 49 and 64 GPa, the two carbonates exhibit a eutectoid texture. In the sample heated at 110 GPa, the carbonates form rounded ~150-nm-diameter grains with a higher modal proportion of interspersed diamonds. The presence of reduced iron in the deep lower mantle and core-mantle boundary region will promote the formation of diamonds in carbonate-bearing subducted slabs. The complete reaction of metallic iron to oxides and carbides in the presence of mantle carbonate supports the formation of these phases at the Earth's core-mantle boundary and in ultra-low velocity zones.

Observations of impact-induced molten metal-silicate partitioning

NASA Technical Reports Server (NTRS)

Rowan, Linda R.; Ahrens, Thomas J.

1994-01-01

Observations of molten mid-ocean ridge basalt (MORB)-molybdenum (Mo) interactions produced by shock experiments provide insight into impact and differentiation processes involving metal-silicate partitioning. Analysis of fragments recovered from experiments (achieving MORB liquid shock pressures from 0.8 to 6 GPa) revealed significant changes in the composition of the MORB and Mo due to reaction of the silicate and metal liquids on a short time scale (less than 13 s). The FeO concentration of the shocked liquid decreases systematically with increasing pressure. In fact, the most highly shocked liquid (6 GPa) contains only 0.1 wt% FeO compared to an initial concentration of 9 wt% in the MORB. We infer from the presence of micrometer-sized Fe-, Si- and Mo-rich metallic spheres in the shocked glass that the Fe and Si oxides in the MORB were reduced in an estimated oxygen fugacity of 10(exp -17) bar and subsequently alloyed with the Mo. The in-situ reduction of FeO in the shocked molten basalt implies that shock-induced reduction of impact melt should be considered a viable mechanism for the formation of metallic phases. Similar metallic phases may form during impact accretion of planets and in impacted material found on the lunar surface and near terrestrial impact craters. In particular, the minute, isolated Fe particles found in lunar soils may have formed by such a process. Furthermore, the metallic spheres within the shocked glass have a globular texture similar to the textures of metallic spheroids from lunar samples and the estimated, slow cooling rate of less than or equal to 140 C/s for our spheres is consistent with the interpretation that the lunar spheroids formed by slow cooling within a melted target.

Geological and geochemical studies of the Shujiadian porphyry Cu deposit, Anhui Province, Eastern China: Implications for ore genesis

NASA Astrophysics Data System (ADS)

Wang, Shiwei; Zhou, Taofa; Yuan, Feng; Fan, Yu; White, Noel C.; Lin, Fengjie

2015-05-01

Most porphyry deposits in the world occur in magmatic arc settings and are related to subduction of oceanic plates. A small proportion of porphyry deposits occur in intracontinental settings, however they are still poorly understood. Shujiadian, a newly-discovered porphyry Cu deposit, is located in the Middle-Lower Yangtze River Valley metallogenic belt and belongs to the intracontinental class. The deposit has classic alteration zones defined by a core of potassic alteration and local Ca-silicate alteration, which is overprinted by a feldspar-destructive alteration zone and cut by veins containing epidote and chlorite. Wallrocks of the deposit are unreactive quartz-rich sedimentary rocks. Three main paragenetic stages have been recognized based on petrographic observations; silicate stage, quartz-sulfide stage, and sulfide-carbonate stage. Quartz + pyrite + chalcopyrite ± molybdenite veins, and quartz + chalcopyrite + pyrite veins of the quartz-sulfide stage contribute most of the copper, and chalcopyrite + chlorite ± pyrite ± pyrrhotite ± quartz ± illite veins of the sulfide-carbonate stage also contribute part of the copper; all the mineralized veins are associated with feldspar-destructive alteration. Investigations on the fluid inclusions in Shujiadian indicate that the ore-forming fluids had four evolutionary episodes: immiscibility and overpressure in the silicate stage, boiling in the quartz-sulfide stage and mixing with meteoric water in the sulfide-carbonate stage. Sulfur and strontium isotope studies suggest that ore metals were mainly derived from magmatic-hydrothermal fluids, and combined with our study of fluid inclusions, we infer that decompression, changes in oxygen fugacity and sulfur content were the main factors that caused Cu precipitation. Compared with porphyry deposits in magmatic arc settings, there are some differences in the ore-bearing rock, alteration, and the composition of ore-forming fluids.

Sulfides from Martian and Lunar Basalts: Comparative Chemistry for Ni Co Cu and Se

DOE Office of Scientific and Technical Information (OSTI.GOV)

J Papike; P Burger; C Shearer

2011-12-31

Here Mars and Moon are used as 'natural laboratories' with Moon displaying lower oxygen fugacities ({approx}IW-1) than Mars ({approx}IW to FMQ). Moon has lower concentrations of Ni and Co in basaltic melts than does Mars. The major sulfides are troilite (FeS) in lunar basalts and pyrrhotite (Fe{sub 1-x}S) in martian basalts. This study focuses on the concentrations of Ni, Co, Cu, and Se. We chose these elements because of their geochemical importance and the feasibility of analyzing them with a combination of synchrotron X-ray fluorescence (SXRF) and electron microprobe (EPMA) techniques. The selenium concentrations could only be analyzed, at highmore » precision, with SXRF techniques as they are <150 ppm, similar to concentrations seen in carbonaceous chondrites and interplanetary dust particles (IDPs). Nickel and Co are in higher concentrations in martian sulfides than lunar and are higher in martian olivine-bearing lithologies than olivine-free varieties. The sulfides in individual samples show very large ranges in concentration (e.g., Ni ranges from 50 000 ppm to <5 ppm). These large ranges are mainly due to compositional heterogeneities within individual grains due to diffusion and phase separation. Electron microprobe wavelength-dispersive (WDS) mapping of Ni, Co, and Cu show the diffusion trajectories. Nickel and Co have almost identical diffusion trajectories leading to the likely nucleation of pentlandite (Ni,Co,Fe){sub 9}S{sub 8}, and copper diffuses along separate pathways likely toward chalcopyrite nucleation sites (CuFeS{sub 2}). The systematics of Ni and Co in lunar and martian sulfides clearly distinguish the two parent bodies, with martian sulfides displaced to higher Ni and Co values.« less

Composition-thermal expandability relations and oxidation processes in tourmaline studied by in situ Raman spectroscopy

NASA Astrophysics Data System (ADS)

Watenphul, Anke; Malcherek, Thomas; Wilke, Franziska D. H.; Schlüter, Jochen; Mihailova, Boriana

2017-11-01

The crystal chemistry of tourmaline, XY3Z6(T6O18)(BO3)3V3W, has a strong influence on the structure and physical properties. Since tourmalines occur in a wide range of geological settings and have large temperature and pressure stability fields, the understanding of the relation between the tourmaline chemistry and thermal expansion allows for better thermodynamic modeling of geological processes. Here, we report dynamic and static thermal expansions as well as mode Grüneisen parameters studied by Raman spectroscopy and single-crystal X-ray diffraction data on several tourmaline species. In addition, oxidation processes in fluor-schorl and Fe2+-bearing elbaite were followed by Raman spectroscopy. Our results emphasize the role of Y-/Z-site occupancy disorder to reduce the local strains and demonstrate that small-size octahedrally coordinated cations perturb the topology of the SiO4 rings, which in turn seems to enhance the anisotropic thermal-expansion response. In addition, it is shown that the temperature-dependent behavior of the VOH modes primarily depends on the occupancy of the Y site, whereas that of the WOH modes depends on the occupancy of the X site. High-temperature Raman experiments in air allowed to follow the oxidation of Fe2+ to Fe3+ in fluor-schorl by analyzing both the framework and OH-stretching phonon modes. It is further demonstrated that under the same conditions, no oxidation of iron is observed for Fe2+-bearing elbaite, which implies that at high oxygen fugacity, iron is only oxidized in tourmaline species with prevalent divalent cations at the Y site.

Experimental determination of activities of FeO and Fe 2O 3 components in hydrous silicic melts under oxidizing conditions

NASA Astrophysics Data System (ADS)

Gaillard, Fabrice; Pichavant, Michel; Scaillet, Bruno

2003-11-01

The critical role of iron on crystal-silicate liquid relationships and melt differentiation is mainly controlled by the redox conditions prevailing in magmas, but the presently available database merely constrains the thermodynamic properties of iron-bearing components in strongly reduced and anhydrous molten silicate where iron is in the ferrous form. This paper provides new standard states for pure ferrous (FeOliq) and ferric (Fe2O3liq) molten iron oxides and extends the experimental database towards oxidizing and water-bearing domains. Iron-iridium, iron-platinum alloys, magnetite or hematite were equilibrated with synthetic silicic liquids at high temperature and high pressure under controlled oxygen fugacity (fO2) to determine activity-composition relationships for FeOliq and Fe2O3liq. Between 1000 and 1300°C, the fO2 ranges from that in air to 3-log units below that of the nickel-nickel oxide buffer (NNO). Experiments were performed on both anhydrous and hydrous melts containing up to 6-wt.% water. Incorporation of water under reducing conditions increases the activity coefficient of FeOliq but has an opposite effect on Fe2O3liq. As calcium is added to system, the effect of water becomes weaker and is inverted for Fe2O3liq. Under oxidizing conditions, water has a negligible effect on both activities of FeOliq and Fe2O3liq. In contrast, changes in redox conditions dominate the activity coefficients of both FeOliq and Fe2O3liq, which increase significantly with increasing fO2. The present results combined with the previous work provide a specific database on the energetics of iron in silicate melts that cover most of the condition prevailing in natural magmas.

Synthesis of Ti Oxides at Reducing Conditions: Implications for Beamline Standards and Cosmochemistry

NASA Technical Reports Server (NTRS)

Righter, K.; Pando, K. A.; Butterworth, A. L.; Gainsforth, Z.; Jilly-Rehak, C. E.; Westphal, A. J.

2017-01-01

These initial experiments demonstrate the great potential for synthesizing customized compounds for use as standards, or in buffering experiments at reducing conditions. We are also investigating Cr and V oxides, as well as compounds containing these elements such as FeV2O4 and FeCr2O4. Oxygen fugacity exerts a major control on mineral major element chemistry and elemental valence of minerals in any plane-tary compositional system [1]. For Earth, Fe is multivalent ranging from nearly Fe0 at low fO2 in the deep mantle to Fe2+ to Fe3+ at high low fO2. For solar nebular and meteoritic materials fO2 ranges from near IW to 10 log fO2 units below the IW buffer [1]. Phases in CAIs, for example, contain no Fe2+, but may contain Ti4+, Ti3+, or Ti2+, and Cr3+ or Cr2+, and V3+ or V2+ [1,2,3]. De-tailed study of inclusions may reveal important differences in fO2 thus reflecting different environments in the solar nebula [4]. XANES, FEG-SEM, and TEM can reveal such variations in micro and nano samples such as Stardust and cosmic dust particles [5], but successful application to reduced conditions depends upon the availability of well characterized standards. Acquiring appropriate standards for reduced phases that contain Ti3+ or Ti2+, Cr3+ or Cr2+, and V3+ or V2+ can be a challenge. Here we report our preliminary results at synthesizing reduced Ti bearing standards, and focus on the preliminary characterization.

Comet Dust: The Diversity of "Primitive" Particles and Implications

NASA Technical Reports Server (NTRS)

Wooden, Diane H.; Ishii, Hope A.; Bradley, John P.; Zolensky, Michael E.

2016-01-01

Comet dust is primitive and shows significant diversity. Our knowledge of the properties of primitive particles has expanded significantly through microscale investigations of cosmic dust samples ( IDP's(Interplanetary Dust Particles) and AMM's (Antarctic Micrometeorites)) and of comet dust samples (Stardust and Rosetta's COSIMA), as well as through remote sensing (spectroscopy and imaging) via Spitzer and via spacecraft encounters with 103P/Hartley 2 and 67P/Churyumov-Gerasimenko. Microscale investigations show that comet dust and cosmic dust are particles of unequilibrated materials, including aggregates of materials unequilibrated at submicron scales. We call unequilibrated materials "primitive" and we deduce they were incorporated into ice-rich (H2O-, CO2-, and CO-ice) parent bodies that remained cold, i.e., into comets, because of the lack of aqueous or thermal alteration since particle aggregation; yet some Stardust olivines suggest mild thermal metamorphism. Primitive particles exhibit a diverse range of: structure and typology; size and size distribution of constituents; concentration and form of carbonaceous and organic matter; D-, N-, and O- isotopic enhancements over solar; Mg-, Fe-contents of the silicate minerals; the compositions and concentrations of sulfides, and of less abundant mineral species such as chondrules, CAIs and carbonates. The uniformity within a group of samples points to: aerodynamic sorting of particles and/or particle constituents; the inclusion of a limited range of oxygen fugacities; the inclusion or exclusion of chondrules; a selection of organics. The properties of primitive particles imply there were disk processes that resulted in different comets having particular selections of primitive materials. The diversity of primitive particles has implications for the diversity of materials in the protoplanetary disk present at the time and in the region where the comets formed.

Comet Dust: The Diversity of Primitive Particles and Implications

NASA Technical Reports Server (NTRS)

John Bradley; Zolensky, Michael E.

2016-01-01

Comet dust is primitive and shows significant diversity. Our knowledge of the properties of primitive particles has expanded significantly through microscale investigations of cosmic dust samples (IDPs and AMMs) and of comet dust samples (Stardust and Rosetta's COSIMA), as well as through remote sensing (spectroscopy and imaging) via Spitzer and via spacecraft encounters with 103P/Hartley 2 and 67P/Churyumov-Gerasimenko. Microscale investigations show that comet dust and cosmic dust are particles of unequilibrated materials, including aggregates of materials unequilibrated at submicron scales. We call unequilibrated materials "primitive" and we deduce they were incorporated into ice-­-rich (H2O-, CO2-, and CO-ice) parent bodies that remained cold, i.e., into comets, because of the lack of aqueous or thermal alteration since particle aggregation; yet some Stardust olivines suggest mild thermal metamorphism. Primitive particles exhibit a diverse range of: structure and typology; size and size distribution of constituents; concentration and form of carbonaceous and organic matter; D-, N-, and O- isotopic enhancements over solar; Mg-, Fe-contentsof thesilicate minerals; the compositions and concentrations of sulfides, and of less abundant mineral species such as chondrules, CAIs and carbonates. The unifomity within a group of samples points to: aerodynamic sorting of particles and/or particle constituents; the inclusion of a limited range of oxygen fugacities; the inclusion or exclusion of chondrules; a selection of organics. The properites of primitive particles imply there were disk processes that resulted in different comets having particular selections of primitive materials. The diversity of primitive particles has implications for the diversity of materials in the protoplanetary disk present at the time and in the region where the comets formed.

Grain growth kinetics of ringwoodite and majorite garnet mixtures and implications for the rheology of the transition zone

NASA Astrophysics Data System (ADS)

Ezad, I.; Dobson, D. P.; Brodholt, J. P.; Thomson, A.; Hunt, S.

2017-12-01

The grain size of the transition zone is a poorly known but important geophysical parameter. Among others, the grain size may control the rheology, seismic attenuation and radiative thermal conductivity of the mantle. However, the grain size of the transition zone minerals ringwoodite (Mg,Fe)2SiO4 and majorite garnet MgSiO3 under appropriate zone conditions is currently unknown and there are very few experiments with which to constrain it. In order to determine the grain size of the transition zone, the grain growth kinetics must be determined for a range of mantle compositions. We have, therefore, experimentally determined the grain growth kinetics of the lowermost transition zone minerals through multi anvil experiments at University College London (UCL). This is achieved through a comprehensive set of time series experiments at pressures of 21 GPa and temperatures relevant to the transition zone. We have also determined the effect of varying water content, oxygen fugacity, iron content and aluminium content also discussed by Dobson and Mariani., (2014). Our initial grain growth experiments conducted at 1200°C and 1400°C at 18 GPa show extremely slow grain growth kinetics; time series experiments extended to 105.8 seconds are unable to produce grains larger than 100 nm. This suggests that fine-grained material at the base of the transition zone will persist on geological timescales. Such small grains size suggests that diffusion creep might be the dominant deformation mechanism in this region. Reference: Dobson, D.P., Mariani, E., 2014. The kinetics of the reaction of majorite plus ferropericlase to ringwoodite: Implications for mantle upwellings crossing the 660 km discontinuity. Earth Planet. Sci. Lett. 408, 110-118. doi:10.1016/j.epsl.2014.10.009

Modelling of Equilibrium Between Mantle and Core: Refractory, Volatile, and Highly Siderophile Elements

NASA Technical Reports Server (NTRS)

Righter, K.; Danielson, L.; Pando, K.; Shofner, G.; Lee, C. -T.

