Andesites from northeastern Kanaga Island, Aleutians

NASA Astrophysics Data System (ADS)

Brophy, James G.

1990-04-01

Kanaga island is located in the central Aleutian island arc. Northeastern Kanaga is a currently active late Tertiary to Recent calc-alkaline volcanic complex. Basaltic andesite to andesite lavas record three episodes (series) of volcanic activity. Series I and Series II lavas are all andesite while Series III lavas are basaltic andesite to andesite. Four Series II andesites contain abundant quenched magmatic inclusions ranging in composition from high-MgO low-alumina basalt to low-MgO highalumina basalt. The spectrum of lava compositions is due primarily to fractional crystallization of a parental low-MgO high-alumina basalt but with variable degrees of crustal contamination and magma mixing. The earliest Series I lavas represent mixing between high-alumina basalt and silicic andesite with maximum SiO2 contents of 65 67 wt %. Later Series I and all Series II lavas are due to mixing of andesite magmas of similar composition. The maximum SiO2 content of the pre-mixed andesites magmas is estimated at 60 63 wt %. The youngest lavas (Series III) are all non-mixed and have maximum estimated SiO2 contents of 59 wt %. The earliest Series I lavas contain a significant crustal component while all later lavas do not. It is concluded that the maximum SiO2 contents of silicic magmas, the contribution of crustal material to silicic magma generation, and the role of magma mixing all decrease with time. Furthermore, silicic magmas generated by fractional crystallization at this volcanic center have a maximum SiO2 content of 63 wt %. All of these features have also been documented at the central Aleutian Cold Bay Volcanic Center (Brophy 1987). Based on data from these two centers a model of Aleutian calc-alkaline magma chamber development is proposed. The main features are: (1) a single low pressure magma chamber is continuously supplied by primitive low-alumina basalt; (2) non-primary high-alumina basalt is formed along the chamber margins by selective gravitational settling of olivine and clinopyroxene and retention of plagioclase; (3) sidewall crystallization accompanied by crustal melting produces buoyant silicic (>63 wt % SiO2) liquids that pond at the top of the chamber, and; (4) continued sidewall crystallization, now isolated from the chamber wall, produces silicic liquids with ≤63 wt % SiO2 that increase the thickness and lowers the overall SiO2 content of the upper silicic zone. It is suggested that the maximum SiO2 content of 63% imposed on fractionation-generated magmas is due to a rheological barrier that prohibits the extraction of more silicic liquids from a crystal-liquid mush along the chamber wall.

Galactic Hearts of Glass

NASA Technical Reports Server (NTRS)

2006-01-01

[figure removed for brevity, see original site] Click on image for larger graph

This artist's concept shows delicate greenish crystals sprinkled throughout the violent core of a pair of colliding galaxies. The white spots represent a thriving population of stars of all sizes and ages. NASA's Spitzer Space Telescope detected more than 20 bright and dusty galactic mergers like the one depicted here, all teeming with the tiny gem-like crystals.

When galaxies collide, they trigger the birth of large numbers of massive stars. Astronomers believe these blazing hot stars act like furnaces to produce silicate crystals in the same way that glass is made from sand. The stars probably shed the crystals as they age, and as they blow apart in supernovae explosions.

At the same time the crystals are being churned out, they are also being destroyed. Fast-moving particles from supernova blasts easily convert silicates crystals back to their amorphous, or shapeless, form.

How is Spitzer seeing the crystals if they are rapidly disappearing? Astronomers say that, for a short period of time at the beginning of galactic mergers, massive stars might be producing silicate crystals faster than they are eliminating them. When our own galaxy merges with the Andromeda galaxy in a few billion years, a similar burst of massive stars and silicate crystals might occur.

Crystal Storm in Distant Galaxy The graph (see inset above) of infrared data from NASA's Spitzer Space Telescope tells astronomers that a distant galaxy called IRAS 08752+3915 is experiencing a storm of tiny crystals made up of silicates. The crystals are similar to the glass-like grains of sand found on Earth's many beaches.

The data were taken by Spitzer's infrared spectrograph, which splits light open to reveal its rainbow-like components. The resulting spectrum shown here reveals the signatures of both crystalline (green) and non-crystalline (brown) silicates.

Spitzer detected the same crystals in 20 additional galaxies, all belonging to a class called ultraluminous infrared galaxies. These extremely bright and dusty galaxies usually consist of two galaxies in the process of smashing into each other. Astronomers believe massive stars at the hearts of the galaxies are churning out clouds of silicate crystals. This phenomenon may represent a short-lived phase in the evolution of galactic mergers.

Silicate Crystal Formation in the Disk of an Erupting Star Artist Concept

NASA Image and Video Library

2009-05-13

This artist's concept illustrates how silicate crystals like those found in comets can be created by an outburst from a growing star. The image shows a young sun-like star encircled by its planet-forming disk of gas and dust. The silicate that makes up most of the dust would have begun as non-crystallized, amorphous particles. Streams of material are seen spiraling from the disk onto the star increasing its mass and causing the star to brighten and heat up dramatically. The outburst causes temperatures to rise in the star's surrounding disk. The animation (figure 1) zooms into the disk to show close-ups of silicate particles. When the disk warms from the star's outburst, the amorphous particles of silicate melt. As they cool off, they transform into forsterite (figure 2), a type of silicate crystal often found in comets in our solar system. In April 2008, NASA's Spitzer Space Telescope detected evidence of this process taking place on the disk of a young sun-like star called EX Lupi. http://photojournal.jpl.nasa.gov/catalog/PIA12008

Kinetic D/H fractionation during hydration and dehydration of silicate glasses, melts and nominally anhydrous minerals

NASA Astrophysics Data System (ADS)

Roskosz, M.; Deloule, E.; Ingrin, J.; Depecker, C.; Laporte, D.; Merkel, S.; Remusat, L.; Leroux, H.

2018-07-01

The distribution of hydrogen isotopes during diffusion-driven aqueous processes in silicate glasses, melts and crystals was investigated. Hydration/dehydration experiments were performed on silica glasses at 1000 °C and 1 bar total pressure. Dehydration triggered by decompression-driven bubble nucleation and growth was performed on rhyolitic melts at 800 °C and a few hundred MPa. Hydrogen extraction from a nominally anhydrous mineral (grossular) single crystal was carried out at 800 °C and ambient pressure. After these three series of experiments, pronounced water (sensu lato) concentration profiles were observed in all recovered samples. In the grossular single-crystal, a large spatial variation in H isotopes (δD variation > 550‰) was measured across the sample. This isotopic distribution correlates with the hydrogen extraction profile. The fit to the data suggests an extreme decoupling between hydrogen and deuterium diffusion coefficients (DH and DD respectively), akin to the decoupling expected in a dilute ideal gas (DH/DD ≈ 1.41). Conversely, no measurable spatially- and time-resolved isotopic variations were measured in silicate glasses and melts. This contrasted behavior of hydrogen isotopes likely stands in the different water speciation and solution mechanisms in the three different materials. Glasses and melts contain essentially hydroxyl and molecular water groups but the mobile species is molecular water in both cases. Protonated defects make up most of the water accommodated in grossular and other nominally anhydrous minerals (NAM). These defects are also the mobile species that diffuse against polarons. These results are crucial to accurately model the degassing behavior of terrestrial and lunar magmas and to derive the initial D/H of water trapped in fluid inclusions commonly analyzed in mantle NAMs, which suffered complex geological histories.

Variation in Pockels constants of silicate glass-ceramics prepared by perfect surface crystallization

NASA Astrophysics Data System (ADS)

Takano, Kazuya; Takahashi, Yoshihiro; Miyazaki, Takamichi; Terakado, Nobuaki; Fujiwara, Takumi

2018-01-01

We investigated the Pockels effect in polycrystalline materials consisting of highly oriented polar fresnoite-type Sr2TiSi2O8 fabricated using perfectly surface-crystallized glass-ceramics (PSC-GCs). The chemical composition of the precursor glass was shown to significantly affect the crystallized texture, e.g., the crystal orientation and appearance of amorphous nanoparasites in the domains, resulting in variations in the Pockels constants. Single crystals exhibiting spontaneous polarization possessed large structural anisotropy, leading to a strong dependence of the nonlinear-optical properties on the direction of polarized light. This study suggests that variations in the Pockels constants (r13 and r33) and tuning of the r13/r33 ratio can be realized in PSC-GC materials.

High chloride content calcium silicate glasses.

PubMed

Chen, Xiaojing; Karpukhina, Natalia; Brauer, Delia S; Hill, Robert G

2017-03-08

Chloride is known to volatilize from silicate glass melts and until now, only a limited number of studies on oxychloride silicate glasses have been reported. In this paper we have synthesized silicate glasses that retain large amounts of CaCl 2 . The CaCl 2 has been added to the calcium metasilicate composition (CaO·SiO 2 ). Glasses were produced via a melt quench route and an average of 70% of the chloride was retained after melting. Up to 31.6 mol% CaCl 2 has been successfully incorporated into these silicate glasses without the occurrence of crystallization. 29 Si MAS-NMR spectra showed the silicon being present mainly as a Q 2 silicate species. This suggests that chloride formed Cl-Ca(n) species, rather than Si-Cl bonds. Upon increasing the CaCl 2 content, the T g reduced markedly from 782 °C to 370 °C. Glass density and glass crystallization temperature decreased linearly with an increase in the CaCl 2 content. However, both linear regressions revealed a breakpoint at a CaCl 2 content just below 20 mol%. This might be attributed to a significant change in the structure and is also correlated with the nature of the crystallizing phases formed upon heat treatment. The glasses with less than 19.2 mol% CaCl 2 crystallized to wollastonite, whilst the compositions with CaCl 2 content equal to or greater than 19.2 mol% are thought to crystallize to CaCl 2 . In practice, the crystallization of CaCl 2 could not occur until the crystallization temperature fell below the melting point of CaCl 2 . The implications of the results along with the high chloride retention are discussed.

Chinese Journal of Lasers (Selected Articles),

DTIC Science & Technology

1986-04-22

properties We first investigated silicate based glasses, then the other inorganic glasses such as borate, phosphate, germanate. tellurate ...of the growth of high melting temperature I.~ oxides, several upward pulling single crystal furnaces with nigh precision mechanical movement and high...automatic electronic weighting systems, and programmable automatic movement correction systems. The reliability of most of these control systems

Dynamic observations of vesiculation reveal the role of silicate crystals in bubble nucleation and growth in andesitic magmas

NASA Astrophysics Data System (ADS)

Pleše, P.; Higgins, M. D.; Mancini, L.; Lanzafame, G.; Brun, F.; Fife, J. L.; Casselman, J.; Baker, D. R.

2018-01-01

Bubble nucleation and growth control the explosivity of volcanic eruptions, and the kinetics of these processes are generally determined from examinations of natural samples and quenched experimental run products. These samples, however, only provide a view of the final state, from which the initial conditions of a time-evolving magmatic system are then inferred. The interpretations that follow are inexact due to the inability of determining the exact conditions of nucleation and the potential detachment of bubbles from their nucleation sites, an uncertainty that can obscure their nucleation location - either homogeneously within the melt or heterogeneously at the interface between crystals and melts. We present results of a series of dynamic, real-time 4D X-ray tomographic microscopy experiments where we observed the development of bubbles in crystal bearing silicate magmas. Experimentally synthesized andesitic glasses with 0.25-0.5 wt% H2O and seed silicate crystals were heated at 1 atm to induce bubble nucleation and track bubble growth and movement. In contrast to previous studies on natural and experimentally produced samples, we found that bubbles readily nucleated on plagioclase and clinopyroxene crystals, that their contact angle changes during growth and that they can grow to sizes many times that of the silicate on whose surface they originated. The rapid heterogeneous nucleation of bubbles at low degrees of supersaturation in the presence of silicate crystals demonstrates that silicates can affect when vesiculation ensues, influencing subsequent permeability development and effusive vs. explosive transition in volcanic eruptions.

Preparations of PbSe quantum dots in silicate glasses by a melt-annealing technique

NASA Astrophysics Data System (ADS)

Ma, D. W.; Cheng, C.; Zhang, Y. N.; Xu, Z. S.

2014-11-01

Silicate glass containing PbSe quantum dots (QDs) has important prospective applications in near infra-red optoelectronic devices. In this study, single-stage and double-stage heat-treatment methods were used respectively to prepare PbSe QDs in silicate glasses. Investigation results show that the double-stage heat-treatment is a favorable method to synthesize PbSe QDs with strong photoluminescence (PL) intensity and narrow full weight at half maximum (FWHM) in PL peak. Therefore, the method to prepare PbSe QDs was emphasized on the double-stage heat-treatment. Transmission electron microscopy measurements show that the standard deviations of the average QD sizes from the samples heat-treated at the development temperature of 550 °C fluctuate slightly in the range of 0.6-0.8 nm, while this deviation increases up to 1.2 nm for the sample with the development temperature of 600 °C. In addition, the linear relationship between the QD size and holding time indicates that the crystallization behavior of PbSe QDs in silicate glasses is interface-controlled growth in early stage of crystallization. The growth rates of PbSe QDs are determined to be 0.24 nm/h at 550 °C and 0.72 nm/h at 600 °C. In short, the double-stage heat-treatment at 450 °C for 20 h followed by heat-treatment at 550 °C for 5 h is a preferred process for the crystallization of PbSe QDs in silicate glass. Through this treatment, PbSe QDs with a narrow size dispersion of 5.0 ± 0.6 nm can be obtained, the PL peak from this sample is highest in intensity and narrowest in FWHM among all samples, and the peak is centered on 1575 nm, very close to the most common wavelength of 1550 nm in fiber-optic communication systems.

Predicting the Sources and Formation Mechanisms of Evolved Lunar Crust by Linking K/Ca Ratios of Lunar Granites to Analogous Terrestrial Igneous Rocks

NASA Technical Reports Server (NTRS)

Mills, R. D.; Simon, J. I.

2012-01-01

Although silicic rocks (i.e. granites and rhyolites) comprise a minor component of the sampled portion of the lunar crust, recent remote sensing studies [e.g., 1-4] indicate that several un-sampled regions of the Moon have significantly higher concentrations of silicic material (also high in [K], [U], and [Th]) than sampled regions. Within these areas are morphological features that are best explained by the existence of chemically evolved volcanic rocks. Observations of silicic domes [e.g., 1-5] suggest that sizable networks of silicic melt were present during crust formation. Isotopic data indicate that silicic melts were generated over a prolonged timespan from 4.3 to 3.9 Ga [e.g., 6-8]. The protracted age range and broad distribution of silicic rocks on the Moon indicate that their petrogenesis was an important mechanism for secondary crust formation. Understanding the origin and evolution of such silicic magmas is critical to determining the composition of the lunar crustal highlands and will help to distinguish between opposing ideas for the Moon's bulk composition and differentiation. The two main hypotheses for generating silicic melts on Earth are fractional crystallization or partial melting. On the Moon silicic melts are thought to have been generated during extreme fractional crystallization involving end-stage silicate liquid immiscibility (SLI) [e.g. 9, 10]. However, SLI cannot account for the production of significant volumes of silicic melt and its wide distribution, as reported by the remote global surveys [1, 2, 3]. In addition, experimental and natural products of SLI show that U and Th, which are abundant in the lunar granites and seen in the remote sensing data of the domes, are preferentially partitioned into the depolymerized ferrobasaltic magma and not the silicic portion [11, 12]. If SLI is not the mechanism that generated silicic magmas on the Moon then alternative processes such as fractional crystallization (only crystal-liquid separation) or partial melting should be considered as viable possibilities to be tested.

The influence of oxalate-promoted growth of saponite and talc crystals

USGS Publications Warehouse

Schumann, Dirk; Hartman, Hyman; Eberl, Dennis D.; Sears, S. Kelly; Hesse, Reinhard; Vali, Hojatollah

2013-01-01

The intercalating growth of new silicate layers or metal hydroxide layers in the interlayer space of other clay minerals is known from various mixed-layer clay minerals such as illite-smectite (I-S), chlorite-vermiculite, and mica-vermiculite. In a recent study, the present authors proposed that smectite-group minerals can be synthesized from solution as new 2:1 silicate layers within the low-charge interlayers of rectorite. That study showed how oxalate catalyzes the crystallization of saponite from a silicate gel at low temperatures (60ºC) and ambient pressure. As an extension of this work the aim of the present study was to test the claim that new 2:1 silicate layers can be synthesized as new intercalating layers in the low-charge interlayers of rectorite and whether oxalate could promote such an intercalation synthesis. Two experiments were conducted at 60ºC and atmospheric pressure. First, disodium oxalate solution was added to a suspension of rectorite in order to investigate the effects that oxalate anions have on the structure of rectorite. In a second experiment, silicate gel of saponitic composition (calculated interlayer charge −0.33 eq/O10(OH)2) was mixed with a suspension of rectorite and incubated in disodium oxalate solution. The synthesis products were extracted after 3 months and analyzed by X-ray diffraction and high-resolution transmission electron microscopy (HRTEM). The treatment of ultrathin sections with octadecylammonium (nC = 18) cations revealed the presence of 2:1 layer silicates with different interlayer charges that grew from the silicate gel. The oxalate-promoted nucleation of saponite and talc crystallites on the rectorite led to the alteration and ultimately to the destruction of the rectorite structure. The change was documented in HRTEM lattice-fringe images. The crystallization of new 2:1 layer silicates also occurred within the expandable interlayers of rectorite but not as new 2:1 silicate layers parallel to the previous 2:1 silicate layers. Instead, they grew independently of any orientation predetermined by the rectorite crystal substrate and their crystallization was responsible for the destruction of the rectorite structure.

Sol-Gel Synthesis and Crystallization of Magnesium and Calcium Rich Silicate Dust Analogs

NASA Astrophysics Data System (ADS)

Gillot, J.; Roskosz, M.; Depecker, C.; Roussel, P.; Leroux, H.

2009-03-01

A new sol-gel method optimized to synthesize amorphous and porous silicate dust analogs is proposed. The crystallization of such analogs is metastable and polyphasic. Their high reactivity is probably due to high surface/volume ratio.

Abundant Cool Magnesium-Rich Pyroxene Crystals in Comet Hale-Bopp

NASA Technical Reports Server (NTRS)

Wooden, D. H.

1999-01-01

Modeling of the observed dust emission from Comet Hale-Bopp over a large range of heliocentric distances (2.8 AU - 0.93 AU -1.7 AU) led to the discovery of Mg-rich pyroxene crystals in the coma These pyroxene crystals are apparent in the 10 micron spectrum only when the comet is close to perihelion (r(sub h) = 1.2 AU) because they are cooler than the other silicate minerals. The pyroxene crystals are cooler than the other species because of their high Mg-content. They do not absorb as efficiently as the other silicate minerals. Given the same high Mg content of Mg/(Mg + Fe) = 0.9, radiative equilibrium computations show that pyroxene crystals are expected to be 150 K cooler than olivine crystals. The pyroxene crystals are also about 10x more abundant than the other silicate mineral species. Their high Mg content and relatively large abundance are in agreement with the preponderance of pyroxene interplanetary dust particles (IDPs) and the recent reanalysis of the PUMA-I flyby of Comet Halley. Before Hale-Bopp, only olivine crystals were detected spectroscopically in comets, probably because the pyroxene crystals are less optically active, hence significantly cooler and harder to detect in contrast to the warmer silicate species. Determining the relative abundances of silicate minerals depends on their Mg contents. If the pyroxene crystals in Comet Hale-Bopp are solar nebula condensates, then they probably had to form during the early FU Orionis epoch when the inner disk was hot enough and be transported out to the region of formation of icy planetesimals without being reheated. Reheating events appear to reincorporate Fe back into the crystals or form Fe-rich rims, which are not consistent with the high-Mg-content crystals. The condensation of Mg-rich pyroxene crystals is expected from solar nebula thermal equilibrium computations. However, their subsequent transport to the outer solar nebula unaltered has yet to be theoretically demonstrated. The discovery of Mg-rich crystals in Comet Hale-Bopp and in AGB stars opens the possibility that these crystals are relic interstellar grains. One-third of IDPs have been shown to have significant deuterium enrichments, thus indicating that they contain presolar material. By spectroscopic analogy to IDPs the Mg-rich pyroxene crystals in Comet Hale-Bopp may be presolar grains. If so, then the comet contains largely ISM silicates. ISM grains may have been the dominant source of dust in the outer early solar nebula.

The Beta Pictoris Phenomenon in Young Stars With Accreting Gas

NASA Technical Reports Server (NTRS)

Grady, Carol A.

1999-01-01

Program Hae2BPIC resulted in usable ISO spectra of three young, Herbig Ae stars: HR 5999 (A7e, t=0.6 Myr), SV Cep (al-2e, t=1-3 Myr), and MW Vul (Al-2e, t=1-3 Myr). While too small a sample to pursue our original goal of surveying the silicate emission in these young, protoplanetary disk systems, comparison of these data with ground-based IR spectra, and published ISO observations of other HAe stars (especially the posters at PPIV) reveals the following: The known binary stars in the sample show signatures of partially crystal line silicate features by t=0.6 Myr, at an epoch when ostensibly single Herbig Ae stars have substantially stronger silicate emission dominated by amorphous grains. The known binary stars also show deficits in the optically thick continuum flux relative to coeval single stars. Comparison of ISO spectra indicates that the flux deficit seen in WD 163296 over 10-100 microns relative to AB Aur reflects a real deficit of material interior to 300.

The crystalline revolution :ISO's finding opens a new research field, "astro-mineralogy"

NASA Astrophysics Data System (ADS)

2000-02-01

Silicate minerals were known to be a main component of dust in space, but detecting them in a crystallised state has been a surprise. It allows the identification of precise silicates in astronomical objects, which will open "a totally new field in astronomy: astro-mineralogy. This is the crystalline revolution", said the author, Dutch astronomer Rens Waters of Amsterdam university. "It's really fantastic, this possibility of identifying the silicates. Before ISO everybody thought that all silicates in space were amorphous, without a well-ordered internal structure; that means you cannot differentiate among the many different silicates existing. Now we can try to identify them and track their presence in different regions. A whole new research field is starting", said Rens Waters, who brought to the press conference samples of several terrestrial crystalline silicates: olivine and pyroxene, the most common silicates on Earth. Crystals give key clues about the physical conditions and evolutionary history of crystal-bearing objects. The precise mechanisms for crystal-making are now being researched now very actively in the laboratories, although some working-hypotheses are already being used. For instance, crystals can be made by heating the material to temperatures above 1 300 degrees Centigrade and then cooling it down slowly. Those found so far by ISO are at -170 degrees Centigrade, both in stellar envelopes and in protoplanetary discs. In the case of the old stars -red giant stars, where crystals are found to account for as much as 20% of all the surrounding dust, astronomers think that that the high temperatures near the star triggered the crystallisation of the silicates. In the protoplanetary discs some experts postulate that electric shocks - like lightning flashes - heated the dust, which cooled afterwards. "The crystals detected by ISO in these discs have a size of about a thousandth of a millimetre. They collide with each other, forming bigger and bigger bodies. Models predict that in about ten to one hundred million years they will make planets", Waters says. "In fact, crystalline silicates are very common in our own Solar System. You also have them in the comet Hale Bopp!". The reason why crystalline silicates had not been detected before in stars has to do with their low temperatures. Cold material emits mostly infrared light, which means an infrared space telescope like ESA's ISO was needed. The two high-resolution spectrometers on-board the satellite, able to detect the 'chemical fingerprint' of the crystals, did the rest. Astronomers are sure about the discovery because those chemical fingerprints, the spectra, can be compared in laboratories with spectra from crystalline silicates found on Earth. This method has demonstrated the crystalline structure and has even already allowed the identification of some of the crystals, such as forsterite and enstatite. However, crystalline silicates are a large family and their chemical signatures can be very similar; to enlarge the list of precise crystals more work will be needed, say experts in space chemistry. That is just one of the open questions requiring lab work. There's at least another one: crystalline silicates are found around old stars, in protoplanetary disks and in our own Solar System, but not in the space among the stars; astronomers can't explain it yet. "Crystalline silicates are synthesised around the stars; then that dust goes into the interstellar space, and enriches the raw material out of which more stars and planets will form. So you would expect crystals also to be in the interstellar medium! Crystals will certainly make us learn a lot...", says Waters. "This finding shows that ISO is really unveiling the chemistry of the Universe", says ESA astronomer Alberto Salama, chairman of the workshop about ISO results in spectroscopy held this week at ESA's Villafranca station in Madrid where the results were presented to the scientific community. "This is becoming more and more a 'hot field' of research. Initially we intended to organise a modest workshop, but we have had 150 astronomers coming from all over Europe!".

The structure of and origin of nodular chromite from the Troodos ophiolite, Cyprus, revealed using high-resolution X-ray computed tomography and electron backscatter diffraction

NASA Astrophysics Data System (ADS)

Prichard, H. M.; Barnes, S. J.; Godel, B.; Reddy, S. M.; Vukmanovic, Z.; Halfpenny, A.; Neary, C. R.; Fisher, P. C.

2015-03-01

Nodular chromite is a characteristic feature of ophiolitic podiform chromitite and there has been much debate about how it forms. Nodular chromite from the Troodos ophiolite in Cyprus is unusual in that it contains skeletal crystals enclosed within the centres of the nodules and interstitial to them. 3D imaging and electron backscatter diffraction have shown that the skeletal crystals within the nodules are single crystals that are surrounded by a rim of polycrystalline chromite. 3D analysis reveals that the skeletal crystals are partially or completely formed cage or hopper structures elongated along the < 111 > axis. The rim is composed of a patchwork of chromite grains that are truncated on the outer edge of the rim. The skeletal crystals formed first from a magma supersaturated in chromite and silicate minerals crystallised from melt trapped between the chromite skeletal crystal blades as they grew. The formation of skeletal crystals was followed by a crystallisation event which formed a silicate-poor rim of chromite grains around the skeletal crystals. These crystals show a weak preferred orientation related to the orientation of the core skeletal crystal implying that they formed by nucleation and growth on this core, and did not form by random mechanical aggregation. Patches of equilibrium adcumulate textures within the rim attest to in situ development of such textures. The nodules were subsequently exposed to chromite undersaturated magma resulting in dissolution, recorded by truncated grain boundaries in the rim and a smooth outer surface to the nodule. None of these stages of formation require a turbulent magma. Lastly the nodules impinged on each other causing local deformation at points of contact.

BX90: A new diamond anvil cell design for X-ray diffraction and optical measurements

NASA Astrophysics Data System (ADS)

Kantor, I.; Prakapenka, V.; Kantor, A.; Dera, P.; Kurnosov, A.; Sinogeikin, S.; Dubrovinskaia, N.; Dubrovinsky, L.

2012-12-01

We present a new design of a universal diamond anvil cell, suitable for different kinds of experimental studies under high pressures. Main features of the cell are an ultimate 90-degrees symmetrical axial opening and high stability, making the presented cell design suitable for a whole range of techniques from optical absorption to single-crystal X-ray diffraction studies, also in combination with external resistive or double-side laser heating. Three examples of the cell applications are provided: a Brillouin scattering of neon, single-crystal X-ray diffraction of α-Cr2O3, and resistivity measurements on the (Mg0.60Fe0.40)(Si0.63Al0.37)O3 silicate perovskite.

Igneous petrology of the new ureilites Nova 001 and Nullarbor 010

NASA Technical Reports Server (NTRS)

Triman, Allan H.; Berkley, John L.

1994-01-01

The Nova 001 (= Nuevo Mercurio (b)) and Nullarbor 010 meteorites are ureilites, both of which contain euhedral graphite crystals. The bulk of the meteorites are olivine (Fo79) and pyroxenes (Wo9En73Fs18, Wo3En77Fs20), with a few percent graphite and minor amounts of troilite, Ni-Fe metal, and possibly diamond. The rims of olivine grains are reduced (to Fo91) and contain abundant blebs of Fe metal. Silicate mineral grains are equant, anhedral, up to 2 mm across, and lack obvious preferred orientations. Euhedral graphite crystals (to 1 mm x 0.3 mm) are present at silicate grain boundaries, along boundaries and protruding into the silicates, and entirely within silicate mineral grains. Graphite euhedra are also present as radiating clusters and groups of parallel plates grains embedded in olivine; no other ureilite has comparable graphite textures. Minute lumps within graphite grains are possible diamond, inferred to be a result of shock. Other shock effects are limited to undulatory extinction and fracturing. Both ureilites have been weathered significantly. Considering their similar mineralogies, identical mineral compositions, and identical unusual textures, Nova 001 and Nullarbor 010 are probably paired. Based on olivine compositions, Nova 001 and Nullarbor 010 are in Group 1 (FeO-rich) of Berkley et al. (1980). Silicate mineral compositions are consistent with those of others known ureilites. The presence of euhedral graphite crystals within the silicate minerals is consistent with an igneous origin, and suggests that large proportions of silicate magma were present locally and crystallized in situ.

Shock recovery of a magnesium-silicate spinelloid

NASA Astrophysics Data System (ADS)

Tschauner, O. D.; Asimow, P. D.; Ahrens, T. J.; Kostandova, N.

2009-12-01

Previously it was believed that some high pressure polymorphs (e.g. of framework silicates) form under shock via growth from shock-induced precursor microscopic melt zones. Since diffusion in the melt was assumed to control crystallization rates, absence of shock recovery of any of those minerals was attributed to the short duration of laboratory shock (0.1 to 1 microsecond) experiments. In contrast to laboratory experiments, grains of high pressure polymorphs of 1 - 100 micrometer diameter have been found in melt veins of shocked meteorites and were widely believed to have formed via diffusion-controlled growth that occurred over seconds to minute time scales. Recently we reported formation of wadsleyite from a shock-generated melt in a laboratory shock experiment by analysis of the recovery products [1]. The growth rate of wadsleyite crystals at the experimental temperature of 2000 to 3000 K was estimated to be several m/s suggesting that diffusion was not the dominant factor in this ultra-rapid crystal growth. Consequently, S6 shock events in chondrites may not always be related to long shock duration and large impactors. Here we report formation of another high-pressure magnesium silicate polymorph in a shock experiment. The starting materials for this 30 GPa shot was single-crystal synthetic forsterite in a NIST 1157 tool-steel chamber. The recovered material was analyzed by micro-Raman spectroscopy and by synchrotron-based micro-X ray diffraction. Diffraction experiments were conducted in Gandolfi-geometry at station B2, CHESS, using a MAR345 image plate detector and a primary beam of 25 keV energy. Melted regions of the sample contained a spinelloid isotypic to a magnesium-gallium germanate spinelloid synthesized at ambient pressure [2]. As in the previous study [1] we observe oxidation of iron from melted metal of the recovery chamber wall entrained by the silicate melt while silicon is partially reduced. The new high-pressure silicate may have formed at less than the peak pressure experienced by the sample. [1]: O.Tschauner, P.D. Asimow, N. Kostandova,T.J. Ahrens, C. Ma, S. Sinogeikin, Z. Liu, S. Fakra, N. Tamura, Proc. Nat. Acad. Sci. USA 106, 13691-5 (2009) , [2]: Barbier, J., Hyde, B.G.,Acta Cryst. B 43, 34-40 (1987).

Identification and Control of Gravity Related Defect Formation During Melt Growth of Electro-Optic Single Crystals Bismuth Silicate(Bi12SiO20)

NASA Technical Reports Server (NTRS)

Becia, Piotr; Wiegel, Michaela E. K.

2004-01-01

A research carried out under Award Number NAG8-1487 was aimed at to the design, conduct and analysis of experiments directed at the identification and control of gravitational effects on crystal growth, segregation and defect formation in the Sillenite system: bismuth silicate (Bi(12)SiO(20)). Correlation analyses was conducted in order to establish the influence of gravity related defects introduced during crystal growth on critical, application specific properties. Achievement of the states objective was conducted during the period from Feb. 01, 1998 to Dec. 31, 2003 with the following anticipated milestones: 1. Establishment of capabilities for (a) reproducible Czochralski and Bridgman-type growth of BSO single crystals and (b) for comprehensive analysis of crystalline and chemical defects as well as for selective property characterization of grown crystals (year 1). 2. Design and execution of critical space growth experiment(s) based on analyses of prefatory space results (experiments aimed at establishing the viability of planned approaches and procedures) and on unresolved issues related to growth, segregation and defect formation associated with conventional growth in Bridgman geometries. Comparative analysis of growth under conventional and under mu-g conditions; identification of gravity related defect formation during conventional Bridgman growth and formulation of approaches for their control (years 2 and 3). Development of charge confinement system which permits growth interface demarcation (in a mu-g environment) as well as minimization of confinement related stress and contamination during growth; design of complementary mu-g growth experiments aimed at quantitative mu-g growth and segregation analyses (year 4). 3. Conduct of quantitative mu-g growth experiments directed at: (a) identification and control of gravity related crystalline and chemical defect formation during single crystal growth of Bi(12)SiO(20) and at (b) defect engineering -the development of approaches to the controlled generation during crystal growth of specified point defects in homogeneous distribution (year 5). The proposed research places focus on a class of materials which have outstanding electrical and optical properties but have so far failed to reach their potential, primarily because of our inability to control adequately their stoichiometry and crystal defect formation as well as confinement related contamination and lattice stress.

Surface-structural Control on Minor Element Zoning and Growth Mechanism in Synthetic Magmatic Clinopyroxene

NASA Astrophysics Data System (ADS)

Paquette, J.; Deakin, M.; Baker, D. R.

2006-12-01

Because in situ observations of actively growing surfaces are technically impractical, our understanding of crystal growth mechanisms at hydrothermal and magmatic conditions lags behind that of minerals that can be grown from aqueous solutions at or near room temperature. Growing silicate minerals from hydrous synthetic carbonate melts offers the opportunity to relate directly minor element incorporation to their surface microtopography. Natural hydrothermal diopside was used to seed experiments in which synthetic clinopyroxene crystals were grown at 800 degrees C and 10 kbars for 24 hours, from alkaline melts modelled after the lavas of the Tanzanian volcano Oldoinyo Lengai. The melts were prepared from Na2CO3, K2CO3, CaCO3, MgCO3 and Fe3O4 reagents. One run was anhydrous and the others contained either 2.5 or 5 wt. % H2O. Euhedral tabular crystals ranging in size from 100 to 300 ìm across were found in all three runs, hand-picked and freed from their carbonate matrix by overnight immersion in dilute acetic acid. The crystals consist of \\{110\\} prism, \\{100\\} and \\{001\\} pinacoids and a \\{111\\} dipyramid. AFM images resolved a distinct surface microtopography on each form: arrays of broad macrosteps on \\{100\\}, lens- shaped islands on \\{001\\} facets and striated fiber-like crystallites on \\{110\\}. EMP analyses of polished grain mounts show that compositional zoning of Na and Fe occurs not only among non-equivalent growth sectors but also within single \\{100\\} sectors. Electron microprobe maps of sequentially polished sections indicate that zoning within \\{100\\} sectors reflects differential uptake of Na and Fe on symmetrically non-equivalent steps. Near the crystal surface, the non- equivalent coeval vicinal faces of growth hillocks on \\{100\\} are either diopside-like, Na.007Ca1.00(Mg0.754Fe2+0.22Mn2+0.013Al_{0.003)Si2.00O6 , or acmitic, Ca0.63Na0.35(Mg0.64Fe3+ 0.36)Al0.01Si1.99O6 in composition. Step-specific incorporation of minor elements in a clinopyroxene face has only been documented once, in a hydrothermal diopside from Orford (Quebec), where Fe(II) and Mn(II) were differentially incorporated on steps oriented parallel to [010] on \\{100\\} faces. This natural example and our synthetic crystals reflect growth regimes where minor element incorporation was limited by surface-structural kinetics rather than diffusion- controlled kinetics. Such step-specific surface-structural control has never been reported in clinopyroxenes grown from silicate melts. Is it present, but more subtle, or do silicate melts promote a significantly different growth regime? Comparing zoning patterns in synthetic silicates grown from carbonate versus silicate melts could put new constraints on current models of element partitioning.

Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7}: Structural, spectroscopic and computational studies on a sorosilicate

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

Kahlenberg, Volker, E-mail: volker.kahlenberg@uibk.ac.at; Brunello, Emanuele; Hejny, Clivia

2015-05-15

Synthesis experiments in the system Li{sub 2}O–CaO–SiO{sub 2} resulted in the formation of single-crystals of Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7}. Structural investigations were based on single-crystal diffraction. At ambient conditions the compound has the following basic crystallographic data: hexagonal symmetry, space group P6{sub 1}22, a=5.0961(2) Å, c=41.264(2) Å, V=928.07(6) Å{sup 3}, Z=6. Structure solution was performed using direct methods. The final least-squares refinement calculations converged at a residual of R(|F|)=0.0260. From a structural point the lithium calcium silicate belongs to the group of pyrosilicates containing [Si{sub 2}O{sub 7}]-groups. Additional lithium and calcium cations are incorporated between the silicate dimers andmore » are coordinated by four and six nearest oxygen neighbours, respectively. Each [LiO{sub 4}]-tetrahedron shares two common corners with directly neighboring tetrahedra forming zweier single-chains which are running parallel to 〈1 0 0〉 in z-levels defined by the presence of the 6{sub 1}{sup [0} {sup 0} {sup 1]}-screw axes. From the corner-sharing [LiO{sub 4}]- and [SiO{sub 4}]-moieties a three dimensional framework can be constructed. An interesting feature of this framework is the presence of an O{sup [3]}-type bridging oxygen linking three tetrahedra (one [LiO{sub 4}]- and two [SiO{sub 4}]-units). Structural similarities with other silicates are discussed in detail. The high-temperature behavior of the Si–O, Ca–O and Li–O bond distances in Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7} was investigated by in{sub -}situ single-crystal X-ray diffraction in the range between 65 and 700 °C. From the evolution of the lattice parameters, the thermal expansion tensor α{sub ij} has been determined. The structural characterization has been supplemented by micro-Raman spectroscopy. Interpretation of the spectroscopic data including the allocation of the bands to certain vibrational species has been aided by DFT-calculations. - Graphical abstract: Framework of [SiO{sub 4}]- and [LiO{sub 4}]-tetrahedra in the crystal structure of Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7}. - Highlights: • We report the crystal structure of the sorosilicate Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7} at ambient conditions. • The thermal expansion tensor as well as the evolution of the structure between 25 and 700 °C was studied. • A topological analysis of the tetrahedral framework based on [SiO{sub 4}]- and [LiO{sub 4}]-units is presented. • The crystal structure of Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7} is discussed with respect to related compounds. • Interpretation of the Raman spectra of the crystals has been aided by DFT-calculations.« less

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

Pleše, P.; Higgins, M. D.; Mancini, L.

Bubble nucleation and growth control the explosivity of volcanic eruptions, and the kinetics of these processes are generally determined from examinations of natural samples and quenched experimental run products. These samples, however, only provide a view of the final state, from which the initial conditions of a time-evolving magmatic system are then inferred. The interpretations that follow are inexact due to the inability of determining the exact conditions of nucleation and the potential detachment of bubbles from their nucleation sites, an uncertainty that can obscure their nucleation location – either homogeneously within the melt or heterogeneously at the interface betweenmore » crystals and melts. We present results of a series of dynamic, real-time 4D X-ray tomographic microscopy experiments where we observed the development of bubbles in crystal bearing silicate magmas. Experimentally synthesized andesitic glasses with 0.25–0.5 wt% H2O and seed silicate crystals were heated at 1 atm to induce bubble nucleation and track bubble growth and movement. In contrast to previous studies on natural and experimentally produced samples, we found that bubbles readily nucleated on plagioclase and clinopyroxene crystals, that their contact angle changes during growth and that they can grow to sizes many times that of the silicate on whose surface they originated. The rapid heterogeneous nucleation of bubbles at low degrees of supersaturation in the presence of silicate crystals demonstrates that silicates can affect when vesiculation ensues, influencing subsequent permeability development and effusive vs. explosive transition in volcanic eruptions.« less

Fabrication and Evaluation of Bis-GMA/TEGDMA Dental Resins/Composites Containing Nano Fibrillar Silicate

PubMed Central

Tian, Ming; Gao, Yi; Liu, Yi; Liao, Yiliang; Hedin, Nyle E.; Fong, Hao

2008-01-01

Objective To investigate the reinforcement of Bis-GMA/TEGDMA dental resins (without conventional glass filler) and composites (with conventional glass filler) with various mass fractions of nano fibrillar silicate (FS). Methods Three dispersion methods were studied to separate the silanized FS as nano-scaled single crystals and uniformly distribute them into dental matrices. The photo-curing behaviors of the Bis-GMA/TEGDMA/FS resins were monitored in situ by RT-NIR to study the photopolymerization rate and the vinyl double bond conversion. Mechanical properties (flexural strength, elastic modulus and work of fracture) of the nano FS reinforced resins/composites were tested, and Analysis of Variance (ANOVA) was used for the statistical analysis of the acquired data. The morphology of nano FS and the representative fracture surfaces of its reinforced resins/composites were examined by SEM/TEM. Results Impregnation of small mass fractions (1 % and 2.5 %) of nano FS into Bis-GMA/TEGDMA (50/50 mass ratio) dental resins/composites improved the mechanical properties substantially. Larger mass fraction of impregnation (7.5 %), however, did not further improve the mechanical properties (one way ANOVA, P > 0.05) and may even reduce the mechanical properties. The high degree of separation and uniform distribution of nano FS into dental resins/composites was a challenge. Impregnation of nano FS into dental resins/composites could result in two opposite effects: a reinforcing effect due to the highly separated and uniformly distributed nano FS single crystals, or a weakening effect due to the formation of FS agglomerates/particles. Significance Uniform distribution of highly separated nano FS single crystals into dental resins/composites could significantly improve the mechanical properties of the resins/composites. PMID:17572485

In Situ X-ray Diffraction of Forsterite Under Shock Compression to 52 GPa: Time Resolved Observation of Changes in Crystal Structure and Phase

NASA Astrophysics Data System (ADS)

Akin, M. C.; Maddox, B.; Teruya, A.; Asimow, P. D.

2015-12-01

The Earth's mantle is composed primarily of ferromagnesian silicates, of which Forsterite (Fo) is the magnesium-rich end member of the dominant upper mantle phase, olivine. Fo is thought to undergo a chemical decomposition associated with a structural phase transition when dynamically loaded to 40-71 GPa, but previous inferences about such decomposition have been based only on pressure-density data with no direct phase identification. To obtain direct data on the phase evolution of shocked Fo, synthetic single crystal samples of Mg2SiO4 Fo were loaded to pressures of 52 GPa using a two stage light gas gun. X-ray diffraction (XRD) patterns were collected on the static and the loaded samples in situ using a single pulse Mo Kα anode to provide a 17 keV X-ray source. X-ray polycapillary optics were used to couple the source to the sample. Clear Laue spots were observed in the static images, while the dynamic images show the appearance of new spots at early times and powder-like rings at late times. The angles of the dynamically driven spots and rings overlap with each other and indicate the change in phase of forsterite under pressure through a process that begins with the formation of single crystals and ends with polycrystalline material. Efforts are underway to identify the high-pressure phases from among the library of dense magnesium silicates, and further experiments covering a larger pressure range will be completed shortly. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Fabrication and evaluation of Bis-GMA/TEGDMA dental resins/composites containing nano fibrillar silicate.

PubMed

Tian, Ming; Gao, Yi; Liu, Yi; Liao, Yiliang; Hedin, Nyle E; Fong, Hao

2008-02-01

To investigate the reinforcement of Bis-GMA/TEGDMA dental resins (without conventional glass filler) and composites (with conventional glass filler) with various mass fractions of nano fibrillar silicate (FS). Three dispersion methods were studied to separate the silanized FS as nano-scaled single crystals and uniformly distribute them into dental matrices. The photo-curing behaviors of the Bis-GMA/TEGDMA/FS resins were monitored in situ by RT-NIR to study the photopolymerization rate and the vinyl double bond conversion. Mechanical properties (flexural strength, elastic modulus and work-of-fracture) of the nano FS reinforced resins/composites were tested, and analysis of variance (ANOVA) was used for the statistical analysis of the acquired data. The morphology of nano FS and the representative fracture surfaces of its reinforced resins/composites were examined by SEM/TEM. Impregnation of small mass fractions (1% and 2.5%) of nano FS into Bis-GMA/TEGDMA (50/50 mass ratio) dental resins/composites improved the mechanical properties substantially. Larger mass fraction of impregnation (7.5%), however, did not further improve the mechanical properties (one way ANOVA, P>0.05) and may even reduce the mechanical properties. The high degree of separation and uniform distribution of nano FS into dental resins/composites was a challenge. Impregnation of nano FS into dental resins/composites could result in two opposite effects: a reinforcing effect due to the highly separated and uniformly distributed nano FS single crystals, or a weakening effect due to the formation of FS agglomerates/particles. Uniform distribution of highly separated nano FS single crystals into dental resins/composites could significantly improve the mechanical properties of the resins/composites.

Elasticity of α-Cristobalite: A Silicon Dioxide with a Negative Poisson's Ratio

NASA Astrophysics Data System (ADS)

Yeganeh-Haeri, Amir; Weidner, Donald J.; Parise, John B.

1992-07-01

Laser Brillouin spectroscopy was used to determine the adiabatic single-crystal elastic stiffness coefficients of silicon dioxide (SiO_2) in the α-cristobalite structure. This SiO_2 polymorph, unlike other silicas and silicates, exhibits a negative Poisson's ratio; α-cristobalite contracts laterally when compressed and expands laterally when stretched. Tensorial analysis of the elastic coefficients shows that Poisson's ratio reaches a maximum value of -0.5 in some directions, whereas averaged values for the single-phased aggregate yield a Poisson's ratio of -0.16.

Growth and luminescent properties of Lu2SiO5 and Lu2SiO5:Ce single crystalline films

NASA Astrophysics Data System (ADS)

Zorenko, Yu; Nikl, M.; Gorbenko, V.; Mares, J. A.; Savchyn, V.; Voznyak, T.; Solsky, I.; Grynyov, B.; Sidletskiy, O.; Kurtsev, D.; Beitlerova, A.; Kucerkova, R.

2010-11-01

Single crystalline films (SCF) of Lu2SiO5 (LSO) and Lu2SiO5:Ce (LSO:Ce) silicates with thickness of 2.5-21 μm were crystallised by liquid phase epitaxy method onto undoped LSO substrates from melt-solution based on PbO-B2O3 flux. The luminescence and scintillation properties of LSO and LSO:Ce SCFs were compared with the properties of a reference LSO:Ce and LYSO:Ce crystals. The light yield (LY) of LSO and LSO:Ce SCF reaches up 30 % and 145 %, respectively, of that of a reference LSO:Ce crystal under excitation by α-particles of 241Am source (5.5 MeV). We found that the luminescence spectrum of LSO:Ce SCF is red-shifted with respect to the spectrum of a reference LSO:Ce crystal. Differences in luminescence properties of LSO:Ce SCF and single crystal are explained by the different distribution of Ce3+ over the Lu1 and Lu2 positions of LSO host and are also due to Pb2+ contamination in the former.

Shattuckite and plancheite: A crystal chemical study

USGS Publications Warehouse

Evans, Howard T.; Mrose, Mary E.

1966-01-01

The orthorhombic crystal structures of shattuckite, Cu5( SiO3)4(OH)2 and planchétite, Cu8(Si4011)2(OH)4 H2O, have been solved. Shattuckite contains silicate chains similar to pyroxene in a complex association with copper atoms, while the closely related planchéite contains silicate chains similar to amphibole.

Influence of substrate mineralogy on bacterial mineralization of calcium carbonate: implications for stone conservation.

PubMed

Rodriguez-Navarro, Carlos; Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

2012-06-01

The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed.

Influence of Substrate Mineralogy on Bacterial Mineralization of Calcium Carbonate: Implications for Stone Conservation

PubMed Central

Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

2012-01-01

The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed. PMID:22447589

High-temperature, high-pressure hydrothermal synthesis, characterization, and structural relationships of mixed-alkali metals uranyl silicates

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

Chen, Yi-Hsin; Liu, Hsin-Kuan; Chang, Wen-Jung

2016-04-15

Three mixed-alkali metals uranyl silicates, Na{sub 3}K{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}]·2H{sub 2}O (1), Na{sub 3}Rb{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}] (2), and Na{sub 6}Rb{sub 4}[(UO{sub 2}){sub 4}Si{sub 12}O{sub 33}] (3), have been synthesized by high-temperature, high-pressure hydrothermal reactions at 550 °C and 1440 bar, and characterized by single-crystal X-ray diffraction, photoluminescence, and thermogravimetric analysis. Compound 1 and 2 are isostructural and contain layers of uranyl disilicate. The smaller cation, Na{sup +}, is located in the intralayer channels, whereas the larger cations, K{sup +} and Rb{sup +}, and water molecule are located in the interlayer region. The absencemore » of lattice water in 2 can be understood according to the valence-matching principle. The structure is related to that of a previously reported mixed-valence uranium(V,VI) silicate. Compound 3 adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain with the structural formula {uB,4"1_∞}[{sup 3}Si{sub 12}O{sub 33}] formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si. The connectivity of the Si atoms in the Si{sub 12}O{sub 33}{sup 18−} anion can be interpreted on the basis of Zintl–Klemm concept. Crystal data for compound 1: triclinic, P-1, a=5.7981(2) Å, b=7.5875(3) Å, c=12.8068(5) Å, α=103.593(2)°, β=102.879(2)°, γ=90.064(2)°, V=533.00(3) Å{sup 3}, Z=1, R1=0.0278; compound 2: triclinic, P-1, a=5.7993(3) Å, b=7.5745(3) Å, c=12.9369(6) Å, α=78.265(2)°, β=79.137(2)°, γ=89.936(2)°, V=546.02(4) Å{sup 3}, Z=1, R1=0.0287; compound 3: monoclinic, C2/m, a=23.748(1) Å, b=7.3301(3) Å, c=15.2556(7) Å, β=129.116(2)°, V=2060.4(2) Å{sup 3}, Z=2, R1=0.0304. - Graphical abstract: Three mixed-alkali metals uranyl silicates were synthesized under hydrothermal conditions at 550 °C and 1400 bar and structurally characterized by single-crystal X-ray diffraction. Two of them have a layer structure with the alkali metal cations within and between the layers. The third one adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si. - Highlights: • Three new mixed-alkali metals uranyl silicates were synthesized by high-T, high-P hydrothermal method and structurally. • Two compounds adopt a layer structure and the third one has a 3D framework structure. • The 3D framework structure contains a unique unbranched dreier fourfold silicate chain formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si.« less

High-Pressure γ-CaMgSi2O6: Does Penta-Coordinated Silicon Exist in the Earth's Mantle?

NASA Astrophysics Data System (ADS)

Hu, Yi; Kiefer, Boris; Bina, Craig R.; Zhang, Dongzhou; Dera, Przemeslaw K.

2017-11-01

In situ X-ray diffraction experiments with natural Fe- and Al- bearing diopside single crystals and density functional theory (DFT) calculations on diopside end-member composition indicate the existence of a new high-pressure γ-diopside polymorph with rare penta-coordinated silicon. On compression α-diopside transforms to the γ-phase at ˜50 GPa, which in turn, on decompression is observed to convert to the known β-phase below 47 GPa. The new γ-diopside polymorph constitutes another recent example of penta-coordinated silicon (VSi) in overcompressed metastable crystalline silicates, suggesting that VSi may exist in the transition zone and the uppermost lower mantle in appreciable quantities, not only in silicate glass and melts but also in crystalline phases contained in the coldest parts of subducted stagnant slabs. VSi may have significant influences on buoyancy, wave velocity anomalies, deformation mechanisms, chemical reactivity of silicate rocks, and seismicity within the slab.

Loss of halogens from crystallized and glassy silicic volcanic rocks

USGS Publications Warehouse

Noble, D.C.; Smith, V.C.; Peck, L.C.

1967-01-01

One hundred and sixty-four F and Cl analyses of silicic welded tuffs and lavas and glass separates are presented. Comparison of the F and Cl contents of crystallized rocks with those of nonhydrated glass and hydrated glassy rocks from the same rock units shows that most of the halogens originally present were lost on crystallization. An average of about half of the F and four-fifths of the Cl originally present was lost. Analyses of hydrated natural glasses and of glassy rocks indicate that in some cases significant amounts of halogens may be removed from or added to hydrated glass through prolonged contact with ground water. The data show that the original halogen contents of the groundmass of a silicic volcanic rock can be reliably determined only from nonhydrated glass. ?? 1967.

Single and multiphase inclusions in metapelitic garnets of the Rhodope Metamorphic Province, NE Greece.

PubMed

Mposkos, Evripidis; Perraki, Maria; Palikari, Sarra

2009-08-01

Single and multiphase inclusions in garnet porphyroblasts from the diamond-bearing pelitic gneisses were studied by means of combined Raman Spectroscopy and Electron Scanning Microscopy (SEM/EDX). They are either randomly distributed or with preferred orientation within the garnet host and their dimensions vary from less than 5 up to 60 microm. In the single-phase inclusions quartz, rutile, kyanite and graphite dominate. Biotite, zircon, apatite, monazite and allanite are also common. Two types of multiphase inclusions were recognized, hydrous silicate (Type I) and silicate-carbonate (Type II) ones. The carbon-bearing multiphase inclusions predominantly consist of Mg-siderite+graphite+CO(2)+muscovite+quartz formed by a high density carboniferous fluid rich in Fe, Mg, Si and less Ca, Mn, Al and K trapped in the growing garnet in a prograde stage of metamorphism at high-pressure (HP) conditions. The carbon-free multiphase inclusions predominantly consist of biotite+quartz+rutile+/-kyanite+muscovite formed through decompression-dehydration/melting reactions of pre-existing phengite. Single and multiphase inclusions are characterized by polygonal to negative crystal shape formed by dissolution-reprecipitation mechanism between the garnet host and the inclusions during the long lasting cooling period (>100 Ma) of the Kimi Complex.

Analyses of Cometary Silicate Crystals: DDA Spectral Modeling of Forsterite

NASA Technical Reports Server (NTRS)

Wooden, Diane

2012-01-01

Comets are the Solar System's deep freezers of gases, ices, and particulates that were present in the outer protoplanetary disk. Where comet nuclei accreted was so cold that CO ice (approximately 50K) and other supervolatile ices like ethane (C2H2) were preserved. However, comets also accreted high temperature minerals: silicate crystals that either condensed (greater than or equal to 1400 K) or that were annealed from amorphous (glassy) silicates (greater than 850-1000 K). By their rarity in the interstellar medium, cometary crystalline silicates are thought to be grains that formed in the inner disk and were then radially transported out to the cold and ice-rich regimes near Neptune. The questions that comets can potentially address are: How fast, how far, and over what duration were crystals that formed in the inner disk transported out to the comet-forming region(s)? In comets, the mass fractions of silicates that are crystalline, f_cryst, translate to benchmarks for protoplanetary disk radial transport models. The infamous comet Hale-Bopp has crystalline fractions of over 55%. The values for cometary crystalline mass fractions, however, are derived assuming that the mineralogy assessed for the submicron to micron-sized portion of the size distribution represents the compositional makeup of all larger grains in the coma. Models for fitting cometary SEDs make this assumption because models can only fit the observed features with submicron to micron-sized discrete crystals. On the other hand, larger (0.1-100 micrometer radii) porous grains composed of amorphous silicates and amorphous carbon can be easily computed with mixed medium theory wherein vacuum mixed into a spherical particle mimics a porous aggregate. If crystalline silicates are mixed in, the models completely fail to match the observations. Moreover, models for a size distribution of discrete crystalline forsterite grains commonly employs the CDE computational method for ellipsoidal platelets (c:a:b=8.14x8.14xl in shape with geometrical factors of x:y:z=1:1:10, Fabian et al. 2001; Harker et al. 2007). Alternatively, models for forsterite employ statistical methods like the Distribution of Hollow Spheres (Min et al. 2008; Oliveira et al. 2011) or Gaussian Random Spheres (GRS) or RGF (Gielen et al. 200S). Pancakes, hollow spheres, or GRS shapes similar to wheat sheaf crystal habit (e.g., Volten et al. 2001; Veihelmann et al. 2006), however, do not have the sharp edges, flat faces, and vertices seen in images of cometary crystals in interplanetary dust particles (IDPs) or in Stardust samples. Cometary forsterite crystals often have equant or tabular crystal habit (J. Bradley). To simulate cometary crystals, we have computed absorption efficiencies of forsterite using the Discrete Dipole Approximation (DDA) DDSCAT code on NAS supercomputers. We compute thermal models that employ a size distribution of discrete irregularly shaped forsterite crystals (nonspherical shapes with faces and vertices) to explore how crystal shape affects the shape and wavelength positions of the forsterite spectral features and to explore whether cometary crystal shapes support either condensation or annealing scenarios (Lindsay et al. 2012a, b). We find forsterite crystal shapes that best-fit comet Hale-Bopp are tetrahedron, bricks or brick platelets, essentially equant or tabular (Lindsay et al. 2012a,b), commensurate with high temperature condensation experiments (Kobatake et al. 2008). We also have computed porous aggregates with crystal monomers and find that the crystal resonances are amplified. i.e., the crystalline fraction is lower in the aggregate than is derived by fitting a linear mix of spectral features from discrete subcomponents, and the crystal resonances 'appear' to be from larger crystals (Wooden et al. 2012). These results may indicate that the crystalline mass fraction in comets with comae dominated by aggregates may be lower than deduced by popular methods that only emoy ensembles of discrete crystals.

X-ray diffraction studies of shocked lunar analogs

NASA Technical Reports Server (NTRS)

Hanss, R. E.

1979-01-01

The X-ray diffraction experiments on shocked rock and mineral analogs of particular significance to lunar geology are described. Materials naturally shocked by meteorite impact, nuclear-shocked, or artificially shocked in a flat plate accelerator were utilized. Four areas were outlined for investigation: powder diffractometer studies of shocked single crystal silicate minerals (quartz, orthoclase, oligoclase, pyroxene), powder diffractometer studies of shocked polycrystalline monomineralic samples (dunite), Debye-Scherrer studies of single grains of shocked granodiorite, and powder diffractometer studies of shocked whole rock samples. Quantitative interpretation of peak shock pressures experienced by materials found in lunar or terrestrial impact structures is presented.

Petrogenesis of Western Cascades Silicic Volcanics Near Sweet Home, Oregon

NASA Astrophysics Data System (ADS)

Cook, G. W.; White, C. M.

2002-12-01

Silicic lavas in the Menagerie Wilderness east of Sweet Home, Oregon are Oligocene to Miocene in age and range in composition from dacite (low K) to trachydacite (high K) and rhyolite (medium K). Three distinct silicic centers have been distinguished through a combination of field observation, chemistry and petrography. Phenocryst assemblages in rocks of the centers are plagioclase-hornblende-magnetite (Rooster Rock rhyolite), plagioclase-quartz-magnetite (Soda Fork rhyolite) and quartz-plagioclase-biotite-hornblende-magnetite (Moose Mt. rhyolite). The silicic volcanics in the study area are similar in terms of mineral content and overall chemical composition. Despite this, chemical evidence suggests that the three centers are petrologically unrelated. REE variations and least squares modeling of major element compositions are consistent with fractionation of plagioclase and hornblende. The rhyolites have moderate Eu anomalies and have flat MREE and HREE signatures. Least squares models and bivariate plots of major and trace elements also suggest fractionation of the aforementioned phases for both the andesite to dacite, and dacite to rhyolite steps. Comparisons with similar silicic centers show the Menagerie rocks share affinities with High Cascades rocks thought to have been derived through fractional crystallization (Crater Lake and South Sister). Plots of ratios of incompatible trace elements were utilized to determine if assimilation played some role alongside fractional crystallization in differentiation. Plots of Ba/La vs. Ba, Rb/Zr vs. Rb and Rb/Th vs. Rb show systematic positive increases in the ratios between a plausible parent magma (icelandite) and the rhyolites. These increases are not easily explained by fractional crystallization but can be modeled by assimilation of silicic crust. Overall, it seems likely that the three centers evolved independently through similar petrogenetic processes from an andesitic parent. The most plausible petrogenetic scenario involves some combination of fractional crystallization and assimilation of partial melts of silicic crust.

Origin of silicic magmas along the Central American volcanic front: Genetic relationship to mafic melts

NASA Astrophysics Data System (ADS)

Vogel, Thomas A.; Patino, Lina C.; Eaton, Jonathon K.; Valley, John W.; Rose, William I.; Alvarado, Guillermo E.; Viray, Ela L.

2006-09-01

Silicic pyroclastic flows and related deposits are abundant along the Central American volcanic front. These silicic magmas erupted through both the non-continental Chorotega block to the southeast and the Paleozoic continental Chortis block to the northwest. The along-arc variations of the silicic deposits with respect to diagnostic trace element ratios (Ba/La, U/Th, Ce/Pb), oxygen isotopes, Nd and Sr isotope ratios mimic the along-arc variation in the basaltic and andesitic lavas. This variation in the lavas has been interpreted to indicate relative contributions from the slab and asthenosphere to the basaltic magmas [Carr, M.J., Feigenson, M.D., Bennett, E.A., 1990. Incompatible element and isotopic evidence for tectonic control of source mixing and melt extraction along the Central American arc. Contributions to Mineralogy and Petrology, 105, 369-380.; Patino, L.C., Carr, M.J. and Feigenson, M.D., 2000. Local and regional variations in Central American arc lavas controlled by variations in subducted sediment input. Contributions to Mineralogy and Petrology, 138 (3), 265-283.]. With respect to along-arc trends in basaltic lavas the largest contribution of slab fluids is in Nicaragua and the smallest input from the slab is in central Costa Rica — similar trends are observed in the silicic pyroclastic deposits. Data from melting experiments of primitive basalts and basaltic andesites demonstrate that it is difficult to produce high K 2O/Na 2O silicic magmas by fractional crystallization or partial melting of low-K 2O/Na 2O sources. However fractional crystallization or partial melting of medium- to high-K basalts can produce these silicic magmas. We interpret that the high-silica magmas associated Central America volcanic front are partial melts of penecontemporaneous, mantle-derived, evolved magmas that have ponded and crystallized in the mid-crust — or are melts extracted from these nearly completely crystallized magmas.

SilMush: A procedure for modeling of the geochemical evolution of silicic magmas and granitic rocks

NASA Astrophysics Data System (ADS)

Hertogen, Jan; Mareels, Joyce

2016-07-01

A boundary layer crystallization modeling program is presented that specifically addresses the chemical fractionation in silicic magma systems and the solidification of plutonic bodies. The model is a Langmuir (1989) type approach and does not invoke crystal settling in high-viscosity silicic melts. The primary aim is to model a granitic rock as a congealed crystal-liquid mush, and to integrate major element and trace element modeling. The procedure allows for some exploratory investigation of the exsolution of H2O-fluids and of the fluid/melt partitioning of trace elements. The procedure is implemented as a collection of subroutines for the MS Excel spreadsheet environment and is coded in the Visual Basic for Applications (VBA) language. To increase the flexibility of the modeling, the procedure is based on discrete numeric process simulation rather than on solution of continuous differential equations. The program is applied to a study of the geochemical variation within and among three granitic units (Senones, Natzwiller, Kagenfels) from the Variscan Northern Vosges Massif, France. The three units cover the compositional range from monzogranite, over syenogranite to alkali-feldspar granite. An extensive set of new major element and trace element data is presented. Special attention is paid to the essential role of accessory minerals in the fractionation of the Rare Earth Elements. The crystallization model is able to reproduce the essential major and trace element variation trends in the data sets of the three separate granitic plutons. The Kagenfels alkali-feldspar leucogranite couples very limited variation in major element composition to a considerable and complex variation of trace elements. The modeling results can serve as a guide for the reconstruction of the emplacement sequence of petrographically distinct units. Although the modeling procedure essentially deals with geochemical fractionation within a single pluton, the modeling results bring up a number of questions about the petrogenetic relationships among parental magmas of nearly coeval granitic units emplaced in close proximity.

Discrete dipole approximation models of chrystalline forsterite: Applications to cometary crystalline silicates

NASA Astrophysics Data System (ADS)

Lindsay, Sean Stephen

The shape, size, and composition of crystalline silicates observed in comet comae and external proto-planetary disks are indicative of the formation and evolution of the dust grains during the processes of planetary formation. In this dissertation, I present the 3 -- 40 mum absorption efficiencies( Qabs) of irregularly shaped forsterite crystals computed with the discrete dipole approximation (DDA) code DDSCAT developed by Draine and Flatau and run on the NASA Advanced Supercomputing facility Pleiades. An investigation of grain shapes ranging from spheroidal to irregular indicate that the strong spectral features from forsterite are sensitive to grain shape and are potentially degenerate with the effects of crystal solid state composition (Mg-content). The 10, 11, 18, 23, and 33.5 mum features are found to be the most crystal shape sensitive and should be avoided in determining Mg-content. The distinct spectral features for the three shape classes are connected with crystal formation environment using a condensation experiment by (Kobatake et al., 2008). The condensation experiment demonstrates that condensed forsterite crystal shapes are dependent on the condensation environmental temperature. I generate DDSCAT target analog shapes to the condensed crystal shapes. These analog shapes are represented by the three shape classes: 1) equant, 2) a, c-columns, and 3) b-shortened platelets. Each of these shape classes exhibit distinct spectral features that can be used to interpret grain shape characteristics from 8 --- 40 mum spectroscopy of astronomical objects containing crystalline silicates. Synthetic spectral energy distributions (SEDs) of the coma of Hale-Bopp at rh = 2.8 AU are generated by thermally modeling the flux contributions of 5 mineral species present in comets. The synthetic SEDs are constrained using a chi2- minimization technique. The mineral species are amorphous carbon, amorphous pyroxene, amorphous olivine, crystalline enstatite, and crystalline forsterite. Using the DDSCAT computed absorption efficiencies for a large variety of forsterite crystal shapes, which are computed for 66 grain sizes between 0.1 -- 5.0 mum, the flux contribution of irregularly shaped forsterite is computed. The forsterite flux contribution is then summed with the amorphous and crystalline enstatite contributions to generate the total synthetic SED. The DDSCAT forsterite grain shape synthetic SEDs reveal that the crystalline silicates in the coma of Hale-Bopp are irregular in shape with two distinct shape characteristics related to specific formation mechanisms: 1) equant grains with sharp ( ≲ 90°) angles between the faces, edges, and vertices that formed as high temperature condensates in the inner 1 -- 3 AU radial region of the Solar System's protoplanetary disk; and 2) c-shortened platelet shapes that likely formed from collisional processing of the crystals. The 8 -- 40 mum silicate spectral features of Hale-Bopp's coma are compared to the silicate spectral features of the comae of 17P/Holmes during 2007 outburst and 9P/Tempel 1 during the Deep Impact experiment to show that the silicate features with crystalline resonances are remarkably similar. The similarity in silicate spectral features suggests that the grain populations in the comae of these comets are similar in shape, size, and compositon. However, Hale-Bopp is a nearly isotropic comet (NIC) that dynamically came from the Oort cloud, and 17P and 9P are ecliptic comets (ECs) that dynamically came from the Scattered Disk. The different dynamical source regions yet similar silicate (amorphous and crystalline) grain populations suggest that ECs and NICs innately have similar grains and that the typically weaker silicate features of ECs are an effect of the surface grains becoming compacted with numerous perihelion passages. Hence, the differences in silicate between ECs and NICs are the result of grain structure and not grain composition. (Abstract shortened by UMI.)

Ultrasmall Zeolite L Crystals Prepared from Highly-Interdispersed Alkali-Silicate Precursors.

PubMed

Li, Rui; Linares, Noemi; Sutjianto, James G; Chawla, Aseem; Garcia Martinez, Javier; Rimer, Jeffrey D

2018-06-19

The preparation of nanosized zeolites is critical for applications where mass transport limitations within microporous networks hinder their performance. Oftentimes the ability to generate ultrasmall zeolite crystals is dependent upon the use of expensive organics with limited commercial relevance. Here, we report the generation of zeolite L crystals with uniform sizes less than 30 nm using a facile, organic-free method. Time-resolved analysis of precursor assembly and evolution during nonclassical crystallization highlights key differences among silicon sources. Our findings reveal that a homogenous dispersion of potassium ions throughout silicate precursors is critical to enhancing the rate of nucleation and facilitating the formation of ultrasmall crystals. Intimate contact between the inorganic structure-directing agent and silica leads to the formation of a metastable nonporous phase, identified as KAlSi2O6, which undergoes an intercrystalline transformation to zeolite L. The presence of highly-interdispersed alkali-silicate precursors is seemingly integral to a reduced zeolite induction time and may facilitate the development of ultrasmall crystals. Given the general difficulty of achieving nanosized crystals in zeolite synthesis, it is likely that using well-dispersed precursors does not have the same effect on all framework types; however, in select cases it may provide an alternative strategy for optimizing zeolite synthesis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using MELTS to understand the evolution of silicic magmas: Challenges and successes in modeling the Highland Range Volcanic Sequence (NV)

NASA Astrophysics Data System (ADS)

Vaum, R. C.; Gualda, G. A.; Ghiorso, M. S.; Miller, C. F.; Colombini, L. L.

2009-12-01

The Highland Range near Searchlight, Nevada is comprised of mid-Miocene, intermediate to silicic volcanic rocks. This study focuses on the most silicic portion of the eruptive sequence (16.0-16.5 Ma). The first eruptions during this interval were effusive and produced trachydacite (66-70 wt% SiO2), but later the eruptive style shifted to explosive and compositions were more evolved (70-78 wt% SiO2). Glass compositions in rocks saturated in both quartz and sanidine align along the 150 MPa quartz+sanidine saturation surface, suggesting that the Highland Range magmas equilibrated in a single reservoir at that pressure. We are interested in better understanding this transition in eruptive style from effusive to eruptive, and our approach is based on modeling melt evolution using MELTS thermodynamic modeling software. We selected representative samples from key stratigraphic units, and focused on samples for which whole-rock and glass compositions, as well as mineral abundances, are available. This allows for direct comparison of simulation results with existing data. Initial simulations showed that MELTS predicts unrealistic paths of evolution when compared to the glass compositions and to the phase relations in the Qz-Ab-Or ternary. In particular, the stability field of quartz predicted by MELTS is much too small, causing melts to become exceedingly silicic (>80 wt% SiO2). Sanidine, on the other hand, has fairly sodic compositions and crystallizes too early in the sequence; therefore, simulated melt compositions are never as potassic as the analyzed glasses. Similar results are obtained when modeling the evolution of the Bishop and Campanian magmas, showing that these are systematic problems in MELTS calibration. Accordingly, we have adjusted the enthalpy of quartz and potassium end-member of the feldspar solid solution in MELTS so that the quartz-sanidine saturation surface is correctly predicted. We find that this modified version of MELTS much better models the evolution of silicic magmas. Sanidine begins to crystallize at lower temperatures, causing evolved melts to become significantly more potassic. Also, MELTS prediction of quartz saturation is in agreement with the position of the experimentally determined 150 MPa quartz+sanidine saturation surface. Importantly, the melt evolution that this modified version of MELTS predicts is very consistent with whole-rock data, glass chemistry, and mineral abundances in samples from the Highland Range. Simulations using the modified version of MELTS show that it works remarkably well, at least for relatively low degrees of crystallization. But a more reliable model to simulate the evolution of silicic magmas is necessary to more properly simulate the evolution of silicic systems, in particular at high degrees of crystallinity. We are currently working to create gMELTS, an associated solution model of the haplogranitic system, which, once completed, will be optimized to simulate the evolution of silicic systems.

Low-temperature crystallization of silicate dust in circumstellar disks.

PubMed

Molster, F J; Yamamura, I; Waters, L B; Tielens, A G; de Graauw, T; de Jong, T; de Koter, A; Malfait, K; van den Ancker, M E; van Winckel, H; Voors, R H; Waelkens, C

1999-10-07

Silicate dust in the interstellar medium is observed to be amorphous, yet silicate dust in comets and interplanetary dust particles is sometimes partially crystalline. The dust in disks that are thought to be forming planets around some young stars also appears to be partially crystalline. These observations suggest that as the dust goes from the precursor clouds to a planetary system, it must undergo some processing, but the nature and extent of this processing remain unknown. Here we report observations of highly crystalline silicate dust in the disks surrounding binary red-giant stars. The dust was created in amorphous form in the outer atmospheres of the red giants, and therefore must be processed in the disks to become crystalline. The temperatures in these disks are too low for the grains to anneal; therefore, some low-temperature process must be responsible. As the physical properties of the disks around young stars and red giants are similar, our results suggest that low-temperature crystallization of silicate grains also can occur in protoplanetary systems.

Geobarometry of ultramafic xenoliths from Loihi Seamount, Hawaii, on the basis of CO2 inclusions in olivine

USGS Publications Warehouse

Roedder, E.

1983-01-01

Abundant fluid inclusions in olivine of dunite xenoliths (???1-3 cm) in basalt dredged from the young Loihi Seamount, 30 km southeast of Hawaii, are evidence for three coexisting immiscible fluid phases-silicate melt (now glass), sulfide melt (now solid), and dense supercritical CO2 (now liquid + gas)-during growth and later fracturing of some of these olivine crystals. Some olivine xenocrysts, probably from disaggregation of xenoliths, contain similar inclusions. Most of the inclusions (2-10 ??m) are on secondary planes, trapped during healing of fractures after the original crystal growth. Some such planes end abruptly within single crystals and are termed pseudosecondary, because they formed during the growth of the host olivine crystals. The "vapor" bubble in a few large (20-60 ??m), isolated, and hence primary, silicate melt inclusions is too large to be the result of simple differential shrinkage. Under correct viewing conditions, these bubbles are seen to consist of CO2 liquid and gas, with an aggregate ??{variant} = ??? 0.5-0.75 g cm-3, and represent trapped globules of dense supercritical CO2 (i.e., incipient "vesiculation" at depth). Some spinel crystals enclosed within olivine have attached CO2 blebs. Spherical sulfide blebs having widely variable volume ratios to CO2 and silicate glass are found in both primary and pseudosecondary inclusions, demonstrating that an immiscible sulfide melt was also present. Assuming olivine growth at ??? 1200??C and hydrostatic pressure from a liquid lava column, extrapolation of CO2 P-V-T data indicates that the primary inclusions were trapped at ??? 220-470 MPa (2200-4700 bars), or ??? 8-17 km depth in basalt magma of ??{variant} = 2.7 g cm-3. Because the temperature cannot change much during the rise to eruption, the range of CO2 densities reveals the change in pressure from that during original olivine growth to later deformation and rise to eruption on the sea floor. The presence of numerous decrepitated inclusions indicates that the inclusion sample studied is biased by the loss of higher-density inclusions and suggests that some part of these olivine xenoliths formed at greater depths. ?? 1983.

Tribochemical wear of single crystal aluminum in NaCl solution studied by atomic force microscopy

NASA Astrophysics Data System (ADS)

Cai, M.; Langford, S. C.; Dickinson, J. T.

2011-09-01

We report a systematic study of chemically enhanced wear of single crystal aluminum surfaces in aqueous solutions using an environmentally equipped atomic force microscope (AFM). The experiments were conducted by using a standard Si3N4 AFM tip to apply a localized force on a polished, single crystal aluminum (110) surface. Most measurements were performed in 0.5 M NaCl solution. We show the effect of applied force, number of scans, chemical solution, and temperature on the chemical-mechanical wear of aluminum on the nanometer scale. Aggressive chemical environments significantly enhance the wear of aluminum relative to scanning in dry air. Quantitative measurements show that the wear volume increases in proportion to the square root of force and the number of scans (or time). Arrhenius plots of wear volume versus temperature are consistent with an activation energy of 31 kJ/mol for scanning in 0.5 M NaCl. The wear of the AFM tip and the aluminum substrate is explained in terms of the synergistic surface chemical reactions and mechanical action of the tip. We compare these results to previous studies of AFM wear of silicate glass.