2013-01-01

Siderophile elements have been used to constrain conditions of core formation and differentiation for the Earth, Mars and other differentiated bodies [1]. Recent models for the Earth have concluded that the mantle and core did not fully equilibrate and the siderophile element contents of the mantle can only be explained under conditions where the oxygen fugacity changes from low to high during accretion and the mantle and core do not fully equilibrate [2,3]. However these conclusions go against several physical and chemical constraints. First, calculations suggest that even with the composition of accreting material changing from reduced to oxidized over time, the fO2 defined by metal-silicate equilibrium does not change substantially, only by approximately 1 logfO2 unit [4]. An increase of more than 2 logfO2 units in mantle oxidation are required in models of [2,3]. Secondly, calculations also show that metallic impacting material will become deformed and sheared during accretion to a large body, such that it becomes emulsified to a fine scale that allows equilibrium at nearly all conditions except for possibly the length scale for giant impacts [5] (contrary to conclusions of [6]). Using new data for D(Mo) metal/silicate at high pressures, together with updated partitioning expressions for many other elements, we will show that metal-silicate equilibrium across a long span of Earth s accretion history may explain the concentrations of many siderophile elements in Earth's mantle. The modeling includes refractory elements Ni, Co, Mo, and W, as well as highly siderophile elements Au, Pd and Pt, and volatile elements Cd, In, Bi, Sb, Ge and As.

Behaviour of Structural Carbonate Stable Carbon and Oxygen Isotope Compositions in Bioapatite During Burning of Bone

NASA Astrophysics Data System (ADS)

Munro, L. E.; Longstaffe, F. J.; White, C. D.

2003-12-01

Bioapatite, the principal inorganic phase comprising bone, commonly contains a small fraction of carbonate, which has been substituted into the phosphate structure during bone formation. The isotopic compositions of both the phosphate oxygen and the structural carbonate oxygen are now commonly used in palaeoclimatological and bioarchaeological investigations. The potential for post-mortem alteration of these isotopic compositions, therefore, is of interest, with the behaviour of structural carbonate being of most concern. In bioarchaeological studies, alteration of bone isotopic compositions has the potential to occur not only during low-temperature processes associated with burial but also during food preparation involving heating (burning, boiling). Here, we examine the stable isotopic behaviour of structural carbonate oxygen and carbon, and coexisting phosphate oxygen during the burning of bone. Freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned and incrementally heated from 25 to 900° C, in 25° intervals. The samples were then ground to a standardized grain-size (45<63μ m), and changes in bioapatite crystallinity (CI) were determined using powder X-ray diffraction (pXRD), and Fourier transform infra-red spectroscopy (FTIR). Combined differential thermal and thermogravimetric analyses (DTA/TG) were used to evaluate weight loss and associated reactions during heating. Stable carbon isotope compositions of the bioapatite remain relatively constant (+/-1‰ ) during heating to 650° C. A 4‰ increase in stable carbon isotopic composition then occurs between 650-750° C, accompanied by an increase in CI, followed by a 10‰ decline at temperatures above 800° C, as carbonate carbon is lost. Carbonate and phosphate oxygen isotopic compositions are correlated over the entire heating range, with carbonate being enriched relative to phosphate by about 8-10‰ below 500° C, 5-6‰ between 500-700° C, and 8-10‰ above 700° C. CI and oxygen isotopic compositions of carbonate and phosphate are not well correlated. Only modest CI changes are recorded from 25-675° C, compared with much larger changes in oxygen isotopic composition, especially above 300° C. On average, original isotopic compositions are largely preserved for both phosphate (+/-1‰ ) and carbonate (+/-2‰ ) oxygen at <300° C. At higher temperatures, however, both phosphate and carbonate oxygen in the bioapatite are systematically depleted of oxygen-18 relative to original values.

Oxygen ion-conducting dense ceramic

DOEpatents

Balachandran, Uthamalingam; Kleefisch, Mark S.; Kobylinski, Thaddeus P.; Morissette, Sherry L.; Pei, Shiyou

1998-01-01

Preparation, structure, and properties of mixed metal oxide compositions and their uses are described. Mixed metal oxide compositions of the invention have stratified crystalline structure identifiable by means of powder X-ray diffraction patterns. In the form of dense ceramic membranes, the present compositions demonstrate an ability to separate oxygen selectively from a gaseous mixture containing oxygen and one or more other volatile components by means of ionic conductivities.

Theoretical estimation of Photons flow rate Production in quark gluon interaction at high energies

NASA Astrophysics Data System (ADS)

Al-Agealy, Hadi J. M.; Hamza Hussein, Hyder; Mustafa Hussein, Saba

2018-05-01

photons emitted from higher energetic collisions in quark-gluon system have been theoretical studied depending on color quantum theory. A simple model for photons emission at quark-gluon system have been investigated. In this model, we use a quantum consideration which enhances to describing the quark system. The photons current rate are estimation for two system at different fugacity coefficient. We discussion the behavior of photons rate and quark gluon system properties in different photons energies with Boltzmann model. The photons rate depending on anisotropic coefficient : strong constant, photons energy, color number, fugacity parameter, thermal energy and critical energy of system are also discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sverjensky, Dimitri A.; Huang, Fang

Diamond formation has typically been attributed to redox reactions during precipitation from fluids or magmas. Either the oxidation of methane or the reduction of carbon dioxide has been suggested, based on simplistic models of deep fluids consisting of mixtures of dissolved neutral gas molecules without consideration of aqueous ions. The role of pH changes associated with water–silicate rock interactions during diamond formation is unknown. Here we show that diamonds could form due to a drop in pH during water–rock interactions. We use a recent theoretical model of deep fluids that includes ions, to show that fluid can react irreversibly withmore » eclogite at 900 °C and 5.0 GPa, generating diamond and secondary minerals due to a decrease in pH at almost constant oxygen fugacity. Overall, our results constitute a new quantitative theory of diamond formation as a consequence of the reaction of deep fluids with the rock types that they encounter during migration. Diamond can form in the deep Earth during water–rock interactions without changes in oxidation state.« less

Experimental determination of the partitioning of gallium between solid iron metal and synthetic basaltic melt Electron and ion microprobe study

NASA Technical Reports Server (NTRS)

Drake, M. J.; Newsom, H. E.; Reed, S. J. B.; Enright, M. C.

1984-01-01

The distribution of Ga between solid Fe metal and synthetic basaltic melt is investigated experimentally at temperatures of 1190 and 1330 C, and over a narrow range of oxygen fugacities. Metal-silicate reversal experiments were conducted, indicating a close approach to equilibrium. The analysis of the partitioned products was performed using electron and ion microprobes. At one bar total pressure, the solid metal/silicate melt partition coefficient D(Ga) is used to evaluate metal-silicate fractionation processes in the earth, moon, and Eucrite Parent Body (EPB). It is found that the depletion of Ga abundances in the EPB is due to the extraction of Ga into a metallic core. Likewise, the depletion of Ga in the lunar mantle is consistent with the extraction of Ga into a smaller lunar core if Ga was originally present in a subchondritic concentration. The relatively high Ga abundances in the earth's mantle are discussed, with reference to several theoretical models.

Zirconium, hafnium, and rare earth element partition coefficients for ilmenite and other minerals in high-Ti lunar mare basalts - An experimental study

NASA Technical Reports Server (NTRS)

Mckay, G.; Wagstaff, J.; Yang, S.-R.

1986-01-01

Partition coefficients were determined for Gd, Lu, Hf and Zr among ilmenite, armalcolite, and synthetic high-Ti mare basaltic melts at temperatures from 1122 deg to 1150 deg, and at oxygen fugacities of IW x 10 exp 0.5, by in situ analysis with an electron microprobe, using samples doped to present concentration levels. Coefficients for Zr were also measured for samples containing 600-1600 ppm Zr using this microprobe. In addition, coefficients were determined for Hf and Zr between chromian ulvospinel and melt, for Hf between pigeonite and melt, and for Lu between olivine and melt by microprobe analysis of samples doped to present levels. Values measured using the microprobe were in agreement with the values measured by analyzing mineral separates from the same run products by isotope dilution. Coefficient values for ilmenite are less than 0.01 for the LREE, are around 0.1 for the HREE, and are several times greater than this for Zr and Hf.

Petrology of Igneous Clasts in Regolithic Howardite EET 87503

NASA Technical Reports Server (NTRS)

Hodges, Z. V.; Mittlefehldt, D. W.

2017-01-01

The howardite, eucrite and diogenite (HED) clan of meteorites is widely considered to originate from asteroid 4 Vesta, as a result of a global magma ocean style of differentiation. A global magmatic stage would allow silicate material to be well mixed, destroying any initial heterogeneity that may have been present resulting in the uniformity of eucrite and diogenite delta(exp 17)O, for example. The Fe/Mn ratio of mafic phases in planetary basalts can be diagnostic of different source bodies as this ratio is little-affected by igneous processes, so long as the oxygen and sulphur fugacities are buffered. Here, pyroxene Fe/Mn ratios in mafic clasts in howardite EET 87503 have been determined to further evaluate whether the HED parent asteroid is uniform. Uniformity would suggest that the parent asteroid was subject to homogenization prior to the formation of HED lithologies, likely through an extensive melting phase. Whereas, distinct differences may point towards heterogeneity of the parent body.

Guidelines for the Utilization of Composite Materials in Oxygen Storage Tanks

NASA Technical Reports Server (NTRS)

Davis, Samuel E.; Herald, Stephen

2006-01-01

Space travel is inherently dangerous and, currently, quite expensive. NASA has always done everything possible to minimize the risk associated with the materials chosen for space travel applications by requiring that all materials associated with NASA programs meet the strict requirements established by NASA testing standard NASA-STD-600 1 Flammability, Odor, Offgassing, and Compatibility Requirements and Test Procedures for Materials in Environments that Support Combustion. NASA also has the need to develop lighter weight structural materials that will allow more payload weight to be carried into space. NASA is utilizing composite materials inside the orbiter to lighten the overall weight, but has not considered composite materials for oxygen tanks because of the inherent incompatibility of composite materials with atomic oxygen. This presentation will focus on how oxygen tanks can be built from composite materials. Details will be provided for the design and compatibility testing techniques that will be utilized to create a new NASA standard, NASA-HDBK-6018, which will serve as the starting point for the design of oxygen tanks made from composite materials.

The role of oxygen vacancies in resistive switching behavior of organic-TiO2 hybrid composite

NASA Astrophysics Data System (ADS)

Zhang, Jiahua; Chen, Da; Huang, Shihua

2017-10-01

Effects of polyethylene glycol (PEG) on resistive switching behaviors and mechanisms in organic-TiO2 hybrid composites were investigated. The reversed current-voltage curves in the negative bias during the initial voltage sweeps were first observed in the composites annealed at 150, 200 and 250 °C, which is ascribed to the accumulation of oxygen vacancies and the inhibition effect of polarities of PEG chains. In addition, the volatility of composites with relatively high content of PEG is caused by the inhibition effect of PEG on creating oxygen vacancies. The formation and rupture of oxygen-vacancy filaments was considered as the resistive switching mechanism. Finally, the charging and discharging process in PEG-TiO2 composite annealed at 150 °C results in the instability of the electron-occupied oxygen vacancies and the inhibition of PEG chains. This study demonstrates a new way to investigate the interaction between polymers and TiO2 for understanding the resistive switching mechanism of TiO2-based memories.

A Model of Volcanic Outgassing for Earth's Early Atmosphere

NASA Astrophysics Data System (ADS)

Dhaliwal, J. K.; Kasting, J. F.; Zhang, Z.

2017-12-01

We build on historical paradigms of volcanic degassing [1] to account for non-linear relations among C-O-H-S volatiles, their speciation, solubility and concentrations in magmatic melts, and the resulting contribution to atmospheric volatile inventories. We focus on the build-up of greenhouse-relevant carbon species (CO2 and CH4) and molecular oxygen to better understand the environments of early life and the Great Oxygenation Event [2,3,4]. The mantle is an important reservoir of C-O-H-S volatiles [5], and melt concentrations depend on temperature, pressure and oxygen fugacity. We present a preliminary chemical model that simulates volatile concentrations released into the Earth's atmosphere at 1 bar, or pressures corresponding to the early Earth prior to 2.4 Ga. We maintain redox balance in the system using H+ [2, 6] because the melt oxidation state evolves with volatile melt concentrations [7] and affects the composition of degassed compounds. For example, low fO2 in the melt degasses CO, CH4, H2S and H2 while high fO2 yields CO2, SO2 and H2O [1,8,9]. Our calculations incorporate empirical relations from experimental petrology studies [e.g., 10, 11] to account for inter-dependencies among volatile element solubility trends. This model has implications for exploring planetary atmospheric evolution and potential greenhouse effects on Venus and Mars [12]­, and possibly exoplanets. A future direction of this work would be to link this chemical degassing model with different tectonic regimes [13] to account for degassing and ingassing, such as during subduction. References: [1] Holland, H. D. (1984) The chemical evolution of the atmosphere and oceans [2] Kasting, J. F. (2013) Chem. Geo. 362, 13-25 [3] Kasting, J.F. (1993) Sci. 259, 920-926 [4] Duncan, M.S. & Dasgupta, R. (2017) Nat. Geoscience 10, 387-392. [5] Hier-Majumder, S. & Hirschmann, M.M. (2017) G3, doi: 10.1002/2017GC006937 [6] Gaillard, F. et al. (2003) GCA 67, 2427- 2441 [7] Moussalam, Y. et al. (2014) EPSL 393, 200-209 [8] Holloway, J. R. & Blank, J. G. (1994) Rev. in Min. 30, 187-187 [9] Hirschmann, M. M. (2012) EPSL 341, 48-57 [10] Iacono-Marziano, G. et al. (2012) GCA 97, 1-23 [11] O'Neill, H. St. C. & Mavrogenes, J.A. (2002) J. of Pet. 6, 1049-1087 [12] Gaillard, F. & Scaillet, B. (2014) EPSL 403, 307-316. [13] Rozel, A.B. et al. (2017) Nature 545, 332-335.

A Late Variscan Sn province: the Arburese region (SW Sardinia, Italy)

NASA Astrophysics Data System (ADS)

Naitza, Stefano; Secchi, Francesco; Oggiano, Giacomo; Cuccuru, Stefano

2015-04-01

Late Variscan Sn - rich European provinces (e. g. Erzgebirge, Cornwall) are of particular relevance as they offer key insights into crustal evolution, intrusive processes and ore genesis. In Sardinia (Italy), small Sn deposits are only known in the Arburese historical mining region (SW Sardinia), hosted in low-grade metamorphics close to the contacts with intrusives. This region is characterised by two late variscan intrusions, which differ in age and composition: the Arbus and the Monte Linas pluton, aging 304 ± 1 Ma, and 289 ± 1 Ma respectively. They emplaced at shallow crustal levels and crosscut the basal thrust between the alloctonous prism and the foreland of the Variscan belt of Sardinia. The Arbus Pluton (AP) is a composite intrusion of piroxene- and amphibole- granodiorites hosting minor amounts of monzogabbroic rocks and cordierite-bearing granites with a wide core of leuco-monzogranites. Tourmaline greisens and pegmatites garnish the contact between the border facies and the host metamorphic rocks. The Monte Linas Pluton (MLP) has biotite monzogranite composition. The pluton is internally zoned, from medium grained monzogranite in the core to hololeucocratic fine-grained rock-types at the top, where often F-greisen, fayalite-pegmatite pods and sill are common. In both plutons the igneous associations are high-K ilmenite series, suggesting derivation from low- fO2 magmas possibly linked to a common crustal contribution; however, in the Linas Pluton magnetite in the fine-grained facies may indicate an increase in oxygen fugacity. The AP-related Sn ores consist of high-temperature As-Sn quartz veins. They are vertically zoned, from quartz-chlorite-cassiterite to large quartz-arsenopyrite veins. Ore microscopy and SEM-EDS analyses evidenced a vein texture made of thick idiomorphic and frequently twinned cassiterite crystals, alternated with several generations of banded/geodic quartz. Chlinoclore aggregates are included into the quartz. The arsenopyrite ore shows alternating bands of microgranular to crystalline millimetric arsenopyrite with quartz. Field and analytical data suggest genetic mechanisms dominated by mobilization of residual Sn by chloride and other complexes in reducing, As- and S- rich, low- fO2 juvenile fluids. Cassiterite and successive arsenopyrite precipitation occurred under changing physicochemical conditions (e.g. oxygen contents; temperature decrease; pH). The MLP Sn metallogeny include Sn- Pb-Zn-Cu veins (Canale Serci old mine). Cassiterite occurs as fine-grained corroded crystals. Optical and SEM-EDS analyses evidence a high-temperature oxide stage (quartz-chlorite- cassiterite) followed, after brecciation, by mesothermal sulfide stages, with progressive deposition of sphalerite, pyrite, chalcopyrite, tetrahedrite, galena, marcasite. Arsenopyrite is strikingly absent. These evidences indicate possible derivation of the ore from residual, reducing juvenile fluids, capable to carry Sn- complexes from monzogranite magmas from which cassiterite precipitated in consequence of an increasing in fO2. Despite their limited amount, the Sn ores of SW Sardinia have high metallogenic relevance, indicating the persistence, of geochemical conditions,which lasted 15 Ma, favorable to the genesis of a Sn metallogenic province.

Oxygen Transport Membrane Reactors for Oxy-Fuel Combustion and Carbon Capture Purposes

NASA Astrophysics Data System (ADS)

Falkenstein-Smith, Ryan L.