Paleointensity, solar wind and magnetopause 3.45 billion years ago (Invited)

NASA Astrophysics Data System (ADS)

Tarduno, J. A.; Cottrell, R. D.; Watkeys, M. K.; Hofmann, A.; Doubrovine, P. V.; Nelson, J.; Usui, Y.

2009-12-01

The standoff of the solar wind by the magnetic field produced by a core dynamo defines atmospheric shielding and prevention of volatile loss important for the evolution of a habitable planet. Yet little is known about magnetic field strength for the earliest Earth. Therefore, the potential for intense radiation from the young, rapidly rotating Sun modifying the atmosphere is uncertain. We report Thellier paleointensity results from single silicate crystals bearing magnetic inclusions that indicate the presence of a Paleoarchean geodynamo between 3.40 and 3.45 billion years ago. The field is somewhat weaker than the current field and when combined with the a greater solar wind pressure suggest steady-state Paleoarchean magnetopause standoff distances similar to those observed during recent solar storms. We will discuss efforts to further extend the paleointensity record, using single crystals with magnetic inclusions, such as zircons, eroded from older igneous rocks and now found within Archean sedimentary units.

Scanning electron microscope view of iron crystal growing on pyroxene crystal

NASA Technical Reports Server (NTRS)

1972-01-01

A scanning electron microscope photograph of a four-micron size iron crystal growing on a pyroxene crystal (calcium-magnesium-iron silicate) from the Apollo 15 Hadley-Apennino lunar landing site. The well developed crystal faces indicate that the crystal was formed from a hot vapor as the rock was cooling.

Magmatic Longevity Constrained by ID-TIMS U-Pb Dating of Zircon and Titanite

NASA Astrophysics Data System (ADS)

Szymanowski, D.; Wotzlaw, J. F.; Ellis, B. S.; Bachmann, O.; Von Quadt, A.

2016-12-01

Clues about the timescales and thermal conditions associated with the growth and evacuation of large silicic magma reservoirs are frequently drawn from radiometric dating, diffusion modelling, or thermomechanical modelling. A growing amount of petrological and geochronological evidence, supported by thermal modelling, suggests that many silicic magma reservoirs may exist for some 104-106 years in the form of high-crystallinity mushes at relatively low temperatures ( 700-750°C; [1-3]). Geochronological studies addressing this issue typically utilise the U-Pb system in zircon capable of recording extended periods of crystallisation, particularly in evolved calc-alkaline systems that spend most of their lifetime zircon-saturated. In this study, we integrate U-Pb dating of zircon and titanite to investigate the longevity of the magma reservoir that produced the Kneeling Nun Tuff, a 35 Ma, >900 km3 crystal-rich rhyolitic super-eruption from the Mogollon-Datil volcanic field in New Mexico (USA). High-precision ID-TIMS U-Pb dates of single crystals of both zircon and titanite independently record a continuous crystallisation history over >400,000 years. We combine the dating of both accessory phases with textural, major, trace element and isotopic studies of single crystals, placing tight constraints on the thermal conditions of magma accumulation and storage while recording differentiation and rejuvenation processes within the magma reservoir. The results suggest a protracted `cool' upper-crustal storage of magma prior to the Kneeling Nun Tuff eruption followed by a melting event which reduced the magma crystallinity and conditioned it for eruption. [1] Bachmann & Bergantz (2004), J. Petrol. 45, 1565-1582. [2] Gelman et al. (2013), Geology 41, 759-762. [3] Cooper & Kent (2014), Nature 506, 480-483.

A Kinetic Study of the Effect of Basicity on the Mold Fluxes Crystallization

NASA Astrophysics Data System (ADS)

Zhou, Lejun; Wang, Wanlin; Ma, Fanjun; Li, Jin; Wei, Juan; Matsuura, Hiroyuki; Tsukihashi, Fumitaka

2012-04-01

The effect of basicity on the mold fluxes crystallization was investigated in this article. The time-temperature-transformation (TTT) diagrams and continuous-cooling-transformation (CCT) diagrams of mold fluxes with different basicity were constructed by using single, hot thermocouple technology (SHTT). The results showed that with the increase of basicity, the incubation time of isothermal crystallization became shorter, the crystallization temperature was getting higher, and the critical cooling rate of continuous cooling crystallization became faster. The X-ray diffraction analysis suggested that calcium silicate (CaO·SiO2) was precipitated at the upper part of the TTT diagram and cuspidine (Ca4Si2O7F2) was formed at the lower part, when the basicity of mold fluxes was within 1.0 to 1.2. However, when basicity was 0.8, only the cuspidine phase was formed. A kinetic study of isothermal crystallization process indicated that the increase of the basicity tended to enhance the mold flux crystallization, and the crystallization activation energy became smaller. The crystallization mechanism of cupsidine was changing from one-dimensional growth to three-dimensional growth with a constant number of nuclei, when the basicity of mold fluxes varied from 0.8 to 1.2.

Powder XRD, TEM, FTIR and thermal studies of strontium tartrate nano particles

NASA Astrophysics Data System (ADS)

Lathiya, U. M.; Jethva, H. O.; Joshi, M. J.; Vyas, P. M.

2017-05-01

Strontium tartrate finds several applications, e.g., as non-linear optical and dielectric material, in tracer composition and ammunition unit, in treating structural integrity of bone. The growth of single crystals of strontium tartrate in silica gel has been widely reported. In the present study, strontium tartrate nano particles were synthesized by wet chemical method using strontium chloride, tartaric acid and sodium meta-silicate solutions in the presence of Triton X -100 surfactant. It was found that the presence of sodium meta-silicate facilitated the reaction for strontium tartrate product. The powder XRD study of strontium tartrate nano-particles suggested monoclinic crystal system and the average crystallite size was found to be 40 nm determined by applying Scherrer's formula. The TEM analysis indicated that the nano particles were spherical in nature. The FTIR spectrum confirmed the presence of various functional groups such as O-H,C-H, and C=O stretching mode. The thermal analysis was carried out by using TGA and DTA studies. The nano-particles were found to be stable up to 175°C and then decomposed through various stages. The results are compared with the bulk crystalline material available in the literature.

The origin of chondrules - Experimental investigation of metastable liquids in the system Mg2SiO4-SiO2

NASA Technical Reports Server (NTRS)

Blander, M.; Planner, H. N.; Keil, K.; Nelson, L. S.; Richardson, N. L.

1976-01-01

Laser-melted magnesium silicate droplets were supercooled 400-750 C below their equilibrium liquidus temperatures before crystallization and their texture was compared with that of meteoritic and lunar chondrules. Crystal morphology, width and texture were studied in relation to nucleation temperature and bulk composition. It was found that the only phase to nucleate from the forsterite-enstatite normative melts was forsterite. Highly siliceous glass, about 65% SiO2 by weight, was identified interstitially to the forsterite crystals in seven of the MgSiO4 spherules and was thought to be present in all.

MAS-NMR investigations of the crystallization behaviour of lithium aluminum silicate (LAS) glasses containing P 2O 5 and TiO 2 nucleants

NASA Astrophysics Data System (ADS)

Ananthanarayanan, A.; Kothiyal, G. P.; Montagne, L.; Revel, B.

2010-06-01

Lithium aluminum silicate (LAS) glass of composition (mol%) 20.4Li 2O-4.0Al 2O 3-68.6SiO 2-3.0K 2O-2.6B 2O 3-0.5P 2O 5-0.9TiO 2 was prepared by melt quenching. The glass was then nucleated and crystallized based on differential thermal analysis (DTA) data and was characterized by 29Si, 31P, 11B and 27Al MAS-NMR. XRD and 29Si NMR showed that lithium metasilicate (Li 2SiO 3) is the first phase to c form followed by cristobalite (SiO 2) and lithium disilicate (Li 2Si 2O 5). 29Si MAS-NMR revealed a change in the network structure already for the glasses nucleated at 550 °C. Since crystalline Li 3PO 4, as observed by 31P MAS-NMR, forms concurrently with the silicate phases, we conclude that crystalline Li 3PO 4 does not act as a nucleating agent for lithium silicate phases. Moreover, 31P NMR indicates the formation of M-PO 4 ( M=B, Al or Ti) complexes. The presence of BO 3 and BO 4 structural units in all the glass/glass-ceramic samples is revealed through 11B MAS-NMR. B remains in the residual glass and the crystallization of silicate phases causes a reduction in the number of alkali ions available for charge compensation. As a result, the number of trigonally coordinated B (BO 3) increases at the expense of tetrahedrally coordinated B (BO 4). The 27Al MAS-NMR spectra indicate the presence of tetrahedrally coordinated Al species, which are only slightly perturbed by the crystallization.

Porphyrin-Embedded Silicate Materials for Detection of Hydrocarbon Solvents

DTIC Science & Technology

2011-01-14

Sensors 2011, 11, 886-904; doi:10.3390/s110100886 sensors ISSN 1424-8220 www.mdpi.com/journal/ sensors Article Porphyrin-Embedded Silicate...Prescribed by ANSI Std Z39-18 Sensors 2011, 11 887 1. Introduction Mesoporous silicates have been widely described in sensing...absorption spectroscopy, quartz crystal microbalance ( QCM ), and FTIR have been utilized for aromatic hydrocarbon sensing applications based on these

Photo- and electroluminescence of sulfide and silicate phosphors embedded in synthetic opal

NASA Astrophysics Data System (ADS)

Kaplan, S. F.; Kartenko, N. F.; Kurdyukov, D. A.; Medvedev, A. V.; Badalyan, A. G.; Golubev, V. G.

2007-02-01

The sulfide (ZnS:Mn, Zn xCd 1 -xS:Mn, Zn xCd 1- xS:Ag) and silicate (Zn 2SiO 4:Mn) phosphors were synthesized directly inside the pores of synthetic opal by chemical bath deposition. These composites are perfect three-dimensional photonic crystals, which produce effective photo- and electroluminescence at room temperature. The emission spectra are considerably modified by the photonic crystal structure to become anisotropic in accordance with the photonic band gap angular dispersion.

Bubble accumulation and its role in the evolution of magma reservoirs in the upper crust.

PubMed

Parmigiani, A; Faroughi, S; Huber, C; Bachmann, O; Su, Y

2016-04-28

Volcanic eruptions transfer huge amounts of gas to the atmosphere. In particular, the sulfur released during large silicic explosive eruptions can induce global cooling. A fundamental goal in volcanology, therefore, is to assess the potential for eruption of the large volumes of crystal-poor, silicic magma that are stored at shallow depths in the crust, and to obtain theoretical bounds for the amount of volatiles that can be released during these eruptions. It is puzzling that highly evolved, crystal-poor silicic magmas are more likely to generate volcanic rocks than plutonic rocks. This observation suggests that such magmas are more prone to erupting than are their crystal-rich counterparts. Moreover, well studied examples of largely crystal-poor eruptions (for example, Katmai, Taupo and Minoan) often exhibit a release of sulfur that is 10 to 20 times higher than the amount of sulfur estimated to be stored in the melt. Here we argue that these two observations rest on how the magmatic volatile phase (MVP) behaves as it rises buoyantly in zoned magma reservoirs. By investigating the fluid dynamics that controls the transport of the MVP in crystal-rich and crystal-poor magmas, we show how the interplay between capillary stresses and the viscosity contrast between the MVP and the host melt results in a counterintuitive dynamics, whereby the MVP tends to migrate efficiently in crystal-rich parts of a magma reservoir and accumulate in crystal-poor regions. The accumulation of low-density bubbles of MVP in crystal-poor magmas has implications for the eruptive potential of such magmas, and is the likely source of the excess sulfur released during explosive eruptions.

Geochemistry, thermometry and isotope ratios on the same zircon crystals: the tandem use of quadrupole LA-ICPMS and CA-TIMS

NASA Astrophysics Data System (ADS)

Olin, P. H.; Schmitz, M. D.; Crowley, J. L.

2011-12-01

Current trends in igneous petrology include the extraction of diverse geochemical information from smaller sample targets by ever more efficient and cost effective means. Igneous zircons are repositories of several types of petrogenetic information, such as magmatic crystallization ages obtained using U-Pb geochronology, magmatic temperatures using Ti-in-zircon geothermometry, and magmatic differentiation and/or mixing trends using trace element contents. Here we demonstrate a tandem quadrupole LA-ICPMS and CA-TIMS approach on single zircon crystals and within domains in single crystals, which extracts all of these data from a single laser spot analysis and then guides the acquisition of CA-TIMS ages at precisions relevant to magmatic histories. We present data from zircon-bearing intrusive and extrusive rocks spanning the compositional spectrum, and highlight results from silicic volcanic rocks with different affinities. The utility of our approach is illustrated in zircons from the Temora diorite, a commonly used standard material which we analysed using 25-μm ablation spots placed on dozens of grains which had been previously annealed and chemically abraded prior to mounting in epoxy. Our LA-ICPMS results illustrate a 3- to 5-fold variation in trace element concentrations and trace element ratios over >150 degrees of cooling as estimated from Ti-in-zircon thermometry. Some geochemical parameters (e.g., Nb/Ta variations and Eu anomalies) are consistent with crystal fractionation during progressive crystallization, while others are bimodal (e.g., Hf and U contents), suggesting the mixing of crystal/magma batches prior to final solidification. LA-ICPMS U-Pb spot ages reproduce the accepted CA-TIMS age within 2% precision and accuracy, while our CA-TIMS results on the same grains constrain the development of the observed geochemical variability to within 100 ka. Other zircon standard materials to be presented include Plesovich syenite, FC1 gabbro, and R33 diorite. Analyses of zircons from selected western Snake River Plain silicic volcanic units further demonstrate the capability of our approach. These units are targeted with the overarching goal of better understanding magmatism in the region and to identify geochemical fingerprints to better distinguish among and to correlate between units. Several rhyolites distributed along the northern margin of the plain have LA-ICPMS ages of ca. 11 Ma, within error of each other and their CA-TIMS ages, and reveal differences in temperatures of crystallization and trace element contents and ratios. Individual units have crystallization temperatures that span 100 degrees or more, and show correlations with whole-rock major and trace element contents and ratios. In many cases, zircon geochemical parameters such as REE and Y contents, and Nb/Ta and Th/U ratios allow units proximal to each other to be distinguished from one another while also providing fingerprints to correlate to distal units on the south side of the plain or elsewhere in the province.

Shock wave compression of iron-silicate garnet.

NASA Technical Reports Server (NTRS)

Graham, E. K.; Ahrens, T. J.

1973-01-01

Shock wave compression data to over 650 kb are presented for single-crystal almandine garnet. The data indicate the initiation of a phase transformation near 200 kb. Total transition to the high-pressure polymorph occurs at approximately 300 kb. The elastic properties of the high-pressure phase are calculated from the metastable Hugoniot data by using the linear shock velocity-particle velocity relationships. The overall results obtained strongly suggest that upper mantle minerals are likely to occur in the ilmenite structure over a substantial part of the lower mantle.

Fluorine sites in glasses and transparent glass-ceramics of the system Na{sub 2}O/K{sub 2}O/Al{sub 2}O{sub 3}/SiO{sub 2}/BaF{sub 2}

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

Bocker, Christian, E-mail: christian.bocker@uni-jena.d; Munoz, Francisco; Duran, Alicia

2011-02-15

The transparent glass-ceramics obtained in the silicate system Na{sub 2}O/K{sub 2}O/SiO{sub 2}/BaF{sub 2} show homogeneously dispersed BaF{sub 2} nano crystals with a narrow size distribution. The X-ray diffraction and the nuclear magnetic resonance spectroscopy were applied to glasses and the respective glass-ceramics in order to clarify the crystallization mechanism and the role of fluorine during crystallization. With an increasing annealing time, the concentration and also the number of crystals remain approximately constant. With an increasing annealing temperature, the crystalline fraction increases until a saturation limit is reached, while the number of crystals decreases and the size of the crystals increases.more » Fluoride in the glassy network occurs as Al-F-Ba, Al-F-Na and also as Ba-F structures. The latter are transformed into crystalline BaF{sub 2} and fluoride is removed from the Al-F-Ba/Na bonds. However, some fluorine is still present in the glassy phase after the crystallization. -- Graphical abstract: The X-ray diffraction and the nuclear magnetic resonance spectroscopy were applied to glasses in the silicate system Na{sub 2}O/K{sub 2}O/SiO{sub 2}/BaF{sub 2} and the respective glass-ceramics with BaF{sub 2} nano crystals in order to clarify the crystallization mechanism and the role of fluorine during crystallization. Display Omitted Research highlights: {yields} BaF{sub 2} nano crystals are precipitated from a silicate glass system. {yields} Ostwald ripening during the late stage of crystallization does not occur. {yields} Fluorine in the glass is coordinated with Ba as well as Al together with Ba or Na.{yields} In the glass-ceramics, the residual fluorine is coordinated as Al-F-Ba/Na.« less

Silica-rich orthopyroxenite in the Bovedy chondrite

NASA Technical Reports Server (NTRS)

Ruzicka, Alex; Kring, David A.; Hill, Dolores H.; Boynton, William V.; Clayton, Robert N.; Mayeda, Toshiko K.

1995-01-01

A large (greater than 4.5 x 7 x 4 mm), igneous-textured clast in the Bovedy (L3) chondrite is notable for its high bulk SiO2 content (is approximately equal to 57.5 wt%). The clast consists of normally zoned orthopyroxene (83.8 vol%), tridymite (6.2%), an intergrowth of feldspar (5.8%) and sodic glass (3.1%), pigeonite (1.0%), and small amounts of chromite (0.2%), augite, and Fe,Ni-metal; it is best described as a silica-rich orthopyroxenite. The oxygen-isotopic composition of the clast is similar, but not identical, to Bovedy and other ordinary chondrites. The clast has a superchondritic Si/Mg ratio, but has Mg/(Mg + Fe) and Fe/Mn ratios that are similar to ordinary chondrite silicate. The closest chemical analogues to the clast are radial-pyroxene chondrules, diogenites, pyroxene-silica objects in ordinary chondrites, and silicates in the IIE iron meteorite Weekeroo Station. The clast crystallized from a siliceous melt that cooled fast enough to prevent complete attainment of equilibrium but slow enough to allow nearly complete crystallization. The texture, form, size and composition of the clast suggestion that it is an igneous differentiate from an asteroid or planetesimal that formed in the vicinity of ordinary chondrites. The melt probably cooled in the near-surface region of the parent object. It appears that in the source region of the clast, metallic and silicate partial melt were largely-to-completely lost during a relatively low degree of melting, and that during a higher degree of melting, olivine and low-Ca pyroxene separated from the remaining liquid, which ultimately solidified to form the clast. While these fractionation steps could not have all occurred at the same temperature, they could have been accomplished in a single melting episode, possibly as a result of heating by radionuclides or by electromagnetic induction. Fractionated magmas can also account for other Si-rich objects in chondrites.

Crystal chemistry and the role of ionic radius in rare earth tetrasilicates: Ba2RE2Si4O12F2 (RE = Er3+-Lu3+) and Ba2RE2Si4O13 (RE = La3+-Ho3+).

PubMed

Fulle, Kyle; Sanjeewa, Liurukara D; McMillen, Colin D; Kolis, Joseph W

2017-10-01

Structural variations across a series of barium rare earth (RE) tetrasilicates are studied. Two different formulas are observed, namely those of a new cyclo-silicate fluoride, BaRE 2 Si 4 O 12 F 2 (RE = Er 3+ -Lu 3+ ) and new compounds in the Ba 2 RE 2 Si 4 O 13 (RE = La 3+ -Ho 3+ ) family, covering the whole range of ionic radii for the rare earth ions. The Ba 2 RE 2 Si 4 O 13 series is further subdivided into two polymorphs, also showing a dependence on rare earth ionic radius (space group P{\\overline 1} for La 3+ -Nd 3+ , and space group C2/c for Sm 3+ -Ho 3+ ). Two of the structure types identified are based on dinuclear rare earth units that differ in their crystal chemistries, particularly with respect to the role of fluorine as a structural director. The broad study of rare earth ions provides greater insight into understanding structural variations within silicate frameworks and the nature of f-block incorporation in oxyanion frameworks. The single crystals are grown from high-temperature (ca 953 K) hydrothermal fluids, demonstrating the versatility of the technique to access new phases containing recalcitrant rare earth oxides, enabling the study of structural trends.

Impact-melt origin for the Simondium, Pinnaroo, and Hainholz mesosiderites: implicatiions for impact processes beyond the Earth--Moon system

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

Floran, R J; Caulfield, J B.D.; Harlow, G E

The Simondium, Pinnaroo, and Hainholz mesosiderites are interpreted to be clast-laden impact melts that crystallized from immiscible silicate, metallic (Fe-FeS) liquids. The existence of silicate melts is shown by intergranular basaltic textures. Metallic melts are inferred on the basis of smooth boundaries between metal and troilite and the occurrence of troilite as anastomosing areas that radiate outward into the silicate fractions. These relations suggest that troilite crystallized after silicates, concentrating as a late-stage residuum. Evidence for impact melting includes: diversity and abundance of clast types (mineral, metal, lithic) in various stages of recrystallization and assimilation; differences in mineral chemistries betweenmore » clasts and igneous-textured matrix silicates; unusual metal plus silicate bulk composition. Silicate clasts consist primarily of orthopyroxene and minor olivine with a range of Fe/Fe + Mg ratios, anorthitic plagioclase, and rare orthopyroxenite (diogenite) fragments. Substantial amounts of Fe-Ni metal were melted during the impact events and minor amounts were incorporated into the melts as clasts. The clast populations suggest that at least four rock types were melted and mixed: (a) diogenite, (b) a plagioclase-rich source, possibly cumulate eucrite, (c) dunite, and (d) metal. Most orthopyroxene appears to have been derived from fragmentation of diogenites. Orthopyroxene (En/sub 82-61/) and olivine (Fo/sub 86-67/) clasts include much material unsampled as individual meteorites and probably represent a variety of source rocks.« less

Crystallization of Polymers in Confined Environments: Structural Development of Semi-crystalline Polymer-Layered Silicate Nanocomposites

NASA Astrophysics Data System (ADS)

Vaia, Richard A.; Lincoln, Derek M.; Wang, Zhi-Gang; Hsiao, Benjamin S.; Krishnamoorti, Ramanan

2000-03-01

Over the last decade, the utility of ultrafine dispersions of inorganic nanoparticles to enhance polymer performance and function as precursors to form self-passivating / self-healing inorganic coatings on the polymer surface has been established. Before developing the fundamental structure-property relationships though, a detailed understanding of processing / morphology relationships is necessary. As with other multiphase systems exhibiting nano (1-100 nm) and meso (100-500 nm) order (such as biopolymers, block-copolymers, colloidal suspensions, liquid crystals), physical properties ranging from toughness to optical clarity are determined by morphology on various length scales which in turn arise from processing history. This is anticipated to be especially important for blends containing two or more constituents with fundamental structural features on the nanoscale, such as crystal lamellae and aluminosilicate sheets. Small-angle x-ray scattering experiments with synchrotron radiation reveal the presence of ultra-long range (20-60 nm) mesoscopic ordering of the layered silicate in molten polyamide 6-layered silicate nanocomposites. This superstructure of these semi-rigid inorganic sheets provides a confined environment to examine the crystallization of polyamide 6 with traditional bulk characterization techniques. In addition to a change lamellae organization and lamellae size, the presence of the aluminosilicate layers and extent of interfacial interactions (end-tethered v. physiadsorbed chains) substantially alters the nucleation rate, growth kinetics and Brill transition of the crystal phase as revealed by isothermal crystallization experiments monitored in-situ with synchrotron radiation. These exfoliated nanocomposites provide new opportunities to investigate confined polymer crystallization as well as provide insight into the origin of various property enhancements in these systems.

Field and Experimental Constraints on the Dynamics of Replenished Silicic Magma Chambers

NASA Astrophysics Data System (ADS)

Bain, A. A.; Jellinek, M.

2008-12-01

The underlying causes of catastrophic caldera-forming volcanic eruptions remain poorly understood. However, the occurrence of magma mixing within bimodal systems has become increasingly linked with such eruptions. In particular, buoyancy effects related to unstable density contrasts arising as a result of silicic- basaltic magma interactions may play an important role in the growth, differentiation and catastrophic eruption of silicic magma chambers. Evidence of such magmatic interactions can be found in layered intrusions from the Coastal Maine Magmatic Province (USA), where well-exposed cross-sections reveal hundreds of laterally-extensive basaltic sheets, apparently injected as intrusive lava flows onto the growing floors of silicic magma chambers. Interfaces between mafic and silicic layers are commonly sharply defined and exhibit deformation parallel to the inferred direction of palaeo-gravity. Our field observations suggest that the cooling, settling and buckling of gravitationally-unstable mafic replenishments may have driven large-scale (basalt layer depth) and small- scale (crystal diameter) upwelling and/or overturning of underlying buoyant silicic cumulate material. In order to characterize the full range of buoyancy effects, we carried out extensive spectral analysis of high- resolution digital field measurements from the Pleasant Bay and Mount Desert Island intrusions. In many cases, Rayleigh-Taylor theory and the longest measured wavelength of deformation indicate that a large and potentially-quantifiable fraction of the original, pre-replenishment silicic cumulate thickness may be missing, implying that vertical mass transfer has occurred. In addition, the shortest wavelengths of deformation are generally consistent with observed length-scales of crystals and clumps of crystals at these localities. With the aim of understanding the initial conditions that gave rise to these field observations, we conduct a series of laboratory experiments in which we observe the development of a Rayleigh-Taylor instability between a buoyant basal fluid layer overlain by a denser fluid layer. In order to identify the important parameters in the problem, we perform these experiments for a wide range of density contrasts, layer thicknesses and fluid rheologies (i.e. we vary particle concentration from the dilute to highly-crystalline limits to simulate freezing basalt and re-heated silicic cumulate rheologies). Regimes in which the entire silicic layer becomes unstable are potentially responsible for overturning the system and iniating large volcanic eruptions.

Pockels effect of silicate glass-ceramics: Observation of optical modulation in Mach–Zehnder system

PubMed Central

Yamaoka, Kazuki; Takahashi, Yoshihiro; Yamazaki, Yoshiki; Terakado, Nobuaki; Miyazaki, Takamichi; Fujiwara, Takumi

2015-01-01

Silicate glass has been used for long time because of its advantages from material’s viewpoint. In this paper, we report the observation of Pockels effect by Mach–Zehnder interferometer in polycrystalline ceramics made from a ternary silicate glass via crystallization due to heat-treatment, i.e., glass-ceramics. Since the silicate system is employed as the precursor, merits of glass material are fully utilized to fabricate the optical device component, in addition to that of functional crystalline material, leading us to provide an electro-optic device, which is introducible into glass-fiber network. PMID:26184722

Lithium conductivity in an Li-bearing double-ring silicate mineral, sogdianite

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

Park, S.-H.; Hoelzel, M.; Forschungsneutronenquelle Heinz Maier-Leibnitz

The crystal structure of an Li-bearing double-ring silicate mineral, sogdianite ((Zr{sub 1.18}Fe{sup 3+} {sub 0.55}Ti{sub 0.24}Al{sub 0.03})(Y {sub 1.64},Na{sub 0.36})K{sub 0.85}[Li{sub 3}Si{sub 12}O{sub 30}], P6/mcc, a{approx}10.06 A, c{approx}14.30 A, Z=2), was investigated by neutron powder diffraction from 300 up to 1273 K. Rietveld refinements of displacement parameters revealed high anisotropic Li motions perpendicular to the crystallographic c-axis, indicating an exchange process between tetrahedral T2 and octahedral A sites. AC impedance spectra of a sogdianite single crystal (0.04x0.09x0.25 cm{sup 3}) show that the material is an ionic conductor with conductivity values of {sigma}=4.1x10{sup -5} S cm{sup -1} at 923 K andmore » 1.2x10{sup -3} S cm{sup -1} at 1219 K perpendicular to the c-axis, involving two relaxation processes with activation energies of 1.26(3) and 1.08(3) eV, respectively. - Graphical abstract: Structure of sogdianite with atomic displacement parameter (ADP) ellipsoids at 1273 K.« less

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

PubMed

Shellnutt, J Gregory

2018-01-01

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

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

PubMed Central

2018-01-01

Geochemical modeling using the basalt composition analyzed at the Vega 2 landing site indicates that intermediate to silicic liquids can be generated by fractional crystallization and equilibrium partial melting. Fractional crystallization modeling using variable pressures (0.01 GPa to 0.5 GPa) and relative oxidation states (FMQ 0 and FMQ -1) of either a wet (H2O = 0.5 wt%) or dry (H2O = 0 wt%) parental magma can yield silicic (SiO2 > 60 wt%) compositions that are similar to terrestrial ferroan rhyolite. Hydrous (H2O = 0.5 wt%) partial melting can yield intermediate (trachyandesite to andesite) to silicic (trachydacite) compositions at all pressures but requires relatively high temperatures (≥ 950°C) to generate the initial melt at intermediate to low pressure whereas at high pressure (0.5 GPa) the first melts will be generated at much lower temperatures (< 800°C). Anhydrous partial melt modeling yielded mafic (basaltic andesite) and alkaline compositions (trachybasalt) but the temperature required to produce the first liquid is very high (≥ 1130°C). Consequently, anhydrous partial melting is an unlikely process to generate derivative liquids. The modeling results indicate that, under certain conditions, the Vega 2 composition can generate silicic liquids that produce granitic and rhyolitic rocks. The implication is that silicic igneous rocks may form a small but important component of the northeast Aphrodite Terra. PMID:29584745

Perspectives on Magmatic Differentiation of Mercury

NASA Astrophysics Data System (ADS)

Charlier, B.; Namur, O.; Cartier, C.

2018-05-01

Silicate/metal liquid immiscibility, crystallization of a magma ocean, partial melting of mantle rocks, and surface crystallization have shaped Mercury as we know it today. We review these processes based on high-T experiments at reducing conditions.

Design and fabrication of bismith-silicate photonic crystal fiber

NASA Astrophysics Data System (ADS)

Hasegawa, Tomoharu

2012-09-01

The process of design and fabrication of bismuth-silicate photonic crystal fiber (Bi-PCF) is reported. The Bi-PCF was fabricated by stack and draw method. This is the first trial of the fabrication of photonic crystal fiber made of bismuth-based glass with stack and draw method. The Bi-PCF structure was designed to reduce group-velocity-dispersion (GVD) in a plausible process. Thermal properties of the glass are investigated to establish the fabrication process. The applying pressure and pumping in fiber preform preparation were effectively utilized to control the air-hole diameter and arrangement. The fabricated Bi-PCF shows the well reduced GVD as the numerical calculation predicted. Fusion splicing between Bi-PCF and SMF-28 was also demonstrated.

IN SITU INFRARED MEASUREMENTS OF FREE-FLYING SILICATE DURING CONDENSATION IN THE LABORATORY

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

Ishizuka, Shinnosuke; Kimura, Yuki; Sakon, Itsuki

2015-04-20

We developed a new experimental system for infrared (IR) measurements on free-flying nucleating nanoparticles in situ and applied it to studies on silicate particles. We monitored the condensation of magnesium-bearing silicate nanoparticles from thermally evaporated magnesium and silicon monoxide vapor under an atmosphere of oxygen and argon. The IR spectrum of newly condensed particles showed a spectral feature for non-crystalline magnesium-bearing silicate that is remarkably consistent with the IR spectrum of astronomically observed non-crystalline silicate around oxygen-rich evolved stars. The silicate crystallized at <500 K and eventually developed a high crystallinity. Because of the size effects of nanoparticles, the silicatemore » would be expected to be like a liquid at least during the initial stages of nucleation and growth. Our experimental results therefore suggest decreasing the possible formation temperature of crystalline silicates in dust formation environments with relatively higher pressure.« less

Elasticity of the Earth's Lower Mantle Minerals at High Pressures: Implications to Understanding Seismic Observations of the Deep Mantle

NASA Astrophysics Data System (ADS)

Lin, J. F.; Yang, J.; Fu, S.

2017-12-01

Elasticity of the candidate lower-mantle minerals at relevant P-T conditions of the region provides critical information in understanding seismic profiles, compositional and mineralogical models, and geodynamic processes of the Earth's interior. Here we will discuss recent major research advances in the investigation of the elasticity of major lower-mantle minerals in a high-pressure diamond anvil cell coupled with Brillouin Light Scattering, Impulsive Stimulated Scattering (ISS), and X-ray diffraction. These have permitted direct and reliable measurements of both Vp and Vs to derive full elastic constants of single-crystal ferropericlase and (Fe, Al)-bearing bridgmanite as well as velocity profiles of polycrystalline silicate post-perovskite at relevant lower-mantle pressures. The effects of the spin transition on the single-crystal elasticity of ferropericlase are now well understood experimentally and theoretically1,2: the spin transition causes drastic softening in elastic constants involving the compressive stress component (C11 and C12) due to the additional Gibbs free energy term arising from the mixing of the high-spin and low-spin states, while the elastic constant(s) related to the shear stress component (C44) is not affected. This leads to significant reduction in VP/VS ratio within the spin transition of ferropericlase in the mid-lower mantle. The derived single-crystal Cij of bridgmanite at lower mantle pressures display relatively small elastic Vp and Vs anisotropies as compared to the ferropericlase counterpart. Using thermoelastic modelling, we will discuss the application of the elasticity of ferropericlase, bridgmanite, and silicate post-perovskite at relevant conditions of the Earth's lower mantle to differentiate the role of the thermal vs. chemical perturbations as well as the spin transition and iron partitioning effects in the reported seismic lateral heterogeneity in lower mantle as well as the D″ zone region3,4. We will address how recent elasticity results are applied to advance our understanding of seismic structures, mineralogical models, and geodynamic processes of the deep Earth's interior. References: 1Yang et al., Sci. Rep., 2015; 2Fu et al., Phys. Rev. Lett., 2017; 3Yang et al., J. Geophys. Res., 2016; 4Wu et al., Nature Comm., 2017.

Glass formation and crystallization in high-temperature glass-ceramics and Si3N4

NASA Technical Reports Server (NTRS)

Drummond, Charles H., III

1991-01-01

The softening of glassy grain boundaries in ceramic matrix composites and Si3N4 at high temperatures reduces mechanical strength and the upper-use temperature. By crystallizing this glass to a more refractory crystalline phase, a material which performs at higher temperatures may result. Three systems were examined: a cordierite composition with ZrO2 as a nucleating agent; celsian compositions; and yttrium silicate glasses both in bulk and intergranular in Si3N4. For the cordierite compositions, a series of metastable phases was obtained. The crystallization of these compositions was summarized in terms of metastable ternary isothermal sections. Zircon formed at the expense of ZrO2 and spinel. In SiC composites, the transformations were slower. In celsian, two polymorphs were crystallized. One phase, hexacelsian, which always crystallized, even when metastable, had an undesirable volume change. The other phase, celsian, was very difficult to crystallize. In yttrium silicate bulk glasses, similar in composition to the intergranular glass in Si3N4, a number of polymorphs of Y2Si2O7 were crystallized. The conditions under which these polymorphs formed are compared with crystallization in Si3N4.

Scanning electron microscope view of iron crystal

NASA Technical Reports Server (NTRS)

1972-01-01

A scanning electron microscope photograph of iron crystals which grow in a small vug or cavity in a recrystallized breccia (fragmented rock) from the Apollo 15 Hadley-Apennino lunar landing site. The largest crystal is three microns across. Perfectly developed crystals such as these indicate slow formation from a hot vapor as the rock was cooling. The crystals are resting on an interlocking lattice of pyroxene (calsium-magnesium-iron silicate).

Scanning electron microscope view of iron crystal

NASA Image and Video Library

1972-11-10

A scanning electron microscope photograph of iron crystals which grow in a small vug or cavity in a recrystallized breccia (fragmented rock) from the Apollo 15 Hadley-Apennino lunar landing site. The largest crystal is three microns across. Perfectly developed crystals such as these indicate slow formation from a hot vapor as the rock was cooling. The crystals are resting on an interlocking lattice of pyroxene (calsium-magnesium-iron silicate).

Rietveld refinement of the crystal structures of Rb2 XSi5O12 (X = Ni, Mn).

PubMed

Bell, Anthony M T; Henderson, C Michael B

2016-02-01

The synthetic leucite silicate framework mineral analogues Rb2 XSi5O12 {X = Ni [dirubidium nickel(II) penta-silicate] and Mn [dirubidium manganese(II) penta-silicate]} have been prepared by high-temperature solid-state synthesis. The results of Rietveld refinements, using X-ray powder diffraction data collected using Cu Kα X-rays, show that the title compounds crystallize in the space group Pbca and adopt the cation-ordered structure of Cs2CdSi5O12 and other leucites. The structures consist of tetra-hedral SiO4 and XO4 units sharing corners to form a partially substituted silicate framework. Extraframework Rb(+) cations sit in channels in the framework. All atoms occupy the 8c general position for this space group. In these refined structures, silicon and X atoms are ordered onto separate tetra-hedrally coordinated sites (T-sites). However, the Ni displacement parameter and the Ni-O bond lengths suggest that for the X = Ni sample, there may actually be some T-site cation disorder.

Rietveld refinement of the crystal structures of Rb2 XSi5O12 (X = Ni, Mn)

PubMed Central

Bell, Anthony M. T.; Henderson, C. Michael B.

2016-01-01

The synthetic leucite silicate framework mineral analogues Rb2 XSi5O12 {X = Ni [dirubidium nickel(II) penta­silicate] and Mn [dirubidium manganese(II) penta­silicate]} have been prepared by high-temperature solid-state synthesis. The results of Rietveld refinements, using X-ray powder diffraction data collected using Cu Kα X-rays, show that the title compounds crystallize in the space group Pbca and adopt the cation-ordered structure of Cs2CdSi5O12 and other leucites. The structures consist of tetra­hedral SiO4 and XO4 units sharing corners to form a partially substituted silicate framework. Extraframework Rb+ cations sit in channels in the framework. All atoms occupy the 8c general position for this space group. In these refined structures, silicon and X atoms are ordered onto separate tetra­hedrally coordinated sites (T-sites). However, the Ni displacement parameter and the Ni—O bond lengths suggest that for the X = Ni sample, there may actually be some T-site cation disorder. PMID:26958399

Magmatic interactions as recorded in plagioclase phenocrysts of Chaos Crags, Lassen Volcanic Center, California

USGS Publications Warehouse

Tepley, F. J.; Davidson, J.P.; Clynne, M.A.

1999-01-01

The silicic lava domes of Chaos Crags in Lassen Volcanic National Park contain a suite of variably quenched, hybrid basaltic andesite magmatic inclusions. The inclusions represent thorough mixing between rhyodacite and basalt recharge liquids accompanied by some mechanical disaggregation of the inclusions resulting in crystals mixing into the rhyodacite host preserved by quenching on dome emplacement. 87Sr/86Sr ratios (~0.7037-0.7038) of the inclusions are distinctly lower than those of the host rhyodacite (~0.704-0.7041), which are used to fingerprint the origin of mineral components and to monitor the mixing and mingling process. Chemical, isotopic, and textural characteristics indicate that the inclusions are hybrid magmas formed from the mixing and undercooling of recharge basaltic magma with rhyodacitic magma. All the host magma phenocrysts (biotite, plagioclase, hornblende and quartz crystals) also occur in the inclusions, where they are rimmed by reaction products. Compositional and strontium isotopic data from cores of unresorbed plagioclase crystals in the host rhyodacite, partially resorbed plagioclase crystals enclosed within basaltic andesite inclusions, and partially resorbed plagioclase crystals in the rhyodacitic host are all similar. Rim 87Sr/86Sr ratios of the partially resorbed plagioclase crystals in both inclusions and host are lower and close to those of the whole-rock hybrid basaltic andesite values. This observation indicates that some crystals originally crystallized in the silicic host, were partially resorbed and subsequently overgrown in the hybrid basaltic andesite magma, and then some of these partially resorbed plagioclase crystals were recycled back into the host rhyodacite. Textural evidence, in the form of sieve zones and major dissolution boundaries of the resorbed plagioclase crystals, indicates immersion of crystals into a hotter, more calcic magma. The occurrence of partially resorbed plagioclase together with plagioclase microlites and olivine crystals reflects disaggregation of inclusions and mingling of this material into the silicic host. These processes are commonplace in some orogenic magma systems and may be elucidated by isotopic microsampling and analysis of the plagioclases crystallizing from them.

Crystal settling and crystal growth caused by Ostwald Ripening in a terrestrial magma ocean under rotation

NASA Astrophysics Data System (ADS)

Maas, C.; Moeller, A.; Hansen, U.

2013-12-01

About 4.5 billion years ago the earth was covered by a heavily convecting and rotating global magma ocean which was caused by an impact of a mars-sized impactor in a later stage of the earth's accretion. After the separation of metal and silicate (see A. Möller, U. Hansen (2013)) and the formation of the earth's core it began to crystallize. Small silicate crystals emerge and grow by Ostwald Ripening when the fluid is supersaturated. This process results in shrinking of small crystals and growing of large crystals on behalf of the smaller ones. This leads to an altering of the crystal settling time. One question which is still under great debate is whether fractional or equilibrium crystallization occurred in the magma ocean. Fractional crystallization means that different mineral fractions settle one after the other which would lead to a strongly differentiated mantle after solidification of the magma ocean. In contrast to that equilibrium crystallization would result in a well mixed mantle. Whether fractional or equilibrium crystallization occurred is for example important for the starting model of plate tectonics or the understanding of the mantle development until today. To study the change of crystal radius in a convecting and rotating magma ocean we employed a 3D numerical model. Due to the low viscosity and strong rotation the influence of rotation on the early magma Ocean cannot be neglected. In the model the crystals are able to influence each other and the fluid flow. They are able to grow, shrink, vanish and form and gravitational, Coriolis and drag forces due to the fluid act on them. In our present work we study the crystal settling depending on different rotation rates and rotation axes with two configurations. For the polar setting the rotation axis is parallel, at the equator it is perpendicular to gravity. Low rotation at the pole leads to a large fraction of suspended crystals. With increasing rotation the crystals settle and form a thick layer at the bottom of the magma ocean. At the equator we find three regimes (see A. Möller, U. Hansen (2013)) depending on the rotation strength. At low rotation a high fraction of silicate crystals settle at the bottom. At higher rotation the crystals form a thick layer in the bottom 1/3 of box. At high rotation all crystals are suspended and we observe a ribbon structure in the middle of the box. With a second model we investigate growing and shrinking of crystals by Ostwald Ripening and include formation and melting. In general we observe the same behaviour and regimes as described above, however due to Ostwald Ripening the evolution of crystal radius with time depends on the strength of rotation and on the orientation of the rotation axis. Very first results show that at the pole the growth of the silicate crystals is limited. The resulting small radius leads to a slow crystal settling. At the equator the crystals are able to grow larger than at the pole and therefore settle faster. This could lead to an asymmetrical crystallization of the magma ocean. In an extreme case due to the different settling times this could lead to a well mixed mantle at the pole whereas at the equator the mantle could be strongly differentiated after the solidification of the magma ocean.

An Investigation of Armenite, BaCa2Al6Si9O302H2O.H2O Molecules and H Bonding in Microporous Silicates

NASA Astrophysics Data System (ADS)

Geiger, C. A.; Gatta, G.; Xue, X.; McIntyre, G.

2012-12-01

The crystal chemistry of armenite, ideally BaCa2Al6Si9O30.2H2O, a double-ring structure belonging to the milarite group, was studied to better understand the nature of extra-framework "Ca-oxygen-anion-H2O-molecule quasi-clusters" and H bonding behavior in microporous silicates. Neutron and X-ray single-crystal diffraction and IR powder and 1H NMR spectroscopic measurements were made. Four crystallographically independent Ca and H2O molecule sites were refined from the diffraction data, whereby both sites appear to have partial occupancies such that locally a Ca atom can have only a single H2O molecule bonded to it through an ion-dipole interaction. The Ca cation is further bonded to six O atoms of the framework forming a quasi cluster around it. The neutron results give the first static description of the protons in armenite, allowing bond distances and angles relating to the H2O molecules and H bonds to be determined. The IR spectrum of armenite is characterized in the OH-stretching region at RT by two broad bands at roughly 3470 and 3410 cm-1 and by a single H2O bending mode at 1654 cm-1. At 10 K four intense OH bands are located at 3479, 3454, 3401 and 3384 cm-1 and two H2O bending modes at 1650 and 1606 cm-1. The 1H MAS NMR spectrum shows a single strong resonance near 5.3 ppm and a smaller one near 2.7 ppm. The former can be assigned to H2O molecules bonded to Ca and the latter to weakly bonded H2O located at a site at the center of the structural double ring and it is partially occupied. The nature of H bonding in the microporous Ca-bearing zeolites scolecite, wairakite and epistilbite are also analyzed. The average OH stretching wavenumber shown by the IR spectra of armenite (~3435 cm-1) and scolecite (~3430 cm-1) are similar, while the average OH wavenumbers for wairakite (~3475 cm-1) and epistilbite (~3500 cm-1) are greater. In all cases the average OH stretching wavenumber is more similar to that of liquid water (~3400 cm-1) than of ice (~3220 cm-1). The strength of hydrogen bonding of the H2O molecules in microporous silicates does not appear to change greatly with decreasing temperatures from 300 K down to 10 K. The reason for this and also understanding better the ion-dipole interaction and its effect on H-bonding strength in Ca-quasi clusters need further study. The crystal structure of armenite viewed down [001] and [010].

Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

NASA Astrophysics Data System (ADS)

Pahlevan, K.; Karato, S. I.

2016-12-01

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

Molybdenite tricks with titanite give history of the Central Indian Tectonic Zone

NASA Astrophysics Data System (ADS)

Stein, Holly J.; Hannah, Judith L.; Pandit, Manoj K.; Mohanty, Saradaprasad; Corfu, Fernando; Zimmerman, Aaron

2014-05-01

The time that the cratonic blocks joined to form peninsular India creating the E-W-trending Central Indian Tectonic Zone (CITZ) is important for tectonic reconstructions and Paleoproterozoic glaciations, and fundamental to understanding how sutures behave through time. An abundance of recent literature highlights ~1.0 Ga as the time of suturing. This late 1.0 Ga meeting of the two cratons, however, is increasingly difficult to reconcile. One of the well-studied and well-mapped terranes in the southern part of the CITZ is the Sausar Belt [1]. The metasedimentary and metavolcanic rocks comprising the extensive Paleoproterozoic Sausar Group are multiply deformed. To examine the history of the Sausar Belt from a new vantage, we employed Re-Os dating of molybdenite, a sulfide that serves faithfully as a single-mineral radiometric clock in both magmatic and metamorphic environments [2]. Molybdenite is rare in the Sausar belt. Samples containing a 1-cm molybdenite patch and coarse-grained, euhedral, clear brown titanite were acquired from two different varieties of calc-silicate rocks near the village of Umri in central India. The molybdenite occurs in a calcite-quartz vein that clearly cross-cuts a strongly deformed calc-silicate host with quartz-biotite and quartz bands at the cm scale. This vein, metamorphic in character, is about 1-cm-wide and slightly deformed. The molybdenite was contained wholly within the vein. To check for possible Re-Os decoupling [2], we split the molybdenite patch into seven subsamples, analyzing each fraction separately; in sum, these seven fractions account for the entire molybdenite crystal. We obtained extremely disparate ages for the individual fractions, ranging from 1.4 to 3.1 Ga. These data were recombined on an atomic basis to calculate the Re-Os age for the entire crystal, a trick we employed after affirming there was no additional sulfide and no additional molybdenite that might compete for Re and Os in our hand-sample of 10 x 15 cm. This circumstance provided us the opportunity to turn Re-Os decoupling to our advantage. The whole-crystal Re-Os molybdenite age on combining data from individual separates is between 2.41 and 2.45 Ga, depending on estimates of very minor silicate dilution as the crystal was extracted piecemeal from the vein. The U-Pb age for euhedral titanite crystals in a dense massive calc-silicate host, not unexpectedly, is ~1.0 Ga. The molybdenite and titanite record two different episodes of metamorphism. These results suggest that the Sausar Group calc-silicate rocks we analyzed are earliest Paleoproterozoic, >2.41 Ga. Shortly after deposition these rocks were metamorphosed - the first event in a long history of metamorphism and deformation continually focused along an ancient suture. These results have implications for the CITZ, and are similar to ages found in terranes on either side of this continental scale collisional belt [3,4]. This study was funded by the U.S. National Science Foundation (EAR-1119655). References Cited [1] Mohanty, S. (2010) Journal of Asian Earth Sciences 39: 516-526. [2] Stein et al. (2003) Geochimica et Cosmochimica Acta 67: 3673-3686. [3] Stein et al. (2004) Precambrian Research 134: 189-226. [4] Radhakrishna et al. (2013) Precambrian Research 226: 91-104.

Synthesis, characterization of CaF2 doped silicate glass-ceramics.

PubMed

Riaz, Madeeha; Zia, Rehana; Mirza, Ambreen; Hussain, Tousif; Bashir, Farooq; Anjum, Safia

2017-06-01

This paper reports the fabrication and characterization of silicate glass-ceramics doped with (0-12mol%) CaF 2 . TGA-DSC analysis was carried out to determine the crystallization temperature and stability of glass measured by two glass parameters; Hruby parameter K H =(T x -T g )/(T L -T x ) and Weinberg parameter K W =(T c -T g )/T L . It was found that with CaF 2 doping improved sinterability at low temperature and provided stability to the glass. The XRD pattern exhibits a single phase of combeite and doping of CaF 2 cause increase in crystallite size. Microstructure of samples was also improved with CaF 2 addition, pores were significantly reduced. After 15days immersion in simulated body fluid all samples developed apatite layer onto its surface. Hence, the addition of CaF 2 provided bioactive glass-ceramic material having a low processing temperature. Copyright © 2017 Elsevier B.V. All rights reserved.

Coherent Transient Systems Evaluation

DTIC Science & Technology

1993-06-17

europium doped yttrium silicate in collaboration with IBM Almaden Research Center. Research into divalent ion doped crystals as photon gated materials...noise limited model and ignore the non-ideal properties of the medium, nonlinear effects, spatial crosstalk, gating efficiencies, local heating, the...demonstration of the coherent transient continuous optical processor was performed in europium doped yttrium silicate. Though hyperfine split ground

A new nonlinear optical silicate carbonate K2Ca[Si2O5](CO3) with a hybrid structure of kalsilite and soda-like layered fragments

NASA Astrophysics Data System (ADS)

Belokoneva, Elena L.; Stefanovich, Sergey Yu.; Volkov, Anatoly S.; Dimitrova, Olga V.

2016-10-01

Single crystals of a new silicate carbonate, K2Ca[Si2O5](CO3), have been synthesized in a multi-components hydrothermal solution with a pH value close to neutral and a high concentration of a carbonate mineralizer. The new compound has an axial structure (s.g. P6322) with unit cell parameters a = 5.04789 (15), c = 17.8668 (6) Å. Pseudosymmetry of the structure corresponds to s.g. P63/mmc which is broken only by one oxygen position. The structure consists of two layered fragments: one of the type of the mineral kalsilite (KAlSiO4) and the other of the high-temperature soda-like α-Na2CO3, Ca substituting for Na. The electro-neutral layer K2[Si2O5] (denoted K) as well as the layer Ca(CO3) (denoted S) may separately correspond to individual structures. In K2Ca[Si2O5](CO3) the S-K layers are connected together via Ca-O interactions between Ca atoms from the carbonate layer and apical O atoms from the silicate one, and also via K-O interlayer interactions. A hypothetical acentric structure, sp.gr. P-62c, is predicted on the basis of the order-disorder theory. It presents another symmetrical option for the arrangement of K-layers relative to S-layers. The K,Ca-silicate-carbonate powder produces a moderate SHG signal that is two times larger that of the α-quartz powder standard and close to other silicates with acentric structures and low electronic polarizability.

Fractionation products of basaltic komatiite magmas at lower crustal pressures: implications for genesis of silicic magmas in the Archean

NASA Astrophysics Data System (ADS)

Mandler, B. E.; Grove, T. L.

2015-12-01

Hypotheses for the origin of crustal silicic magmas include both partial melting of basalts and fractional crystallization of mantle-derived melts[1]. Both are recognized as important processes in modern environments. When it comes to Archean rocks, however, partial melting hypotheses dominate the literature. Tonalite-trondhjemite-granodiorite (TTG)-type silicic magmas, ubiquitous in the Archean, are widely thought to be produced by partial melting of subducted, delaminated or otherwise deeply buried hydrated basalts[2]. The potential for a fractional crystallization origin for TTG-type magmas remains largely unexplored. To rectify this asymmetry in approaches to modern vs. ancient rocks, we have performed experiments at high pressures and temperatures to closely simulate fractional crystallization of a basaltic komatiite magma in the lowermost crust. These represent the first experimental determinations of the fractionation products of komatiite-type magmas at elevated pressures. The aim is to test the possibility of a genetic link between basaltic komatiites and TTGs, which are both magmas found predominantly in Archean terranes and less so in modern environments. We will present the 12-kbar fractionation paths of both Al-depleted and Al-undepleted basaltic komatiite magmas, and discuss their implications for the relative importance of magmatic fractionation vs. partial melting in producing more evolved, silicic magmas in the Archean. [1] Annen et al., J. Petrol., 47, 505-539, 2006. [2] Moyen J-F. & Martin H., Lithos, 148, 312-336, 2012.

Crystalline Silicates in Comets: Modeling Irregularly-Shaped Forsterite Crystals and Its Implications on Condensation Conditions

NASA Technical Reports Server (NTRS)

Wooden, Diane H.; Lindsay, Sean S.

2011-01-01

Crystalline silicates in comets are a product of the condensation in the hot inner regions (T > or approx. equals 1400 K [1]) of our proto-planetary disk or annealing at somewhat lower temperatures (T > or approx. equals 1000-1200 K) [2, 3, 4] in shocks coupled with disk evolutionary processes that include radial transport of crystals from their formation locations out to the cold outer regions where comet nuclei formed. The grain shape of forsterite (crystals) could be indicative of their formation pathways at high temperatures through vapor-solid condensation or at lower temperatures through vapor-liquid-solid formation and growth [5, 6, 7]. Experiments demonstrate that crystals that formed from a rapidly cooled highly supersaturated silicate vapor are characterized by bulky, platy, columnar/needle and droplet shapes for values of temperature and supersaturation, T and sigma, of 1000-1450 C and < 97, 700-1000 C and 97-161, 580-820 C and 131-230, and <500 C and > 230, respectively [7]. The experimental columnar/needle shapes, which form by vapor-liquid-solid at lower temperatures (<820 C), are extended stacks of plates, where the extension is not correlated with an axial direction: columnar/needles may be extended in the c-axis or a-axis direction, can change directions, and/or are off-kilter or a bit askew extending in a combination of the a- and c-axis direction.

Dehydroxylated clay silicates on Mars: Riddles about the Martian regolith solved with ferrian saponites

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1992-01-01

Clay silicates, resulting from the chemical weathering of volcanic glasses and basaltic rocks of Mars, are generally believed to be major constituents of the martian regolith and atmospheric dust. Because little attention has been given to the role, if any, of Mg-bearing clay silicates on the martian surface, the crystal chemistry, stability, and reactivity of Mg-Fe smectites are examined. Partially dehydroxylated ferrian saponites are suggested to be major constituents of the surface of Mars, regulating several properties of the regolith.

A Study of Defect Behavior in Almandine Garnet

NASA Astrophysics Data System (ADS)

Geiger, C. A.; Brearley, A. J.; Dachs, E.; Tipplet, G.; Rossman, G. R.

2016-12-01

Transport and diffusion in crystals are controlled by defects. However, a good understanding of the defect types in many silicates, including garnet, is not at hand. We undertook a study on synthetic almandine, ideal end-member Fe3Al2Si3O12, to better understand its precise chemical and physical properties and defect behavior. Crystals were synthesized at high pressures and temperatures under different fO2 conditions using various starting materials with H2O and without. The almandine obtained came in polycrystalline and single-crystal form. The synthetic reaction products and crystals were carefully characterized using X-ray powder diffraction, electron microprobe and TEM analysis and with 57Fe Mössbauer, UV/VIS single-crystal absorption and IR single-crystal spectroscopy. Various possible intrinsic defects, such as the Frenkel, Schottky and site-disorder types, along with Fe3+, in both synthetic and natural almandine crystals, were analyzed based on model defects expressed in Kröger-Vink notation. Certain types of minor microscopic- to macroscopic-sized precipitation or exsolution phases, including some that are nanosized, that are observed in synthetic almandine (e.g., magnetite), as well as in more compositionally complex natural crystals (e.g., magnetite, rutile, ilmenite), may result from defect reactions. An explanation for their origin through minor amounts of defects in garnet has certain advantages over other models that have been put forth in the literature that assume strict garnet stoichiometry for their formation and/or open-system atomic transport over relatively long length scales. Physical properties, including magnetic, electrical conductivity and diffusion behavior, as well as the color, of almandine are also analyzed in terms of various possible model defects. It is difficult, if not impossible, to synthesize stoichiometric end-member almandine, Fe3Al2Si3O12, in the laboratory, as small amounts of extrinsic OH- and/or Fe3+ defects, for example, are typically present depending on the synthesis route. The nature of possible nonstoichiometry in synthetic almandine and natural almandine-rich crystals is discussed and compared.

Deformation, Stress Relaxation, and Crystallization of Lithium Silicate Glass Fibers Below the Glass Transition Temperature

NASA Technical Reports Server (NTRS)

Ray, Chandra S.; Brow, Richard K.; Kim, Cheol W.; Reis, Signo T.

2004-01-01

The deformation and crystallization of Li(sub 2)O (center dot) 2SiO2 and Li(sub 2)O (center dot) 1.6SiO2 glass fibers subjected to a bending stress were measured as a function of time over the temperature range -50 to -150 C below the glass transition temperature (Tg). The glass fibers can be permanently deformed at temperatures about 100 C below T (sub)g, and they crystallize significantly at temperatures close to, but below T,, about 150 C lower than the onset temperature for crystallization for these glasses in the no-stress condition. The crystallization was found to occur only on the surface of the glass fibers with no detectable difference in the extent of crystallization in tensile and compressive stress regions. The relaxation mechanism for fiber deformation can be best described by a stretched exponential (Kohlrausch-Williams-Watt (KWW) approximation), rather than a single exponential model.The activation energy for stress relaxation, Es, for the glass fibers ranges between 175 and 195 kJ/mol, which is considerably smaller than the activation energy for viscous flow, E, (about 400 kJ/mol) near T, for these glasses at normal, stress-free condition. It is suspected that a viscosity relaxation mechanism could be responsible for permanent deformation and crystallization of the glass fibers below T,

Experimental study on the Neapolitan Yellow Tuff: Salt weathering and consolidation

NASA Astrophysics Data System (ADS)

La Russa, Mauro Francesco; Ruffolo, Silvestro Antonio; Alvarez de Buergo, Monica; Ricca, Michela; Belfiore, Cristina Maria; Pezzino, Antonino; Mirocle Crisci, Gino

2016-04-01

Salt crystallization is one of the major weathering agents in porous building materials due to the crystallization pressure exerted by salt crystals growing in confined pores. The consolidation of such degraded stone materials is a crucial issue in the field of Cultural Heritage restoration. This contribution deals with laboratory experimentation carried out on the Neapolitan Tuff, a pyroclastic rock largely used in the Campanian architecture. Several specimens, collected from a historical quarry nearby the city of Naples, were treated with two different consolidating products: a suspension of nanosilica in water (Syton X30®) and ethyl silicate (Estel 1000®) dispersed in organic solvent (TEOS). Then, in order to assess the effectiveness of consolidation treatments, both treated and untreated samples underwent accelerated degradation through salt crystallization tests. A multi-analytical approach, including mercury intrusion porosimetry, peeling tests and point load test, was employed to evaluate the correlation between the salt crystallization and the micro-structural features of the examined tuff specimens. In addition, the calculation of the crystallization pressures was also performed in order to make a correlation between the porous structure of the tuff and its susceptivity to salt crystallization. Obtained results show that both the tested products increase the resistance of tuff to salt crystallization, although inducing an increase of crystallization pressure. Ethyl silicate, however, shows a better behaviour in terms of superficial cohesion, even after several degradation cycles.

Quantum Mechanical Metric for Internal Cohesion in Cement Crystals

PubMed Central

Dharmawardhana, C. C.; Misra, A.; Ching, Wai-Yim

2014-01-01

Calcium silicate hydrate (CSH) is the main binding phase of Portland cement, the single most important structural material in use worldwide. Due to the complex structure and chemistry of CSH at various length scales, the focus has progressively turned towards its atomic level comprehension. We study electronic structure and bonding of a large subset of the known CSH minerals. Our results reveal a wide range of contributions from each type of bonding, especially hydrogen bonding, which should enable critical analysis of spectroscopic measurements and construction of realistic C-S-H models. We find the total bond order density (TBOD) as the ideal overall metric for assessing crystal cohesion of these complex materials and should replace conventional measures such as Ca:Si ratio. A rarely known orthorhombic phase Suolunite is found to have higher cohesion (TBOD) in comparison to Jennite and Tobermorite, which are considered the backbone of hydrated Portland cement. PMID:25476741

Atomic force microscopy of atomic-scale ledges and etch pits formed during dissolution of quartz

NASA Technical Reports Server (NTRS)

Gratz, A. J.; Manne, S.; Hansma, P. K.

1991-01-01

The processes involved in the dissolution and growth of crystals are closely related. Atomic force microscopy (AFM) of faceted pits (called negative crystals) formed during quartz dissolution reveals subtle details of these underlying physical mechanisms for silicates. In imaging these surfaces, the AFM detected ledges less than 1 nm high that were spaced 10 to 90 nm apart. A dislocation pit, invisible to optical and scanning electron microscopy measurements and serving as a ledge source, was also imaged. These observations confirm the applicability of ledge-motion models to dissolution and growth of silicates; coupled with measurements of dissolution rate on facets, these methods provide a powerful tool for probing mineral surface kinetics.

The nature and origin of ureilites

NASA Technical Reports Server (NTRS)

Berkley, J. L.; Taylor, G. J.; Keil, K.; Harlow, G. E.; Prinz, M.

1980-01-01

A theory of the origin of ureilites is presented based on mineralogical and petrological investigation of eight species including Kenna, Novo Urei, and Goalpara. The theory suggests that ureilites are primarily olivine-pigeonite cumulates crystallized from a silicate liquid which also contained suspended solid carbon phases. The carbon induced reduction of the melt and affected the ureilite mineral compositions. Petrofabric analyses show that mafic silicates are oriented in lineated and foliated patterns similar to cumulate rocks; strain rate of silicates suggests that ureilites were deformed after lithification by a mild tectonic stress and a moderate to severe shock.

Rapid cooling and cold storage in a silicic magma reservoir recorded in individual crystals.

PubMed

Rubin, Allison E; Cooper, Kari M; Till, Christy B; Kent, Adam J R; Costa, Fidel; Bose, Maitrayee; Gravley, Darren; Deering, Chad; Cole, Jim

2017-06-16

Silicic volcanic eruptions pose considerable hazards, yet the processes leading to these eruptions remain poorly known. A missing link is knowledge of the thermal history of magma feeding such eruptions, which largely controls crystallinity and therefore eruptability. We have determined the thermal history of individual zircon crystals from an eruption of the Taupo Volcanic Zone, New Zealand. Results show that although zircons resided in the magmatic system for 10 3 to 10 5 years, they experienced temperatures >650° to 750°C for only years to centuries. This implies near-solidus long-term crystal storage, punctuated by rapid heating and cooling. Reconciling these data with existing models of magma storage requires considering multiple small intrusions and multiple spatial scales, and our approach can help to quantify heat input to and output from magma reservoirs. Copyright © 2017, American Association for the Advancement of Science.

Laboratory Annealing Experiments Of Refractory Silicate Grain Analogs Using Differential Scanning Calorimetry

NASA Technical Reports Server (NTRS)

Kimura, Yuki; Nuth, Joseph A., III; Tsukamota, Katsuo; Kaito, Chihiro

2010-01-01

Exothermic reactions during the annealing of laboratory synthesized amorphous magnesium-bearing silicate particles used as grain analogs of cosmic dust were detected by differential scanning calorimetry (DSC) in air. With infrared spectroscopy and transmission electron microscopy, we show that cosmic dust could possibly undergo fusion to larger particles, with oxidation of magnesium silicide and crystallization of forsterite as exothermic reactions in the early solar system. The reactions begin at approximately 425, approximately 625, and approximately 1000 K, respectively, and the reaction energies (enthalpies) are at least 727, 4151, and 160.22 J per gram, respectively. During the crystallization of forsterite particles, the spectral evolution of the 10 micrometer feature from amorphous to crystalline was observed to begin at lower temperature than the crystallization temperature of 1003 K. During spectral evolution at lower temperature, nucleation and/or the formation of nanocrystallites of forsterite at the surface of the grain analogs was observed.

Mid-infrared spectra of cometary dust: the evasion of its silicate mineralogy

NASA Astrophysics Data System (ADS)

Kimura, H.; Chigai, T.; Yamamoto, T.

2008-04-01

Infrared spectra of dust in cometary comae provide a way to identify its silicate constituents, and this is crucial for correctly understanding the condition under which our planetary system is formed. Recent studies assign a newly detected peak at a wavelength of 9.3 μm to pyroxenes and regard them as the most abundant silicate minerals in comets. Here we dispense with this pyroxene hypothesis to numerically reproduce the infrared features of cometary dust in the framework of our interstellar dust models. Presolar interstellar dust in a comet is modeled as fluffy aggregates consisting of submicrometer-sized organic grains with an amorphous-silicate core that undergoes nonthermal crystallization in a coma. We assert that forsterite (Mg2SiO4) is the carrier of all the observed features, including the 9.3 μm peak and that the major phase of iron is sulfides rather than iron-rich silicates.

Along and Across Arc Variation of the Central Andes by Single Crystal Trace Element Analaysis

NASA Astrophysics Data System (ADS)

Michelfelder, G.; Sundell, T.; Wilder, A.; Salings, E. E.

2017-12-01

Along arc and across arc geochemical variations at continental volcanic arcs are influenced by a number of factors including the composition and thickness of the continental crust, mantle heterogeneity, and fluids from the subducted slab. Whole rock geochemical trends along and across the arc front of the Central Volcanic Zone (CVZ) have been suggested to be primarily influenced by the composition and thickness of the crust. In the CVZ, Pb isotopic domains relate volcanic rock compositions to the crustal basement and systematically varies with crustal age. It has been shown repeatedly that incompatible trace element trends and trace element ratios can be used to infer systematic geochemical changes. However, there is no rule linking magmatic process or chemical heterogeneity/ homogeneity as a result of large crustal magma storage reservoirs such as MASH zones to the observed variation. Here we present a combination of whole rock major- and trace element data, isotopic data and in situ single crystal data from plagioclase, pyroxene and olivine for six stratovolcanoes along the arc front and in the back arc of the CVZ. We compare geochemical trends at the whole and single crystal scale. These volcanoes include lava flows and domes from Cerro Uturuncu in the back-arc, Aucanquilcha, Ollagüe, San Pedro-San Pablo, Lascar, and Lazufre from the arc front. On an arc-wide scale, whole rock samples of silicic lavas from these six composite volcanoes display systematically higher K2O, LILE, REE and HFSE contents and 87Sr/86Sr ratios with increasing distance from the arc-front. In contrast, the lavas have systematically lower Na2O, Sr, and Ba contents; LILE/HFSE ratios; 143Nd/144Nd ratios; and more negative Eu anomalies. Silicic magmas along the arc-front reflecting melting of young, mafic composition source rocks with the continental crust becoming increasingly older and more felsic toward the east. These trends are paralleled in the trace element compositions of plagioclase cores which systematically become less diverse in composition in younger lava flows from each center. We suggest these trends result from progressively smaller degrees of mantle partial melting, primary melt generation, and crustal hybridization with distance from the arc-front and varying influence of MASH zone processes.

CUMULATE ROCKS ASSOCIATED WITH CARBONATE ASSIMILATION, HORTAVÆR COMPLEX, NORTH-CENTRAL NORWAY

NASA Astrophysics Data System (ADS)

Barnes, C. G.; Prestvik, T.; Li, Y.

2009-12-01

The Hortavær igneous complex intruded high-grade metamorphic rocks of the Caledonian Helgeland Nappe Complex at ca. 466 Ma. The complex is an unusual mafic-silicic layered intrusion (MASLI) because the principal felsic rock type is syenite and because the syenite formed in situ rather than by deep-seated partial melting of crustal rocks. Magma differentiation in the complex was by assimilation, primarily of calc-silicate rocks and melts with contributions from marble and semi-pelites, plus fractional crystallization. The effect of assimilation of calcite-rich rocks was to enhance stability of fassaitic clinopyroxene at the expense of olivine, which resulted in alkali-rich residual melts and lowering of silica activity. This combination of MASLI-style emplacement and carbonate assimilation produced three types of cumulate rocks: (1) Syenitic cumulates formed by liquid-crystal separation. As sheets of mafic magma were loaded on crystal-rich syenitic magma, residual liquid was expelled, penetrating the overlying mafic sheets in flame structures, and leaving a cumulate syenite. (2) Reaction cumulates. Carbonate assimilation, illustrated by a simple assimilation reaction: olivine + calcite + melt = clinopyroxene + CO2 resulted in cpx-rich cumulates such as clinopyroxenite, gabbro, and mela-monzodiorite, many of which contain igneous calcite. (3) Magmatic skarns. Calc-silicate host rocks underwent partial melting during assimilation, yielding a Ca-rich melt as the principal assimilated material and permitting extensive reaction with surrounding magma to form Kspar + cpx + garnet-rich ‘cumulate’ rocks. Cumulate types (2) and (3) do not reflect traditional views of cumulate rocks but instead result from a series of melt-present discontinuous (peritectic) reactions and partial melting of calc-silicate xenoliths. In the Hortavær complex, such cumulates are evident because of the distinctive peritectic cumulate assemblages. It is unclear whether assimilation of ‘normal’ silicate rocks results in peritectic assemblages, or whether they could be identified as such if they exist.

Multistage Core Formation in Planetesimals Revealed by Numerical Modeling and Hf-W Chronometry of Iron Meteorites

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

Neumann, W.; Kruijer, T. S.; Breuer, D.

Iron meteorites provide some of the most direct insights into the processes and timescales of core formation in planetesimals. Of these, group IVB irons stand out by having one of the youngest 182Hf- 182W model ages for metal segregation (2.9 ± 0.6 Ma after solar system formation), as well as the lowest bulk sulfur content and hence highest liquidus temperature. Here in this paper, using a new model for the internal evolution of the IVB parent body, we show that a single stage of metal-silicate separation cannot account for the complete melting of pure Fe metal at the relatively latemore » time given by the Hf-W model age. Instead, a complex metal-silicate separation scenario is required that includes migration of partial silicate melts, formation of a shallow magma ocean, and core formation in two distinct stages of metal segregation. In the first stage, a protocore formed at ≈1.5 Ma via settling of metal particles in a mantle magma ocean, followed by metal segregation from a shallow magma ocean at ≈5.4 Ma. As these stages of metal segregation occurred at different times, the two metal fractions had different 182W compositions. Consequently, the final 182W composition of the IVB core does not correspond to a single differentiation event, but represents the average composition of early- and late-segregated core fractions. Our best fit model indicates an ≈100 km radius for the IVB parent body and provides an accretion age of ≈0.1–0.5 Ma after solar system formation. The computed solidification time is, furthermore, consistent with the Re-Os age for crystallization of the IVB core.« less

Multistage Core Formation in Planetesimals Revealed by Numerical Modeling and Hf-W Chronometry of Iron Meteorites

DOE PAGES

Neumann, W.; Kruijer, T. S.; Breuer, D.; ...

2018-02-01

Iron meteorites provide some of the most direct insights into the processes and timescales of core formation in planetesimals. Of these, group IVB irons stand out by having one of the youngest 182Hf- 182W model ages for metal segregation (2.9 ± 0.6 Ma after solar system formation), as well as the lowest bulk sulfur content and hence highest liquidus temperature. Here in this paper, using a new model for the internal evolution of the IVB parent body, we show that a single stage of metal-silicate separation cannot account for the complete melting of pure Fe metal at the relatively latemore » time given by the Hf-W model age. Instead, a complex metal-silicate separation scenario is required that includes migration of partial silicate melts, formation of a shallow magma ocean, and core formation in two distinct stages of metal segregation. In the first stage, a protocore formed at ≈1.5 Ma via settling of metal particles in a mantle magma ocean, followed by metal segregation from a shallow magma ocean at ≈5.4 Ma. As these stages of metal segregation occurred at different times, the two metal fractions had different 182W compositions. Consequently, the final 182W composition of the IVB core does not correspond to a single differentiation event, but represents the average composition of early- and late-segregated core fractions. Our best fit model indicates an ≈100 km radius for the IVB parent body and provides an accretion age of ≈0.1–0.5 Ma after solar system formation. The computed solidification time is, furthermore, consistent with the Re-Os age for crystallization of the IVB core.« less

Multistage Core Formation in Planetesimals Revealed by Numerical Modeling and Hf-W Chronometry of Iron Meteorites

NASA Astrophysics Data System (ADS)

Neumann, W.; Kruijer, T. S.; Breuer, D.; Kleine, T.

2018-02-01

Iron meteorites provide some of the most direct insights into the processes and timescales of core formation in planetesimals. Of these, group IVB irons stand out by having one of the youngest 182Hf-182W model ages for metal segregation (2.9 ± 0.6 Ma after solar system formation), as well as the lowest bulk sulfur content and hence highest liquidus temperature. Here, using a new model for the internal evolution of the IVB parent body, we show that a single stage of metal-silicate separation cannot account for the complete melting of pure Fe metal at the relatively late time given by the Hf-W model age. Instead, a complex metal-silicate separation scenario is required that includes migration of partial silicate melts, formation of a shallow magma ocean, and core formation in two distinct stages of metal segregation. In the first stage, a protocore formed at ≈1.5 Ma via settling of metal particles in a mantle magma ocean, followed by metal segregation from a shallow magma ocean at ≈5.4 Ma. As these stages of metal segregation occurred at different times, the two metal fractions had different 182W compositions. Consequently, the final 182W composition of the IVB core does not correspond to a single differentiation event, but represents the average composition of early- and late-segregated core fractions. Our best fit model indicates an ≈100 km radius for the IVB parent body and provides an accretion age of ≈0.1-0.5 Ma after solar system formation. The computed solidification time is, furthermore, consistent with the Re-Os age for crystallization of the IVB core.

Formation of replicating saponite from a gel in the presence of oxalate: implications for the formation of clay minerals in carbonaceous chondrites and the origin of life.