This thesis investigates oxygen transport membrane reactors (OTMs) for the application of oxy-fuel combustion. This is done by evaluating the material properties and oxygen permeability of different OTM compositions subjected to a variety of operating conditions. The scope of this work consists of three components: (1) evaluate the oxygen permeation capabilities of perovskite-type materials for the application of oxy-fuel combustion; (2) determine the effects of dual-phase membrane compositions on the oxygen permeation performance and membrane characteristics; and (3) develop a new method for estimating the oxygen permeation performance of OTMs utilized for the application of oxy-fuel combustion. SrSc0.1Co0.9O3-delta (SSC) is selected as the primary perovskite-type material used in this research due to its reported high ionic and electronic conductive properties and chemical stability. SSC's oxygen ion diffusivity is investigated using a conductivity relaxation technique and thermogravimetric analysis. Material properties such as chemical structure, morphology, and ionic and electronic conductivity are examined by X-ray diffraction (XRD), Scanning Electron Microscope (SEM), and conductivity testing using a four-probe method, respectively. Oxygen permeation tests study the oxygen permeability OTMs under modified membrane temperatures, sweeping gas flow rates, sweeping gas compositions, membrane configurations, and membrane compositions. When utilizing a pure CO2 sweeping gas, the membrane composition was modified with the addition of Sm0.2Ce0.8O1.9-delta (SDC) at varying wt.% to improve the membranes mechanical stability. A newly developed method to evaluate the oxygen permeation performance of OTMs is also presented by fitting OTM's oxygen permeability to the methane fraction in the sweeping gas composition. The fitted data is used to estimate the overall performance and size of OTMs utilized for the application of oxy-fuel combustion. The findings from this research show that under a wide range of membrane temperatures and in a variety of atmospheres, a pure SSC OTM can achieve superior surface exchange and oxygen chemical diffusion coefficients compared to other commonly studied materials. SSC's high oxygen permeability (>1 ml.min -1.cm-2) demonstrates the material's candidacy for the application of oxy-fuel combustion. However, in the presence of rich CO 2 atmospheres, SSC shows mechanical and chemical instabilities due to the carbonate formation on the perovskite structure. The addition of SDC in the membrane composition produces a dual-phase OTM which is observed to improve the oxygen permeation flux when subjected to pure CO2 sweeping gases. When subjected to pure methane sweeping gases, dual-phase OTM compositions exhibits lower oxygen permeability compared to the single-phase SSC OTM. Despite the decline in the oxygen permeation flux, some dual-phase compositions still exhibit a high oxygen permeability, indicating their potential for the application of oxy-fuel combustion. Furthermore, a newly developed method for evaluating OTMs for the application of oxy-fuel combustion is presented in a portion of this work. This new method calculates key components such as the average oxygen permeation flux, approximate effective surface area, and the impact of additional recirculated exhaust into the incoming sweeping gas to provide a detailed understanding of OTM's application for oxy-fuel combustion. The development of this approach will aid in the evaluation of newly developed materials and create a new standard for implementing OTMs for the application of oxy-fuel combustion.

Experimental investigation of condensation predictions for dust-enriched systems

NASA Astrophysics Data System (ADS)

Ustunisik, Gokce; Ebel, Denton S.; Walker, David; Boesenberg, Joseph S.

2014-10-01

Condensation models describe the equilibrium distribution of elements between coexisting phases (mineral solid solutions, silicate liquid, and vapor) in a closed chemical system, where the vapor phase is always present, using equations of state of the phases involved at a fixed total pressure (<1 bar) and temperature (T). The VAPORS code uses a CaO-MgO-Al2O3-SiO2 (CMAS) liquid model at T above the stability field of olivine, and the MELTS thermodynamics algorithm at lower T. Quenched high-T crystal + liquid assemblages are preserved in meteorites as Type B Ca-, Al-rich inclusions (CAIs), and olivine-rich ferromagnesian chondrules. Experimental tests of compositional regions within 100 K of the predicted T of olivine stability may clarify the nature of the phases present, the phase boundaries, and the partition of trace elements among these phases. Twenty-three Pt-loop equilibrium experiments in seven phase fields on twelve bulk compositions at specific T and dust enrichment factors tested the predicted stability fields of forsteritic olivine (Mg2SiO4), enstatite (MgSiO3), Cr-bearing spinel (MgAl2O4), perovskite (CaTiO3), melilite (Ca2Al2SiO7-Ca2Mg2Si2O7) and/or grossite (CaAl4O7) crystallizing from liquid. Experimental results for forsterite, enstatite, and grossite are in very good agreement with predictions, both in chemistry and phase abundances. On the other hand the stability of spinel with olivine, and stability of perovskite and gehlenite are quite different from predictions. Perovskite is absent in all experiments. Even at low oxygen fugacity (IW-3.4), the most TiO2-rich experiments do not crystallize Al-, Ti-bearing calcic pyroxene. The stability of spinel and olivine together is limited to a smaller phase field than is predicted. The melilite stability field is much larger than predicted, indicating a deficiency of current liquid or melilite activity models. In that respect, these experiments contribute to improving the data for calibrating thermodynamic models including MELTS.

Suitability of chondrules for studying the magnetic field of the early solar system: an examination of synthetically produced dusty olivine

NASA Astrophysics Data System (ADS)

Hu, Y.; Feinberg, J. M.; Church, N.; Bromiley, G.; Bowles, J.; Jackson, M.; Moskowitz, B. M.; Harrison, R. J.

2008-12-01

Chondritic meteorites are rare, yet incredibly valuable windows into the geophysical and geochemical environment of the early solar system. Dusty olivine grains containing exsolved nanometer-scale iron-nickel alloy inclusions are present in many chondritic meteorites and their remanent magnetization may give insight into the strength of the solar dynamo at the time of chondrule formation. Laboratory methods for determining the paleointensity of these rare materials must be optimized prior to conducting experiments on actual meteorite samples. To this end, we have used high temperature recrystallization techniques to produce synthetic dusty olivine samples with textures remarkably similar to those observed in chondritic meteorites. The olivine grains used in these annealing experiments are from the 13 kya Haleyjabunga picritic basalt flow in Iceland and have compositions of Fo90, which closely resembles the olivine composition observed in chondritic meteorites. Samples were annealed at 1350°C either under vacuum in the presence of graphite or under controlled oxygen fugacity using pure CO gas. The laboratory-produced magnetic mineral assemblages in two sets of samples have been characterized using low and high temperature remanence and susceptibility measurements, hysteresis loops, FORC diagrams, and scanning electron microscopy. The room-temperature remanence properties of these materials have been explored using stepwise IRM and ARM acquisition and alternating field demagnetization. These synthesis techniques allow us to produce a wide rage of iron-nickel grain sizes with correspondingly large variations in coercivity (between 0 and 500 mT). High temperature measurements of saturation magnetization show that both samples reach their Curie temperatures at ~760°C, consistent with kamacite, a low-Ni high-Fe metal alloy. Multiple experiments have shown that care must be taken to rigorously control the atmosphere in which the samples are heated and cooled in order to avoid forming trace amounts of magnetite on the surface of the samples. Future research will explore the feasibility of using modified Thellier protocols to determine the paleointensity of laboratory-induced thermoremanent magnetizations.

Evaluation of gas data from high-temperature fumaroles at Mount St. Helens, 1980-1982

USGS Publications Warehouse

Gerlach, T.M.; Casadevall, T.J.

1986-01-01

The Mount St. Helens fumarole gases show linear composition trends during periods of noneruptive degassing between September 1980 and October 1981. The trends are characterized by increasing H2O and decreasing CO2 and sulfur. Maximum fumarole temperatures also show a linear decrease during this period. High-temperature fumarole gases collected from the crater and dome between September 1980 and July 1982 are all H2O-rich (> 90%) with 1-10% CO2 and small amounts of H2S, SO2, H2, CO, HC, and HF. Trace amounts of COS and S2 are present, and occasional observations of minor CH4 appear to result from contamination or low-temperature reactions in sample vessels. The O2 fugacities of the gases remain near Ni-NiO during cooling. The low sulfur content of the gases obviates the need for extensive gas-rock oxygen exchange to maintain fO2's near Ni-NiO. A detailed thermodynamic analysis of 50 gas samples collected between September 1980 and December 1981 led to improved compositions for 22 samples. The gases were initially in a state of equilibrium, but disequilibrium modifications from atmospheric oxidation of H2 and, to a lesser extent, CO occurred within the upper portions of the fumarole vents. The last temperatures of equilibrium for the fumarole gases range from 800??C to 650??C and are nearly always higher than the collection temperatures. No evidence was found of disequilibrium admixture of surface waters; if such modifications of the fumarole gases occurred, the water must have been added at depth and have reequilibrated with the other gas species at magmatic or near-magmatic temperatures. The highest quality analytical data are obtained by field gas chromatograph measurements and from caustic soda bottle samples. Samples collected in evacuated bottles or by pumping through double stopcock tubes tend to be severely deficient in sulfur due to post-collection reactions between H2S and SO2. It is also necessary to infer the water content of the latter samples. ?? 1986.

Magmatic controls on the genesis of porphyry Cu-Mo-Au deposits: The Bingham Canyon example

NASA Astrophysics Data System (ADS)

Grondahl, Carter; Zajacz, Zoltán

2017-12-01

Bingham Canyon is one of the world's largest porphyry Cu-Mo-Au deposits and was previously used as an example to emphasize the role of magma mixing and magmatic sulphide saturation in the enhancement of ore fertility of magmatic systems. We analyzed whole rocks, minerals, and silicate melt inclusions (SMI) from the co-genetic, ore-contemporaneous volcanic package (∼38 Ma). As opposed to previous propositions, whole-rock trace element signatures preclude shoshonite-latite genesis via mixing of melanephelinite and trachyte or rhyolite, whereas core to rim compositional profiles of large clinopyroxene phenocrysts suggests the amalgamation of the ore-related magma reservoir by episodic recharge of shoshonitic to latitic magmas with various degrees of differentiation. Major and trace element and Sr and Nd isotopic signatures indicate that the ore-related shoshonite-latite series were generated by low-degree partial melting of an ancient metasomatized mantle source yielding volatile and ore metal rich magmas. Latite and SMI compositions can be reproduced by MELTS modeling assuming 2-step lower and upper crustal fractionation of a primary shoshonite with minimal country rock assimilation. High oxygen fugacities (≈ NNO + 1) are prevalent as evidenced by olivine-spinel oxybarometry, high SO3 in apatite, and anhydrite saturation. The magma could therefore carry significantly more S than would have been possible at more reducing conditions, and the extent of ore metal sequestration by magmatic sulphide saturation was minimal. The SMI data show that the latites were Cu rich, with Cu concentrations in the silicate melt reaching up to 300-400 ppm at about 60 wt% SiO2. The Au and Ag concentrations are also high (1.5-4 and 50-200 ppb, respectively), but show less variation with SiO2. A sudden drop in Cu and S concentrations in the silicate melt at around 65 wt% SiO2 in the presence of high Cl, Mo, Ag, and Au shows that the onset of effective metal extraction by fluid exsolution occurred at a relatively late stage of magma evolution. Overall, our results show that fluid exsolution during simple magmatic differentiation of oxidized alkaline magmas is capable of producing giant porphyry Cu deposits.

Ar-39 - Ar-40 Dating of Unusual Eucrite NWA-011: Is it from Vesta?

NASA Technical Reports Server (NTRS)

Bogard, D. D.; Garrison, D. H.

2004-01-01

Basaltic meteorite NWA-011 is similar to eucrites in many aspects, but its oxygen isotopic composition lies far off the oxygen fractionation line defined by eucrites. It was suggested that NWA011 may have derived from a different parent body from that of eucrites, which are thought to derive from the asteroid Vesta. Some other eucrites also show small anomalous oxygen compositions. This suggests that for all eucrites to derive from Vesta, it must be compositionally inhomogeneous. Some workers have speculated whether early, large impactors on Vesta might have contributed the anomalous oxygen.

Multifunctional materials and composites

DOEpatents

Seo, Dong-Kyun; Jeon, Ki-Wan

2017-08-22

Forming multifunctional materials and composites thereof includes contacting a first material having a plurality of oxygen-containing functional groups with a chalcogenide compound, and initiating a chemical reaction between the first material and the chalcogenide compound, thereby replacing oxygen in some of the oxygen-containing functional groups with chalcogen from the chalcogen-containing compound to yield a second material having chalcogen-containing functional groups and oxygen-containing functional groups. The first material is a carbonaceous material or a macromolecular material. A product including the second material is collected and may be processed further to yield a modified product or a composite.

Coordinated Petrography and Oxygen Isotopic Compositions of Al-Rich Chondrules from CV3 Chondrites

NASA Astrophysics Data System (ADS)

Zhang, M. M.; Lin, Y. T.; Tang, G. Q.; Li, X. H.

2017-07-01

In this study, we coordinated the petrology, bulk compositions and oxygen isotope compositions of 12 ARCs from Allende and Leoville and Ningqiang chondrites in order to elucidate any potential genetic relationships between ARCs, CAIs and FMCs.

The solubility of Pd and Au in hydrous intermediate silicate melts: The effect of oxygen fugacity and the addition of Cl and S

NASA Astrophysics Data System (ADS)

Sullivan, Neal A.; Zajacz, Zoltan; Brenan, James M.

2018-06-01

The solubilities of Pd and Au in a hydrous trachyandesitic melt were experimentally determined at 1000 °C and 200 MPa at oxygen fugacity (ƒO2) from 0.45 log units below to 6.55 log units above the Ni-NiO buffer (NNO). The effect of adding metal-binding ligands (i.e. Cl and S) to the silicate melt was also studied. The solubility of Au increases from 0.15 ± 0.1 to 3.85 ± 1.48 ppm in Cl- and S-free melts with ƒO2 increasing from NNO-0.45 to NNO+6.55 with a slope that suggests that it is present in 1+ oxidation state over the entire studied ƒO2 range. On the other hand, Pd solubility, shows a more moderate increase with ƒO2, especially in the lower half of the studied range, increasing from 2.66 ± 0.25 ppm at NNO-0.45 to only 3.62 ± 0.38 ppm at NNO+1.72 in Cl- and S-free melts. Overall, the variation in Pd solubility as a function of ƒO2 indicates Pd being dissolved in the silicate melt in both zero and 1+ oxidation state, with the former being dominant below NNO+4.5. At NNO-0.45 to +3.48, the addition of 3170-4060 ppm Cl to the silicate melt increased the solubility of Au by an average factor of 1.5, in comparison to Cl-free melts. However, at NNO+6.55, Au solubility increased by a factor of 2.5. The addition of Cl had a negligible effect on the solubility of Pd except for a large increase (factor of 2.4) at NNO+6.55. At reducing conditions (NNO-0.45), the addition of 170 ppm S to the silicate melt increased the solubility of Au by a factor of ∼4 but did not change the solubility of Pd in comparison to S-free melts. The observation that Pd is dominantly present as Pd0 at NNO < +4.5 may explain the lack of complexation with potential reduced sulfur-bearing and chloride ligands. As one may expect similar behavior in fluids degassing from magmas at depth, the lack of oxidized Pd species could be an important factor behind the scarcity of economically viable Pd-rich magmatic-hydrothermal deposits observed in nature.

Upper mantle oxygen fugacity recorded by peridotite xenoliths from oceanic islands

NASA Astrophysics Data System (ADS)

Davis, F. A.; Wall, K. T.; Cottrell, E.

2017-12-01

Oxygen fugacity (fO2) in Earth's mantle is a key variable influencing mineral and fluid stability, the onset of melting, and mantle rheology; but fO2 is not uniform across mantle spatial domains. Peridotite xenoliths erupted in oceanic island basalts (OIB) potentially record fO2 of their lithospheric source - the convecting upper mantle. Many of these xenoliths have reacted with OIB as they transited the lithosphere. These xenoliths may record fO2 of the OIB source, potentially recording fO2 heterogeneity within the upper mantle. We investigate fO2heterogeneity by analyzing coexisting olivine, opx, and spinel in 41 peridotite xenoliths from islands associated with four different hotspots: Oahu (Hawaii), Savai'i (Samoa), Tubuai (Austral), and Tahiti (Society). Elevated spinel TiO2 concentrations (TiO2 >0.2 wt.%) in xenoliths from Oahu, Tubuai, and Tahiti may indicate interaction with OIB magmas [1]. Such assemblages record higher fO2 on average (QFM+0.4 to QFM+1.0) than peridotites and lavas from mid-ocean ridges (QFM-2 to QFM) [2,3,4]. This suggests that Hawaiian, Society, and Austral basalts with fO2 ≥ QFM+0.4 are more oxidized than MORB. (None of the Samoan xenoliths have spinel TiO2 >0.05 wt.%). Xenoliths with TiO2 <0.2 wt.% that have not reacted with OIB show a great degree of fO2 heterogeneity (QFM-1.5 to QFM+1.0) reflective of heterogeneity in lithospheric fO2. Although some heterogeneity may indicate spatial variability in bulk mantle chemistry, it is likely that it is partly driven by metamorphic reactions as lithosphere cools or is reheated by a mantle plume. Increased temperature causes the (Mg,Fe)Al2O4 component of spinel to dissolve into pyroxene; this concentrates the magnetite component in spinel and increases fO2 [5]. We observed evidence of this reaction at the grain-scale. Spinels in spinel-cpx symplectites and rims of equant spinels are >1 log unit more oxidized and have lower Al2O3 concentrations than interiors of the equant spinels. These results indicate that fO2 of the oceanic lithosphere is affected by subsolidus metamorphic reactions, which must be considered when relating fO2 of peridotites to fO2 of the convecting upper mantle. [1] Pearce et al. 2000, CMP; [2] Bryndzia and Wood 1990, AJS; [3] Bézos and Humler 2005, GCA; [4] Cottrell and Kelley 2011, EPSL; [5] Canil and O'Neill 1996, JPet

Space environmental effects on polymer composites: Research needs and opportunities

NASA Technical Reports Server (NTRS)

Jang, Bor Z.; Bianchi, J.; Liu, Y. M.; Chang, C. P.

1993-01-01

The long-term performance of polymer-based composites in the space environment is discussed. Both thermoset and thermoplastic matrix composites are included in this discussion. Previous efforts on the space environmental effects on composites are briefly reviewed. Focus of this review is placed on the effects of hygrothermal stresses, atomic oxygen, ultraviolet (UV), and space debris/micrometeoroid impacts along with the potential synergism. Potential approaches to estimating the residual strength of polymer composites after exposure to atomic oxygen erosion or space debris/micrometeoroid impact are evaluated. New ground-based data are then utilized to illustrate the effects of atomic oxygen and thermal cycling on the failure behavior of polymer composites. Finally, research needs, challenges, and opportunities in the field of space environmental effects on composite materials are highlighted.

Understanding the fate and transport of petroleum hydrocarbons from coal tar within gasholders.

PubMed

Coulon, Frédéric; Orsi, Roberto; Turner, Claire; Walton, Chris; Daly, Paddy; Pollard, Simon J T

2009-02-01

Coal tars have been identified as posing a threat to human health due to their toxic, mutagenic and carcinogenic characteristics. Workers involved in former gasholders decommissioning are potentially exposed to relevant concentrations of volatile and semi-volatile hydrocarbons upon opening up derelict tanks and during tar excavation/removal. While information on contaminated sites air-quality and its implications on medium-long term exposure is available, acute exposure issues associated with the execution of critical tasks are less understood. Calculations indicated that the concentration of a given contaminant in the gasholder vapour phase only depends on the coal tar composition, being only barely affected by the presence of water in the gasholder and the tar volume/void space ratio. Fugacity modelling suggested that risk-critical compounds such as benzene, naphthalene and other monocyclic and polycyclic aromatic hydrocarbons may gather in the gasholder air phase at significant concentrations. Gasholder emissions were measured on-site and compared with the workplace exposure limits (WELs) currently in use in UK. While levels for most of the toxic compounds were far lower than WELs, benzene air-concentrations where found to be above the accepted threshold. In addition due to the long exposure periods involved in gasholder decommissioning and the significant contribution given by naphthalene to the total coal tar vapour concentration, the adoption of a WEL for naphthalene may need to be considered to support operators in preventing human health risk at the workplace. The Level I fugacity approach used in this study demonstrated its suitability for applications to sealed environments such as gasholders and its further refining could provide a useful tool for land remediation risk assessors.

The OceanFlux Greenhouse Gases methodology for deriving a sea surface climatology of CO2 fugacity in support of air-sea gas flux studies

NASA Astrophysics Data System (ADS)

Goddijn-Murphy, L. M.; Woolf, D. K.; Land, P. E.; Shutler, J. D.; Donlon, C.

2015-07-01

Climatologies, or long-term averages, of essential climate variables are useful for evaluating models and providing a baseline for studying anomalies. The Surface Ocean CO2 Atlas (SOCAT) has made millions of global underway sea surface measurements of CO2 publicly available, all in a uniform format and presented as fugacity, fCO2. As fCO2 is highly sensitive to temperature, the measurements are only valid for the instantaneous sea surface temperature (SST) that is measured concurrently with the in-water CO2 measurement. To create a climatology of fCO2 data suitable for calculating air-sea CO2 fluxes, it is therefore desirable to calculate fCO2 valid for a more consistent and averaged SST. This paper presents the OceanFlux Greenhouse Gases methodology for creating such a climatology. We recomputed SOCAT's fCO2 values for their respective measurement month and year using monthly composite SST data on a 1° × 1° grid from satellite Earth observation and then extrapolated the resulting fCO2 values to reference year 2010. The data were then spatially interpolated onto a 1° × 1° grid of the global oceans to produce 12 monthly fCO2 distributions for 2010, including the prediction errors of fCO2 produced by the spatial interpolation technique. The partial pressure of CO2 (pCO2) is also provided for those who prefer to use pCO2. The CO2 concentration difference between ocean and atmosphere is the thermodynamic driving force of the air-sea CO2 flux, and hence the presented fCO2 distributions can be used in air-sea gas flux calculations together with climatologies of other climate variables.

Crystal growth and disequilibrium distribution of oxygen isotopes in an igneous Ca-Al-rich inclusion from the Allende carbonaceous chondrite

NASA Astrophysics Data System (ADS)

Kawasaki, Noriyuki; Simon, Steven B.; Grossman, Lawrence; Sakamoto, Naoya; Yurimoto, Hisayoshi

2018-01-01

TS34 is a Type B1 Ca-Al-rich inclusion (CAI) from the Allende CV3 chondrite, consisting of spinel, melilite, Ti-Al-rich clinopyroxene (fassaite) and minor anorthite in an igneous texture. Oxygen and magnesium isotopic compositions were measured by secondary ion mass spectrometry in spots of known chemical composition in all major minerals in TS34. Using the sequence of formation from dynamic crystallization experiments and from chemical compositions of melilite and fassaite, the oxygen isotopic evolution of the CAI melt was established. Oxygen isotopic compositions of the constituent minerals plot along the carbonaceous chondrite anhydrous mineral line. The spinel grains are uniformly 16O-rich (Δ17O = -22.7 ± 1.7‰, 2SD), while the melilite grains are uniformly 16O-poor (Δ17O = -2.8 ± 1.8‰) irrespective of their åkermanite content and thus their relative time of crystallization. The fassaite crystals exhibit growth zoning overprinting poorly-developed sector zoning; they generally grow from Ti-rich to Ti-poor compositions. The fassaite crystals also show continuous variations in Δ17O along the inferred directions of crystal growth, from 16O-poor (Δ17O ∼ -3‰) to 16O-rich (Δ17O ∼ -23‰), covering the full range of oxygen isotopic compositions observed in TS34. The early-crystallized 16O-poor fassaite and the melilite are in oxygen isotope equilibrium and formed simultaneously. The correlation of oxygen isotopic compositions with Ti content in the fassaite imply that the oxygen isotopic composition of the CAI melt evolved from 16O-poor to 16O-rich during fassaite crystallization, presumably due to oxygen isotope exchange with a surrounding 16O-rich nebular gas. Formation of spinel, the liquidus phase in melts of this composition, predates crystallization of all other phases, so its 16O-rich composition is a relic of an earlier stage. Anorthite exhibits oxygen isotopic compositions between Δ17O ∼ -2‰ and -9‰, within the range of those of fassaite, indicating co-crystallization of these two minerals during the earliest to intermediate stage of fassaite growth. The melilite and fassaite yield an 26Al-26Mg mineral isochron with an initial value of (26Al/27Al)0 = (5.003 ± 0.075) × 10-5, corresponding to a relative age of 0.05 ± 0.02 Myr from the canonical Al-Mg age of CAIs. These data demonstrate that both 16O-rich and 16O-poor reservoirs existed in the solar nebula at least ∼0.05 Myr after the birth of the Solar System.

Oxidation of Carbon Fibers in a Cracked Ceramic Matrix Composite Modeled as a Function of Temperature

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Cawley, James D.; Eckel, Andrew J.

2003-01-01

The oxidation model simulates the oxidation of the reinforcing carbon fibers within a ceramic matrix composite material containing as-fabricated microcracks. The physics-based oxidation model uses theoretically and experimentally determined variables as input for the model. The model simulates the ingress of oxygen through microcracks into a two-dimensional plane within the composite material. Model input includes temperature, oxygen concentration, the reaction rate constant, the diffusion coefficient, and the crack opening width as a function of the mechanical and thermal loads. The model is run in an iterative process for a two-dimensional grid system in which oxygen diffuses through the porous and cracked regions of the material and reacts with carbon in short time steps. The model allows the local oxygen concentrations and carbon volumes from the edge to the interior of the composite to be determined over time. Oxidation damage predicted by the model was compared with that observed from microstructural analysis of experimentally tested composite material to validate the model for two temperatures of interest. When the model is run for low-temperature conditions, the kinetics are reaction controlled. Carbon and oxygen reactions occur relatively slowly. Therefore, oxygen can bypass the carbon near the outer edge and diffuse into the interior so that it saturates the entire composite at relatively high concentrations. The kinetics are limited by the reaction rate between carbon and oxygen. This results in an interior that has high local concentrations of oxygen and a similar amount of consumed carbon throughout the cross section. When the model is run for high-temperature conditions, the kinetics are diffusion controlled. Carbon and oxygen reactions occur very quickly. The carbon consumes oxygen as soon as it is supplied. The kinetics are limited by the relatively slow rate at which oxygen is supplied in comparison to the relatively fast rate at which carbon and oxygen reactions occur. This results in a sharp gradient in oxygen concentration from the edge where it is supplied to the nearest source of carbon, which is where the oxygen is quickly consumed. A moving reaction front is seen in which the outlaying carbon is consumed before the next inner layer of carbon begins to react.

Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update

NASA Technical Reports Server (NTRS)

Karner, J. M.; Sutton, S. R.; Papike, J. J.; Shearer, C. K.; Jones, J. H.; Newville, M.

2004-01-01

We have been developing an oxygen barometer based on the valence state of V (V(2+), V(3+), V(4+), and V(5+)) in solar system basaltic glasses. The V valence is determined by synchrotron micro x-ray absorption near edge structure (XANES), which uses x-ray absorption associated with core-electronic transitions (absorption edges) to reveal a pre-edge peak whose intensity is directly proportional to the valence state of an element. XANES has advantages over other techniques that determine elemental valence because measurements can be made non-destructively in air and in situ on conventional thin sections at a micrometer spatial resolution with elemental sensitivities of approx. 100 ppm. Recent results show that fO2 values derived from the V valence technique are consistent with fO2 estimates determined by other techniques for materials that crystallized above the IW buffer. The fO2's determined by V valence (IW-3.8 to IW-2) for the lunar pyroclastic glasses, however, are on the order of 1 to 2.8 log units below previous estimates. Furthermore, the calculated fO2's decrease with increasing TiO2 contents from the A17 VLT to the A17 Orange glasses. In order to investigate these results further, we have synthesized lunar green and orange glasses and examined them by XANES.

Oxidation of SiC Fiber-Reinforced SiC Matrix Composites with a BN Interphase

NASA Technical Reports Server (NTRS)

Opila, Elizabeth; Boyd, Meredith K.

2010-01-01

SiC-fiber reinforced SiC matrix composites with a BN interphase were oxidized in reduced oxygen partial pressures of oxygen to simulate the environment for hypersonic vehicle leading edge applications. The constituent fibers as well as composite coupons were oxidized in oxygen partial pressures ranging from 1000 ppm O2 to 5% O2 balance argon. Exposure temperatures ranged from 816 C to 1353 C (1500 F to 2450 F). The oxidation kinetics of the coated fibers were monitored by thermogravimetric analysis (TGA). An initial rapid transient weight gain was observed followed by parabolic kinetics. Possible mechanisms for the transient oxidation are discussed. One edge of the composite coupon seal coat was ground off to simulate damage to the composite which allowed oxygen ingress to the interior of the composite. Oxidation kinetics of the coupons were characterized by scanning electron microscopy since the weight changes were minimal. It was found that sealing of the coupon edge by silica formation occurred. Differences in the amount and morphology of the sealing silica as a function of time, temperature and oxygen partial pressure are discussed. Implications for use of these materials for hypersonic vehicle leading edge materials are summarized.

Experimental determination of CO2 content at graphite saturation along a natural basalt-peridotite melt join: Implications for the fate of carbon in terrestrial magma oceans

NASA Astrophysics Data System (ADS)

Duncan, Megan S.; Dasgupta, Rajdeep; Tsuno, Kyusei

2017-05-01

Knowledge of the carbon carrying capacity of peridotite melt at reducing conditions is critical to constrain the mantle budget and planet-scale distribution of carbon set at early stage of differentiation. Yet, neither measurements of CO2 content in reduced peridotite melt nor a reliable model to extrapolate the known solubility of CO2 in basaltic (mafic) melt to solubility in peridotitic (ultramafic) melt exist. There are several reasons for this gap; one reason is due to the unknown relative contributions of individual network modifying cations, such as Ca2+ versus Mg2+, on carbonate dissolution particularly at reducing conditions. Here we conducted high pressure, temperature experiments to estimate the CO2 contents in silicate melts at graphite saturation over a compositional range from natural basalts toward peridotite at a fixed pressure (P) of 1.0 GPa, temperature (T) of 1600 °C, and oxygen fugacity (log ⁡ fO2 ∼ IW + 1.6). We also conducted experiments to determine the relative effects of variable Ca and Mg contents in mafic compositions on the dissolution of carbonate. Carbon in quenched glasses was measured and characterized using Fourier transform infrared spectroscopy (FTIR) and Raman Spectroscopy and was found to be dissolved as carbonate (CO32-). The FTIR spectra showed CO32- doublets that shifted systematically with the MgO and CaO content of silicate melts. Using our data and previous work we constructed a new composition-based model to determine the CO2 content of ultramafic (peridotitic) melt representative of an early Earth, magma ocean composition at graphite saturation. Our data and model suggest that the dissolved CO2 content of reduced, peridotite melt is significantly higher than that of basaltic melt at shallow magma ocean conditions; however, the difference in C content between the basaltic and peridotitic melts may diminish with depth as the more depolymerized peridotite melt is more compressible. Using our model of CO2 content at graphite saturation as a function of P-T-fO2-melt composition, we predict that a superliquidus shallow magma ocean should degas CO2. Whereas if the increase of fO2 with depth is weak, a magma ocean may ingas a modest amount of carbon during crystallization. Further, using the carbon content of peridotite melt at log ⁡ fO2 of IW and the knowledge of C content of Fe-rich alloy melt, we also consider the core-mantle partitioning of carbon, showing that DCmetal/peridotite of a shallow magma ocean is generally higher than previously estimated.

Petrologic evidence that most ocean islands derive from thermally driven mantle plumes

NASA Astrophysics Data System (ADS)

Putirka, K. D.

2006-12-01

Perhaps the most crucial test of the mantle plume hypothesis concerns whether hot spots are indeed hot. To conduct this test, olivine-liquid equilibria are used to estimate mantle potential temperatures (Tp) for 15 putative plume localities (using the GEOROC database). Ocean islands (OIB) were selected on the availability of rocks that attain olivine control (where olivine addition/removal alone controls rock composition) so that primitive FeO contents could be estimated. Several other variables in addition to FeO must also be known: Except at Iceland and Hawaii, where large numbers of olivine analyses allow individual estimates for the maximum forsterite contents (Fomax) of olivines, a single Fomax value, 91.5, is adopted for all OIB (and MORB; determined from a global database of olivine compositions); as a null hypothesis, MORB-like values for oxygen fugacity (QFM-1; Bezos and Humler, 2005) and the Fe-Mg exchange coefficient between olivine and liquid (0.31; calculated from Toplis, 2005, Herzberg and O'Hara, 1998) are adopted. Generalized differences in water contents between OIB and MORB (Dixon et al., 2002) are also accounted for. All temperatures are calculated at 1 GPa, using averages of existing (Beattie, 1993) and new (Putirka et al., 2006) olivine geothermometers. Except for Galapagos, primitive OIBs have nearly uniform FeO contents that are higher compared to MORB (at MgO>10 wt. %, mean OIB FeOt = 11.6 wt. %). These high FeO contents require higher mean temperatures of olivine-liquid equilibration for OIB, by an average of 150±20°C compared to MORB. Olivine equilibration temperatures do not depend on mantle source composition, so are independent of whether eclogite-type components occur in the mantle. If a peridotite bulk composition is assumed (to estimate melt fraction from partial melting experiments) olivine equilibration temperatures can be converted to Tp; OIB (Galapagos excepted) yield a mean Tp of 1583°C, compared to 1397°C for MORB. When inter- island compositional variation is accounted for, all OIB except Galapagos yield excess temperatures (Tp^{OIB} - Tp^{MORB}) of 133-280°C, with a mean of 186± 36°C. Galapagos lavas yield an excess temperature of 16°C; perhaps mixing has diluted its thermal signal, but in any event, its Tp is essentially identical to MORB. Nevertheless, most OIB (93% in this sample) exhibit large excess temperatures. Thermally driven mantle plumes, as proposed by Morgan (1971), thus appear to be common, not rare. A second implication, less certain than the first, involves the narrow standard deviation of ±36°C for Tp at OIB, which almost certainly reflects a lower limit to actual thermal variability. This narrow range indicates that all hot spots derive from a single thermal boundary layer.