PubMed

Schumann, Dirk; Hartman, Hyman; Eberl, Dennis D; Sears, S Kelly; Hesse, Reinhard; Vali, Hojatollah

2012-06-01

The potential role of clay minerals in the abiotic origin of life has been the subject of ongoing debate for the past several decades. At issue are the clay minerals found in a class of meteorites known as carbonaceous chondrites. These clay minerals are the product of aqueous alteration of anhydrous mineral phases, such as olivine and orthopyroxene, that are often present in the chondrules. Moreover, there is a strong correlation in the occurrence of clay minerals and the presence of polar organic molecules. It has been shown in laboratory experiments at low temperature and ambient pressure that polar organic molecules, such as the oxalate found in meteorites, can catalyze the crystallization of clay minerals. In this study, we show that oxalate is a robust catalyst in the crystallization of saponite, an Al- and Mg-rich, trioctahedral 2:1 layer silicate, from a silicate gel at 60°C and ambient pressure. High-resolution transmission electron microscopy analysis of the saponite treated with octadecylammonium (n(C)=18) cations revealed the presence of 2:1 layer structures that have variable interlayer charge. The crystallization of these differently charged 2:1 layer silicates most likely occurred independently. The fact that 2:1 layer silicates with variable charge formed in the same gel has implications for our understanding of the origin of life, as these 2:1 clay minerals most likely replicate by a mechanism of template-catalyzed polymerization and transmit the charge distribution from layer to layer. If polar organic molecules like oxalate can catalyze the formation of clay-mineral crystals, which in turn promote clay microenvironments and provide abundant adsorption sites for other organic molecules present in solution, the interaction among these adsorbed molecules could lead to the polymerization of more complex organic molecules like RNA from nucleotides on early Earth.

Formation of replicating saponite from a gel in the presence of oxalate: implications for the formation of clay minerals in carbonaceous chondrites and the origin of life

USGS Publications Warehouse

Schumann, Dirk; Hartman, Hyman; Eberl, Dennis D.; Sears, S. Kelly; Hesse, Reinhard; Vali, Hojatollah

2012-01-01

The potential role of clay minerals in the abiotic origin of life has been the subject of ongoing debate for the past several decades. At issue are the clay minerals found in a class of meteorites known as carbonaceous chondrites. These clay minerals are the product of aqueous alteration of anhydrous mineral phases, such as olivine and orthopyroxene, that are often present in the chondrules. Moreover, there is a strong correlation in the occurrence of clay minerals and the presence of polar organic molecules. It has been shown in laboratory experiments at low temperature and ambient pressure that polar organic molecules, such as the oxalate found in meteorites, can catalyze the crystallization of clay minerals. In this study, we show that oxalate is a robust catalyst in the crystallization of saponite, an Al- and Mg-rich, trioctahedral 2:1 layer silicate, from a silicate gel at 60°C and ambient pressure. High-resolution transmission electron microscopy analysis of the saponite treated with octadecylammonium (n(C)=18) cations revealed the presence of 2:1 layer structures that have variable interlayer charge. The crystallization of these differently charged 2:1 layer silicates most likely occurred independently. The fact that 2:1 layer silicates with variable charge formed in the same gel has implications for our understanding of the origin of life, as these 2:1 clay minerals most likely replicate by a mechanism of template-catalyzed polymerization and transmit the charge distribution from layer to layer. If polar organic molecules like oxalate can catalyze the formation of clay-mineral crystals, which in turn promote clay microenvironments and provide abundant adsorption sites for other organic molecules present in solution, the interaction among these adsorbed molecules could lead to the polymerization of more complex organic molecules like RNA from nucleotides on early Earth.

The Brittle-Ductile Transition in Crystal and Bubble-bearing Magmas

NASA Astrophysics Data System (ADS)

Caricchi, L.; Pistone, M.; Cordonnier, B.; Tripoli, B.; Ulmer, P.; Reusser, E.; Marone, F.; Burlini, L.

2011-12-01

The strain response of magma is critically dependent upon its viscosity, the magnitude of the applied stress and the experimental time-scale. The brittle-ductile transition in pure silicate melts is expected for an applied stress approaching 108±0.5 Pa (Dingwell, 1997). However, magmas are mostly mixture of crystal and bubble-bearing silicate melts. To date, there are no data to constrain the ductile-brittle transition for three-phase magmas. Thus, we conducted consistent torsion experiments at high temperature (673-973 K) and high pressure (200 MPa), in the strain rate range 1*10-5-4*10-3 s-1, using a HT-HP internally-heated Paterson-type rock deformation apparatus. The samples are composed of hydrous haplogranitic glass, quartz crystals (24-65 vol%) and CO2-rich gas-pressurized bubbles (9-12 vol%). The applied strain rate was increased until brittle failure occurred; micro-fracturing and healing processes commonly occurred before sample macroscopic fracturing. The experimental results highlight a clear relationship between the effective viscosity of the three-phase magmas, strain rate, temperature and the onset of brittle-ductile behavior. Crystal- and bubble-free melts at high viscosity (1011-1011.6 Pa*s at 673 K) show brittle behavior in the strain rate range between 1*10-4 and 5*10-4 s-1. For comparable viscosities crystal and bubble-bearing magmas show a transition to brittle behavior at lower strain rates. Synchrotron-based 3D imaging of fractured samples, show the presence of fractures with an antithetic trend with respect to shear strain directions. The law found in this study expresses the transition from ductile to brittle behavior for real magmas and could significantly improve our understanding of the control of brittle processes on extrusion of high-viscosity magmas and degassing at silicic volcanoes.

Multistage crack seal vein and hydrothermal Ni enrichment in serpentinized ultramafic rocks (Koniambo massif, New Caledonia)

NASA Astrophysics Data System (ADS)

Cathelineau, Michel; Myagkiy, Andrey; Quesnel, Benoit; Boiron, Marie-Christine; Gautier, Pierre; Boulvais, Philippe; Ulrich, Marc; Truche, Laurent; Golfier, Fabrice; Drouillet, Maxime

2017-10-01

Sets of fractures and breccia sealed by Ni-rich silicates and quartz occur within saprock of the New Caledonian regolith developed over ultramafic rocks. The crystallization sequence in fractures is as follows: (1) serpentine stage: lizardite > polygonal serpentine > white lizardite; (2) Ni stage: Ni-Mg kerolite followed by red-brown microcrystalline quartz; and (3) supergene stages. The red-brown microcrystalline quartz corresponds to the very last stage of the Ni sequence and is inferred to have precipitated within the 50-95 °C temperature range. It constitutes also the main cement of breccia that has all the typical features of hydraulic fracturing. The whole sequence is therefore interpreted as the result of hydrothermal fluid circulation under medium to low temperature and fluctuating fluid pressure. Although frequently described as the result of a single downward redistribution of Ni and Mg leached in the upper part of the regolith under ambient temperature, the Ni silicate veins thus appear as the result of recurrent crack and seal process, corresponding to upward medium temperature fluid convection, hydraulic fracturing and subsequent fluid mixing, and mineral deposition.

Fluorine follows water: Effect on electrical conductivity of silicate minerals by experimental constraints from phlogopite

NASA Astrophysics Data System (ADS)

Li, Yan; Jiang, Haotian; Yang, Xiaozhi

2017-11-01

Fluorine and hydroxyl groups are minor constituents of silicate minerals, and share a lot of similarities concerning their physical and chemical properties. Hydroxyl groups significantly enhance the electrical conductivity of many silicate minerals, and it is expected that fluorine would have a comparable effect. This, however, has never been documented quantitatively. Here we present experimental approaches on this issue, by investigating the electrical conductivity of phlogopite with a wide range of fluorine content (but with broadly similar contents for other major elements). Electrical conductivities of gem-quality single crystal phlogopites, with samples prepared along the same orientation (normal to the (0 0 1) plane), were determined at 1 GPa and 200-650 °C using an end-loaded piston cylinder apparatus and a Solartron-1260 Impedance/Gain Phase Analyzer over the frequency range of 106 to 0.1 Hz. The complex spectra usually show an arc in the high frequency range and a short tail in the low frequency range, which are caused by lattice conduction and electrode effects, respectively. The electrical conductivity increases with increasing fluorine content, and the main charge carriers are fluorine. The activation enthalpies are ∼180 to 200 kJ/mol, nearly independent of fluorine content. The conductivity is linearly proportional to the content of fluorine, with an exponent factor of ∼1. The results demonstrate that conduction by fluorine leads to very high electrical conductivity at high temperatures. The influence of fluorine on electrical conductivity may be compared to that of hydrogen in nominally anhydrous minerals. This, along with the close association of fluorine and hydroxyl groups in silicate minerals and their similar crystal-chemical behaviors, suggests a more general role of fluorine in enhancing the electrical conductivity of many silicate minerals. Fluorine-rich assemblages, e.g., phlogopite and amphibole, could be locally enriched in the upper mantle, and if they form connected networks as observed for some natural samples, regionally high electrical conductivities could be produced. It has been recently proposed that the transition zone is probably a major reservoir for fluorine in the mantle, due to the significant dissolution of fluorine in wadsleyite and ringwoodite and the coupled incorporation with hydroxyl groups. As such, geophysically-resolved high electrical conductivities in the transition zone may be accounted for by fluorine in the dominant minerals, rather than by hydroxyl groups. The results of this work would stimulate a wide scope of future studies on the deep fluorine cycle, the deep water cycle and the geodynamical properties of the mantle.

Age of the Lava Creek supereruption and magma chamber assembly at Yellowstone based on 40Ar/39Ar and U-Pb dating of sanidine and zircon crystals

NASA Astrophysics Data System (ADS)

Vazquez, J. A.; Matthews, N. E.; Calvert, A. T.

2015-12-01

The last supereruption from the Yellowstone Plateau formed Yellowstone caldera and ejected the >1000 km3 of rhyolite that composes the Lava Creek Tuff (LCT). Tephra from the eruption blanketed much of the western United States, and is a key Quaternary chronostratigraphic marker, in particular for dating deposition of mid-Pleistocene glacial and pluvial deposits in western North America. We performed 40Ar/39Ar dating of single sanidines to delimit eruption age, and ion microprobe U-Pb and trace-element analyses of crystal faces on single zircons to characterize magmatic evolution and date near-eruption crystallization, as well as analyses of crystal interiors to date the interval of zircon crystallization. Sanidines from the two LCT members A and B yield an 40Ar/39Ar isochron date of 631 ± 4 ka (2σ). Crystal faces on zircons from both members yield a weighted mean 206Pb/238U date of 627 ± 6 ka (2σ) and have trace element concentrations that vary with eruptive stratigraphy. Zircon interiors yield a weighted mean 206Pb/238U date of 660 ± 6 ka, and reveal reverse and/or oscillatory zoning of trace element concentrations, with many crystals containing high-U concentrations and dark cathodoluminescence (CL) cores. These crystals with high-U cores are possibly sourced from 'defrosting' of melt-impregnated margins of the growing subvolcanic reservoir. LCT sanidines mirror the variation of zircon composition within the eruptive stratigraphy, with crystals from upper LCT-A and basal LCT-B having bright-CL rims with high Ba concentrations, suggesting late crystallization after addition of less evolved silicic magma. The occurrence of distal LCT in stratigraphic sequences marking the Marine Isotope Stage 16-15 transition supports the apparent eruption age of ca. 631 ka. These results reveal that Lava Creek zircons record episodic heating, renewed crystallization, and an overall up-temperature evolution for Yellowstone's subvolcanic reservoir in the 103-104 year interval before eruption.

Pyroxene thermometry of rhyolite lavas of the Bruneau-Jarbidge eruptive center, Central Snake River Plain

NASA Astrophysics Data System (ADS)

Cathey, Henrietta E.; Nash, Barbara P.

2009-11-01

The Bruneau-Jarbidge eruptive center of the central Snake River Plain in southern Idaho, USA produced multiple rhyolite lava flows with volumes of <10 km 3 to 200 km 3 each from ~11.2 to 8.1 Ma, most of which follow its climactic phase of large-volume explosive volcanism, represented by the Cougar Point Tuff, from 12.7 to 10.5 Ma. These lavas represent the waning stages of silicic volcanism at a major eruptive center of the Yellowstone hotspot track. Here we provide pyroxene compositions and thermometry results from several lavas that demonstrate that the demise of the silicic volcanic system was characterized by sustained, high pre-eruptive magma temperatures (mostly ≥950 °C) prior to the onset of exclusively basaltic volcanism at the eruptive center. Pyroxenes display a variety of textures in single samples, including solitary euhedral crystals as well as glomerocrysts, crystal clots and annealed microgranular inclusions of pyroxene ± magnetite ± plagioclase. Pigeonite and augite crystals are unzoned, and there are no detectable differences in major and minor element compositions according to textural variety — mineral compositions in the microgranular inclusions and crystal clots are identical to those of phenocrysts in the host lavas. In contrast to members of the preceding Cougar Point Tuff that host polymodal glass and mineral populations, pyroxene compositions in each of the lavas are characterized by single rather than multiple discrete compositional modes. Collectively, the lavas reproduce and extend the range of Fe-Mg pyroxene compositional modes observed in the Cougar Point Tuff to more Mg-rich varieties. The compositionally homogeneous populations of pyroxene in each of the lavas, as well as the lack of core-to-rim zonation in individual crystals suggest that individual eruptions each were fed by compositionally homogeneous magma reservoirs, and similarities with the Cougar Point Tuff suggest consanguinity of such reservoirs to those that supplied the polymodal Cougar Point Tuff. Pyroxene thermometry results obtained using QUILF equilibria yield pre-eruptive magma temperatures of 905 to 980 °C, and individual modes consistently record higher Ca content and higher temperatures than pyroxenes with equivalent Fe-Mg ratios in the preceding Cougar Point Tuff. As is the case with the Cougar Point Tuff, evidence for up-temperature zonation within single crystals that would be consistent with recycling of sub- or near-solidus material from antecedent magma reservoirs by rapid reheating is extremely rare. Also, the absence of intra-crystal zonation, particularly at crystal rims, is not easily reconciled with cannibalization of caldera fill that subsided into pre-eruptive reservoirs. The textural, compositional and thermometric results rather are consistent with minor re-equilibration to higher temperatures of the unerupted crystalline residue from the explosive phase of volcanism, or perhaps with newly generated magmas from source materials very similar to those for the Cougar Point Tuff. Collectively, the data suggest that most of the pyroxene compositional diversity that is represented by the tuffs and lavas was produced early in the history of the eruptive center and that compositions across this range were preserved or duplicated through much of its lifetime. Mineral compositions and thermometry of the multiple lavas suggest that unerupted magmas residual to the explosive phase of volcanism may have been stored at sustained, high temperatures subsequent to the explosive phase of volcanism. If so, such persistent high temperatures and large eruptive magma volumes likewise require an abundant and persistent supply of basalt magmas to the lower and/or mid-crust, consistent with the tectonic setting of a continental hotspot.

The evolution of young silicic lavas at Medicine Lake Volcano, California: Implications for the origin of compositional gaps in calc-alkaline series lavas

USGS Publications Warehouse

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

1986-01-01

At Medicine Lake Volcano, California, the compositional gap between andesite (57-62 wt.% SiO2) and rhyolite (73-74 wt.% SiO2) has been generated by fractional crystallization. Assimilation of silicic crust has also occurred along with fractionation. Two varieties of inclusions found in Holocene rhyolite flows, hornblende gabbros and aphyric andesites, provide information on the crystallization path followed by lavas parental to the rhyolite. The hornblende gabbros are magmatic cumulate residues and their mineral assemblages are preserved evidence of the phases that crystallized from an andesitic precursor lava to generate the rhyolite lavas. The andesitic inclusions represent samples of a parental andesite and record the early part of the differentiation history. Olivine, plagioclase and augite crystallization begins the differentiation history, followed by the disappearance of olivine and augite through reaction with the liquid to form orthopyroxene and amphibole. Further crystallization of the assemblage plagioclase, amphibole, orthopyroxene, magnetite, and apatite from a high-SiO2 andesite leads to rhyolite. This final crystallization process occurs on a cotectic that is nearly horizontal in temperature-composition space. Since a large amount of crystallization occurs over a limited temperature interval, a compositional gap develops between rhyolite and high SiO2 andesite. Liquidus surfaces with shallow slopes in temperature-composition space are characteristic of several late-stage crystallization assemblages in the andesite to rhyolite compositional range. Experimentally produced plagioclase+ amphibole+orthopyroxene+magnetite and plagioclase+ augite+low-Ca pyroxene+magnetite cotectics have liquidus slopes that are nearly flat. At other calc-alkaline volcanic centers crystallization processes involving large compositional changes over small temperature intervals may also be important in the development of bimodal volcanism (i.e. the existence of a composition gap). At Mt. Mazama and Mt. St. Helens, USA and Aso Caldera and Shikotsu, Japan the amphibole-bearing assemblage was important. At Krakatau, Indonesia and Katmai, USA, an augite+orthopyroxene-bearing assemblage was important. In addition to its role in the production of a compositional gap between intermediate and rhyolitic lavas, the crystallization process increases the H2O content of the residual liquid. This rapid increase in residual liquid volatile content which results from the precipitation of a large proportion of crystalline solids may be an important factor among several that lead to explosive silicic eruptions. ?? 1986 Springer-Verlag.

Experimental dynamic metamorphism of mineral single crystals

USGS Publications Warehouse

Kirby, S.H.; Stern, L.A.

1993-01-01

This paper is a review of some of the rich and varied interactions between non-hydrostatic stress and phase transformations or mineral reactions, drawn mainly from results of experiments done on mineral single crystals in our laboratory or our co-authors. The state of stress and inelastic deformation can enter explicitly into the equilibrium phase relations and kinetics of mineral reactions. Alternatively, phase transformations can have prominent effects on theology and on the nature of inelastic deformation. Our examples represent five types of structural phase changes, each of which is distinguished by particular mechanical effects. In increasing structural complexity, these include: (1) displacive phase transformations involving no bond-breaking, which may produce anomalous brittle behavior. A primary example is the a-?? quartz transition which shows anomalously low fracture strength and tertiary creep behavior near the transition temperature; (2) martensitic-like transformations involving transformation strains dominated by shear deformation. Examples include the orthoenstatite ??? clinoenstatite and w u ??rtzite ??? sphalerite transformations; (3) coherent exsolution or precipitation of a mineral solute from a supersaturated solid-solution, with anisotropy of precipitation and creep rates produced under nonhydrostatic stress. Examples include exsolution of corundum from MgO ?? nAl2O3 spinels and Ca-clinopyroxene from orthopyroxene; (4) order-disorder transformations that are believed to cause anomalous plastic yield strengthening, such as MgO - nAl2O3 spinels; and (5) near-surface devolatilization of hydrous silicate single-crystals that produces a fundamental brittleness thought to be connected with dehydration at microcracks at temperatures well below nominal macroscopic dehydration temperatures. As none of these interactions between single-crystal phase transformations and non-hydrostatic stress is understood in detail, this paper serves as a challenge to field structural geologists to test whether interactions of these types occur in nature, and to theoreticians to reach a deeper understanding of the complex relations between phase transformations, the local state of stress and associated deformation and deformation rates. ?? 1993.

Structural studies on a high-pressure polymorph of NaYSi 2O 6

NASA Astrophysics Data System (ADS)

Kahlenberg, Volker; Konzett, Jürgen; Kaindl, Reinhard

2007-06-01

High-pressure synthesis experiments in the system Na 2O-Y 2O 3-SiO 2 revealed the existence of a previously unknown polymorph of NaYSi 2O 6 or Na 3Y 3[Si 3O 9] 2 which was quenched from 3.0 GPa and 1000 °C. Structural investigations on this modification have been performed using single-crystal X-ray diffraction data collected at ambient conditions. Furthermore, unpolarized micro-Raman spectra have been obtained from single-crystal material. The high-P modification of NaYSi 2O 6 crystallizes in the centrosymmetric space group C2/ c with 12 formula units per cell ( a=8.2131(9) Å, b=10.3983(14) Å, c=17.6542(21) Å, β=100.804(9)°, V=1481.0(3) Å 3, R(| F|)=0.033 for 1142 independent observed reflections) and belongs to the group of cyclo-silicates. Basic building units are isolated three-membered [Si 3O 9] rings located in layers parallel to (010). Within a single layer the rings are concentrated in strings parallel to [100]. The sequence of directedness of up ( U) or down ( D) pointing tetrahedra of a single ring is UUU or DDD, respectively. Stacking of the layers parallel to b results in the formation of a three-dimensional structure in which yttrium and sodium cations are incorporated for charge compensation. In more detail, four non-tetrahedral cation positions can be differentiated which are coordinated by 6 and 8 oxygen ligands. Refinements of the site occupancies did not reveal any indication for mixed Na-Y populations on these positions. Finally, several geometrical parameters of rings occurring in cyclo-trisilicate structures have been compiled and are discussed.

Partial Melting of the Indarch (EH4) Meteorite : A Textural, Chemical and Phase Relations View of Melting and Melt Migration

NASA Technical Reports Server (NTRS)

McCoy, Timothy J.; Dickinson, Tamara L.; Lofgren, Gary E.

2000-01-01

To Test whether Aubrites can be formed by melting of enstatite Chondrites and to understand igneous processes at very low oxygen fugacities, we have conducted partial melting experiments on the Indarch (EH4) chondrite at 1000-1500 C. Silicate melting begins at 1000 C. Substantial melt migration occurs at 1300-1400 C and metal migrates out of the silicate change at 1450 C and approx. 50% silicate partial melting. As a group, our experiments contain three immiscible metallic melts 9Si-, and C-rich), two immiscible sulfide melts(Fe-and FeMgMnCa-rich) and Silicate melt. Our partial melting experiments on the Indarch (EH4) enstatite Chondrite suggest that igneous processes at low fO2 exhibit serveral unique features. The complete melting of sulfides at 1000 C suggest that aubritic sulfides are not relicts. Aubritic oldhamite may have crystallized from Ca and S complexed in the silicate melt. Significant metal-sulfide melt migration might occur at relatively low degrees of silicate partial melting. Substantial elemental exchange occurred between different melts (e.g., between sulfide and silicate, Si between silicate and metal), a feature not observed during experiments at higher fO2. This exchange may help explain the formation of aubrites from known enstatite chondrites.

Origin of silicic crust by rifting and bimodal plume volcanism in the Afar Depression

NASA Astrophysics Data System (ADS)

Ghatak, A.; Basu, A. R.; Ebinger, C. J.

2010-12-01

The youngest mantle plume province worldwide occurs at the seismically and volcanically active East African - Red Sea - Gulf of Aden (Afar) triple junction, where one or more upwellings has impinged the thick cratonic lithosphere since ~45 Ma. A spectacular example of magmatism in the Afar depression is seen in the present to < 2 Ma old bimodal fissural mafic and peralkaline silicic eruptions in the ~60 km-long Dabbahu-Manda Hararo (DMH) Rift. In this study we report major, trace elements, and Nd-Sr-Pb isotopes in recent basaltic and silicic rocks originating from the center of the DMH rift segment, exposed along the rift axis and flanks of this segment. The rare earth element (REE) patterns of the silicic rocks and basalts are different in two significant ways: (1) the silicic rocks show a prominent positive Ce-anomaly that is extremely rare in volcanic rocks; and (2) this positive Ce-anomaly is accompanied by a strong negative Eu-anomaly. These anomalies are absent in the basaltic rocks. The positive Ce-anomaly is probably due to interaction in a magma chamber, similar in composition to the basalts, with deep saline aquifer or brines that typically show positive Ce-anomaly. The REE patterns of the two lava groups are interpreted to be due to fractional crystallization of plagioclase in a magma chamber similar in REE composition as the basalts that erupted in the DMH segments. We interpret the silicic rocks to be residues after ~20% fractional crystallization of plagioclase in the DMH basalts. The Nd-Pb isotopic composition of the basalts and rhyolites of the DMH are similar to the Ethiopian plume as defined by the ~30 Ma old Ethiopian flood basalts. Based on their high 3He/4He ratios (R/RA ~30) and Nd-Sr-Pb isotopic data, the source of the Ethiopian plume is generally believed to be in the lower mantle. Therefore, the similarity of the Nd-Pb and Pb-Pb isotopic variations between the Ethiopian plume and the DMH lavas indicates that these lavas were sourced from the lower mantle, and this source zone showed little variation over the past 30 Ma. Some of the silicic lavas fall distinctly outside the plume field toward more radiogenic 87Sr/86Sr at relatively restricted Nd and Pb isotopic compositions. This excursion in Sr-isotopic ratios of the silicic lavas, in concert with their positive Ce-anomaly, is interpreted to be due to mixing of the Afar plume derived basaltic magma with fluids from saline aquifers. We conclude that the bimodal lavas are consanguineous, the silicic lavas being generated by fractional crystallization of plagioclase in a lower mantle plume-derived basaltic magma-chamber, caused by the interaction with saline aquifers. The generation of bimodal volcanism from parental primitive basalts without any contribution from pre-existing continental crust in Dabbahu may explain other similar intraplate magmatism including early Archean-Hadean continental crust formation prior to onset of arc-volcanism.

Evidence for seismogenic fracture of silicic magma.

PubMed

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

2008-05-22

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

The Principal Hugoniot of Forsterite to 950 GPa

NASA Astrophysics Data System (ADS)

Root, Seth; Townsend, Joshua P.; Davies, Erik; Lemke, Raymond W.; Bliss, David E.; Fratanduono, Dayne E.; Kraus, Richard G.; Millot, Marius; Spaulding, Dylan K.; Shulenburger, Luke; Stewart, Sarah T.; Jacobsen, Stein B.

2018-05-01

Forsterite (Mg2SiO4) single crystals were shock compressed to pressures between 200 and 950 GPa using independent plate-impact steady shocks and laser-driven decaying shock compression experiments. Additionally, we performed density functional theory-based molecular dynamics to aid interpretation of the experimental data and to investigate possible phase transformations and phase separations along the Hugoniot. We show that the experimentally obtained Hugoniot cannot distinguish between a pure liquid Mg2SiO4 and an assemblage of solid MgO plus liquid magnesium silicate. The measured reflectivity is nonzero and increases with pressure, which implies that the liquid is a poor electrical conductor at low pressures and that the conductivity increases with pressure.

Paleomagnetism of a primitive achondrite parent body: The acapulcoite-lodranites

NASA Astrophysics Data System (ADS)

Schnepf, N. R.; Weiss, B. P.; Andrade Lima, E.; Fu, R. R.; Uehara, M.; Gattacceca, J.; Wang, H.; Suavet, C. R.

2014-12-01

Primitive achondrites are a recently recognized meteorite grouping with textures and compositions intermediate between unmelted meteorites (chondrites) and igneous meteorites (achondrites). Their existence demonstrates prima facie that some planetesimals only experienced partial rather than complete melting. We present the first paleomagnetic measurements of acapulcoite-lodranite meteorites to determine the existence and intensity of ancient magnetic fields on their parent body. Our paleomagnetic study tests the hypothesis that their parent body had an advecting metallic core, with the goal of providing one of the first geophysical constraints on its large-scale structure and the extent of interior differentiation. In particular, by analyzing samples whose petrologic textures require an origin on a partially differentiated body, we will be able to critically test a recent proposal that some achondrites and chondrite groups could have originated on a single body (Weiss and Elkins-Tanton 2013). We analyzed samples of the meteorites Acapulco and Lodran. Like other acapulcoites and lodranites, these meteorites are granular rocks containing large (~0.1-0.3 mm) kamacite and taenite grains along with similarly sized silicate crystals. Many silicate grains contain numerous fine (1-10 μm) FeNi metal inclusions. Our compositional measurements and rock magnetic data suggest that tetrataenite is rare or absent. Bulk paleomagnetic measurements were done on four mutually oriented bulk samples of Acapulco and one bulk sample of Lodran. Alternating field (AF) demagnetization revealed that the magnetization of the bulk samples is highly unstable, likely due to the large (~0.1-0.3 mm) interstitial kamacite grains throughout the samples. To overcome this challenge, we are analyzing individual ~0.2 mm mutually oriented silicate grains extracted using a wire saw micromill. Preliminary SQUID microscopy measurements of a Lodran silicate grain suggest magnetization stable to AF levels of at least 25-40 mT.

Effect of silica fume on the characterization of the geopolymer materials

NASA Astrophysics Data System (ADS)

Khater, Hisham M.

2013-12-01

The influence of silica fume (SF) addition on properties of geopolymer materials produced from alkaline activation of alumino-silicates metakaolin and waste concrete produced from demolition works has been studied through the measurement of compressive strength, Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy (SEM) analysis. Alumino-silicate materials are coarse aggregate included waste concrete and fired kaolin (metakaolin) at 800°C for 3 h, both passing a sieve of 90 μm. Mix specimens containing silica fume were prepared at water/binder ratios in a range of 0.30 under water curing. The used activators are an equal mix of sodium hydroxide and silicate in the ratio of 3:3 wt.%. The control geopolymer mix is composed of metakaolin and waste concrete in an equal mix (50:50, wt.%). Waste concrete was partially replaced by silica fume by 1 to 10 wt.%. The results indicated that compressive strengths of geopolymer mixes incorporating SF increased up to 7% substitution and then decreased up to 10% but still higher than that of the control mix. Results indicated that compressive strengths of geopolymer mixes incorporating SF increases up to 7% substitution and then decreases up to 10% but still higher than the control mix, where 7% SF-digested calcium hydroxide (CH) crystals, decreased the orientation of CH crystals, reduced the crystal size of CH gathered at the interface, and improved the interface more effectively.

Characterization of iron-phosphate-silicate chemical garden structures.

PubMed

Barge, Laura M; Doloboff, Ivria J; White, Lauren M; Stucky, Galen D; Russell, Michael J; Kanik, Isik

2012-02-28

Chemical gardens form when ferrous chloride hydrate seed crystals are added or concentrated solutions are injected into solutions of sodium silicate and potassium phosphate. Various precipitation morphologies are observed depending on silicate and phosphate concentrations, including hollow plumes, bulbs, and tubes. The growth of precipitates is controlled by the internal osmotic pressure, fluid buoyancy, and membrane strength. Additionally, rapid bubble-led growth is observed when silicate concentrations are high. ESEM/EDX analysis confirms compositional gradients within the membranes, and voltage measurements across the membranes during growth show a final potential of around 150-200 mV, indicating that electrochemical gradients are maintained across the membranes as growth proceeds. The characterization of chemical gardens formed with iron, silicate, and phosphate, three important components of an early earth prebiotic hydrothermal system, can help us understand the properties of analogous structures that likely formed at submarine alkaline hydrothermal vents in the Hadean-structures offering themselves as the hatchery of life. © 2011 American Chemical Society

Silicon K-edge XANES spectra of silicate minerals

NASA Astrophysics Data System (ADS)

Li, Dien; Bancroft, G. M.; Fleet, M. E.; Feng, X. H.

1995-03-01

Silicon K-edge x-ray absorption near-edge structure (XANES) spectra of a selection of silicate and aluminosilicate minerals have been measured using synchrotron radiation (SR). The spectra are qualitatively interpreted based on MO calculation of the tetrahedral SiO{4/4-}cluster. The Si K-edge generally shifts to higher energy with increased polymerization of silicates by about 1.3 eV, but with considerable overlap for silicates of different polymerization types. The substitution of Al for Si shifts the Si K-edge to lower energy. The chemical shift of Si K-edge is also sensitive to cations in more distant atom shells; for example, the Si K-edge shifts to lower energy with the substitution of Al for Mg in octahedral sites. The shifts of the Si K-edge show weak correlation with average Si-O bond distance (dSi-O), Si-O bond valence (sSi-O) and distortion of SiO4 tetrahedra, due to the crystal structure complexity of silicate minerals and multiple factors effecting the x-ray absorption processes.

Contact fatigue mechanisms as a function of crystal aspect ratio in baria-silicate glass ceramics

NASA Astrophysics Data System (ADS)

Suputtamongkol, Kallaya

2003-10-01

Ceramic materials are potentially useful for dental applications because of their esthetic potential and biocompatibility. However, the existence of fatigue damage in ceramics raises considerable concern regarding its effect on the life prediction of dental prostheses. During normal mastication, dental restorations are subjected to repeated loading more than a thousand times per day and relatively high clinical failure rates for ceramic prostheses have been reported. To simulate the intraoral loads, Hertzian indentation loading was used in this study to characterize the fatigue failure mechanisms of ceramic materials using clinically relevant parameters. The baria-silicate system was chosen because of the nearly identical composition between the crystal and the glass matrix. Little or no residual stress is expected from the elastic modulus and thermal expansion mismatches between the two phases. Crystallites with different aspect ratios can also be produced by controlled heat treatment schedules. The objective of this study was to characterize the effect of crystal morphology on the fatigue mechanisms of bariasilicate glass-ceramics under clinically relevant conditions. The results show that the failure of materials with a low toughness such as baria-silicate glass (0.7 MPa•m1/2) and glass-ceramic with an aspect ratio of 3/1 (1.3 MPa•m1/2) initiated from a cone crack developed during cyclic loading for 103 to 105 cycles. The mean strength values of baria-silicate glass and glass-ceramic with an aspect ratio of 3/1 decreased significantly as a result of the presence of a cone crack. Failure of baria-silicate glass-ceramics with an aspect ratio of 8/1 (Kc = 2.1 MPa•m1/2) was initiated from surface flaws caused by either polishing or cyclic loading. The gradual decrease of fracture stress was observed in specimens with an aspect ratio of 8/1 after loading in air for 103 to 10 5 cycles. A reduction of approximately 50% in fracture stress levels was found for specimens with an aspect ratio of 8/1 after loading for 10 5 cycles in deionized water. The mechanisms for cyclic fatigue crack propagation in baria-silicate glass-ceramics are similar to those observed under quasi-static loading conditions. An intergranular fracture path was observed in glass-ceramics with an aspect ratio of 3/1. For an aspect ratio of 8/1, a transgranular fracture mode was dominant.

The role of boric acid in the synthesis of Eni Carbon Silicates.

PubMed

Zanardi, Stefano; Bellussi, Giuseppe; Parker, Wallace O'Neil; Montanari, Erica; Bellettato, Michela; Cruciani, Giuseppe; Carati, Angela; Guidetti, Stefania; Rizzo, Caterina; Millini, Roberto

2014-07-21

The influence of H3BO3 on the crystallization of hybrid organic-inorganic aluminosilicates denoted as Eni Carbon Silicates (ECS's) was investigated. Syntheses were carried out at 100 °C under different experimental conditions, using bridged silsesquioxanes of general formula (EtO)3Si-R-Si(OEt)3 (R = -C6H4- (BTEB), -C10H6- (BTEN) and -C6H4-C6H4- (BTEBP)), in the presence of equimolar concentrations of NaAlO2 and H3BO3. The study, involving the synthesis of three different but structurally related phases (ECS-14 from BTEB, ECS-13 here described for the first time from BTEN, and ECS-5 from BTEBP), confirmed a catalytic role for H3BO3 which in general increased the crystallization rate and improved the product quality in terms of amount of crystallized phase (crystallinity), size of the crystallites and phase purity, while it was weakly incorporated in trace amounts in the framework of ECS's.

Impact fracture experiments simulating interstellar grain-grain collisions

NASA Technical Reports Server (NTRS)

Freund, Friedemann; Chang, Sherwood; Dickinson, J. Thomas

1990-01-01

Oxide and silicate grains condensing during the early phases of the formation of the solar system or in the outflow of stars are exposed to high partial pressures of the low-z elements H, C, N and O and their simple gaseous compounds. Though refractory minerals are nominally anhydrous and non-carbonate, if they crystallize in the presence of H2O, N2 and CO or CO2 gases, they dissolve traces of the gaseous components. The question arises: How does the presence of dissolved gases or gas components manifest itself when grain-grain collisions occur. What are the gases emitted when grains are shattered during a collision event. Researchers report on fracture experiments in ultrahigh vacuum (UHV, approximately less than 10 to the -8th power mbar) designed to measure (by means of a quadrupole mass spectrometer, QMS, with microns to ms time resolution) the emission of gases and vapors during and after impact (up to 1.5 sec). Two terrestrial materials were chosen which represent structural and compositional extremes: olivine (San Carlos, AZ), a densely packed Mg-Fe(2+) silicate from the upper mantle, available as 6 to 12 mm single crystals, and obsidian (Oregon), a structurally open, alkaline-SiO2-rich volcanic glass. In the olivine crystals OH- groups have been identified spectroscopically, as well as H2 molecules. Obsidian is a water-rich glass containing OH- besides H2O molecules. Olivine from the mantle often contains CO2, either as CO2-rich fluid in fluid inclusions or structurally dissolved or both. By analogy to synthetic glasses CO2 in the obsidian may be present in form of CO2 molecules in voids of molecular dimensions, or as carbonate anions, CO3(2-). No organic molecules have been detected spectroscopically in either material. Results indicate that refractory oxide/silicates which contain dissolved traces of the H2O and CO/CO2 components but no spectroscopically detectable traces of organics may release complex H-C-O (possibly H-C-N-O) molecules upon fracture, plus metal vapor. This points: (1) at complex reaction mechanisms between dissolved H2O, CO/CO2 (and N2) components within the mineral structure or during fracture, and (2) at the possibility that similar emission processes occur following grain-grain collisions in interstellar dust clouds.

A New Method Using Single-Particle Mass Spectrometry Data to Distinguish Mineral Dust and Biological Aerosols

NASA Astrophysics Data System (ADS)

Al-Mashat, H.; Kristensen, L.; Sultana, C. M.; Prather, K. A.

2016-12-01

The ability to distinguish types of particles present within a cloud is important for determining accurate inputs to climate models. The chemical composition of particles within cloud liquid droplets and ice crystals can have a significant impact on the timing, location, and amount of precipitation that falls. Precipitation efficiency is increased by the presence of ice crystals in clouds, and both mineral dust and biological aerosols have been shown to be effective ice nucleating particles (INPs) in the atmosphere. A current challenge in aerosol science is distinguishing mineral dust and biological material in the analysis of real-time, ambient, single-particle mass spectral data. Single-particle mass spectrometers are capable of measuring the size-resolved chemical composition of individual atmospheric particles. However, there is no consistent analytical method for distinguishing dust and biological aerosols. Sampling and characterization of control samples (i.e. of known identity) of mineral dust and bacteria were performed by the Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) as part of the Fifth Ice Nucleation (FIN01) Workshop at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) facility in Karlsruhe, Germany. Using data collected by the ATOFMS of control samples, a new metric has been developed to classify single particles as dust or biological independent of spectral cluster analysis. This method, involving the use of a ratio of mass spectral peak areas for organic nitrogen and silicates, is easily reproducible and does not rely on extensive knowledge of particle chemistry or the ionization characteristics of mass spectrometers. This represents a step toward rapidly distinguishing particle types responsible for ice nucleation activity during real-time sampling in clouds. The ability to distinguish types of particles present within a cloud is important for determining accurate inputs to climate models. The chemical composition of particles within cloud liquid droplets and ice crystals can have a significant impact on the timing, location, and amount of precipitation that falls. Precipitation efficiency is increased by the presence of ice crystals in clouds, and both mineral dust and biological aerosols have been shown to be effective ice nucleating particles (INPs) in the atmosphere. A current challenge in aerosol science is distinguishing mineral dust and biological material in the analysis of real-time, ambient, single-particle mass spectral data. Single-particle mass spectrometers are capable of measuring the size-resolved chemical composition of individual atmospheric particles. However, there is no consistent analytical method for distinguishing dust and biological aerosols. Sampling and characterization of control samples (i.e. of known identity) of mineral dust and bacteria were performed by the Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) as part of the Fifth Ice Nucleation (FIN01) Workshop at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) facility in Karlsruhe, Germany. Using data collected by the ATOFMS of control samples, a new metric has been developed to classify single particles as dust or biological independent of spectral cluster analysis. This method, involving the use of a ratio of mass spectral peak areas for organic nitrogen and silicates, is easily reproducible and does not rely on extensive knowledge of particle chemistry or the ionization characteristics of mass spectrometers. This represents a step toward rapidly distinguishing particle types responsible for ice nucleation activity during real-time sampling in clouds.

Molecular orbital (SCF-X-α-SW) theory of Fe2+-Mn3+, Fe3+-Mn2+, and Fe3+-Mn3+ charge transfer and magnetic exchange in oxides and silicates

USGS Publications Warehouse

Sherman, David M.

1990-01-01

Metal-metal charge-transfer and magnetic exchange interactions have important effects on the optical spectra, crystal chemistry, and physics of minerals. Previous molecular orbital calculations have provided insight on the nature of Fe2+-Fe3+ and Fe2+-Ti4+ charge-transfer transitions in oxides and silicates. In this work, spin-unrestricted molecular orbital calculations on (FeMnO10) clusters are used to study the nature of magnetic exchange and electron delocalization (charge transfer) associated with Fe3+-Mn2+, Fe3+-Mn3+, and Fe2+-Mn3+ interactions in oxides and silicates. 

Uranium distribution in pseudowollastonite slag from a phosphorus furnace

USGS Publications Warehouse

Young, Edward; Altschuler, Zalman S.

1956-01-01

Silicate slag from the Victor Chemical Company phosphorus furnace at Tarpon Springs, Fla., has been found to consist essentially of pseudowollastonite, α-CaSiO3. The first-formed crystals are euhedral laths which form a mesh making up most of the slag. As the slag continues to solidify, its composition changes slightly and more equant, subhedral crystals of pseudowollastonite are deposited within the framework of the earlier material. Finally, anherdral masses of fibrous, poorly crystallized material are deposited in the remaining pore spaces which are not always completely filled. Spherules of iron phosphide, Fe2P, occur very sparsely in the slag as inclusions from the immiscible iron phosphide melt. Uranium content increases in the later crystal products of the slag, and by heavy-liquid fractionation it has been possible to segregate partially the phases and to obtain a fourfold concentration of uranium in 5 percent of the material and a twofold concentration in 30 percent of the material. Nuclear-emulsion studies indicate that the last phases of the silicate slag are actually eight times as radioactive as the early phases. In addition, the iron phosphide spherules are comparably enriches in uranium.

Trondhjemitic melts produced by in-situ differentiation of a tholeiitic lava flow, Reykjanes Peninsula, Iceland.

NASA Astrophysics Data System (ADS)

Martin, E.; Sigmarsson, O.

2006-12-01

How the continental crust began to form early in Earth's history is unconstrained. However, it is reasonable to presume that higher heat flow in the past, resulted in more frequent interaction of mantle plumes and mid- oceanic ridges. If true, then Iceland could be a good analogue for processes occurring on Earth at its youth stage. This is supported by the relatively high abundance of silicic rocks in Iceland but their rarity on other oceanic hot spots. The origin of Icelandic silicic rocks has been a subject of a lively debate but has been shown to be principally formed by partial melting of hydrothermally altered basaltic crust. However, in rare cases, their origin by fractional crystallization from mantle derived basalts is suggested. Segregation veins in lava flows frequently contain interstitial glasses of silicic compositions. Moreover, they allow an exceptional overview of the fractional crystallization mechanism. These veins form by gas filter pressing during cooling and degassing of solidifying lava flows, after approximately 50% fractional crystallization of anhydrous minerals. Pairs of samples, host lava and associated segregation veins, from Reykjanes Peninsula (Iceland), Lanzarote (Canary Island) and Masaya's volcano (Nicaragua), allow the assessment of a near-complete fractional crystallization of olivine tholeiitic basalt at pressure close to one atmosphere. Interstitial glass patches in segregation veins represent the final product of this process (80 97 % of fractional crystallization). These ultimate liquids are of granitic composition in the case of Lanzarote and Masaya but overwhelmingly trondhjemitic at Reykjanes. It appears that the initial K2O/Na2O of the basaltic liquid controls the evolution path of the residual liquid composition produced at pressure close to 0.1 MPa (1 bar). Granitic liquids are generated from basalts of high initial K2O/Na2O whereas low initial K2O/Na2O leads to trondhjemitic compositions. The trondhjemitic composition of glass patches from the segregation vein at Reykjanes Peninsula differs from Icelandic silicic magmas but is close to those of the Archaean TTG (trondhjemite-tonalite-granodiorite) suite. Taken at face value, this may imply that fractional crystallisation of olivine tholeiites (low K2O/Na2O) could have played a significant role during the formation of the early continental crust. At higher pressure, where garnet is on liquidus, fractional crystallisation can generate the observed trace element patterns observed in TTG. The progressive cooling, crystallization and degassing of basaltic magma ocean, thought to have been prevailing during the Hadean, could have led to high degree of fractional crystallization producing significant volume of trondhjemitic melts that because of its buoyancy contributed to the formation of the earliest continental crust.

Generation of volcanic ash: a textural study of ash produced in various laboratory experiments

NASA Astrophysics Data System (ADS)

Lavallée, Yan; Kueppers, Ulrich; Dingwell, Donald B.

2010-05-01

In volcanology, ash is commonly understood as a fragment of a bubble wall that gets disrupted during explosive eruptions. Most volcanic ashes are indeed the product of explosive eruptions, but the true definition is however that of a particle size being inferior to 2 mm. The term does not hold any information about its genesis. During fragmentation, particles of all sizes in various amounts are generated. In nature, fragmentation is a brittle response of the material (whether a rock or magma) caused by changes in 1) strain rate and 2) temperature, and/or 3) chemical composition. Here we used different experimental techniques to produce ash and study their physical characteristics. The effects of strain rate were investigated by deforming volcanic rocks and magma (pure silicate melt and crystal-bearing magma) at different temperatures and stresses in a uniaxial compression apparatus. Failure of pure silicate melts is spontaneous and generates more ash particles than fragmentation of crystal-bearing melts. In the latter, the abundance of generated ash correlates positively with the strain rate. We complemented this investigation with a study of particles generated during rapid decompression of porous rocks, using a fragmentation apparatus. Products of decompression experiments at different initial applied pore pressure show that the amount of ash generated by bubble burst increase with the initial applied pressure and the open porosity. The effects of temperature were investigated by dropping pure silicate melts and crystal-bearing magma at 900 and 1100°C in water at room temperature. Quenching of the material is accompanied by rapid contraction and near instantaneous fragmentation. Pure silicate melts respond more violently to the interaction with water and completely fragmented into small particles, including a variety of ash morphologies and surface textures. Crystal-bearing magmas however fragmented only very partially when in contact with water and produced a few ash particles (< 0.05 g). The morphology and surface textures of the experimentally generated ash particles were imaged through scanning electron microscopy, and the observations will be discussed in terms of fragmentation processes.

A model that helps explain Sr-isotope disequilibrium between feldspar phenocrysts and melt in large-volume silicic magma systems

USGS Publications Warehouse

Duffield, W.A.; Ruiz, J.

1998-01-01

Feldspar phenocrysts of silicic volcanic rocks are commonly in Sr-isotopic disequilibrium with groundmass. In some cases the feldspar is more radiogenic, and in others it is less radiogenic. Several explanations have been published previously, but none of these is able to accommodate both senses of disequilibrium. We present a model by which either more- or less-radiogenic feldspar (or even both within a single eruptive unit) can originate. The model requires a magma body open to interaction with biotite- and feldspar-bearing wall rock. Magma is incrementally contaminated as wall rock melts incongruently. Biotite preferentially melts first, followed by feldspar. Such melting behavior, which is supported by both field and experimental studies, first contaminates magma with a relatively radiogenic addition, followed by a less-radiogenic addition. Feldspar phenocrysts lag behind melt (groundmass of volcanic rock) in incorporating the influx of contaminant, thus resulting in Sr-isotopic disequilibrium between the crystals and melt. The sense of disequilibrium recorded in a volcanic rock depends on when eruption quenches the contamination process. This model is testable by isotopic fingerprinting of individual feldspar crystals. For a given set of geologic boundary conditions, specific core-to-rim Sr-isotopic profiles are expectable. Moreover, phenocrysts that nucleate at different times during the contamination process should record different and predictable parts of the history. Initial results of Sr-isotopic fingerprinting of sanidine phenocrysts from the Taylor Creek Rhyolite are consistent with the model. More tests of the model are desirable.Feldspar phenocrysts of silicic volcanic rocks are commonly in Sr-isotopic disequilibrium with groundmass. In some cases the feldspar is more radiogenic, and in others it is less radiogenic. Several explanations have been published previously, but none of these is able to accommodate both senses of disequilibrium. We present a model by which either more- or less-radiogenic feldspar (or even both within a single eruptive unit) can originate. The model requires a magma body open to interaction with biotite- and feldspar-bearing wall rock. Magma is incrementally contaminated as wall rock melts incongruently. Biotite preferentially melts first, followed by feldspar. Such melting behavior, which is supported by both field and experimental studies, first contaminates magma with a relatively radiogenic addition, followed by a less-radiogenic addition. Feldspar phenocrysts lag behind melt (groundmass of volcanic rock) in incorporating the influx of contaminant, thus resulting in Sr-isotopic disequilibrium between the crystals and melt. The sense of disequilibrium recorded in a volcanic rock depends on when eruption quenches the contamination process. This model is testable by isotopic fingerprinting of individual feldspar crystals. For a given set of geologic boundary conditions, specific core-to-rim Sr-isotopic profiles are expectable. Moreover, phenocrysts that nucleate at different times during the contamination process should record different and predictable parts of the history. Initial results of Sr-isotopic fingerprinting of sanidine phenocrysts from the Taylor Creek Rhyolite are consistent with the model. More tests of the model are desirable.

Crystal Structure and Chemical Composition of a Presolar Silicate from the Queen Elizabeth Range 99177 Meteorite

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Keller, L. P.; Rahman, Z.; Messenger, S.

2013-01-01

Mineral characterization of presolar silicate grains, the most abundant stardust phase, has provided valuable information about the formation conditions in circumstellar environments and in super-nova (SN) outflows. Spectroscopic observations of dust around evolved stars suggest a majority of amor-phous, Mg-rich olivine grains, but crystalline silicates, most of which are pyroxene, have also been observed [1]. The chemical compositions of hundreds of presolar silicates have been determined by Auger spectroscopy and reveal high Fe contents and nonstoichiometric compositions intermediate to olivine and pyroxene [2-6]. The unexpectedly high Fe contents can partly be attributed to secondary alteration on the meteorite parent bodies, as some grains have Fe isotopic anomalies from their parent stellar source [7]. Only about 35 presolar silicates have been studied for their mineral structures and chemical compositions by transmission electron microscopy (TEM). These grains display a wide range of compositions and structures, including crystalline forsterite, crystalline pyroxene, nanocrystalline grains, and a majority of amorphous nonstoichiometric grains. Most of these grains were identified in the primitive Acfer 094 meteorite. Presolar silicates from this meteorite show a wide range of Fe-contents, suggestive of secondary processing on the meteorite parent body. The CR chondrite QUE 99177 has not suffered as much alteration [8] and displays the highest presolar silicate abundance to date among carbonaceous chondrites [3, 6]. However, no mineralogical studies of presolar silicates from this meteorite have been performed. Here we examine the mineralogy of a presolar silicate from QUE 99177.

Late-stage magmatic to deuteric/metasomatic accessory minerals from the Cerro Boggiani agpaitic complex (Alto Paraguay Alkaline Province)

NASA Astrophysics Data System (ADS)

Comin-Chiaramonti, Piero; Renzulli, Alberto; Ridolfi, Filippo; Enrich, Gaston E. R.; Gomes, Celso B.; De Min, Angelo; Azzone, Rogério G.; Ruberti, Excelso

2016-11-01

This work describes rare accessory minerals in volcanic and subvolcanic silica-undersaturated peralkaline and agpaitic rocks from the Permo-Triassic Cerro Boggiani complex (Eastern Paraguay) in the Alto Paraguay Alkaline Province. These accessory phases consist of various minerals including Th-U oxides/silicates, Nb-oxide, REE-Sr-Ba bearing carbonates-fluorcarbonates-phosphates-silicates and Zr-Na rich silicates. They form a late-stage magmatic to deuteric/metasomatic assemblage in agpaitic nepheline syenites and phonolite dykes/lava flows made of sodalite, analcime, albite, fluorite, calcite, ilmenite-pyrophanite, titanite and zircon. It is inferred that carbonatitic fluids rich in F, Na and REE percolated into the subvolcanic system and metasomatically interacted with the Cerro Boggiani peralkaline and agpaitic silicate melts at the thermal boundary layers of the magma chamber, during and shortly after their late-stage magmatic crystallization and hydrothermal deuteric alteration.

P-V-T equation of state of clinohumite up to 25 GPa and 750 K

NASA Astrophysics Data System (ADS)

Qin, F.; Wu, X.; Jacobsen, S. D.; Zhang, D.

2016-12-01

The dense hydrous magnesium silicate (DHMS) minerals along the brucite-forsterite join have been proposed as the major carriers of water into the Earth's mantle. The natural occurrence of humite-group minerals makes knowledge of their phase relations and crystal chemistry under high pressure and temperature conditions important to geochemical and geophysical studies of volatile cycling between the crust and upper mantle. In natural high-grade metamorphic rocks and carbonates, clinohumite (P21/c) typically contains F at the hydroxyl site and Ti in one of the octahedral sites. Here, we have studied the thermal and compressional behaviors of clinohumite up to 25 GPa and 750 K. Synchrotron X-ray diffraction of single-crystal clinohumite was carried out at the 13 BMC beamline (GSECARS) of the Advanced Photon Source. Our experimental results clearly show that there is no indication of structural phase transition of clinohumite at high P-T conditions relevant to the subducted zone environments. Knowledge of humite-group crystal chemistry at high P-T conditions will also contribute more broadly to the field of mineralogy because of the morphotropic relationship with the minerals olivine and brucite.

Potential Applications of Alkali-Activated Alumino-Silicate Binders in Military Operations

DTIC Science & Technology

1985-11-01

Geopolymers for Reinforced Plastics/ Composits ," PACTEC 󈨓, Society of Plastic Engineers, Costa Mesa, CA, 1979, pp. 151-153. Davidovits, Joseph. 1983...34 Geopolymers II, Processing and Applications of Ultra-High Temperature, Inorganic Matrix Resin for Cast Composite Structures, Molds and Tools for RP/C and...alumino-silicate hydrates with an approximate composition of 3CaO - AI20 3 • 2i0 2 2120, begin to crystallize. As the gels begin to coalesce, bound water

The largest volcanic eruptions on Earth

NASA Astrophysics Data System (ADS)

Bryan, Scott E.; Peate, Ingrid Ukstins; Peate, David W.; Self, Stephen; Jerram, Dougal A.; Mawby, Michael R.; Marsh, J. S. (Goonie); Miller, Jodie A.

2010-10-01

Large igneous provinces (LIPs) are sites of the most frequently recurring, largest volume basaltic and silicic eruptions in Earth history. These large-volume (> 1000 km 3 dense rock equivalent) and large-magnitude (> M8) eruptions produce areally extensive (10 4-10 5 km 2) basaltic lava flow fields and silicic ignimbrites that are the main building blocks of LIPs. Available information on the largest eruptive units are primarily from the Columbia River and Deccan provinces for the dimensions of flood basalt eruptions, and the Paraná-Etendeka and Afro-Arabian provinces for the silicic ignimbrite eruptions. In addition, three large-volume (675-2000 km 3) silicic lava flows have also been mapped out in the Proterozoic Gawler Range province (Australia), an interpreted LIP remnant. Magma volumes of > 1000 km 3 have also been emplaced as high-level basaltic and rhyolitic sills in LIPs. The data sets indicate comparable eruption magnitudes between the basaltic and silicic eruptions, but due to considerable volumes residing as co-ignimbrite ash deposits, the current volume constraints for the silicic ignimbrite eruptions may be considerably underestimated. Magma composition thus appears to be no barrier to the volume of magma emitted during an individual eruption. Despite this general similarity in magnitude, flood basaltic and silicic eruptions are very different in terms of eruption style, duration, intensity, vent configuration, and emplacement style. Flood basaltic eruptions are dominantly effusive and Hawaiian-Strombolian in style, with magma discharge rates of ~ 10 6-10 8 kg s -1 and eruption durations estimated at years to tens of years that emplace dominantly compound pahoehoe lava flow fields. Effusive and fissural eruptions have also emplaced some large-volume silicic lavas, but discharge rates are unknown, and may be up to an order of magnitude greater than those of flood basalt lava eruptions for emplacement to be on realistic time scales (< 10 years). Most silicic eruptions, however, are moderately to highly explosive, producing co-current pyroclastic fountains (rarely Plinian) with discharge rates of 10 9-10 11 kg s -1 that emplace welded to rheomorphic ignimbrites. At present, durations for the large-magnitude silicic eruptions are unconstrained; at discharge rates of 10 9 kg s -1, equivalent to the peak of the 1991 Mt Pinatubo eruption, the largest silicic eruptions would take many months to evacuate > 5000 km 3 of magma. The generally simple deposit structure is more suggestive of short-duration (hours to days) and high intensity (~ 10 11 kg s -1) eruptions, perhaps with hiatuses in some cases. These extreme discharge rates would be facilitated by multiple point, fissure and/or ring fracture venting of magma. Eruption frequencies are much elevated for large-magnitude eruptions of both magma types during LIP-forming episodes. However, in basalt-dominated provinces (continental and ocean basin flood basalt provinces, oceanic plateaus, volcanic rifted margins), large magnitude (> M8) basaltic eruptions have much shorter recurrence intervals of 10 3-10 4 years, whereas similar magnitude silicic eruptions may have recurrence intervals of up to 10 5 years. The Paraná-Etendeka province was the site of at least nine > M8 silicic eruptions over an ~ 1 Myr period at ~ 132 Ma; a similar eruption frequency, although with a fewer number of silicic eruptions is also observed for the Afro-Arabian Province. The huge volumes of basaltic and silicic magma erupted in quick succession during LIP events raises several unresolved issues in terms of locus of magma generation and storage (if any) in the crust prior to eruption, and paths and rates of ascent from magma reservoirs to the surface. Available data indicate four end-member magma petrogenetic pathways in LIPs: 1) flood basalt magmas with primitive, mantle-dominated geochemical signatures (often high-Ti basalt magma types) that were either transferred directly from melting regions in the upper mantle to fissure vents at surface, or resided temporarily in reservoirs in the upper mantle or in mafic underplate thereby preventing extensive crustal contamination or crystallisation; 2) flood basalt magmas (often low-Ti types) that have undergone storage at lower ± upper crustal depths resulting in crustal assimilation, crystallisation, and degassing; 3) generation of high-temperature anhydrous, crystal-poor silicic magmas (e.g., Paraná-Etendeka quartz latites) by large-scale AFC processes involving lower crustal granulite melting and/or basaltic underplate remelting; and 4) rejuvenation of upper-crustal batholiths (mainly near-solidus crystal mush) by shallow intrusion and underplating by mafic magma providing thermal and volatile input to produce large volumes of crystal-rich (30-50%) dacitic to rhyolitic magma and for ignimbrite-producing eruptions, well-defined calderas up to 80 km diameter (e.g., Fish Canyon Tuff model), and which characterise of some silicic eruptions in silicic LIPs.

Rapid pre-eruptive thermal rejuvenation in a large silicic magma body: the case of the Masonic Park Tuff, Southern Rocky Mountain volcanic field, CO, USA

NASA Astrophysics Data System (ADS)

Sliwinski, J. T.; Bachmann, O.; Dungan, M. A.; Huber, C.; Deering, C. D.; Lipman, P. W.; Martin, L. H. J.; Liebske, C.

2017-05-01

Determining the mechanisms involved in generating large-volume eruptions (>100 km3) of silicic magma with crystallinities approaching rheological lock-up ( 50 vol% crystals) remains a challenge for volcanologists. The Cenozoic Southern Rocky Mountain volcanic field, in Colorado and northernmost New Mexico, USA, produced ten such crystal-rich ignimbrites within 3 m.y. This work focuses on the 28.7 Ma Masonic Park Tuff, a dacitic ( 62-65 wt% SiO2) ignimbrite with an estimated erupted volume of 500 km3 and an average of 45 vol% crystals. Near-absence of quartz, titanite, and sanidine, pronounced An-rich spikes near the rims of plagioclase, and reverse zoning in clinopyroxene record the reheating (from 750 to >800 °C) of an upper crustal mush in response to hotter recharge from below. Zircon U-Pb ages suggest prolonged magmatic residence, while Yb/Dy vs temperature trends indicate co-crystallization with titanite which was later resorbed. High Sr, Ba, and Ti concentrations in plagioclase microlites and phenocryst rims require in-situ feldspar melting and concurrent, but limited, mass addition provided by the recharge, likely in the form of a melt-gas mixture. The larger Fish Canyon Tuff, which erupted from the same location 0.7 m.y. later, also underwent pre-eruptive reheating and partial melting of quartz, titanite, and feldspars in a long-lived upper crustal mush following the underplating of hotter magma. The Fish Canyon Tuff, however, records cooler pre-eruptive temperatures ( 710-760 °C) and a mineral assemblage indicative of higher magmatic water contents (abundant resorbed sanidine and quartz, euhedral amphibole and titanite, and absence of pyroxene). These similar pre-eruptive mush-reactivation histories, despite differing mineral assemblages and pre-eruptive temperatures, indicate that thermal rejuvenation is a key step in the eruption of crystal-rich silicic volcanics over a wide range of conditions.

X-ray Raman scattering study of MgSiO3 glass at high pressure: Implication for triclustered MgSiO3 melt in Earth's mantle

PubMed Central

Lee, Sung Keun; Lin, Jung-Fu; Cai, Yong Q.; Hiraoka, Nozomu; Eng, Peter J.; Okuchi, Takuo; Mao, Ho-kwang; Meng, Yue; Hu, Michael Y.; Chow, Paul; Shu, Jinfu; Li, Baosheng; Fukui, Hiroshi; Lee, Bum Han; Kim, Hyun Na; Yoo, Choong-Shik

2008-01-01

Silicate melts at the top of the transition zone and the core-mantle boundary have significant influences on the dynamics and properties of Earth's interior. MgSiO3-rich silicate melts were among the primary components of the magma ocean and thus played essential roles in the chemical differentiation of the early Earth. Diverse macroscopic properties of silicate melts in Earth's interior, such as density, viscosity, and crystal-melt partitioning, depend on their electronic and short-range local structures at high pressures and temperatures. Despite essential roles of silicate melts in many geophysical and geodynamic problems, little is known about their nature under the conditions of Earth's interior, including the densification mechanisms and the atomistic origins of the macroscopic properties at high pressures. Here, we have probed local electronic structures of MgSiO3 glass (as a precursor to Mg-silicate melts), using high-pressure x-ray Raman spectroscopy up to 39 GPa, in which high-pressure oxygen K-edge features suggest the formation of tricluster oxygens (oxygen coordinated with three Si frameworks; [3]O) between 12 and 20 GPa. Our results indicate that the densification in MgSiO3 melt is thus likely to be accompanied with the formation of triculster, in addition to a reduction in nonbridging oxygens. The pressure-induced increase in the fraction of oxygen triclusters >20 GPa would result in enhanced density, viscosity, and crystal-melt partitioning, and reduced element diffusivity in the MgSiO3 melt toward deeper part of the Earth's lower mantle. PMID:18535140

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.

Generalized Ellipsometry on Complex Nanostructures and Low-Symmetry Materials

NASA Astrophysics Data System (ADS)

Mock, Alyssa Lynn

In this thesis, complex anisotropic materials are investigated and characterized by generalized ellipsometry. In recent years, anisotropic materials have gained considerable interest for novel applications in electronic and optoelectronic devices, mostly due to unique properties that originate from reduced crystal symmetry. Examples include white solid-state lighting devices which have become ubiquitous just recently, and the emergence of high-power, high-voltage electronic transistors and switches in all-electric vehicles. The incorporation of single crystalline material with low crystal symmetry into novel device structures requires reconsideration of existing optical characterization approaches. Here, the generalized ellipsometry concept is extended to include applications for materials with monoclinic and triclinic symmetries. A model eigendielectric displacement vector approach is developed, described and utilized to characterize monoclinic materials. Materials are investigated in spectral regions spanning from the far-infrared to the vacuum ultraviolet. Examples are demonstrated for phonon mode determination in cadmium tungstate and yttrium silicate and for band-to-band transitions in gallia (beta-Ga2O3) single crystals. Furthermore, the anisotropic optical properties of an emerging class of spatially coherent heterostructure materials with nanostructure dimensions are investigated. The so-called anisotropic effective medium approximation for slanted columnar thin films is extended to the concept of slanted columnar heterostructure thin films as well as core-shell heterostructure thin films. Examples include the determination of band-to-band transitions, phonon modes and oxidation properties of cobalt-oxide core shell structures and gas-liquid-solid distribution during controlled adsorption of organic solvents in silicon slanted columnar thin films.

Well-aligned polycrystalline lanthanum silicate oxyapatite grown by reactive diffusion between solid La{sub 2}SiO{sub 5} and gases [SiO+1/2O{sub 2}

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

Fukuda, Koichiro, E-mail: fukuda.koichiro@nitech.ac.jp; Hasegawa, Ryo; Kitagawa, Takuya

2016-03-15

The c-axis-oriented polycrystalline lanthanum silicate oxyapatite, La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} (□ denotes a vacancy in the Si site), was successfully prepared by the reactive diffusion between randomly grain-oriented La{sub 2}SiO{sub 5} polycrystal and [SiO+1/2O{sub 2}] gases at 1873 K in Ar atmosphere. The polycrystal was characterized using optical microscopy, scanning electron microscopy equipped with energy dispersive X-ray spectroscopy, micro-Raman spectroscopy, X-ray diffractometry, and impedance spectroscopy. The crystal structure (space group P6{sub 3}/m) showed the deficiency of Si site at ca. 1.9%. The bulk oxide-ion conductivity along the grain-alignment direction steadily increased from 9.2 × 10{sup −3} to 1.17 ×more » 10{sup −2} S/cm with increasing temperature from 923 to 1073 K. The activation energy of conduction was 0.23(2) eV. - Graphical abstract: We have successfully prepared the highly c-axis-oriented polycrystalline La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} by the reactive diffusion between randomly grain-oriented La{sub 2}SiO{sub 5} polycrystal and [SiO + 1/2O{sub 2}] gases at 1873 K in Ar atmosphere. The crystal structure (space group P6{sub 3}/m) showed the deficiency of Si site of ca. 1.9%. - Highlights: • The c-axis-oriented polycrystalline La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} is successfully prepared. • Crystal structure of La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} is determined by single-crystal XRD. • The polycrystal shows relatively high oxide ion conductivity along the common c-axis. • Reactive diffusion is successfully used for the preparation of grain-aligned ceramics.« less

Diagenesis of Miocene siliceous shales, Temblor Range, California

USGS Publications Warehouse

Murata, K.J.; Larson, R.R.

1975-01-01

Siliceous Monterey Shale and related shales of the Temblor Range, Calif., are subdivided into three depth-controlled zones characterized by different forms of silica. These are, in descending stratigraphic order: (1) Biogenic opal zone, with remains of diatoms and other siliceous organisms, (2) diagenetic cristobalite zone, and (3) diagenetic quartz zone. Using the top of the youngest marine unit, the overlying Etchegoin Formation, as datum, the transition from biogenic opal to disordered cristobalite occurs within the Monterey Shale of Chico Martinez Creek at -730 m, and the ordered cristobalite-to-microquartz transition at about -2,030 m. Temperatures that prevailed at these transition depths while the sedimentary pile lay at the bottom of the sea are estimated at about 50° and 110°C, respectively. Diagenetic cristobalite manifests, downward through a 1,300-m interval of section, a progressive decrease in its d(101) spacing because of a gradual ordering of its internal structure through adjustments in the solid state. Diagenetic microquartz forms only from well-ordered cristobalite that provides the most appropriate concentration of dissolved silica for precipitation of microquartz. Scanning electron micrographs of the silica mineral in pores of rocks made up of disordered cristobalite show aggregates of well-formed bladed crystals, like those described from deep-sea cherts. The pore silica minerals in rocks made up of ordered cristobalite occur as dendritic growths of poorly formed stubby crystals, and the change in crystal habit could be an external expression of the internal ordering process.

Anionic silicate organic frameworks constructed from hexacoordinate silicon centres

NASA Astrophysics Data System (ADS)

Roeser, Jérôme; Prill, Dragica; Bojdys, Michael J.; Fayon, Pierre; Trewin, Abbie; Fitch, Andrew N.; Schmidt, Martin U.; Thomas, Arne

2017-10-01

Crystalline frameworks composed of hexacoordinate silicon species have thus far only been observed in a few high pressure silicate phases. By implementing reversible Si-O chemistry for the crystallization of covalent organic frameworks, we demonstrate the simple one-pot synthesis of silicate organic frameworks based on octahedral dianionic SiO6 building units. Clear evidence of the hexacoordinate environment around the silicon atoms is given by 29Si nuclear magnetic resonance analysis. Characterization by high-resolution powder X-ray diffraction, density functional theory calculation and analysis of the pair-distribution function showed that those anionic frameworks—M2[Si(C16H10O4)1.5], where M = Li, Na, K and C16H10O4 is 9,10-dimethylanthracene-2,3,6,7-tetraolate—crystallize as two-dimensional hexagonal layers stabilized in a fully eclipsed stacking arrangement with pronounced disorder in the stacking direction. Permanent microporosity with high surface area (up to 1,276 m2 g-1) was evidenced by gas-sorption measurements. The negatively charged backbone balanced with extra-framework cations and the permanent microporosity are characteristics that are shared with zeolites.

Calcium titanium silicate based glass-ceramic for nuclear waste immobilisation

NASA Astrophysics Data System (ADS)

Sharma, K.; Srivastav, A. P.; Goswami, M.; Krishnan, Madangopal

2018-04-01

Titanate based ceramics (synroc) have been studied for immobilisation of nuclear wastes due to their high radiation and thermal stability. The aim of this study is to synthesis glass-ceramic with stable phases from alumino silicate glass composition and study the loading behavior of actinides in glass-ceramics. The effects of CaO and TiO2 addition on phase evolution and structural properties of alumino silicate based glasses with nominal composition x(10CaO-9TiO2)-y(10Na2O-5 Al2O3-56SiO2-10B2O3); where z = x/y = 1.4-1.8 are reported. The glasses are prepared by melt-quench technique and characterized for thermal and structural properties using DTA and Raman Spectroscopy. Glass transition and peak crystallization temperatures decrease with increase of CaO and TiO2 content, which implies the weakening of glass network and increased tendency of glasses towards crystallization. Sphene (CaTiSiO5) and perovskite (CaTiO3) crystalline phases are confirmed from XRD which are well known stable phase for conditioning of actinides. The microsturcture and elemental analysis indicate the presence of actinide in stable crystalline phases.

The Principal Hugoniot of Forsterite to 950 GPa

DOE PAGES

Root, Seth; Townsend, Joshua P.; Davies, Erik; ...

2018-04-27

Forsterite (Mg 2SiO 4) single crystals were shock compressed to pressures between 200 and 950 GPa using independent plate–impact steady shocks and laser–driven decaying shock compression experiments. Additionally, we performed density functional theory–based molecular dynamics to aid interpretation of the experimental data and to investigate possible phase transformations and phase separations along the Hugoniot. We show that the experimentally obtained Hugoniot cannot distinguish between a pure liquid Mg 2SiO 4 and an assemblage of solid MgO plus liquid magnesium silicate. In conclusion, the measured reflectivity is nonzero and increases with pressure, which implies that the liquid is a poor electricalmore » conductor at low pressures and that the conductivity increases with pressure.« less

The Principal Hugoniot of Forsterite to 950 GPa

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

Root, Seth; Townsend, Joshua P.; Davies, Erik

Forsterite (Mg 2SiO 4) single crystals were shock compressed to pressures between 200 and 950 GPa using independent plate–impact steady shocks and laser–driven decaying shock compression experiments. Additionally, we performed density functional theory–based molecular dynamics to aid interpretation of the experimental data and to investigate possible phase transformations and phase separations along the Hugoniot. We show that the experimentally obtained Hugoniot cannot distinguish between a pure liquid Mg 2SiO 4 and an assemblage of solid MgO plus liquid magnesium silicate. In conclusion, the measured reflectivity is nonzero and increases with pressure, which implies that the liquid is a poor electricalmore » conductor at low pressures and that the conductivity increases with pressure.« less

Structure and stability of hydrous minerals at high pressure

NASA Technical Reports Server (NTRS)

Duffy, T. S.; Fei, Y.; Meade, C.; Hemley, R. J.; Mao, H. K.

1994-01-01

The presence of even small amounts of hydrogen in the Earth's deep interior may have profound effects on mantle melting, rheology, and electrical conductivity. The recent discovery of a large class of high-pressure H-bearing silicates further underscores the potentially important role for hydrous minerals in the Earth's mantle. Hydrogen may also be a significant component of the Earth's core, as has been recently documented by studies of iron hydride at high pressure. In this study, we explore the role of H in crystal structures at high pressure through detailed Raman spectroscopic and x ray diffraction studies of hydrous minerals compressed in diamond anvil cells. Brucite, Mg(OH)2, has a simple structure and serves as an analogue for the more complex hydrous silicates. Over the past five years, this material has been studied at high pressure using shock-compression, powder x ray diffraction, infrared spectroscopy, Raman spectroscopy, and neutron diffraction. In addition, we have recently carried out single-crystal synchrotron x-ray diffraction on Mg(OH)2 and Raman spectroscopy on Mg(OD)2 at elevated pressure. From all these studies, an interesting picture of the crystal chemical behavior of this material at high pressure is beginning to emerge. Some of the primary conclusions are as follows: First, hydrogen bonding is enhanced by the application of pressure. Second, layered minerals which are elastically anisotropic at low pressure may not be so at high pressure. Furthermore, the brucite data place constraints on the effect of hydrogen on seismic velocities and density at very high pressure. Third, the stability of hydrous minerals may be enhanced at high P by subtle structural rearrangements that are difficult to detect using traditional probes and require detailed spectroscopic analyses. Finally, brucite appears to be unique in that it undergoes pressure-induced disordering that is confined solely to the H-containing layers of the structure.

Crystal structure, thermal expansivity, and elasticity of OH-chondrodite: Trends among dense hydrous magnesium silicates

DOE PAGES

Ye, Yu; Jacobsen, Steven D.; Mao, Zhu; ...

2015-04-01

Here, we report the structure and thermoelastic properties of OH-chondrodite. The sample was synthesized at 12 GPa and 1523 K, coexisting with hydroxyl-clinohumite and hydrous olivine. The Fe content Fe/(Fe+Mg) is 1.1 mol%, and the monoclinic unit-cell parameters are: a = 4.7459(2) Å, b = 10.3480(7) Å, c = 7.9002(6) Å, α = 108.702(7)°, and V = 367.50(4) Å3. At ambient conditions the crystal structure was refined in space group P 21/b from 1915 unique reflection intensities measured by single-crystal x-ray diffraction. The volume thermal expansion coefficient was measured between 150 and 800 K, resulting in α V = 2.8(5)×10more » -9(K -2) × T + 40.9(7) × 10 -6(K -1) – 0.81(3)(K)/T 2, with an average value of 38.0(9)×10 -6 K -1. Brillouin spectroscopy was used to measure a set of acoustic velocities from which all thirteen components (C ij) of the elastic tensor were determined. The Voigt-Reuss-Hill average of the moduli yield for the adiabatic bulk modulus, K S0 = 117.9(12) GPa, and for shear modulus, G 0 = 70.1(5) GPa. The Reuss bound on the isothermal bulk modulus (K T0) is 114.2(14) GPa. From the measured thermodynamic properties, the Grüneisen parameter (γ) is calculated to be 1.66(4). Fitting previous static compression data using our independently measured bulk modulus (isothermal Reuss bound) as a fixed parameter, we refined the first pressure derivative of the bulk modulus, K T’ = 5.5(1). Systematic trends between H 2O content and physical properties are evaluated among dense hydrous magnesium silicate (DHMS) phases along the forsterite-brucite join.« less

Genesis of IIICD Iron Meteorites: Evidence From Silicate Inclusions

NASA Astrophysics Data System (ADS)

McCoy, T. J.; Keil, K.; Scott, E. R. D.; Haack, H.

1992-07-01

The IAB and IIICD iron meteorite groups exhibit much larger ranges in siderophile concentrations than other groups and commonly contain silicate inclusions. Extensive studies of metal in both groups and silicates in IAB irons have led to a variety of ideas to explain the genesis of these groups. Wasson et al. (1980) envision each meteorite forming in a separate impact melt pool. Kracher (1982, 1985) suggested that the siderophile trends might result from fractional crystallization of both metal and troilite in a S-saturated magma. A role for oxidation-reduction in these groups has been proposed by Scott and Bild (1974). Similarities in siderophile elemental trends indicate that IIICD metal has a similar origin, although data on silicate inclusions in IIICD irons are scarce (Ramdohr, 1973; Scott and Bild, 1974; Kracher and Kurat, 1977; Prinz et al., 1982; Clayton et al., 1983). We report the first detailed study of silicate inclusions in IIICD iron meteorites in an attempt to elucidate their history. We have studied the only silicate-bearing IIICD irons - Carlton, Dayton, and the recently reported Maltahohe. Silicate-graphite-phosphate inclusions comprise at most a few percent of the bulk meteorite, and silicates comprise <25 vol% of the inclusion. Silicate mineralogy and chemistry vary systematically with increasing M content of the metal. Maltahohe (10.7 wt% Ni) and Carlton (13.0%) contain olivine, pyroxene, and plagioclase, whereas Dayton (17.0%) contains pyroxene, plagioclase, and SiO2. Pyroxene becomes more FeO-rich from Maltahohe (FS(sub)7.8) to Carlton (Fs(sub)9.7) to Dayton (Fs(sub)11.6). Inverse FeO zoning in silicates and lower Fa than Fs indicate reduction in all three meteorites. Plagioclase compositions in IIICD (An(sub)1.1-4.9) are lower than IAB (An(sub)9.2-2l.5) and uncorrelated with Ni content. The abundances of associated phases also vary. Graphite comprises ~25 vol% of Maltahohe silicate inclusions, but only a few percent in Carlton, and is absent in Dayton silicate inclusions. Phosphate mineralogy and modal abundance also vary, with phosphates absent in Maltahohe, chlorapatite comprising 0-70 vol% of inclusions in Carlton, and the unusual phosphates brianite and panethite, along with whitlockite, comprising up to 55 vol% of Dayton's inclusions. The small number of silicate-bearing IIICD irons require that any conclusions must be considered tentative. The precursor silicate assemblage was similar for IAB and IIICD, as suggested by the general similarity between Maltahohe and IAB silicate inclusions. With increasing Ni contents, however, IIICD and IAB silicate inclusions become dramatically different, as indicated by the mineralogical and chemical trends present in IIICD and absent in IAB silicate inclusions. Silicate inclusions in the Ni-rich IAB irons (e.g., San Cristobal, 25 wt% Ni) do not resemble the phosphate-rich, evolved-silicate assemblages observed in Dayton. It is clear that one or more processes were capable of producing changes in metal compositions and silicate inclusion mineralogy, which correlated with one another. None of the observed trends in silicate mineralogy are predicted by the impact-melt model, although impact might have played a role in mixing silicates into the metallic magma. Some trends are consistent with oxidation-reduction, but variations in some siderophiles (e.g., Ir, Cu) cannot be explained easily by this mechanism. We believe that solid silicates must have been mixed with an evolving metallic melt, with the metallic magma dramatically influencing the mineralogy and chemistry of the inclusion, similar to the fractional crystallization model of Kracher (1982,1985). However, many details of this process remain obscure, including the mechanism that concentrated a S-rich melt, the mixing of metal and silicates, and the fractionation of S. References: Clayton et al. (1983) EPSL 65, 229-232. Kracher (1982) GRL 9, 412-415. Kracher (1985) PLPSC 15, C689-C698. Kracher and Kurat (1977) Meteoritics 12, 282-283. Scott and Bild (1974) GCA 38, 1379-1391. Prinz et al. (1982) LPSC XIlI, 632-633. Ramdohr (1973) Elsevier Pub. Co. Wasson et al. (1980) Z. Naturforsch. 35a, 781-795.

Silicate Inclusions in IAB Irons: Correlations Between Metal Composition and Inclusion Properties, and Inferences for Their Origin

NASA Astrophysics Data System (ADS)

Benedix, G. K.; McCoy, T. J.; Keil, K.

1995-09-01

IAB irons are the largest group of iron meteorites, exhibit a large range of siderophile element concentrations in their metal, and commonly contain silicate inclusions with roughly chondritic composition. They are closely related to IIICD irons [1,2] and their inclusions resemble winonaites [3]. It has been suggested that IAB's and IIICD's formed in individual impact melt pools [4,2] on a common parent body. However, it has also been suggested that fractional crystallization [5,6] of a S-saturated core could produce the observed siderophile element trends. Metal composition is correlated with silicate inclusion mineralogy in IIICD's [1], indicating reactions between solid silicates and the metallic magma in a core. These trends observed in IIICD's differ from those in IAB's, suggesting different parent bodies. A bi-modal grouping, based primarily on mineralogy and mineral abundances, was suggested for IAB inclusions [7]. However, recent recoveries of several new silicate-bearing IAB's, along with the emergence of new ideas on their origins, prompted a comprehensive study to document more fully the range of inclusions within IAB irons, to examine possible correlations between the compositions of the metallic host and the silicate inclusions, and to elucidate the origin of IAB irons. We are studying troilite-graphite-silicate inclusions in 24 IAB irons with Ni concentrations ranging from 6.6-25.0%. These include Odessa and Copiapo types [7], newly recovered meteorites (e.g., Lueders [8]) and meteorites with extreme Ni contents (e.g., Jenny's Creek, 6.8%; San Cristobal, 25.0% [9]). The inclusions exhibit a range of textures from recrystallized to partial melts (e.g., Caddo County [10]). Rigorous classification [7] is hampered by heterogeneities between group meteorites, between different samples of distinct meteorites, and within individual inclusions. While intergroup heterogeneities make comparisons between the suite of IAB's somewhat difficult, some general trends do exist. Inclusion mineralogy progresses from graphite-troilite nodules in low Ni IAB's, to silicate-dominated inclusions in high Ni IAB's. With increasing Ni abundance in the metal, systematic variations are found in several properties. Two groups are delineated on a Ni vs Fa content plot and both are positively correlated with Ni content. Graphite abundance noticeably decreases with increasing Ni content [7]. Graphite location also varies with Ni: graphite is primarily found interstitial to the silicates in low Ni IAB's, but is located at metal-silicate boundaries in those with higher Ni abundances. With increasing Ni, daubreelite disappears. Inclusion shape also varies [7]: more angular inclusions are associated with low Ni, while more rounded inclusions exist at high Ni contents. These systematic changes suggest interaction between the silicate inclusions and an evolving metallic magma. Troilite and graphite abundances may be related to early nucleation on silicates, hence their depletion in high Ni (later crystallizing) irons. The presence of abundant graphite creates reducing conditions which would result in the formation of daubreelite. Conditions become more oxidizing with loss of graphite, evidenced by lack of daubreelite and more FeO-rich silicates in high Ni irons. Although an overall trend exists, the story is complicated by heterogeneities. Significant variations are found between paired samples (e.g., Toluca and Tacubaya), as well as within individual inclusions (daubreelite and chromite in same inclusion). Local oxidation conditions may be controlled by graphite abundance. Heterogeneities within specific meteorites need documentation. Most of the inclusions exhibit similar textural (metamorphic) features, but a few show evidence of partial melting and melt migration, further complicating the parent body history. While a variety of processes (oxidation-reduction, metamorphism, partial melting) affected the inclusions during formation, systematic changes observed here indicate that the silicates were interacting with a single evolving metallic magma. We suggest that the requirement for a common system is more compatible with core formation [5,6] than with impact-melt pools [2,4]. References: [1] McCoy T. J. et al. (1993) Meteoritics, 28, 552-560. [2] Choi B.-G. et al. (1995) GCA, 59, 593-612. [3] Benedix G. K. et al. (1995) LPS XXVI, 99-100. [4] Wasson J. T. et al. (1980) Z. Naturforsch., 35a, 781-795. [5] Kracher A. (1982) GRL, 9, 412-415. [6] Kracher A. (1985) Proc. LPSC 15th, in JGR, 90, C689-C698. [7] Bunch T. E. et al. (1970) Contrib. Mineral. Petrol., 25, 297-340. [8] McCoy et al. (1995) Meteoritics, in preparation. [9] Scott E. R. D. and Bild R. W. (1974) GCA, 38, 1379-1391. [10] Takeda H. et al. (1993) Meteoritics, 28, 447.

Elasticity of Single-Crystal Phase D across the Spin Transitions of Ferrous and Ferric Iron in the Lower Mantle

NASA Astrophysics Data System (ADS)

Wu, X.; Lin, J. F.; Liu, J.; Mao, Z.; Guo, X.; Yoshino, T.; McCammon, C. A.; Xiao, Y.; Prakapenka, V.

2014-12-01

Phase D, the densest hydrous magnesium silicate synthesized at the Earth's mantle P-T conditions thus far, has been proposed to be a potential candidate for transportation of H2O into the lower mantle by subduction of the hydrated oceanic lithosphere. A certain amount of iron, the most abundant transition metal element in the Earth's interior, is expected to be incorporated into the phase D. Here we synthesized high-quality single-crystal Fe,Al-bearing Phase D (Mg0.89Fe0.11Al0.37Si1.55H2.65O6, ~13.3wt% H2O) with grain sizes of ~200 micron using the Kawai multianvil apparatus at 21 GPa and 1200 °C at the Institute for Study of the Earth's Interior, University of Oakayama, Japan. Conventional Mössbauer results indicate that the sample contains both ferrous and ferric iron that occupy the octahedral sites of the hexagonal structure. In situ high-pressure single crystal XRD and NFS experiments were performed up to megabar pressures at 13IDD beamline (GSECARS) and 16IDD beamline (HPCAT) of the Advanced Photon Source, respectively. Both experimental results clearly show that both Fe2+ and Fe3+ undergo a HS-LS transition at high pressures. High-resolution XRD results further indicate an abnormal compression behavior at approximately 37 GPa that can be linked with the previously proposed hydrogen bond symmetrization. Elasticity of phase D has a marked influence by the two-step spin transitions of both Fe2+ and Fe3+ and the hydrogen bond symmetrization, presenting in the seismic wave model, which is of implication for our understanding of the deep-Earth geophysics and geochemistry especially along the subducted slabs.

Closed system oxygen isotope redistribution in igneous CAIs upon spinel dissolution

NASA Astrophysics Data System (ADS)

Aléon, Jérôme

2018-01-01

In several Calcium-Aluminum-rich Inclusions (CAIs) from the CV3 chondrites Allende and Efremovka, representative of the most common igneous CAI types (type A, type B and Fractionated with Unknown Nuclear isotopic anomalies, FUN), the relationship between 16O-excesses and TiO2 content in pyroxene indicates that the latter commonly begins to crystallize with a near-terrestrial 16O-poor composition and becomes 16O-enriched during crystallization, reaching a near-solar composition. Mass balance calculations were performed to investigate the contribution of spinel to this 16O-enrichment. It is found that a back-reaction of early-crystallized 16O-rich spinel with a silicate partial melt having undergone a 16O-depletion is consistent with the O isotopic evolution of CAI minerals during magmatic crystallization. Dissolution of spinel explains the O isotopic composition (16O-excess and extent of mass fractionation) of pyroxene as well as that of primary anorthite/dmisteinbergite and possibly that of the last melilite crystallizing immediately before pyroxene. It requires that igneous CAIs behaved as closed-systems relative to oxygen from nebular gas during a significant fraction of their cooling history, contrary to the common assumption that CAI partial melts constantly equilibrated with gas. The mineralogical control on O isotopes in igneous CAIs is thus simply explained by a single 16O-depletion during magmatic crystallization. This 16O-depletion occurred in an early stage of the thermal history, after the crystallization of spinel, i.e. in the temperature range for melilite crystallization/partial melting and did not require multiple, complex or late isotope exchange. More experimental work is however required to deduce the protoplanetary disk conditions associated with this 16O-depletion.

Sintering polycrystalline olivine and polycrystalline clinopyroxene containing trace amount of graphite from natural crystals

NASA Astrophysics Data System (ADS)

Tsubokawa, Yumiko; Ishikawa, Masahiro

2017-09-01

Graphite-bearing polycrystalline olivine and polycrystalline clinopyroxene with submicron to micron grain size were successfully sintered from a single crystal of naturally occurring olivine (Fo88-92Fa12-8: Mg1.76-1.84Fe0.16-0.24SiO4) and a single crystal of naturally occurring clinopyroxene (Di99Hed1: Ca0.92Na0.07Mn0.01Mg0.93Fe0.01Al0.06Si2O6). The milled powders of both these crystals were sintered under argon gas flow at temperatures ranging from 1130 to 1350 °C for 2 h. As the sintering temperature increased, the average grain size of olivine increased from 0.2 to 1.4 µm and that of clinopyroxene increased from 0.1 to 2.4 µm. The porosity of sintered samples remained at an almost-constant volume of 2-5% for olivine and 3-4% for clinopyroxene. The samples sintered from powders milled with ethanol exhibited trace amount of graphite, identified via Raman spectroscopy analysis. As the sintering temperature increased, the intensity of the graphite Raman peak decreased, compared with both olivine and clinopyroxene peaks. The carbon content of the sintered samples was estimated to be a few hundred ppm. The in-plane size ( L a ) of graphite in the sintered olivine was estimated to be <15 nm. Our experiments demonstrate new possibilities for preparing graphite-bearing silicate-mantle mineral rocks, and this method might be useful in understanding the influence of the physical properties of graphite on grain-size-sensitive rheology or the seismic velocity of the Earth's mantle.[Figure not available: see fulltext.

Analysis of H2O in silicate glass using attenuated total reflectance (ATR) micro-FTIR spectroscopy

USGS Publications Warehouse

Lowenstern, Jacob B.; Pitcher, Bradley W.

2013-01-01

We present a calibration for attenuated total reflectance (ATR) micro-FTIR for analysis of H2O in hydrous glass. A Ge ATR accessory was used to measure evanescent wave absorption by H2O within hydrous rhyolite and other standards. Absorbance at 3450 cm−1 (representing total H2O or H2Ot) and 1630 cm−1 (molecular H2O or H2Om) showed high correlation with measured H2O in the glasses as determined by transmission FTIR spectroscopy and manometry. For rhyolite, wt%H2O=245(±9)×A3450-0.22(±0.03) and wt%H2Om=235(±11)×A1630-0.20(±0.03) where A3450 and A1630 represent the ATR absorption at the relevant infrared wavelengths. The calibration permits determination of volatiles in singly polished glass samples with spot size down to ~5 μm (for H2O-rich samples) and detection limits of ~0.1 wt% H2O. Basaltic, basaltic andesite and dacitic glasses of known H2O concentrations fall along a density-adjusted calibration, indicating that ATR is relatively insensitive to glass composition, at least for calc-alkaline glasses. The following equation allows quantification of H2O in silicate glasses that range in composition from basalt to rhyolite: wt%H2O=(ω×A3450/ρ)+b where ω = 550 ± 21, b = −0.19 ± 0.03, ρ = density, in g/cm3, and A3450 is the ATR absorbance at 3450 cm−1. The ATR micro-FTIR technique is less sensitive than transmission FTIR, but requires only a singly polished sample for quantitative results, thus minimizing time for sample preparation. Compared with specular reflectance, it is more sensitive and better suited for imaging of H2O variations in heterogeneous samples such as melt inclusions. One drawback is that the technique can damage fragile samples and we therefore recommend mounting of unknowns in epoxy prior to polishing. Our calibration should hold for any Ge ATR crystals with the same incident angle (31°). Use of a different crystal type or geometry would require measurement of several H2O-bearing standards to provide a crystal-specific calibration.

How Mercury can be the most reduced terrestrial planet and still store iron in its mantle

NASA Astrophysics Data System (ADS)

Malavergne, Valérie; Cordier, Patrick; Righter, Kevin; Brunet, Fabrice; Zanda, Brigitte; Addad, Ahmed; Smith, Thomas; Bureau, Hélène; Surblé, Suzy; Raepsaet, Caroline; Charon, Emeline; Hewins, Roger H.

2014-05-01

Mercury is notorious as the most reduced planet with the highest metal/silicate ratio, yet paradoxically data from the MESSENGER spacecraft show that its iron-poor crust is high in sulfur (up to ˜6 wt%, ˜80× Earth crust abundance) present mainly as Ca-rich sulfides on its surface. These particularities are simply impossible on the other terrestrial planets. In order to understand the role played by sulfur during the formation of Mercury, we investigated the phase relationships in Mercurian analogs of enstatite chondrite-like composition experimentally under conditions relevant to differentiation of Mercury (˜1 GPa and 1300-2000 °C). Our results show that Mg-rich and Ca-rich sulfides, which both contain Fe, crystallize successively from reduced silicate melts upon cooling below 1550 °C. As the iron concentration in the reduced silicates stays very low (≪1 wt%), these sulfides represent new host phases for both iron and sulfur in the run products. Extrapolated to Mercury, these results show that Mg-rich sulfide crystallization provides the first viable and fundamental means for retaining iron as well as sulfur in the mantle during differentiation, while sulfides richer in Ca would crystallize at shallower levels. The distribution of iron in the differentiating mantle of Mercury was mainly determined by its partitioning between metal (or troilite) and Mg-Fe-Ca-rich sulfides rather than by its partitioning between metal (or troilite) and silicates. Moreover, the primitive mantle might also be boosted in Fe by a reaction at the core mantle boundary (CMB) between Mg-rich sulfides of the mantle and FeS-rich outer core materials to produce (Fe, Mg)S. The stability of Mg-Fe-Ca-rich sulfides over a large range of depths up to the surface of Mercury would be consistent with sulfur, calcium and iron abundances measured by MESSENGER.

Sulfur Saturation Limits in Silicate Melts and their Implications for Core Formation Scenarios for Terrestrial Planets

NASA Technical Reports Server (NTRS)

Holzheid, Astrid; Grove, Timothy L.

2002-01-01

This study explores the controls of temperature, pressure, and silicate melt composition on S solubility in silicate liquids. The solubility of S in FeO-containing silicate melts in equilibrium with metal sulfide increases significantly with increasing temperature but decreases with increasing pressure. The silicate melt structure also exercises a control on S solubility. Increasing the degree of polymerization of the silicate melt structure lowers the S solubility in the silicate liquid. The new set of experimental data is used to expand the model of Mavrogenes and O'Neill(1999) for S solubility in silicate liquids by incorporating the influence of the silicate melt structure. The expected S solubility in the ascending magma is calculated using the expanded model. Because the negative pressure dependence of S solubility is more influential than the positive temperature dependence, decompression and adiabatic ascent of a formerly S-saturated silicate magma will lead to S undersaturation. A primitive magma that is S-saturated in its source region will, therefore, become S-undersaturated as it ascends to shallower depth. In order to precipitate magmatic sulfides, the magma must first cool and undergo fractional crystallization to reach S saturation. The S content in a metallic liquid that is in equilibrium with a magma ocean that contains approx. 200 ppm S (i.e., Earth's bulk mantle S content) ranges from 5.5 to 12 wt% S. This range of S values encompasses the amount of S (9 to 12 wt%) that would be present in the outer core if S is the light element. Thus, the Earth's proto-mantle could be in equilibrium (in terms of the preserved S abundance) with a core-forming metallic phase.

A Physical Model for Three-Phase Compaction in Silicic Magma Reservoirs

NASA Astrophysics Data System (ADS)

Huber, Christian; Parmigiani, Andrea

2018-04-01

We develop a model for phase separation in magma reservoirs containing a mixture of silicate melt, crystals, and fluids (exsolved volatiles). The interplay between the three phases controls the dynamics of phase separation and consequently the chemical and physical evolution of magma reservoirs. The model we propose is based on the two-phase damage theory approach of Bercovici et al. (2001, https://doi.org/10.1029/2000JB900430) and Bercovici and Ricard (2003, https://doi.org/10.1046/j.1365-246X.2003.01854.x) because it offers the leverage of considering interface (in the macroscopic limit) between phases that can deform depending on the mechanical work and phase changes taking place locally in the magma. Damage models also offer the advantage that pressure is defined uniquely to each phase and does not need to be equal among phases, which will enable us to consider, in future studies, the large capillary pressure at which fluids are mobilized in mature, crystal-rich, magma bodies. In this first analysis of three-phase compaction, we solve the three-phase compaction equations numerically for a simple 1-D problem where we focus on the effect of fluids on the efficiency of melt-crystal separation considering the competition between viscous and buoyancy stresses only. We contrast three sets of simulations to explore the behavior of three-phase compaction, a melt-crystal reference compaction scenario (two-phase compaction), a three-phase scenario without phase changes, and finally a three-phase scenario with a parameterized second boiling (crystallization-induced exsolution). The simulations show a dramatic difference between two-phase (melt crystals) and three-phase (melt-crystals-exsolved volatiles) compaction-driven phase separation. We find that the presence of a lighter, significantly less viscous fluid hinders melt-crystal separation.

Sidewall crystallization and saturation front formation in silicic magma chambers

NASA Astrophysics Data System (ADS)

Lake, E. T.

2012-12-01

The cooling and crystallization style of silicic magma bodies in the upper crust falls on a continuum between whole-chamber processes of convection, crystal settling, and cumulate formation and interface driven processes of conduction and crystallization front migration. In the former case, volatile saturation occurs uniformly chamber wide, in the latter volatile saturation occurs along an inward propagating front. Ambient thermal gradient primarily controls the propagation rate; warm (> 30 °C / km) geothermal gradients promote 1000m+ thick crystal mush zones but slow crystallization front propagation. Cold geothermal gradients support the opposite. Magma chamber geometry plays a second order role in controlling propagation rates; bodies with high surface to magma ratio and large Earth's surface parallel faces exhibit more rapid propagation and smaller mush zones. Crystallization front propagation occurs at speeds of up to 6 cm/year (rhyolitic magma, thin sill geometry, 10 °C / km geotherm), far faster than diffusion of volatiles in magma and faster than bubbles can nucleate and ascend under certain conditions. Saturation front propagation is fixed by pressure and magma crystal content; above certain modest initial water contents (4.4 wt% in a dacite) mobile magma above 10 km depth always contains a saturation front. Saturation fronts propagate down from the magma chamber roof at lower water contents (3.3 wt% in a dacite at 5 km depth), creating an upper saturated interface for most common (4 - 6 wt%) magma water contents. This upper interface promotes the production of a fluid pocket underneath the apex of the magma chamber. Magma de-densification by bubble nucleation promotes convection and homogenization in dacitic systems. If the fluid pocket grew rapidly without draining, hydro-fracturing and eruption would result. The combination of fluid escape pathways and metal scavenging would generate economic vein or porphyry deposits.

The Assembly and Emplacement of the Mushy Magma Model: A Historical Perspective

NASA Astrophysics Data System (ADS)

Bergantz, G. W.

2012-12-01

The "mush model" for magmatic systems has emerged as an alternative to the classic notion of a silicate liquid dominated reservoir, the so-called big tank model. The mush model is motivated by a concurrence of geochemical, geophysical and geological observations and new ideas on multiphase fluid dynamics. This presentation will review the historical development and remaining open questions about the mush model as it pertains to silicic systems. The observation that rhyolites have extreme depletions in Sr, Ba and Eu, as well as depletions in Zr and LREE, precluded an origin by direct crustal melting, instead requiring crystallization differentiation. This initially motivated the sidewall crystallization model, where less dense, evolved liquid originated and percolated upwards through a crystal-rich boundary zone, adjacent to a liquid dominated reservoir. The 'defrosting' or remobilization of this sidewall was proposed as a mechanism for producing complex temporal signatures in erupted suites, and this notion later found additional support in the recognition of so-called 'antecrysts.' Lab bench scale tank models of crystallizing salt solutions were offered as analogs for these boundary layer driven magmatic systems. However, it was recognized that features of this boundary layer model that did not agree with seismic, gravity and magnetotelluric, and geological observations. Seismic studies of silicic systems typically indicate P-wave velocity anomalies of 15% or greater for both shallow and deeper systems. But they do not show velocity anomalies that would indicate substantial regions of pure liquid in the core. Rather, the geophysical anomalies, are consistent with a with a spatially extensive crystal mush with an overlying thin melt lens. In addition the observation that erupted crystal poor liquids abruptly transition into crystal rich magmas with interstitial liquid compositions that are nearly identical to the crystal poor ones, provides evidence of a geometrical and source relationship between crystal poor and subjacent crystal rich mush. Lastly, it was appreciated that the boundary layer fluid dynamic models lacked geological verisimilitude, and invoked assumptions on heat transfer rates that were not in accord with geological conditions. Taken together this required a new conceptual model that could honor a broader range of constraints, and led to the 'full chamber' mush model as described by Hildreth (2001, 2004, 2007) and subsequently Bachmann and Bergantz (2004, 2008). However there are many open questions about this model, particularly how they are assembled, the physics of melt movement and mixing, and the way they respond to open system events. For example it is now recognized that crystal mushes can be remobilized rapidly and mineral isotopic and trace element zoning requires that the mush can go through some re-melting, consistent with the unzipping model of Burgisser and Bergantz (2011).

Mass spectra features of biomass burning boiler and coal burning boiler emitted particles by single particle aerosol mass spectrometer.

PubMed

Xu, Jiao; Li, Mei; Shi, Guoliang; Wang, Haiting; Ma, Xian; Wu, Jianhui; Shi, Xurong; Feng, Yinchang

2017-11-15

In this study, single particle mass spectra signatures of both coal burning boiler and biomass burning boiler emitted particles were studied. Particle samples were suspended in clean Resuspension Chamber, and analyzed by ELPI and SPAMS simultaneously. The size distribution of BBB (biomass burning boiler sample) and CBB (coal burning boiler sample) are different, as BBB peaks at smaller size, and CBB peaks at larger size. Mass spectra signatures of two samples were studied by analyzing the average mass spectrum of each particle cluster extracted by ART-2a in different size ranges. In conclusion, BBB sample mostly consists of OC and EC containing particles, and a small fraction of K-rich particles in the size range of 0.2-0.5μm. In 0.5-1.0μm, BBB sample consists of EC, OC, K-rich and Al_Silicate containing particles; CBB sample consists of EC, ECOC containing particles, while Al_Silicate (including Al_Ca_Ti_Silicate, Al_Ti_Silicate, Al_Silicate) containing particles got higher fractions as size increase. The similarity of single particle mass spectrum signatures between two samples were studied by analyzing the dot product, results indicated that part of the single particle mass spectra of two samples in the same size range are similar, which bring challenge to the future source apportionment activity by using single particle aerosol mass spectrometer. Results of this study will provide physicochemical information of important sources which contribute to particle pollution, and will support source apportionment activities. Copyright © 2017. Published by Elsevier B.V.

Water-bearing, high-pressure Ca-silicates

NASA Astrophysics Data System (ADS)

Németh, Péter; Leinenweber, Kurt; Ohfuji, Hiroaki; Groy, Thomas; Domanik, Kenneth J.; Kovács, István J.; Kovács, Judit S.; Buseck, Peter R.

2017-07-01

Water-bearing minerals provide fundamental knowledge regarding the water budget of the mantle and are geophysically significant through their influence on the rheological and seismic properties of Earth's interior. Here we investigate the CaO-SiO2-H2O system at 17 GPa and 1773 K, corresponding to mantle transition-zone condition, report new high-pressure (HP) water-bearing Ca-silicates and reveal the structural complexity of these phases. We document the HP polymorph of hartrurite (Ca3SiO5), post-hartrurite, which is tetragonal with space group P4/ncc, a = 6.820 (5), c = 10.243 (8) Å, V = 476.4 (8) Å3, and Z = 4, and is isostructural with Sr3SiO5. Post-hartrurite occurs in hydrous and anhydrous forms and coexists with larnite (Ca2SiO4), which we find also has a hydrous counterpart. Si is 4-coordinated in both post-hartrurite and larnite. In their hydrous forms, H substitutes for Si (4H for each Si; hydrogrossular substitution). Fourier transform infrared (FTIR) spectroscopy shows broad hydroxyl absorption bands at ∼3550 cm-1 and at 3500-3550 cm-1 for hydrous post-hartrurite and hydrous larnite, respectively. Hydrous post-hartrurite has a defect composition of Ca2.663Si0.826O5H1.370 (5.84 weight % H2O) according to electron-probe microanalysis (EPMA), and the Si deficiency relative to Ca is also observed in the single-crystal data. Hydrous larnite has average composition of Ca1.924Si0.851O4H0.748 (4.06 weight % H2O) according to EPMA, and it is in agreement with the Si occupancy obtained using X-ray data collected on a single crystal. Superlattice reflections occur in electron-diffraction patterns of the hydrous larnite and could indicate crystallographic ordering of the hydroxyl groups and their associated cation defects. Although textural and EPMA-based compositional evidence suggests that hydrous perovskite may occur in high-Ca-containing (or low silica-activity) systems, the FTIR measurement does not show a well-defined hydroxyl absorption band for this phase, implying the water content, at least in the quenched glass, is below the limit of detection (100-1000 ppm). We conclude that at high pressure, as at ambient pressure, some calcium silicates have a high affinity for H2O and high dehydration temperatures. The thermal stability of these hydrous phases suggests that they could exist along a typical mantle geotherm and thus they might be relevant for understanding the mineralogy and water content of Earth's mantle.

Mineral resource of the month: Vermiculite

USGS Publications Warehouse

Tanner, Arnold O.

2014-01-01

Vermiculite comprises a group of hydrated, laminar magnesium-aluminum-iron silicate minerals resembling mica. They are secondary minerals, typically altered biotite, iron-rich phlogopite or other micas or clay-like minerals that are themselves sometimes alteration products of amphibole, chlorite, olivine and pyroxene. Vermiculite deposits are associated with volcanic ultramafic rocks rich in magnesium silicate minerals, and flakes of the mineral range in color from black to shades of brown and yellow. The crystal structure of vermiculite contains water molecules, a property that is critical to its processing for common uses.

Molecular Simulations of the Synthesis of Periodic Mesoporous Silica Phases at High Surfactant Concentrations

DOE PAGES

Chien, Szu-Chia; Pérez-Sánchez, Germán; Gomes, José R. B.; ...

2017-02-17

Molecular dynamics simulations of a coarse-grained model are used to study the formation mechanism of periodic mesoporous silica over a wide range of cationic surfactant concentrations. This follows up on an earlier study of systems with low surfactant concentrations. We started by studying the phase diagram of the surfactant–water system and found that our model shows good qualitative agreement with experiments with respect to the surfactant concentrations where various phases appear. We then considered the impact of silicate species upon the morphologies formed. We have found that even in concentrated surfactant systems—in the concentration range where pure surfactant solutions yieldmore » a liquid crystal phase—the liquid-crystal templating mechanism is not viable because the preformed liquid crystal collapses as silica monomers are added into the solution. Upon the addition of silica dimers, a new phase-separated hexagonal array is formed. The preformed liquid crystals were found to be unstable in the presence of monomeric silicates. In addition, the silica dimer is found to be essential for mesoscale ordering at both low and high surfactant concentrations. Our results support the view that a cooperative interaction of anionic silica oligomers and cationic surfactants determines the mesostructure formation in the M41S family of materials.« less

Primary melt and fluid inclusions in regenerated crystals and phenocrysts of olivine from kimberlites of the Udachnaya-East Pipe, Yakutia: The problem of the kimberlite melt

NASA Astrophysics Data System (ADS)

Tomilenko, A. A.; Kuzmin, D. V.; Bul'bak, T. A.; Sobolev, N. V.

2017-08-01

The primary melt and fluid inclusions in regenerated zonal crystals of olivine and homogeneous phenocrysts of olivine from kimberlites of the Udachnaya-East pipe, were first studied by means of microthermometry, optic and scanning electron microscopy, electron and ion microprobe analysis (SIMS), inductively coupled plasma mass-spectrometry (ICP MSC), and Raman spectroscopy. It was established that olivine crystals were regenerated from silicate-carbonate melts at a temperature of 1100°C.

High temperature crystal field spectra of transition metal-bearing minerals - Relevance to remote-sensed spectra of planetary surfaces

NASA Technical Reports Server (NTRS)

Parkin, K. M.; Burns, R. G.

1980-01-01

It is pointed out that transition metal ions in silicate minerals, glasses, and crystalline and amorphous oxyhydroxides and salts contribute to the visible-near infrared spectral profiles of planetary surfaces. Investigations are conducted to obtain spectral information which might be helpful in the interpretation of the remote-sensed spectra of planetary surfaces. A description is presented of the results of high temperature crystal field spectral measurements of a variety of heated minerals containing Cr(3+), Fe(3+), Fe(++), and Mn(++) ions in different coordination symmetries, taking into account a correlation of the temperature-induced variations with those previously observed for octahedrally coordinated Fe(++)-bearing silicates. The employed experimental methods are also discussed, giving attention to the preparation of the samples, the determination of the absorption spectra, electron microprobe analyses, and the curve fitting procedure.

MTA and F-doped MTA cements used as sealers with warm gutta-percha. Long-term study of sealing ability.

PubMed

Gandolfi, M G; Prati, C

2010-10-01

To evaluate the long-term sealing ability (up to 6 months) of two experimental calcium silicate MTA cements used as root canal sealers in association with warm gutta-percha. Calcium silicate (MTA) and calcium-fluoro-silicate powders were prepared. Sodium fluoride was included in FMTA (Fluoride-doped Mineral Trioxide Aggregate) as an expansive and retardant agent. Single-rooted teeth were instrumented with NiTi rotary instruments, filled with warm gutta-percha in association with one of the experimental sealers or with AH Plus as a control (n = 20 for each sealer) and stored at 37 °C. Sealing was assessed at 24, 48 h, 1, 2 weeks and 1, 3, 6 months by a fluid filtration method. Scanning electron microscopy with energy dispersive analysis (SEM/EDX) was used to study the dentine/sealer interface of roots stored for 6 months and the surface of cement disks stored for 24 h. All sealers revealed a statistically significant reduction (P < 0.05) in fluid filtration after the first 2 weeks. No statistically significant differences were observed between FMTA and AH Plus at all analysis times. At short times (24, 48-h), no statistically significant differences were found between the experimental cements and AH Plus. At long-term evaluations (1, 3, 6 months), FMTA and AH Plus sealed significantly better (P < 0.05) than MTA. FMTA was associated with lower fluid filtration rates, and the seal was stable from 48 h to 6 months, thus proving the most effective material. Scanning electron microscopy with energy dispersive analysis of root sections filled with calcium silicate sealers revealed the formation of a blend layer of gutta-percha and cement consequent to the warm gutta-percha condensation technique. Scanning electron microscopy with energy dispersive analysis of 24-h-stored disks identified a Ca-rich coating on the outer surface consisting of globular particles (calcium hydroxide and calcium carbonate), and a deeper internal Ca- and Si-rich region consisting of needle-like ettringite crystals and round formations of calcium silicate hydrate gel. Fluoride-doped MTA demonstrated stable sealing during a period of up to 6 months and significantly better than conventional calcium silicate MTA cements and comparable to AH Plus. The study supports the suitability of calcium silicate MTA cements as sealers in association with warm gutta-percha for root filling. © 2010 International Endodontic Journal.

Femtosecond laser-induced refractive index modification in multicomponent glasses

NASA Astrophysics Data System (ADS)

Bhardwaj, V. R.; Simova, E.; Corkum, P. B.; Rayner, D. M.; Hnatovsky, C.; Taylor, R. S.; Schreder, B.; Kluge, M.; Zimmer, J.

2005-04-01

We present a comprehensive study on femtosecond laser-induced refractive index modification in a wide variety of multicomponent glasses grouped as borosilicate, aluminum-silicate, and heavy-metal oxide glasses along with lanthanum-borate and sodium-phosphate glasses. By using high-spatial resolution refractive index profiling techniques, we demonstrate that under a wide range of writing conditions the refractive index modification in multicomponent glasses can be positive, negative, or nonuniform, and exhibits a strong dependence on the glass composition. With the exception of some aluminum-silicate glasses all other glasses exhibited a negative/nonuniform index change. We also demonstrate direct writing of waveguides in photosensitive Foturan® glass with a femtosecond laser without initiating crystallization by thermal treatment. Upon ceramization of lithium-aluminum-silicate glasses such as Foturan®, Zerodur®, and Robax® we observe switching of laser-induced refractive index change from being positive to negative. The measured transmission losses in the waveguides at 1550nm agree with the index profile measurements in alkali-free aluminum-silicate glasses.

Multiscale understanding of tricalcium silicate hydration reactions.

PubMed

Cuesta, Ana; Zea-Garcia, Jesus D; Londono-Zuluaga, Diana; De la Torre, Angeles G; Santacruz, Isabel; Vallcorba, Oriol; Dapiaggi, Monica; Sanfélix, Susana G; Aranda, Miguel A G

2018-06-04

Tricalcium silicate, the main constituent of Portland cement, hydrates to produce crystalline calcium hydroxide and calcium-silicate-hydrates (C-S-H) nanocrystalline gel. This hydration reaction is poorly understood at the nanoscale. The understanding of atomic arrangement in nanocrystalline phases is intrinsically complicated and this challenge is exacerbated by the presence of additional crystalline phase(s). Here, we use calorimetry and synchrotron X-ray powder diffraction to quantitatively follow tricalcium silicate hydration process: i) its dissolution, ii) portlandite crystallization and iii) C-S-H gel precipitation. Chiefly, synchrotron pair distribution function (PDF) allows to identify a defective clinotobermorite, Ca 11 Si 9 O 28 (OH) 2 . 8.5H 2 O, as the nanocrystalline component of C-S-H. Furthermore, PDF analysis also indicates that C-S-H gel contains monolayer calcium hydroxide which is stretched as recently predicted by first principles calculations. These outcomes, plus additional laboratory characterization, yielded a multiscale picture for C-S-H nanocomposite gel which explains the observed densities and Ca/Si atomic ratios at the nano- and meso- scales.

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

Kahlenberg, Volker; Konzett, Juergen; Kaindl, Reinhard

High-pressure synthesis experiments in the system Na{sub 2}O-Y{sub 2}O{sub 3}-SiO{sub 2} revealed the existence of a previously unknown polymorph of NaYSi{sub 2}O{sub 6} or Na{sub 3}Y{sub 3}[Si{sub 3}O{sub 9}]{sub 2} which was quenched from 3.0 GPa and 1000 deg. C. Structural investigations on this modification have been performed using single-crystal X-ray diffraction data collected at ambient conditions. Furthermore, unpolarized micro-Raman spectra have been obtained from single-crystal material. The high-P modification of NaYSi{sub 2}O{sub 6} crystallizes in the centrosymmetric space group C2/c with 12 formula units per cell (a=8.2131(9) A, b=10.3983(14) A, c=17.6542(21) A, {beta}=100.804(9){sup o}, V=1481.0(3) A{sup 3}, R(|F|)=0.033 formore » 1142 independent observed reflections) and belongs to the group of cyclo-silicates. Basic building units are isolated three-membered [Si{sub 3}O{sub 9}] rings located in layers parallel to (010). Within a single layer the rings are concentrated in strings parallel to [100]. The sequence of directedness of up (U) or down (D) pointing tetrahedra of a single ring is UUU or DDD, respectively. Stacking of the layers parallel to b results in the formation of a three-dimensional structure in which yttrium and sodium cations are incorporated for charge compensation. In more detail, four non-tetrahedral cation positions can be differentiated which are coordinated by 6 and 8 oxygen ligands. Refinements of the site occupancies did not reveal any indication for mixed Na-Y populations on these positions. Finally, several geometrical parameters of rings occurring in cyclo-trisilicate structures have been compiled and are discussed. - Graphical abstract: Projection of the whole structure of high-P NaYSi{sub 2}O{sub 6} parallel to [100].« less

Petalite under pressure: Elastic behavior and phase stability

DOE PAGES

Ross, Nancy L.; Zhao, Jing; Slebodnick, Carla; ...

2015-04-01

The lithium aluminosilicate mineral petalite (LiAlSi 4O 10) has been studied using high-pressure single-crystal X-ray diffraction (HP-XRD) up to 5 GPa. Petalite undergoes two pressure-induced first-order phase transitions, never reported in the literature, at ca. 1.5 and 2.5 GPa. The first of these transforms the low-pressure α-phase of petalite (P2/c) to an intermediate β-phase that then fully converts to the high-pressure β-phase at ca. 2.5 GPa. The α→β transition is isomorphic and is associated with a commensurate modulation that triples the unit cell volume. Analysis of the HP-XRD data show that although the fundamental features of the petalite structure aremore » retained through this transition, there are subtle alterations in the internal structure of the silicate double-layers in the β-phase relative to the α-phase. Measurement of the unit cell parameters of petalite as a function of pressure, and fitting of the data with 3rd order Birch-Murnaghan equations of state, has provided revised elastic constants for petalite. The bulk moduli of the α and β-phases are 49(1) and 35(3) GPa, respectively. These values indicate that the compressibility of the- phase of petalite lies between the alkali feldpsars and alkali feldspathoids, whereas the β-phase has a compressibility more comparable with layered silicates. Structure analysis has shown that the compression of the -phase is facilitated by the rigid body movement of the Si 2O 7 units from which the silicate double-layers are constructed.« less

Hydration behaviors of calcium silicate-based biomaterials.

PubMed

Lee, Yuan-Ling; Wang, Wen-Hsi; Lin, Feng-Huie; Lin, Chun-Pin

2017-06-01

Calcium silicate (CS)-based biomaterials, such as mineral trioxide aggregate (MTA), have become the most popular and convincing material used in restorative endodontic treatments. However, the commercially available CS-based biomaterials all contain different minor additives, which may affect their hydration behaviors and material properties. The purpose of this study was to evaluate the hydration behavior of CS-based biomaterials with/without minor additives. A novel CS-based biomaterial with a simplified composition, without mineral oxides as minor additives, was produced. The characteristics of this biomaterial during hydration were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectrometry. The hydration behaviors of commercially available gray and white MTAs with mineral oxide as minor additives were also evaluated for reference. For all three test materials, the XRD analysis revealed similar diffraction patterns after hydration, but MTAs presented a significant decrease in the intensities of Bi 2 O 3 -related peaks. SEM results demonstrated similar porous microstructures with some hexagonal and facetted crystals on the outer surfaces. In addition, compared to CS with a simplified composition, the FTIR plot indicated that hydrated MTAs with mineral oxides were better for the polymerization of calcium silicate hydrate (CSH), presenting Si-O band shifting to higher wave numbers, and contained more water crystals within CSH, presenting sharper bands for O-H bending. Mineral oxides might not result in significant changes in the crystal phases or microstructures during the hydration of CS-based biomaterials, but these compounds affected the hydration behavior at the molecular level. Copyright © 2016. Published by Elsevier B.V.

Fe-Ti-oxide textures and microstructures in shear zones from oceanic gabbros at Atlantis Bank, Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Till, Jessica; Morales, Luiz F. G.; Rybacki, Erik

2016-04-01

Ocean drilling expeditions at several oceanic core complexes formed at slow- and ultra-slow-spreading ridges have recovered cores containing numerous zones of oxide-rich gabbros containing ilmenite and magnetite. In these cores, high modal concentrations of Fe-Ti-oxides are systematically associated with high-temperature plastic deformation features in silicates. We present observations of Fe-Ti-oxide mineral structures and textural characteristics from a series of oxide-rich shear zones from Atlantis Bank (ODP Site 735B) on the Southwest Indian Ridge aimed at determining how oxide mineral abundances relate to strain localization. Fe-Ti-oxide minerals in undeformed oxide gabbros and in highly deformed samples from natural shear zones generally have morphologies characteristic of crystallized melt, including highly cuspate grains and low dihedral angles. Anisotropy of magnetic susceptibility in oxide-rich shear zones is very strong, with fabrics mainly characterized by strong magnetic foliations parallel to the macroscopic foliation. Crystallographic preferred orientations (CPO) in magnetite are generally weak, with occasionally well-defined textures. Ilmenite typically displays well-developed CPOs, however, the melt-like ilmenite grain shapes indicate that at least part of the crystallographic texture results from oriented ilmenite growth during post-deformation crystallization. The oxides are hypothesized to have initially been present as isolated pockets of trapped melt (intercumulus liquid) in a load-bearing silicate framework. Progressive plastic deformation of silicate phases at high-temperature mainly produced two features: (i) elongated melt pockets, which crystallized to form strings of opaque minerals and (ii), interconnected networks of melt regions. The latter lead to intense strain localization of the rock, which appears as oxide-rich mylonites in the samples. In some samples, abundant low-angle grain boundaries in both magnetite and ilmenite suggest that deformation may have continued after crystallization of the late melt, imposing a weak strain on the oxides. Recent experimental deformation results indicate that magnetite and ilmenite should be weaker than most mafic silicates under anhydrous conditions. However, melt-like oxide morphologies observed in Atlantis Bank shear zones indicate that the redistribution of Fe-Ti-oxide melts may have more influence on the strength and strain localization behavior of oceanic gabbros than their solid-state rheology.

Experimental and theoretical investigation of the elastic moduli of silicate glasses and crystals

NASA Astrophysics Data System (ADS)

Philipps, Katharina; Stoffel, Ralf Peter; Dronskowski, Richard; Conradt, Reinhard

2017-02-01

A combined quantum-mechanical and thermodynamic approach to the mechanical properties of multicomponent silicate glasses is presented. Quantum chemical calculations based on density-functional theory (DFT) on various silicate systems were performed to explore the crystalline polymorphs existing for a given chemical composition. These calculations reproduced the properties of known polymorphs even in systems with extensive polymorphism, like MgSiO3. Properties resting on the atomic and electronic structure, i.e., molar volumes (densities) and bulk moduli were predicted correctly. The theoretical data (molar equilibrium volumes, bulk moduli) were then used to complement the available experimental data. In a phenomenological evaluation, experimental data of bulk moduli, a macroscopic property resting on phononic structure, were found to linearly scale with the ratios of atomic space demand to actual molar volume in a universal way. Silicates ranging from high-pressure polymorphs to glasses were represented by a single master line. This suggests that above the Debye limit (in practice: above room temperature), the elastic waves probe the short range order coordination polyhedra and their next-neighbor linkage only, while the presence or absence of an extended translational symmetry is irrelevant. As a result, glasses can be treated - with respect to the properties investigated - as commensurable members of polymorphic series. Binary glasses fit the very same line as their one-component end-members, again both in the crystalline and glassy state. Finally, it is shown that the macroscopic properties of multicomponent glasses also are linear superpositions of the properties of their constitutional phases (as determined from phase diagrams or by thermochemical calculations) taken in their respective glassy states. This is verified experimentally for heat capacities and Young’s moduli of industrial glass compositions. It can be concluded, that the combined quantum mechanical and thermochemical approach is a truly quantitative approach for the design of glasses with desired mechanical properties, e.g., for the development of high-modulus glasses.

Contribution of early impact events to metal-silicate separation, thermal annealing, and volatile redistribution: Evidence in the Pułtusk H chondrite

NASA Astrophysics Data System (ADS)

Krzesińska, Agata M.

2017-11-01

Three-dimensional X-ray tomographic reconstructions and petrologic studies reveal voluminous accumulations of metal in Pułtusk H chondrite. At the contact of these accumulations, the chondritic rock is enriched in troilite. The rock contains plagioclase-rich bands, with textures suggesting crystallization from melt. Unusually large phosphates are associated with the plagioclase and consist of assemblages of merrillite, and fluorapatite and chlorapatite. The metal accumulations were formed by impact melting, rapid segregation of metal-sulfide melt and the incorporation of this melt into the fractured crater basement. The impact most likely occurred in the early evolution of the H chondrite parent body, when post-impact heat overlapped with radiogenic heat. This enabled slow cooling and separation of the metallic melt into metal-rich and sulfide-rich fractions. This led to recrystallization of chondritic rock in contact with the metal accumulations and the crystallization of shock melts. Phosphorus was liberated from the metal and subsumed by the silicate shock melt, owing to oxidative conditions upon slow cooling. The melt was also a host for volatiles. Upon further cooling, phosphorus reacted with silicates leading to the formation of merrillite, while volatiles partitioned into the residual halogen-rich, dry fluid. In the late stages, the fluid altered merrillite to patchy Cl/F-apatite. The above sequence of alterations demonstrates that impact during the early evolution of chondritic parent bodies might have contributed to local metal segregation and silicate melting. In addition, postshock conditions supported secondary processes: compositional/textural equilibration, redistribution of volatiles, and fluid alterations.

Does size matter? Statistical limits of paleomagnetic field reconstruction from small rock specimens

NASA Astrophysics Data System (ADS)

Berndt, Thomas; Muxworthy, Adrian R.; Fabian, Karl

2016-01-01

As samples of ever decreasing sizes are being studied paleomagnetically, care has to be taken that the underlying assumptions of statistical thermodynamics (Maxwell-Boltzmann statistics) are being met. Here we determine how many grains and how large a magnetic moment a sample needs to have to be able to accurately record an ambient field. It is found that for samples with a thermoremanent magnetic moment larger than 10-11Am2 the assumption of a sufficiently large number of grains is usually given. Standard 25 mm diameter paleomagnetic samples usually contain enough magnetic grains such that statistical errors are negligible, but "single silicate crystal" works on, for example, zircon, plagioclase, and olivine crystals are approaching the limits of what is physically possible, leading to statistic errors in both the angular deviation and paleointensity that are comparable to other sources of error. The reliability of nanopaleomagnetic imaging techniques capable of resolving individual grains (used, for example, to study the cloudy zone in meteorites), however, is questionable due to the limited area of the material covered.

Synthesis of non-siliceous mesoporous oxides.

PubMed

Gu, Dong; Schüth, Ferdi

2014-01-07

Mesoporous non-siliceous oxides have attracted great interest due to their unique properties and potential applications. Since the discovery of mesoporous silicates in 1990s, organic-inorganic assembly processes by using surfactants or block copolymers as soft templates have been considered as a feasible path for creating mesopores in metal oxides. However, the harsh sol-gel conditions and low thermal stabilities have limited the expansion of this method to various metal oxide species. Nanocasting, using ordered mesoporous silica or carbon as a hard template, has provided possibilities for preparing novel mesoporous materials with new structures, compositions and high thermal stabilities. This review concerns the synthesis, composition, and parameter control of mesoporous non-siliceous oxides. Four synthesis routes, i.e. soft-templating (surfactants or block copolymers as templates), hard-templating (mesoporous silicas or carbons as sacrificial templates), colloidal crystal templating (3-D ordered colloidal particles as a template), and super lattice routes, are summarized in this review. Mesoporous metal oxides with different compositions have different properties. Non-siliceous mesoporous oxides are comprehensively described, including a discussion of constituting elements, synthesis, and structures. General aspects concerning pore size control, atomic scale crystallinity, and phase control are also reviewed.

Fabrication of Single Crystal MgO Capsules

NASA Technical Reports Server (NTRS)

Danielson, Lisa

2012-01-01

A method has been developed for machining MgO crystal blocks into forms for containing metallic and silicate liquids at temperatures up to 2,400 C, and pressures up to at least 320 kilobars. Possible custom shapes include tubes, rods, insulators, capsules, and guides. Key differences in this innovative method include drilling along the crystallographic zone axes, use of a vibration minimizing material to secure the workpiece, and constant flushing of material swarf with a cooling medium/lubricant (water). A single crystal MgO block is cut into a section .5 mm thick, 1 cm on a side, using a low-speed saw with a 0.004 blade. The cut is made parallel to the direction of cleavage. The block may be cut to any thickness to achieve the desired length of the piece. To minimize drilling vibrations, the MgO block is mounted on a piece of adhesive putty in a vise. The putty wad cradles the bottom half of the entire block. Diamond coring tools are used to drill the MgO to the desired custom shape, with water used to wet and wash the surface of swarf. Compressed air may also be used to remove swarf during breaks in drilling. The MgO workpiece must be kept cool at all times with water. After all the swarf is rinsed off, the piece is left to dry overnight. If the workpiece is still attached to the base of the MgO block after drilling, it may be cut off by using a diamond cutoff wheel on a rotary hand tool or by using a low-speed saw.

Anisotropic surface chemistry properties and adsorption behavior of silicate mineral crystals.

PubMed

Xu, Longhua; Tian, Jia; Wu, Houqin; Fang, Shuai; Lu, Zhongyuan; Ma, Caifeng; Sun, Wei; Hu, Yuehua

2018-03-07

Anisotropic surface properties of minerals play an important role in a variety of fields. With a focus on the two most intensively investigated silicate minerals (i.e., phyllosilicate minerals and pegmatite aluminosilicate minerals), this review highlights the research on their anisotropic surface properties based on their crystal structures. Four surface features comprise the anisotropic surface chemistry of minerals: broken bonds, energy, wettability, and charge. Analysis of surface broken bond and energy anisotropy helps to explain the cleavage and growth properties of mineral crystals, and understanding surface wettability and charge anisotropy is critical to the analysis of minerals' solution behavior, such as their flotation performance and rheological properties. In a specific reaction, the anisotropic surface properties of minerals are reflected in the adsorption strengths of reagents on different mineral surfaces. Combined with the knowledge of mineral crushing and grinding, a thorough understanding of the anisotropic surface chemistry properties and the anisotropic adsorption behavior of minerals will lead to the development of effective relational models comprising their crystal structure, surface chemistry properties, and targeted reagent adsorption. Overall, such a comprehensive approach is expected to firmly establish the connection between selective cleavage of mineral crystals for desired surfaces and designing novel reagents selectively adsorbed on the mineral surfaces. As tools to characterize the anisotropic surface chemistry properties of minerals, DLVO theory, atomic force microscopy (AFM), and molecular dynamics (MD) simulations are also reviewed. Copyright © 2017 Elsevier B.V. All rights reserved.

Co-settling of Chromite and Sulfide Melt Droplets and Trace Element Partitioning between Sulfide and Silicate Melts

NASA Astrophysics Data System (ADS)

Manoochehri, S.; Schmidt, M. W.; Guenther, D.

2013-12-01

Gravitational settling of immiscible, dense sulfide melt droplets together with other cumulate phases such as chromite, combined with downward percolation of these droplets through a cumulate pile, is thought to be one of the possible processes leading to the formation of PGE rich sulfide deposits in layered mafic intrusions. Furthermore some chromitite seams in the Merensky Reef (Bushveld Complex) are considered to be acting as a filter or barrier for further downward percolation of sulfide melts into footwall layers. To investigate the feasibility of such mechanical processes and to study the partitioning behavior of 50 elements including transition metals and REEs (but not PGEs) between a silicate and a sulfide melt, two separate series of high temperature (1250-1380 °C) centrifuge-assisted experiments at 1000 g, 0.4-0.6 GPa were conducted. A synthetic silicate glass with a composition representative of the parental magma of the Bushveld Complex (~ 55 wt% SiO2) was mixed with pure FeS powder. For the first series of experiments, 15 or 25 wt% natural chromite with average grain sizes of ~ 5 or 31 μm were added to a mixture of silicate glass and FeS (10 wt%) adding 1 wt% water. For the second series, a mixture of the same glass and FeS was doped with 50 trace elements. These mixtures were first statically equilibrated and then centrifuged. In the first experimental series, sulfide melt droplets settled together with, but did not segregate from chromite grains even after centrifugation at 1000 g for 12 hours. A change in initial chromite grain size and proportions didn't have any effect on segregation. Without chromite, the starting mixture resulted in the formation of large sulfide melt pools together with finer droplets still disseminated through the silicate glass and both at the bottom of the capsule. The incomplete segregation of sulfide melt is interpreted as being due to high interfacial energies between sulfide and silicate melts/crystals which hinder both, the nucleation of newly formed sulfide droplets and the interconnectivity of separate droplets. The interfacial energies between sulfide melt and silicate or oxide crystals is even higher than for silicate melt, consequently in experiments with chromite, sulfide segregation is even more hindered. Partition coefficients of 50 elements between a sulfide and a silicate melt are determined as a function of differing temperature between 1250 - 1380 °C. As a proxy to investigate the bond strength of network modifier cations, the relation between the partition coefficients and ionic potentials of different groups of elements has been determined.

Quaternary silicic pyroclastic deposits of Atitlán Caldera, Guatemala

USGS Publications Warehouse

Rose, William I.; Newhall, Christopher G.; Bornhorst, Theodore J.; Self, Stephen

1987-01-01

Atitlán caldera has been the site of several silicic eruptions within the last 150,000 years, following a period of basalt/andesite volcanism. The silicic volcanism began with 5–10 km3 of rhyodacites, erupted as plinian fall and pyroclastic flows, about 126,000 yr. B.P. At 85,000 yr. B.P. 270–280 km3 of compositionally distinct rhyolite was erupted in the Los Chocoyos event which produced widely dispersed, plinian fall deposits and widespread, mobile pyroclastic flows. In the latter parts of this eruption rhyodacite and minor dacite were erupted which compositionally resembled the earliest silicic magmas of the Atitlán center. As a result of this major eruption, the modern Atitlán (III) caldera formed. Following this event, rhyodacites were again erupted in smaller (5–13 km3) volumes, partly through the lake, and mafic volcanism resumed, forming three composite volcanoes within the caldera. The bimodal mafic/silicic Atitlán volcanism is similar to that which has occurred elsewhere in the Guatemalan Highlands, but is significantly more voluminous. Mafic lavas are thought to originate in the mantle, but rise, intrude and underplate the lower crust and partly escape to the surface. Eventually, silicic melts form in the crust, possibly partly derived from underplated basaltic material, rise, crystallize and erupt. The renewed mafic volcanism could reflect either regional magmato-tectonic adjustment after the large silicic eruption or the onset of a new cycle.

Variations of trace element concentration of magnetite and ilmenite from the Taihe layered intrusion, Emeishan large igneous province, SW China: Implications for magmatic fractionation and origin of Fe-Ti-V oxide ore deposits

NASA Astrophysics Data System (ADS)

She, Yu-Wei; Song, Xie-Yan; Yu, Song-Yue; He, Hai-Long

2015-12-01

In situ LA-ICP-MS trace elemental analysis has been applied to magnetite and ilmenite of the Taihe layered intrusion, Emeishan large igneous province, SW China, in order to understand better fractionation processes of magma and origin of Fe-Ti-V oxide ore deposits. The periodic reversals in Mg, Ti, Mn in magnetite and Mg, Sc in ilmenite are found in the Middle Zone of the intrusion and agree with fractionation trends as recorded by olivine (Fo), plagioclase (An) and clinopyroxene (Mg#) compositions. These suggest the Taihe intrusion formed from open magma chamber processes in a magma conduit with multiple replenishments of more primitive magmas. The V and Cr of magnetite are well correlated with V and Cr of clinopyroxene indicating that they became liquidus phases almost simultaneously at an early stage of magma evolution. Ilmenite from the Middle and Upper Zones shows variable Cr, Ni, V, Mg, Nb, Ta and Sc contents indicating that ilmenite at some stratigraphic levels crystallized slightly earlier than magnetite and clinopyroxene. The early crystallization of magnetite and ilmenite is the result of the high FeOt and TiO2 contents in the parental magma. The ilmenite crystallization before magnetite in the Middle and Upper Zones can be attributed to higher TiO2 content of the magma due to the remelting of pre-existing ilmenite in a middle-level magma chamber. Compared to the coeval high-Ti basalts, the relatively low Zr, Hf, Nb and Ta contents in both magnetite and ilmenite throughout the Taihe intrusion indicate that they crystallized from Fe-Ti-(P)-rich silicate magmas. Positive correlations of Ti with Mg, Mn, Sc and Zr of magnetite, and Zr with Sc, Hf and Nb of ilmenite also suggest that magnetite and ilmenite crystallized continuously from the homogeneous silicate magma rather than an immiscible Fe-rich melt. Therefore, frequent replenishments of Fe-Ti-(P)-rich silicate magma and gravitational sorting and settling are crucial for the formation the massive and apatite-rich disseminated ores in the Lower and Middle Zones of the Taihe intrusion.

The origin and evolution of silicic magmas during continental rifting: new constraints from trace elements and oxygen isotopes from Ethiopian volcanoes

NASA Astrophysics Data System (ADS)

Hutchison, W.; Boyce, A.; Mather, T. A.; Pyle, D. M.; Yirgu, G.; Gleeson, M. L.

2017-12-01

The petrologic diversity of rift magmas is generated by two key processes: interaction with the crust via partial melting or assimilation; and closed-system fractional crystallization of the parental magma. It is not yet known whether these two petrogenetic processes vary spatially between different rift settings, and whether there are any significant secular variations during rift evolution. The Ethiopian Rift is the ideal setting to test these hypotheses because it captures the transition from continental rifting to sea-floor spreading and has witnessed the eruption of large volumes of mafic and silicic volcanic rocks since 30 Ma. We use new oxygen isotope (δ18O) and trace element data to fingerprint fractional crystallisation and partial crustal melting processes in Ethiopia and evaluate spatial variations between three active rift segments. δ18O measurements are used to examine partial crustal melting processes. We find that most δ18O data from basalts to rhyolites fall within the bounds of modelled fractional crystallization trajectories (i.e., 5.5-6.5 ‰). Few samples deviate from this trend, emphasising that fractional crystallization is the dominant petrogenetic processes and that little fusible Precambrian crustal material (δ18O of 7-18 ‰) remain to be assimilated beneath the magmatic segments. Trace element systematics (e.g., Ba, Sr, Rb, Th and Zr) further underscore the dominant role of fractional crystallization but also reveal important variations in the degree of melt evolution between the volcanic systems. We find that the most evolved silicic magmas, i.e., those with greatest peralkalinity (molar Na2O+K2O>Al2O3), are promoted in regions of lowest magma flux off-axis and along rift. Our findings provide new information on the nature of the crust beneath Ethiopia's active magmatic segments and also have relevance for understanding ancient rift zones and the geotectonic settings that promote genesis of economically-valuable mineral deposits.

Rheological properties of molten Kilauea Iki basalt containing suspended crystals. Revision 2

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

Weed, H.C.; Ryerson, F.J.; Piwinskii, A.J.

1984-01-01

In order to model the flow behavior of molten silicate suspensions, such as magmas and slags, the rheological behavior must be known as a function of the concentration of suspended crystals, melt composition, and external conditions. We have determined the viscosity and crystallization sequence for a Kilauea Iki basalt between 1250/sup 0/C and 1149/sup 0/C at 100 kPa total pressure and fO/sub 2/ corresponding to the quartz-fayalite-magnetite buffer in an iron-saturated Pt30Rh rotating cup viscometer of the Couette type. The apparent viscosity varies from 9 to 879 Pa.s. The concentration of suspended cyrstals varies from 18 volume percent at 1250/supmore » 0/C to 59 volume percent at 1149/sup 0/C. The molten silicate suspension shows power-law behavior: log tau yx = A/sub 0/ + A/sub 1/ log du/dx, where tau/sub yx/ is the shear stress and (du/dx) the shear rate. Since A/sub 1/ less than or equal to 1, the apparent viscosity decreases with increasing shear rate and the system is pseudoplastic. 15 refs., 4 figs., 5 tabs.« less

Highly siderophile elements were stripped from Earth’s mantle by iron sulfide segregation

NASA Astrophysics Data System (ADS)

Rubie, David C.; Laurenz, Vera; Jacobson, Seth A.; Morbidelli, Alessandro; Palme, Herbert; Vogel, Antje K.; Frost, Daniel J.

2016-09-01

Highly siderophile elements (HSEs) are strongly depleted in the bulk silicate Earth (BSE) but are present in near-chondritic relative abundances. The conventional explanation is that the HSEs were stripped from the mantle by the segregation of metal during core formation but were added back in near-chondritic proportions by late accretion, after core formation had ceased. Here we show that metal-silicate equilibration and segregation during Earth’s core formation actually increased HSE mantle concentrations because HSE partition coefficients are relatively low at the high pressures of core formation within Earth. The pervasive exsolution and segregation of iron sulfide liquid from silicate liquid (the “Hadean matte”) stripped magma oceans of HSEs during cooling and crystallization, before late accretion, and resulted in slightly suprachondritic palladium/iridium and ruthenium/iridium ratios.

Highly Siderophile Elements in Pallasites and Diogenites, Including the New Pallasite, CMS 04071

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Humayun, M.; Righter, K.

2006-01-01

Pallasites are long thought to represent a metallic core-silicate mantle boundary, where the IIIAB irons are linked to the crystallization history of the metallic fraction, and the HED meteorites may be linked to the silicate fraction. However, measurement of trace elements in individual metallic and silicate phases is necessary in order to fully under-stand the petrogenetic history of pallasites, as well as any magmatic processes which may link pallasites to both IIIAB irons and HED meteorites. In order to achieve this objective, abundances of a suite of elements were measured, including the highly siderophile elements (HSEs), in kamacite, taenite, troilite, schreibersite, chromite and olivine for the pallasites Admire, Imilac, Springwater, CMS 04071. In the diogenites GRO 95555, LAP 91900, and MET 00436, metal, sulfide, spinel, pyroxene, and silica were individually measured.

An Observational Test for Shock-induced Crystallization of Cometary Silicates

NASA Technical Reports Server (NTRS)

Nuth, J. A.; Johnson, N. M.

2003-01-01

Crystalline silicates have been observed in comets and in protostellar nebulae, and there are currently at least two explanations for their formation: thermal annealing in the inner nebula, followed by transport to the regions of cometary formation and in-situ shock processing of amorphous grains at 5 - 10 AU in the Solar Nebula. The tests suggested to date to validate these models have not yet been carried out: some of these tests require a longterm commitment to observe both the dust and gas compositions in a large number of comets. Here we suggest a simpler test.

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.

Insights into the martian hydrosphere from the nakhlites

NASA Astrophysics Data System (ADS)

Tomkinson, T.; Mark, D. F.; Lee, M.; Lindgren, P.; Stuart, F.

2011-12-01

The nakhlite meteorites contain minerals including clays, salts and carbonates that crystallized from water within an impact-induced hydrothermal system or subsurface aquifer [1,2]. These minerals can be used to explore the longevity, scale and evolution of the aqueous system. However, such work has proven to be challenging owing to their very fine crystal size and their compositional complexity. In this study we have used a suite of techniques including CT tomography, scanning and transmission electron microscopy and Ar/Ar dating to explore the history of secondary mineralization in the nakhlites. In total there are thirteen nakhlites, however, this study has focused on Nakhla as it is the only fall. To further understand their alteration relationships we also plan to study Lafayette, MIL 003346, Yamato 000593, 000749 and NWA 5790. In contrast to previous studies that have used polished thin sections, we have examined secondary minerals exposed on freshly produced fracture surfaces from the interior of the Nakhla meteorite. This technique has revealed six textures that have not previously been described. (1) Areas of nanocrystalline/amorphous growth of sheeted silicates appearing to nucleate from underlying Cl and C rich fibrous material. (2) Underlying material which forms on the olivine grains surface with a nanoscale fibrous structure contains intergrown <5 μm sized euhedral calcium sulphate crystals. (3) The overlying sheeted silicates are also cross-cut by veins of this Cl and C enriched fibrous material. (4) A concentrically Si, Cl, Ca, Mn and Fe zoned region of alteration with a diameter of ~90 μm that has also been observed potentially sourcing enrichments from an underlying halite grain and augite and magnetite inclusions formed from symplectic exsolution in the host olivine [3]. Additionally, we have observed (5) radial growth structures emanating from halite grains and (6) etch pits in the surfaces of olivines. We will also present preliminary Ar/Ar ages for the K-bearing alteration material within the nakhlites. The textures that we have observed suggest that the sheeted silicate material formed either during fluctuations in fluid compositions or as a result of these newly discovered sites of nucleation growth from the underlying Cl and C enriched fibrous material. The presence of the fibrous material cross-cutting the silicate could indicate the following: a subsequent injection of a saline fluid, an expansion of the fibrous material rupturing the silicate, or the remobilisation of the fibrous material. The sharp contacts of the silicate with these cross cutting veins of fibrous material suggest that this material (likely brine) was exposed to only very low temperatures [4] thus not remobilising and equilibrating with the surrounding material. Some of the features that we have found would have been lost in conventional thin section manufacture and may explain why they have not been observed previously.

A Cesium Rare-Earth Silicate Cs3 RESi6 O15 (RE=Dy-Lu, Y, In): The Parent of an Unusual Structural Class Featuring a Remarkable 57 Å Unit Cell Axis.

PubMed

Terry, Rylan; Vinton, Daniel; McMillen, Colin D; Kolis, Joseph W

2018-02-19

The structure of Cs 3 RESi 6 O 15 , where RE=Dy-Lu, Y, In, is unusual in that it contains octahedrally coordinated rare-earth ions; their relative orientation dictates the structure, as they rotate about the c-axis supported by the cyclic Si 6 O 15 framework. The repeat unit of the rotation is eight units generating a very long (ca. 57 Å) unit cell axis. This unusual repeat unit is created by the structural flexibility of the hexasilicate ring, which is in turn affected by the size of the rare earth ion as well as the size of alkali ion residing within the silicate layers. Previous work showed for the smaller Sc 3+ ion, the rotation of the octahedra is not sufficient to achieve closure at an integral repeat unit and an incommensurate structure results. The products are prepared as large, high quality single crystals using a high-temperature (650 °C) hydrothermal method with CsOH and F - mineralizers. The presence of fluoride is essential to the formation of the product. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding Vesuvius magmatic processes: Evidence from primitive silicate-melt inclusions in medieval scoria clinopyroxenes (Terzigno formation)

USGS Publications Warehouse

Lima, A.; Belkin, H.E.; Torok, K.

1999-01-01

Microthermometric investigations of silicate-melt inclusions and electron microprobe analyses were conducted on experimentally homogenized silicate-melt inclusions and on the host clinopyroxenes from 4 scoria samples of different layers from the Mt. Somma-Vesuvius medieval eruption (Formazione di Terzigno, 893 A.D.). The temperature of homogenization, considered the minimum trapping temperature, ranges from 1190 to 1260??5 ??C for all clinopyroxene-hosted silicate melt inclusions. The major and minor-element compositional trends shown by Terzigno scoria and matrix glass chemical analysis are largely compatible with fractional crystallization of clinopyroxene and Fe-Ti oxides. Sulfur contents of the homogenized silicate-melt inclusions in clinopyroxene phenocrysts compared with that in the host scoria show that S has been significantly degassed in the erupted products; whereas, Cl has about the same abundance in the inclusions and in host scoria. Fluorine is low (infrequently up to 800 ppm) in the silicate-melt inclusions compared to 2400 ppm in the bulk scoria. Electron microprobe analyses of silicate-melt inclusions show that they have primitive magma compositions (Mg# = 75-91). The composition of the host clinopyroxene phenocrysts varies from typical plinian-related (Mg#???85) to non-plinian related (Mg#???85). The mixed source of the host clinopyroxenes and primitive nature of the silicate-melt inclusions implies that these phenocrysts, in part, may be residual and/or have a polygenetic origin. The similar variation trends of major and minor-elements between homogenized silicate-melt inclusions from the Terzigno scoria, and silicate-melt inclusions in olivine and diopside phenocrysts from plinian eruptions (Marianelli et al., 1995) suggest that the trapped inclusions represent melts similar to those that supplied the plinian and sub-plinian magma chambers. These geochemical characteristics suggest that the Vesuvius magmatic system retained a vestige of the most recent plinian event.

Pt, Au, Pd and Ru Partitioning Between Mineral and Silicate Melts: The Role of Metal Nanonuggets

NASA Technical Reports Server (NTRS)

Malavergne, V.; Charon, E.; Jones, J.; Agranier, A.; Campbell, A.

2012-01-01

The partition coefficients of Pt and other Pt Group Elements (PGE) between metal and silicate D(sub Metal-Silicate) and also between silicate minerals and silicate melts D(sub Metal-Silicate) are among the most challenging coefficients to obtain precisely. The PGE are highly siderophile elements (HSE) with D(sub Metal-Silicate) >10(exp 3) due to the fact that their concentrations in silicates are very low (ppb to ppt range). Therefore, the analytical difficulty is increased by the possible presence of HSE-rich-nuggets in reduced silicate melts during experiments). These tiny HSE nuggets complicate the interpretation of measured HSE concentrations. If the HSE micro-nuggets are just sample artifacts, then their contributions should be removed before calculations of the final concentration. On the other hand, if they are produced during the quench, then they should be included in the analysis. We still don't understand the mechanism of nugget formation well. Are they formed during the quench by precipitation from precursor species dissolved homogeneously in the melts, or are they precipitated in situ at high temperature due to oversaturation? As these elements are important tracers of early planetary processes such as core formation, it is important to take up this analytical and experimental challenge. In the case of the Earth for example, chondritic relative abundances of the HSE in some mantle xenoliths have led to the concept of the "late veneer" as a source of volatiles (such as water) and siderophiles in the silicate Earth. Silicate crystal/liquid fractionation is responsible for most, if not all, the HSE variation in the martian meteorite suites (SNC) and Pt is the element least affected by these fractionations. Therefore, in terms of reconstructing mantle HSE abundances for Mars, Pt becomes a very important player. In the present study, we have performed high temperature experiments under various redox conditions in order to determine the abundances of Pt, Au, Ru and Pd in minerals (olivine and diopside) and in silicate melts, but also to characterize the sizes, density and chemistry of HSE nuggets when present in the samples.

Thermal diffusivity of electrical insulators at high temperatures: Evidence for diffusion of bulk phonon-polaritons at infrared frequencies augmenting phonon heat conduction

NASA Astrophysics Data System (ADS)

Hofmeister, Anne M.; Dong, Jianjun; Branlund, Joy M.

2014-04-01

We show that laser-flash analysis measurements of the temperature (T) dependence of thermal diffusivity (D) for diverse non-metallic (e.g., silicates) single-crystals is consistently represented by D(T) = FT-G + HT above 298 K, with G ranging from 0.3 to 2, depending on structure, and H being ˜10-4 K-1 for 51 single-crystals, 3 polycrystals, and two glasses unaffected by disorder or reconstructive phase transitions. Materials exhibiting this behavior include complex silicates with variable amounts of cation disorder, perovskite structured materials, and graphite. The high-temperature term HT becomes important by ˜1300 K, above which temperature its contribution to D(T) exceeds that of the FT-G term. The combination of the FT-G and HT terms produces the nearly temperature independent high-temperature region of D previously interpreted as the minimal phonon mean free path being limited by the finite interatomic spacing. Based on the simplicity of the fit and large number of materials it represents, this finding has repercussions for high-temperature models of heat transport. One explanation is that the two terms describing D(T) are associated with two distinct microscopic mechanisms; here, we explore the possibility that the thermal diffusivity of an electrical insulator could include both a contribution of lattice phonons (the FT-G term) and a contribution of diffusive bulk phonon-polaritons (BPP) at infrared (IR) frequencies (the HT term). The proposed BPP diffusion exists over length scales smaller than the laboratory sample sizes, and transfers mixed light and vibrational energy at a speed significantly smaller than the speed of light. Our diffusive IR-BPP hypothesis is consistent with other experimental observations such as polarization behavior, dependence of D on the number of IR peaks, and H = 0 for Ge and Si, which lack IR fundamentals. A simple quasi-particle thermal diffusion model is presented to begin understanding the contribution from bulk phonon-polaritons to overall heat conduction.

Rapid assembly and rejuvenation of a large silicic magmatic system: Insights from mineral diffusive profiles in the Kidnappers and Rocky Hill deposits, New Zealand

NASA Astrophysics Data System (ADS)

Cooper, George F.; Morgan, Daniel J.; Wilson, Colin J. N.