Lithospheric mantle evolution above a subducting plate: Direct constraints from Antarctic Peninsula spinel peridotite xenoliths

NASA Astrophysics Data System (ADS)

Gibson, Lydia; Gibson, Sally; Leat, Phil

2010-05-01

Our understanding of the tectono-magmatic processes in subduction zones generally relies on interpretations of the bulk-rock compositions of associated volcanic rocks. These, however, have typically undergone extensive modification in the crust (fractionation and/or contamination) and interpreting the mantle processes that have contributed to their genesis is complex. Direct evidence of the composition of the mantle beneath subduction-related volcanics is rare as mantle xenoliths are seldom brought to the surface. An exception is the Antarctic Peninsula, which consists of a series of suspect arc terranes accreted to the margin of Gondwana. Subduction occurred along a trench, off the west coast, and lasted over 200 Ma. It finally ceased after a series of ridge-trench collisions, which began at ~50 Ma in the south and ended at ca. 4 Ma in the north. This was followed by extensive alkaline volcanism along the length of the Antarctic Peninsula. At several localities these post-subduction volcanics contain abundant, fresh spinel-bearing lherzolites, harzburgites and pyroxenites. The widest variety of xenoliths were collected from basanites and tephrites emplaced on Alexander Island and Rothschild Island in the accreted Western Domain. The mineral chemistry of the xenolith suite as a whole is highly varied, e.g. olivine ranges in composition from Fo77 to Fo91, but within individual xenoliths typically only limited variation is apparent. Xenolith textures and plots of mineral chemistry suggest that the constituent mineral phases are in equilibrium and can be used to determine pressures and temperatures. PT estimates based on pyroxene compositions indicate that the lithosphere beneath the Antarctic Peninsula has a normal, unperturbed mantle geotherm and a thickness of ~90 km; the base of the mechanical boundary layer is at ~70 km and the xenoliths appear to have been entrained from within this region. Preliminary modelling of incompatible-trace-element ratios of diopsides and augites in the peridotites suggests that they are not all simple residues of mantle melting. They have a wide range of [La/Sm]n ratios (0.01 to 8.56) and appear to have undergone variable degrees of modal metasomatism, which has also resulted in an increase in bulk-rock concentrations of major elements, such as Fe and Al. Variable Ti enrichment in spinels and very-high oxygen fugacities suggest that an extreme range of melt compositions may have interacted with the mantle beneath the Antarctic Peninsula and produced the diverse lithologies that we have observed in the mantle xenolith suite. These include boninites (Mg-rich, hydrous melts) and small-fraction melts. We propose that metasomatic enrichment by silicate melts may have occurred during subduction whereas carbonate metasomatism modified the lithosphere following the formation of a 'window' in the underlying slab.

Oxygen ion-conducting dense ceramic

DOEpatents

Balachandran, Uthamalingam; Kleefisch, Mark S.; Kobylinski, Thaddeus P.; Morissette, Sherry L.; Pei, Shiyou

1996-01-01

Preparation, structure, and properties of mixed metal oxide compositions containing at least strontium, cobalt, iron and oxygen are described. The crystalline mixed metal oxide compositions of this invention have, for example, structure represented by Sr.sub..alpha. (Fe.sub.1-x Co.sub.x).sub..alpha.+.beta. O.sub..delta. where x is a number in a range from 0.01 to about 1, .alpha. is a number in a range from about 1 to about 4, .beta. is a number in a range upward from 0 to about 20, and .delta. is a number which renders the compound charge neutral, and wherein the composition has a non-perovskite structure. Use of the mixed metal oxides in dense ceramic membranes which exhibit oxygen ionic conductivity and selective oxygen separation, are described as well as their use in separation of oxygen from an oxygen-containing gaseous mixture.

Oxygen ion-conducting dense ceramic

DOEpatents

Balachandran, Uthamalingam; Kleefisch, Mark S.; Kobylinski, Thaddeus P.; Morissette, Sherry L.; Pei, Shiyou

1997-01-01

Preparation, structure, and properties of mixed metal oxide compositions containing at least strontium, cobalt, iron and oxygen are described. The crystalline mixed metal oxide compositions of this invention have, for example, structure represented by Sr.sub..alpha. (Fe.sub.1-x Co.sub.x).sub..alpha.+.beta. O.sub..delta. where x is a number in a range from 0.01 to about 1, .alpha. is a number in a range from about 1 to about 4, .beta. is a number in a range upward from 0 to about 20, and .delta. is a number which renders the compound charge neutral, and wherein the composition has a non-perovskite structure. Use of the mixed metal oxides in dense ceramic membranes which exhibit oxygen ionic conductivity and selective oxygen separation, are described as well as their use in separation of oxygen from an oxygen-containing gaseous mixture.

Oxygen sensitive, refractory oxide composition

DOEpatents

Holcombe, Jr., Cressie E.; Smith, Douglas D.

1976-01-01

Oxide compositions containing niobium pentoxide and an oxide selected from the group consisting of hafnia, titania, and zirconia have electrical conductivity characteristics which vary greatly depending on the oxygen content.

Potential of Organic Matrix Composites for Liquid Oxygen Tank

NASA Technical Reports Server (NTRS)

Davis, Samuel E.; Herald, Stephen D.; Stolzfus, Joel M.; Engel, Carl D.; Bohlen, James W.; Palm, Tod; Robinson, Michael J.

2005-01-01

Composite materials are being considered for the tankage of cryogenic propellants in access to space because of potentially lower structural weights. A major hurdle for composites is an inherent concern about the safety of using flammable structural materials in contact with liquid and gaseous oxygen. A hazards analysis approach addresses a series of specific concerns that must be addressed based upon test data. Under the 2nd Generation Reusable Launch Vehicle contracts, testing was begun for a variety of organic matrix composite materials both to aid in the selection of materials and to provide needed test data to support hazards analyses. The work has continued at NASA MSFC and the NASA WSTF to provide information on the potential for using composite materials in oxygen systems. Appropriate methods for oxygen compatibility testing of structural materials and data for a range of composite materials from impact, friction, flammability and electrostatic discharge testing are presented. Remaining concerns and conclusions about composite tank structures, and recommendations for additional testing are discussed. Requirements for system specific hazards analysis are identified.

Oxygen Compatibility Testing of Composite Materials

NASA Technical Reports Server (NTRS)

Graf, Neil A.; Hudgins, Richard J.; McBain, Michael

2000-01-01

The development of polymer composite liquid oxygen LO2 tanks is a critical step in creating the next generation of launch vehicles. Future launch vehicles need to minimize the gross liftoff weight (GLOW), which is possible due to the 25%-40% reduction in weight that composite materials could provide over current aluminum technology. Although a composite LO2 tank makes these weight savings feasible, composite materials have not historically been viewed as "LO2 compatible." To be considered LO2 compatible, materials must be selected that will resist any type of detrimental, combustible reaction when exposed to usage environments. This is traditionally evaluated using a standard set of tests. However, materials that do not pass the standard tests can be shown to be safe for a particular application. This paper documents the approach and results of a joint NASA/Lockheed Martin program to select and verify LO2 compatible composite materials for liquid oxygen fuel tanks. The test approach developed included tests such as mechanical impact, particle impact, puncture, electrostatic discharge, friction, and pyrotechnic shock. These tests showed that composite liquid oxygen tanks are indeed feasible for future launch vehicles.

Fugacity analysis of polycyclic aromatic hydrocarbons between microplastics and seawater

NASA Astrophysics Data System (ADS)

Lee, Hwang; Chang, Sein; Kim, Seung-Kyu; Kwon, Jung-Hwan

2017-03-01

Recently, the accumulation of plastic debris in the marine environment has become a great concern worldwide. Although plastics are biologically and chemically inert, plastic debris has been suspected of causing adverse effects on ecosystems due to the increase in reactivity by size reduction and/or micropollutants associated with plastics. Because of the high sorption capacity of microplastics toward organic micropollutants, it is suspected that microplastics may play roles in the distribution and fate of micropollutants. In order to quantitatively evaluate the "net flow" of environmental contaminants in water-plastic-organism systems, a fugacity analysis was conducted using concentrations of polycyclic aromatic hydrocarbons (PAHs) in open oceans and in polyethylene as a representative material of plastic debris. Ratio of fugacity in polyethylene to that in seawater showed a decreasing trend with increasing partition coefficient between polyethylene and seawater (KPE/sw). This indicates that phase equilibrium between polyethylene and seawater is not attained for higher molecular weight PAHs. Disequilibrium of high molecular weight PAHs suggests that transfer from seawater to plastic debris is thermodynamically driven and the role of plastic debris as a vector to transfer them to living organisms would be minimal. However, additives may slowly migrate from plastics into the environment causing potentially serious effects on ecosystems.

The effect of oxygen-plasma treatment on Kevlar fibers and the properties of Kevlar fibers/bismaleimide composites

NASA Astrophysics Data System (ADS)

Su, Min; Gu, Aijuan; Liang, Guozheng; Yuan, Li

2011-02-01

The effect of oxygen-plasma treatment for Kevlar fibers on the interfacial adhesion and typical macro-properties of Kevlar fiber/bismaleimide composites was intensively studied. It is found that oxygen-plasma treatment significantly affects the interfacial adhesion by changing the chemistry and morphology of the surfaces of the fibers, and thus leading to improved interlaminar shear strength, water resistance and dielectric properties of the composites. However, the improvement is closely related to the treatment power and time. The best condition for treating Kevlar fiber is 70 W for 5 min. Oxygen-plasma treatment provides an effective technique for overcoming the poor interfacial adhesion of Kevlar fiber based composites, and thus showing great potential in fabricating high performance copper clad laminates.

Effects of oxygen plasma treatment power on Aramid fiber III/BMI composite humidity resistance properties

NASA Astrophysics Data System (ADS)

Wang, Jing; Shi, Chen; Feng, Jiayue; Long, Xi; Meng, Lingzhi; Ren, Hang

2018-01-01

The effects of oxygen plasma treatment power on Aramid Fiber III chemical structure and its reinforced bismaleimides (BMI) composite humidity resistance properties were investigated in this work. The aramid fiber III chemical structure under different plasma treatment power were measured by FTIR. The composite bending strength and interlinear shear strength with different plasma treatment power before and after absorption water were tested respectively. The composite rupture morphology was observed by SEM. The FTIR results showed that oxygen plasma treatment do not change the fiber bulk chemical structure. The composite humidity resistance of bending strength and interlinear shear strength are similar for untreated and plasma treated samples. The retention rate of composite bending strength and interlinear shear strength are about 75% and 94%, respectively. The composite rupture mode turns to be the fiber failure after water absorption.

Observation of CO2 in Comet C/2012 K5 LINEAR

NASA Astrophysics Data System (ADS)

McKay, Adam; Kelley, Michael; DiSanti, Michael; Chanover, Nancy

2012-12-01

The study of cometary composition is important to understanding the formation and evolution of our solar system. Comets have undergone very little thermal evolution in their lifetimes, which results in their near pristine composition. The nucleus of a comet is very rarely detected directly. Instead, we observe the coma that surrounds the nucleus. Physical and chemical processes in the coma affect its composition, and therefore coma composition is not a direct representation of nuclear composition. An important trend is the observed variation of coma composition with heliocentric distance, most likely influenced by the volatility of the main surface ices, H2O, CO2, and CO. Infrared studies of these molecules are complicated by telluric features, so often daughter molecules of these species such as OH are observed instead. A potentially effective tracer for these primary ices is atomic oxygen in the coma. However, the relationship between these ices and atomic oxygen is only understood at a qualitative level. We propose to use Spitzer observations in IRAC's 4.5 micron band pass to observe the CO2 v3 band at 4.26 microns in comet C/2012 K5 LINEAR. These observations will be coordinated with observations of atomic oxygen obtained at Apache Point Observatory and observations of H2O at Keck. These near simultaneous observations of H2O, CO2, and atomic oxygen in a cometary coma will increase our understanding of the link between these primary ices and atomic oxygen. With a complete understanding of the relationship between atomic oxygen and the primary ices on the nucleus, observations of atomic oxygen can serve as a powerful proxy for the production of these primary volatiles and aid our understanding of the variation in coma composition as a function of heliocentric distance, and therefore the composition of the nucleus and how our solar system was formed.

Oxidation of SiC/BN/SiC Composites in Reduced Oxygen Partial Pressures

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.; Boyd, Meredith

2010-01-01

SiC fiber-reinforced SiC composites with a BN interphase are proposed for use as leading edge structures of hypersonic vehicles. The durability of these materials under hypersonic flight conditions is therefore of interest. Thermogravimetric analysis was used to characterize the oxidation kinetics of both the constituent fibers and composite coupons at four temperatures: 816, 1149, 1343, and 1538 C (1500, 2100, 2450, and 2800 F) and in oxygen partial pressures between 5% and 0.1% (balance argon) at 1 atm total pressure. One edge of the coupons was ground off so the effects of oxygen ingress into the composite could be monitored by post-test SEM and EDS. Additional characterization of the oxidation products was conducted by XPS and TOF-SIMS. Under most conditions, the BN oxidized rapidly, leading to the formation of borosilicate glass. Rapid initial oxidation followed by volatilization of boria lead to protective oxide formation and further oxidation was slow. At 1538C in 5% oxygen, both the fibers and coupons exhibited borosilicate glass formation and bubbling. At 1538C in 0.1% oxygen, active oxidation of both the fibers and the composites was observed leading to rapid SiC degradation. BN oxidation at 1538C in 0.1% oxygen was not significant.

Inorganic and Organic Carbon, Nutrient, and Oxygen Data from the R/V Ronald H. Brown Repeat Hydrography Cruise in the Atlantic Ocean: CLIVAR CO2 Section A16N_2003a (4 June-11 August, 2003)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kozyr, Alex

2005-08-30

This report presents methods and analytical and quality control procedures for nutrient, oxygen, and inorganic carbon system parameters performed during the A16N_2003a cruise, which took place from June 4 to August 11, 2003 aboard NOAA Ship R/V Ronald H. Brown under auspices of the National Oceanic and Atmospheric Administration (NOAA). The first hydrographic leg (June 19–July 10) was from Reykjavik, Iceland, to Funchal, Madeira, Portugal along the 20°W meridian, and the second leg (July 15–August 11) continued operations from Funchal, Portugal to Natal, Brazil, on a track southward and ending at 6°S, 25°W. The research was the first in amore » decadal series of repeat hydrography sections jointly funded by NOAA and the National Science Foundation (NSF) as part of the CLIVAR/CO 2/hydrography/tracer program. Samples were taken from up to 34 depths at 150 stations. The data presented in this report includes the analyses of water samples for total inorganic carbon (TCO2), fugacity of CO 2 (fCO 2), total alkalinity (TALK), pH, nitrate (NO 3), nitrite (NO 2), phosphate (PO 4), silicate (SiO4), and dissolved oxygen (O 2). The R/V Ronald H. Brown A16N_2003a data set is available free of charge as a numeric data package (NDP) from the Carbon Dioxide Information Analysis Center (CDIAC). The NDP consists of the oceanographic data files and this printed documentation, which describes the procedures and methods used to obtain the data.« less

Geometric and compositional factors on critical current density in YBa2Cu3O7‑δ films containing nanorods

NASA Astrophysics Data System (ADS)

Horide, Tomoya; Nagao, Sho; Izutsu, Ryosuke; Ishimaru, Manabu; Kita, Ryusuke; Matsumoto, Kaname

2018-06-01

Critical current density (J c) was investigated in YBa2Cu3O7‑δ films containing nanorods prepared with various nanorod materials, with variation of nanorod content, substrate temperature, and oxidization condition. Three types of compositional situation were realized: films containing strain induced oxygen vacancies; fully oxidized films containing cation compositional deviation; and oxygen deficient films. Normalized J c‑B behavior was determined via the matching field, which is a geometric factor, regardless of the compositional details. A J c‑critical temperature (T c) relation depending on distribution and fraction of compositional deviation (cation compositional deviation and strain induced oxygen vacancies) was found: the J c values decreased with decreasing T c due to the effect of T c on nanorod pinning strength in the fully oxidized films; J c decreased with decreasing oxygen pressure in the film cooling process after film deposition in spite of T c remaining almost the same, due to reduction of the effective area for current flow in the oxygen deficient films. Thus, a J c landscape based on geometric and compositional factors was obtained. The study highlights the importance of the J c‑T c analysis in the understanding of J c in YBa2Cu3O7‑δ films containing nanorods.

Triple Oxygen Isotope Constraints on Seawater δ18O and Temperature

NASA Astrophysics Data System (ADS)

Hayles, J.; Shen, B.; Homann, M.; Yeung, L.

2017-12-01

One point of contention among geoscientists is whether the 18O/16O ratio of seawater is roughly constant, or if it varies considerably throughout geologic time. On one hand, the oxygen isotope composition of the ocean is thought to be well buffered by high- and low-temperature interactions between seawater and seafloor rocks. If these interactions do not vary on billion-year timescales, the oxygen-isotope compositions of marine sedimentary rocks mostly relate to changes in seawater temperature and global ice volume. On the other hand, long-term cooling of the planetary interior would alter these water-rock interactions leading to a secular change in the oxygen isotope composition of seawater. Models suggest that this secular change would enrich seawater with heavy oxygen isotopes over time. In this study, we present new, high precision, triple-oxygen-isotope (18O/16O, 17O/16O) analyses of marine chert samples from 3.45 Ga to 460Ma. The results of these analyses are paired with a new theoretical quartz-water equilibrium curve and a simplified seawater model to provide possible pairings of δ'18O and Δ'17O for the water which these samples could have formed in equilibrium with. Analysis of the new sample data, in addition to published chert triple oxygen isotope compositions, shows a general trend of older chert samples being progressively incompatible with waters possessing a modern-like seawater triple oxygen isotope composition. Implications on constraining the secular evolution of seawater δ18O and temperature will be discussed.