2017-09-01

The timescales over which magmas in large silicic systems are reactivated, assembled and stored remains a fundamental question in volcanology. To address this question, we study timescales from Fe-Mg interdiffusion in orthopyroxenes and Ti diffusion in quartz from the caldera-forming 1200 km3 Kidnappers and 200 km3 Rocky Hill eruptions from the Mangakino volcanic centre (Taupo Volcanic Zone, New Zealand). The two eruptions came from the same source area, have indistinguishable 40Ar/39Ar ages (∼1.0 Ma) and zircon U-Pb age spectra, but their respective deposits are separated by a short period of erosion. Compositions of pumice, glass and mineral species in the collective eruption deposits define multiple melt dominant bodies but indicate that these shared a common magmatic mush zone. Diffusion timescales from both eruptions are used to build on chemical and textural crystal signatures and interpret both the crystal growth histories and the timing of magma accumulation. Fe-Mg interdiffusion profiles in orthopyroxenes imply that the three melt-dominant bodies, established through extraction of melt and crystals from the common source, were generated within 600 years and with peak accumulation rates within 100 years of each eruption. In addition, a less-evolved melt interacted with the Kidnappers magma, beginning ∼30 years prior to and peaking within 3 years of the eruption. This interaction did not directly trigger the eruption, but may have primed the magmatic system. Orthopyroxene crystals with the same zoning patterns from the Kidnappers and Rocky Hill pumices yield consistently different diffusion timescales, suggesting a time break between the eruptions of ∼20 years (from core-rim zones) to ∼10 years (outer rim zones). Diffusion of Ti in quartz reveals similarly short timescales and magmatic residence times of <30 years, suggesting quartz is only recording the last period of crystallization within the final eruptible melt. Accumulation of the eruptible magma for these two, closely successive eruptions was accomplished over centuries to decades, in contrast to the gestation time of the magmatic system of ∼200 kyr, as indicated by zircon age patterns. The magmatic system was able to recover after the Kidnappers eruption in only ∼10-20 years to accumulate enough eruptible melt and crystals for a second ∼ 200 km3 eruption. Our data support concepts of large silicic systems being stored as long-lived crystal mushes, with eruptible melts generated over extraordinarily short timescales prior to eruption.

The crystal structure of the interrupted framework silicate K{sub 9.6}Ca{sub 1.2}Si{sub 12}O{sub 30} determined from laboratory X-ray diffraction data

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

Kahlenberg, V.; Kaindl, R.; Christian-Doppler-Laboratory for Advanced Hard Coatings at the Institute of Mineralogy and Petrography, University of Innsbruck, Innrain 52, A-6020 Innsbruck

2006-07-15

The crystal structure of a potassium calcium silicate with composition K{sub 9.6}Ca{sub 1.2}Si{sub 12}O{sub 30} (or K{sub 8}CaSi{sub 10}O{sub 25}) has been solved by direct methods aided by distance least squares optimization from laboratory X-ray powder diffraction data. The trigonal compound adopts the non-centrosymmetric space group R3c with the following basic crystallographic data: a=11.13623(5)A, c=21.9890(2)A, V=2361.63(2)A{sup 3}, Z=3, D{sub calc}=2.617gcm{sup -3}. The crystal structure can be classified as an interrupted framework with exclusively Q{sup 3}-units. It can be thought of as being built from layers parallel to (001) containing isolated six-membered tetrahedral rings in UDUDUD conformation. Corner sharing of tetrahedramore » belonging to adjacent sheets results in a tetrahedral framework. The framework density of the structure is 15.2 T-atoms/1000A{sup 3}. The coordination sequences are identical for both silicon atoms in the asymmetric unit: 3-6-11-20-32-46-60-80-102-122. The vertex symbols for the two tetrahedral centers are 10{sub 2}.10{sub 2}.6{sub 1}. Topologically, the structure can be described as an Archimedean three-dimensional 3-connected net. It can be derived from the diamond or cristobalite net by removing 20% of the knots. Charge compensation in the structure is achieved by the incorporation of mono- and divalent M-cations (M: K, Ca). These extra-framework ions are coordinated by six to nine oxygen ligands. Ca/K distributions for the five symmetrically independent M-sites were obtained from a combination of bond distance considerations, site occupancy refinements and the bulk chemical composition. The structural characterization is completed by a detailed Raman spectroscopic study. Furthermore, possible implications of the structural chemistry of interrupted framework silicates for the field of silicate glass research are addressed.« less

Kinetic Controls on Formation of Textures in Rapidly Cooled Rocks

NASA Technical Reports Server (NTRS)

Lofgren, Gary E.

2006-01-01

The crystallization of silicate melts is a complex process involving melts usually produced by partial melting and cooling environments that are rapid in volcanic lavas or so slow as to be auto-metamorphic in plutonic regimes. The volcanic lavas are amenable to laboratory study as are chondrules that comprise the bulk of chondritic meteorites. Dynamic crystallization studies of basalt and chondrule melts have shown that nucleation has a more profound effect on the final texture than the cooling or crystal growth rates. The sequence of crystal shapes grown at increasing degrees of supercooling (DELTA T) or cooling rate demonstrates the effect of increasing growth rate. Equant or euhedral crystals become skeletal, then dendritic and ultimately spherulitic indicating the nucleation temperature and the DELTA T when growth began. Because crystals cannot grow until they nucleate, cooling rate does not always correlate with crystal growth rate and thus crystal shape. Silicate melts cooled at the same rate can have drastically different textures depending on the temperature of nucleation. A dynamic crystallization study of basaltic rocks shows that basaltic lavas must erupt with sufficient crystals present in the melt to act as nuclei and foster growth. With nuclei present, growth will begin when the temperature drops below the liquidus temperature and typical basaltic textures such as intersertal, intergranular or subophitic will form. If nuclei are not present, crystallization will not begin immediately and the DELTA T will increase until embryos in the melts become nuclei. The DELTA T present when grow begins dictates the growth rate and the crystal shapes and thus the rock texture. If nucleation is delayed, growth will take place at high DELTA T and the crystals will favor skeletal or dendritic shapes. Chondrules are usually considered crystallized melt droplets and clearly some are, but most are not. Most chondrules have porphyritic textures that cannot develop from totally melted droplets because nucleation is delayed during cooling and growth occurs at high DELTA T and the resulting textures are dendritic or spherulitic. The porphyritic textures will develop only if the chondrule is partially molten and begins to crystallize immediately upon cooling. Chondrule compositions are close to komatiites and these studies bear on the origin of their textures as well.

Eruption and emplacement of a laterally extensive, crystal-rich, and pumice-free ignimbrite (the Cretaceous Kusandong Tuff, Korea)

NASA Astrophysics Data System (ADS)

Sohn, Y. K.; Son, M.; Jeong, J. O.; Jeon, Y. M.

2009-10-01

The Cretaceous Kusandong Tuff, Korea, is a thin (1-5 m thick) but laterally extensive (~ 200 km) silicic ignimbrite emplaced in a fluviolacustrine basin adjacent to a continental volcanic arc. The tuff has been used as an excellent key bed because of its great lateral continuity and unique lithology, characterized by the virtual absence of juvenile clasts and an abundance of quartz and feldspar crystals (up to 55-73 vol.%). The tuff is mostly massive and ungraded and locally shows crude internal layering, basal inverse grading and near-top normal grading of crystals, either erosional or non-erosional lower surfaces, and flat-lying to imbricated grain fabrics. Fragile intraformational clasts of mudstone and tuff are also included. These features provide only ambiguous information on the properties of the responsible pyroclastic density currents: i.e. whether they were dense and laminar or dilute and turbulent. The overall lateral continuity and sheet-like geometry of the tuff suggests, however, that the transport system of the currents was highly expanded, dilute, and turbulent. A plug-flow or slab-flow model cannot explain the origin of crude internal layering, imbricated grain fabrics, and the high crystal content, which is most likely the result of vigorous sorting processes within a dilute and turbulent current. Features indicative of deposition from a dense and laminar transporting medium are locally present, suggesting that a dense and laminar depositional system could develop locally at the base of the dilute and turbulent transport system. The virtual absence of juvenile clasts in the tuff is interpreted to be due to rapid ascent, sudden decompression, and full fragmentation of silicic magma into fine glass shards and crystals. Scarcity of basement-derived accidental components together with the absence of pumiceous fallout deposits beneath the tuff is interpreted to be due to shallow-level fragmentation of magma followed by immediate generation of pyroclastic density currents from shallow-level blasts at the onset of eruption. The eruption occurred through multiple vent sites in a short period of time, producing a seemingly single but actually composite ignimbrite unit. Such an eruption was probably possible because of a regional tectonic event within the basin or in its vicinity. It is proposed that a composite ignimbrite with the characteristics of the Kusandong Tuff can be an exemplary product of syntectonic volcanism that can provide an insight into the interpretation of structural and stratigraphic evolution of a sedimentary basin.

First finding of impact melt in the IIE Netschaëvo meteorite

NASA Astrophysics Data System (ADS)

Roosbroek, N.; Pittarello, L.; Greshake, A.; Debaille, V.; Claeys, P.

2016-02-01

About half of the IIE nonmagmatic iron meteorites contain silicate inclusions with a primitive to differentiated nature. The presence of preserved chondrules has been reported for two IIE meteorites so far, Netschaëvo and Mont Dieu, which represent the most primitive silicate material within this group. In this study, silicate inclusions from two samples of Netschaëvo were examined. Both silicate inclusions are characterized by a porphyritic texture dominated by clusters of coarse-grained olivine and pyroxene, set in a fine-grained groundmass that consists of new crystals of olivine and a glassy appearing matrix. This texture does not correspond to the description of the previously examined pieces of Netschaëvo, which consist of primitive chondrule-bearing angular clasts. Detailed petrographic observations and geochemical analyses suggest that the investigated samples of Netschaëvo consist of quenched impact melt. This implies that Netschaëvo is a breccia containing metamorphosed and impact-melt rock (IMR) clasts and that collisions played a major role in the formation of the IIE group.

Low-(18)O Silicic Magmas: Why Are They So Rare?

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

Balsley, S.D.; Gregory, R.T.

1998-10-15

LOW-180 silicic magmas are reported from only a small number of localities (e.g., Yellowstone and Iceland), yet petrologic evidence points to upper crustal assimilation coupled with fractional crystallization (AFC) during magma genesis for nearly all silicic magmas. The rarity of 10W-l `O magmas in intracontinental caldera settings is remarkable given the evidence of intense 10W-l*O meteoric hydrothermal alteration in the subvolcanic remnants of larger caldera systems. In the Platoro caldera complex, regional ignimbrites (150-1000 km3) have plagioclase 6180 values of 6.8 + 0.1%., whereas the Middle Tuff, a small-volume (est. 50-100 km3) post-caldera collapse pyroclastic sequence, has plagioclase 8]80 valuesmore » between 5.5 and 6.8%o. On average, the plagioclase phenocrysts from the Middle Tuff are depleted by only 0.3%0 relative to those in the regional tuffs. At Yellowstone, small-volume post-caldera collapse intracaldera rhyolites are up to 5.5%o depleted relative to the regional ignimbrites. Two important differences between the Middle Tuff and the Yellowstone 10W-180 rhyolites elucidate the problem. Middle Tuff magmas reached water saturation and erupted explosively, whereas most of the 10W-l 80 Yellowstone rhyolites erupted effusively as domes or flows, and are nearly devoid of hydrous phenocrysts. Comparing the two eruptive types indicates that assimilation of 10W-180 material, combined with fractional crystallization, drives silicic melts to water oversaturation. Water saturated magmas either erupt explosively or quench as subsurface porphyrins bejiire the magmatic 180 can be dramatically lowered. Partial melting of low- 180 subvolcanic rocks by near-anhydrous magmas at Yellowstone produced small- volume, 10W-180 magmas directly, thereby circumventing the water saturation barrier encountered through normal AFC processes.« less

Spade: An H Chondrite Impact-melt Breccia that Experienced Post-shock Annealing

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Jones, Rhian H.

2006-01-01

The low modal abundances of relict chondrules (1.8 Vol%) and of coarse (i.e. >= 2200 micron-size) isolated mafic silicate grains (1.8 Vol%) in Spade relative to mean H6 chondrites (11.4 and 9.8 vol%, respectively) show Spade to be a rock that has experienced a significant degree of melting. Various petrographic features (e.g., chromite-plagioclase assemblages, chromite veinlets, silicate darkening) indicate that melting was caused by shock. Plagioclase was melted during the shock event and flowed so that it partially to completely surrounded nearby mafic silicate grains. During crystallization, plagioclase developed igneous zoning. Low-Ca pyroxene that crystallized from the melt (or equilibrated with the melt at high temperatures) acquired relatively high amounts of CaO. Metallic Fe-Ni cooled rapidly below the Fe-Ni solws and transformed into martensite. Subsequent reheating of the rock caused transformation of martensite into abundant duplex plessite. Ambiguities exist in the shock stage assignment of Spade. The extensive silicate darkening, the occurrence of chromite-plagioclase assemblages, and the impact-melted characteristics of Spade are consistent with shock stage S6. Low shock (stage S2) is indicated by the undulose extinction and lack of planar fractures in olivine. This suggests that Spade reached a maximum prior shock level equivalent to stage S6 and then experienced post-shock annealing (probably to stage Sl). These events were followed by a less intense impact that produced the undulose extinction in the olivine, characteristic of shock stage S2. Annealing could have occurred if Spade were emplaced near impact melts beneath the crater floor or deposited in close proximity to hot debris within an ejecta blanket. Spade firmly establishes the case for post-shock annealing. This may have been a common process on ordinary chondrites (OC) asteroids.

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

PubMed

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

2012-02-01

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

Localized rejuvenation of a crystal mush recorded in zircon temporal and compositional variation at the Lassen Volcanic Center, northern California

USGS Publications Warehouse

Klemetti, Erik W.; Clynne, Michael A.

2014-01-01

Zircon ages and trace element compositions from recent silicic eruptions in the Lassen Volcanic Center (LVC) allow for an evaluation of the timing and conditions of rejuvenation (reheating and mobilization of crystals) within the LVC magmatic system. The LVC is the southernmost active Cascade volcano and, prior to the 1980 eruption of Mount St. Helens, was the site of the only eruption in the Cascade arc during the last century. The three most recent silicic eruptions from the LVC were very small to moderate-sized lava flows and domes of dacite (1915 and 27 ka eruptions of Lassen Peak) and rhyodacite (1.1 ka eruption of Chaos Crags). These eruptions produced mixed and mingled lavas that contain a diverse crystal cargo, including zircon. 238U-230Th model ages from interior and surface analyses of zircon reveal ages from ~17 ka to secular equilibrium (>350 ka), with most zircon crystallizing during a period between ~60–200 ka. These data support a model for localized rejuvenation of crystal mush beneath the LVC. This crystal mush evidently is the remnant of magmatism that ended ~190 ka. Most zircon are thought to have been captured from “cold storage” in the crystal mush (670–725°C, Hf >10,000 ppm, Eu/Eu* 0.25–0.4) locally remobilized by intrusion of mafic magma. A smaller population of zircon (>730°C, Hf <10,000 ppm, Eu/Eu* >0.4) grew in, and are captured from, rejuvenation zones. These data suggest the dominant method to produce eruptible melt within the LVC is small-scale, local rejuvenation of the crystal mush accompanied by magma mixing and mingling. Based on zircon stability, the time required to heat, erupt and then cool to background conditions is relatively short, lasting a maximum of 10 s–1000 s years. Rejuvenation events in the LVC are ephemeral and permit eruption within an otherwise waning and cooling magmatic body.

Localized rejuvenation of a crystal mush recorded in zircon temporal and compositional variation at the Lassen Volcanic Center, northern California.

PubMed

Klemetti, Erik W; Clynne, Michael A

2014-01-01

Zircon ages and trace element compositions from recent silicic eruptions in the Lassen Volcanic Center (LVC) allow for an evaluation of the timing and conditions of rejuvenation (reheating and mobilization of crystals) within the LVC magmatic system. The LVC is the southernmost active Cascade volcano and, prior to the 1980 eruption of Mount St. Helens, was the site of the only eruption in the Cascade arc during the last century. The three most recent silicic eruptions from the LVC were very small to moderate-sized lava flows and domes of dacite (1915 and 27 ka eruptions of Lassen Peak) and rhyodacite (1.1 ka eruption of Chaos Crags). These eruptions produced mixed and mingled lavas that contain a diverse crystal cargo, including zircon. 238U-230Th model ages from interior and surface analyses of zircon reveal ages from ∼17 ka to secular equilibrium (>350 ka), with most zircon crystallizing during a period between ∼60-200 ka. These data support a model for localized rejuvenation of crystal mush beneath the LVC. This crystal mush evidently is the remnant of magmatism that ended ∼190 ka. Most zircon are thought to have been captured from "cold storage" in the crystal mush (670-725°C, Hf >10,000 ppm, Eu/Eu* 0.25-0.4) locally remobilized by intrusion of mafic magma. A smaller population of zircon (>730°C, Hf <10,000 ppm, Eu/Eu* >0.4) grew in, and are captured from, rejuvenation zones. These data suggest the dominant method to produce eruptible melt within the LVC is small-scale, local rejuvenation of the crystal mush accompanied by magma mixing and mingling. Based on zircon stability, the time required to heat, erupt and then cool to background conditions is relatively short, lasting a maximum of 10 s-1000 s years. Rejuvenation events in the LVC are ephemeral and permit eruption within an otherwise waning and cooling magmatic body.

Comment on "Rapid cooling and cold storage in a silicic magma reservoir recorded in individual crystals".

PubMed

Wilson, Colin J N; Morgan, Daniel J; Charlier, Bruce L A; Barker, Simon J

2017-12-22

Rubin et al (Reports, 16 June 2017, p. 1154) proposed that gradients in lithium abundance in zircons from a rhyolitic eruption in New Zealand reflected short-lived residence at magmatic temperatures interleaved with long-term "cold" (<650°C) storage. Important issues arise with the interpretation of these lithium gradients and consequent crystal thermal histories that raise concerns about the validity of this conclusion. Copyright © 2017, American Association for the Advancement of Science.

Growth of large zeolite crystals in space

NASA Technical Reports Server (NTRS)

Sacco, A., Jr.; Dixon, A.; Thompson, R.; Scott, G.; Ditr, J.

1988-01-01

Synthesis studies performed using close analogs of triethanolamine (TEA) have shown that all three hydroxyl groups and the amine group in this molecule are necessary to provide nucleation suppression. Studies using C-13 nuclear magnetic resonance (NMR) revealed that the hydroxyl ions and the amine group are involved in the formation of an aluminum complex. It was also shown that silicate species fo not interact this way with TEA in an alkaline solution. These results suggest that successful aluminum complexation leads to nucleation in zeolite-A crystallization.

Error Measurements in an Acousto-Optic Tunable Filter Fiber Bragg Grating Sensor System

DTIC Science & Technology

1994-05-01

for an ideal AOTF, at 833 and 838 nm using a TeO2 crystal ............................ 33 Figure 3.12. Frequency characteristics of Equation (3.43...multiple channels in an AOTF requires the presence of multiple RF frequencies to establish the complex grating. Since the crystal used in the AOTF ( TeO2 ) is...in germano- silicate glass . This index modulation, Bragg grating, acts as an optical band rejection filter for those wavelengths that meet the Bragg

Zircon crystallization and recycling in the magma chamber of the rhyolitic Kos Plateau Tuff (Aegean arc)

USGS Publications Warehouse

Bachman, O.; Charlier, B.L.A.; Lowenstern, J. B.

2007-01-01

In contrast to most large-volume silicic magmas in continental arcs, which are thought to evolve as open systems with significant assimilation of preexisting crust, the Kos Plateau Tuff magma formed dominantly by crystal fractionation of mafic parents. Deposits from this ~60 km3 pyroclastic eruption (the largest known in the Aegean arc) lack xenocrystic zircons [secondary ion mass spectrometry (SIMS) U-Pb ages on zircon cores never older than 500 ka] and display Sr-Nd whole-rock isotopic ratios within the range of European mantle in an area with exposed Paleozoic and Tertiary continental crust; this evidence implies a nearly closed-system chemical differentiation. Consequently, the age range provided by zircon SIMS U-Th-Pb dating is a reliable indicator of the duration of assembly and longevity of the silicic magma body above its solidus. The age distribution from 160 ka (age of eruption by sanidine 40Ar/39Ar dating; Smith et al., 1996) to ca. 500 ka combined with textural characteristics (high crystal content, corrosion of most anhydrous phenocrysts, but stability of hydrous phases) suggest (1) a protracted residence in the crust as a crystal mush and (2) rejuvenation (reduced crystallization and even partial resorption of minerals) prior to eruption probably induced by new influx of heat (and volatiles). This extended evolution chemically isolated from the surrounding crust is a likely consequence of the regional geodynamics because the thinned Aegean microplate acts as a refractory container for magmas in the dying Aegean subduction zone (continent-continent subduction).

Crystallization of accessory phases in magmas by local saturation adjacent to phenocrysts

USGS Publications Warehouse

Bacon, C.R.

1989-01-01

Accessory minerals commonly occur attached to or included in the major crystalline phases of felsic and some intermediate igneous rocks. Apatite is particularly common as inclusions, but Fe-Ti oxides, pyrrhotite, zircon, monazite, chevkinite and xenotime are also known from silicic rocks. Accessories may nucleate near the host crystal/ liquid interface as a result of local saturation owing to formation of a differentiated chemical boundary layer in which accessory mineral solubility would be lower than in the surrounding liquid. Differentiation of this boundary layer would be greatest adjacent to ferromagnesian phenocrysts, especially Fe-Ti oxides; it is with oxides that accessories are most commonly associated in rocks. A boundary layer may develop if the crystal grows more rapidly than diffusion can transport incorporated and rejected elements to and from the phenocryst. Diffusion must dominate over convection as a mode of mass transfer near the advancing crystal/liquid interface in order for a boundary layer to exist. Accumulation of essential structural constituent elements of accessory minerals owing to their slow diffusion in evolved silicate melt also may force local saturation, but this is not a process that applies to all cases. Local saturation is an attractive mechanism for enhancing fractionation during crystallization differentiation. If accessory minerals attached to or included in phenocrysts formed because of local saturation, their host phenocrysts must have grown rapidly when accessories nucleated in comparison to lifetimes of magma reservoirs. Some inconsistencies remain in a local saturation origin for accessory phases that cannot be evaluated without additional information. ?? 1989.

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.

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

Nguyen, Ann N.; Keller, Lindsay P.; Messenger, Scott, E-mail: lan-anh.n.nguyen@nasa.gov

We report the chemical and structural analysis of nine presolar silicate grains and one presolar oxide grain from the ungrouped chondrite Acfer 094 and the CR chondrite Queen Alexandra Range 99177. Oxygen isotopic analyses indicate that five of these grains condensed in the outflows of asymptotic giant branch (AGB) stars, four have supernova (SN) origins, and one grain likely has a nova origin. Transmission electron microscopy studies show that most of the grains are amorphous with widely varying non-stoichiometric chemical compositions. Three crystalline AGB grains were identified: a clinoenstatite-containing grain assemblage, a Fe-rich olivine grain, and a nanocrystalline enstatite grainmore » encased in an amorphous silicate shell. An amorphous stoichiometric enstatite (MgSiO{sub 3}) SN grain likely condensed as a crystal and was later rendered amorphous. We do not observe a systematic difference in the chemistries and mineralogies of presolar silicates from different stellar sources, suggesting that the grains formed under a similar range of conditions.« less

Coordination of Fe, Ga and Ge in high pressure glasses by Moessbauer, Raman and X-ray absorption spectroscopy, and geological implications

NASA Technical Reports Server (NTRS)

Fleet, M. E.; Henderson, G. S.; Herzberg, C. T.; Crozier, E. D.; Osborne, M. D.; Scarfe, C. M.

1984-01-01

For some time, it has been recognized that the structure of silicate liquids has a great bearing on such magma properties as viscosity, diffusivity, and thermal expansion and on the extrapolation of thermodynamic quantities outside of the experimentally measurable range. In this connection it is vital to know if pressure imposes changes in melt structure similar to the pressure-induced reconstructive transformations in crystals. In the present study on 1 bar and high pressure glasses, an investigation is conducted regarding the coordination of Fe(3+) in Fe silicate glasses by Moessbauer spectroscopy. Raman spectroscopy is employed to explore the coordinations of Ge(4+) in GeO2 glasses and of Ga(3+) in NaGa silicate glasses, while the coordination of Ga(3+) in NaGaSiO4 glasses is studied with the aid of methods of X-ray absorption spectroscopy.

Coordination of Fe, Ga and Ge in high pressure glasses by Moessbauer, Raman and X-ray absorption spectroscopy, and geological implications

NASA Astrophysics Data System (ADS)

Fleet, M. E.; Herzberg, C. T.; Henderson, G. S.; Crozier, E. D.; Osborne, M. D.; Scarfe, C. M.

1984-07-01

For some time, it has been recognized that the structure of silicate liquids has a great bearing on such magma properties as viscosity, diffusivity, and thermal expansion and on the extrapolation of thermodynamic quantities outside of the experimentally measurable range. In this connection it is vital to know if pressure imposes changes in melt structure similar to the pressure-induced reconstructive transformations in crystals. In the present study on 1 bar and high pressure glasses, an investigation is conducted regarding the coordination of Fe(3+) in Fe silicate glasses by Moessbauer spectroscopy. Raman spectroscopy is employed to explore the coordinations of Ge(4+) in GeO2 glasses and of Ga(3+) in NaGa silicate glasses, while the coordination of Ga(3+) in NaGaSiO4 glasses is studied with the aid of methods of X-ray absorption spectroscopy.

Formation of dust grains with impurities in red giant winds

NASA Technical Reports Server (NTRS)

Dominik, Carsten

1994-01-01

Among the several proposed carriers of diffuse interstellar bands (DIB's) are impurities in small dust grains, especially in iron oxide grains (Huffman 1977) and silicate grains (Huffman 1970). Most promising are single ion impurities since they can reproduce the observed band widths (Whittet 1992). These oxygen-rich grains are believed to originate mostly in the mass flows from red giants and in supernovae ejecta (e.g. Gehrz 1989). A question of considerable impact for the origin of DIB's is therefore, whether these grains are produced as mainly clean crystals or as some dirty materials. A formalism has been developed that allows tracking of the heterogeneous growth of a dust grain and its internal structure during the dust formation process. This formalism has been applied to the dust formation in the outflow from a red giant star.

Hydrogen isotope investigation of amphibole and biotite phenocrysts in silicic magmas erupted at Lassen Volcanic Center, California

USGS Publications Warehouse

Underwood, S.J.; Feeley, T.C.; Clynne, M.A.

2012-01-01

Hydrogen isotope ratio, water content and Fe3 +/Fe2 + in coexisting amphibole and biotite phenocrysts in volcanic rocks can provide insight into shallow pre- and syn-eruptive magmatic processes such as vesiculation, and lava drainback with mixing into less devolatilized magma that erupts later in a volcanic sequence. We studied four ~ 35 ka and younger eruption sequences (i.e. Kings Creek, Lassen Peak, Chaos Crags, and 1915) at the Lassen Volcanic Center (LVC), California, where intrusion of crystal-rich silicic magma mushes by mafic magmas is inferred from the varying abundances of mafic magmatic inclusions (MMIs) in the silicic volcanic rocks. Types and relative proportions of reacted and unreacted hydrous phenocryst populations are evaluated with accompanying chemical and H isotope changes. Biotite phenocrysts were more susceptible to rehydration in older vesicular glassy volcanic rocks than coexisting amphibole phenocrysts. Biotite and magnesiohornblende phenocrysts toward the core of the Lassen Peak dome are extensively dehydroxylated and reacted from prolonged exposure to high temperature, low pressure, and higher fO2 conditions from post-emplacement cooling. In silicic volcanic rocks not affected by alteration, biotite phenocrysts are often relatively more dehydroxylated than are magnesiohornblende phenocrysts of similar size; this is likely due to the ca 10 times larger overall bulk H diffusion coefficient in biotite. A simplified model of dehydrogenation in hydrous phenocrysts above reaction closure temperature suggests that eruption and quench of magma ascended to the surface in a few hours is too short a time for substantial H loss from amphibole. In contrast, slowly ascended magma can have extremely dehydrogenated and possibly dehydrated biotite, relatively less dehydrogenated magnesiohornblende and reaction rims on both phases. Eruptive products containing the highest proportions of mottled dehydrogenated crystals could indicate that within a few days prior to eruption, degassed vesiculated magma or lava had drained back down the volcanic conduit and mixed with less devolatilized magma. The vesiculated magma contained hydrous phenocrysts with lattice damage, which locally raised the effective H diffusion coefficient by ca 10–100 × and resulted in increased mineral dehydrogenation. Remobilization of dacite magma mush by relatively more reduced mafic magma appears to have generated further fO2 variations in May 1915 as oxidized magma from shallow levels circulated to depths where dehydrogenation of hydrous phenocrysts began. The δDMagmatic H2O expressed in LVC acid hot springs is likely a mixture derived from devolatilized ascending mafic magmas and crystallizing silicic magma mush.

Geochemical and Isotopic Data from Micron to Across-Arc Scales in the Andean Central Volcanic Zone: Applications for Resolving Crustal Magmatic Differentiation and Modification Processes

NASA Astrophysics Data System (ADS)

Michelfelder, G.; Wilder, A.; Feeley, T.

2014-12-01

Plagioclase crystals from silicic (andesitic to dacitic) lavas and domes at Volcán Uturuncu, a potentially active volcano in the back-arc of the Andean CVZ (22.3°S, 67.2°W), exhibit large variations in An contents, textures, and core to rim 87Sr/86Sr ratios. Many of the isotopic variations can not have existed at magmatic temperatures for more than a few thousand years. The crystals likely derived from different locations in the crustal magmatic system and mixed just prior to eruption. Uturuncu magmas initially assimilated crustal rocks with high 87Sr/86Sr ratios. The magmas were subsequently modified by frequent recharge of more mafic magmas with lower 87Sr/86Sr ratios. A typical Uturuncu silicic magma therefore only attains its final composition just prior to or during eruption. In the Lazufre region of active surface uplift (~25˚14'S; Volcán Lastarria and Cordon del Azufre) closed system differentiation processes are not the only factors influencing silicic magma compositions. 87Sr/86Sr (0.70651-0.70715) and 206Pb/204Pb ratios (18.83-18.88) are highly elevated and143Nd/144Nd ratios (0.512364 -0.512493) are low relative to similar composition rocks from the "southern Cordillera domain." These data, along with major and trace element trends, reflect a multitude of differentiation processes and magma sources including crystallization-differentiation of more mafic magmas, melting and assimilation of older crustal rocks, and magma mixing and mingling. On an arc-wide scale silicic lavas erupted from three well-characterized composite volcanoes between 21oS and 22oS (Aucanquilcha, Ollagüe, and Uturuncu) display systematically higher K2O, LILE, REE and HFSE contents and 87Sr/86Sr ratios with increasing distance from the arc-front. In contrast, the lavas have systematically lower Na2O, Sr, and Ba contents; LILE/HFSE ratios; 143Nd/144Nd ratios; and more negative Eu anomalies. Silicic magmas along the arc-front apparently reflect melting of relatively young, mafic composition amphibolitic source rocks with the continental crust becoming increasingly older with a more felsic bulk composition toward the east. We suggest this results from progressively smaller degrees of mantle partial melting, primary melt generation, and crustal hybridization with distance from the arc-front.

The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; Merdian, Alexandra; Holmden, Chris; Kleinhanns, Ilka C.; Haßler, Kathrin; Wille, Martin; Reitter, Elmar

2016-06-01

The depletion of chromium in Earth's mantle (∼2700 ppm) in comparison to chondrites (∼4400 ppm) indicates significant incorporation of chromium into the core during our planet's metal-silicate differentiation, assuming that there was no significant escape of the moderately volatile element chromium during the accretionary phase of Earth. Stable Cr isotope compositions - expressed as the ‰-difference in 53Cr/52Cr from the terrestrial reference material SRM979 (δ53/52CrSRM979 values) - of planetary silicate reservoirs might thus yield information about the conditions of planetary metal segregation processes when compared to chondrites. The stable Cr isotopic compositions of 7 carbonaceous chondrites, 11 ordinary chondrites, 5 HED achondrites and 2 martian meteorites determined by a double spike MC-ICP-MS method are within uncertainties indistinguishable from each other and from the previously determined δ53/52CrSRM979 value of -0.124 ± 0.101‰ for the igneous silicate Earth. Extensive quality tests support the accuracy of the stable Cr isotope determinations of various meteorites and terrestrial silicates reported here. The uniformity in stable Cr isotope compositions of samples from planetary silicate mantles and undifferentiated meteorites indicates that metal-silicate differentiation of Earth, Mars and the HED parent body did not cause measurable stable Cr isotope fractionation between these two reservoirs. Our results also imply that the accretionary disc, at least in the inner solar system, was homogeneous in its stable Cr isotopic composition and that potential volatility loss of chromium during accretion of the terrestrial planets was not accompanied by measurable stable isotopic fractionation. Small but reproducible variations in δ53/52CrSRM979 values of terrestrial magmatic rocks point to natural stable Cr isotope variations within Earth's silicate reservoirs. Further and more detailed studies are required to investigate whether silicate differentiation processes, such as partial mantle melting and crystal fractionation, can cause stable Cr isotopic fractionation on Earth and other planetary bodies.

Silicate Melts of the Protolunar Disk and the Formation of the Magma Ocean from AB Initio Simulations

NASA Astrophysics Data System (ADS)

Caracas, R.; Stewart, S. T.

2018-05-01

We employ large-scale first-principles molecular dynamics simulations to understand the physical and chemical behavior of the evolution of the molten protolunar disk from its formation all the way to the crystallization of the magma ocean.

Carbonate Mineral Assemblages as Inclusions in Yakutian Diamonds: TEM Verifications

NASA Astrophysics Data System (ADS)

Logvinova, A. M.; Wirth, R.; Sobolev, N. V.; Taylor, L. A.

2014-12-01

Carbonate mineral inclusions are quite rare in diamonds from the upper mantle, but are evidence for a carbonate abundance in the mantle. It is believed that such carbonatitic inclusions originated from high-density fluids (HDFs) that were enclosed in diamond during its growth. Using TEM and EPMA, several kinds of carbonate inclusions have been identified in Yakutian diamonds : aragonite, dolomite, magnesite, Ba-, Sr-, and Fe-rich carbonates. Most of them are represented by multi-phase inclusions of various chemically distinct carbonates, rich in Ca, Mg, and K and associated with minor amounts of silicate, oxide, saline, and volatile phases. Volatiles, leaving some porosity, played a significant role in the diamond growth. A single crystal of aragonite (60μm) is herein reported for the first time. This inclusion is located in the center of a diamond from the Komsomolskaya pipe. Careful CL imaging reveals the total absence of cracks around the aragonite inclusion - i.e., closed system. This inclusion has been identified by X-ray diffraction and microprobe analysis. At temperatures above 1000 0C, aragonite is only stable at high pressures of 5-6 GPa. Inside this aragonite, we observed nanocrystalline inclusions of titanite, Ni-rich sulfide, magnetite, water-bearing Mg-silicate, and fluid bubbles. Dolomite is common in carbonate multi-phase inclusions in diamonds from the Internatsionalnaya, Yubileinaya, and Udachnaya kimberlite pipes. Alluvial diamonds of the northeastern Siberian Platform are divided into two groups based on the composition of HDFs: 1) Mg-rich multi-phase inclusions (60% magnesite + dolomite + Fe-spinel + Ti-silicate + fluid bubbles); and 2) Ca-rich multi-phase inclusions (Ca,Ba-, Ca,Sr-, Ca,Fe-carbonates + Ti-silicate + Ba-apatite + fluid bubbles). High-density fluids also contain K. Volatiles in the fluid bubbles are represented by water, Cl, F, S, CO2, CH4, and heavy hydrocarbons. Origin of the second group of HDFs may be related to the non-silicate carbonatitic melt. We consider the primary hydrous, Сa-rich and Mg-poor carbonate melts as having formed in subducted oceanic crust. Variations of carbonate-inclusion compositions among diamonds indicate the variability in the source media during the formation of diamond and may be the result of metasomatic interaction with host rocks.

Paleomagnetic Evidence for Partial Differentiation of the Silicate-Bearing IIE Iron Meteorite Parent Body

NASA Astrophysics Data System (ADS)

Maurel, C.; Bryson, J. F. J.; Weiss, B. P.; Scholl, A.

2016-12-01

The identification of dozens of petrologically diverse chondritic and achondritic meteoritic groups indicates that a diversity of planetesimals formed in the early solar system. It is commonly thought that planetesimals formed as either unmelted or else fully differentiated bodies, implying that chondrites and achondrites cannot have originated on a single body. However, it has been suggested that partially melted bodies with chondritic crusts and achondritic interiors may also have formed. This alternative proposal is supported by the recent identification of post-accretional remanent magnetization in CV, H chondrites, and also possibly in CM chondrites, which has been interpreted as possible evidence for a core dynamo on their parent bodies. Other piece of evidence suggesting the existence of partially differentiated bodies is the existence of the silicate-bearing IIE iron meteorites. The IIEs are composed of a Fe-Ni alloy matrix containing a mixture of chondritic, primitive achondritic, and chondritic silicate inclusions that likely formed on a single parent body. Therefore, IIEs may sample all three putative layers of a layered, partially differentiated body. On the other hand, the siderophile element compositions of the matrix metal demonstrate that it is not the product of fractional crystallization of a molten core. This suggests that the matrix metal is derived from isolated reservoirs of metal in the mantle and/or crust. It is unknown whether a large-scale metallic core, not represented by known meteorite samples, also formed on the same parent planetesimal. We can search for evidence of a molten, advecting core by assessing whether IIE irons contain remanent magnetization produced by a core dynamo. With this goal, we studied the paleomagnetism of a cloudy zone (CZ) interface in the Fe-Ni matrix of the IIE iron Colomera using X-ray photoelectron emission microscopy (XPEEM). Our initial results suggest that a steady, intense magnetic field was present during the gradual formation of the CZ. This may indicate the existence of an advecting core on the IIE parent body, which would support the hypothesis of a partially differentiated structure. We are continuing to test this conclusion with further XPEEM measurements on Colomera and other IIE irons.

Paleomagnetic Evidence for Partial Differentiation of the Silicate-Bearing IIE Iron Meteorite Parent Body

NASA Astrophysics Data System (ADS)

Maurel, C.; Bryson, J. F. J.; Weiss, B. P.; Scholl, A.

2017-12-01

The identification of dozens of petrologically diverse chondritic and achondritic meteoritic groups indicates that a diversity of planetesimals formed in the early solar system. It is commonly thought that planetesimals formed as either unmelted or else fully differentiated bodies, implying that chondrites and achondrites cannot have originated on a single body. However, it has been suggested that partially melted bodies with chondritic crusts and achondritic interiors may also have formed. This alternative proposal is supported by the recent identification of post-accretional remanent magnetization in CV, H chondrites, and also possibly in CM chondrites, which has been interpreted as possible evidence for a core dynamo on their parent bodies. Other piece of evidence suggesting the existence of partially differentiated bodies is the existence of the silicate-bearing IIE iron meteorites. The IIEs are composed of a Fe-Ni alloy matrix containing a mixture of chondritic, primitive achondritic, and chondritic silicate inclusions that likely formed on a single parent body. Therefore, IIEs may sample all three putative layers of a layered, partially differentiated body. On the other hand, the siderophile element compositions of the matrix metal demonstrate that it is not the product of fractional crystallization of a molten core. This suggests that the matrix metal is derived from isolated reservoirs of metal in the mantle and/or crust. It is unknown whether a large-scale metallic core, not represented by known meteorite samples, also formed on the same parent planetesimal. We can search for evidence of a molten, advecting core by assessing whether IIE irons contain remanent magnetization produced by a core dynamo. With this goal, we studied the paleomagnetism of a cloudy zone (CZ) interface in the Fe-Ni matrix of the IIE iron Colomera using X-ray photoelectron emission microscopy (XPEEM). Our initial results suggest that a steady, intense magnetic field was present during the gradual formation of the CZ. This may indicate the existence of an advecting core on the IIE parent body, which would support the hypothesis of a partially differentiated structure. We are continuing to test this conclusion with further XPEEM measurements on Colomera and other IIE irons.

Shock-Induced Phase Transitions in the Martian Meteorite Tissint: Mechanisms and Constraints on Shock Pressure

NASA Astrophysics Data System (ADS)

Sharp, T. G.; Hu, J.; Walton, E. L.

2013-12-01

Martian meteorites are important samples for understanding the origin and age of the Martian crust. All of these samples have been shocked to some degree during their ejection from Mars or earlier. Tissint, a picritic shergottite, has many high-pressure phases that have been used to constrain shock conditions and suggest a deep crustal origin [1] and to argue for multiple impact events [2]. Here we investigate the products and mechanisms of various olivine transformation reactions. Olivine in and adjacent to shock-melt veins and pockets is transformed into high-pressure minerals. In the hottest parts of the sample, olivine dissociated into 50-nm crystals of magnesiowüstite intergrown with either a pyroxene-composition glass or with low-Ca clinopyroxene. In both cases, the olivine is inferred to have transformed to silicate perovskite + magnesiowüstite during shock with subsequent breakdown of the perovskite after pressure release. Olivine along the margins of shock veins transformed into ringwoodite. Polycrystalline ringwoodite formed at the olivine-melt interface wheras coherent ringwoodite lamellae formed farther from the melt. These ringwoodite lamellae have the same topotaxial relationship to olivine as seen in static high-pressure experiments [3] and shocked meteorites [4]: (100)Ol || {111}Rw and [011]Ol || <110>Rw. The various olivine reactions can be explained by a single shock to above 24 GPa where only the highest temperatures allowed the dissociation of olivine to silicate-perovskite plus magnesiowüstite. The silicate perovskite in the melt pocket transformed to pyroxene because the melt pocket remained very hot after pressure release. At lower temperatures, the kinetically easier polymorphic transformation of olivine to metastable ringwoodite occurred. At the lowest temperatures, this reaction was facilitated by nucleation of ringwoodite lamellae on stacking faults in olivine. The variation in assemblages that we see are consistent with a single shock and a relatively short shock pulse. References: [1] Baziotis1, I. P. et. al 2013 Nature Communications 4:1404, [2] El Goresey, A. et. al 2013 #1037. 44th LPSC. [3] Kerschhofer, L. et. al 1996 Science 274, 79-81. [4] Miyahara et. al, 2010 EPSL. 295, 321-327.

From illite/smectite clay to mesoporous silicate adsorbent for efficient removal of chlortetracycline from water.

PubMed

Wang, Wenbo; Tian, Guangyan; Zong, Li; Zhou, Yanmin; Kang, Yuru; Wang, Qin; Wang, Aiqin

2017-01-01

A series of mesoporous silicate adsorbents with superior adsorption performance for hazardous chlortetracycline (CTC) were sucessfully prepared via a facile one-pot hydrothermal reaction using low-cost illite/smectite (IS) clay, sodium silicate and magnesium sulfate as the starting materials. In this process, IS clay was "teared up" and then "rebuilt" as new porous silicate adsorbent with high specific surface area of 363.52m 2 /g (about 8.7 folds higher than that of IS clay) and very negative Zeta potential (-34.5mV). The inert SiOSi (Mg, Al) bonds in crystal framework of IS were broken to form Si(Al) O - groups with good adsorption activity, which greatly increased the adsorption sites served for holding much CTC molecules. Systematic evaluation on adsorption properties reveals the optimal silicate adsorbent can adsorb 408.81mg/g of CTC (only 159.7mg/g for raw IS clay) and remove 99.3% (only 46.5% for raw IS clay) of CTC from 100mg/L initial solution (pH3.51; adsorption temperature 30°C; adsorbent dosage, 3g/L). The adsorption behaviors of CTC onto the adsorbent follows the Langmuir isotherm model, Temkin equation and pseudo second-order kinetic model. The mesopore adsorption, electrostatic attraction and chemical association mainly contribute to the enhanced adsorption properties. As a whole, the high-efficient silicate adsorbent could be candidates to remove CTC from the wastewater with high amounts of CTC. Copyright © 2016. Published by Elsevier B.V.

New Elastic Moduli for Amphiboles and Feldspars: Impact on Interpretations of Seismic Velocities

NASA Astrophysics Data System (ADS)

Brown, J. M.; Angel, R. J.

2016-12-01

Seismic properties (both isotropic and anisotropic) of the crust and upper mantle require re-evaluation in light of improved single crystal properties for feldspars and amphiboles as a function of elemental partitioning. Together these minerals constitute more than half of the crust and are locally important in the lithospheric mantle. Their contribution in understanding seismic structures (both in the crust and mantle) has long been recognized. However, published single crystal elastic moduli, required in predictions of seismic velocities based on mineral properties, have remained inadequate for over 50 years. For example, the contribution of amphiboles to seismic velocities has often been approximated on the basis of the reported moduli for two hornblende crystals of unknown composition. New measurements now accurately characterize the plagioclase feldspars, the potassium feldspars, and the calcium and calcium-sodium amphiboles (including a range of compositions for common hornblende). The new moduli allow successful predictions of rock velocities with and without crystal preferred orientations. In contrast, the older moduli required inappropriate use of the Voigt upper aggregate bound in order to rationalize laboratory measurements. These minerals are also more anisotropic than suggested on the basis of the earlier work where cracks and open cleavage surfaces may have artificially depressed the apparent anisotropy. Both feldspars and amphiboles are nearly as anisotropic as sheet silicates with compressional velocity anisotropy of greater than 50%. The plagioclase feldspars show strong compositional trends with small discontinuities between minor structural transitions. In contrast, potassium substitution for sodium and differences in aluminum ordering have little impact on elastic moduli. In the amphiboles, elastic properties are strongly dependent on total aluminum and iron composition. The bulk modulus is most sensitive to aluminum and the shear modulus is more sensitive to iron. Variations in Poisson's ratio (which depends on the ratio of isotropic compressional and shear wave velocities) associated with compositions within the amphiboles and the feldspars are larger than previously predicted. The extent of modifications to seismic interpretations is evaluated.

Peralkaline nephelinites. I. Comparative petrology of Shombole and Oldoinyo L'engai, East Africa

NASA Astrophysics Data System (ADS)

Peterson, Tony D.

1989-04-01

Shombole, a nephelinite-carbonatite volcano in south Kenya, erupted silicate lavas, carbonatite dikes and tuffs, and pyroclastic rocks similar to those at other East African alkaline centres. Shombole lavas containing cpx + nepheline + accessory minerals range from perovskite-bearing nephelinites (43% SiO2, volatile-free) to sphene-bearing and phonolitic nephelinites (46 49% SiO2) and phonolites (49 56% SiO2) and have low peralkalinity ([Na+K]/Al ≈ 1.15) which does not correlate with SiO2. Early fractionation of olivine and clinopyroxene strongly depleted Ni and Cr concentrations (≈10 ppm); fractionation of perovskite, melanite, sphene, and apatite produced negative correlations of all REE with SiO2. Many lavas contain cognate intrusive xenoliths and xenocrysts and oscillatory zoning is a common feature of clinopyroxene, nepheline, and melanite crystals, indicating recycling of intrusive material. Irregular calcite-rich bodies in many samples are interpreted as quenched immiscible Ca-carbonatite liquid, and [Ca-carbonate]-silicate liquid immiscibility is observed in experiments with one nephelinite. Chemical variation in the Shombole suite can be modeled as a combination of crystal fractionation (clinopyroxene and heavy minor phases) and retention of neutral density nepheline derived from disaggregated xenoliths entrained during emplacement of dike swarms. Six newly analyzed lavas from Oldoinyo L'engai, northern Tanzania, are geochemically similar to Shombole nephelinites except that they have relatively high Na2O+K2O (average 18% vs 12%) and Zr (average 680 ppm vs 400 ppm). They are extremely peralkaline and are not typical of nephelinites from other centres. Three with [Na+K]/Al≈1.5 contain euhedral wollastonite phenocrysts; three with [Na+K]/Al≈2.0 contain combeite (Na2Ca2Si3O9) phenocrysts and pseudomorphs after wollastonite. Both types contain abundant sodalite phenocrysts (+nepheline+clinopyroxene+melanite+sphene). Seven other wollastonite nephelinite samples from L'engai have been described, but it is a lava type rarely seen in other centres. Combeite has been described from only two other locations (Mt. Shaheru, Zaire; Mayener Feld, Eifel). The hyperalkaline L'engai nephelinites have compositions similar to those of experimental silicate liquids immiscible with natrocarbonatite. Textural evidence for both carbonate-silicate (as carbonate globules) and silicate-silicate (as two optically discrete glasses with distinct compositions) liquid immiscibility is observed in the samples.

Lithic breccia and ignimbrite erupted during the collapse of Crater Lake Caldera, Oregon

USGS Publications Warehouse

Druitt, T.H.; Bacon, C.R.

1986-01-01

The climactic eruption of Mount Mazama (6845 y.B.P.) vented a total of ???50 km3 of compositionally zoned rhyodacitic to basaltic magma from: (a) a single vent as a Plinian pumice fall deposit and the overlying Wineglass Welded Tuff, and (b) ring vents as ignimbrite and coignimbrite lithic breccia accompanying the collapse of Crater Lake caldera. New field and grain-size data for the ring-vent products are presented in this report. The coarse-grained, poorly bedded, clast-supported lithic breccia extends as far as 18 km from the caldera center. Like the associated ignimbrite, the breccia is compositionally zoned both radially and vertically, and silicic, mixed, and mafic types can be recognized, based on the proportion of rhyodacitic pumice. Matrix fractions in silicic breccias are depleted of fines and are lithic- and crystal-enriched relative to silicic ignimbrite due to vigorous gas sorting during emplacement. Ignimbrite occurs as a proximal veneer deposit overlying the breccia, a medial (??? 8 to ??? 25 km from the caldera center), compositionally zoned valley fill as much as > 110 m thick, and an unzoned distal ({slanted equal to or greater-than} 20 km) facies which extends as far as 55 km from the caldera. Breccia within ??? 9 km of the caldera center is interpreted as a coignimbrite lag breccia formed within the deflation zone of the collapsing ring-vent eruption columns. Expanded pyroclastic flows of the deflation zone were probably vertically graded in both size and concentration of blocks, as recently postulated for some turbidity currents. An inflection in the rate of falloff of lithic-clast size within the lithic breccia at ??? 9 km may mark the outer edge of the deflation zone or may be an artifact of incomplete exposure. The onset of ring-vent activity at Mt. Mazama was accompanied by a marked increase in eruptive discharge. Pyroclastic flows were emplaced as a semicontinuous stream, as few ignimbrite flow-unit boundaries are evident. As eruption from the ring vents progressed, flow-runout distance and the extent of breccia deposition decreased due to (a) greater internal flow friction, and (b) decreasing eruption column heights. Effect (b) probably resulted from a progressive decrease in magmatic gas content and discharge rate. Waning discharge may have been promoted by the tapping of more viscous, crystal-rich magma, collapse of conduit walls, and declining caldera collapse rate. ?? 1986.

Determining Kinetic Parameters for Isothermal Crystallization of Glasses

NASA Technical Reports Server (NTRS)

Ray, C. S.; Zhang, T.; Reis, S. T.; Brow, R. K.

2006-01-01

Non-isothermal crystallization techniques are frequently used to determine the kinetic parameters for crystallization in glasses. These techniques are experimentally simple and quick compared to the isothermal techniques. However, the analytical models used for non-isothermal data analysis, originally developed for describing isothermal transformation kinetics, are fundamentally flawed. The present paper describes a technique for determining the kinetic parameters for isothermal crystallization in glasses, which eliminates most of the common problems that generally make the studies of isothermal crystallization laborious and time consuming. In this technique, the volume fraction of glass that is crystallized as a function of time during an isothermal hold was determined using differential thermal analysis (DTA). The crystallization parameters for the lithium-disilicate (Li2O.2SiO2) model glass were first determined and compared to the same parameters determined by other techniques to establish the accuracy and usefulness of the present technique. This technique was then used to describe the crystallization kinetics of a complex Ca-Sr-Zn-silicate glass developed for sealing solid oxide fuel cells.

The spectral properties of interplanetary dust particles

NASA Technical Reports Server (NTRS)

Sandford, Scott A.

1988-01-01

The observed spectral and mineralogical properties of interplanetary dust particles (IDP) allows the conclusion that: (1) the majority of IDP infrared spectra are dominated by olivine, pyroxene, or layer lattice silicate minerals, (2) to the first order the emission spectra of comets Halley and Kohoutek can be matched by mixtures of these IDP infrared types, implying that comets contain mixtures of these different crystalline silicates and may vary from comet to comet and perhaps even within a single comet, (3) do not expect to observe a single 20 micron feature in cometary spectra, (4) carbonaceous materials dominate the visible spectra properties of the IDPs even though the mass in these particles consists primarily of silicates, and (5) the particle characteristics summarized need to be properly accounted for in future cometary emission models.

Crystal growth of cholesterol in hydrogels and its characterization

NASA Astrophysics Data System (ADS)

Manuel Bravo-Arredondo, J.; Moreno, A.; Mendoza, M. E.

2014-09-01

In this work, we report the crystallization of cholesterol in ethanol solution and in three different hydrogel media: tetramethyl orthosilane, sodium metasilicate, and poly(vinyl)alcohol, whose structures are similar to the gel-like polymer structure of mucin, which is found in the mucus present in bile stone formation. The monohydrated triclinic phase was identified in all the samples by means of X-ray powder diffraction. The characteristic polymorphic crystalline transition of the anhydrous cholesterol was detected by differential thermal analysis and modulated differential scanning calorimetry only in crystals grown in ethanol, sodium silicate, and tetramethyl orthosilane. Finally, hysteresis of the phase transition temperature was measured by modulated differential scanning calorimetry in crystals grown in ethanol. The biological implications of the crystallization of cholesterol for bile stones formation are discussed in the last part of this contribution.

Placing Tighter Constraints on Mercurian Surface Fe Abundances Through the Synthesis and Characterization of Fe-Poor Silicates

NASA Astrophysics Data System (ADS)

Vander Kaaden, K. E.; McCubbin, F. M.; Rowland, R. L.; Morris, R. V.; Reppart, J. J.; Klima, R. L.

2018-05-01

We have crystallized and characterized synthetic Fe-poor minerals to make advancements towards reconciling the discrepancy between the lack of a 1-µm absorption band observed on the surface of Mercury, despite wt% levels of Fe observed by XRS.

Trace-element patterns of fibrous and monocrystalline diamonds: Insights into mantle fluids

NASA Astrophysics Data System (ADS)

Rege, S.; Griffin, W. L.; Pearson, N. J.; Araujo, D.; Zedgenizov, D.; O'Reilly, S. Y.

2010-08-01

During their growth diamonds may trap micron-scale inclusions of the fluids from which they grew, and these "time capsules" provide insights into the metasomatic processes that have modified the subcontinental lithospheric mantle. LAM-ICPMS analysis of trace elements in > 500 fibrous and monocrystalline diamonds worldwide has been used to understand the nature of these fluids. Analyses of fibrous diamonds define two general types of pattern, a "fibrous-high" (FH) one with high contents of LREE, Ba and K, and a "fibrous-low" (FL) pattern characterized by depletion in LREE/MREE, Ba and K, negative anomalies in Sr and Y, and subchondritic Zr/Hf and Nb/Ta. Both types may be found in fibrous diamonds from single deposits, and in three Yakutian pipes some diamonds show abrupt transitions from inclusion-rich cores with FH patterns to clearer rims with FL patterns. Most monocrystalline diamonds show FL-type patterns, but some have patterns that resemble those of FH fibrous diamonds. Peridotitic and eclogitic monocrystalline diamonds may show either patterns with relatively flat REE, or patterns with more strongly depleted LREE. Kimberlites that contain peridotitic diamonds with "high" patterns also contain eclogitic diamonds with "high" patterns. Strong similarities in the patterns of these two groups of diamonds may suggest high fluid/rock ratios. Many diamonds of the "superdeep" paragenesis have trace-element patterns similar to those of other monocrystalline diamonds. This may be evidence that the trace-element compositions of deep-seated fluids are generally similar to those that form diamonds in the subcontinental lithospheric mantle. The element fractionations observed between the FH and FL patterns are consistent with the immiscible separation of a silicic fluid from a carbonatite-silicate fluid, leaving a residual carbonatitic fluid strongly enriched in LREE, Ba and alkalies. This model would suggest that most monocrystalline diamonds crystallized from the more silicic fraction. Comparison with studies of single fluid inclusions in fibrous diamonds suggests that the FH patterns reflect trapped inclusions of high-Mg and low-Mg carbonatitic high-density fluids. In terms of the rock-forming elements, the fluids that precipitated the rims of some fibrous diamonds (FL pattern) and most monocrystalline diamonds are broadly similar to some hydro-silicic high-density fluids found in fibrous diamonds. However, there are still significant differences between the trace-element patterns of most monocrystalline diamonds and known high-density fluids, and further research is required to understand the formation and growth of these diamonds.

Development of a Monte Carlo Simulation for APD-Based PET Detectors Using a Continuous Scintillating Crystal

NASA Astrophysics Data System (ADS)

Clowes, P.; Mccallum, S.; Welch, A.

2006-10-01

We are currently developing a multilayer avalanche photodiode (APD)-based detector for use in positron emission tomography (PET), which utilizes thin continuous crystals. In this paper, we developed a Monte Carlo-based simulation to aid in the design of such detectors. We measured the performance of a detector comprising a single thin continuous crystal (3.1 mm times 9.5 mm times 9.5 mm) of lutetium yttrium ortho-silicate (LYSO) and an APD array (4times4) elements; each element 1.6 mm2 and on a 2.3 mm pitch. We showed that a spatial resolution of better than 2.12 mm is achievable throughout the crystal provided that we adopt a Statistics Based Positioning (SBP) Algorithm. We then used Monte Carlo simulation to model the behavior of the detector. The accuracy of the Monte Carlo simulation was verified by comparing measured and simulated parent datasets (PDS) for the SBP algorithm. These datasets consisted of data for point sources at 49 positions uniformly distributed over the detector area. We also calculated the noise in the detector circuit and verified this value by measurement. The noise value was included in the simulation. We show that the performance of the simulation closely matches the measured performance. The simulations were extended to investigate the effect of different noise levels on positioning accuracy. This paper showed that if modest improvements could be made in the circuit noise then positioning accuracy would be greatly improved. In summary, we have developed a model that can be used to simulate the performance of a variety of APD-based continuous crystal PET detectors

238U-230Th dating of chevkinite in high-silica rhyolites from La Primavera and Yellowstone calderas

USGS Publications Warehouse

Vazquez, Jorge A.; Velasco, Noel O.; Schmitt, Axel K.; Bleick, Heather A.; Stelten, Mark E.

2014-01-01

Application of 238U-230Th disequilibrium dating of accessory minerals with contrasting stabilities and compositions can provide a unique perspective on magmatic evolution by placing the thermochemical evolution of magma within the framework of absolute time. Chevkinite, a Th-rich accessory mineral that occurs in peralkaline and metaluminous rhyolites, may be particularly useful as a chronometer of crystallization and differentiation because its composition may reflect the chemical changes of its host melt. Ion microprobe 128U-230Th dating of single chevkinite microphenocrysts from pre- and post-caldera La Primavera, Mexico, rhyolites yields model crystallization ages that are within 10's of k.y. of their corresponding K-Ar ages of ca. 125 ka to 85 ka, while chevkinite microphenocrysts from a post-caldera Yellowstone, USA, rhyolite yield a range of ages from ca. 110 ka to 250 ka, which is indistinguishable from the age distribution of coexisting zircon. Internal chevkinite-zircon isochrons from La Primavera yield Pleistocene ages with ~5% precision due to the nearly two order difference in Th/U between both minerals. Coupling chevkinite 238U-230Th ages and compositional analyses reveals a secular trend of Th/U and rare earth elements recorded in Yellowstone rhyolite, likely reflecting progressive compositional evolution of host magma. The relatively short timescale between chevkinite-zircon crystallization and eruption suggests that crystal-poor rhyolites at La Primavera were erupted shortly after differentiation and/or reheating. These results indicate that 238U-230Th dating of chevkinite via ion microprobe analysis may be used to date crystallization and chemical evolution of silicic magmas.

Occurrence of wide-chain Ca-pyriboles as primary crystals in the Salton Sea Geothermal Field, California, USA

NASA Astrophysics Data System (ADS)

Yau, Yu-Chyi; Peacor, Donald R.; Essene, Eric J.

1986-09-01

Amphiboles and pyroxenes occurring in the Salton Sea Geothermal Field were found to contain coherent intergrowths of chain silicates with other than double and single chain widths by using transmission and analytical electron microscopy. Both occur in the biotite zone at the temperature (depth) interval of 310° C (1,060 m) to 330° C (1,547m) which approximately corresponds to temperatures of the greenschist facies. The amphiboles occur as euhedral fibrous crystals occupying void space and are composed primarily of irregularly alternating (010) slabs of double or triple chains, with rare quadruple and quintuple chains. Primary crystallization from solution results in euhedral crystals. Clinopyroxenes formed mainly as a porefilling cement and subordinately as prismatic crystals coexisting with fibrous amphiboles. Fine lamellae of double and triple chains are irregularly intercalated with pyroxene. AEM analyses yield formulae (Ca1.8Mg2.9Fe1.9Mn0.1) Si8O21.8(OH)1.8 (310° C) and (Ca2.0Fe2.5Mg2.3) Si8O21.8 (OH)2.0 (330° C) for amphiboles and (Ca1.1Fe0.6Mg0.3) Si2O6 for clinopyroxene. Thermodynamic calculations at Pfluid=100 bar of equilibrium reactions of (1) 3 chlorite +10 calcite + 21 quartz = 3 actinolite + 2 clinozoisite + 8 H2O + 10 CO2 and (2) actinolite+ 3 calcite+ 2 quartz = 5 clinopyroxene + H2O + 3 CO2 using Mg-end member phases indicate that formation of amphibole and pyroxene require very water-rich conditions (X_{CO_2 } < 0.06) at temperatures below 330° C.

Carbonate-silicate liquid immiscibility in the mantle propels kimberlite magma ascent

NASA Astrophysics Data System (ADS)

Kamenetsky, Vadim S.; Yaxley, Gregory M.

2015-06-01

Kimberlite is a rare volcanic rock renowned as the major host of diamonds and originated at the base of the subcontinental lithospheric mantle. Although kimberlite magmas are dense in crystals and deeply-derived rock fragments, they ascend to the surface extremely rapidly, enabling diamonds to survive. The unique physical properties of kimberlite magmas depend on the specific compositions of their parental melts that, in absence of historical eruptions and due to pervasive alteration of kimberlite rocks, remain highly debatable. We explain exceptionally rapid ascent of kimberlite magma from mantle depths by combining empirical data on the essentially carbonatite composition of the kimberlite primary melts and experimental evidence on interaction of the carbonate liquids with mantle minerals. Our experimental study shows that orthopyroxene is completely dissolved in a Na2CO3 melt at 2.0-5.0 GPa and 1000-1200 °C. The dissolution of orthopyroxene results in homogeneous silicate-carbonate melt at 5.0 GPa and 1200 °C, and is followed by unmixing of carbonate and carbonated silicate melts and formation of stable magmatic emulsion at lower pressures and temperatures. The dispersed silicate melt has a significant capacity for storing a carbonate component in the deep mantle (13 wt% CO2 at 2.0 GPa). We envisage that this component reaches saturation and is gradually released as CO2 bubbles, as the silicate melt globules are transported upwards through the lithosphere by the carbonatite magma. The globules of unmixed, CO2-rich silicate melt are continuously produced upon further reaction between the natrocarbonatite melt and mantle peridotite. On decompression the dispersed silicate melt phase ensures a continuous supply of CO2 bubbles that decrease density and increase buoyancy and promote rapid ascent of the magmatic emulsion.

Glass formation and crystallization in the alumina-silica-lanthanum phosphate system for ceramics composites

NASA Astrophysics Data System (ADS)

Guo, Shuling

The formation, structure, and dynamics of glasses in the alumina-silica-lanthanum phosphate system and their crystallization were investigated as a function of composition. These are of interest because of their potential as precursors for synthesizing ceramic-matrix-composites via co-crystallization of lanthanum monazite and either mullite or alumina into finely mixed microstructures. The glasses were characterized by X-Ray Diffraction (XRD), Raman spectroscopy, Differential Scanning Calorimetry (DSC), Nuclear Magnetic Resonance (NMR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Electron Energy Loss Spectrometry (EELS). Glass formation from rapidly quenched liquids was easiest and most consistent for compositions containing silica, such as for mullitemonazite compositions, and more difficult for alumina-monazite compositions. For mullite-monazite glasses, the glass transition temperatures increased linearly from 845°C to 906°C with increasing mullite content. An analysis of the glass structure indicated a network consisting of corner-linked aluminate, silicate and phosphate tetrahedra where aluminum played a central role of separating silicon and phosphorous. It was hypothesized that the glass network consisted of domains of aluminum silicate network edged by phosphate tetrahedra. A maximum in the crystallization temperature was attributed to the complexity of the glass network. At relatively mullite-rich compositions, simultaneous and cooperative crystallization of lanthanum phosphate and mullite correlated with the highest crystallization temperatures, and the lowest activation energies of crystallization. This was preceded by amorphous phase segregation in the glass at lower temperatures. An intermediate phase of lanthanum phosphate was discovered with an orthorhombic unit cell. For compositions of high phosphate contents, lanthanum phosphate precipitated first at about 900°C leaving an essentially pure mullite glass. Mullite crystallized at about 1000°C, matching the conditions for crystallizing pure mullite glass. The phosphate phase transformed to monazite at even higher temperatures. No amorphous phase segregation was observed in these cases. Microstructures were correlated with nucleation and growth conditions such that the continuous and isolated phases could be manipulated. Optimum nucleation temperatures were close to the glass transition temperature. Conditions were identified for forming a continuous boundary phase of monazite that isolated mullite grains, which is desired for fabricating ceramic-matrix-composites.

Group IVA irons: New constraints on the crystallization and cooling history of an asteroidal core with a complex history

NASA Astrophysics Data System (ADS)

McCoy, T. J.; Walker, R. J.; Goldstein, J. I.; Yang, J.; McDonough, W. F.; Rumble, D.; Chabot, N. L.; Ash, R. D.; Corrigan, C. M.; Michael, J. R.; Kotula, P. G.

2011-11-01

We report analyses of 14 group IVA iron meteorites, and the ungrouped but possibly related, Elephant Moraine (EET) 83230, for siderophile elements by laser ablation ICP-MS and isotope dilution. EET was also analyzed for oxygen isotopic composition and metallographic structure, and Fuzzy Creek, currently the IVA with the highest Ni concentration, was analyzed for metallographic structure. Highly siderophile elements (HSE) Re, Os and Ir concentrations vary by nearly three orders of magnitude over the entire range of IVA irons, while Ru, Pt and Pd vary by less than factors of five. Chondrite normalized abundances of HSE form nested patterns consistent with progressive crystal-liquid fractionation. Attempts to collectively model the HSE abundances resulting from fractional crystallization achieved best results for 3 wt.% S, compared to 0.5 or 9 wt.% S. Consistent with prior studies, concentrations of HSE and other refractory siderophile elements estimated for the bulk IVA core and its parent body are in generally chondritic proportions. Projected abundances of Pd and Au, relative to more refractory HSE, are slightly elevated and modestly differ from L/LL chondrites, which some have linked with group IVA, based on oxygen isotope similarities. Abundance trends for the moderately volatile and siderophile element Ga cannot be adequately modeled for any S concentration, the cause of which remains enigmatic. Further, concentrations of some moderately volatile and siderophile elements indicate marked, progressive depletions in the IVA system. However, if the IVA core began crystallization with ˜3 wt.% S, depletions of more volatile elements cannot be explained as a result of prior volatilization/condensation processes. The initial IVA core had an approximately chondritic Ni/Co ratio, but a fractionated Fe/Ni ratio of ˜10, indicates an Fe-depleted core. This composition is most easily accounted for by assuming that the surrounding silicate shell was enriched in iron, consistent with an oxidized parent body. The depletions in Ga may reflect decreased siderophilic behavior in a relatively oxidized body, and more favorable partitioning into the silicate portion of the parent body. Phosphate inclusions in EET show Δ 17O values within the range measured for silicates in IVA iron meteorites. EET has a typical ataxitic microstructure with precipitates of kamacite within a matrix of plessite. Chemical and isotopic evidence for a genetic relation between EET and group IVA is strong, but the high Ni content and the newly determined, rapid cooling rate of this meteorite show that it should continue to be classified as ungrouped. Previously reported metallographic cooling rates for IVA iron meteorites have been interpreted to indicate an inwardly crystallizing, ˜150 km radius metallic body with little or no silicate mantle. Hence, the IVA group was likely formed as a mass of molten metal separated from a much larger parent body that was broken apart by a large impact. Given the apparent genetic relation with IVA, EET was most likely generated via crystal-liquid fractionation in another, smaller body spawned from the same initial liquid during the impact event that generated the IVA body.

Silica and Pyroxene in IVA Irons; Possible Formation of the IVA Magma by Impact Melting and Reduction of L-LL-Chondrite Materials Followed by Crystallization and Cooling

NASA Technical Reports Server (NTRS)

Wasson, John T.; Matsunami, Yoshiyuki; Rubin, Alan E.

2006-01-01

Group IVA is a large magmatic group of iron meteorites. The mean DELTA O-17 (= delta O-17 - 0.52(raised dot) delta O-18) of the silicates is approx. plus or minus 1.2%o, similar to the highest values in L chondrites and the lowest values in LL chondrites; delta O-18 values are also in the L/LL range. This strongly suggests that IVA irons formed by melting L-LL parental material, but the mean Ni content of IVA irons (83 mg/g) is much lower than that of a presumed L-LL parent (approx. 170 mg/g) and the low-Ca pyroxene present in two IVA meteorites is Fs13, much lower than the Fs20-29 values in L and LL chondrites. Thus, formation from L-LL precursors requires extensive addition of metallic Fe, probably produced by reduction of FeS and FeO. Group IVA also has S/Ni, Ga/Ni, and Ge/Ni ratios that are much lower than those in L-LL chondrites or any chondrite group that preserves nebular compositions, implying loss of these volatile elements during asteroidal processing. We suggest that these reduction and loss processes occurred near the surface of the asteroid during impact heating, and resulted partly from reduction by C, and partly from the thermal dissociation of FeS and FeO with loss of O and S. The hot (approx. 1770 K) low-viscosity melt quickly moved through channels in the porous asteroid to form a core. Two members of the IVA group, Sao Joao Nepomuceno (hereafter, SJN) and Steinbach, contain moderate amounts of orthopyroxene and silica, and minor amounts of low-Ca clinopyroxene. Even though SJN formed after approx. 26% crystallization and Steinbach formed after approx. 77% Crystallization of the IVA core, both could have originated within several tens of meters of the core-mantle interface if 99% of the crystallization occurred from the center outwards. Two other members of the group (Gibeon and Bishop Canyon) contain tabular tridymite, which we infer to have initially formed as veins deposited from a cooling SiO-rich vapor. The silicates were clearly introduced into IVA irons after the initial magma crystallized. Because the y-iron crystals in SJN are typically about 5 cm across, an order of magnitude smaller than in IVA irons that do not contain massive silicates, we infer that the metal was in the gamma-iron field when the silicates were injected. The SJN and Steinbach silicate compositions are near the low-Ca-pyroxene/silica eutectic compositions. We suggest that a tectonic event produced a eutectic-like liquid and injected it together with unmelted pyroxene grains into fissures in the solid metal core. Published estimates of IVA metallographic cooling rates range from 20 to 3000 K/Ma, leading to a hypothesized breakup of the core during a major impact followed by scrambling of the core and mantle debris [Haack, H., Scott, E.R.D., Love, S.G., Brearley, A. 1996. Thermal histories of IVA stony-iron and iron meteorites: evidence for asteroid fragmentation and reaccretion. Geochim. Cosmochim. Acta 60, 3103-3113]. This scrambling model is physically implausible and cannot explain the strong correlation of estimated cooling rates with metal composition. Previous workers concluded that the low-Ca clinopyroxene in SJN and Steinbach formed from protopyroxene by quenching at a cooling rate of 10(sup 12) K/Ma, and suggested that this also supported an impact-scrambling model. This implausible spike in cooling rate by a factor of 10(sup 10) can be avoided if the low-Ca clinopyroxene were formed by a late shock event that converted orthopyroxene to clinopyroxene followed by minimal growth in the clinopyroxene field, probably because melt was also produced. We suggest that metallographic cooling-rate estimates (e.g., based on island taenite) giving similar values throughout the metal compositional range are more plausible, and that the IVA parent asteroid can be modeled by monotonic cooling followed by a high-temperature impact event that introduced silicates into the metal and a low-temperature impact event that partially converted thopyroxene into low-Ca clinopyroxene.

Paleoarchean and Cambrian observations of the geodynamo in light of new estimates of core thermal conductivity

NASA Astrophysics Data System (ADS)

Tarduno, John; Bono, Richard; Cottrell, Rory

2015-04-01

Recent estimates of core thermal conductivity are larger than prior values by a factor of approximately three. These new estimates suggest that the inner core is a relatively young feature, perhaps as young as 500 million years old, and that the core-mantle heat flux required to drive the early dynamo was greater than previously assumed (Nimmo, 2015). Here, we focus on paleomagnetic studies of two key time intervals important for understanding core evolution in light of the revisions of core conductivity values. 1. Hadean to Paleoarchean (4.4-3.4 Ga). Single silicate crystal paleointensity analyses suggest a relatively strong magnetic field at 3.4-3.45 Ga (Tarduno et al., 2010). Paleointenity data from zircons of the Jack Hills (Western Australia) further suggest the presence of a geodynamo between 3.5 and 3.6 Ga (Tarduno and Cottrell, 2014). We will discuss our efforts to test for the absence/presence of the geodynamo in older Eoarchean and Hadean times. 2. Ediacaran to Early Cambrian (~635-530 Ma). Disparate directions seen in some paleomagnetic studies from this time interval have been interpreted as recording inertial interchange true polar wander (IITPW). Recent single silicate paleomagnetic analyses fail to find evidence for IITPW; instead a reversing field overprinted by secondary magnetizations is defined (Bono and Tarduno, 2015). Preliminary analyses suggest the field may have been unusually weak. We will discuss our on-going tests of the hypothesis that this interval represents the time of onset of inner core growth. References: Bono, R.K. & Tarduno, J.A., Geology, in press (2015); Nimmo, F., Treatise Geophys., in press (2015); Tarduno, J.A., et al., Science (2010); Tarduno, J.A. & Cottrell, R.D., AGU Fall Meeting (2014).

Carbon isotope geochemistry of graphite vein deposits from New Hampshire, U.S.A.

NASA Astrophysics Data System (ADS)

Rumble, Douglas, III; Hoering, Thomas C.

1986-06-01

Graphite veins of hydrothermal origin occur throughout central New Hampshire. Veins truncate sillimanite-grade, metasedimentary rocks of Early Devonian-Silurian age and range in size from microscopic to meters in thickness. In addition to graphite, veins may contain quartz, tourmaline, ilmenite, rutile, sillimanite, muscovite or chlorite. Vein mineralogy is generally compatible with wall rock mineral assemblages. Mineralization structures include wall-rock alteration zones, coxcomb graphite crystals on vein walls, and botryoidal, concentrically layered graphite-silicate nodules. The δ13C values of graphite in 14 deposits studied range from - 28%. (PDB) to - 9%. Veins whose textures give evidence of a single stage of mineralization have a narrow range of δ13C values (± 0.2%.). Other veins record successive episodes of graphite precipitation and have ranges of 3-6%. In one sample, adjacent layers of graphite differ by 3%. The wide range of δ13C may be explained by mixing carbon from two crustal reservoirs: biogenic, reduced carbon and carbonate. Precipitation of graphite results from mixing two or more aqueous fluids with different CO 2/CH 4 ratios. Parental fluids are produced by devolatilization during metamorphism. Water-rich fluids with CH4 > CO2 and low δ13C are derived from pelites that contained organic matter; whereas fluids with CO2 > CH4 and high δ13C come from siliceous carbonates.

Effect of ultrasound treatment on the morpho-structural and luminescent characteristics of cerium doped yttrium silicate phosphors

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

Muresan, L.E., E-mail: laura_muresan2003@yahoo.com; Cadis, A.I.; Perhaita, I.

Highlights: • Y{sub 2}SiO{sub 5}:Ce is prepared by gel combustion in ultrasound conditions (US). • Morpho-structural characteristics are revealed based on FTIR, SEM, XRD, BET. • Incorporation of Ce{sup 3+} in X1/X2 type centers depends on preparative conditions. • US treatment increases the luminescent performances up to 151%. - Abstract: Cerium activated yttrium silicate (Y{sub 2}SiO{sub 5}:Ce) phosphors were prepared by gel-combustion, using yttrium–cerium nitrate as oxidizer, aspartic acid as fuel and TEOS as source of silicon. Two modalities for samples preparation were approached namely: the classical gel-combustion and sonication gel-combustion. The ultrasound treatment during the gelling stage has amore » positive effect on the structural and luminescent characteristics of the final product. Therefore, a well crystallized single X2–Y{sub 2}SiO{sub 5} phase phosphor was obtained at 1200 °C. Based on FT-IR and XRD investigations, conversion of X1 to X2–Y{sub 2}SiO{sub 5} phases is observed as the firing temperature is varied (1100 °C, 1200 °C, 1300 °C 1400 °C). The ultrasound treatment leads to smaller particle size and enhances the luminescent performances up to 151% in comparison with samples prepared by classical way.« less

Catalytic crystallization of ices by small silicate smokes at temperatures less than 20K

NASA Technical Reports Server (NTRS)

Moore, M.; Ferrante, R.; Hudson, R.; Tanabe, T.; Nuth, J.

1993-01-01

Samples of methanol and water ices condensed from the vapor onto aluminum substrates at low temperatures (below approximately 80 K) form amorphous ices; annealing at temperatures in excess of 140-155 K is usually required to convert such amorphous samples to crystalline ices. However, we have found that when either methanol or water vapor is deposited on to aluminum substrates that have been coated with a thin (0.1-0.5 mm) layer of amorphous silicate smoke, the ices condense in crystalline form. We believe that crystalline ice forms as the result of energy liberated at the ice/silicate interface perhaps due to weak bonding of the ice at defect sites on the grains and the very high surface to volume ratio and defect density of these smokes. Annealing of amorphous water ice mixed with more volatile components such as methane, carbon monoxide, etc., has been suggested as an efficient way to produce clatherates in the outer solar nebula and thus explain the volatile content of comets and icy satellites of the outer planets. This hypothesis may need to be re-examined if amorphous ice does not form on cold silicate grains.

Calcio-carbonatite melts and metasomatism in the mantle beneath Mt. Vulture (Southern Italy)

NASA Astrophysics Data System (ADS)

Rosatelli, Gianluigi; Wall, Frances; Stoppa, Francesco

2007-12-01

At Mt. Vulture volcano (Basilicata, Italy) calcite globules (5-150 μm) are hosted by silicate glass pools or veins cross-cutting amphibole-bearing, or more common spinel-bearing mantle xenoliths and xenocrysts. The carbonate globules are rounded or elongated and are composed of a mosaic of 2-20 μm crystals, with varying optical orientation. These features are consistent with formation from a quenched calciocarbonatite melt. Where in contact with carbonate amphibole has reacted to form fassaitic pyroxene. Some of these globules contain liquid/gaseous CO 2 bubbles and sulphide inclusions, and are pierced by quench microphenocrysts of silicate phases. The carbonate composition varies from calcite to Mg-calcite (3.8-5.0 wt.% MgO) both within the carbonate globules and from globule to globule. Trace element contents of the carbonate, determined by LAICPMS, are similar to those of carbonatites worldwide including ΣREE up to 123 ppm. The Sr-Nd isotope ratios of the xenolith carbonate are similar to the extrusive carbonatite and silicate rocks of Mt. Vulture testifying to derivation from the same mantle source. Formation of immiscibile silicate-carbonatite liquids within mantle xenoliths occurred via disequilibrium immiscibility during their exhumation.

The solubility of carbon monoxide in silicate melts at high pressures and its effect on silicate phase relations. [in terrestrial and other planetary interiors

NASA Technical Reports Server (NTRS)

Eggler, D. H.; Mysen, B. O.; Hoering, T. C.; Holloway, J. R.

1979-01-01

Autoradiographic analysis and gas chromatography were used to measure the solubility in silicate melts of CO-CO2 vapors (30 to 40% CO by thermodynamic calculation) in equilibrium with graphite at temperatures up to 1700 deg C and pressures to 30 kbar. At near-liquidus temperatures CO-CO2 vapors were found to be slightly more soluble than CO2 alone. As a result of the apparently negative temperature dependence of CO solubility, the solubility of CO-CO2 at superliquidus temperatures is less than that of CO2. Melting points of two silicates were depressed more by CO than by CO2. Phase boundary orientations suggest that CO/CO + CO2 is greater in the liquid than in the vapor. The effect of the presence of CO on periodotite phase relations was investigated, and it was found that melts containing both CO and CO2 are nearly as polymerized as those containing only CO2. These results suggest that crystallization processes in planetary interiors can be expected to be about the same, whether the melts contain CO2 alone or CO2 and CO.

Long term mechanical properties of alkali activated slag

NASA Astrophysics Data System (ADS)

Zhu, J.; Zheng, W. Z.; Xu, Z. Z.; Leng, Y. F.; Qin, C. Z.

2018-01-01

This article reports a study on the microstructural and long-term mechanical properties of the alkali activated slag up to 180 days, and cement paste is studied as the comparison. The mechanical properties including compressive strength, flexural strength, axis tensile strength and splitting tensile strength are analyzed. The results showed that the alkali activated slag had higher compressive and tensile strength, Slag is activated by potassium silicate (K2SiO3) and sodium hydroxide (NaOH) solutions for attaining silicate modulus of 1 using 12 potassium silicate and 5.35% sodium hydroxide. The volume dosage of water is 35% and 42%. The results indicate that alkali activated slag is a kind of rapid hardening and early strength cementitious material with excellent long-term mechanical properties. Single row of holes block compressive strength, single-hole block compressive strength and standard solid brick compressive strength basically meet engineering requirements. The microstructures of alkali activated slag are studied by X-ray diffraction (XRD). The hydration products of alkali-activated slag are assured as hydrated calcium silicate and hydrated calcium aluminate.

High-Temperature Controlled Redox Crystallization Studies

NASA Technical Reports Server (NTRS)

Williams, R. J.

1985-01-01

The crystallization of silicates containing redox sensitive ions (e.g., Fe, Ti, Ce) must be performed under controlled and known redox conditions in order to obtain the maximum scientific benefit from experimental study. Furthermore, many compositions crystallize dense phases which settle during ground-based experiments. This settling influences the texture and chemical evolution of the crystallizing system. The purpose of this investigation is to develop a test system in which controlled redox experiments can be performed in the microgravity environment. The system will use solid ceramic oxygen electrolyte cells for control, measurements, and production of the required redox conditions. A preliminary design for a prototype is developed, the electrolyte and furnace tested, and a tentative protocol for experiment developed. The control parameter is to be established and a laboratory prototype built.

Studies of Nucleation, Growth, Specific Heat, and Viscosity of Undercooled Melts of Quasicrystals and Polytetrahedral-Phase-Forming Alloys

NASA Technical Reports Server (NTRS)

Kelton, K. F.; Croat, T. K.; Gangopadhyay, A.; Holland-Moritz, D.; Hyers, Robert W.; Rathz, Thomas J.; Robinson, Michael B.; Rogers, Jan R.

2001-01-01

Undercooling experiments and thermal physical property measurements of metallic alloys on the International Space Station (ISS) are planned. This recently-funded research focuses on fundamental issues of the formation and structure of highly-ordered non-crystallographic phases (quasicrystals) and related crystal phases (crystal approximants), and the connections between the atomic structures of these phases and those of liquids and glasses. It extends studies made previously by us of the composition dependence of crystal nucleation processes in silicate and metallic glasses, to the case of nucleation from the liquid phase. Motivating results from rf-levitation and drop-tube measurements of the undercooling of Ti/Zr-based liquids that form quasicrystals and crystal approximants are discussed. Preliminary measurements by electrostatic levitation (ESL) are presented.

The influence of Si in Ni on the interface modification and the band alignment between Ni and alumina

NASA Astrophysics Data System (ADS)

Yoshitake, Michiko; Nemšák, Slavomír; Skála, Tomáš; Tsud, Nataliya; Matolín, Vladimír; Prince, Kevin C.

2018-06-01

The influence of a small amount of Si in a Ni single crystal on the interface formation between aluminum oxide and Ni has been investigated. The interface was formed by in-situ growth of the oxide by simultaneous supply of Al and oxygen onto Ni(1 1 1) in an ultrahigh vacuum chamber equipped with XPS apparatus. The oxide growth and the interface formation were compared between Si-containing Ni(1 1 1) and pure Ni(1 1 1). It was revealed that Si segregated on the surface of Ni and oxidized, forming an epitaxial thin alumino-silicate film. Valence band spectra demonstrated that the band offset between the oxide and Ni (energy level difference between the valence band top and the Fermi level) is different due to the oxidized Si segregation at the interface.

Geodynamo, solar wind, and magnetopause 3.4 to 3.45 billion years ago.

PubMed

Tarduno, John A; Cottrell, Rory D; Watkeys, Michael K; Hofmann, Axel; Doubrovine, Pavel V; Mamajek, Eric E; Liu, Dunji; Sibeck, David G; Neukirch, Levi P; Usui, Yoichi

2010-03-05

Stellar wind standoff by a planetary magnetic field prevents atmospheric erosion and water loss. Although the early Earth retained its water and atmosphere, and thus evolved as a habitable planet, little is known about Earth's magnetic field strength during that time. We report paleointensity results from single silicate crystals bearing magnetic inclusions that record a geodynamo 3.4 to 3.45 billion years ago. The measured field strength is approximately 50 to 70% that of the present-day field. When combined with a greater Paleoarchean solar wind pressure, the paleofield strength data suggest steady-state magnetopause standoff distances of < or = 5 Earth radii, similar to values observed during recent coronal mass ejection events. The data also suggest lower-latitude aurora and increases in polar cap area, as well as heating, expansion, and volatile loss from the exosphere that would have affected long-term atmospheric composition.

Petrogenesis of mid-Miocene rhyolites from the Idaho-Oregon-Nevada region, USA: Implications from feldspar Sr and Pb isotope data

NASA Astrophysics Data System (ADS)

Wypych, A.; Hart, W. K.

2012-12-01

The Idaho-Oregon-Nevada (ION) region provides an excellent natural laboratory for studying the complex processes that form continental crust. During the Oligocene-Miocene, the ION region underwent widespread extension and volcanism with bimodal (silicic and mafic) volcanism dominating the mid-Miocene [1]. This bimodal volcanism is temporally related to the main Columbia River flood basalt activity to the north, and initiated with mafic eruptions at ~17 Ma, followed closely by silicic magmatism at ~16.5 Ma. This intimate link between mafic and silicic activity continued until ~13 Ma. The ION region is situated on a boundary between Proterozoic cratonic lithosphere to the east and Mesozoic accreted terrains to the west as defined by Sr and Nd isotopic compositions. In this region, however, the boundary is not sharp and distinctive, but rather forms a heterogeneous "transitional zone" between the two lithospheric domains. Another feature adding to the complexity of this region is the fact that it lies at the junction of two major volcanic trends: the Snake River Plain- Yellowstone (SRP-Y) progressing in time and space to the northeast and the High Lava Plains - Newberry (HPL-N) progressing to the northwest. The ION region volcanism as well as the SRP-Y and HLP-N volcanic trends is caused by mantle upwelling behind the subducting Juan de Fuca slab, voluminous mafic magma injections into the crust, melting of spatially, temporally, and compositionally heterogeneous crust, and mixing of the primitive and more evolved products [1,2,3]. An ongoing petrographic, major and trace element and Sr-Nd-Pb-Hf isotope investigation of 24 pairs of glass separates and whole rock samples from five ION silicic centers representing a west (off-craton) to east (on-craton) transect across this zone of transitional lithosphere provides evidence of open system processes involved in the production of the silicic material as well as spatial, temporal and compositional diversity within and between the silicic centers [4]. The samples demonstrate involvement of fractional crystallization of less evolved mafic material along with assimilation of partial crustal melts, however the degree of involvement of each process remains difficult to quantify, as do the contributions from mantle and crustal reservoirs. To further investigate these issues, we here present petrological, major and trace element, along with lead and strontium isotopic examination of feldspar crystals from three selected silicic centers: 1) westernmost, off-craton, 2) central region of transitional lithosphere, and 3) eastern transition zone to on-craton. The textural evidence for open system behavior is only partially supported by bulk feldspar Pb and Sr isotopic compositions where the differences between whole rock, glass and crystal separate aliquots of the same eruptive units are a maximum of 0.3 in 208Pb/204Pb, 0.2 in 206Pb/204Pb and 0.002 in 87Sr/86Sr. Models combining these results with the spatial availability of geochemically distinct magma source reservoirs will be discussed. [1] Brueseke et al. (2008) Bull. Volc. 70, 343-360. [2] Nash et al. (2006) Earth Plant. Sci. Lett. 247, 143-156. [3] Christiansen and McCurry (2008) Bull. Volc., 70, 251-267. [4] Wypych and Hart (2011) Min. Magazine, 75 (3), 2186.

Characteristics of Young Rhyolites at Taupo, New Zealand: Implications for the Sub-Surface Plutonic System

NASA Astrophysics Data System (ADS)

Wilson, C. J.; Charlier, B. L.

2007-12-01

The young history of Taupo volcano captures the growth and destruction in the 26.5 ka ca. 530 km3 Oruanui eruption of a large rhyolitic magma body, together with the subsequent rejuvenation of magma sources below the volcano. Integration of field information with petrological and isotopic studies at the whole-pumice and single- crystal scales provide a picture of this history. Several important contrasts are inferred to exist between Taupo and comparably-sized, long-lived silicic foci such at Long Valley and in the Bishop Tuff. At Taupo the following are demonstrable. 1. Even in crystal-poor rhyolites like the Oruanui, many grains are inherited antecrysts or xenocrysts. The Oruanui crystal-poor rhyolite body was an open system, with influxes of crystals (plus melt) from remobilised older crystal mush, melted metasedimentary country rocks and plutonics, and crystal-poor basaltic to andesitic magmas. 2. All the Taupo rhyolites were well mixed prior to eruption, and there are no gradients in the eruption products to suggest that the holding chamber(s) were stratified to any extent. 3. Mafic magmas rose into, interacted with, and ponded on the floors of crystal-poor rhyolite in the Oruanui and Waimihia (3.5 ka) examples, again implying that the chamber floor was sharply defined, not a gradual progression down into a more crystal- rich root zone. 4. Pre-Oruanui activity involved contrasting magma types being generated simultaneously, but erupting from geographically separated vents. Post-Oruanui activity has seen (subtly) contrasting magma groups being erupted from vents in the same geographic area, but separated in time. The Oruanui and post-Oruanui magmas are different and do not appear to be related by consanguinity or by mixing - the Oruanui eruption effectively destroyed its magma body. These features are consistent with rhyolite magma generation at Taupo that is exceptionally fast, driven by high fluxes of mafic magmas into a highly heterogeneous crustal melange of metasedimentary and igneous lithologies. There is no voluminous crystal mush body to act as a buffer for the rhyolite generation processes; the eruption frequency at Taupo gives no chance for such a body to develop.

Using experimental petrology to constrain genesis of wet, silicic magmas in the Tonga-Kermadec island arc

NASA Astrophysics Data System (ADS)

Brens, R.; Rushmer, T. A.; Turner, S.; Adam, J.

2012-12-01

The Tongan arc system is comprised of a pair of island chains, where the western chain is the active volcanic arc. A range of rock suites, from basaltic andesites (53-56% SiO2) to dacites (64-66% SiO2), has been recovered from Late, Tofua and Fonualei in the Tonga-Kermadec primitive island arc system. For which the question arises: What is the mechanism that allows for silicic magmas to develop in a primitive island arc system? Caufield et al. (2012) suggest that fractional crystallization of a multi magma chamber process, with varying depth, is responsible for the silicic magma generation in this arc. Models such as this one have been proposed and experimentally tested in other systems (Novarupta, Alaska) to explain the origin of these silicic rocks. Our Tongan suite of rocks has had a full geochemical analysis for majors, traces and isotopes. The lavas from Tofua and Late are Fe-rich and have low concentrations of K, Rb, Ba, Zr, REE, Pb and U. However, experimental studies are needed to complement the extensive geochemical analysis done on the Tongan arc. Former geochemical work done on the igneous rocks from both of these volcanic suites from this arc suggests that the source of these rocks extend from 1.5-5.5 km in depth (Caulfield et al., 2012). Here, we present an experimental study of the phase equilibria on a natural andesitic sample (Late 1, from Ewart et al., 1975) from the island of Late. Experiments were run using the temperature constraints between 900 to 1220oC, pressure from 5 to 25 kbars and H2O addition of mostly 5wt% (but some results were obtained at 2wt% in the rocks). In the presence of 5 wt% water, phase equilibria of these experiments show the garnet stability field at >10 kb for 900 oC and increases with increasing temperature, while plagioclase enters at lower pressures when garnet exits. Experimental results currently suggests, at lower temperatures (900-950oC), a fractional crystallization relationship due to shallow level pressures of these rocks and further reinforcing Brophy's (2009) model of crystal fractionation of basalt to dacite in the presence of water, as an important process for which silica-rich magmas are produced within a primitive oceanic island arc.

How To Use Crystallographic Information in Teaching First-Year Chemistry.

ERIC Educational Resources Information Center

Bevan, D. J. M.; And Others

1988-01-01

Emphasizes the role that crystallography plays and has played in building up the body of chemical fact. Shows how the teaching of much of this material is illuminated by reference to crystal structures and crystallochemical relationships in all areas of chemistry. Discusses close packing, silicate structures, and salt hydrates. (CW)

Formation of the Fe,Mg-Silicates, Fe0, and Graphite (Diamond) Assemblage as a Result of Cohenite Oxidation under Lithospheric Mantle Conditions

NASA Astrophysics Data System (ADS)

Bataleva, Yu. V.; Palyanov, Yu. N.; Borzdov, Yu. M.; Zdrokov, E. V.; Novoselov, I. D.; Sobolev, N. V.

2018-03-01

Experimental studies in the Fe3C-SiO2-MgO system ( P = 6.3 GPa, T = 1100-1500°C, t = 20-40 h) have been carried out. It has been established that carbide-oxide interaction resulted in the formation of Fe-orthopyroxene, graphite, wustite, and cohenite (1100 and 1200°C), as well as a Fe-C-O melt (1300-1500°C). The main processes occurring in the system at 1100 and 1200°C are the oxidation of cohenite, the extraction of carbon from carbide, and the crystallization of metastable graphite, as well as the formation of ferrosilicates. At T ≥ 1300°C, graphite crystallization and diamond growth occur as a result of the redox interaction of a predominantly metallic melt (Fe-C-O) with oxides and silicates. The carbide-oxide interaction studied can be considered as the basis for modeling a number of carbon-producing processes in the lithospheric mantle at fO2 values near the iron-wustite buffer.

Bioactive Glass-Ceramic Scaffolds from Novel ‘Inorganic Gel Casting’ and Sinter-Crystallization

PubMed Central

Elsayed, Hamada; Rincón Romero, Acacio; Ferroni, Letizia; Gardin, Chiara; Zavan, Barbara; Bernardo, Enrico

2017-01-01

Highly porous wollastonite-diopside glass-ceramics have been successfully obtained by a new gel-casting technique. The gelation of an aqueous slurry of glass powders was not achieved according to the polymerization of an organic monomer, but as the result of alkali activation. The alkali activation of a Ca-Mg silicate glass (with a composition close to 50 mol % wollastonite—50 mol % diopside, with minor amounts of Na2O and P2O5) allowed for the obtainment of well-dispersed concentrated suspensions, undergoing progressive hardening by curing at low temperature (40 °C), owing to the formation of a C–S–H (calcium silicate hydrate) gel. An extensive direct foaming was achieved by vigorous mechanical stirring of partially gelified suspensions, comprising also a surfactant. The open-celled structure resulting from mechanical foaming could be ‘frozen’ by the subsequent sintering treatment, at 900–1000 °C, causing substantial crystallization. A total porosity exceeding 80%, comprising both well-interconnected macro-pores and micro-pores on cell walls, was accompanied by an excellent compressive strength, even above 5 MPa. PMID:28772531

Effects of Irradiation on Albite's Chemical Durability.

PubMed

Hsiao, Yi-Hsuan; La Plante, Erika Callagon; Krishnan, N M Anoop; Le Pape, Yann; Neithalath, Narayanan; Bauchy, Mathieu; Sant, Gaurav

2017-10-19

Albite (NaAlSi 3 O 8 ), a framework silicate of the plagioclase feldspar family and a common constituent of felsic rocks, is often present in the siliceous mineral aggregates that compose concrete. When exposed to radiation (e.g., in the form of neutrons) in nuclear power plants, the crystal structure of albite can undergo significant alterations. These alterations may degrade its chemical durability. Indeed, careful examinations of Ar + -implanted albite carried out using Fourier transform infrared spectroscopy (FTIR) and molecular dynamics simulations show that albite's crystal structure, upon irradiation, undergoes progressive disordering, resulting in an expansion in its molar volume (i.e., a reduction of density) and a reduction in the connectivity of its atomic network. This loss of network connectivity (i.e., rigidity) results in an enhancement of the aqueous dissolution rate of albite-measured using vertical scanning interferometry (VSI) in alkaline environments-by a factor of 20. This enhancement in the dissolution rate (i.e., reduction in chemical durability) of albite following irradiation has significant impacts on the durability of felsic rocks and of concrete containing them upon their exposure to radiation in nuclear power plant (NPP) environments.

Elasticity of stishovite at high pressure

NASA Astrophysics Data System (ADS)

Li, Baosheng; Rigden, Sally M.; Liebermann, Robert C.

1996-08-01

The elastic-wave velocities of stishovite, the rutile-structured polymorph of SiO 2, were measured to 3 GPa at room temperature in a piston cylinder apparatus using ultrasonic interferometry on polycrystalline samples. These polycrystalline samples (2-3 mm in length and diameter) were hot-pressed at 14 GPa and 1050°C in a 2000 ton uniaxial split-sphere apparatus (USSA-2000) using fused silica rods as starting material. They were characterized as low porosity (less than 1%), single phase, fine grained, free of cracks and preferred orientation, and acoustically isotropic by using density measurement, X-ray diffraction, scanning electron microscopy, and bench-top velocity measurements. On the basis of subsequent in situ X-ray diffraction study at high P and T on peak broadening on similar specimens, it is evident that the single crystal grains within these polycrystalline aggregates are well equilibrated and that these specimens are free of residual strain. P- and S-wave velocities measured at 1 atm are within 1.5% of the Hashin-Shtrikman bounds calculated from single-crystal elastic moduli. Measured pressure derivatives of the bulk and shear moduli, K' 0 = 5.3 ± 0.1 and G' 0 = 1.8 ± 0.1, are not unusual compared with values measured for other transition zone phases such as silicate spinel and majorite garnet. Isothermal compression curves calculated with the measured values of K0 and K' 0 agree well with experimental P-V data to 16 GPa. The experimental value of dG /dP is in excellent agreement with predictions based on elasticity systematics. Theoretical models are not yet able to replicate the measured values of K' 0 and G' 0.

Ultra-selective high-flux membranes from directly synthesized zeolite nanosheets

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

Jeon, Mi Young; Kim, Donghun; Kumar, Prashant

A zeolite with structure type MFI is an aluminosilicate or silicate material that has a three-dimensionally connected pore network, which enables molecular recognition in the size range 0.5-0.6 nm. These micropore dimensions are relevant for many valuable chemical intermediates, and therefore MFI-type zeolites are widely used in the chemical industry as selective catalysts or adsorbents. As with all zeolites, strategies to tailor them for specific applications include controlling their crystal size and shape. Nanometre-thick MFI crystals (nanosheets) have been introduced in pillared and self-pillared (intergrown) architectures, offering improved mass-transfer characteristics for certain adsorption and catalysis applications. Moreover, single (non-intergrown andmore » nonlayered) nanosheets have been used to prepare thin membranes that could be used to improve the energy efficiency of separation processes. However, until now, single MFI nanosheets have been prepared using a multi-step approach based on the exfoliation of layered MFI9,15, followed by centrifugation to remove non-exfoliated particles. This top-down method is time-consuming, costly and low-yield and it produces fragmented nanosheets with submicrometre lateral dimensions. Alternatively, direct (bottom-up) synthesis could produce high-aspect-ratio zeolite nanosheets, with improved yield and at lower cost. Here we use a nanocrystal-seeded growth method triggered by a single rotational intergrowth to synthesize high-aspect-ratio MFI nanosheets with a thickness of 5 nanometres (2.5 unit cells). These high-aspect-ratio nanosheets allow the fabrication of thin and defect-free coatings that effectively cover porous substrates. Finally, these coatings can be intergrown to produce high-flux and ultra-selective MFI membranes that compare favourably with other MFI membranes prepared from existing MFI materials (such as exfoliated nanosheets or nanocrystals).« less

Ultra-selective high-flux membranes from directly synthesized zeolite nanosheets

DOE PAGES

Jeon, Mi Young; Kim, Donghun; Kumar, Prashant; ...

2017-03-15

A zeolite with structure type MFI is an aluminosilicate or silicate material that has a three-dimensionally connected pore network, which enables molecular recognition in the size range 0.5-0.6 nm. These micropore dimensions are relevant for many valuable chemical intermediates, and therefore MFI-type zeolites are widely used in the chemical industry as selective catalysts or adsorbents. As with all zeolites, strategies to tailor them for specific applications include controlling their crystal size and shape. Nanometre-thick MFI crystals (nanosheets) have been introduced in pillared and self-pillared (intergrown) architectures, offering improved mass-transfer characteristics for certain adsorption and catalysis applications. Moreover, single (non-intergrown andmore » nonlayered) nanosheets have been used to prepare thin membranes that could be used to improve the energy efficiency of separation processes. However, until now, single MFI nanosheets have been prepared using a multi-step approach based on the exfoliation of layered MFI9,15, followed by centrifugation to remove non-exfoliated particles. This top-down method is time-consuming, costly and low-yield and it produces fragmented nanosheets with submicrometre lateral dimensions. Alternatively, direct (bottom-up) synthesis could produce high-aspect-ratio zeolite nanosheets, with improved yield and at lower cost. Here we use a nanocrystal-seeded growth method triggered by a single rotational intergrowth to synthesize high-aspect-ratio MFI nanosheets with a thickness of 5 nanometres (2.5 unit cells). These high-aspect-ratio nanosheets allow the fabrication of thin and defect-free coatings that effectively cover porous substrates. Finally, these coatings can be intergrown to produce high-flux and ultra-selective MFI membranes that compare favourably with other MFI membranes prepared from existing MFI materials (such as exfoliated nanosheets or nanocrystals).« less

Localized Rejuvenation of a Crystal Mush Recorded in Zircon Temporal and Compositional Variation at the Lassen Volcanic Center, Northern California

PubMed Central

Klemetti, Erik W.; Clynne, Michael A.

2014-01-01

Zircon ages and trace element compositions from recent silicic eruptions in the Lassen Volcanic Center (LVC) allow for an evaluation of the timing and conditions of rejuvenation (reheating and mobilization of crystals) within the LVC magmatic system. The LVC is the southernmost active Cascade volcano and, prior to the 1980 eruption of Mount St. Helens, was the site of the only eruption in the Cascade arc during the last century. The three most recent silicic eruptions from the LVC were very small to moderate-sized lava flows and domes of dacite (1915 and 27 ka eruptions of Lassen Peak) and rhyodacite (1.1 ka eruption of Chaos Crags). These eruptions produced mixed and mingled lavas that contain a diverse crystal cargo, including zircon. 238U-230Th model ages from interior and surface analyses of zircon reveal ages from ∼17 ka to secular equilibrium (>350 ka), with most zircon crystallizing during a period between ∼60–200 ka. These data support a model for localized rejuvenation of crystal mush beneath the LVC. This crystal mush evidently is the remnant of magmatism that ended ∼190 ka. Most zircon are thought to have been captured from “cold storage” in the crystal mush (670–725°C, Hf >10,000 ppm, Eu/Eu* 0.25–0.4) locally remobilized by intrusion of mafic magma. A smaller population of zircon (>730°C, Hf <10,000 ppm, Eu/Eu* >0.4) grew in, and are captured from, rejuvenation zones. These data suggest the dominant method to produce eruptible melt within the LVC is small-scale, local rejuvenation of the crystal mush accompanied by magma mixing and mingling. Based on zircon stability, the time required to heat, erupt and then cool to background conditions is relatively short, lasting a maximum of 10 s–1000 s years. Rejuvenation events in the LVC are ephemeral and permit eruption within an otherwise waning and cooling magmatic body. PMID:25470726

Gels composed of sodium-aluminum silicate, Lake Magadi, Kenya

USGS Publications Warehouse

Eugster, H.P.; Jones, B.F.

1968-01-01

Sodium-aluminum silicate gels are found in surftcial deposits as thick as 5 centimeters in the Magadi area of Kenya. Chemical data indicate they are formed by the interaction of hot alkaline springwaters (67?? to 82??C; pH, about 9) with alkali trachyte flows and their detritus, rather than by direct precipitation. In the process, Na2O is added from and silica is released to the saline waters of the springs. Algal mats protect the gels from erosion and act as thermal insulators. The gels are probably yearly accumulates that are washed into the lakes during floods. Crystallization of these gels in the laboratory yields analcite; this fact suggests that some analcite beds in lacustrine deposits may have formed from gels. Textural evidence indicates that cherts of rocks of the Pleistocene chert series in the Magadi area may have formed from soft sodium silicate gels. Similar gels may have acted as substrates for the accumulation and preservation of prebiological organic matter during the Precambrian.

Ar-Ar and I-Xe Ages of Caddo County and Thermal History of IAB Iron Meteorites

NASA Technical Reports Server (NTRS)

Bogard, Donald D.; Garrison, Daniel H.; Takeda, Hiroshi

2005-01-01

Inclusions in IAB iron meteorites include non-chondritic silicate and those with more primitive chondritic silicate composition. Coarse-grained gabbroic material rich in plagioclase and diopside occurs in the Caddo County IAB iron meteorite and represents a new type of chemically differentiated, extra-terrestrial, andesitic silicate. Other parts of Caddo contain mostly andesitic material. Caddo thus exhibits petrologic characteristics of parent body metamorphism of a chondrite-like parent and inhomogeneous segregation of melts. Proposed IAB formation models include parent body partial melting and fractional crystallization or incomplete differentiation due to internal heat sources, and impact/induced melting and mixing. Benedix et al. prefer a hybrid model whereby the IAB parent body largely melted, then underwent collisional breakup, partial mixing of phases, and reassembly. Most reported 129I- Xe-129 ages of IABs are greater than 4.56 Gyr and a few are greater than or = 4.567 Gyr. These oldest ages exceed the 4.567 Gyr Pb-Pb age of Ca, Al-rich inclusions in primitive meteorites,

Reflectance spectra of 'featureless' materials and the surface mineralogies of M- and E-class asteroids

NASA Technical Reports Server (NTRS)

Cloutis, Edward A.; Smith, Dorian G.; Lambert, Richard St. J.; Gaffey, Michael J.

1990-01-01

In a search for diagnostic spectral parameters which can be used to distinguish different materials on the surface of asteroids and to provide information on the detection limits for mafic silicates, the 0.3- to 2.6-micron reflectance spectra of meteoritic enstatite (nearly pure MgSiO3), iron meteorite metal, magnetite, and amorphous carbon as well as various mixtures of these materials with mafic silicates were examined. Results are presented on the dependence of the spectral detectability of mafic silicates associated with metal, carbon, and magnetite on the particle sizes of the phases, their chemistries, crystal structures, and abundances. It is shown that the observational data for a representative M-class asteroid, (16) Psyche, are largely consistent with a fine-grained metal-rich surface assemblage, whereas data for the E-class asteroid (44) Nysa indicate that its surface is composed of fine-grained material similar to enstatite achondrites, with a small amount of material comparable to the chondritic inclusions found in the Cumberland Falls aubrite.

A SEM-ATEM and stable isotope study of carbonates from the Haughton impact crater, Canada

NASA Astrophysics Data System (ADS)

Martinez, Isabelle; Agrinier, Pierre; Schärer, Urs; Javoy, Marc

1994-02-01

Highly and intermediately shocked carbonate-rich fragments of the allochtonous polymict breccia from the Haughton impact crater (Canada) were studied by Scanning Electron Microscopy (SEM), Analytical Transmission Electron Microscopy (ATEM) and analyses of carbon and oxygen stable isotopes ( δ13C and δ18O). In areas subjected to severe shock conditions, carbonates represent only about 10 vol% of the shocked samples and they are located in holes and fractures within a matrix of SiO 2-rich glass. Shock features are absent in these crystals. High-temperature reactions have occurred between molten silicates and carbonates, producing Ca sbnd Mg-rich glasses, or crystalline phases such as augite and larnite (Ca 2SiO 4). The carbonates are dominated by calcite and they generally have significantly positive δ13C, ranging up to +9‰, with a weighted average value of +1.75‰. Their δ18O values range between +15‰ and +20‰ and they are about 5‰ lower than in unshocked reference sediments, a trend consistent with that resulting from silicate-carbonate reactions. The microstructures of the carbonates suggest that they did not undergo shock conditions but, instead, were produced by back-reactions between impact-released CO 2 and highly reactive residual oxides. Such a process would introduce isotope fractionations, which might explain the positive δ13C values observed. A simple kinetic fractionation model involving a Rayleigh distillation process is used to estimate the CO 2 fraction actually lost from the carbonates. It appears that this fraction is related to the amount of high-temperature carbonate-silicate reactions. Moderately shocked fragments from other areas of the polymict breccia consist of 40-81 vol% carbonates. Their δ13C values lie in the range of unshocked reference sediments between -2‰ and -4‰, whereas their δ18O values are by about 5‰ lower than in the unshocked equivalents. No evidence for important decarbonatization is observed from 13C, and 18O is again buffered by isotope exchange reactions between molten silicates and carbonate crystals producing Ca and Mg enriched SiO 2 glass and Ca sbnd Mg silicate crystals such as monoclinic pigeonite, which is indicative of fast cooling. This study indicates that significant evidence for outgassing is limited to a narrow zone in the centre of the crater, where peak shock pressures reached 50-60 GPa. Moreover, we suggest that, within this area, a large fraction of the shock-produced gas recombines with the highly reactive residual oxides and, in consequence, that such back-reactions might be a general mechanism for retaining impact-produced volatiles during impact events.

Shock, Post-Shock Annealing, and Post-Annealing Shock in Ureilites

NASA Technical Reports Server (NTRS)

Rubin, Alan E.

2006-01-01

The thermal and shock histories of ureilites can be divided into four periods: 1) formation, 2) initial shock, 3) post-shock annealing, and 4) post-annealing shock. Period 1 occurred approx.4.55 Ga ago when ureilites formed by melting chondritic material. Impact events during period 2 caused silicate darkening, undulose to mosaic extinction in olivines, and the formation of diamond, lonsdaleite, and chaoite from indigenous carbonaceous material. Alkali-rich fine-grained silicates may have been introduced by impact injection into ureilites during this period. About 57% of the ureilites were unchanged after period 2. During period 3 events, impact-induced annealing caused previously mosaicized olivine grains to become aggregates of small unstrained crystals. Some ureilites experienced reduction as FeO at the edges of olivine grains reacted with C from the matrix. Annealing may also be responsible for coarsening of graphite in a few ureilites, forming euhedral-appearing, idioblastic crystals. Orthopyroxene in Meteorite Hills (MET) 78008 may have formed from pigeonite by annealing during this period. The Rb-Sr internal isochron age of approx.4.0 Ga for MET 78008 probably dates the annealing event. At this late date, impacts are the only viable heat source. About 36% of ureilites experienced period 3 events, but remained unchanged afterwards. During period 4, approx.7% of the ureilites were shocked again, as is evident in the polymict breccia, Elephant Moraine (EET) 83309. This rock contains annealed mosaicized olivine aggregates composed of small individual olivine crystals that exhibit undulose extinction. Ureilites may have formed by impact-melting chondritic material on a primitive body with heterogeneous O isotopes. Plagioclase was preferentially lost from the system due to its low impedance to shock compression. Brief melting and rapid burial minimized the escape of planetary-type noble gases from the ureilitic melts. Incomplete separation of metal from silicates during impact melting left ureilites with relatively high concentrations of trace siderophile elements.

Teaching Introductory Mineralogy With the GeoWall

NASA Astrophysics Data System (ADS)

Anderson, C. D.; Haymon, R. M.

2003-12-01

Mineralogy, like many topics in Earth Sciences, contains inherently three-dimensional topics that are difficult to teach. Concepts such as crystal symmetry and forms, Miller indices, the polymerization of silica tetrahedra and resulting structures of silicate mineral groups, and the interaction of light and minerals are particularly difficult. Two-dimensional diagrams are limited in their effectiveness, and physical models, while effective, are expensive and do not work as well in large class settings. The GeoWall system brings the effectiveness of physical models to the large classroom. In Fall 2003, we will integrate the GeoWall into our introductory mineralogy classes at UCSB using a combination of commercial software, atomic structure models available on the web, and custom content created in-house. The commercial software SHAPE (www.shapesoftware.com) allows users to build and display crystal shapes and their symmetry. Though not designed for the GeoWall, the software's stereopair display mode works perfectly on the system. Using the Chime web browser plug-in (www.mdl.com), computer models of silicate minerals available from the Virtual Museum of Minerals and Molecules (www.soils.umn.eduvirtual_museum) provide an interactive display of silicate mineral structure that illustrates the tetrahedral framework. Again, while not developed for the GeoWall, the Chime plug-in works seamlessly with the GeoWall hardware. 3-D GeoWall images that display light paths through minerals, and reveal relationships between crystal symmetry and optical indicatrix properties, have been developed in-house using a combination of SHAPE and 3D modeling software. The 3-D GeoWall images should convey in an instant these difficult concepts that students historically have struggled to visualize. Initial assessment of the GeoWall's effectiveness as a mineralogy teaching aid at UCSB in Fall 2003 will come from the instructor's impressions and by comparing test scores with classes from previous years.

Exploring Iron Silicate Precursors of Ancient Iron Formations through Rock Record, Laboratory and Field Analogue Investigations

NASA Astrophysics Data System (ADS)

Johnson, J. E.; Rasmussen, B.; Muhling, J.; Benzerara, K.; Jezequel, D.; Cosmidis, J.; Templeton, A. S.

2016-12-01

In direct contrast to today's oceans, iron-rich chemical precipitates dominate the deep marine sedimentary record > 2.3 billion years ago. The deposition of these minerals resulted in massive iron formations and indicate that the ocean was previously ferruginous and largely anoxic. To precipitate and concentrate iron in the sediments, many hypotheses have centered on the oxidation of soluble Fe(II) to solid Fe(III)-oxyhydroxides; these ideas have stimulated extensive research using iron-oxidizing bacteria to produce Fe(III)-oxides and trace metal sorption experiments on Fe(III)-oxides, leading to inferences of trace metal availability and implications for enzymatic and microbial evolution as well as pO2 levels and seawater chemistry. However, recent discoveries of disseminated iron-silicate nanoparticles in early-silicifying chert indicate that iron-silicates may have instead been the primary precipitates from these Archean ferruginous oceans (Rasmussen et al, 2015). Considering the significant paradigm shift this discovery implies for interpretations of Archean elemental cycling, redox state and potential microbial metabolisms, we investigated these iron-silicate inclusions and their implications for ancient seawater chemistry in a multi-faceted approach using spectroscopic- and diffraction-based techniques. The crystal structure, Fe oxidation state and Fe coordination environment of iron-silicate nanoparticles have been interrogated using microscale X-ray absorption spectroscopy, TEM and nanoscale scanning transmission X-ray microscopy. To further explore the chemical and potential biological controls on iron-silicate formation, we have also performed laboratory experiments to mimic Archean seawater and precipitate iron-bearing silicate minerals under abiotic conditions and in the presence of iron-oxidizing bacteria. In a complementary study, sediments from a natural Archean analogue system were sampled to determine if iron-silicate minerals form in Mexican crater lakes that are variably iron- and silica-rich. As we continue to probe the mechanism of Fe(II/III)-silicate formation, we can constrain the activity of silica, pH, and pO2 on early Earth and describe any potential influence of microbial activity on the precipitation of these phases.

Zircon U-Th and U-Pb Ages From Quaternary Silicic Volcanic and Plutonic Rocks, and Their Bearing on Granitoid Batholiths

NASA Astrophysics Data System (ADS)

Bacon, C. R.

2007-12-01

In the ten years since publication of M. Reid et al.'s seminal paper on zircon ages from rhyolites (EPSL 150:2-39, 1997) >20 papers have appeared on SIMS 238U-230Th and 238U-206Pb geochronology of zircon from silicic volcanic rocks, plutonic xenoliths, and young intrusions. In some cases, as well as for U-Pb studies of Tertiary granitoids, plutonic samples are interpreted in the context of related volcanism. These geochronologic data have advanced conceptual models of silicic magma genesis and pluton construction. Of fundamental importance are discoveries that zircons in volcanic rocks typically pre-date eruption by 10's to 100's of kyr and that multiple zircon populations are common; these crystals are "antecrysts" recycled from intrusive rocks or crystal mush of the system that vented. Resolving such age differences is possible with U-Th at <300 ka but is challenging with U-Pb, where SIMS precision limits resolution of differences on the order of 100 kyr for Pleistocene-Miocene zircons. Cathodoluminescence (CL) imaging of polished crystals guides beam placement but leads to sampling bias that favors high-U regions. Thus, although model-age histograms and relative probability plots identify zircon age populations, they are unlikely to accurately define relative abundances of age groups. Microbeam analysis collects data for the entire volume sampled but only SIMS depth-profiling into crystal faces can spatially resolve fine zones. ID-TIMS analysis of CL-imaged zircon fragments can improve U-Pb precision. SIMS complements geochronology with trace element fingerprints of zircon growth environments and enables Ti-in-zircon thermometry. Literature examples illustrate recent findings: (1) rhyodacite lava at Crater Lake contains zircons derived from late Pleistocene granodiorite represented by blocks ejected in the caldera-forming eruption; (2) zircons in Mount St. Helens dacites grew at sub-eruption temperatures and pre-date eruptions by up to 250 kyr; (3) Miocene plutons near Mount Rainier and the Colorado River were emplaced and crystallized in pulses over ~2-3-Myr periods, some with coeval volcanics; and (4) Cretaceous batholiths in the Sierra Nevada and North Cascades preserve evidence of assembly over as much as 10 Myr; individual samples contain zircons that crystallized during intervals of >1 Myr. Zircon ages and wide-ranging trace element concentrations suggest crystallization mainly in differentiated melt pockets in high-crystallinity magmas that may repeatedly freeze and thaw. Some high-Th/U, incompatible-element rich, spongy textured zircons grew very late, in the presence of oxidizing fluid. Not all zircons survive recycling into undersaturated magmas, in which zircon will dissolve given enough time, depending on temperature and dissolved volatiles. Recent zircon geochronologic results for volcanic and plutonic rocks lend credence to the "mush model" of rhyolite genesis and batholith consolidation. Crystal-poor rhyolites and leucogranites are melts segregated by compaction or gas-driven filter pressing from granitoid crystal mush emplaced incrementally in the middle to upper crust and powered by basaltic magma repeatedly injected into the lower reaches of the mush column. Balance between heat loss and basaltic influx determines whether the mush freezes or partially thaws at any given time, blurs internal contacts in resulting plutons, and can produce large volumes of crystal-rich ignimbrite or rapid separation and eruption of crystal-poor rhyolite. Lifetimes of the largest volcano-plutonic systems, such as the Altiplano-Puna or Southern Rocky Mountains volcanic fields, are comparable to the ~10 Myr of the Tuolumne Intrusive Suite.

Questioning the Sedimentary Paradigm for Granites

NASA Astrophysics Data System (ADS)

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

2007-12-01

A critical question regarding volcano-pluton links is whether plutons are samples of magma that passed through on its way to eruption, or residues left behind after volcanic rocks were extracted. A persistent theme of recent work on granites sensu lato is that many are sedimentary accumulations of crystals that lost significant volumes of magmatic liquid. This view is based on observations of structures that clearly seem to reflect deposition on a magma chamber floor (e.g., flows of chilled mafic magma into silicic magma) and on the inference that many other structures, such as modal layering, truncated layering, and crystal accumulations, reflect crystal sedimentation on such chamber floors. There are significant physical and geochemical reasons to question this view, based on observations in the Sierra Nevada of California and similar results from other batholiths. First, few granites show the enrichments in Ba, Sr, and relative Eu that feldspar accumulation should produce. Second, sedimentary features such as graded bedding and cross-bedding form in highly turbulent flows, but turbulence is unachievable in viscous silicic liquids, where velocities on the order of 104 m/s would be required to induce turbulence in a liquid with η=104 Pa s. Third, tabular modally layered domains commonly cut surrounding modal layering on both sides, and orientations of modal layering and of the troughs of "ladder dikes" commonly scatter widely within hectare-sized areas; it is difficult to reconcile these features with gravity-driven settling. Fourth, accumulations of K-feldspar megacrysts are typically inferred to be depositional, but this is precluded by crystallization of most K- feldspar after rheologic lock-up occurs. Finally, accumulations of K-feldspar and hornblende are typically packed too tightly to be depositional. With analogy to layered mafic intrusions, many features attributed to crystal sedimentation in granites may be better explained by crystal aging and other in situ chemical processes. In particular, many of these features may record pore-melt flow paths rather than depositional processes.

Zircon crytallization and recycling in the magma chamber of the rhyolitic Kos Plateau Tuff (Aegean arc)

USGS Publications Warehouse

Bachman, O.; Charlier, B.L.A.; Lowenstern, J. B.

2007-01-01

In contrast to most large-volume silicic magmas in continental arcs, which are thought to evolve as open systems with significant assimilation of preexisting crust, the Kos Plateau Miff magma formed dominantly by crystal fractionation of mafic parents. Deposits from this ??? 60 km3 pyroclastic eruption (the largest known in the Aegean arc) lack xenocrystic zircons [secondary ion mass spectrometry (SIMS) U-Pb ages on zircon cores never older than 500 ka] and display Sr-Nd whole-rock isotopic ratios within the range of European mantle in an area with exposed Paleozoic and Tertiary continental crust; this evidence implies a nearly closed-system chemical differentiation. Consequently, the age range provided by zircon SIMS U-Th-Pb dating is a reliable indicator of the duration of assembly and longevity of the silicic magma body above its solidus. The age distribution from 160 ka (age of eruption by sanidine 40Ar/39Ar dating; Smith et al., 1996) to ca. 500 ka combined with textural characteristics (high crystal content, corrosion of most anhydrous phenocrysts, but stability of hydrous phases) suggest (1) a protracted residence in the crust as a crystal mush and (2) rejuvenation (reduced crystallization and even partial resorption of minerals) prior to eruption probably induced by new influx of heat (and volatiles). This extended evolution chemically isolated from the surrounding crust is a likely consequence of the regional geodynamics because the thinned Aegean microplate acts as a refractory container for magmas in the dying Aegean subduction zone (continent-continent subduction). ?? 2007 Geological Society of America.

Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization.

PubMed

Varitis, S; Kavouras, P; Pavlidou, E; Pantazopoulou, E; Vourlias, G; Chrissafis, K; Zouboulis, A I; Karakostas, Th; Komninou, Ph

2017-01-01

The vitrification process was applied for the stabilization and solidification of a rich in chromium ash that was the by-product of incineration of tannery sludge. Six different batch compositions were produced, based on silica as the glass former and sodium and calcium oxides as flux agents. As-vitrified products (monoliths) were either composed of silicate matrices with separated from the melt Eskolaite (Cr 2 O 3 ) crystallites or were homogeneous glasses (in one case). All as-vitrified products were thermally treated in order to transform them to partially crystallized, i.e. devitrified products. Devitrification is an important part of the work since studying the transformation of the initial as-vitrified products into glass-ceramics with better properties could result to stabilized products with potential added value. The devitrified products were diversified by the effective crystallization mode and separated crystal phase composition. These variations originated from differences in: (a) batch composition of the initial as-vitrified products and (b) thermal treatment conditions. In devitrified products crystallization led to the separation of Devitrite (Na 2 Ca 3 Si 6 O 16 ), Combeite (Na 4 Ca 4 Si 6 O 18 ) and Wollastonite (CaSiO 3 ) crystalline phases, while Eskolaite crystallites were not affected by thermal treatment. Leaching test results revealed that chromium was successfully stabilized inside the as-vitrified monoliths. Devitrification impairs chromium stabilization, only in the case where the initial as-vitrified product was a homogeneous glass. In all other cases, devitrification did not affect successful chromium stabilization. Copyright © 2016 Elsevier Ltd. All rights reserved.

Constraining Cometary Crystal Shapes from IR Spectral Features

NASA Technical Reports Server (NTRS)

Wooden, Diane H.; Lindsay, Sean; Harker, David E.; Kelley, Michael S. P.; Woodward, Charles E.; Murphy, James Richard

2013-01-01

A major challenge in deriving the silicate mineralogy of comets is ascertaining how the anisotropic nature of forsterite crystals affects the spectral features' wavelength, relative intensity, and asymmetry. Forsterite features are identified in cometary comae near 10, 11.05-11.2, 16, 19, 23.5, 27.5 and 33 microns [1-10], so accurate models for forsterite's absorption efficiency (Qabs) are a primary requirement to compute IR spectral energy distributions (SEDs, lambdaF lambda vs. lambda) and constrain the silicate mineralogy of comets. Forsterite is an anisotropic crystal, with three crystallographic axes with distinct indices of refraction for the a-, b-, and c-axis. The shape of a forsterite crystal significantly affects its spectral features [13-16]. We need models that account for crystal shape. The IR absorption efficiencies of forsterite are computed using the discrete dipole approximation (DDA) code DDSCAT [11,12]. Starting from a fiducial crystal shape of a cube, we systematically elongate/reduce one of the crystallographic axes. Also, we elongate/reduce one axis while the lengths of the other two axes are slightly asymmetric (0.8:1.2). The most significant grain shape characteristic that affects the crystalline spectral features is the relative lengths of the crystallographic axes. The second significant grain shape characteristic is breaking the symmetry of all three axes [17]. Synthetic spectral energy distributions using seven crystal shape classes [17] are fit to the observed SED of comet C/1995 O1 (Hale-Bopp). The Hale-Bopp crystalline residual better matches equant, b-platelets, c-platelets, and b-columns spectral shape classes, while a-platelets, a-columns and c-columns worsen the spectral fits. Forsterite condensation and partial evaporation experiments demonstrate that environmental temperature and grain shape are connected [18-20]. Thus, grain shape is a potential probe for protoplanetary disk temperatures where the cometary crystalline forsterite formed. The forsterite crystal shapes (equant, b-platelets, c-platelets, b-columns - excluding a- and c-columns) derived from our modeling [17] of comet Hale- Bopp, compared to laboratory synthesis experiments [18], suggests that these crystals are high temperature condensates. By observing and modeling the crystalline features in comet ISON, we may constrain forsterite crystal shape(s) and link to their formation temperature(s) and environment(s).

The double-edged sword of high-precision U-Pb geochronology or be careful what you wish for. (Invited)

NASA Astrophysics Data System (ADS)

Bowring, S. A.

2010-12-01

Over the past two decades, U-Pb geochronology by ID-TIMS has been refined to achieve internal (analytical) uncertainties on a single grain analysis of ± ~ 0.1-0.2%, and 0.05% or better on weighted mean dates. This level of precision enables unprecedented evaluation of the rates and durations of geological processes, from magma chamber evolution to mass extinctions and recoveries. The increased precision, however, exposes complexity in magmatic/volcanic systems and highlights the importance of corrections related to disequilibrium partitioning of intermediate daughter products, and raises questions as to how best to interpret the complex spectrum of dates characteristic of many volcanic rocks. In addition, the increased precision requires renewed emphasis on the accuracy of U decay constants, the isotopic composition of U, the calibration of isotopic tracers, and the accurate propagation of uncertainties It is now commonplace in the high precision dating of volcanic ash-beds to analyze 5-20 single grains of zircon in an attempt to resolve the eruption/depositional age. Data sets with dispersion far in excess of analytical uncertainties are interpreted to reflect Pb-loss, inheritance, and protracted crystallization, often supported with zircon chemistry. In most cases, a weighted mean of the youngest reproducible dates is interpreted as the time of eruption/deposition. Crystallization histories of silicic magmatic systems recovered from plutonic rocks may also be protracted, though may not be directly applicable to silicic eruptions; each sample must be evaluated independently. A key to robust interpretations is the integration high-spatial resolution zircon trace element geochemistry with high-precision ID-TIMS analyses. The EARTHTIME initiative has focused on many of these issues, and the larger subject of constructing a timeline for earth history using both U-Pb and Ar-Ar chronometers. Despite continuing improvements in both, comparing dates for the same rock with both chronometers is not straightforward. Compelling issues range from pre-eruptive magma chamber residence, recognizing open system behavior, accurately correcting for disequilibrium amounts of 230Th and 231Pa, precise and accurate dates of fluence monitors for 40Ar/39Ar, and inter-laboratory biases. At present, despite the level of internal precision achievable by each technique, obstacles remain to combining both chronometers.

Synthesis, characterization and modelling of zinc and silicate co-substituted hydroxyapatite

PubMed Central

Friederichs, Robert J.; Chappell, Helen F.; Shepherd, David V.; Best, Serena M.

2015-01-01

Experimental chemistry and atomic modelling studies were performed here to investigate a novel ionic co-substitution in hydroxyapatite (HA). Zinc, silicate co-substituted HA (ZnSiHA) remained phase pure after heating to 1100°C with Zn and Si amounts of 0.6 wt% and 1.2 wt%, respectively. Unique lattice expansions in ZnSiHA, silicate Fourier transform infrared peaks and changes to the hydroxyl IR stretching region suggested Zn and silicate co-substitution in ZnSiHA. Zn and silicate insertion into HA was modelled using density functional theory (DFT). Different scenarios were considered where Zn substituted for different calcium sites or at a 2b site along the c-axis, which was suspected in singly substituted ZnHA. The most energetically favourable site in ZnSiHA was Zn positioned at a previously unreported interstitial site just off the c-axis near a silicate tetrahedron sitting on a phosphate site. A combination of experimental chemistry and DFT modelling provided insight into these complex co-substituted calcium phosphates that could find biomedical application as a synthetic bone mineral substitute. PMID:26040597

A novel multifunctional pharmaceutical excipient: modification of the permeability of starch by processing with magnesium silicate.

PubMed

Rashid, Iyad; Al-Remawi, Mayyas; Leharne, Stephen A; Chowdhry, Babur Z; Badwan, Adnan

2011-06-15

A directly compressible excipient has been developed by co-processing starch with magnesium silicate. The foregoing was achieved either by co-precipitation of magnesium silicate onto different types of starch or by dry granulation of maize starch with magnesium silicate. A variety of techniques (permeability, water retention/swelling, compression analysis, scanning electron microscopy, tensile strength and disintegration/dissolution studies) were used to characterize these systems. The permeability of the formulations produced using the two methods was evaluated experimentally using Darcy's permeability law. Magnesium silicate, as an anti-adhering agent, increases the permeability of both maize and partially pregelatinized starch, resulting in compacts of high mechanical strength, short disintegration time and low lubricant sensitivity. Such advantages are evident when the properties of the physical mixture of maize starch with magnesium silicate are compared with the co-precipitation and dry granulation techniques. Formulation with this novel excipient system, using paracetamol as a model drug, indicated its suitability as a single multifunctional excipient. Copyright © 2011 Elsevier B.V. All rights reserved.

Phosphorus Equilibria Among Mafic Silicate Phases

NASA Technical Reports Server (NTRS)

Berlin, Jana; Xirouchakis, Dimitris

2002-01-01

Phosphorus incorporation in major rock-forming silicate minerals has the following implications: (1) Reactions between phosphorus-hosting major silicates and accessory phosphates, which are also major trace element carriers, may control the stability of the latter and thus may affect the amount of phosphorus and other trace elements released to the coexisting melt or fluid phase. (2) Less of a phosphate mineral is needed to account for the bulk phosphorus of planetaty mantles. (3) During partial melting of mantle mineral assemblages or equilibrium fractional crystallization of basaltic magmas, and in the absence or prior to saturation with a phosphate mineral, silicate melts may become enriched in phosphorus, especially in the geochemically important low melt fraction regime, Although the small differences in the ionic radii of IVp5+, IVSi4+, and IV Al3+ makes phosphoms incorporation into crystalline silicates perhaps unsurprising, isostructural silicate and phosphate crystalline solids do not readily form solutions, e.g., (Fe, Mg)2SiO4 vs. LiMgPO4, SiO)2 VS. AlPO4. Nonetheless, there are reports of, poorly characterized silico-phosphate phases in angrites , 2-4 wt% P2O5 in olivine and pyroxene grains in pallasites and reduced terestrial basalts which are little understood but potentially useful, and up to 17 wt% P2O5 in olivine from ancient slags. However, such enrichments are rare and only underscore the likelihood of phosphoms incorporation in silicate minerals. The mechanisms that allow phosphorus to enter major rock-forming silicate minerals (e.g., Oliv, Px, Gt) remain little understood and the relevant data base is limited. Nonetheless, old and new high-pressure (5-10 GPa) experimental data suggest that P2O5 wt% decreases from silica-poor to silica-rich compositions or from orthosilicate to chain silicate structures (garnet > olivine > orthopyroxene) which implies that phosphorus incorporation in silicates is perhaps more structure-than site-specific. The data also indicate that DXVliQP2O5 decrease in the same order, but DOVLiQP2O5 and DOpx/LiQP205 are likely constant, respectively equal to 0.08(3) and 0.007(4), in contrast, DG1ILiQP205 increases from 0.15(3) to 0.36(10) as garnet becomes majoritic, thus silica-enriched, and may also depend on liquid composition (SiO2, P2O5 and Na2O wt%).

Calcium-silicate mesoporous nanoparticles loaded with chlorhexidine for both anti- Enterococcus faecalis and mineralization properties.

PubMed

Fan, Wei; Li, Yanyun; Sun, Qing; Ma, Tengjiao; Fan, Bing

2016-10-21

In infected periapical tissues, Enterococcus faecalis is one of the most common dominant bacteria. Chlorhexidine has been proved to show strong antibacterial ability against E. faecalis but is ineffective in promoting mineralization for tissues around root apex. Mesoporous calcium-silicate nanoparticles are newly synthesized biomaterials with excellent ability to promote mineralization and carry-release bioactive molecules in a controlled manner. In this study, mesoporous calcium-silicate nanoparticles were functionalized with chlorhexidine and their releasing profile, antibacterial ability, effect on cell proliferation and in vitro mineralization property were evaluated. The chlorhexidine was successfully incorporated into mesoporous calcium-silicate nanoparticles by a mixing-coupling method. The new material could release chlorhexidine as well as Ca 2+ and SiO 3 2- in a sustained manner with an alkaline pH value under different conditions. The antimicrobial ability against planktonic E. faecalis was dramatically improved after chlorhexidine incorporation. The nanoparticles with chlorhexidine showed no negative effect on cell proliferation with low concentrations. On dentin slices, the new synthesized material demonstrated a similar inhibitory effect on E. faecalis as the chlorhexidine. After being immersed in SBF for 9 days, numerous apatite crystals could be observed on surfaces of the material tablets. Mesoporous calcium-silicate nanoparticles loaded with chlorhexidine exhibited release of ions and chlorhexidine, low cytotoxicity, excellent antibacterial ability and in vitro mineralization. This material could be developed into a new effective intra-canal medication in dentistry or a new bone defect filling material for infected bone defects.

Recent achievements on polyanion-type compounds for sodium-ion batteries: Syntheses, crystal chemistry and electrochemical performance

NASA Astrophysics Data System (ADS)

Guo, Sheng-Ping; Li, Jia-Chuang; Xu, Qian-Ting; Ma, Ze; Xue, Huai-Guo

2017-09-01

In the past several years, many efforts have been made to develop polyanion-type cathode materials for sodium ion batteries by chemists and material scientists. These materials are one of the main types of promising cathodes though the studies are still in their infancy. This paper reviews almost all the important advances of polyanion-type cathodes on their syntheses, crystal structures, morphologies, electrochemical performance and Na redox mechanisms. It specifically focuses on their crystal chemistry and electrochemical behaviors. The contents are divided into several categories according to their chemical compositions. After introduction of the synthetic methods, phosphates (ortho-, pyro- and fluoro-), silicates, sulfates, and mixed anions type cathodes are summarized and discussed successively.

Nucleation and Crystallization as Induced by Bending Stress in Lithium Silicate Glass Fibers

NASA Technical Reports Server (NTRS)

Reis, Signo T.; Kim, Cheol W.; Brow, Richard K.; Ray, Chandra S.

2003-01-01

Glass Fibers of Li2O.2SiO2 (LS2) and Li2O.1.6SiO2 (LS1.6) compositions were heated near, but below, the glass transition temperature for different times while subjected to a constant bending stress of about 1.2 GPa. The nucleation density and the crystallization tendency estimated by differential thermal analysis (DTA) of a glass sample in the vicinity of the maximum of the bending stress increased relative to that of stress-free glass fibers. LS2 glass fibers were found more resistant to nucleation and crystallization than the Ls1.6 glass fibers. These results are discussed in regards to shear thinning effects on glass stability.

Simultaneous presence of (Si{sub 3}O{sub 10}){sup 8−} and (Si{sub 2}O{sub 7}){sup 6−} groups in new synthetic mixed sorosilicates: BaY{sub 4}(Si{sub 2}O{sub 7})(Si{sub 3}O{sub 10}) and isotypic compounds, studied by single-crystal X-ray diffraction, Raman spectroscopy and DFT calculations

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

Wierzbicka-Wieczorek, Maria, E-mail: maria.wierzbicka-wieczorek@uni-jena.de; Többens, Daniel M.; Kolitsch, Uwe

2013-11-15

Three new, isotypic silicate compounds, BaY{sub 4}(Si{sub 2}O{sub 7})(Si{sub 3}O{sub 10}), SrYb{sub 4}(Si{sub 2}O{sub 7})(Si{sub 3}O{sub 10}) and SrSc{sub 4}(Si{sub 2}O{sub 7})(Si{sub 3}O{sub 10}), were synthesized using high-temperature flux growth techniques, and their crystal structures were solved from single-crystal X-ray intensity data: monoclinic, P2{sub 1}/m, with a=5.532(1)/5.469(1)/5.278(1), b=19.734(4)/19.447(4)/19.221(4), c=6.868(1)/6.785(1)/6.562(1) Å, β=106.53(3)/106.20(3)/106.50(3)°, V=718.8(2)/693.0(2)/638.3(2) Å{sup 3}, R(F)=0.0225/0.0204/0.0270, respectively. The topology of the novel structure type contains isolated horseshoe-shaped Si{sub 3}O{sub 10} groups (Si–Si–Si=93.15–95.98°), Si{sub 2}O{sub 7} groups (Si–O{sub bridge}–Si=180°, symmetry-restricted) and edge-sharing M(1)O{sub 6} and M(2)O{sub 6} octahedra. Single-crystal Raman spectra of the title compounds were measured and compared with Raman spectroscopicmore » data of chemically and topologically related disilicates and trisilicates, including BaY{sub 2}(Si{sub 3}O{sub 10}) and SrY{sub 2}(Si{sub 3}O{sub 10}). The band assignments are supported by additional theoretical calculation of Raman vibrations by DFT methods. - Graphical abstract: View of BaY{sub 4}(Si{sub 2}O{sub 7})(Si{sub 3}O{sub 10}) along [100], showing zigzag chains and the tri- and disilicate groups. The unit cell is outlined. Display Omitted - Highlights: • We report a novel interesting crystal structure type for mixed sorosilicates containing Y, Yb, and Sc. • Synthesis of such mixed sorosilicates is possible by a high-temperature flux-growth technique. • Calculation of Raman vibrations by advanced DFT methods allows a considerably improved interpretation of measured Raman spectra.« less

Experimental constraints on mantle metasomatism caused by silicate and carbonate melts

NASA Astrophysics Data System (ADS)

Gervasoni, Fernanda; Klemme, Stephan; Rohrbach, Arno; Grützner, Tobias; Berndt, Jasper

2017-06-01

Metasomatic processes are responsible for many of the heterogeneities found in the upper mantle. To better understand the metasomatism in the lithospheric mantle and to illustrate the differences between metasomatism caused by hydrous silicate and carbonate-rich melts, we performed various interaction experiments: (1) Reactions between hydrous eclogite-derived melts and peridotite at 2.2-2.5 GPa and 900-1000 °C reproduce the metasomatism in the mantle wedge above subduction zones. (2) Reactions between carbonate-rich melts and peridotite at 2.5 GPa and 1050-1000 °C, and at 6 GPa and 1200-1250 °C simulate metasomatism of carbonatite and ultramafic silicate-carbonate melts in different regions of cratonic lithosphere. Our experimental results show that partial melting of hydrous eclogite produces hydrous Si- and Al-rich melts that react with peridotite and form bi-mineralic assemblages of Al-rich orthopyroxene and Mg-rich amphibole. We also found that carbonate-rich melts with different compositions react with peridotite and form new metasomatic wehrlitic mineral assemblages. Metasomatic reactions caused by Ca-rich carbonatite melt consume the primary peridotite and produce large amounts of metasomatic clinopyroxene; on the other hand, metasomatism caused by ultramafic silicate-carbonate melts produces less clinopyroxene. Furthermore, our experiments show that ultramafic silicate-carbonate melts react strongly with peridotite and cause crystallization of large amounts of metasomatic Fe-Ti oxides. The reactions of metasomatic melts with peridotite also change the melt composition. For instance, if the carbonatite melt is not entirely consumed during the metasomatic reactions, its melt composition may change dramatically, generating an alkali-rich carbonated silicate melt that is similar in composition to type I kimberlites.

Glasses, ceramics, and composites from lunar materials

NASA Technical Reports Server (NTRS)

Beall, George H.

1992-01-01

A variety of useful silicate materials can be synthesized from lunar rocks and soils. The simplest to manufacture are glasses and glass-ceramics. Glass fibers can be drawn from a variety of basaltic glasses. Glass articles formed from titania-rich basalts are capable of fine-grained internal crystallization, with resulting strength and abrasion resistance allowing their wide application in construction. Specialty glass-ceramics and fiber-reinforced composites would rely on chemical separation of magnesium silicates and aluminosilicates as well as oxides titania and alumina. Polycrystalline enstatite with induced lamellar twinning has high fracture toughness, while cordierite glass-ceramics combine excellent thermal shock resistance with high flexural strengths. If sapphire or rutile whiskers can be made, composites of even better mechanical properties are envisioned.

Genesis of recent silicic magmatism in the Medicine Lake Highland, California - Evidence from cognate inclusions found at Little Glass Mountain

NASA Technical Reports Server (NTRS)

Mertzman, S. A.; Williams, R. J.

1981-01-01

Sparse, granular inclusions of early-formed minerals found within the Little Glass Mountain rhyolite flows in northern California are shown to provide a means of characterizing the physical conditions, at depth, beneath the Medicine Lake Highland during the latest phase of volcanic activity. Mineral compositions, in combination with thermodynamic calculations and experiments, suggest crystalization at a pressure of 5,200 bars within a 966-836 C temperature range; implying that mineral segregation and equilibration occurred at a depth of 15-18 km beneath the surface. In addition, mass balance calculations indicate that the Medicine Lake flow is a close approximation to the parental magma for the latest silicic lavas.

Composition of primary fluid and melt inclusions in regenerated olivines from hypabyssal kimberlites of the Malokuonapskaya pipe (Yakutia)

NASA Astrophysics Data System (ADS)

Tomilenko, A. A.; Kuzmin, D. V.; Bulbak, T. A.; Timina, T. Yu.; Sobolev, N. V.

2015-11-01

The primary fluid and melt inclusions in regenerated zonal crystals of olivine from kimberlites of the Malokuonapskaya pipe were first examined by means of microthermometry, optic and scanning electron microscopy, and Raman spectroscopy. The high-pressure genesis of homogenous central parts of the olivines was revealed, probably under intense metasomatism at early hypogene stages with subsequent regeneration in the kimberlitic melt. The olivine crystals were regenerated from silicate-carbonate melts at about 1100°C. The composition of the kimberlitic melt was changed by way of an increase in the calcium content.

GROWTH AND CHARACTERIZATION OF SINGLE CRYSTALS OF RARE EARTH COMPOUNDS.

DTIC Science & Technology

SINGLE CRYSTALS, CRYSTAL GROWTH), (*CRYSTAL GROWTH, SINGLE CRYSTALS), (*RARE EARTH COMPOUNDS, SINGLE CRYSTALS), EPITAXIAL GROWTH, SODIUM COMPOUNDS, CHLORIDES, VAPOR PLATING, ELECTROSTATIC FIELDS, ENERGY, ATOMIC PROPERTIES , BONDING

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

Porphyry Cu (Mo-Au) and epithermal Au-Ag ores are globally associated with shallow hydrous, strongly oxidized, and sulfur-rich arc intrusions. In many localities, long-lived magmatism includes evolution from early andesitic volcanic (v) and plutonic (p) rocks to later dacitic or rhyolitic compositions dominated by plutons. We compare zircon compositions from three igneous suites with different time spans: Yerington, USA (1 m.y., p>v), El Salvador, Chile (4 m.y., p>v), and Yanacocha, Peru (6 m.y., v>p). At Yerington granite dikes and ores formed in one event, at ES in 2 to 3 events spanning 3 m.y., and at Yanacocha in 6 events spanning 5 m.y. At both ES and Yanacocha, high-Al amphiboles likely crystallized at high temperature in the mid-crust and attest to deep magmas that periodically recharged the shallow chambers. At Yanacocha, these amphiboles contain anhydrite inclusions that require magmas were sulfur-rich and strongly oxidized (~NNO+2). The Ti-in-zircon geothermometer provides estimates of 920º to 620º C for zircon crystallization, and records both core to rim cooling and locally high temperature rim overgrowths. Ore-related silicic porphyries yield near-solidus crystallization temperatures of 750-650°C consistent with low zircon saturation temperatures. The latter zircons have large positive Ce/Ce* and small negative Eu/Eu*≥0.4 anomalies attesting to strongly oxidized conditions (Ballard et al., 2001), which we propose result from crystallization and SO2 loss to the magmatic-hydrothermal ore fluid (Dilles et al., 2015). The Hf, REE, Y, U, and Th contents of zircons are diverse in the magma suites, and Th/U vs Yb/Gd plots suggest a dominant role of crystal fractionation with lesser roles for both crustal contamination and mixing with high temperature deep-sourced mafic magma. Ce/Sm vs Yb/Gd plots suggest that magma REE contents at <900°C are dominated by early crystallization of hornblende and apatite, and late crystallization (~<780°C) of titanite. Magma mixing and crustal contamination are most evident in pre-ore magmas, whereas ore-forming intrusions at low temperatures are dominated by crystal fractionation. Thus, zircon provides evidence for cyclic crystallization and mafic recharge that enrich late silicic melts in incompatible ore components water, sulfur, chlorine and metals.

The Life and Times of Supervolcanoes: Inferences from Long Valley Caldera

NASA Technical Reports Server (NTRS)

Simon, Justin

2014-01-01

Cataclysmic eruptions of silicic magma from "supervolcanoes" are among the most awe-inspiring natural phenomena found in the geologic record, in terms of size, power, and potential hazard. Based on the repose intervals between eruptions of this magnitude, the magmas responsible for them could accumulate gradually in the shallow crust over time scales that may be in excess of a million years (Smith, 1979; Spera and Crisp, 1981; Shaw, 1985). Pre-eruption magma residence time scales can also be inferred from the age difference between eruption (i.e., using 40Ar/39Ar dating to determine the time when hot erupted material cools to below its Ar closure temperature, 200 to 600 degC) and early pre-eruption crystallization (i.e., zircon saturation temperatures; Reid et al., 1997). I will discuss observations from Long Valley a Quaternary volcanic center in California. Long Valley is a voluminous, dominantly silicic caldera system. Based on extensive dating of accessory minerals (e.g., U-Th-Pb dating of zircon and allanite) along with geochemical and isotopic data we find that silicic magmas begin to crystallize 10's to 100's of thousands of years prior to their eruption and that rhyolites record episodes of punctuated and independent evolution rather than the periodic tapping of a long-lived magma. The more punctuated versus more gradual magma accumulation rates required by the absolute and model ages, respectively, imply important differences in the mass and heat fluxes associated with the generation, differentiation, and storage of voluminous rhyolites and emphasize the need to reconcile the magmatic age differences.

Looking through the Zircon Kaleidoscope: Durations, Rates, and Fluxes in Silicic Magmatic System

NASA Astrophysics Data System (ADS)

Schaltegger, U.; Wotzlaw, J. F.