Macroevolutionary trends of atomic composition and related functional group proportion in eukaryotic and prokaryotic proteins.

PubMed

Zhang, Yu-Juan; Yang, Chun-Lin; Hao, You-Jin; Li, Ying; Chen, Bin; Wen, Jian-Fan

2014-01-25

To fully explore the trends of atomic composition during the macroevolution from prokaryote to eukaryote, five atoms (oxygen, sulfur, nitrogen, carbon, hydrogen) and related functional groups in prokaryotic and eukaryotic proteins were surveyed and compared. Genome-wide analysis showed that eukaryotic proteins have more oxygen, sulfur and nitrogen atoms than prokaryotes do. Clusters of Orthologous Groups (COG) analysis revealed that oxygen, sulfur, carbon and hydrogen frequencies are higher in eukaryotic proteins than in their prokaryotic orthologs. Furthermore, functional group analysis demonstrated that eukaryotic proteins tend to have higher proportions of sulfhydryl, hydroxyl and acylamino, but lower of sulfide and carboxyl. Taken together, an apparent trend of increase was observed for oxygen and sulfur atoms in the macroevolution; the variation of oxygen and sulfur compositions and their related functional groups in macroevolution made eukaryotic proteins carry more useful functional groups. These results will be helpful for better understanding the functional significances of atomic composition evolution. Copyright © 2013 Elsevier B.V. All rights reserved.

The Derivation Of A CO2 Fugacity Climatology From SOCAT's Global In SITU Data

NASA Astrophysics Data System (ADS)

Goddijn-Murphy, L. M.; Woolf, D. K.; Land, P. E.; Shutler, J. D.

2013-12-01

The Surface Ocean CO2 Atlas (SOCAT) has made millions of global underway sea surface measurements of CO2 publicly available, all in a uniform format and presented as fugacity, fCO2. However, these fCO2 values are valid strictly only for the instantaneous temperature at measurement and are not ideal for climatology. We recomputed these fCO2 values for the measurement month to be applicable to climatological sea surface temperatures, extrapolated to reference year 2010. The data were then spatially interpolated on a 1°×1° grid of the global oceans to produce 12 monthly fCO2 distributions. Our climatology data will be shared with the science community.

The Fortuna gold skarn, Nambija district, Ecuador - A mineralogical and fluid inclusion study

NASA Astrophysics Data System (ADS)

Markowski, A.; Fontboté, L.; Chiaradia, M.

2003-04-01

La Fortuna gold skarn is located in the nothern part of the Nambija gold district, southern Ecuador. As other Nambija deposits (Meinert, 2000) it is an oxidized-calcic gold skarn. The skarn has developed on volcanic rocks belonging to the Triassic Piunza Formation and nearby undated felsic intrusions. Main skarn bodies and Au concentrations occur near major N40°-60°faults. Garnet is the dominant phase at the Fortuna skarn, which displays two types according to garnet color and composition: a brown massive garnet (Ad99-37) skarn and a green garnet (Ad55-13) skarn. Garnets are strongly zoned and compositions out of these ranges exist too. Additionally, the correlation between color and composition is not always clear. Some honey-reddish garnet (Ad97.0-99.5) nodules up to a few centimeters in size occur both within the brown and the green garnet skarns. Because of its position typically at the borders of open space fillings, this garnet is interpreted to reflect the composition of the fluid. Pyroxene is present as a minor phase except in the northern part of the concession and around the presently mined site ("mina 2") where pyroxene and pyroxene-garnet skarns are recognized, respectively. Compositions range from Hd42Di47Jo11 to Hd17Di63Jo20. Increases in Mn (2.5-6 wt%) and, less pronounced, in Fe (7-11 wt%) are recognized from the presently mined site to 1 km to the north. Pyroxene occurs mainly as small subidiomorphic grains, which in part appear to replace garnet (mainly the green variety). In the northern part of the mine, epidote (Epi9.8-17.7) occurs as the main phase, and is a retrograde product of garnet. The small amount of amphibole present at Fortuna is attributed to the original scarcity of pyroxene of which amphibole is the typical retrograde product. Chlorite is also an abundant phase, mainly nearby faults, and reveals variable compositions with a F/FM ranging from 0.87 to 0.38. As pyroxene, chlorite shows an enrichement in Mn (up to 4 wt.%) to the north. Other retrograde minerals are K-feldspar, plagioclase, quartz and calcite. These minerals, together with epidote and chlorite, occur mainly within cm-wide veins (N40E-N60E) and irregular open spaces. Thinner calcite veinlets do not show preferential orientation. Native gold (Ag content: 5.9 to 14.6 wt%, traces of Cu and Hg) occurs with calcite and quartz within garnet fractures or between mineral joints. Hematite seems to appear more frequently than pyrite when gold is present and could indicate a high oxygen fugacity during gold deposition. Quartz inclusions have homogenization temperatures between 350°C and 200°C, low salinities (1.2-6.0 wt% NaCl eq.), and variable liquid/vapor ratios.

Effect of oxygen concentration in ZDP containing oils on surface composition and wear

NASA Technical Reports Server (NTRS)

Brainard, W. A.; Ferrante, J.

1983-01-01

A pin-on-disk wear study was performed with the lubricants dibutyl sebacate (DBS) and mineral oil (MO) with and without 1 weight percent zinc-dialkyl-dithiophospatee (ZDP) as an additive. The pin was annealed pure iron and the disk was M-2 tool steel. The selected load and speed guaranteed boundary lubrication. The ambient atmospheric oxygen concentration in an oxygen-nitrogen mixture was varied from 0 percent to 20 percent in order to examine its relationship to ZDP effectiveness. Auger electron spectroscopy combined with argon ion bombardment (depth profiling) was used to determine surface elemental composition on the pin when tested in DBS with and without ZDP. The ambient atmosphere was found to cause large variations in wear rate and surface composition. With MO, ZDP reduced wear under all conditions, but had little advantage over oxides formed at 20 percent oxygen atmosphere. With DBS, ZDP reduced wear at 0 percent oxygen, but gave varied results at other oxygen concentrations. Depth profiling revealed sulfuide formation at 0 percent oxygen and probably sulfates at 20 percent oxygen. The results are significant because varied oxygen concentrations can occur under actual lubricating conditions in practical machinery.

Triple oxygen isotope composition of photosynthetic oxygen

NASA Astrophysics Data System (ADS)

van der Meer, Anne; Kaiser, Jan

2013-04-01

The measurement of biological production rates is essential for our understanding how marine ecosystems are sustained and how much CO2 is taken up through aquatic photosynthesis. Traditional techniques to measure marine production are laborious and subject to systematic errors. A biogeochemical approach based on triple oxygen isotope measurements in dissolved oxygen (O2) has been developed over the last few years, which allows the derivation of gross productivity integrated over the depth of the mixed layer and the time-scale of O2 gas exchange (Luz and Barkan, 2000). This approach exploits the relative 17O/16O and 18O/16O isotope ratio differences of dissolved O2 compared to atmospheric O2 to work out the rate of biological production. Two parameters are key for this calculation: the isotopic composition of dissolved O2 in equilibrium with air and the isotopic composition of photosynthetic oxygen. Recently, a controversy has emerged in the literature over these parameters (Kaiser, 2011) and one of the goals of this research is to provide additional data to resolve this controversy. In order to obtain more information on the isotopic signature of biological oxygen, laboratory experiments have been conducted to determine the isotopic composition of oxygen produced by different phytoplankton cultures.

Electrocatalytic performances of g-C3N4-LaNiO3 composite as bi-functional catalysts for lithium-oxygen batteries

PubMed Central

Wu, Yixin; Wang, Taohuan; Zhang, Yidie; Xin, Sen; He, Xiaojun; Zhang, Dawei; Shui, Jianglan

2016-01-01

A low cost and non-precious metal composite material g-C3N4-LaNiO3 (CNL) was synthesized as a bifunctional electrocatalyst for the air electrode of lithium-oxygen (Li-O2) batteries. The composition strategy changed the electron structure of LaNiO3 and g-C3N4, ensures high Ni3+/Ni2+ ratio and more absorbed hydroxyl on the surface of CNL that can promote the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The composite catalyst presents higher activities than the individual components g-C3N4 and LaNiO3 for both ORR and OER. In non-aqueous Li-O2 batteries, CNL shows higher capacity, lower overpotentials and better cycling stability than XC-72 carbon and LaNiO3 catalysts. Our results suggest that CNL composite is a promising cathode catalyst for Li-O2 batteries. PMID:27074882

Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

NASA Astrophysics Data System (ADS)

Nielson, Kristine E.; Bowen, Gabriel J.

2010-03-01

Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

Isotopic Composition of Oxygen in Lunar Zircons

NASA Technical Reports Server (NTRS)

Nemchin, A. A.; Whitehouse, M. J.; Pidgeon, R. T.; Meyer, C.

2005-01-01

The recent discovery of heavy oxygen in zircons from the Jack Hills conglomerates Wilde et al. and Mojzsis et al. was interpreted as an indication of presence of liquid water on the surface of Early Earth. The distribution of ages of Jack Hills zircons and lunar zircons appears to be very similar and therefore analysis of oxygen in the lunar grains may provide a reference frame for further study of the early history of the Earth as well as give additional information regarding processes that operated on the Moon. In the present study we have analysed the oxygen isotopic composition of zircon grains from three lunar samples using the Swedish Museum of Natural History CAMECA 1270 ion microprobe. The samples were selected as likely tests for variations in lunar oxygen isotopic composition. Additional information is included in the original extended abstract.

Liquid oxygen-compatible filament-winding matrix resin

NASA Technical Reports Server (NTRS)

Harrison, E. S.

1973-01-01

Polyurethanes derived from hydroxy terminated polyperfluoro propylene oxide prepolymers were evaluated as matrix resins for filament wound composites which would be exposed to liquid (and 100% gaseous) oxygen environments. A number of structural modifications were brought about by variations in prepolymer molecular weight, and alternative curing agents which allowed retention of the oxygen compatibility. Although satisfactory performance was achieved at sub-ambient temperatures, the derived composites suffered considerable property loss at ambient or slightly elevated temperatures. To attain overall effectiveness of the composite system, upgrading of the polymer thermomechanical properties must first be achieved.

Mesoporous nitrogen-doped carbon-glass ceramic cathodes for solid-state lithium-oxygen batteries.

PubMed

Kichambare, Padmakar; Rodrigues, Stanley; Kumar, Jitendra

2012-01-01

The composite of nitrogen-doped carbon (N-C) blend with lithium aluminum germanium phosphate (LAGP) was studied as cathode material in a solid-state lithium-oxygen cell. Composite electrodes exhibit high electrochemical activity toward oxygen reduction. Compared to the cell capacity of N-C blend cathode, N-C/LAGP composite cathode exhibits six times higher discharge cell capacity. A significant enhancement in cell capacity is attributed to higher electrocatalytic activity and fast lithium ion conduction ability of LAGP in the cathode. © 2011 American Chemical Society

Proximate composition and lipid stability of dourado (Salminus brasilensis, Cuvier, 1817) fillets exposed to different levels of ammonia and oxygen in vivo.

PubMed

Veeck, Ana Paula L; Garcia, Luciano O; Baldisserotto, Bernardo; Zaniboni Filho, Evoy; Emanuelli, Tatiana

2013-08-15

The ammonia and oxygen levels of water are physicochemical parameters that affect fish physiology. Thus, we hypothesized that in vivo exposure to stressful ammonia and oxygen levels will affect the post-mortem quality of the fish. Therefore, in this study, the effects of in vivo exposure to stressful ammonia and oxygen levels on the composition and content of thiobarbituric acid reactive substances in fillets from dourado (Salminus brasiliensis) and on the lipid oxidation of these fillets during frozen storage were evaluated. Short-term exposure (12 h) to stressful environmental conditions (low oxygen and high ammonia levels) did not change the composition of the flesh. However, longer exposure (15 days) to these stressful conditions caused significant changes in the composition of the flesh. Exposure to a stressful ammonia level before slaughtering increased the susceptibility of the fish fillets to lipid oxidation during frozen storage. In contrast, exposure to low oxygen levels did not increase the lipid oxidation rate of the fillets. These results indicate that the in vivo exposure to high ammonia levels may reduce the quality and stability of dourado fillets. © 2013 Society of Chemical Industry.

Assessment of oceanic productivity with the triple-isotope composition of dissolved oxygen.

PubMed

Luz, B; Barkan, E

2000-06-16

Plant production in the sea is a primary mechanism of global oxygen formation and carbon fixation. For this reason, and also because the ocean is a major sink for fossil fuel carbon dioxide, much attention has been given to estimating marine primary production. Here, we describe an approach for estimating production of photosynthetic oxygen, based on the isotopic composition of dissolved oxygen of seawater. This method allows the estimation of integrated oceanic productivity on a time scale of weeks.

Surface pressure measurement by oxygen quenching of luminescence

NASA Technical Reports Server (NTRS)

Gouterman, Martin P. (Inventor); Kavandi, Janet L. (Inventor); Gallery, Jean (Inventor); Callis, James B. (Inventor)

1993-01-01

Methods and compositions for measuring the pressure of an oxygen-containing gas on an aerodynamic surface, by oxygen-quenching of luminescence of molecular sensors is disclosed. Objects are coated with luminescent films containing a first sensor and at least one of two additional sensors, each of the sensors having luminescences that have different dependencies on temperature and oxygen pressure. Methods and compositions are also provided for improving pressure measurements (qualitative or quantitive) on surfaces coated with a film having one or more types of sensor.

Surface pressure measurement by oxygen quenching of luminescence

NASA Technical Reports Server (NTRS)

Gouterman, Martin P. (Inventor); Kavandi, Janet L. (Inventor); Gallery, Jean (Inventor); Callis, James B. (Inventor)

1994-01-01

Methods and compositions for measuring the pressure of an oxygen-containing gas on an aerodynamic surface, by oxygen-quenching of luminescence of molecular sensors is disclosed. Objects are coated with luminescent films containing a first sensor and at least one of two additional sensors, each of the sensors having luminescences that have different dependencies on temperature and oxygen pressure. Methods and compositions are also provided for improving pressure measurements (qualitative or quantitive) on surfaces coated with a film having one or more types of sensor.

Solubility of oxygen in CdS single crystals and their physicochemical properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morozova, N. K., E-mail: MorozovaNK@mail.ru; Kanakhin, A. A.; Shnitnikov, A. S.

2016-07-15

The specific features of oxygen dissolution in CdS using the example of single crystals grown by the gas-transport method with deviations from stoichiometry at 1100°C are considered. The effect of various types of intrinsic point defects in crystals of different composition on the form in the presence of oxygen is analyzed. It is shown that the most stable composition thermodynamically is that corresponding to nonstoichiometric “self-activated cadmium sulphide” stabilized with oxygen.

Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

DOEpatents

Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

2010-07-20

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

Paleoclimate Reconstruction at Lamanai, Belize Using Oxygen-Isotope Tropical Dendrochronology

NASA Astrophysics Data System (ADS)

Prentice, A.; Webb, E. A.; White, C. D.; Graham, E.

2009-05-01

Tropical dendrochronology can be complicated because many trees growing in these areas lack distinct visible annual rings. However, the oxygen-isotope composition of wood growing in tropical regions can provide a record of seasonal fluctuations in the amount of precipitation even when visible rings are absent. Variations in the oxygen-isotope compositions of cellulose as the trees grow can be related to the relative timing of wet and dry seasons and used to identify periods of drought. In this study, the oxygen-isotope composition was determined for cellulose extracted from living trees at the site of Lamanai, Belize to assess the variation in oxygen-isotope values that result from heterogeneity within individual tree rings and seasonal fluctuations in amount of precipitation. In temperate regions, the latewood rings that form during periods of reduced growth are traditionally selected for oxygen-isotope analysis of cellulose because their oxygen-isotope compositions are more directly influenced by climate and precipitation during the growing season. However, in tropical isotope dendrochronology, when visible rings are present, detailed sampling of both the light coloured earlywood and the denser latewood is required. At Lamanai, a seasonal signal was evident in the oxygen- isotope composition of the cellulose when tree rings were sectioned in very small increments (approximately every mm), sub-sampling both earlywood and latewood. However, the visible rings did not always correspond with minimum or maximum oxygen-isotope values. As a result, the amplitude of the oxygen-isotope signal obtained by considering only latewood samples is smaller than that obtained from fine-increment sampling. Hence, the oxygen-isotope values of latewood samples alone did not provide accurate data for climate reconstruction. Multiple series of latewood samples extracted from different cross-sections of the same tree did not consistently show the same trends in oxygen isotope values, which can differ by up to 2 permil around the circumference of the same ring. This indicates that even when visible rings are present in tropical trees, the rings may not be annual or continuous. However, the amplitude of variation in the oxygen-isotope values of cellulose from both early and latewood can be related to seasonal signals across the modern tree rings. These signals will be compared to the oxygen-isotope composition of tree ring cellulose extracted from a wood sample excavated from an ancient tomb at the site of Lamanai to assess the preservation of the cellulose- isotope signal in this artefact. If similar oxygen-isotope patterns are preserved in ancient cellulose they can be used as a proxy to determine past climate conditions, such as those experienced by the ancient Maya populations in Belize.