2014-12-01

The crystallization rate of zircon in a cooling magma depends on the cooling rate through the saturation interval in addition to compositional and kinetic factors. Repeated influx of hot magma over 10-20 ka leads to short-amplitude temperature oscillations, which are recorded by resorption/crystallization cycles of zircon. Plotting the number of dated zircons versus their high-precision U-Pb date results in curves that qualitatively relate to the evolution of magma temperature over time [1], [2]. The trace elemental, O and Hf isotopic composition of zircon gives indications about the degree of magma homogenization and thermal evolution. Zircons from systems with small volumes and magma fluxes record non-systematic chemical and Hf isotopic heterogeneity, suggesting crystallization in non-homogenized ephemeral magma batches. Such systems typically lead to small, mid-upper crustal plutons [3]. Zircons from large-volume crystal-poor rhyolites record initial heterogeneities and rapid amalgamation of smaller magma batches over 10 ka [4], while zircons from monotonous intermediates record magma evolution over several 100 ka with coherent fractionation trends suggesting homogenization and a coherent thermal evolution [2]. In both cases, volumes and flux rates were sufficient to produce large volumes of eruptible magma on very contrasting time scales. Zircon is therefore recording cyclic crystallization-rejuvenation processes during temperature fluctuations in intermediate to upper crustal magma reservoirs but may not relate to the physical pluton emplacement or eruption. We can quantify volumes, rates of magma influx, rates of cooling and crystallization, and the degree of convective homogenization from zircon data, and infer reservoir assembly and eruption trigger mechanisms. These parameters largely control the evolution of long-lived, low-flux silicic magmatic system typical for mid-to-upper crustal plutons, monotonous intermediates are characterized by intermediate durations and fluxes while short-lived, high-flux systems preferentially produce crystal-poor rhyolites. References: [1] Caricchi et al. (2014) Nature 511, 457-461; [2] Wotzlaw et al. (2013) Geology 41, 867-870; [3] Broderick (2013) PhD thesis, Univ. of Geneva; [3] Wotzlaw et al. (2014) Geology, doi:10.1130/G35979.1

Post-magmatic solid solutions of CaCeAl2(Fe3+ 2/3□1/3)[Si2O7][SiO4]O(OH), allanite-(Ce) and REE-bearing epidote in miarolitic pegmatites of Permian Baveno granite (Verbania, central-southern alps, Italy)

NASA Astrophysics Data System (ADS)

Guastoni, Alessandro; Nestola, Fabrizio; Schiazza, Mariangela

2017-06-01

CaCeAl2(Fe3+ 2/3□1/3)[Si2O7][SiO4]O(OH), allanite-(Ce) and rare earth element (REE)-bearing epidote occur as globular aggregates and platy prismatic crystals in miarolitic cavities in a niobium, yttrium, fluorine (NYF) granitic pegmatite at Baveno, Verbania, Southern Alps, Italy. These samples were investigated by means of an electron probe micro-analyser (EPMA) and single-crystal X-ray diffraction. Our EPMA results show that the globular aggregates have the highest REE content in the core portion and decreases to REE-bearing epidote towards the rim whereas the prismatic crystals are characterized by marked oscillatory zoning that have the highest REE contents at the rim of the crystal. The unit-cell parameters of "allanites" have an intermediate unit-cell between CaCeAl2(Fe3+ 2/3□1/3)[Si2O7][SiO4]O(OH), allanite-(Ce) and REE-free epidote, because reflect the strong chemical heterogeneity of the samples which form complete solid solutions. Hydrothermal fluids control the activity and precipitation of incompatible elements like high field strength elements (HFSE), Sc and REE by hydrous F-rich fluids below the critical temperature which allow to deposit accessory minerals in the cavities with decreasing temperature. The source of REE and Y are the sheet and REE-silicates like siderophyllite-annite, and gadolinite-(Y) which underwent partial to complete decomposition by the activity of aggressive F-rich hydrothermal fluids.

Seismic anisotropy of the crust: electron-backscatter diffraction measurements from the Basin and Range

NASA Astrophysics Data System (ADS)

Erdman, Monica E.; Hacker, Bradley R.; Zandt, George; Seward, Gareth

2013-11-01

Crystal preferred orientations were measured in a suite of rocks from three locations in the Basin and Range using electron-backscatter diffraction. Anisotropic velocities were calculated for all rocks using single-crystal stiffnesses, the Christoffel equation and Voigt-Reuss-Hill averaging. Anisotropic velocities were calculated for all three crustal sections using these values combined with rock proportions as exposed in the field. One suite of rocks previously measured in the laboratory was used as a benchmark to evaluate the accuracy of the calculated velocities. Differences in the seismic anisotropy of the Funeral Mountains, Ruby Mountains and East Humboldt Range sections arise because of differences in mineralogy and strain, with the calc-silicate dominated Ruby Mountains section having higher P-wave speeds and VP/VS ratios because of the reduced quartz content. In all cases, the velocities show either transverse isotropy or nearly so, with a unique slow axis normal to the foliation. Velocity anisotropy can thus be used to infer the flow plane, but not the flow direction in typical crustal rocks. Areas with a subhorizontal foliation have minimal shear wave splitting for vertically propagating waves and are thus good places to measure mantle anisotropy using SKS-splitting.

Possible lunar ores

NASA Technical Reports Server (NTRS)

Gillett, Stephen L.

1991-01-01

Despite the conventional wisdom that there are no lunar ores, geochemical considerations suggest that local concentrations of useful rare elements exist on the Moon in spite of its extreme dryness. The Moon underwent protracted igneous activity in its history, and certain magmatic processes can concentrate incompatible elements even if anhydrous. Such processes include: (1) separation of a magma into immiscible liquid phases (depending on composition, these could be silicate-silicate, silicate-oxide, silicate-sulfide, or silicate-salt); (2) cumulate deposits in layered igneous intrusions; and (3) concentrations of rare, refractory, lithophile elements (e.g., Be, Li, Zr) in highly differentiated, silica-rich magmas, as in the lunar granites. Terrestrial mining experience indicates that the single most important characteristic of a potential ore is its concentration of the desire element. The utility of a planet as a resource base is that the welter of interacting processes over geologic time can concentrate rare element automatically. This advantage is squandered if adequate exploration for ores is not first carried out.

Experimental Partitioning of Chalcophile Elements between Mantle Silicate Minerals and Basaltic Melt at High Pressures and Temperatures - Implications for Sulfur Geochemistry of Mantle and Crust

NASA Astrophysics Data System (ADS)

Dasgupta, R.; Jego, S.; Ding, S.; Li, Y.; Lee, C. T.

2015-12-01

The behavior of chalcophile elements during mantle melting, melt extraction, and basalt differentiation is critical for formation of ore deposits and geochemical model and evolution of crust-mantle system. While chalcophile elements are strongly partitioned into sulfides, their behavior with different extent of melting, in particular, in the absence of sulfides, can only be modeled with complete knowledge of the partitioning behavior of these elements between dominant mantle minerals and basaltic melt with or without dissolved sulfide (S2-). However, experimental data on mineral-melt partitioning are lacking for many chalcophile elements. Crystallization experiments were conducted at 3 GPa and 1450-1600 °C using a piston cylinder and synthetic silicate melt compositions similar to low-degree partial melt of peridotite. Starting silicate mixes doped with 100-300 ppm of each of various chalcophile elements were loaded into Pt/graphite double capsules. To test the effect of dissolved sulfur in silicate melt on mineral-melt partitioning of chalcophile elements, experiments were conducted on both sulfur-free and sulfur-bearing (1100-1400 ppm S in melt) systems. Experimental phases were analyzed by EPMA (for major elements and S) and LA-ICP-MS (for trace elements). All experiments produced an assemblage of cpx + melt ± garnet ± olivine ± spinel and yielded new partition coefficients (D) for Sn, Zn, Mo, Sb, Bi, Pb, and Se for cpx/melt, olivine/melt, and garnet/melt pairs. Derived Ds (mineral/basalt) reveal little effect of S2- in the melt on mineral-melt partition coefficients of the measured chalcophile elements, with Ds for Zn, Mo, Bi, Pb decreasing by less than a factor of 2 from S-free to S-bearing melt systems or remaining similar, within error, between S-free and S-bearing melt systems. By combining our data with existing partitioning data between sulfide phases and silicate melt we model the fractionation of these elements during mantle melting and basalt crystallization. The model results are compared with the chalcophile element abundance in oceanic basalts. We will discuss the implications of our new partitioning data and model results on sulfur and chalcophile element geochemistry of mantle source regions of ocean floor basalts and the fate of sulfides during mantle melting.

Sulfur and sulfides in chondrules

NASA Astrophysics Data System (ADS)

Marrocchi, Yves; Libourel, Guy

2013-10-01

The nature and distribution of sulfides within type I PO, POP and PP chondrules of the carbonaceous chondrite Vigarano (CV3) have been studied by secondary electron microscopy and electron microprobe. They occur predominantly as spheroidal blebs composed entirely of low-Ni iron sulfide (troilite, FeS) or troilite + magnetite but in less abundance in association with metallic Fe-Ni beads in opaque assemblages. Troilites are mainly located within the low-Ca pyroxene outer zone and their amounts increase with the abundance of low-Ca pyroxene within chondrules, suggesting co-crystallization of troilite and low-Ca pyroxene during high-temperature events. We show that sulfur concentration and sulfide occurrence in chondrules obey high temperature sulfur solubility and saturation laws. Depending on the fS2 and fO2 of the surrounding gas and on the melt composition, mainly the FeO content, sulfur dissolved in chondrule melts may eventually reach a concentration limit, the sulfur content at sulfide saturation (SCSS), at which an immiscible iron sulfide liquid separates from the silicate melt. The occurrence of both a silicate melt and an immiscible iron sulfide liquid is further supported by the non-wetting behavior of sulfides on silicate phases in chondrules due to the high interfacial tension between their precursor iron-sulfide liquid droplets and the surrounding silicate melt during the high temperature chondrule-forming event. The evolution of chondrule melts from PO to PP towards more silicic compositions, very likely due to high PSiO(g) of the surrounding nebular gas, induces saturation of FeS at much lower S content in PP than in PO chondrules, leading to the co-crystallization of iron sulfides and low-Ca pyroxenes. Conditions of co-saturation of low-Ca pyroxene and FeS are only achieved in non canonical environments characterized by high partial pressures of sulfur and SiO and redox conditions more oxidizing than IW-3. Fe and S mass balance calculations also suggest the occurrence of an external source of iron, very likely gaseous, during chondrule formation. We therefore propose that enrichments in sulfur (and other volatile and moderately volatile elements) from PO to PP type I bulk chondrule compositions towards chondritic values result from progressive reaction between partially depleted olivine-bearing precursors and a volatile-rich gas phase.

Silicate melts density, buoyancy relations and the dynamics of magmatic processes in the upper mantle

NASA Astrophysics Data System (ADS)

Sanchez-Valle, Carmen; Malfait, Wim J.

2016-04-01

Although silicate melts comprise only a minor volume fraction of the present day Earth, they play a critical role on the Earth's geochemical and geodynamical evolution. Their physical properties, namely the density, are a key control on many magmatic processes, including magma chamber dynamics and volcanic eruptions, melt extraction from residual rocks during partial melting, as well as crystal settling and melt migration. However, the quantitative modeling of these processes has been long limited by the scarcity of data on the density and compressibility of volatile-bearing silicate melts at relevant pressure and temperature conditions. In the last decade, new experimental designs namely combining large volume presses and synchrotron-based techniques have opened the possibility for determining in situ the density of a wide range of dry and volatile-bearing (H2O and CO2) silicate melt compositions at high pressure-high temperature conditions. In this contribution we will illustrate some of these progresses with focus on recent results on the density of dry and hydrous felsic and intermediate melt compositions (rhyolite, phonolite and andesite melts) at crustal and upper mantle conditions (up to 4 GPa and 2000 K). The new data on felsic-intermediate melts has been combined with in situ data on (ultra)mafic systems and ambient pressure dilatometry and sound velocity data to calibrate a continuous, predictive density model for hydrous and CO2-bearing silicate melts with applications to magmatic processes down to the conditions of the mantle transition zone (up to 2773 K and 22 GPa). The calibration dataset consist of more than 370 density measurements on high-pressure and/or water-and CO2-bearing melts and it is formulated in terms of the partial molar properties of the oxide components. The model predicts the density of volatile-bearing liquids to within 42 kg/m3 in the calibration interval and the model extrapolations up to 3000 K and 100 GPa are in good agreement with results from ab initio calculations. The density model has been applied to examine the mineral-melt buoyancy relations at depth and the implications of these results for the dynamics of magma chambers, crystal settling and the stability and mobility of magmas in the upper mantle will be discussed.

Hemimorphite as a natural sink for arsenic in zinc deposits and related mine tailings: Evidence from single-crystal EPR spectroscopy and hydrothermal synthesis

NASA Astrophysics Data System (ADS)

Mao, Mao; Lin, Jinru; Pan, Yuanming

2010-05-01

Hemimorphite is a refractory mineral in surface environments and occurs commonly in supergene non-sulfide Zn deposits and Zn mine tailings. Single-crystal electron paramagnetic resonance (EPR) spectra of gamma-ray-irradiated hemimorphite from Mapimi (Durango, Mexico) reveal two arsenic-associated oxyradicals: [AsO 4] 4- and [AsO 4] 2-. Inductively coupled plasma mass spectrometry analyses confirm this sample to contain 270 ppm As and that hemimorphite from other Zn deposits has appreciable amounts of arsenic as well. Spin Hamiltonian parameters, including matrices g, A ( 75As) and P( 75As), show that the [AsO 4] 4- radical formed from electron trapping by a locally uncompensated [AsO 4] 3- ion substituting for [SiO 4] 4-. Matrices g, A( 75As) and P( 75As) of the [AsO 4] 2- radical show it to have the unpaired spin on the bridging oxygen of an [AsO 4] 3- ion at a Si site and linked to a monovalent impurity ion. This structural model for the [AsO 4] 2- radical is further supported by observed 29Si and 1H superhyperfine structures arising from interactions with a single Si atom (A/g eβe = ˜1 mT at B// c) and two equivalent H atoms (A/g eβe = ˜0.3 mT at B∧ b = 10°), respectively. Hydrothermal experiments at 200 °C and ˜9.5 MPa show that hemimorphite contains up to ˜2.5 wt% As 2O 5 and suggest that both the arsenate concentration and the pH value in the solution affect the As content in hemimorphite. These results demonstrate that hemimorphite is capable of sequestering arsenate in its crystal lattice, hence is a natural sink for attenuating As in supergene non-sulfide Zn deposits and Zn mine tailings. Moreover, results from hemimorphite potentially have more far-reaching implications for major silicates such as zeolites in the immobilization and removal of arsenic in surface environments.

Infinite charge mobility in muscovite at 300 K

NASA Astrophysics Data System (ADS)

Russell, F. Michael; Archilla, Juan F. R.; Frutos, Fabian; Medina-Carrasco, Santiago

2017-11-01

Evidence is presented for infinite charge mobility in natural crystals of muscovite mica at room temperature. Muscovite has a basic layered structure containing a flat monatomic sheet of potassium sandwiched between mirror silicate layers. It is an excellent electrical insulator. Studies of defects in muscovite crystals indicated that positive charge could propagate over great distances along atomic chains in the potassium sheets in the absence of an applied electric potential. The charge moved in association with anharmonic lattice excitations that moved at about sonic speed and created by nuclear recoil of the radioactive isotope 40K. This was verified by measuring currents passing through crystals when irradiated with energetic alpha particles at room temperature. The charge propagated more than 1000 times the range of the alpha particles of average energy and 250 times the range of channelling particles of maximum energy. The range is limited only by size of the crystal.

Partitioning of Ru, Rh, Pd, Re, Ir and Pt between liquid metal and silicate at high pressures and high temperatures - Implications for the origin of highly siderophile element concentrations in the Earth's mantle

NASA Astrophysics Data System (ADS)

Mann, Ute; Frost, Daniel J.; Rubie, David C.; Becker, Harry; Audétat, Andreas

2012-05-01

The apparent overabundance of the highly siderophile elements (HSEs: Pt-group elements, Re and Au) in the mantles of Earth, Moon and Mars has not been satisfactorily explained. Although late accretion of a chondritic component seems to provide the most plausible explanation, metal-silicate equilibration in a magma ocean cannot be ruled out due to a lack of HSE partitioning data suitable for extrapolations to the relevant high pressure and high temperature conditions. We provide a new data set of partition coefficients simultaneously determined for Ru, Rh, Pd, Re, Ir and Pt over a range of 3.5-18 GPa and 2423-2773 K. In multianvil experiments, molten peridotite was equilibrated in MgO single crystal capsules with liquid Fe-alloy that contained bulk HSE concentrations of 53.2-98.9 wt% (XFe = 0.03-0.67) such that oxygen fugacities of IW - 1.5 to IW + 1.6 (i.e. logarithmic units relative to the iron-wüstite buffer) were established at run conditions. To analyse trace concentrations of the HSEs in the silicate melt with LA-ICP-MS, two silicate glass standards (1-119 ppm Ru, Rh, Pd, Re, Ir, Pt) were produced and evaluated for this study. Using an asymmetric regular solution model we have corrected experimental partition coefficients to account for the differences between HSE metal activities in the multicomponent Fe-alloys and infinite dilution. Based on the experimental data, the P and T dependence of the partition coefficients (D) was parameterized. The partition coefficients of all HSEs studied decrease with increasing pressure and to a greater extent with increasing temperature. Except for Pt, the decrease with pressure is stronger below ˜6 GPa and much weaker in the range 6-18 GPa. This change might result from pressure induced coordination changes in the silicate liquid. Extrapolating the D values over a large range of potential P-T conditions in a terrestrial magma ocean (peridotite liquidus at P ⩽ 60-80 GPa) we conclude that the P-T-induced decrease of D would not have been sufficient to explain HSE mantle abundances by metal-silicate equilibration at a common set of P-T-oxygen fugacity conditions. Therefore, the mantle concentrations of most HSEs cannot have been established during core formation. The comparatively less siderophile Pd might have been partly retained in the magma ocean if effective equilibration pressures reached 35-50 GPa. To a much smaller extent this could also apply to Pt and Rh providing that equilibration pressures reached ⩾60 GPa in the late stage of accretion. With most of the HSE partition coefficients at 60 GPa still differing by 0.5-3 orders of magnitude, metal-silicate equilibration alone cannot have produced the observed near-chondritic HSE abundances of the mantles of the Earth as well as of the Moon or Mars. Our results show that an additional process, such as the accretion of a late veneer composed of some type of chondritic material, was required. The results, therefore, support recent hybrid models, which propose that the observed HSE signatures are a combined result of both metal-silicate partitioning as well as an overprint by late accretion.

Mineralogy of the Almahata Sitta Ureilite

NASA Technical Reports Server (NTRS)

Zolensky, Michael E.; Herrin, J.; Friedrich, J. M.; Rumble, D.; Steele, A.; Jenniskens, P.; Shaddad, M. H.; Le, L.; Robinson, G. A.

2009-01-01

Mineralogy & Petrography: Almahata Sitta, deriving from the asteroid 2008 TC3, is a coarse-grained- to porous, fine-grained, fragmental breccia with subrounded mineral fragments and olivine aggregates embedded in a cataclastic matrix of ureilitic material. Mineral fragments include polycrystalline olivine, low-calcium, pigeonite, and augite. Abundant carbonaceous aggregates containing graphite, microdiamonds and aliphatics. Kamacite, Cr-rich troilite, silica and schreibersite are abundant. The compositional range of the silicates is characteristic of the ureilites as a group, but unusually broad for an individual ureilite. The dense lithology is typical for ureilites, but the porous lithology is anomalous. In the porous lithology pore walls are largely coated by crystals of olivine. Classification: Almahata Sitta is an anomalous, polymict eucrite. Anomalous features include large compositional range of silicates, high abundance and large size of pores, crystalline pore wall linings, and fine-grained texture. Tomography reveals that the pores define thin, discontinuous "sheets" connected in three dimensions, suggesting that they outline grains that have been incompletely welded together. The crystals lining the pore walls are probably vapor phase deposits. Therefore Almahata Sitta may represent an agglomeration of coarse- to fine-grained, incompletely reduced pellets formed during impact, and subsequently welded together at high temperature.

Glass-Ceramic Material from the SiO2-Al2O3-CaO System Using Sugar-Cane Bagasse Ash (SCBA)

NASA Astrophysics Data System (ADS)

Teixeira, S. R.; Romero, M.; Ma Rincón, J.; Magalhães, R. S.; Souza, A. E.; Santos, G. T. A.; Silva, R. A.

2011-10-01

Brazil is the world's largest producer of alcohol and sugar from sugarcane. Currently, sugarcane bagasse is burned in boilers to produce steam and electrical energy, producing a huge volume of ash. The major component of the ash is SiO2, and among the minor components there are some mineralizing agents or fluxing. Published works have shown the potential of transforming silicate-based residues into glass-ceramic products of great utility. This work reports the research results of SCBA use to produce glass-ceramics with wollastonite, rankinite and gehlenite as the major phases. These silicates have important applications as building industry materials, principally wollastonite, due to their special properties: high resistance to weathering, zero water absorption, and hardness among others. The glasses (frits) were prepared mixing ash, calcium carbonate and sodium or potassium carbonates as flux agents, in different concentrations. X-ray fluorescence was used to determine the chemical composition of the glasses and their crystallization was assessed by using thermal analysis (DTA/DSC/TGA) and X-ray diffraction. The crystallization kinetics was evaluated using the Kissinger method, giving activation energies ranging from 200 to 600 kJ/mol.

Spodumene, α-LiAlSi2O6 - A new natural SRS-active crystal with three χ(3)-promoting vibrational modes

NASA Astrophysics Data System (ADS)

Kaminskii, Alexander A.; Bohatý, Ladislav; Libowitzky, Eugen; Rhee, Hanjo; Lux, Oliver; Eichler, Hans J.; Kleinschrodt, Reiner; Yoneda, Hitoki; Shirakawa, Akira; Becker, Petra

2018-04-01

α-LiAlSi2O6, known as mineral spodumene, is introduced as a novel SRS-active crystal with monoclinic symmetry C2/c. Under picosecond laser excitation Raman-induced steady-state χ(3)-nonlinear generation in the visible and near-IR is observed in the crystals. All recorded Stokes and anti-Stokes high-order lasing components are identified and correspond to three SRS-promoting phonon modes with ωSRS1 ≈ 709 cm-1, ωSRS2 ≈ 357 cm-1 and ωSRS3 ≈ 1074 cm-1. On the basis of the results of a spontaneous Raman scattering study they were assigned to vibrations of the tetrahedral [SiO4] groups of the silicate chains and lattice modes of Li-O or Al-O of the crystal structure. A brief review in tabular form of so far known SRS-active natural crystals (minerals) is given as well.

Extra-terrestrial igneous granites and related rocks: A review of their occurrence and petrogenesis

NASA Astrophysics Data System (ADS)

Bonin, Bernard

2012-11-01

The telluric planets and the asteroid belt display the same internal structure with a metallic inner core and a silicate outer shell. Experimental data and petrological evidence in silicate systems show that granite can be produced by extreme igneous differentiation through various types of igneous processes. On Moon, 4.4-3.9 Ga granite clasts display dry mineral assemblages. They correspond to at least 8 discrete intrusive events. Large K/Ca enrichment and low REE abundances in granite relative to KREEP are consistent with silicate liquid immiscibility, a process observed in melt inclusions within olivine of lunar basalts and in lunar meteorites. Steep-sided domes identified by remote sensing can represent intrusive or extrusive felsic formations. On Mars, black-and-white rhythmic layers observed on the Tharsis rise along the flanks of the peripheral scarps of the Tharsis Montes giant volcanoes suggest the possible eruption of felsic pyroclastites. Though no true granites were found so far in the Martian SNC meteorites, felsic glasses and mesostases were identified and a component close to terrestrial continental (granitic) crust is inferred from trace element and isotope systematics. Venus has suffered extensive volcanic resurfacing, whereas folded and faulted areas resemble terrestrial continents. Near large shield volcanoes, with dominant basaltic compositions, steep-sided domes have been interpreted as non-degassed silicic extrusions. The hypothesis of a granitic component is "tantalising". Extra-terrestrial granite is frequently found as clasts and mesostases in asteroidal meteorites. Porphyritic textures, with alkali feldspar crystals up to several centimetres in size, were observed in silicate enclaves within iron meteorites. In the chondrite clan, polymict breccias can contain granitic clasts, whose provenance is debated. One clast from the Adzhi-Bogdo meteorite yields a 4.53 ± 0.03 Ga Pb-Pb age, making it the oldest known granite in the solar system. The vast majority of granitic materials recognised so far in the extra-terrestrial record are characterised by ferroan A-type compositions, characterised by high to very high K2O and medium CaO contents, sodic varieties being exceedingly rare. Textural evidence of graphic quartz-alkali feldspar intergrowths within crystallised products suggests that they are igneous in origin and crystallised quickly from a liquid. In water-depleted to water-free environments, fluorine and chlorine can play significant roles, as their effects on liquidus temperatures and crystallising assemblages are nearly identical to those of water. The distribution of alkalis and alkaline earths cannot be related only to extensive crystal fractionation, but is likely induced by supplementary silicate liquid immiscibility. Medium-temperature silicate liquid immiscibility is well known as a mode of differentiation in experimental petrology studies at very low pressures on systems dominated by Fe, Ti, K, and P as major elements. The ultimate question is, therefore, not whether granite (s.l.) occurs in any given planetary body, but if sufficient volumes of granitic materials could have been produced to constitute stable continental nuclei.

High-pressure phases of cordierite from single-crystal X-ray diffraction to 15 GPa

DOE PAGES

Finkelstein, Gregory J.; Dera, Przemyslaw K.; Duffy, Thomas S.

2015-08-14

High-pressure single-crystal X-ray diffraction experiments were conducted on natural cordierite crystals with composition Mg1.907(18)Fe0.127(6)Al4.01(2)Si4.96(3)Na0.026(3)O18.12(9) using a synchrotron X-ray source. The samples were compressed at 300 K in a diamond anvil cell to a maximum pressure of 15.22(15) GPa with a neon pressure-transmitting medium and a gold pressure calibrant. We observed a recently described orthorhombic to triclinic transition, as well as a further transition to a second triclinic phase. We solved and refined both new triclinic hases in space group P1, and designate them cordierite II and III. The structures of cordierite II and III were refined at 7.52(3) GPa atmore » 15.22(15) GPa, respectively. The lattice parameters at these pressures are a = 15.567(3) Å, b = 9.6235(4) Å, c = 9.0658(6) Å, α = 89.963(5)°, β = 86.252(10)°, and γ = 90.974(8)° for cordierite II, and a = 8.5191(19) Å, b = 8.2448(3) Å, c = 9.1627(4) Å, α = 85.672(4)°, β = 85.986(7)°, and γ = 70.839(10)° for cordierite III. Across the phase transitions there is a significant reduction in the length of the a-axis (~2 Å per phase transition), whereas both the b- and c-axis remain largely unchanged. Cordierite II has four- and five-coordinated Si and Al, while cordierite III has four-, five-, and six-coordinated Si, four- and five-coordinated Al, and five- and six-coordinated Mg. The sequence of high-pressure phases shows increasing polymerization of coordination polyhedra. These results, together with other recent studies, suggest that mixed 4-, 5-, and 6-fold coordination states may occur more commonly in silicate structures compressed at 300 K than previously recognized.« less

Synthesis, characterization and modelling of zinc and silicate co-substituted hydroxyapatite.

PubMed

Friederichs, Robert J; Chappell, Helen F; Shepherd, David V; Best, Serena M

2015-07-06

Experimental chemistry and atomic modelling studies were performed here to investigate a novel ionic co-substitution in hydroxyapatite (HA). Zinc, silicate co-substituted HA (ZnSiHA) remained phase pure after heating to 1100 °C with Zn and Si amounts of 0.6 wt% and 1.2 wt%, respectively. Unique lattice expansions in ZnSiHA, silicate Fourier transform infrared peaks and changes to the hydroxyl IR stretching region suggested Zn and silicate co-substitution in ZnSiHA. Zn and silicate insertion into HA was modelled using density functional theory (DFT). Different scenarios were considered where Zn substituted for different calcium sites or at a 2b site along the c-axis, which was suspected in singly substituted ZnHA. The most energetically favourable site in ZnSiHA was Zn positioned at a previously unreported interstitial site just off the c-axis near a silicate tetrahedron sitting on a phosphate site. A combination of experimental chemistry and DFT modelling provided insight into these complex co-substituted calcium phosphates that could find biomedical application as a synthetic bone mineral substitute. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Carbonate-silicate liquid immiscibility upon impact melting, Ries Crater, Germany

NASA Astrophysics Data System (ADS)

Graup, Guenther

1999-05-01

The 24-km-diameter Ries impact crater in southern Germany is one of the most studied impact structures on Earth. The Ries impactor struck a Triassic to Upper Jurassic sedimentary sequence overlying Hercynian crystalline basement. At the time of impact (14.87 +/- 0.36 Ma; Storzer et al., 1995), the 350 m thick Malm limestone was present only to the S and E of the impact site. To the N and W, the Malm had been eroded away, exposing the underlying Dogger and Lias. The largest proportion of shocked target material is in the impact melt-bearing breccia suevite. The suevite had been believed to be derived entirely from the crystalline basement. Calcite in the suevite has been interpreted as a post-impact hydrothermal deposit. From optical inspection of 540 thin sections of suevite from 32 sites, I find that calcite in the suevite shows textural evidence of liquid immiscibility with the silicate impact melt. Textural evidence of liquid immiscibility between silicate and carbonate melt in the Ries suevite includes: carbonate globules within silicate glass, silicate globules embedded in carbonate, deformable and coalescing carbonate spheres within silicate glass, sharp menisci or cusps and budding between silicate and carbonate melt, fluidal textures and gas vesicles in carbonate schlieren, a quench crystallization sequence of the carbonate, spinifex textured quenched carbonate, separate carbonate spherules in the suevite mineral-fragment-matrix, and inclusions of mineral fragments suspended in carbonate blebs. Given this evidence of liquid immiscibility, the carbonate in the suevite has, therefore, like the silicate melt a primary origin by impact shock melting. Evidence of carbonate-silicate liquid immiscibility is abundant in the suevites to the SW to E of the Ries crater. The rarer suevites to the W to NE of the crater are nearly devoid of carbonate melts. This correspondence between the occurrence of outcropping limestones at the target surface and the formation of carbonate melt, indicates that the Malm limestones are the source rocks of the carbonate impact melt. This correspondence shows that the suevites preserve a compositional memory of their source rocks. From the regional distribution of suevites with or without immiscible carbonate melts, it is inferred that the Ries impactor hit the steep Albtrauf escarpment at its toe, in an oblique impact from the north.

Rapid thermal rejuvenation of high-crystallinity magma linked to porphyry copper deposit formation; evidence from the Koloula Porphyry Prospect, Solomon Islands

NASA Astrophysics Data System (ADS)

Tapster, S.; Condon, D. J.; Naden, J.; Noble, S. R.; Petterson, M. G.; Roberts, N. M. W.; Saunders, A. D.; Smith, D. J.

2016-05-01

Magmas containing the components needed to form porphyry copper deposits are relatively common within arcs, yet mineralising events are uncommon within the long-lived magmatic systems that host them. Understanding what causes the transition from barren to productive intrusions is critical to the development of conceptual deposit models. We have constrained the tempo of pre- and syn-mineralisation magmatic events in relationship to the thermal evolution of the plutonic body that underlies one of the world's youngest exposed plutonic-porphyry systems, the Inamumu Zoned Pluton, Koloula Porphyry Prospect, Solomon Islands. High precision ID-TIMS U-Pb dates of texturally and chemically characterised zircons indicate pluton emplacement over <150 kyr was superseded after ca. 50 kyr by two discrete episodes of mineralising porphyritic melt emplacement. Their associated hydrothermal systems initiated within ca. 30 kyrs of each other. Zircon populations within evolved intrusions contain resorbed cores that were recycled from the deeper magmatic system, yet their youngest dates are statistically indistinguishable from those yielded by crystals lacking resorption. Comparisons of Ti-in-zircon proxy temperatures, modelled zircon saturation temperatures and temperature-crystallinity relationships suggest that prior to being heated and emplaced within the shallow level pluton, magmas were stored at depth in a high-crystallinity (>50% crystals) state, past the point of rheological lock-up. We estimate that thermal rejuvenation of the deeper high-crystallinity magma and generation of a mobile melt fraction may have occurred ≤10 kyr before its transport and emplacement within the porphyry environment. The underlying pluton likely cooled and returned to high-crystallinity states prior to subsequent remobilisation-emplacement events. Titanium-in-zircon geothermometry and whole-rock geochemistry suggest pre-mineralisation intrusions were remobilised by mixing of a silicic magma with a high-temperature, less-evolved melt. In contrast, syn-mineralisation melts were most likely remobilised by the percolation of hot volatiles exsolved from contemporaneous less-evolved intrusions cooling beneath the crystalline silicic magma. The evidence for the rapid thermal rejuvenation and long term storage of highly crystalline silicic magmas is consistent with previous studies that indicate two components of exsolved volatiles contribute to ore forming fluids. We conclude that the liberation of crystal-rich porphyry copper deposit forming magmas, and the addition of the chemical components required for ore formation, are intrinsically linked to the volatiles released during the recharge of less-evolved melt into a highly crystalline silicic magma.

Partitioning of V, Mn, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb, and Bi between sulfide phases and hydrous basanite melt at upper mantle conditions

NASA Astrophysics Data System (ADS)

Li, Yuan; Audétat, Andreas

2012-11-01

The partitioning of 15 major to trace metals between monosulfide solid solution (MSS), sulfide liquid (SL) and mafic silicate melt (SM) was determined in piston-cylinder experiments performed at 1175-1300 °C, 1.5-3.0 GPa and oxygen fugacities ranging from 3.1 log units below to 1.0 log units above the quartz-fayalite-magnetite fO2 buffer, which conditions are representative of partial melting in the upper mantle in different tectonic settings. The silicate melt was produced by partial melting of a natural, amphibole-rich mantle source rock, resulting in hydrous (˜5 wt% H2O) basanitic melts similar to low-degree partial melts of metasomatized mantle, whereas the major element composition of the starting sulfide (˜52 wt% Fe; 39 wt% S; 7 wt% Ni; 2 wt% Cu) was similar to the average composition of sulfides in this environment. SL/SM partition coefficients are high (≥100) for Au, Ni, Cu, Ag, Bi, intermediate (1-100) for Co, Pb, Sn, Sb (±As, Mo), and low (≤1) for the remaining elements. MSS/SM partition coefficients are generally lower than SL/SM partition coefficients and are high (≥100) for Ni, Cu, Au, intermediate (1-100) for Co, Ag (±Bi, Mo), and low (≤1) for the remaining elements. Most sulfide-silicate melt partition coefficients vary as a function of fO2, with Mo, Bi, As (±W) varying by a factor >10 over the investigated fO2 range, Sb, Ag, Sn (±V) varying by a factor of 3-10, and Pb, Cu, Ni, Co, Au, Zn, Mn varying by a factor of 3-10. The partitioning data were used to model the behavior of Cu, Au, Ag, and Bi during partial melting of upper mantle and during fractional crystallization of primitive MORB and arc magmas. Sulfide phase relationships and comparison of the modeling results with reported Cu, Au, Ag, and Bi concentrations from MORB and arc magmas suggest that: (i) MSS is the dominant sulfide in the source region of arc magmas, and thus that Au/Cu ratios in the silicate melt and residual sulfides may decrease with increasing degree of partial melting, (ii) both MSS and sulfide liquid are precipitated during fractional crystallization of MORB, and (iii) fractional crystallization of arc magmas is strongly dominated by MSS.

Microcrystals and Amorphous Material in Comets and Primitive Meteorites: Keys to Understanding Processes in the Early Solar System

NASA Technical Reports Server (NTRS)

Nuth, J. A.; Brearley, A. J.; Scott, E. R. D.

2004-01-01

Comets, fine-grained matrices of chondrites, and chondritic interplanetary dust particles (IDPs) are each composed of both crystalline and amorphous silicates. The primitive solar nebula, in which comets and asteroids accreted, was formed from the collapsed core of a Giant Molecular Cloud, that, in turn, condensed from materials present in the interstellar medium (ISM). Despite observations that reveal the presence of crystalline magnesium silicate minerals in the shells of very high mass-loss-rate stars [1,2], typical silicate grains in the ISM are most likely to be amorphous, given their relatively long residence time in such a high radiation environment. An upper limit of 3% crystalline grains can be derived from their non-detection in spectra of ISM solids [3]. If the vast majority of grains that enter the primitive solar nebula are amorphous, then the observation of crystalline dust in comets and primitive chondrite matrices indicates the action of specific processes required to transform the amorphous starting materials into the crystals that are observed.

Temperature effects on luminescence properties of Cr3+ ions in alkali gallium silicate nanostructured media

NASA Astrophysics Data System (ADS)

Lipinska-Kalita, Kristina E.; Krol, Denise M.; Hemley, Russell J.; Kalita, Patricia E.; Gobin, Cedric L.; Ohki, Yoshimichi

2005-09-01

We have investigated the optical properties of Cr3+ ions in an alkali gallium silicate glass system and in two glass-based nanocomposites with nucleated β-Ga2O3 nanocrystals. The nucleation and growth of the nanocrystalline phase in the host glass matrix were monitored by Raman scattering spectroscopy and angle-dispersive x-ray diffraction. A broadband luminescence, associated with the 4T2-4A2 transition from the weak crystal field of octahedral Cr3+ sites, dominated the emission of the precursor as-quenched glass. The luminescence spectra of the synthesized glass-ceramic nanocomposites revealed a crystal-like 2E-4A2 strong emission and indicated that the major fraction of Cr3+ ions was located within the nanocrystalline environment. The variable-temperature studies of the nanocomposites demonstrated that the fluorescence of Cr3+ ions can be transformed from sharp R lines of the 2E-4A2 transition to a combination of R lines and of the broad band of the 4T2-4A2 transition. We propose a simple distribution model where the major part of Cr3+ ions is located in the nanocrystalline phase of the glass-ceramic composites in the octahedral environment, substituting the gallium atoms in the β-Ga2O3 crystal structure. The developed nanocrystalline glass-ceramics are a promising class of Cr3+-doped oxide glass-based optically active composite materials.

Silicic magma differentiation in ascent conduits. Experimental constraints

NASA Astrophysics Data System (ADS)

Rodríguez, Carmen; Castro, Antonio

2017-02-01

Crystallization of water-bearing silicic magmas in a dynamic thermal boundary layer is reproduced experimentally by using the intrinsic thermal gradient of piston-cylinder assemblies. The standard AGV2 andesite under water-undersaturated conditions is set to crystallize in a dynamic thermal gradient of about 35 °C/mm in 10 mm length capsules. In the hotter area of the capsule, the temperature is initially set at 1200 °C and decreases by programmed cooling at two distinct rates of 0.6 and 9.6 °C/h. Experiments are conducted in horizontally arranged assemblies in a piston cylinder apparatus to avoid any effect of gravity settling and compaction of crystals in long duration runs. The results are conclusive about the effect of water-rich fluids that are expelled out the crystal-rich zone (mush), where water saturation is reached by second boiling in the interstitial liquid. Expelled fluids migrate to the magma ahead of the solidification front contributing to a progressive enrichment in the fluxed components SiO2, K2O and H2O. The composition of water-rich fluids is modelled by mass balance using the chemical composition of glasses (quenched melt). The results are the basis for a model of granite magma differentiation in thermally-zoned conduits with application of in-situ crystallization equations. The intriguing textural and compositional features of the typical autoliths, accompanying granodiorite-tonalite batholiths, can be explained following the results of this study, by critical phenomena leading to splitting of an initially homogeneous magma into two magma systems with sharp boundaries. Magma splitting in thermal boundary layers, formed at the margins of ascent conduits, may operate for several km distances during magma transport from deep sources at the lower crust or upper mantle. Accordingly, conduits may work as chromatographic columns contributing to increase the silica content of ascending magmas and, at the same time, leave behind residual mushes that eventually are dragged as enclaves or autoliths.

Late Pleistocene granodiorite source for recycled zircon and phenocrysts in rhyodacite lava at Crater Lake, Oregon

USGS Publications Warehouse

Bacon, C.R.; Lowenstern, J. B.

2005-01-01

Rhyodacite tephra and three lavas erupted ???27 ka, interpreted to be early leaks from the climactic magma chamber of Mount Mazama, contain ubiquitous resorbed crystals (antecrysts) that were recycled from young granodiorite and related plutonic rocks of the same magmatic system. The shallow composite pluton is represented by blocks ejected in the 7.7-ka climactic eruption that formed Crater Lake caldera. Plagioclase crystals in both rhyodacite and granodiorites commonly have cores with crystallographically oriented Fe-oxide needles exsolved at subsolidus conditions. At least 80% of plagioclase crystals in the rhyodacite are antecrysts derived from plutonic rocks. Other crystals in the rhyodacite, notably zircon, also were recycled. SIMS 238U- 230Th dating indicates that zircons in 4 granodiorite blocks crystallized at various times between ???20 ka and ???300 ka with concentrations of analyses near 50-70, ???110, and ???200 ka that correspond to periods of dacitic volcanism dated by K- Ar. U-Th ages of zircon from a rhyodacite sample yield similar results. No analyzed zircons from the granodiorite or rhyodacite are pre-Quaternary. Zircon minimum ages in blocks from different locations around the caldera reflect ages of nearby volcanic vents and may map the distribution of intrusions within a composite pluton. Survival of zircon in zircon-undersaturated hydrous magma and of Fe-oxide needles in plagioclase suggests that little time elapsed from entrainment of antecrysts to the ???27-ka eruption of the rhyodacite. The ???27-ka rhyodacite is an example of young silicic magma that preserved unstable antecrysts from a known source early during growth of a large high-level magma chamber. In contrast, the voluminous 7.7-ka climactic rhyodacite pumice is virtually lacking in zircon, indicating dissolution of any granodioritic debris in the intervening period. Mineralogical evidence of assimilation may be destroyed in hot, vigorously growing silicic magma bodies such as ultimately produced the climactic eruption of Mount Mazama. ?? 2005 Elsevier B.V. All rights reserved.

Face-specific Replacement of Calcite by Amorphous Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Liesegang, M.; Milke, R.; Neusser, G.; Mizaikoff, B.

2016-12-01

Amorphous silica, composed of nanoscale spheres, is an important biomineral, alteration product of silicate rocks on the Earth's surface, and precursor material for stable silicate minerals. Despite constant progress in silica sphere synthesis, fundamental knowledge of natural silica particle interaction and ordering processes leading to colloidal crystals is absent so far. To understand the formation pathways of silica spheres in a geologic environment, we investigated silicified Cretaceous mollusk shell pseudomorphs from Coober Pedy (South Australia) using focused ion beam (FIB)-SEM tomography, petrographic microscopy, µ-XRD, and EMPA. The shells consist of replaced calcite crystals (<2 mm) composed of ordered arrays of uniform, close-packed silica spheres 300 ± 10 nm in size. Concentric layered spheres composed of 40 nm-sized subparticles provide evidence that, at least in the final stage, particle aggregation was the major sphere growth mechanism. Silica sphere arrays in periodically changing orientations perfectly replicate polysynthetic twinning planes of calcite. FIB-SEM tomography shows that cubic closed-packed sphere arrangements preserve the twin lamellae, while the twin plane consists of a submicrometer layer of randomly ordered spheres and vacancies. To transfer crystallographic information from parent to product, the advancement of synchronized dissolution and precipitation fronts along lattice planes is essential. We assume that the volume-preserving replacement process proceeds via a face-specific dissolution-precipitation mechanism with intermediate subparticle aggregation and subsequent layer-by-layer deposition of spheres along a planar surface. Porosity created during the replacement reaction allows permanent fluid access to the propagating reaction interface. Fluid pH and ionic strength remain constant throughout the replacement process, permitting continuous silica nanoparticle formation and diffusion-limited colloid aggregation. Our study provides a natural example of the transformation of an atomic crystal to an amorphous, mesoscale ordered material; thus, links the research fields of natural colloidal crystal formation, carbonate-silica replacement, and crystallization by oriented particle aggregation (CPA).

Discrete Dipole Approximation Models of Crystalline Forsterite: Applications to Cometary Crystalline Silicates

NASA Astrophysics Data System (ADS)

Lindsay, Sean; Wooden, D. H.; Woodward, C. E.; Harker, D. E.; Kelley, M. S.; Murphy, J. R.

2012-10-01

In cometary comae, the crystalline silicate forsterite (Mg2SiO4) is the dominant crystalline component. Within the 8 - 40 micron spectral range, the crystal shape has been demonstrated to have a measurable effect on the crystalline features’ shape and peak wavelength locations. We present discrete dipole approximation (DDA) absorption efficiencies for a variety of forsterite grain shapes to demonstrate: a) that the 10, 11, 19, 23, and 33.5 micron resonances are sensitive to grain shape; b) spectral trends are associated with variations in crystallographic axial ratios; and c) that groups of similar grain shapes (shape classes) have distinct spectral features. These computations are performed using DDSCAT v7.0 run on the NASA Advanced Supercomputing (NAS) facility Pleiades. We generate synthetic spectral energy distribution (SED) fits to the Infrared Space Observatory (ISO) SWS spectra for the coma of comet C/1995 O1 (Hale-Bopp) at a heliocentric distance of 2.8 AU. Hale-Bopp is best fit by equant grain shapes whereas rounded grain shapes fit significantly poorer than crystals with sharp edges with well-defined faces. Moreover, crystals that are not significantly elongated along a crystallographic axis fit better. By comparison with Kobatake et al. (2008) condensation experiments and Takigawa et al. (2009) evaporation experiments, our analyses suggest that the forsterite crystals in the coma of Hale-Bopp predominantly are high temperature condensates. The laboratory experiments show that grain shape and grain formation temperature, and hence disk environment, are causally linked. Specifically, the Kobatake et al. (2008) condensation experiment reveals three shape classes associated with temperature: 1) ‘Bulky’ grains (1300 K < T < 1700 K), 2) ‘Platy’ grains (1000 K < T < 1300 K), and 3) columnar/needle grains (T < 1000 K). We construct DDA grain shape analogs to these shape classes to connect grain shapes to distinguishable spectral signatures and crystal formation environments.

A case of Alzheimer's disease in magmatic crystals

NASA Astrophysics Data System (ADS)

Costa Rodriguez, F.; Bouvet de Maisonneuve, C.

2012-12-01

The reequilibration of chemical zoning in crystals from volcanic rocks is increasingly used to determine the duration of the processes involved in their origin, residence and transport. There now exist a good number of determinations of diffusion coefficients in olivine (Fe-Mg, Mn, Ca, Ni, Cr), plagioclase (CaAl-NaSi, Mg, Sr, Ba, REE), pyroxenes (Fe-Mg, Mn, Ca, REE) and quartz (Ti), but most studies have used a single element or component in a single mineral group. Although this is a good approach, it can only access a limited range of time scales, typically the short-term memory of the crystal. In other words, for process durations that are longer than the combination of the diffusivity and diffusion distance (and for a constant boundary), the long-term memory of the crystal might have been lost. This could explain why most time determinations of magmatic processes from volcanic rocks give times of about < 100 years, and why these are shorter than the thousands of years obtained from U-Th series disequilibrium isotopes. We have done a series of numerical calculations and natural observation to determine the time windows that can be accessed with different elements and minerals, and how they may affect the time scales and interpretations of processes that the crystals might be recording. We have looked at two end-members representative of mafic and silicic magmas by changing the temperature and mineral compositions. 3 dimensional calculations of diffusion reequilibration at the center of a 1 x 0.5 x 0.5 mm crystal and using a constant boundary as first case. We find that for mafic magma and olivine, 90 % of equilibration of Fe-Mg, Mn, and Ni occurs in a few decades, but gradients in Ca and Cr persist for a few thousand years. These results can for example explain the large ranges of Ca and Cr contents at a given Fe/Mg of olivine, and why apparently contradictory times can be obtained from elements with different diffusivities in the same crystal. At the same time these findings also highlight that there is a long-term memory of the crystal that is typically not accessed by current studies. However, unraveling this memory is more complex because it seems unrealistic to assume a constant composition at the boundary for hundreds or thousands of years, and because crystals can be growing and dissolving multiple times. Additional models considering growth and a variable boundary show that a significant part of the memory is lost by multiple changes in concentration being superimposed at the crystal rim. Here we also report a case where accessing the older history of the crystals might be possible by a combination of X-Ray element maps plus multiple element zoning traverses (Fe-Mg, Ca, Mn, Ni, Al, P, Cr) in olivine from Llaima volcano (Chile). Element distributions reveal that the crystals had an early history of fast growth. The delicate structures of P zoning have been used to recognize any crystal dissolution. Cr, Fe-Mg, Ni, Mn are zoned but the times obtained from Cr are 4 x longer than those of the other elements. Our interpretation is that the Cr zoning records the older memory of the crystal since eruption but that of Fe-Mg has lost part of the memory due to multiple changes at the rim or complete homogenization of the crystal. Thus using multiple elements and minerals allow accessing the long and short term memory of the crystals and associated magma.

An Overview of the Origin of A-type Silicic Magmatism Along the Snake River Plain-Yellowstone Hotspot Track

NASA Astrophysics Data System (ADS)

Christiansen, E. H.; Bindeman, I. N.; Leishman, J. R.

2015-12-01

Disparate models have been proposed for the origin of A-type rhyolites--a volumetrically minor part of modern terrestrial magmatism. But understanding the origin of A-type granites and rhyolites has significance for understanding the formation of the Earth's first silicic crust and for planetary magmatism--small volumes of such granitic materials have been found in lunar rocks, martian and asteroidal meteorites, and have been speculated to have formed on Venus. On other planets, vertical tectonics and plume-like mantle convection dominate, not the recycling of wet, oxidized plates of lithosphere as on Earth. Thus, understanding the origins of A-type silicic magma is important on multiple levels. Voluminous A-type rhyolite were produced on the Snake River Plain-Yellowstone hotspot track and provide the opportunity to better understand these important silicic magmas. Detailed petrologic studies suggest that most Snake River Plain rhyolites ultimately formed by partially melting of previously emplaced basaltic intrusions rather than by fractional crystallization of basalt or melting of Archean crust. This hypothesis is favored because of the bimodal association of rhyolite and basalt without linking intermediate compositions. In addition, incompatible element ratios (e.g., La/Nb, Pb/Ce), a lack of old zircon antecrysts, low-U inherited zircon, high ɛNd and ɛHf values, high eruption temperatures (1050°C to 850°C), low fO2 (near QFM), and H2O (as low as 1.5%), link the rhyolites to a plume-derived basaltic parent through partial melting with lesser incorporation of the Archean to Mesozoic crust that underlies the plain. Moreover, the contrast with wetter, lower temperature rhyolites that must have formed by direct crustal melting (e.g., Arbon Valley Tuff) strengthens this interpretation. Many of the rhyolites also have low δ18O values that must be produced in two stages: first by partial melting of already hydrothermally altered basalt, and subsequently in single volcanic centers, by progressive cannibalism of hydrothermally altered intracaldera rhyolites like those identified in many calderas and the Kimberly drill core. The oxygen and Hf isotopic diversity of zircon found in most units is one of the principle evidences for this pervasive recycling.

Velocity of a freely rising gas bubble in a soda-lime silicate glass melt

NASA Technical Reports Server (NTRS)

Hornyak, E. J.; Weinberg, M. C.

1984-01-01

A comparison is conducted between measured velocities for the buoyant rise of single bubbles of varying size and composition, in a soda-lime silicate glass melt, with the steady state velocities predicted by the Stokes and Hadamard-Rybczynski formulas. In all cases, the data are noted to fit the Hadamard-Rybczynski expression for steady state rise speed considerably better than the Stokes formula.

Crystallization kinetics, optical and dielectric properties of Li2OṡCdOṡBi2O3ṡSiO2 glasses

NASA Astrophysics Data System (ADS)

Rani, Saroj; Sanghi, Sujata; Ahlawat, Neetu; Agarwal, Ashish

2015-10-01

Crystallization kinetics, optical absorption and electrical behavior of lithium cadmium silicate glasses with different amount of bismuth oxide were investigated using non-isothermal crystallization approach, UV-VIS-NIR spectroscopy and impedance spectroscopy, respectively. These glasses were synthesized by normal melt quenching technique. Variation in physical properties, viz. density, molar volume with Bi2O3:SiO2 ratio were related to the structural changes occurring in the glasses. The glass transition temperature (Tg), crystalline peak temperature (Tp) and melting temperature (Tm) of these glasses were determined using differential scanning calorimeter at various heating rates. The dependence of Tg and Tp on heating rate has been used for the determination of the activation energy of glass transition and crystallization. Thermal stability parameters have revealed high stability of the glass prepared with 40 mol% of Bi2O3 content. The crystallization kinetics for the glasses was studied by using the Kissinger and modified Ozawa equations. Appearance of a sharp cut-off and a wide and reasonable transmission in VIS-NIR region makes these glasses suitable for IR transmission window. The cut-off wavelength, optical band gap and Urbach's energy have been analyzed and discussed in terms of changes in the glass structure. By analyzing the impedance spectra, the ac and dc conductivities, activation energy for dc conduction (Edc) and for relaxation (EM″) were calculated. The results obtained from dc conductivity confirm the network forming role of Cd2+ ion in the glasses. The scaling of the conductivity spectra has been used to interpret the temperature dependence of the relaxation dynamics. The observed conductivity spectra follows power law with exponent 's' which decreases with temperature and satisfies the correlated barrier hopping (CBH) model. The perfect overlying of normalized plots of electrical modulus on a single 'master curve' depicts temperature as well as composition independent dynamical process at several frequencies.

Microinclusions in polycrystalline diamonds: insights into processes of diamond formation

NASA Astrophysics Data System (ADS)

Jacob, D. E.; Wirth, R.; Enzmann, F.; Schwarz, J. O.; Kronz, A.

2009-04-01

Polycrystalline diamond aggregates (framesites) contain silicates of eclogitic and peridotitic affinity (e.g. Kurat and Dobosi, 2000). The minerals occur mostly in interstices and are intimately intergrown with the diamonds, indicating contemporaneous crystallization within the diamond stability field in the Earth's mantle. In addition to silicates, rarer phases such as Fe-carbide can sometimes be found in framesites that record unusually low local oxygen fugacity at the time of their formation (Jacob et al., 2004). Furthermore, while most gem-sized diamonds have old, often Archaean formation ages, some polycrystalline diamond aggregates have been shown to form directly preceding the kimberlite eruption (Jacob et al., 2000). Thus, these samples may provide a unique source of information on the nature and timing of small scale processes that lead to diamond formation and complement evidence from gem-sized diamonds. Here, we present a study of micro- and nano-inclusions in diamonds from a polycrystalline diamond aggregate (framesite) from the Orapa Mine (Botswana) and combine results from TEM/FIB analyses with high-resolution computerized micro-tomography (HR-µCT) and electron microprobe analyses to further constrain the formation of diamond in the Earth's mantle. Results In total, 14 microinclusions from fifteen FIB foils were investigated. Micro- and nano-inclusions identified by TEM were smaller than 1µm down to ca. 50nm in size, and are both monomineralic and multi-phase. The cavities are often lath-shaped and oriented parallel to each other; many show lattice dislocations in the surrounding diamond. In addition, inclusions are found along open cracks within the diamond single crystals. Mineral phases in the microinclusions comprise rutile, omphacite and a FeS phase (pyrrhotite). The multiphase inclusions most often consist of cavities that are only partly occupied (less than 50% of the total space), suggesting that the empty space was originally filled by a fluid. One multiphase inclusion was found to be still fluid-bearing, showing characteristic continuous changes in diffraction contrast due to density fluctuations caused by the electron beam. No other elements than carbon were detected during AEM of this area which suggests that the fluid consists of relatively pure C-H-O species. In addition to the fluid, this inclusion contained fine-grained FeS, a silicate phase rich in Fe, P, Mg, Al, Ca and K and a quench phase, rich in Fe, P and Si. Macroinclusions (>5µm) are magnetite, often surrounded by hematite, FeS, low-Cr garnet (Py50Alm39Grs11) and omphacite (Jd23). Garnet and cpx were found as non-touching inclusions and yield 1256°C at 5 GPa. Most of the magnetite inclusions are single crystals and some are strongly deformed with signs of recrystallization. Hematite occurs as porous aggregates of nano-granules of ca. 5-7 nm sizes. High Resolution µ-Computer Tomography (HR-µCT) shows pores in the sample and the included mineral phases as areas of differing grey-values. These are a direct function of the specific x-ray density of the specific phase and can be used to differentiate oxides and silicates. Based on the 3D tomogram, the amount of pores per total volume of the diamond plus inclusion matrix is calculated to be 0.65 vol%, while magnetite inclusions amount to 3.16 vol%. The average equivalent radius of the magnetite grains (radius of a sphere with the same volume as the grain) is 17.8 µm, while that of the pores is 12.6µm. Discussion The occurrence of omphacite, rutile and FeS as microinclusions within the diamond crystals clearly shows that these phases are cogenetic to the diamonds. However, magnetite and hematite were only encountered as large inclusions in cavities that appear to be interstitial porosity. Moreover, analysis of the equivalent radius distribution of the pores and the magnetite inclusions derived from HR-µCT shows a complete overlap of the mode, indicating that magnetite preferentially fills the porosity in the sample. Furthermore, hematite occurs exclusively along the outer rim of the magnetite crystals and textural features suggest that this phase is a late replacement product of magnetite. This shows that the magnetite-bearing cavities were not shielded from the outside by the host diamond and may indicate that magnetite itself was introduced after diamond formation or during a secondary event that may still, however, have taken place at PT conditions of the diamond stability field. The microinclusion suite described here is distinct from that found in fibrous (e.g. Klein-BenDavid et al., 2007) and in microdiamonds (Kvasnytsya et al., 2006). Carbonates, halides and phosphates, that are typical for fibrous and microdiamonds were not encountered in our study. Instead, the microinclusion suite found in the framesite consists of the typical eclogitic minerals (rutile, garnet, omphacite, sulphide) plus a C-H-O fluid. Jacob et al., 2004. Contrib. Mineral. Petrol., 146, 566-576. Jacob et al., 2000. Science, 289, 1182-1185. Klein-BenDavid et al., 2007. Amer. Mineral. 91, 353-365. Kurat and Dobosi, 2000. Mineral. Petrol. 69, 143-159. Kvasnytsya et al., 2006. Ukrainian Geologist 2, 25-36.

Response to Comment on "Rapid cooling and cold storage in a silicic magma reservoir recorded in individual crystals".

PubMed

Cooper, Kari M; Till, Christy B; Kent, Adam J R; Costa, Fidel; Rubin, Allison E; Gravley, Darren; Deering, Chad; Cole, Jim; Bose, Maitrayee

2017-12-22

In a recent paper, we used Li concentration profiles and U-Th ages to constrain the thermal conditions of magma storage. Wilson and co-authors argue that the data instead reflect control of Li behavior by charge balance during partitioning and not by experimentally determined diffusion rates. Their arguments are based on (i) a coupled diffusion mechanism for Li, which has been postulated but has not been documented to occur, and (ii) poorly constrained zircon growth rates combined with the assumption of continuous zircon crystallization. Copyright © 2017, American Association for the Advancement of Science.

Vapor deposition in basaltic stalactites, Kilauea, Hawaii

NASA Astrophysics Data System (ADS)

Baird, A. K.; Mohrig, D. C.; Welday, E. E.

Basaltic stalacties suspended from the ceiling of a large lava tube at Kilauea, Hawaii, have totally enclosed vesicles whose walls are covered with euhedral FeTi oxide and silicate crystals. The walls of the vesicles and the exterior surfaces of stalactites are Fe and Ti enriched and Si depleted compared to common basalt. Minerals in vesicles have surface ornamentations on crystal faces which include alkali-enriched, aluminosilicate glass(?) hemispheres. No sulfide-, chloride-, fluoride-, phosphate- or carbonate-bearing minerals are present. Minerals in the stalactites must have formed by deposition from an iron oxide-rich vapor phase produced by the partial melting and vaporization of wall rocks in the tube.

Concordant ages for the Lava Creek Tuff from high-spatial-resolution U-Pb dating of zircon rim faces and single-crystal sanidine 40Ar/39Ar dating

NASA Astrophysics Data System (ADS)

Matthews, N. E.; Vazquez, J. A.; Calvert, A. T.

2013-12-01

The last great explosive supereruption from the Yellowstone Plateau formed present-day Yellowstone caldera and ejected the >1000 km3 of rhyolite that composes the Lava Creek Tuff (LCT). The LCT eruption blanketed much of the western United States in ash, and consequently is a key chronostratigraphic marker bed for delimiting Quaternary uplift rates, the age of middle Pleistocene glacial and pluvial deposits, and tephra correlation in North America. Previous 40Ar/39Ar dating of the two mineralogically distinct LCT members (A & B) yield ages ranging from ca. 600 ka (Gansecki et al., 1998) to ca. 640 ka (Lanphere et al., 2002). To resolve the timing of eruption and crystallization timescale for the LCT magma, we dated both LCT members using a dual-method approach as follows: (1) ion microprobe (SHRIMP-RG) U-Pb dating and trace-element characterization of the final few micrometers of zircon crystallization by analysis of unpolished rims on indium-mounted crystals, and dating of the onset of zircon crystallization by traditional analysis of sectioned crystal interiors, and (2) laser-fusion 40Ar/39Ar dating of single sanidine crystals from bulk LCT ignimbrite and pumice. The unpolished rims of zircon from LCT members A & B yield indistinguishable ages, with a mean age of 621.8 × 2.5 ka (1σ) after correction for initial 230Th disequilibrium as constrained by ion-probe analyses of LCT melt inclusions. Single sanidine crystals from LCT-B yield a mean age of 624.9 × 2.6 ka (FCT=28.17 Ma) that is indistinguishable from the zircon rim ages for both members. These results indicate that LCT members A & B erupted over a geologically brief interval, which is supported by the direct and gradational contact of their equivalent fallout in distal lacustrine deposits and a lack of field evidence for a significant time-break between the LCT A & B in proximal deposits (Christiansen, 2001), but contrasts with older Yellowstone ignimbrite (e.g., Huckleberry Ridge) that may have erupted as multiple pulses over tens of kyr (Ellis et al., 2012). Both LCT members contain zircon whose interiors yield U-Pb ages that are mostly ca. 40 kyr older than their rims, suggesting a short timescale for assembly of the LCT magma chamber relative to some other voluminous bodies of silicic magma (e.g., Fish Canyon). Trace-element concentrations in zircon from Members A and B appear diagnostic, with the former containing higher U and REE concentrations. Our concordant results from U-Pb and 40Ar/39Ar dating indicating a ca. 625 ka age for the LCT eruption are supported by the stratigraphic position of LCT-B tephra at or near the top of Great Basin pluvial lake bed sequences associated with Marine Isotope Stage 16, whose termination is astronomically dated at 621 ka. Christiansen, 2001, USGS Prof. Pap. 729-G; Ellis et al., 2012, Quat Geochron 9: 31-41; Gansecki et al., 1998, Geology 26(4): 343-346; Lanphere et al., 2002, GSA Bull. 114(5): 559-568.

Months between rejuvenation and volcanic eruption at Yellowstone caldera, Wyoming

USGS Publications Warehouse

Till, Christy B.; Vazquez, Jorge A.; Boyce, Jeremy W

2015-01-01

Rejuvenation of previously intruded silicic magma is an important process leading to effusive rhyolite, which is the most common product of volcanism at calderas with protracted histories of eruption and unrest such as Yellowstone, Long Valley, and Valles, USA. Although orders of magnitude smaller in volume than rare caldera-forming super-eruptions, these relatively frequent effusions of rhyolite are comparable to the largest eruptions of the 20th century and pose a considerable volcanic hazard. However, the physical pathway from rejuvenation to eruption of silicic magma is unclear particularly because the time between reheating of a subvolcanic intrusion and eruption is poorly quantified. This study uses geospeedometry of trace element profiles with nanometer resolution in sanidine crystals to reveal that Yellowstone’s most recent volcanic cycle began when remobilization of a near- or sub-solidus silicic magma occurred less than 10 months prior to eruption, following a 220,000 year period of volcanic repose. Our results reveal a geologically rapid timescale for rejuvenation and effusion of ~3 km3 of high-silica rhyolite lava even after protracted cooling of the subvolcanic system, which is consistent with recent physical modeling that predict a timescale of several years or less. Future renewal of rhyolitic volcanism at Yellowstone is likely to require an energetic intrusion of mafic or silicic magma into the shallow subvolcanic reservoir and could rapidly generate an eruptible rhyolite on timescales similar to those documented here.

Mechanical properties of zirconia reinforced lithium silicate glass-ceramic.

PubMed

Elsaka, Shaymaa E; Elnaghy, Amr M

2016-07-01

The aim of this study was to assess the mechanical properties of recently introduced zirconia reinforced lithium silicate glass-ceramic. Two types of CAD/CAM glass-ceramics (Vita Suprinity (VS); zirconia reinforced lithium silicate and IPS e.max CAD (IC); lithium disilicate) were used. Fracture toughness, flexural strength, elastic modulus, hardness, brittleness index, and microstructures were evaluated. Data were analyzed using independent t tests. Weibull analysis of flexural strength data was also performed. VS had significantly higher fracture toughness (2.31±0.17MPam(0.5)), flexural strength (443.63±38.90MPa), elastic modulus (70.44±1.97GPa), and hardness (6.53±0.49GPa) than IC (P<0.001). On the other hand, VS glass-ceramic revealed significantly a higher brittleness index (2.84±0.26μm(-1/2)) (lower machinability) than IC glass-ceramic (P<0.05). VS demonstrated a homogeneous fine crystalline structure while, IC revealed a structure with needle-shaped fine-grained crystals embedded in a glassy matrix. The VS glass-ceramic revealed a lower probability of failure and a higher strength than IC glass-ceramic according to Weibull analysis. The VS zirconia reinforced lithium silicate glass-ceramic revealed higher mechanical properties compared with IC lithium disilicate glass-ceramic. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Pre-accretional sorting of grains in the outer solar nebula

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

Wozniakiewicz, P. J.; Bradley, J. P.; Ishii, H. A.

2013-12-20

Despite their micrometer-scale dimensions and nanogram masses, chondritic porous interplanetary dust particles (CP IDPs) are an important class of extraterrestrial material since their properties are consistent with a cometary origin and they show no evidence of significant post-accretional parent body alteration. Consequently, they can provide information about grain accretion in the comet-forming region of the outer solar nebula. We have previously reported our comparative study of the sizes and size distributions of crystalline silicate and sulfide grains in CP IDPs, in which we found these components exhibit a size-density relationship consistent with having been sorted together prior to accretion. Heremore » we extend our data set and include GEMS (glass with embedded metal and sulfide), the most abundant amorphous silicate phase observed in CP IDPs. We find that while the silicate and sulfide sorting trend previously observed is maintained, the GEMS size data do not exhibit any clear relationship to these crystalline components. Therefore, GEMS do not appear to have been sorted with the silicate and sulfide crystals. The disparate sorting trends observed in GEMS and the crystalline grains in CP IDPs present an interesting challenge for modeling early transport and accretion processes. They may indicate that several sorting mechanisms operated on these CP IDP components, or alternatively, they may simply be a reflection of different source environments.« less

Chemical Zoning of Feldspars in Lunar Granitoids: Implications for the Origins of Lunar Silicic Magmas

NASA Technical Reports Server (NTRS)

Mills, R. D; Simon, J. I.; Alexander, C.M. O'D.; Wang, J.; Christoffersen, R.; Rahman, Z..

2014-01-01

Fine-scale chemical and textural measurements of alkali and plagioclase feldspars in the Apollo granitoids (ex. Fig. 1) can be used to address their petrologic origin(s). Recent findings suggest that these granitoids may hold clues of global importance, rather than of only local significance for small-scale fractionation. Observations of morphological features that resemble silicic domes on the unsampled portion of the Moon suggest that local, sizable net-works of high-silica melt (>65 wt % SiO2) were present during crust-formation. Remote sensing data from these regions suggest high concentrations of Si and heat-producing elements (K, U, and Th). To help under-stand the role of high-silica melts in the chemical differentiation of the Moon, three questions must be answered: (1) when were these magmas generated?, (2) what was the source material?, and (3) were these magmas produced from internal differentiation. or impact melting and crystallization? Here we focus on #3. It is difficult to produce high-silica melts solely by fractional crystallization. Partial melting of preexisting crust may therefore also have been important and pos-sibly the primary mechanism that produced the silicic magmas on the Moon. Experimental studies demonstrate that partial melting of gabbroic rock under mildly hydrated conditions can produce high-silica compositions and it has been suggested by that partial melting by basaltic underplating is the mechanism by which high-silica melts were produced on the Moon. TEM and SIMS analyses, coordinated with isotopic dating and tracer studies, can help test whether the minerals in the Apollo granitoids formed in a plutonic setting or were the result of impact-induced partial melting. We analyzed granitoid clasts from 3 Apollo samples: polymict breccia 12013,141, crystalline-matrix breccia 14303,353, and breccia 15405,78

Complex origins of silicate veinlets in HED meteorites: A case study of Northwest Africa 1109

NASA Astrophysics Data System (ADS)

Pang, Run-Lian; Zhang, Ai-Cheng; Wang, Ru-Cheng

2017-10-01

We report on the petrography and mineralogy of three types of silicate veinlets in the brecciated eucrite Northwest Africa (NWA) 1109. These include Fe-rich olivine, Mg-rich olivine, and pyroxene veinlets. The Fe-rich olivine veinlets mainly infill fractures in pyroxene and also occur along grain boundaries between pyroxene and plagioclase crystals, in both nonequilibrated and equilibrated lithic clasts. The host pyroxene of Fe-rich olivine veinlets shows large chemical variations between and within grains. The Fe-rich olivine veinlets also contain fine-grained Fe3+-bearing chromite, highly calcic plagioclase, merrillite, apatite, and troilite. Based on texture and mineral chemistry, we argue that the formation of Fe-rich olivine was related to fluid deposition at relatively high temperatures. However, the source of Fe-rich olivine in the veinlets remains unclear. Magnesium-rich olivine veinlets were found in three diogenitic lithic clasts. In one of these, the Mg-rich olivine veinlets only occur in one of the fine-grained interstitial regions and extend into fractures within surrounding coarse-grained orthopyroxene. Based on the texture of the interstitial materials, we suggest that the Mg-rich olivine veinlets formed by shock-induced localized melting and recrystallization. Pyroxene veinlets were only observed in one clast where they infill fractures within large plagioclase grains and are associated with fine-grained pyroxene surrounding coarse-grained pyroxene. The large chemical variations in pyroxene and the fracture-filling texture indicate that the pyroxene veinlets might also have formed by shock-induced localized melting and rapid crystallization. Our study demonstrates that silicate veinlets formed by a range of different surface processes on the surface of Vesta.

Degassing-induced crystallization in silicate melt inclusion: evaluating the role of post-entrapment changes in melt inclusion from the SW volcanic flows of Deccan Large Igneous Province (Deccan LIP) lava.

NASA Astrophysics Data System (ADS)

Rani Choudhary, Babita

2017-04-01

Melt inclusions represent sampling of magma during their growth in magma chambers and during ascent to the surface. Several studies of melt inclusions in Large Igneous Provinces (LIPs) in different parts of the world have been documented in the literature (Sobolev et al. 2011; Kamenetsky et al. 2012). Melt inclusions study from Deccan LIP can provide new insights into the physio-chemical conditions and evolution of this important LIP. The Deccan LIP was fissure eruption mainly emplaced over a very short duration at 66 Ma (Schoene et al. 2015). To better characterize and explain the diversity in geochemical composition, petrogenesis and volatile degassing, melt inclusions studies have been carried out in clinopyroxene and plagioclase feldspar from a suite of samples in the Western Ghats section. Samples were obtained from the upper three formations (the Wai subgroup). The inclusions are primary and range in shape and size varies from a few microns, up to 100 microns. The inclusions are crystalline, and contain daughter phases. Some are glassy, with or without a shrinkage bubble. The melt inclusions show substantial variations in major element composition. Inclusions are significantly enriched in TiO2 (3.68 to 0.08 wt%) and FeO (18.3 to 2.63 wt%). SiO2 ranges from 43.4-66.8 wt% and classification diagrams of total alkali (Na2O+K2O) Vs. silica melt inclusions show that most inclusions are of sub-alkaline to mildly alkaline composition. Al2O3 ranges from 9.7- 22.4wt % and MgO 18.3-1.6. EPMA measurements demonstrated the presence of daughter crystals, such as magnetite and titanomagnetite, and high FeO, TiO2 and CaO within melt inclusions among the silicate daughter crystal clusters. Volatiles are determined have wide range in composition in both plagioclase- and pyroxene-hosted melt inclusions by using FTIR technique, values up to 2wt% H2Ototal and 1808 ppm CO2. Moreover the variability in composition and volatiles the melt from the samples in a single flow suggests that trapped melts were significantly affected by degassing and the post-entrapment changes. After each hiatus of the magmatic pulse the differentiated residual magma was enriched in Fe-Mg-Ti. Post-entrapment crystal aggregates contribute to the alteration of the melt phase within the inclusions (Choudhary and Jadhav 2010) i.e. fractionating tholeiitic lavas follow a trend that reflected by iron saturation until Fe-Ti oxides start to precipitate. Compositional concentrations are affected by diffusion from the plagioclase host into the inclusion, e.g. precipitation of host, resulting the high Al2O3 .Therefore melt inclusions showed evolved fractionated melt with the presence of aggregated crystals indicating that formation of these Fe-Ti oxides have occurred in an aqueous condition. As well, the formation of daughter mineral assemblages (titanomagnetite, and magnetite crystallization inside the inclusions) promotes the diffusion of hydrogen out of the inclusions.

Crystal structures and infrared spectra of two Fe-bearing hydrous magnesium silicates synthesized at high temperature and pressure

NASA Technical Reports Server (NTRS)

Yang, H.; Prewitt, C. T.; Liu, Z.

2002-01-01

The synthesis and characterization of Fe-bearing phase E and phase E' demonstrate that the phase E-type structures can be rather compliant and complex, and that as we further explore the temperature-pressure-composition space, other types of structures that are similar to or related to the structure of phase E may be discovered.

Thermal Energy Transfer Through All Ceramic Restorations

DTIC Science & Technology

2016-06-01

particles, but newer generations have reduced the size and narrowed the range of particles in the matrix . This evolution in ceramics improved the...crystalline second phase. These ceramics have a lithium silicate glass matrix with approximately 70% lithium-disilicate crystal fill. The micron size and... composition category described by Giordano and McLaren are the Interpenetrating Phase Ceramics . These ceramics were developed as an alternative to the

Incremental heating of Bishop Tuff sanidine reveals preeruptive radiogenic Ar and rapid remobilization from cold storage

NASA Astrophysics Data System (ADS)

Andersen, Nathan L.; Jicha, Brian R.; Singer, Brad S.; Hildreth, Wes

2017-11-01

Accurate and precise ages of large silicic eruptions are critical to calibrating the geologic timescale and gauging the tempo of changes in climate, biologic evolution, and magmatic processes throughout Earth history. The conventional approach to dating these eruptive products using the 40Ar/39Ar method is to fuse dozens of individual feldspar crystals. However, dispersion of fusion dates is common and interpretation is complicated by increasingly precise data obtained via multicollector mass spectrometry. Incremental heating of 49 individual Bishop Tuff (BT) sanidine crystals produces 40Ar/39Ar dates with reduced dispersion, yet we find a 16-ky range of plateau dates that is not attributable to excess Ar. We interpret this dispersion to reflect cooling of the magma reservoir margins below ˜475 °C, accumulation of radiogenic Ar, and rapid preeruption remobilization. Accordingly, these data elucidate the recycling of subsolidus material into voluminous rhyolite magma reservoirs and the effect of preeruptive magmatic processes on the 40Ar/39Ar system. The youngest sanidine dates, likely the most representative of the BT eruption age, yield a weighted mean of 764.8 ± 0.3/0.6 ka (2σ analytical/full uncertainty) indicating eruption only ˜7 ky following the Matuyama‑Brunhes magnetic polarity reversal. Single-crystal incremental heating provides leverage with which to interpret complex populations of 40Ar/39Ar sanidine and U-Pb zircon dates and a substantially improved capability to resolve the timing and causal relationship of events in the geologic record.

Incremental heating of Bishop Tuff sanidine reveals preeruptive radiogenic Ar and rapid remobilization from cold storage.