Local structural variation with oxygen fugacity in Fe 2SiO 4+x fayalitic iron silicate melts

DOE PAGES

Alderman, O.L.G.; Lazareva, L.; Wilding, M. C.; ...

2017-01-07

Here, the structure of molten Fe 2SiO 4+x has been studied using both high-energy X-ray diffraction and Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy, combined with aerodynamic levitation and laser beam heating. A wide range of Fe 3+ contents were accessed by varying the levitation and atmospheric gas composition. Diffraction measurements were made in the temperature ( T) and oxygen partial pressure ranges 1624(21) < T < 2183(94) K (uncertainties in parentheses) and –5.6(3) < ΔFMQ < +2.8(5) log units (relative to the Fayalite-Magnetite-Quartz buffer). Iron K-edge XANES measurements covered the ranges 1557(33) < T < 1994(36) K andmore » –2.1(3) < ΔFMQ < +4.4(3) log units. Fe 3+ contents, x = Fe 3+/ΣFe, estimated directly from the pre-edge peaks of the XANES spectra varied between 0.15(1) and 0.40(2). While these agree in some cases with semi-empirical models, notable discrepancies are discussed in the context of the redox kinetics and the limitations in both the models and in the calibrations used to derive oxidation state from XANES spectra. XANES pre-edge peak areas imply average Fe–O coordination numbers, n FeO, close to 5 for all Fe 3+/ΣFe. Diffraction measurements yielded values of 4.4(2) < n FeO < 4.7(1). There is limited evidence for a linear trend n FeO(x) = 4.46(3) + 0.4(1)x. Asymmetric Fe–O bond length distributions peak at around 1.96 Å and have a shoulder arising from longer interatomic distances. Mean r FeO lie close to 2.06 Å, consistent with n FeO close to 5. These observations suggest that Fe 2+ is less efficient at stabilizing tetrahedral Fe 3+ compared to large monovalent alkali cations. Comparison of in-situ XANES estimates of Fe 3+/ΣFe in the melts to those of the quenched solids obtained from XANES as well as Mössbauer spectroscopy indicate rapid oxidation during cooling, enabled by stirring of the melt by the levitation gas flow. As such, the oxidation state of hot komatiitic and other highly fluid melts may not be retained, even during rapid cooling, as it is for cooler basaltic and more silicic magmas.« less

Local structural variation with oxygen fugacity in Fe2SiO4+x fayalitic iron silicate melts

NASA Astrophysics Data System (ADS)

Alderman, O. L. G.; Lazareva, L.; Wilding, M. C.; Benmore, C. J.; Heald, S. M.; Johnson, C. E.; Johnson, J. A.; Hah, H.-Y.; Sendelbach, S.; Tamalonis, A.; Skinner, L. B.; Parise, J. B.; Weber, J. K. R.

2017-04-01

The structure of molten Fe2SiO4+x has been studied using both high-energy X-ray diffraction and Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy, combined with aerodynamic levitation and laser beam heating. A wide range of Fe3+ contents were accessed by varying the levitation and atmospheric gas composition. Diffraction measurements were made in the temperature (T) and oxygen partial pressure ranges 1624(21) < T < 2183(94) K (uncertainties in parentheses) and -5.6(3) < ΔFMQ < +2.8(5) log units (relative to the Fayalite-Magnetite-Quartz buffer). Iron K-edge XANES measurements covered the ranges 1557(33) < T < 1994(36) K and -2.1(3) < ΔFMQ < +4.4(3) log units. Fe3+ contents, x = Fe3+/ΣFe, estimated directly from the pre-edge peaks of the XANES spectra varied between 0.15(1) and 0.40(2). While these agree in some cases with semi-empirical models, notable discrepancies are discussed in the context of the redox kinetics and the limitations in both the models and in the calibrations used to derive oxidation state from XANES spectra. XANES pre-edge peak areas imply average Fe-O coordination numbers, nFeO, close to 5 for all Fe3+/ΣFe. Diffraction measurements yielded values of 4.4(2) < nFeO < 4.7(1). There is limited evidence for a linear trend nFeO(x) = 4.46(3) + 0.4(1)x. Asymmetric Fe-O bond length distributions peak at around 1.96 Å and have a shoulder arising from longer interatomic distances. Mean rFeO lie close to 2.06 Å, consistent with nFeO close to 5. These observations suggest that Fe2+ is less efficient at stabilizing tetrahedral Fe3+ compared to large monovalent alkali cations. Comparison of in-situ XANES estimates of Fe3+/ΣFe in the melts to those of the quenched solids obtained from XANES as well as Mössbauer spectroscopy indicate rapid oxidation during cooling, enabled by stirring of the melt by the levitation gas flow. As such, the oxidation state of hot komatiitic and other highly fluid melts may not be retained, even during rapid cooling, as it is for cooler basaltic and more silicic magmas.

Evaluation of atomic oxygen resistant protective coatings for fiberglass-epoxy composites in LEO

NASA Technical Reports Server (NTRS)

Rutledge, Sharon K.; Paulsen, Phillip E.; Brady, Joyce A.

1989-01-01

Fiberglass-epoxy composite masts are the prime structural members for the Space Station Freedom solar array. At the altitude where Space Station Freedom will operate, atomic oxygen atoms are the most predominant species. Atomic oxygen is highly reactive and has been shown to oxidize organic and some metallic materials. Tests with random and directed atomic oxygen exposure have shown that the epoxy is removed from the composite exposing brittle glass fibers which could be easily removed from the surface where they could contaminate Space Station Freedom Systems. Protection or fiber containment systems; inorganic based paints, aluminum braid, and a metal coating; were evaluated for resistance to atomic oxygen, vacuum ultraviolet radiation, thermal cycling, and mechanical flexing. All appeared to protect well against atomic oxygen and provide fiber containment except for the single aluminum braid covering. UV radiation resistance was acceptable and in general, thermal cycling and flexure had little to no effect on the mass loss rate for most coatings.

Detailed Investigation of Separation Performance of a MMM for Removal of Higher Hydrocarbons under Varying Operating Conditions

PubMed Central

Mushardt, Heike; Müller, Marcus; Shishatskiy, Sergey; Wind, Jan; Brinkmann, Torsten

2016-01-01

Mixed-matrix membranes (MMMs) are promising candidates to improve the competitiveness of membrane technology against energy-intensive conventional technologies. In this work, MMM composed of poly(octylmethylsiloxane) (POMS) and activated carbon (AC) were investigated with respect to separation of higher hydrocarbons (C3+) from permanent gas streams. Membranes were prepared as thin film composite membranes on a technical scale and characterized via scanning electron microscopy (SEM) and permeation measurements with binary mixtures of n-C4H10/CH4 under varying operating conditions (feed and permeate pressure, temperature, feed gas composition) to study the influence on separation performance. SEM showed good contact and absence of defects. Lower permeances but higher selectivities were found for MMM compared to pure POMS membrane. Best results were obtained at high average fugacity and activity of n-C4H10 with the highest selectivity estimated to be 36.4 at n-C4H10 permeance of 12 mN3/(m2·h·bar). Results were complemented by permeation of a multi-component mixture resembling a natural gas application, demonstrating the superior performance of MMM. PMID:26927194

The impact of surface composition on Tafel kinetics leading to enhanced electrochemical insertion of hydrogen in palladium

NASA Astrophysics Data System (ADS)

Dmitriyeva, Olga; Hamm, Steven C.; Knies, David L.; Cantwell, Richard; McConnell, Matt

2018-05-01

Our previous work experimentally demonstrated the enhancement of electrochemical hydrogen insertion into palladium by modifying the chemical composition of the cathode surface with Pb, Pt and Bi, referred to as surface promoters. The experiment demonstrated that an optimal combination of the surface promoters led to an increase in hydrogen fugacity of more than three orders of magnitude, while maintaining the same current density. This manuscript discusses the application of Density Functional Theory (DFT) to elucidate the thermodynamics and kinetics of observed enhancement of electrochemical hydrogen insertion into palladium. We present theoretical simulations that: (1) establish the elevation of hydrogen's chemical potential on Pb and Bi surfaces to enhance hydrogen insertion, (2) confirm the increase of a Tafel activation barrier that results in a decrease of the reaction rate at the given hydrogen overpotential, and (3) explain why the surface promoter's coverage needs to be non-uniform, namely to allow hydrogen insertion into palladium bulk while simultaneously locking hydrogen below the surface (the corking effect). The discussed DFT-based method can be used for efficient scanning of different material configurations to design a highly effective hydrogen storage system.

Gasoline Composition Regulations Affecting LUST Sites

EPA Science Inventory

Passage of the Clean Air Act Amendments in 1990 imposed requirements on gasoline composition in the United States. Impacts to ground water are affected by the provisions that required oxygenated additives and limited benzene concentration. Reformulated and oxygenated gasoline w...

[Effects of oxygenated fuels on emissions and carbon composition of fine particles from diesel engine].

PubMed

Shi, Xiao-Yan; He, Ke-Bin; Zhang, Jie; Ge, Yun-Shan; Tan, Jian-Wei

2009-06-15

Acetal (1,1-diethoxyethane) is considered as an alternative to ethanol as bio-derived additive for diesel fuel, which is miscible in diesel fuel. Biodiesel can improve the oxygen content and flash point of the fuel blend of acetal and diesel fuel. Two oxygenated fuels were prepared: a blend of 10% acetal + 90% diesel fuel and 10% acetal + 10% biodiesel + 80% diesel fuel. The emissions of NO(x), HC and PM2.5 from oxygenated fuels were investigated on a diesel engine bench at five modes according to various loads at two steady speeds and compared with base diesel fuel. Additionally, the carbon compositions of PM2.5 were analyzed by DRI thermal/optical carbon analyzer. Oxygenated fuels have unconspicuous effect on NO(x) emission rate but HC emission rate is observed significantly increased at some modes. The emission rate of PM2.5 is decreased by using oxygenated fuels and it decreases with the increase of fuel oxygen content. The emission rates of TC (total carbon) and EC (elemental carbon) in PM2.5 are also decreased by oxygenated fuels. The emission rate of organic carbon (OC) is greatly decreased at modes of higher engine speed. The OC/EC ratios of PM2.5 from oxygenated fuels are higher than that from base diesel fuel at most modes. The carbon compositions fractions of PM2.5 from the three test fuels are similar, and OC1 and EC1 are contributed to the most fractions of OC and EC, respectively. Compared with base diesel fuel, oxygenated fuels decrease emission rate of PM2.5, and have more OC contribution to PM2.5 but have little effect on carbon composition fractions.

Variations in the Infrared Spectra of Wüstite with Defects and Disorder

NASA Astrophysics Data System (ADS)

Koike, C.; Matsuno, J.; Chihara, H.

2017-08-01

The presence of FeO particles in circumstellar space has been suggested based on the observation of a mysterious 21 μm emission band. However, the complete infrared spectra of FeO have not been obtained so far; hence, data of the infrared (IR) spectra of FeO need to be investigated. We prepared synthetic and commercial samples of FeO, which were obtained by crushing bulk samples, annealing iron oxalate dihydrate ({{FeC}}2{{{O}}}4\\cdot 2{{{H}}}2{{O}}), and mechanical milling of a powder mixture comprising (Fe and {{Fe}}2{{{O}}}3) particles with different milling times. We present a new study on the IR spectra of these samples, and show that these spectra changed according to defects and disorders. Furthermore, FeO particles are very sensitive to oxygen fugacity and temperature. The spectra of FeO particles were compared with the unidentified observed feature. It may be difficult for FeO particles to exist alone in the ISM and circumstellar space. This may be connected to the problem of missing iron in the ISM.

Diamond formation due to a pH drop during fluid–rock interactions

DOE PAGES

Sverjensky, Dimitri A.; Huang, Fang

2015-11-03

Diamond formation has typically been attributed to redox reactions during precipitation from fluids or magmas. Either the oxidation of methane or the reduction of carbon dioxide has been suggested, based on simplistic models of deep fluids consisting of mixtures of dissolved neutral gas molecules without consideration of aqueous ions. The role of pH changes associated with water–silicate rock interactions during diamond formation is unknown. Here we show that diamonds could form due to a drop in pH during water–rock interactions. We use a recent theoretical model of deep fluids that includes ions, to show that fluid can react irreversibly withmore » eclogite at 900 °C and 5.0 GPa, generating diamond and secondary minerals due to a decrease in pH at almost constant oxygen fugacity. Overall, our results constitute a new quantitative theory of diamond formation as a consequence of the reaction of deep fluids with the rock types that they encounter during migration. Diamond can form in the deep Earth during water–rock interactions without changes in oxidation state.« less

Diamond formation due to a pH drop during fluid–rock interactions

PubMed Central

Sverjensky, Dimitri A.; Huang, Fang

2015-01-01

Diamond formation has typically been attributed to redox reactions during precipitation from fluids or magmas. Either the oxidation of methane or the reduction of carbon dioxide has been suggested, based on simplistic models of deep fluids consisting of mixtures of dissolved neutral gas molecules without consideration of aqueous ions. The role of pH changes associated with water–silicate rock interactions during diamond formation is unknown. Here we show that diamonds could form due to a drop in pH during water–rock interactions. We use a recent theoretical model of deep fluids that includes ions, to show that fluid can react irreversibly with eclogite at 900 °C and 5.0 GPa, generating diamond and secondary minerals due to a decrease in pH at almost constant oxygen fugacity. Overall, our results constitute a new quantitative theory of diamond formation as a consequence of the reaction of deep fluids with the rock types that they encounter during migration. Diamond can form in the deep Earth during water–rock interactions without changes in oxidation state. PMID:26529259

Crystal Field Effects and Siderophile Element Partitioning: Implications for Mars HSE Geochemistry

NASA Technical Reports Server (NTRS)

Jones, John H.; Malavergne, V.; Neal, C. R.

2007-01-01

Analyses of martian (SNC) meteorites indicate that Pt abundances do not vary much compared to other highly siderophile elements (HSE). Therefore, Jones et al. [1] inferred that D(Pt) during basalt petrogenesis was of order unity. This inference was at odds with previously published experiments that gave a D(sub ol/liq) for Pt of approx. 0.01 [2]. Because olivine is likely to be an important constituent of any reasonable martian mantle, the implication of these findings is that minor minerals must have D(Pt) much greater than 1, which seemed improbable. However, not only did the SNC evidence point to a D(sub ol/liq) approx. equal to 1, but so did plots of D(sub ol/liq) vs. ionic radius (Onuma diagram). The ionic radius of Pt(2+) suggested that D(sub ol/liq) for Pt was of order unity, in agreement with the inferences from SNC meteorites. New experiments have failed to detect measurable Pt in olivine, even at high oxygen fugacities [3]. Therefore, some other parameter, other than ionic charge and radius, must hold sway during olivine liquid partitioning of Pt.

Evolution of phenolic compounds and astringency during aging of red wine: effect of oxygen exposure before and after bottling.

PubMed

Gambuti, Angelita; Rinaldi, Alessandra; Ugliano, Maurizio; Moio, Luigi

2013-02-27

The aim of this study was to evaluate the effect of oxygen exposure of red wine, before (micro-oxygenation) and after (nano-oxygenation) bottling, on the phenolic composition and astringency of wine. The astringency was evaluated by sensory analysis and by a method based on the SDS-PAGE of salivary proteins after reaction of saliva with wine (SPI, saliva precipitation index). Micro-oxygenation caused a stabilization of color, but this effect disappeared after long aging. For the wine with the lower pH a decrease of wine astringency and SPI was observed 42 months after micro-oxygenation. Oxygen ingress through the closure postbottling was positively correlated with the decrease of SPI. Therefore, the astringency and reactivity of wines toward salivary proteins of a bottled red wine can be modulated by controlled oxygen exposure during aging. For both experiments the effect of oxygen exposure depended on wine composition.

The effects of a CO2-bearing fluid on the rheology of quartz-bearing rocks in subduction zones

NASA Astrophysics Data System (ADS)

Ashley, K. T.; Behr, W. M.

2017-12-01

The weakening effect of water on quartz rheology has been a well-recognized phenomenon for several decades. In many tectonic environments, however, the fluid phase is not pure H2O, but commonly includes other species such as CO2, dissolved silicates, and/or salts. CO2 is especially prevalent in subduction zone fluids due to subduction of carbonates and/or graphitic sediments. Some deformation experiments as well as natural observations suggest that CO2 can affect rheology and development of anisotropy in quartz-rich rocks, but the precise effects of CO2 are poorly understood. Here we take a petrologic approach to assess the role of a mixed H2O-CO2 fluid phase for deforming quartzite in the viscous regime. For quartz dislocation creep, CO2 in the fluid acts as a non-wetting phase, resulting in the reduction of water fugacity. However, for most rocks, the activity-composition (a-X) relationship of a H2O-CO2 fluid phase requires very high CO2 mole fractions to have a significant effect on strain rate. For XCO2 = 0.5 at 500°C, with a differential stress of 10 MPa, the water fugacity is only reduced by 30% and resultant strain rates are slowed by less than a factor of 3 — much less than the inherent uncertainty of the flow law. In contrast, because silica does not form complexes with CO2, its solubility greatly decreases at high carbonic fractions and pressure solution is greatly slowed. For most diagenetic conditions, a 50:50 H2O-CO2 fluid phase compared to a pure-H2O fluid phase results in a strain rate that is an order of magnitude slower. Higher carbonic fractions has dramatic effects on the rate of pressure solution (decreased by >3 orders of magnitude at XCO2 = 0.8). The difference in the response of quartz deformation mechanisms to changes in the fluid composition suggests CO2-rich fluids could result in the suppression of pressure solution and the activation of dislocation creep (or brittle failure) at lower temperatures than expected for a pure H2O fluid.

V/Sc in olivine as a proxy for magma redox conditions

NASA Astrophysics Data System (ADS)

Locmelis, M.; Arevalo, R. D., Jr.; Puchtel, I. S.; Fiorentini, M. L.

2017-12-01

Although olivine is the most abundant mineral in the upper mantle and a major constituent of most mantle-derived rocks, studies on its trace element chemistry are underrepresented. This is especially the case for komatiites, an ultramafic, olivine-dominated rock type that formed via high degrees of partial melting (up to 50%) of the mantle. Komatiites were mostly emplaced in the Archean and therefore provide a unique perspective on the composition and evolution of the early Earth's mantle. Here, we present the V/Sc compositions of olivines from a global set of Paleo- (3.5-3.3 Ga) and Neo-Archean (2.7 Ga) komatiites analyzed via laser ablation ICP-MS. Vanadium and Sc behave similar during partial melting, but V is redox-sensitive (V2+-V5+) and most compatible in olivine as V2+. Scandium is monovalent (Sc3+) and its compatibility in olivine is not affected by the oxygen fugacity (fO2) of the komatiite lava. Therefore, V/Sc ratios in olivines are potentially indicative of the fO2 of the magma they crystallized from. Our data show that V/Sc ratios measured in Neo-Archean olivines (V/Scmean = 1.0 ± 0.1; 2σm) are significantly lower than in their Paleo-Archean counterparts (V/Scmean = 2.1 ± 0.1; 2σm). Geochemical models show that the elevated V/Sc ratios captured by the Paleo-Archean olivines reflect crystallization from magmas that were 1.6 log units (relative to QFM) more reduced than their Neo-Archean counterparts, and thus contained a higher proportion of V2+. Because assimilation of sedimentary bedrocks can alter the composition of komatiites upon emplacement, it may be argued that the redox states recorded by the olivines do not reflect mantle fO2, but the assimilation of crustal material. However, such an effect is not visible in our data as V/Sc ratios in olivines from localities that show evidence of crustal assimilation do not differ from komatiites that did not assimilate significant amounts of crustal rocks. Rather than a crustal signature, the V/Sc ratios suggest a secular increase of fO2 in the Archean mantle of potentially as much as 1.6 log units (relative to QFM) between 3.5-3.3 Ga and 2.7 Ga. These results are intriguing because an increase of only 0.5 log units in mantle fO2 has previously been identified as a sufficient kick-starter for the 2.4 Ga Great Oxidation Event.

Chapter 13 Petrogenesis of the Campanian Ignimbrite: implications for crystal-melt separation and open-system processes from major and trace elements and Th isotopic data

USGS Publications Warehouse

Bohrson, W.A.; Spera, F.J.; Fowler, S.J.; Belkin, H.E.; de Vivo, B.; Rolandi, G.

2006-01-01

The Campanian Ignimbrite is a large-volume trachytic to phonolitic ignimbrite that was deposited at ???39.3 ka and represents one of a number of highly explosive volcanic events that have occurred in the region near Naples, Italy. Thermodynamic modeling using the MELTS algorithm reveals that major element variations are dominated by crystal-liquid separation at 0.15 GPa. Initial dissolved H2O content in the parental melt is ???3 wt.% and the magmatic system fugacity of oxygen was buffered along QFM+1. Significantly, MELTS results also indicate that the liquid line of descent is marked by a large change in the proportion of melt (from 0.46 to 0.09) at ???884??C, which leads to a discontinuity in melt composition (i.e., a compositional gap) and different thermodynamic and transport properties of melt and magma across the gap. Crystallization of alkali feldspar and plagioclase dominates the phase assemblage at this pseudo-invariant point temperature of ???884??C. Evaluation of the variations in the trace elements Zr, Nb, Th, U, Rb, Sm, and Sr using a mass balance equation that accounts for changing bulk mineral-melt partition coefficients as crystallization occurs indicates that crystal-liquid separation and open-system processes were important. Th isotope data yield an apparent isochron that is ???20 kyr younger than the age of the deposit, and age-corrected Th isotope data indicate that the magma body was an open system at the time of eruption. Because open-system behavior can profoundly change isotopic and elemental characteristics of a magma body, these Th results illustrate that it is critical to understand the contribution that open-system processes make to magmatic systems prior to assigning relevance to age or timescale information derived from such systems. Fluid-magma interaction has been proposed as a mechanism to change isotopic and elemental characteristics of magma bodies, but an evaluation of the mass and thermal constraints on such a process suggests large-scale interaction is unlikely. In the case of the magma body associated with the Campanian Ignimbrite, the most likely source of the open-system signatures is assimilation of partial melts of compositionally heterogeneous basement composed of cumulates and intrusive equivalents of volcanic activity that has characterized the Campanian region for over 300 kyr. ?? 2006 Elsevier B.V. All rights reserved.

Potential Temperatures of Sources of MORB, OIB and LIPs Based on AL Partitioning Between Olivine and Spinel

NASA Astrophysics Data System (ADS)

Sobolev, A. V.; Batanova, V. G.; Krasheninnikov, S.; Borisov, A.; Arndt, N.; Kuzmin, D.; Krivolutskaya, N.; Sushevskaya, N.

2013-12-01

Knowledge of potential temperatures of convecting mantle is required for the understanding the global processes on the Earth [1]. The common way to estimate these is the reconstruction of primary melt compositions and liquidus temperatures based on the Fe-Mg partitioning between olivine and melt. This approach requires knowledge of the compositions of primitive melts in equilibrium with olivine alone as well as composition of olivine equilibrium with primary melts. This information is in most cases unavailable or of questionable quality. Here we report a new approach to obtain crystallization temperatures of primary melts based on the olivine-spinel Al-Cr geothermometer [2]. The advantages of this approach are: (1) low rate of diffusion of Al in the olivine, which promises to preserve high magmatic temperatures and (2) common presence of spinel in assemblage with high-Mg olivine. In order to decipher influence of elevated Ti concentrations in spinel we have run several experiments at high temperatures (1400-1200 degree C), atmospheric pressure and controled oxygen fugacity. We also analysed over two thousand spinel inclusions and high-Mg host olivines from different MORB, OIB, LIP and Archean komatiites on the JXA-8230 EPMA at ISTerre, Grenoble, France. Concentrations of Al, Ti, Na, P, Zn, Cr, Mn, Ca, Co, Ni were determined with a precision of 10 ppm (2 standard errors) using a newly developed protocol [3]. When available, we also analysed matrix glass and glass inclusions in olivine and found that temperature estimations from olivine-spinel (Al-Cr) and olivine-melt (Fe-Mg) [4] equilibrium match within (+/-30 degree C). The results show contrasting crystallization temperatures of Mg-rich olivine of the same Fo content from different types of mantle-derived magmas, from the lowest (down to 1220 degree C) for MORB to the highest (up to 1550 degree C) for komatiites and Siberian meimechites. These results match predictions from Fe-Mg olivine-melt equilibrium and confirm the relatively low temperature of the convecting mantle source of MORB and higher temperatures in the mantle plumes that produce the OIB of Iceland, Hawaii, Gorgona, Archean komatiites and several LIPs (e.g. Siberian, Decan). [1] McKenzie & Bickle, 1988, J. Petr. 29, p 625-679. [2] Wan et al, 2008, Am. Min. 93, p1142-1147. [3] Batanova & Sobolev, 2013, Min. Mag.,p 667, DOI :10.1180/minmag2013.077.5.2 [4] Ford et al, 1983, J. Petr. 24, p 256-265.

Oxidation-state dependence of rheology in peralkaline glasses of phonolitic composition

NASA Astrophysics Data System (ADS)

Scherrer, M. C.; Hess, K.-U.; Fehr, K. T.; Dingwell, D. B.

2012-04-01

The precise description of magmatic melts rheology at the glass transition is crucial in understanding dynamic processes in volcanology. The glass transition has been described to scale with the viscosity of the material according to Maxwell's relaxation theory for viscoelastic liquids (Dingwell and Webb, 1989). The temperature dependence of the viscosity of multi-component systems can adequately be calculated using empirical models such as Hess et al. (1996), Giordano et al. (2008) and Hui and Zhang (2008); yet, within these calculations, the influence of oxidation state has been so far considered minor and was consequently neglected. The rheological behavior of some iron-rich silicate melts has shown noteworthy oxidation state-dependent variations (Cukierman and Uhlmann 1974, Dingwell and Virgo 1987). The focus of our study is to improve the viscosity models by investigating the necessity of an additional redox-parameter. Thirteen re-melted glass samples of natural phonolitic composition (peralkaline lavas with 8.5 wt. % FeOtot) were produced under different oxygen fugacity (fO2) conditions in a CO/CO2 gas-mixing furnace. Their oxidation-state (Fe3+/Fetot) ranges from 0.44 to 0.93 (±0.05). The viscosity above the liquidus was recorded via the concentric cylinder technique at a constant temperature of 1186 ° C. Additionally, viscosities were measured in the interval of 107to 1011Pa swith temperatures up to 900 ° C at ambient pressure via a BAEHR micro-penetration viscometer. Glass transition temperatures (Tg) have been determined with a constant heating/cooling rate of 10K/min on a SETARAM Sensys evo DSC using the peak of the specific heat capacity curve. Under a constant temperature in the super-liquidus state, the viscosity increases strongly with increasing fO2. In the sub-liquidus state, the measured calorimetric Tgis shifted to lower temperatures as the ratio of ferrous/total iron decreases from 638 ° C to 610 ° C. However, there is no equivalent measurable effect of the oxidation-state on super-cooled melt viscosity at Tg, within the precision of the micro-penetration experiment (all values are scattered around 10.10 ± 0.2 Pa s). Our results show a large discrepancy of 0.5 log units compared to the predicted viscosity at Tg using the kinetic model of Gottsmann et al. (2002). We further investigate additional relatively iron-rich compositions aiming for the development of an improved model for the viscosity prediction at the glass transition.

Extended HFSE systematics of Apollo samples - wrenching further Secrets from the Lunar Mantle

NASA Astrophysics Data System (ADS)

Thiemens, M. M.; Sprung, P.; Munker, C.

2016-12-01

As Earth's intimate companion, the Moon provides a close extraterrestrial view on planetary differentiation. In turn, investigating chemical and isotopic compositions of lunar rocks for traces of a putative crystallizing Lunar Magma Ocean (LMO) provides a better understanding of the evolution and differentiation of infant planetary bodies.We expand on high-precision extended High Field Strength Element (HFSE) observations of Münker [1]. In detail, we investigate if the HFSE systematics of low- and high- Ti basalts, KREEPy basalts and breccias, soils, and ferroan anorthosites (FAN) are consistent with their formation from the LMO (FAN, KREEP) or mantle sources comprising mixtures of primary LMO products [2] (mare basalts). Of particular interest is the recently discovered dependence of HFSE partitioning on the Ti-concentration of co-existing melts [3] and that of W partitioning on oxygen fugacity [3,4].Our data form a positively correlated array in Zr/Hf vs. Nb/Ta space, similar to previous high-precision [1] but unlike lower-precision data. The HFSE systematics of different rock types from the Apollo missions mostly form distinct groups. High-Ti and some Apollo 12 low-Ti mare basalts form the lower end of the array, KREEPy samples its upper end. Low Zr/Nb in most high-Ti mare basalts and the globally highest Hf/W confirm involvement of Ti-rich-oxide-bearing cumulates in high-Ti formation [e.g., 1,2]. No global lunar trends exist for Hf/W vs. Zr/Nb. Overall, the composition of KREEPy samples agrees reasonably well with model KREEP-compositions assuming a LMO below IW-1 [1,4].Clearly distinct groupings observed for the various rock types and the lack of a global trend in Hf/W vs. Zr/Nb calls for melting of distinct ultramafic sources [1]. The HFSE systematics of Apollo rocks tend to support a LMO scenario, setting the stage for more detailed petrogenetic modeling. Initial modeling suggests that the lunar mantle must possess residual metal to reconcile the HFSE systematics of Apollo rocks within an LMO-scenario, providing an alternative explanation for the very low abundances of HSE in the lunar crust [5].[1] Münker, C. (2010) GCA 74, 7340-7361. [2] Snyder et al. (1992) GCA 56, 3809-3823. [3] Leitzke et al. (in press) Chem. Geol. [4] Fonseca et al. (2014) EPSL 404, 1-13. [5] Day & Walker (2015) EPSL 423, 114-124

Variations in Fe and S redox states in ocean island basalts

NASA Astrophysics Data System (ADS)

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

2016-12-01

The chemical and isotopic compositions of ocean island basalts (OIB) suggest that their mantle sources contain imprints of subducted sediments, altered oceanic crust, undegassed mantle, and/or residues of continental crust formation. By comparing the oxygen fugacities (fO2) of OIBs to the extent to which they contain these imprints, it may be possible to relate specific compositions to spatial and temporal variations in source fO2. To explore this, we present µ-XANES measurements of the oxidation states of Fe and S from pillow glass and olivine-hosted melt inclusions from the Reykjanes Ridge, Mauna Kea, Kilauea, Loihi, Hawaiian South Arch, Reunion Island, and the Ontong Java Plateau; we then compare these measurements with previous determinations of the chemical and isotopic compositions of these OIBs. Reykjanes Ridge and Ontong Java glasses have Fe and S redox states that are similar to MORBs; although these glasses show evidence for assimilation of seawater or crustal components, there is no relationship between indices of assimilation (18O/16O, Cl) and Fe or S redox states. This indicates that assimilation in these settings does not have a major effect on magmatic fO2. Mauna Kea and Kilauea glasses affected by S+H2O degassing have decreased Fe and S redox states, but the least degassed samples from both volcanoes are similar to each other and more oxidized than MORB, Reykjanes Ridge, and Ontong Java glasses. Loihi and South Arch glasses have not lost significant S and H2O to degassing, and they record fO2s similar to the least degassed Mauna Kea and Kilauea glasses. Olivine-hosted melt inclusions from Reunion range in Fe redox from similar to MORBs to more oxidized than Hawaiian volcanoes. These data demonstrate that OIBs are heterogeneous in Fe and S redox states. Although more data are needed for the various OIB end members, with the exception of the two most reduced glasses from Reunion, the data thus far suggest a rough positive correlation between 87Sr/86Sr ratios and Fe and S redox states. If this correlation holds up, it would be consistent with EMI and/or EMII end members having fO2s more oxidized than the upper mantle sources of MORBs, perhaps because these end members contain subducted sediments and/or oceanic crust that were previously oxidized during exposure to the H2O- and O2-rich conditions at Earth's surface.

The Role of Carbon in Core Formation Under Highly Reducing Conditions With Implications for the Planet Mercury

NASA Technical Reports Server (NTRS)

Vander Kaaden, Kathleen E..; McCubbin, Francis M.; Ross, D. Kent; Draper, David S.

2017-01-01

Results from the MErcury Surface, Space ENvironment, GEochemistry and Ranging (MESSENGER) spacecraft have shown elevated abundances of carbon on the surface of Mercury. Furthermore, the X-Ray Spectrometer on board MESSENGER measured elevated abundances of sulfur and low abundances of iron, suggesting the planet's oxygen fugacity (fO2) is several log10 units below the Iron-Wüstite (IW) buffer. Similar to the role of other volatiles (e.g. sulfur) on highly reducing planetary bodies, carbon is expected to behave differently than it would under higher fO2. As discussed by Nittler et al. and Hauck et al., under such highly reducing conditions, the majority of the iron partitions into the core. On Mercury, this resulted in a relatively large core and a thin mantle. Using a composition similar to the largest volcanic field on the planet (the northern volcanic plains), Vander Kaaden and McCubbin conducted sink-float experiments to determine the density of melts and minerals on Mercury. They showed that graphite would be the only buoyant mineral in a mercurian magma ocean. Therefore, Vander Kaaden and McCubbin proposed a possible primary flotation crust on the planet composed of graphite. Concurrently, Peplowski et al. used GRS data from MESSENGER to show an average northern hemisphere abundance of C on the planet of 1.4 +/- 0.9 wt%. However, as this result was only at the one-sigma detection limit, possible carbon abundances at the three-sigma detection limit for Mercury range from 0 to 4.1 wt% carbon. Additionally, Murchie et al. investigated the possible darkening agent on Mercury and concluded that coarse-grained graphite could darken high reflectance plains to the low reflectance material. To further test the possibility of elevated abundances of carbon in Mercury's crust, Peplowski et al. used the low-altitude MESSENGER data to show that carbon is the only material consistent with both the visible to near-infrared spectra and the neutron measurements of low reflectance material on Mercury, confirming that C is the primary darkening agent on Mercury. Confirmation of carbon on the planet prompts many questions regarding the role of carbon during the differentiation and evolution of Mercury. Given the elevated abundances of both S and C on Mercury's surface, it begs the question, what is the core composition of the planet? This study seeks to understand the impact of C as a light element on potential core compositions on Mercury.