PubMed

Andersen, Nathan L; Jicha, Brian R; Singer, Brad S; Hildreth, Wes

2017-11-21

Accurate and precise ages of large silicic eruptions are critical to calibrating the geologic timescale and gauging the tempo of changes in climate, biologic evolution, and magmatic processes throughout Earth history. The conventional approach to dating these eruptive products using the 40 Ar/ 39 Ar method is to fuse dozens of individual feldspar crystals. However, dispersion of fusion dates is common and interpretation is complicated by increasingly precise data obtained via multicollector mass spectrometry. Incremental heating of 49 individual Bishop Tuff (BT) sanidine crystals produces 40 Ar/ 39 Ar dates with reduced dispersion, yet we find a 16-ky range of plateau dates that is not attributable to excess Ar. We interpret this dispersion to reflect cooling of the magma reservoir margins below ∼475 °C, accumulation of radiogenic Ar, and rapid preeruption remobilization. Accordingly, these data elucidate the recycling of subsolidus material into voluminous rhyolite magma reservoirs and the effect of preeruptive magmatic processes on the 40 Ar/ 39 Ar system. The youngest sanidine dates, likely the most representative of the BT eruption age, yield a weighted mean of 764.8 ± 0.3/0.6 ka (2σ analytical/full uncertainty) indicating eruption only ∼7 ky following the Matuyama-Brunhes magnetic polarity reversal. Single-crystal incremental heating provides leverage with which to interpret complex populations of 40 Ar/ 39 Ar sanidine and U-Pb zircon dates and a substantially improved capability to resolve the timing and causal relationship of events in the geologic record.

Early Earth differentiation [rapid communication

NASA Astrophysics Data System (ADS)

Walter, Michael J.; Trønnes, Reidar G.

2004-09-01

The birth and infancy of Earth was a time of profound differentiation involving massive internal reorganization into core, mantle and proto-crust, all within a few hundred million years of solar system formation ( t0). Physical and isotopic evidence indicate that the formation of iron-rich cores generally occurred very early in planetesimals, the building blocks of proto-Earth, within about 3 million years of t0. The final stages of terrestrial planetary accretion involved violent and tremendously energetic giant impacts among core-segregated Mercury- to Mars-sized objects and planetary embryos. As a consequence of impact heating, the early Earth was at times partially or wholly molten, increasing the likelihood for high-pressure and high-temperature equilibration among core- and mantle-forming materials. The Earth's silicate mantle harmoniously possesses abundance levels of the siderophile elements Ni and Co that can be reconciled by equilibration between iron alloy and silicate at conditions comparable to those expected for a deep magma ocean. Solidification of a deep magma ocean possibly involved crystal-melt segregation at high pressures, but subsequent convective stirring of the mantle could have largely erased nascent layering. However, primitive upper mantle rocks apparently have some nonchondritic major and trace element refractory lithophile element ratios that can be plausibly linked to early mantle differentiation of ultra-high-pressure mantle phases. The geochemical effects of crystal fractionation in a deep magma ocean are partly constrained by high-pressure experimentation. Comparison between compositional models for the primitive convecting mantle and bulk silicate Earth generally allows, and possibly favors, 10-15% total fractionation of a deep mantle assemblage comprised predominantly of Mg-perovskite and with minor but geochemically important amounts of Ca-perovskite and ferropericlase. Long-term isolation of such a crystal pile is generally consistent with isotopic constraints for time-integrated Sm/Nd and Lu/Hf ratios in the modern upper mantle and might account for the characteristics of some mantle isotope reservoirs. Although much remains to be learned about the earliest formative period in the Earth's development, a convergence of theoretical, physical, isotopic and geochemical arguments is beginning to yield a self-consistent portrait of the infant Earth.

Iron Isotope Constraints on Planetesimal Core Formation

NASA Astrophysics Data System (ADS)

Jordan, M.; Young, E. D.

2016-12-01

The prevalence of iron in both planetary cores and silicate mantles renders the element a valuable tool for understanding core formation. Magmatic iron meteorites exhibit an enrichment in 57Fe/54Fe relative to chondrites and HED meteorites. This is suggestive of heavy Fe partitioning into the cores of differentiated bodies. If iron isotope fractionation accompanies core formation, we can elucidate details about the history of accretion for planetary bodies as well as their compositions and relative core sizes. The equilibrium 57Fe/54Fe between metal and silicate is necessary for understanding observed iron isotope compositions and placing constraints on core formation. We measure this fractionation in two Aubrite meteorites, Norton County and Mount Egerton, which have known temperatures of equilibration and equilibrated silicon isotopes. Iron was purified using ion-exchange chromatography. Data were collected on a ThermoFinnigan NeptuneTM multiple-collector inductively coupled plasma-source mass spectrometer (MC-ICP-MS) run in wet plasma mode. The measured fractionation Δ57Femetal-silicate is 0.08‰ ± 0.039 (2 SE) for Norton County and 0.09‰ ± 0.019 (2 SE) for Mount Egerton, indicating that the heavy isotopes of Fe partition into the metallic phase. These rocks are in isotopic equilibrium at a temperature of 1130 K and 1200 K ± 80 K, respectively. The concentration of the heavy isotopes of iron in the metallic phase is consistent with recent experimental studies. Using our measured metal-silicate Fe isotope fractionation and the resulting temperature calibration, while taking into account impurities in the metallic phase and temperatures of equilibration, determine that core formation could explain the observed difference between magmatic iron meteorites and chondrites if parent bodies have small cores. In order to verify that Rayleigh distillation during fractional crystallization was not a cause of iron isotope fractionation in iron meteorites, we measured iron isotope ratios in a suite of iron meteorites representing a large range of degrees of fractional crystallization. We find no clear variation in 57Fe/54Fe among these samples.

Sponge-like nanoporous single crystals of gold

PubMed Central

Khristosov, Maria Koifman; Bloch, Leonid; Burghammer, Manfred; Kauffmann, Yaron; Katsman, Alex; Pokroy, Boaz

2015-01-01

Single crystals in nature often demonstrate fascinating intricate porous morphologies rather than classical faceted surfaces. We attempt to grow such crystals, drawing inspiration from biogenic porous single crystals. Here we show that nanoporous single crystals of gold can be grown with no need for any elaborate fabrication steps. These crystals are found to grow following solidification of a eutectic composition melt that forms as a result of the dewetting of nanometric thin films. We also present a kinetic model that shows how this nano-porous single-crystalline structure can be obtained, and which allows the potential size of the porous single crystal to be predicted. Retaining their single-crystalline nature is due to the fact that the full crystallization process is faster than the average period between two subsequent nucleation events. Our findings clearly demonstrate that it is possible to form single-crystalline nano porous metal crystals in a controlled manner. PMID:26554856

Heterogeneous pumice populations in the 2.08-Ma Cerro Galán Ignimbrite: Implications for magma recharge and ascent preceding a large-volume silicic eruption

USGS Publications Warehouse

Wright, Heather M.; Folkes, Christopher B.; Cas, Ray A.F.; Cashman, Katharine V.

2011-01-01

Triggering mechanisms of large silicic eruptions remain a critical unsolved problem. We address this question for the ~2.08-Ma caldera-forming eruption of Cerro Galán volcano, Argentina, which produced distinct pumice populations of two colors: grey (5%) and white (95%) that we believe may hold clues to the onset of eruptive activity. We demonstrate that the color variations correspond to both textural and compositional variations between the clast types. Both pumice types have bulk compositions of high-K, high-silica dacite to low-silica rhyolite, but there are sufficient compositional differences (e.g., ~150 ppm lower Ba at equivalent SiO2 content and 0.03 wt.% higher TiO2 in white pumice than grey) to suggest that the two pumice populations are not related by simple fractionation. Trace element concentrations in crystals mimic bulk variations between clast types, with grey pumice containing elevated Ba, Cu, Pb, and Zn concentrations in both bulk samples (average Cu, Pb, and Zn concentrations are 27, 35, and 82 in grey pumice vs. 11, 19, and 60 in white pumice) and biotite phenocrysts and white pumice showing elevated Li concentrations in biotite and plagioclase phenocrysts. White and grey clasts are also texturally distinct: White pumice clasts contain abundant phenocrysts (44–57%), lack microlites, and have highly evolved groundmass glass compositions (76.4–79.6 wt.% SiO2), whereas grey pumice clasts contain a lower percentage of phenocrysts/microphenocrysts (35–49%), have abundant microlites, and have less evolved groundmass glass compositions (69.4–73.8 wt.% SiO2). There is also evidence for crystal transfer between magma producing white and grey pumice. Thin highly evolved melt rims surround some fragmental crystals in grey pumice clasts and appear to have come from magma that produced white pumice. Furthermore, based on crystal compositions, white bands within banded pumice contain crystals originating in grey magma. Finally, only grey pumice clasts form breadcrusted surface textures. We interpret these compositional and textural variations to indicate distinct magma batches, where grey pumice originated from an originally deeper, more volatile-rich dacite recharge magma that ascended through and mingled with the volumetrically dominant, more highly crystalline chamber that produced white pumice. Shortly before eruption, the grey pumice magma stalled within shallow fractures, forming a vanguard magma phase whose ascent may have provided a trigger for eruption of the highly crystalline rhyodacite magma. We suggest that in the case of the Cerro Galán eruption, grey pumice provides evidence not only for cryptic silicic recharge in a large caldera system but also a probable trigger for the eruption.

Heterogeneous pumice populations in the 2.08-Ma Cerro Galán Ignimbrite: implications for magma recharge and ascent preceding a large-volume silicic eruption

NASA Astrophysics Data System (ADS)

Wright, Heather M. N.; Folkes, Chris B.; Cas, Raymond A. F.; Cashman, Katharine V.

2011-12-01

Triggering mechanisms of large silicic eruptions remain a critical unsolved problem. We address this question for the ~2.08-Ma caldera-forming eruption of Cerro Galán volcano, Argentina, which produced distinct pumice populations of two colors: grey (5%) and white (95%) that we believe may hold clues to the onset of eruptive activity. We demonstrate that the color variations correspond to both textural and compositional variations between the clast types. Both pumice types have bulk compositions of high-K, high-silica dacite to low-silica rhyolite, but there are sufficient compositional differences (e.g., ~150 ppm lower Ba at equivalent SiO2 content and 0.03 wt.% higher TiO2 in white pumice than grey) to suggest that the two pumice populations are not related by simple fractionation. Trace element concentrations in crystals mimic bulk variations between clast types, with grey pumice containing elevated Ba, Cu, Pb, and Zn concentrations in both bulk samples (average Cu, Pb, and Zn concentrations are 27, 35, and 82 in grey pumice vs. 11, 19, and 60 in white pumice) and biotite phenocrysts and white pumice showing elevated Li concentrations in biotite and plagioclase phenocrysts. White and grey clasts are also texturally distinct: White pumice clasts contain abundant phenocrysts (44-57%), lack microlites, and have highly evolved groundmass glass compositions (76.4-79.6 wt.% SiO2), whereas grey pumice clasts contain a lower percentage of phenocrysts/microphenocrysts (35-49%), have abundant microlites, and have less evolved groundmass glass compositions (69.4-73.8 wt.% SiO2). There is also evidence for crystal transfer between magma producing white and grey pumice. Thin highly evolved melt rims surround some fragmental crystals in grey pumice clasts and appear to have come from magma that produced white pumice. Furthermore, based on crystal compositions, white bands within banded pumice contain crystals originating in grey magma. Finally, only grey pumice clasts form breadcrusted surface textures. We interpret these compositional and textural variations to indicate distinct magma batches, where grey pumice originated from an originally deeper, more volatile-rich dacite recharge magma that ascended through and mingled with the volumetrically dominant, more highly crystalline chamber that produced white pumice. Shortly before eruption, the grey pumice magma stalled within shallow fractures, forming a vanguard magma phase whose ascent may have provided a trigger for eruption of the highly crystalline rhyodacite magma. We suggest that in the case of the Cerro Galán eruption, grey pumice provides evidence not only for cryptic silicic recharge in a large caldera system but also a probable trigger for the eruption.

In situ nanomanipulators as a tool to separate individual tobermorite crystals for AFM studies.

PubMed

Yang, Tianhe; Holzer, Lorenz; Kägi, Ralf; Winnefeld, Frank; Keller, Bruno

2007-10-01

Atomic force microscopy (AFM) studies of cementitious materials are limited, mainly due to the lack of appropriate sample preparation techniques. In porous autoclaved aerated concrete (AAC), calcium silicate hydrate (C-S-H) is produced in its crystalline form, tobermorite. The crystals are lath-like with a length of several micrometers. In this work, we demonstrate the application of nanomanipulators to separate an individual tobermorite crystal from the bulk AAC for subsequent AFM investigations. The nanomanipulators are operated directly in an environmental scanning electron microscope (ESEM). We studied the interaction between moisture and the tobermorite surface under controlled relative humidity (RH). The results of topography and adhesion force measurements with AFM suggest that the surface of tobermorite is hydrophobic, which contrasts the macroscopic material properties (e.g. moisture transport in capillary pores).

Growth of single crystals of BaFe12O19 by solid state crystal growth

NASA Astrophysics Data System (ADS)

Fisher, John G.; Sun, Hengyang; Kook, Young-Geun; Kim, Joon-Seong; Le, Phan Gia

2016-10-01

Single crystals of BaFe12O19 are grown for the first time by solid state crystal growth. Seed crystals of BaFe12O19 are buried in BaFe12O19+1 wt% BaCO3 powder, which are then pressed into pellets containing the seed crystals. During sintering, single crystals of BaFe12O19 up to ∼130 μm thick in the c-axis direction grow on the seed crystals by consuming grains from the surrounding polycrystalline matrix. Scanning electron microscopy-energy dispersive spectroscopy analysis shows that the single crystal and the surrounding polycrystalline matrix have the same chemical composition. Micro-Raman scattering shows the single crystal to have the BaFe12O19 structure. The optimum growth temperature is found to be 1200 °C. The single crystal growth behavior is explained using the mixed control theory of grain growth.

Experimental Investigation of the Viscosity of Iron-rich Silicate Melts under Pressure

NASA Astrophysics Data System (ADS)

Edwards, P. M.; Lesher, C. E.; Pommier, A.; O'Dwyer Brown, L.

2017-12-01

The transport properties of silicate melts govern diffusive flow of momentum, heat, and mass in the interior of terrestrial planets. In particular, constraining melt viscosity is critical for dynamic modeling of igneous processes and is thus key to our understanding of magma convection and mixing, melt migration in the mantle, and crystal-liquid fractionation. Among the different constituents of silicate melts, iron is of significant importance as it highly influences some of their properties, such as surface tension, compressibility, and density. We present an experimental study of the viscosity of natural and synthetic iron-rich silicate melts under pressure. In situ falling-sphere measurements of viscosity have been conducted on hedenbergite (CaFeSi2O6) and iron-rich peridotite melts from 1 to 7 GPa and at temperatures between 1750 and 2100 K, using the multi-anvil apparatus at the GSECARS beamline at the Advanced Photon Source, Argonne National Lab. We used double reservoir capsules, with the bottom reservoir containing the sample, while a more refractory material is placed in the upper reservoir (e.g., diopside, enstatite, forsterite). This configuration allows the fall of two rhenium spheres across the sample at different temperatures. Melt viscosity is calculated using Stokes' law and the terminal velocity of the spheres. We observe that melt viscosity slightly decreases with increasing temperature and increasing pressure: for instance, the viscosity of the hedenbergite melt decreases from 1.26 Pa•s to 0.43 Pa•s over the 1 - 3.5 GPa pressure range and between 1820 and 1930 K. Our experimental data are used to develop a viscosity model of iron-rich silicate melts under pressure. Results will be compared with previous viscosity works on iron-free and iron-bearing silicate liquids in order to discuss the effect of iron on melt viscosity and structure at pressure and temperature conditions relevant to terrestrial mantles.

Hard X-ray irradiation of cosmic silicate analogs: structural evolution and astrophysical implications

NASA Astrophysics Data System (ADS)

Gavilan, L.; Jäger, C.; Simionovici, A.; Lemaire, J. L.; Sabri, T.; Foy, E.; Yagoubi, S.; Henning, T.; Salomon, D.; Martinez-Criado, G.

2016-03-01

Context. Protoplanetary disks, interstellar clouds, and active galactic nuclei contain X-ray-dominated regions. X-rays interact with the dust and gas present in such environments. While a few laboratory X-ray irradiation experiments have been performed on ices, X-ray irradiation experiments on bare cosmic dust analogs have been scarce up to now. Aims: Our goal is to study the effects of hard X-rays on cosmic dust analogs via in situ X-ray diffraction. By using a hard X-ray synchrotron nanobeam, we seek to simulate cumulative X-ray exposure on dust grains during their lifetime in these astrophysical environments and provide an upper limit on the effect of hard X-rays on dust grain structure. Methods: We prepared enstatite (MgSiO3) nanograins, which are analogs to cosmic silicates, via the melting-quenching technique. These amorphous grains were then annealed to obtain polycrystalline grains. These were characterized via scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) before irradiation. Powder samples were prepared in X-ray transparent substrates and were irradiated with hard X-rays nanobeams (29.4 keV) provided by beamline ID16B of the European Synchrotron Radiation Facility (Grenoble). X-ray diffraction images were recorded in transmission mode, and the ensuing diffractograms were analyzed as a function of the total X-ray exposure time. Results: We detected the amorphization of polycrystalline silicates embedded in an organic matrix after an accumulated X-ray exposure of 6.4 × 1027 eV cm-2. Pure crystalline silicate grains (without resin) do not exhibit amorphization. None of the amorphous silicate samples (pure and embedded in resin) underwent crystallization. We analyze the evolution of the polycrystalline sample embedded in an organic matrix as a function of X-ray exposure. Conclusions: Loss of diffraction peak intensity, peak broadening, and the disappearance of discrete spots and arcs reveal the amorphization of the resin embedded (originally polycrystalline) silicate sample. We explore the astrophysical implications of this laboratory result as an upper limit to the effect of X-rays on the structure of cosmic silicates.

Computational and experimental studies of iron-bearing carbonates and silicate glasses at lower mantle pressures

NASA Astrophysics Data System (ADS)

Solomatova, N. V.; Jackson, J. M.; Asimow, P. D.; Sturhahn, W.; Rossman, G. R.; Roskosz, M.

2017-12-01

Decomposition of carbonates may be responsible for creating silicate melts within the lower mantle by lowering the melting temperature of surrounding rock. Identifying and characterizing the stability of carbonates is therefore a necessary step towards understanding the transport of carbon in Earth's interior. Dolomite is one of the major mineral forms in which carbon is subducted into the Earth's mantle. Although iron-free dolomite is expected to break down upon compression, high-pressure polymorphs of iron-bearing dolomite may resist decomposition. Using a genetic algorithm that predicts crystal structures, we found a monoclinic phase with space group C2/c that has a lower energy than all previously reported dolomite structures at pressures above 15 GPa, where the substitution of iron for magnesium stabilizes monoclinic dolomite at certain pressures of the lower mantle. Thus, an iron-bearing dolomite polymorph may be an important carbon carrier in regions of Earth's lower mantle. The depth at which carbonates will decompose is dependent on the age, temperature and density of subducting slabs. Decarbonation reactions may lower the melting temperature of surrounding rocks to produce silicate melts. In regions of the mantle where silicate melts may exist, it is important to understand the physical properties and dynamic behavior of the melts because they affect the chemical and thermal evolution of its interior. Composition, degree of polymerization, and iron's spin state affect such properties. The behavior of iron in silicate melts is poorly understood but, in some cases, may be approximated by iron-bearing glasses. We measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to 120 GPa and 100 GPa, respectively, in a neon pressure medium using time-domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe2+-like sites with distinct quadrupole splittings, reflecting the influence of evolving coordination environments with pressure. With the assumption that coordination environments in silicate glasses may serve as a good indicator for those in a melt, this study suggests that ferrous iron in chemically-complex silicate melts likely exists in a high-spin state throughout most of Earth's mantle.

Percolation of isotopically heterogeneous interstitial melts in the crystal mush of the Rum layered intrusion, NW Scotland

NASA Astrophysics Data System (ADS)

O'Driscoll, B.; Hepworth, L. N.; Daly, J. S.; Gertisser, R.; Emeleus, C. H.

2017-12-01

The cumulate stratigraphy of layered intrusions offers a means of interrogating the replenishment and solidification histories of mafic magma chambers. Cumulates comprise cumulus minerals, which accumulate to form a silicate framework, and intercumulus minerals, which represent melt crystallised within the crystal mush. This fundamental textural distinction lies at the heart of cumulus theory and underpins some of the classic models of crystal-liquid differentiation that are based on layered intrusions. In order to shed further light on the importance of postcumulus processes in layered intrusions, and to demonstrate that crystal mushes may behave as open-systems during the crystallisation of cumulates, we investigated mineral-scale textural and geochemical heterogeneity in Unit 10 of the 60 Ma Rum layered intrusion. Numerous ( 1 mm thick) Cr-spinel seams occur throughout the 65 m Unit 10 peridotite stratigraphy. Unusually, intercumulus plagioclase and clinopyroxene crystals in the peridotite several centimetres above and below these seams exhibit complex optical and major element zoning. Sampling of individual intra-crystal zones in these phases was carried out using a New Wave Micromill, for analysis of their 87Sr/86Sr compositions to be measured on unspiked samples by TIMS. Both minerals reveal intra-crystalline isotopic heterogeneity. The maximum range (with 2σ uncertainties) of 87Sr/86Sr in the Unit 10 plagioclase is 0.704026±17-0.704591±8 and in clinopyroxene is 0.703533±23-0.704517±17. Within a single, oscillatory-zoned plagioclase, three discrete zones yield 87Sr/86Sr values of 0.704337±20, 0.704095±20 and 0.704052±11. A complex patchily-zoned clinopyroxene yields a 87Sr/86Sr range of 0.703533±23-0.703894±23. The new data demonstrate that multiple generations of isotopically distinct melts percolated through the Unit 10 crystal mush, suggesting solidification from cumulates that underwent repeated cycles of resorption and recrystallisation at the postcumulus stage. The cumulate products of layered intrusions may therefore form from magma addition within the crystal mush, and such a process might be especially relevant for precious metal enrichment, given the association between isotopic disequilibrium and the locations of Cr-spinel seams observed here.

Sowing the Seeds of Planets? (Artist's Concept)

NASA Technical Reports Server (NTRS)

2005-01-01

[figure removed for brevity, see original site] Planet Clumps and Crystals around Brown Dwarfs

This artist's concept shows microscopic crystals in the dusty disk surrounding a brown dwarf, or 'failed star.' The crystals, made up of a green mineral found on Earth called olivine, are thought to help seed the formation of planets.

NASA's Spitzer Space Telescope detected the tiny crystals circling around five brown dwarfs, the cooler and smaller cousins of stars. Though crystallized minerals have been seen in space before -- in comets and around other stars -- the discovery represents the first time the little gem-like particles have been spotted around confirmed brown dwarfs.

Astronomers believe planets form out of disks of dust that circle young brown dwarfs and stars. Over time, the various minerals making up the disks crystallize and begin to clump together. Eventually, the clumps collide and stick, building up mass like snowmen until planets are born.

About the Graph: Planet Clumps and Crystals around Brown Dwarfs The graph of data from NASA's Spitzer Space Telescope shows the spectra (middle four lines) of dusty disks around four brown dwarfs, or 'failed stars,' located 520 light-years away in the Chamaeleon constellation. The data suggest that the dust in these disks is crystallizing and clumping together in what may be the birth of planets.

Spectra are created by breaking light apart into its basic components, like a prism turning sunlight into a rainbow. Their bumps represent the 'fingerprints' or signatures of different minerals.

Here, the light green vertical bands highlight the spectral fingerprints of crystals made up primarily of a green silicate mineral found on Earth called olivine. As the graph illustrates, three of the four brown dwarfs possess these microscopic gem-like particles. For comparison, the spectra of dust between stars (top) and the comet Hale-Bopp (bottom) are shown. The comet has the tiny crystals, whereas the interstellar dust does not.

The broadening of these spectral features or bumps -- seen here as you move down the graph - indicates silicate grains of increasing size.

Another analysis of this same data shows that some of the brown dwarfs' dusty disks flare in their outer regions, while others are flattened. This flattening is correlated with increasing grain size, and probably occurs because the heavier dust grains are settling downward.

Together, these observations - of crystals, growing dust grains and flattened disks - provide strong evidence that the dust around these brown dwarfs is evolving into what might become planets. Prior to the findings, these first steps of planet formation were seen only in disks around stars, the brighter and bigger cousins to brown dwarfs.

Single-crystal 40Ar/39Ar incremental heating reveals bimodal sanidine ages in the Bishop Tuff

NASA Astrophysics Data System (ADS)

Andersen, N. L.; Jicha, B. R.; Singer, B. S.

2015-12-01

The 650 km3 Bishop Tuff (BT) is among the most studied volcanic deposits because it is an extensive marker bed deposited just after the Matuyama-Brunhes boundary. Reconstructions of the vast BT magma reservoir from which high-silica rhyolite erupted have long influenced thinking about how large silicic magma systems are assembled, crystallized, and mixed. Yet, the longevity of the high silica rhyolitic melt and exact timing of the eruption remain controversial due to recent conflicting 40Ar/39Ar sanidine vs. SIMS and ID-TIMS U-Pb zircon dates. We have undertaken 21 40Ar/39Ar incremental heating ages on 2 mm BT sanidine crystals from pumice in 3 widely separated outcrops of early-erupted fall and flow units. Plateau ages yield a bimodal distribution: a younger group has a mean of 766 ka and an older group gives a range between 772 and 782 ka. The younger population is concordant with the youngest ID-TIMS and SIMS U-Pb zircon ages recently published, as well as the astronomical age of BT in marine sediment. Of 21 crystals, 17 yield older, non-plateau, steps likely affected by excess Ar that would bias traditional 40Ar/39Ar total crystal fusion ages. The small spread in older sanidine ages, together with 25+ kyr of pre-eruptive zircon growth, suggest that the older sanidines are not partially outgassed xenocrysts. A bimodal 40Ar/39Ar age distribution implies that some fraction of rhyolitic melt cooled below the Ar closure temperature at least 10 ky prior to eruption. We propose that rapid "thawing" of a crystalline mush layer released older crystals into rhyolitic melt from which sanidine also nucleated and grew immediately prior to the eruption. High precision 40Ar/39Ar dating can thus provide essential information on thermo-physical processes at the millenial time scale that are critical to interpreting U-Pb zircon age distributions that are complicated by large uncertainties associated with zircon-melt U-Th systematics.

Interaction of peridotite with Ca-rich carbonatite melt at 3.1 and 6.5 GPa: Implication for merwinite formation in upper mantle, and for the metasomatic origin of sublithospheric diamonds with Ca-rich suite of inclusions

NASA Astrophysics Data System (ADS)

Sharygin, Igor S.; Shatskiy, Anton; Litasov, Konstantin D.; Golovin, Alexander V.; Ohtani, Eiji; Pokhilenko, Nikolay P.

2018-03-01

We performed an experimental study, designed to reproduce the formation of an unusual merwinite + olivine-bearing mantle assemblage recently described as a part of a Ca-rich suite of inclusions in sublithospheric diamonds, through the interaction of peridotite with an alkali-rich Ca-carbonatite melt, derived from deeply subducted oceanic crust. In the first set of experiments, we studied the reaction between powdered Mg-silicates, olivine and orthopyroxene, and a model Ca-carbonate melt (molar Na:K:Ca = 1:1:2), in a homogeneous mixture, at 3.1 and 6.5 GPa. In these equilibration experiments, we observed the formation of a merwinite + olivine-bearing assemblage at 3.1 GPa and 1200 °C and at 6.5 GPa and 1300-1400 °C. The melts coexisting with this assemblage have a low Si and high Ca content (Ca# = molar 100 × Ca/(Ca + Mg) > 0.57). In the second set of experiments, we investigated reaction rims produced by interaction of the same Ca-carbonate melt (molar Na:K:Ca = 1:1:2) with Mg-silicate, olivine and orthopyroxene, single crystals at 3.1 GPa and 1300 °C and at 6.5 GPa and 1400 °C. The interaction of the Ca-carbonate melt with olivine leads to merwinite formation through the expected reaction: 2Mg2SiO4 (olivine) + 6CaCO3 (liquid) = Ca3MgSi2O8 (merwinite) + 3CaMg(CO3)2 (liquid). Thus, our experiments confirm the idea that merwinite in the upper mantle may originate via interaction of peridotite with Ca-rich carbonatite melt, and that diamonds hosting merwinite may have a metasomatic origin. It is remarkable that the interaction of the Ca-carbonate melt with orthopyroxene crystals does not produce merwinite both at 3.1 and 6.5 GPa. This indicates that olivine grain boundaries are preferable for merwinite formation in the upper mantle.

Geochemistry, mineralogy, and zircon U-Pb-Hf isotopes in peraluminous A-type granite xenoliths in Pliocene-Pleistocene basalts of northern Pannonian Basin (Slovakia)

NASA Astrophysics Data System (ADS)

Huraiová, Monika; Paquette, Jean-Louis; Konečný, Patrik; Gannoun, Abdel-Mouhcine; Hurai, Vratislav

2017-08-01

Anorogenic granite xenoliths occur in alkali basalts coeval with the Pliocene-Pleistocene continental rifting of the Pannonian Basin. Observed granite varieties include peraluminous, calcic to peralkalic, magnesian to ferroan types. Quartz and feldspars are dominant rock-forming minerals, accompanied by minor early ilmenite and late magnetite-ulvöspinel. Zircon and Nb-U-REE minerals (oxycalciopyrochlore, fergusonite, columbite) are locally abundant accessory phases in calc-alkalic types. Absence of OH-bearing Fe, Mg-silicates and presence of single homogeneous feldspars (plagioclase in calcic types, anorthoclase in calc-alkalic types, ferrian Na-sanidine to anorthoclase in alkalic types) indicate water-deficient, hypersolvus crystallization conditions. Variable volumes of interstitial glass, absence of exsolutions, and lacking deuteric hydrothermal alteration and/or metamorphic/metasomatic overprint are diagnostic of rapid quenching from hypersolidus temperatures. U-Pb zircon ages determined in calcic and calc-alkalic granite xenoliths correspond to a time interval between 5.7 and 5.2 Ma. Positive ɛHf values (14.2 ± 3.9) in zircons from a 5.2-Ma-old calc-alkalic granite xenolith indicate mantle-derived magmas largely unaffected by the assimilation of crustal material. This is in accordance with abundances of diagnostic trace elements (Rb, Y, Nb, Ta), indicating A1-type, OIB-like source magmas. Increased accumulations of Nb-U-REE minerals in these granites indicate higher degree of the magmatic differentiation reflected in Rb-enrichment, contrasting with Ba-enrichment in barren xenoliths. Incipient charnockitization, i.e. orthopyroxene and ilmenite crystallization from interstitial silicate melt, was observed in many granite xenoliths. Thermodynamic modeling using pseudosections showed that the orthopyroxene growth may have been triggered by water exsolution from the melt during ascent of xenoliths in basaltic magma. Euhedral-to-skeletal orthopyroxene growth probably reflects contrasting ascent rates of basaltic magma with xenoliths, intermitted by the stagnation in various crustal levels at a <3 kbar pressure. The Tertiary suite of intra-plate, mantle-derived A1-type granites and syenites is geochemically distinct from pre-Tertiary, post-orogenic A2-type granites of the Carpatho-Pannonian region, which exhibit geochemical features diagnostic of crustal melting along continental margins.

The Origin of Silicic Arc Crust - Insights from the Northern Pacific Volcanic Arcs through Space and Time

NASA Astrophysics Data System (ADS)

Straub, S. M.; Kelemen, P. B.

2016-12-01

The remarkable compositional similarities of andesitic crust at modern convergent margins and the continental crust has long evoked the hypothesis of similar origins. Key to understanding either genesis is understanding the mode of silica enrichment. Silicic crust cannot be directly extracted from the upper mantle. Hence, in modern arcs, numerous studies - observant of the pervasive and irrefutable evidence of melt mixing - proposed that arc andesites formed by mixing of mantle-derived basaltic melts and fusible silicic material from the overlying crust. Mass balance requires the amount of silicic crust in such hybrid andesites to be on the order to tens of percent, implying that their composition to be perceptibly influenced by the various crustal basements. In order to test this hypothesis, major and trace element compositions of mafic and silicic arc magmas with arc-typical low Ce/Pb< 10 of Northern Pacific arcs (Marianas through Mexico) were combined with Pb isotope ratios. Pb isotope ratios are considered highly sensitive to crustal contamination, and hence should reflect the variable composition of the oceanic and continental basement on which these arcs are constructed. In particular, in thick-crust continental arcs where the basement is isotopically different from the mantle and crustal assimilation thought to be most prevalent, silicic magmas must be expected to be distinct from those of the associated mafic melts. However, in a given arc, the Pb isotope ratios are constant with increasing melt silica regardless of the nature of the basement. This observation argues against a melt origin of silicic melts from the crustal basement and suggest them to be controlled by the same slab flux as their co-eval mafic counterparts. This inference is validated by the spatial and temporal pattern of arc Pb isotope ratios along the Northern Pacific margins and throughout the 50 million years of Cenozoic evolution of the Izu Bonin Mariana arc/trench system that are can be related to with systematic, `real-time' changes in the composition of the slab flux with no role of the crustal basement. In summary, these data suggest that that silicic melts are ultimately genetically linked to the mafic co-eval series from the mantle, by such mechanisms as fractional crystallization, or melt-rock reactions, or a combination of both.

Hydrothermal synthesis, characterization, and thermal properties of alumino silicate azide sodalite, Na8[AlSiO4]6(N3)2

NASA Astrophysics Data System (ADS)

Borhade, A. V.; Wakchaure, S. G.; Dholi, A. G.; Kshirsagar, T. A.

2017-07-01

First time we report the synthesis, structural characterization and thermal behavior of an unusual N3 - containing alumino-silicate sodalite mineral. Azide sodalite, Na8[AlSiO4]6(N3)2 has been synthesized under hydrothermal conditions at 433 K in steel lined Teflon autoclave. The structural and microstructural properties of azide sodalite mineral was characterized by various methods including FT-IR, XRD, SEM, TGA, and MAS NMR. Crystal structure have been refined by Rietveld method in P\\bar 43n space group, indicating that the N3 - sodalite has cubic in lattice. High temperature study was carried out to see the effect of thermal expansion on cell dimension ( a o) of azide sodalite. Thermal behavior of sodalite was also assessed by thermogravimetric method.

Inheritance of silicate differentiation during lunar origin by giant impact

NASA Technical Reports Server (NTRS)

Warren, Paul H.

1992-01-01

It is pointed out that the implication of the popular giant impact model of lunar origin (e.g., Hartmann and Davis, 1975; Cameron and Ward, 1976; Stevenson, 1987) is that any depth-related silicate differentiation within the impactor (and/or the earth) at the time of the impact must be partly inherited by the preferentially peripheral matter that forms the moon. This paper presents calculations of the magnitude of the net differentiation of the protolunar matter for a variety of elements and scenarios, with different assumptions regarding the geometries of the 'sampled' peripheral zones, the relative proportions of the earth-derived to impactor-derived matter in the final moon, and the degree to which the impactor mantle had crystallized prior to the giant impact. It is shown that these differention effects constrain the overall plausibility of the giant impact hypothesis.

Superheat in magma oceans

NASA Technical Reports Server (NTRS)

Jakes, Petr

1992-01-01

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

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.

Magnetic mineralogy and rock magnetic properties of silicate and carbonatite rocks from Oldoinyo Lengai volcano (Tanzania)

NASA Astrophysics Data System (ADS)

Mattsson, H. B.; Balashova, A.; Almqvist, B. S. G.; Bosshard-Stadlin, S. A.; Weidendorfer, D.

2018-06-01

Oldoinyo Lengai, a stratovolcano in northern Tanzania, is most famous for being the only currently active carbonatite volcano on Earth. The bulk of the volcanic edifice is dominated by eruptive products produced by silica-undersaturated, peralkaline, silicate magmas (effusive, explosive and/or as cumulates at depth). The recent (2007-2008) explosive eruption produced the first ever recorded pyroclastic flows at this volcano and the accidental lithics incorporated into the pyroclastic flows represent a broad variety of different rock types, comprising both extrusive and intrusive varieties, in addition to various types of cumulates. This mix of different accidental lithics provides a unique insight into the inner workings of the world's only active carbonatite volcano. Here, we focus on the magnetic mineralogy and the rock magnetic properties of a wide selection of samples spanning the spectrum of Oldoinyo Lengai rock types compositionally, as well from a textural point of view. Here we show that the magnetic properties of most extrusive silicate rocks are dominated by magnetite-ulvöspinel solid solutions, and that pyrrhotite plays a larger role in the magnetic properties of the intrusive silicate rocks. The natrocarbonatitic lavas, for which the volcano is best known for, show distinctly different magnetic properties in comparison with the silicate rocks. This discrepancy may be explained by abundant alabandite crystals/blebs in the groundmass of the natrocarbonatitic lavas. A detailed combination of petrological/mineralogical studies with geophysical investigations is an absolute necessity in order to understand, and to better constrain, the overall architecture and inner workings of the subvolcanic plumbing system. The results presented here may also have implications for the quest in order to explain the genesis of the uniquely natrocarbonatitic magmas characteristic of Oldoinyo Lengai.

Multiple (immiscible) melt phases of mafic composition in Chicxulub impact ejecta from northeastern Mexico: New constraints on target lithologies

NASA Astrophysics Data System (ADS)

Schulte, P.; Stinnesbeck, W.; Kontny, A.; Stüben, D.; Kramar, U.; Harting, M.

2002-12-01

Proximal ejecta deposits in sections from NE Mexico (Rancho Nuevo, La Sierrita, El Peñon, El Mimbral) have been investigated by backscattered electron imaging, wave-length dispersive electron microprobe analyses, and cathodoluminiscence, in order to characterize target lithologies, and ejecta mixing, fractionation, and distribution mechanisms. Additional investigations included magnetic properties (Kontny et al, this meeting) and trace element analyses (Harting et al, this meeting). Petrological features of these ejecta deposits are extraordinarily well preserved. They consist of mm-cm sized vesiculated spherical to drop-shaped spherules and angular to filamentous (ejecta-) fragments, as well as carbonate clasts, marl clasts, and rare benthic foraminifera floating in a carbonaceous matrix. Occasionally, spherules and fragments show welding-amalgamation features and enclose other components, thus resulting in a foam-like texture. An origin from the Chicxulub impact is suggested by geographical proximity and morphologically similarity to spherules found in other K-T sites in North to Central America and the Atlantic. The far distribution of such coarse-grained, foamy, and fragile ejecta-clasts as well as welding features suggest ignimbrite-like transport mechanisms or nearby secondary impacts. Several silicic ejecta phases have been observed that occur as distinct phases, even within one ejecta particle with textures indicative of liquid immiscibility: (1) Fe- (25-35 wt%), Mg- (10-15 wt%) rich phases with <25 wt% SiO2, altered to chlorite, (2) K- (5-8 wt.%) and Al- (25-30 wt%) rich hydrated glass with 45-50 wt% SiO2, and (3) rare SiO2- (>60 wt%) rich andesitic glasses. In addition to these silicic phases, abundant carbonate characterizes all studied ejecta deposits. It occurs within spherules and fragments and as clasts and globules, and shows textures indicative of either liquid immiscibility and/or quenching (`feathery calcite'). Quenched carbonates are enriched in Fe and Mg (up to one wt%) and are characterized by dark red-brown luminescence, in contrast to the carbonaceous matrix, which shows bright luminescence colors. Within all phases, but mainly in (1), various inclusions have been observed: (a) Globules enriched in Fe and Mg, (b) schlieren, rich in Ti, K, Fe, (c) garland-shaped Ti-rich lamellae, (d) dendritic and skeletal crystals of Ti-Fe oxides, (e) hematite crystals with a Ni-content up to 0.4 wt%, as well as goethite and rutile crystals, (f) rare μm-sized Co-, Ni-, Fe-rich metallic or sulfidic particles. These compositional phases are present in all studied outcrops, but their individual amount varies with prevailing Fe-rich phases at Rancho Nuevo and La Sierrita and Fe-, K-rich and silicic phases at El Peñon and El Mimbral. These characteristics imply an origin of the ejecta from mafic lithologies and carbonaceous sediments, in addition to contribution from felsic rocks. The occurrence of different compositional phases in single ejecta layers and even within individual ejecta particles suggests strong fractionation effects and/or negligible mixing of different melt phases. The presence of metallic Fe, Ni and Co may indicate that additional contamination by meteoritic material occurred.

Experimental observations on noble metal nanonuggets and Fe-Ti oxides, and the transport of platinum group elements in silicate melts

NASA Astrophysics Data System (ADS)

Anenburg, Michael; Mavrogenes, John A.

2016-11-01

Platinum group element (PGE) nanonuggets are a nuisance in experimental studies designed to measure solubility or partitioning of noble metals in silicate melts. Instead of treating nanonuggets as experimental artifacts, we studied their behaviour motivated by recent discoveries of PGE nanonuggets in a variety of natural settings. We used an experimental setup consisting of AgPd, Pt or AuPd capsules and Fe(-Ti) oxide-saturated hydrous peralkaline silicate melts to maximise nanonugget production. TABS (Te, As, Bi, Sb, Sn) commonly occur in PGM (platinum group minerals), prompting addition of Bi to our experiments to investigate its properties as well. Three-dimensional optical examination by 100× objective and immersion oil reveals variable colour which correlates with nanonugget size and shape due to plasmon resonance effects. We observe two textural types: (1) intermediate-sized nanonuggets dispersed in the glass and adhering to oxides, and (2) abundant fine nanonuggets dispersed in the glass with coarse euhedral crystals in contact with oxides. Slow cooling removes dispersed nanonuggets and greatly coarsens existing oxide-associated metal crystals. Nanonugget-free halos are commonly observed around oxide grains. All metal phases are composed of major (Ag, Pd) and trace (Pt, Ir, Au) capsule material. Our results show reduction processes, imposed by growing oxides, causing local metal saturation in the oxide rich zones with preferential nucleation on smaller oxide grains. The redox gradient then blocks additional metals from diffusing into oxide rich zones, forming halos. As the entire experimental charge is reduced throughout the run, nanonuggets form in the distal glass. Bismuth contents of metal phases do not depend on Bi2O3 amounts dissolved in the melt. Further PGM crystallisation consumes nanonuggets as feedstock. We conclude that the appearance of metallic PGE phases happens in two stages: first as nanonuggets and then as larger PGM. Once formed, nanonuggets cannot be removed by oxidation or dissolution, but only by PGM coarsening. Sulfur-poor PGE ore deposits commonly contain more PGE than permitted by existing estimates of equilibrium solubility in silicate melts. This is commonly explained by initial scavenging of PGE by sulfide liquids followed by S-loss, but evidence for S-loss is not conclusive. We suggest that nanonuggets may be a means to transport PGE from source regions to form ore deposits, followed by direct PGM crystallisation from silicate melt without intermediate concentration by sulfide liquids.

Improving the electrical properties of lanthanum silicate films on ge metal oxide semiconductor capacitors by adopting interfacial barrier and capping layers.

PubMed

Choi, Yu Jin; Lim, Hajin; Lee, Suhyeong; Suh, Sungin; Kim, Joon Rae; Jung, Hyung-Suk; Park, Sanghyun; Lee, Jong Ho; Kim, Seong Gyeong; Hwang, Cheol Seong; Kim, HyeongJoon

2014-05-28

The electrical properties of La-silicate films grown by atomic layer deposition (ALD) on Ge substrates with different film configurations, such as various Si concentrations, Al2O3 interfacial passivation layers, and SiO2 capping layers, were examined. La-silicate thin films were deposited using alternating injections of the La[N{Si(CH3)3}2]3 precursor with O3 as the La and O precursors, respectively, at a substrate temperature of 310 °C. The Si concentration in the La-silicate films was further controlled by adding ALD cycles of SiO2. For comparison, La2O3 films were also grown using [La((i)PrCp)3] and O3 as the La precursor and oxygen source, respectively, at the identical substrate temperature. The capacitance-voltage (C-V) hysteresis decreased with an increasing Si concentration in the La-silicate films, although the films showed a slight increase in the capacitance equivalent oxide thickness. The adoption of Al2O3 at the interface as a passivation layer resulted in lower C-V hysteresis and a low leakage current density. The C-V hysteresis voltages of the La-silicate films with Al2O3 passivation and SiO2 capping layers was significantly decreased to ∼0.1 V, whereas the single layer La-silicate film showed a hysteresis voltage as large as ∼1.0 V.

Mechanical resilience and cementitious processes in Imperial Roman architectural mortar.

PubMed

Jackson, Marie D; Landis, Eric N; Brune, Philip F; Vitti, Massimo; Chen, Heng; Li, Qinfei; Kunz, Martin; Wenk, Hans-Rudolf; Monteiro, Paulo J M; Ingraffea, Anthony R

2014-12-30

The pyroclastic aggregate concrete of Trajan's Markets (110 CE), now Museo Fori Imperiali in Rome, has absorbed energy from seismic ground shaking and long-term foundation settlement for nearly two millenia while remaining largely intact at the structural scale. The scientific basis of this exceptional service record is explored through computed tomography of fracture surfaces and synchroton X-ray microdiffraction analyses of a reproduction of the standardized hydrated lime-volcanic ash mortar that binds decimeter-sized tuff and brick aggregate in the conglomeratic concrete. The mortar reproduction gains fracture toughness over 180 d through progressive coalescence of calcium-aluminum-silicate-hydrate (C-A-S-H) cementing binder with Ca/(Si+Al) ≈ 0.8-0.9 and crystallization of strätlingite and siliceous hydrogarnet (katoite) at ≥ 90 d, after pozzolanic consumption of hydrated lime was complete. Platey strätlingite crystals toughen interfacial zones along scoria perimeters and impede macroscale propagation of crack segments. In the 1,900-y-old mortar, C-A-S-H has low Ca/(Si+Al) ≈ 0.45-0.75. Dense clusters of 2- to 30-µm strätlingite plates further reinforce interfacial zones, the weakest link of modern cement-based concrete, and the cementitious matrix. These crystals formed during long-term autogeneous reaction of dissolved calcite from lime and the alkali-rich scoriae groundmass, clay mineral (halloysite), and zeolite (phillipsite and chabazite) surface textures from the Pozzolane Rosse pyroclastic flow, erupted from the nearby Alban Hills volcano. The clast-supported conglomeratic fabric of the concrete presents further resistance to fracture propagation at the structural scale.

The chemical and isotopic differentiation of an epizonal magma body: Organ Needle pluton, New Mexico

USGS Publications Warehouse

Verplanck, P.L.; Farmer, G.L.; McCurry, M.; Mertzman, S.A.

1999-01-01

Major and trace element, and Nd and Sr isotopic compositions of whole rocks and mineral separates from the Oligocene, alkaline Organ Needle pluton (ONP), southern New Mexico, constrain models for the differentiation of the magma body parental to this compositionally zoned and layered epizonal intrusive body. The data reveal that the pluton is rimmed by lower ??(Nd) (~-5) and higher 87Sr/86Sr (~0.7085) syenitic rocks than those in its interior (??(Nd) ~ 2, 87Sr/86Sr ~0.7060) and that the bulk compositions of the marginal rocks become more felsic with decreasing structural depth. At the deepest exposed levels of the pluton, the ??(Nd)~-5 lithology is a compositionally heterogeneous inequigranular syenite. Modal, compositional and isotopic data from separates of rare earth element (REE)-bearing major and accesory mineral phases (hornblende, titanite, apatite, zircon) demonstrate that this decoupling of trace and major elements in the inequigranular syenite results from accumulation of light REE (LREE)-bearing minerals that were evidently separated from silicic magmas as the latter rose along the sides of the magma chamber. Chemical and isotopic data for microgranular mafic enclaves, as well as for restite xenoliths of Precambrian granite wall rock, indicate that the isotopic distinction between the marginal and interior facies of the ONP probably reflects assimilation of the wall rock by ??(Nd) ~-2 mafic magmas near the base of the magma system. Fractional crystallization and crystal liquid separation of the crystally contaminated magma at the base and along the margins of the chamber generated the highly silicic magmas that ultimately pooled at the chamber top.

No effect of H2O degassing on the oxidation state of magmatic liquids

NASA Astrophysics Data System (ADS)

Waters, Laura E.; Lange, Rebecca A.

2016-08-01

The underlying cause for why subduction-zone magmas are systematically more oxidized than those formed at mid-ocean spreading ridges is a topic of vigorous debate. It is either a primary feature inherited from the subduction of oxidized oceanic crust into the mantle or a secondary feature that develops because of H2O degassing and/or magma differentiation. Low total iron contents and high melt H2O contents render rhyolites sensitive to any effect of H2O degassing on ferric-ferrous ratios. Here, pre-eruptive magmatic Fe2+ concentrations, measured using Fe-Ti oxides that co-crystallized with silicate phenocrysts under hydrous conditions, are compared with Fe2+ post-eruptive concentrations in ten crystal-poor, fully-degassed obsidian samples; five are microlite free. No effect of H2O degassing on the ferric-ferrous ratio is found. In addition, Fe-Ti oxide data from this study and the literature show that arc magmas are systematically more oxidized than both basalts and hydrous silicic melts from Iceland and Yellowstone prior to extensive degassing. Nor is there any evidence that differentiation (i.e., crystal fractionation, crustal assimilation) is the cause of the higher redox state of arc magmas relative to those of Iceland/Yellowstone rhyolites. Instead, the evidence points to subduction of oxidized crust and the release of an H2O-rich fluid and/or melt with a high oxygen fugacity (fO2), which plays a role during H2O-flux melting of the mantle in creating basalts that are relatively oxidized.

Genetic significance of the 867 cm- 1 out-of-plane Raman mode in graphite associated with V-bearing green grossular

NASA Astrophysics Data System (ADS)

Thomas, Rainer; Rericha, Adolf; Pohl, Walter L.; Davidson, Paul

2018-03-01

SE Kenya is the world's largest producer of green vanadium grossular gemstones (tsavorite). Samples from one of the mines near Mwatate, and of occurrences in Tanzania yielded remarkable new insights into the genesis of tsavorite. Graphite is intimately associated with V-grossular and is one of the keys to understanding its origin. In the course of this study we found five different types of graphite. Surprisingly, in one graphite type the "Raman-forbidden" and IR-active 867 cm- 1 band was observed. In this communication, we attempt to find an explanation for this unusual phenomenon. Additionally, our observations also address some of the issues pertaining to the origin of the green grossular-dominated rocks (grossularites), as well as the gem quality tsavorite crystals, since we propose that the anomalous spectroscopic behavior of the graphite is related to the unusual conditions during crystallization of both the grossular and graphite from a near-supercritical volatile- and sulfur-rich silicate melt. The massive green vanadium grossular contains abundant unequivocal crystallized melt inclusions, while the transparent gem quality grossular (tsavorite) displays only fluid inclusions. On the basis of inclusion studies we suggest that anatectic melts originated in the peculiar evaporitic host lithology of the tsavorite deposits. Near peak metamorphic temperatures ( 700 °C) these liquids occurred as a supercritical volatile-rich "fluid/melt phase" characterized by complete miscibility between H2O and silicate liquid. Relatively dry liquid batches precipitated non-transparent green grossular, whereas wet batches segregated fluids that formed transparent tsavorite.

Mechanisms of Photo Degradation for Layered Silicate-Polycarbonate Nanocomposites

DTIC Science & Technology

2005-09-01

crystal was used as the sampling accessory. The UV/VIS spectra were recorded using a Cary 5G UV/VIS/ near - infrared (NIR) spectrometer set to scan in...transform infrared spectroscopy. The results reveal that the carbonate linkages undergo a scission reaction upon UV exposure, thereby compromising the...were wiped clean before spectroscopic analysis. 3.3 Spectroscopic Measurements Infrared measurements were recorded on a Nicolet model 560 Magna

Crystallization dynamics and interface stability of strontium titanate thin films on silicon.

PubMed

Hanzig, Florian; Hanzig, Juliane; Mehner, Erik; Richter, Carsten; Veselý, Jozef; Stöcker, Hartmut; Abendroth, Barbara; Motylenko, Mykhaylo; Klemm, Volker; Novikov, Dmitri; Meyer, Dirk C

2015-04-01

Different physical vapor deposition methods have been used to fabricate strontium titanate thin films. Within the binary phase diagram of SrO and TiO 2 the stoichiometry ranges from Ti rich to Sr rich, respectively. The crystallization of these amorphous SrTiO 3 layers is investigated by in situ grazing-incidence X-ray diffraction using synchrotron radiation. The crystallization dynamics and evolution of the lattice constants as well as crystallite sizes of the SrTiO 3 layers were determined for temperatures up to 1223 K under atmospheric conditions applying different heating rates. At approximately 473 K, crystallization of perovskite-type SrTiO 3 is initiated for Sr-rich electron beam evaporated layers, whereas Sr-depleted sputter-deposited thin films crystallize at 739 K. During annealing, a significant diffusion of Si from the substrate into the SrTiO 3 layers occurs in the case of Sr-rich composition. This leads to the formation of secondary silicate phases which are observed by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy.

Oxygen production by electrolysis of molten lunar regolith

NASA Technical Reports Server (NTRS)

Haskin, Larry A.

1990-01-01

The goal of this study was threefold. First, the theoretical energy requirements of the process were to be defined. This includes studies of the relevant oxidation-reduction reactions in the melt, their kinetics and energies of reaction, and experimental determination of production efficiencies and melt resistivities as functions of melt composition and applied potential. Second, the product(s) of silicate electrolysis were to be characterized. This includes: (1) evaluating the phase relationships in the systems SiO2-TiO2-Al2O3-MgO-FeO-CaO and Fe-Si; (2) estimating the compositions of the metal products as a function of applied potential and feedstock composition based on phase equilibria in the Fe-Si system and free energy values for SiO2 and FeO reported in the literature; (3) definition of compositions of products in actual experiments; and (4) definition of the form the product takes (whether phases separate or remain fixed, whether crystals settle or float in the remaining melt, and how large crystals form). Third, materials for these highly corrosive high-temperature silicate melts were to be identified. This includes identifing materials that may be either inert or thermodynamically stable in these melts, and experimental testing of the materials to confirm that they do not deteriorate. The results are discussed within this framework.

Prolonged magmatic activity on Mars inferred from the detection of felsic rocks

USGS Publications Warehouse

Wray, James J.; Hansen, Sarah T.; Dufek, Josef; Swayze, Scott L.; Murchie, Scott L.; Seelos, Frank P.; Skok, John R.; Irwin, Rossman P.; Ghiorso, Mark S.

2013-01-01

Rocks dominated by the silicate minerals quartz and feldspar are abundant in Earth’s upper continental crust. Yet felsic rocks have not been widely identified on Mars, a planet that seems to lack plate tectonics and the associated magmatic processes that can produce evolved siliceous melts on Earth. If Mars once had a feldspar-rich crust that crystallized from an early magma ocean such as that on the Moon, erosion, sedimentation and volcanism have erased any clear surface evidence for widespread felsic materials. Here we report near-infrared spectral evidence from the Compact Reconnaissance Imaging Spectrometer for Mars onboard the Mars Reconnaissance Orbiter for felsic rocks in three geographically disparate locations on Mars. Spectral characteristics resemble those of feldspar-rich lunar anorthosites, but are accompanied by secondary alteration products (clay minerals). Thermodynamic phase equilibrium calculations demonstrate that fractional crystallization of magma compositionally similar to volcanic flows near one of the detection sites can yield residual melts with compositions consistent with our observations. In addition to an origin by significant magma evolution, the presence of felsic materials could also be explained by feldspar enrichment by fluvial weathering processes. Our finding of felsic materials in several locations on Mars suggests that similar observations by the Curiosity rover in Gale crater may be more widely applicable across the planet.

Mid-infrared observations of sungrazing comet C/2012 S1 (ISON) with the Subaru Telescope

NASA Astrophysics Data System (ADS)

Ootsubo, T.; Usui, F.; Takita, S.; Watanabe, J.; Yanamandra-Fisher, P.; Honda, M.; Kawakita, H.; Furusho, R.

2014-07-01

Comets are the frozen reservoirs of the early solar nebula and are made of ice and dust. The determination of the properties for cometary dust provides us insight into both the early-solar-nebula environment and the formation process of the planetary system. A silicate feature is often observed in comet spectra in the mid-infrared region and may be used for probing the early history of the solar system. In most cases, the feature shows the existence of crystalline silicate (for example, 11.3 microns) together with amorphous silicate [1,2]. Since the crystallization of silicates from amorphous ones generally requires high-temperature annealing above 800 K (e.g., [3,4]), it is believed that the crystalline silicate grains produced at the inner part of the disk were transported to the outer cold regions where the comet nuclei formed. Comet C/2012 S1 (ISON) is a long-period Oort Cloud comet, discovered in September 2012. In particular, comet ISON is a sungrazing comet, which was predicted to pass close by the Sun and the Earth and becoming a bright object. Mid-infrared observations of this new comet and investigation of the 10-micron silicate feature help us understand the formation of crystalline silicate grains in the early solar nebula. We conducted observations of comet ISON in the mid-infrared wavelength region with the Cooled Mid-Infrared Camera and Spectrometer (COMICS) on the Subaru Telescope on Mauna Kea, Hawaii [5,6,7]. The observation of comet ISON was carried out on 2013 October 19 and 21 UT. Since the weather conditions were not so good when we observed, we carried out N-band imaging observations (8.8 and 12.4 microns) and N-band low-resolution spectroscopy. The spectrum of comet ISON can be fit with the 260--265-K blackbody spectrum when we use the regions of 7.8--8.2 and 12.4--13.0 microns as the continuum. The spectrum has only a weak silicate excess feature, which may be able to attribute to small amorphous olivine grains. We could not detect a clear crystalline silicate feature in the spectrum of our observations. We will compare the spectrum with other Oort Cloud comets, such as comets C/2011 L4 (PanSTARRS) and C/2013 R1 (Lovejoy), and discuss the dust properties and the birthplace of comet ISON.

Structural State and Elastic Properties of Perovskites in the Earth's Mantle

NASA Astrophysics Data System (ADS)

Ross, N. L.; Angel, R. J.; Zhao, J.

2005-12-01

Recent advances in laboratory-based single-crystal X-ray diffraction techniques for measuring the intensities of diffraction from crystals held in situ at high pressures in the diamond-anvil cell have been used to determine the role of polyhedral compression in the response of 2:4 and 3:3 GdFeO3-type perovskites to high pressure [1]. These new data clearly demonstrate that, contrary to previous belief, the compression of the octahedral sites is significant and that the evolution of the perovskite structure with pressure is controlled by a new principle; that of equipartition of bond-valence strain across the structure [2]. This new paradigm, together with the minimal information available from high- pressure powder diffraction studies, may provide the possibility of predicting the structural state and elastic properties of perovskites of any composition at mantle pressures and temperatures. Cation partioning between silicate perovskites and other phases should then be predictable through the application of a Brice-style model [3]. The geochemical implications of this type of analysis will be presented as well as the possibility for extending these measurements to higher pressures. References [1] e.g. Zhao, Ross & Angel (2004) Phys Chem Miner. 31: 299; Ross, Zhao,. & Angel (2004). J. Solid State Chemistry 177:1276. [2] Zhao, Ross, & Angel (2004). Acta Cryst. B60:263 [3] e.g Walter et al. (2004) Geochim Cosmochim Acta 68:4267; Blundy & Wood (1994) Nature 372:452

Structural Mineral Physics at Extreme Conditions

NASA Astrophysics Data System (ADS)

Chariton, S.; Dubrovinsky, L. S.; Dubrovinskaia, N.

2017-12-01

Laser heating techniques in diamond anvil cells (DACs) cover a wide pressure-temperature range - above 300 GPa and up to 5000 K. Recent advantages in on-line laser heating techniques resulted in a significant improvement of reliability of in situ X-ray powder diffraction studies in laser-heated DACs, which have become routine at a number of synchrotron facilities including specialized beam-lines at the 3rd generation synchrotrons. However, until recently, existing DAC laser-heating systems could not be used for structural X-ray diffraction studies aimed at structural refinements, i.e. measuring of the diffraction intensities, and not only at determining of lattice parameters. The reason is that in existing DAC laser-heating facilities the laser beam enters the cell at a fixed angle, and a partial rotation of the DAC, as required in monochromatic structural X-ray diffraction experiments, results in a loss of the target crystal and may be even dangerous if the powerful laser light starts to scatter in arbitrary directions by the diamond anvils. In order to overcome this problem we have develop a portable laser heating system and implement it at different diffraction beam lines. We demonstrate the application of this system for simultaneous high-pressure and high-temperature powder and single crystal diffraction studies using examples of studies of chemical and phase relations in the Fe-O system, transition metals carbonates, and silicate perovskites.

XRD, TEM, IR, Raman and NMR Spectroscopy of In Situ Crystallization of Lithium Disilicate Glass

NASA Technical Reports Server (NTRS)

Fuss, T.; Mogus-Milankovic, A.; Ray, C. S.; Lesher, C. E.; Youngman, R.; Day, D. E.

2006-01-01

The structure of a Li2O-2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 C respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si-O-Si bond angle approx.7deg lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa a new high pressure form of lithium metasilicate crystallizes. The new phase, while having lithium metasilicate crystal symmetry, contains at least 4 different Si sites. NMR results for 6 GPa sample indicate the presence of Q4 species with (Q(sup 4))Si-O-Si(Q(sup 4)) bond angles of approx.157deg. This is the first reported occurrence of Q(sup 4) species with such large bond angles in alumina free alkali silicate glass. No five- or six- coordinated Si are found.

Late Holocene hydrous mafic magmatism at the Paint Pot Crater and Callahan flows, Medicine Lake Volcano, N. California and the influence of H2O in the generation of silicic magmas

USGS Publications Warehouse

Kinzler, R.J.; Donnelly-Nolan, J. M.; Grove, T.L.

2000-01-01

This paper characterizes late Holocene basalts and basaltic andesites at Medicine Lake volcano that contain high pre-eruptive H2O contents inherited from a subduction related hydrous component in the mantle. The basaltic andesite of Paint Pot Crater and the compositionally zoned basaltic to andesitic lavas of the Callahan flow erupted approximately 1000 14C years Before Present (14C years B.P.). Petrologic, geochemical and isotopic evidence indicates that this late Holocene mafic magmatism was characterized by H2O contents of 3 to 6 wt% H2O and elevated abundances of large ion lithophile elements (LILE). These hydrous mafic inputs contrast with the preceding episodes of mafic magmatism (from 10,600 to ~3000 14C years B.P.) that was characterized by the eruption of primitive high alumina olivine tholeiite (HAOT) with low H2O (< 0.2 wt%), lower LILE abundance and different isotopic characteristics. Thus, the mantle-derived inputs into the Medicine Lake system have not always been low H2O, primitive HAOT, but have alternated between HAOT and hydrous subduction related, calc-alkaline basalt. This influx of hydrous mafic magma coincides temporally and spatially with rhyolite eruption at Glass Mountain and Little Glass Mountain. The rhyolites contain quenched magmatic inclusions similar in character to the mafic lavas at Callahan and Paint Pot Crater. The influence of H2O on fractional crystallization of hydrous mafic magma and melting of pre-existing granite crust beneath the volcano combined to produce the rhyolite. Fractionation under hydrous conditions at upper crustal pressures leads to the early crystallization of Fe-Mg silicates and the suppression of plagioclase as an early crystallizing phase. In addition, H2O lowers the saturation temperature of Fe and Mg silicates, and brings the temperature of oxide crystallization closer to the liquidus. These combined effects generate SiO2-enrichment that leads to rhyodacitic differentiated lavas. In contrast, low H2O HAOT magmas at Medicine Lake differentiate to iron-rich basaltic liquids. When these Fe-enriched basalts mix with melted granitic crust, the result is an andesitic magma. Since mid-Holocene time, mafic volcanism has been dominated primarily by hydrous basaltic andesite and andesite at Medicine Lake Volcano. However, during the late Holocene, H2O-poor mafic magmas continued to be erupted along with hydrous mafic magmas, although in significantly smaller volumes.

Crucibleless crystal growth and Radioluminescence study of calcium tungstate single crystal fiber

NASA Astrophysics Data System (ADS)

Silva, M. S.; Jesus, L. M.; Barbosa, L. B.; Ardila, D. R.; Andreeta, J. P.; Silva, R. S.

2014-11-01

In this article, single phase and high optical quality scheelite calcium tungstate single crystal fibers were grown by using the crucibleless laser heated pedestal growth technique. The as-synthesized calcium tungstate powders used for shaping seed and feed rods were investigated by X-ray diffraction technique. As-grown crystals were studied by Raman spectroscopy and Radioluminescence measurements. The results indicate that in both two cases, calcined powder and single crystal fiber, only the expected scheelite CaWO4 phase was observed. It was verified large homogeneity in the crystal composition, without the presence of secondary phases. The Radioluminescence spectra of the as-grown single crystal fibers are in agreement with that present in Literature for bulk single crystals, presented a single emission band centered at 420 nm when irradiated with β-rays.

Investigation of the H7 ordinary chondrite, Watson 012: Implications for recognition and classification of Type 7 meteorites

NASA Astrophysics Data System (ADS)

Tait, Alastair W.; Tomkins, Andrew G.; Godel, Bélinda M.; Wilson, Siobhan A.; Hasalova, Pavlina

2014-06-01

Despite the fact that the number of officially classified meteorites is now over 45,000, we lack a clearly defined sequence of samples from a single parent body that records the entire range in metamorphic temperatures from pristine primitive meteorites up to the temperatures required for extensive silicate partial melting. Here, we conduct a detailed analysis of Watson 012, an H7 ordinary chondrite, to generate some clarity on the textural and chemical changes associated with equilibrium-based silicate partial melting in chondritic meteorites. To do this we compare the textures in the meteorite with those preserved in metamorphic contact aureoles on Earth. The most distinctive texture generated by the partial melting that affected Watson 012 is an extensively interconnected plagioclase network, which is clearly observable with a petrographic microscope. Enlarged metal-troilite grains are encapsulated at widenings in this plagioclase network, and this is clearly visible in reflected light. Together with these features, we define a series of other characteristics that can be used to more clearly classify chondritic meteorites as being of petrologic Type 7. To provide comprehensive evidence of silicate partial melting and strengthen the case for using simple petrographic observations to classify similar meteorites, we use high-resolution X-ray computed tomography to demonstrate that the plagioclase network has a high degree of interconnectedness and crystallised as large (cm-scale) skeletal crystals within an olivine-orthopyroxene-clinopyroxene framework, essentially pseudomorphing a melt network. Back-scattered electron imaging and element mapping are used to show that some of the clino- and orthopyroxene in Watson 012 also crystallised from silicate melt, and the order of crystallisation was orthopyroxene → clinopyroxene → plagioclase. X-ray diffraction data, supported by bulk geochemistry, are used to show that plagioclase and ortho- and clinopyroxene were added to the Watson 012 sample by through-flowing basaltic melt. Along with the absence of glass and granophyre, this interconnected network of coarse-grained skeletal plagioclase indicates that the sample cooled slowly at depth within the parent body. The evidence of melt flux indicates that Watson 012 formed in the presence of a gravitational gradient, and thus at significant distance from the centre of the H chondrite parent body (the gravitational gradient at the centre would be zero). Our interpretation is that incipient silicate partial melting in Watson 012 occurred when a region of radiogenically heated H6 material located at considerable depth (possibly at ∼15-20 km from surface) was heated by an additional ca. 200-300 °C in association with a large shock event. Due to insulation at depth within an already hot parent body, the post-shock temperature equilibrated and remained above the solidus long enough for widespread equilibrium-based silicate partial melting, and for melt to migrate. Although the observed melting may have been facilitated by additional heating from an impact event, this is not an example of instantaneous shock melting, which produces thermal disequilibrium at short length scales and distinctly different textures. A small number of H, L and LL chondrites have been previously classified as being of petrologic Type 7; with our new criteria to support that classification, these represent our best opportunity to explore the transition from high temperature sub-solidus metamorphism through the onset of silicate partial melting in three different parent bodies.

Alteration, adsorption and nucleation processes on clay-water interfaces: Mechanisms for the retention of uranium by altered clay surfaces on the nanometer scale

NASA Astrophysics Data System (ADS)

Schindler, Michael; Legrand, Christine A.; Hochella, Michael F.

2015-03-01

Nano-scale processes on the solid-water interface of clay minerals control the mobility of metals in the environment. These processes can occur in confined pore spaces of clay buffers and barriers as well as in contaminated sediments and involve a combination of alteration, adsorption and nucleation processes of multiple species and phases. This study characterizes nano-scale processes on the interface between clay minerals and uranyl-bearing solution near neutral pH. Samples of clay minerals with a contact pH of ∼6.7 are collected from a U mill and mine tailings at Key Lake, Saskatchewan, Canada. The tailings material contains Cu-, As-, Co-, Mo-, Ni-, Se-bearing polymetallic phases and has been deposited with a surplus of Ca(OH)2 and Na2CO3 slaked lime. Small volumes of mill-process solutions containing sulfuric acid and U are occasionally discharged onto the surface of the tailings and are neutralized after discharge by reactions with the slaked lime. Transmission electron microscopy (TEM) in combination with the focused ion beam (FIB) technique and other analytical methods (SEM, XRD, XRF and ICP-OES) are used to characterize the chemical and mineralogical composition of phases within confined pore spaces of the clay minerals montmorillonite and kaolinite and in the surrounding tailings material. Alteration zones around the clay minerals are characterized by different generations of secondary silicates containing variable proportions of adsorbed uranyl- and arsenate-species and by the intergrowth of the silicates with the uranyl-minerals cuprosklodowskite, Cu[(UO2)2(SiO3OH)2](H2O)6 and metazeunerite, Cu[(UO2)(AsO4)2](H2O)8. The majority of alteration phases such as illite, illite-smectite, kaolinite and vermiculite have been most likely formed in the sedimentary basin of the U-ore deposit and contain low amounts of Fe (<5 at.%). Iron-enriched Al-silicates or illite-smectites (Fe >10 at.%) formed most likely in the limed tailings at high contact pH (∼10.5) and their structure is characterized by a low degree of long-range order. Adsorption of U and nucleation of metazeunerite and cuprosklodowskite are strongly controlled by the presence of the adsorbed oxy-anion species arsenate and silica on the Fe-enriched silicates. Heterogeneous nucleation of nano-crystals of the uranyl minerals occurs most likely on adsorption sites of binary uranyl-, arsenate- and silica-complexes as well as on ternary uranyl-arsenate or uranyl-silicate complexes. The uranyl minerals occur as aggregates of misoriented nano-size crystals and are the result of supersaturated solutions and a high number of nucleation sites that prevented the formation of larger crystals through Oswald ripening. The results of this study provide an understanding of interfacial nano-scale processes between uranyl species and altered clay buffers in a potential Nuclear Waste repository as similar alteration conditions of clays may occur in a multi-barrier system.

Single crystalline growth of a soluble organic semiconductor in a parallel aligned liquid crystal solvent using rubbing-treated polyimide films

NASA Astrophysics Data System (ADS)

Matsuzaki, Tomoya; Shibata, Yosei; Takeda, Risa; Ishinabe, Takahiro; Fujikake, Hideo

2017-01-01

For directional control of organic single crystals, we propose a crystal growth method using liquid crystal as the solvent. In this study, we examined the formation of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) single crystals using a parallel aligned liquid crystal (LC) cell and rubbing-treated polyimide films in order to clarify the effects of LC alignment on anisotropic C8-BTBT crystal growth. Based on the results, we found that the crystal growth direction of C8-BTBT single crystals was related to the direction of the aligned LC molecules because of rubbing treatment. Moreover, by optical evaluation, we found that the C8-BTBT single crystals have a aligned molecular structure.

Sealing glass-ceramics with near linear thermal strain, Part II: Sequence of crystallization and phase stability

DOE PAGES

Dai, Steve Xunhu; Rodriguez, Mark A.; Griego, James M.

2016-06-01

Here, the sequence of crystallization in a re-crystallizable lithium silicate sealing glass-ceramic Li 2O-SiO 2-Al 2O 3-K 2O-B 2O 3-P 2O 5-ZnO was analyzed by in situ high temperature X-ray diffraction (HTXRD). Glass-ceramic specimens have been subjected to a 2-stage heat treatment schedule, including rapid cooling from sealing temperature to a 1st hold temperature 650 °C, following by heating to a 2nd hold temperature of 810 °C. Notable growth and saturation of Quartz was observed at 650 °C (1st hold).

Melting behavior and phase relations of lunar samples

NASA Technical Reports Server (NTRS)

Hays, J. F.

1976-01-01

An attempt was made to show that feldspar would float during melting. Large anorthite crystals were placed beneath a silicate glass representative of liquid in which plagioclase accumulation is thought to have occurred. In less than 3 hours at 1,300 C, the crystals rose to the top in a Pt crucible 3 cm deep equilibrated in air and in a Mo crucible 1.5 cm deep equilibrated in an H2/CO2 gas stream of log PO2 = -10.9 (below Fe/FeO). These results suggest that lunar crustal formation by feldspar flotation is possible without special recourse to differential sinking of plagioclase versus mafic minerals or selective elutriation of plagioclase.

Early Age Carbonation Heat and Products of Tricalcium Silicate Paste Subject to Carbon Dioxide Curing.

PubMed

Li, Zhen; He, Zhen; Shao, Yixin

2018-05-04

This paper presents a study on the carbonation reaction heat and products of tricalcium silicate (C₃S) paste exposed to carbon dioxide (CO₂) for rapid curing. Reaction heat was measured using a retrofitted micro-calorimeter. The highest heat flow of a C₃S paste subject to carbonation curing was 200 times higher than that by hydration, and the cumulative heat released by carbonation was three times higher. The compressive strength of a C₃S paste carbonated for 2 h and 24 h was 27.5 MPa and 62.9 MPa, respectively. The 24-h carbonation strength had exceeded the hydration strength at 28 days. The CO₂ uptake of a C₃S paste carbonated for 2 h and 24 h was 17% and 26%, respectively. The X-ray diffraction (XRD), transmission electron microscope coupled with energy dispersive spectrometer (TEM-EDS), and 29 Si magic angle spinning⁻nuclear magnetic resonance ( 29 Si MAS-NMR) results showed that the products of a carbonated C₃S paste were amorphous silica (SiO₂) and calcite crystal. There was no trace of calcium silicate hydrate (C⁻S⁻H) or other polymorphs of calcium carbonate (CaCO₃) detected.

Ag-doped Lithium alumino silicate photostructurable glass for microdevice fabrication

NASA Astrophysics Data System (ADS)

Mishra, Richa; Goswami, Madhumita; Krishnan, Madangopal

2018-04-01

Ag-doped LAS glass of composition (wt.%):74SiO2-6Al2O3-15Li2O-5X (X=other additives) were prepared by melt-quench technique and characterized for thermal and optical properties using DTA and UV-Visible spectrometer. XRD technique was used for phase identification in the heat treated glasses. Glass samples were exposed to UV-light for conversion of Ce3+ to Ce4+ state and Ag+ into Ago metallic state. DTA shows a lower crystallization temperature (Tp) at around 605°C for exposed samples as compared to unexposed base glass which is at around 625°C. UV-Visible spectra shows a broad band at around 305nm which indicates Ce3+ in base glass whereas in case of UV-exposed sample the reduced peak intensity indicates conversion of Ce3+ to Ce4+ ions, which also confirm formation of Ago in glass samples. Ag agglomeration was also confirmed from the band position at 430nm in heat treated sample, found responsible for early growth of meta-silicate phase in exposed sample. The meta-silicate phase was selectively etched for fabrication of micro-devices.

Shock compression of preheated silicate liquids: 30 years of progress

NASA Astrophysics Data System (ADS)

Asimow, Paul

2011-06-01

Tom Ahrens and his students pioneered, beginning around 1981, the technique of determining silicate liquid equations of state for geophysical applications using shock compression of pre-heated, encapsulated samples. In the last decade, we have ported this technique to the Caltech two-stage light gas gun and extended several pre-heated liquid Hugoniots to over 125 GPa. We now have enough compositions studied to perform several tests of the theory of linear mixing or, assuming linear mixing, to describe any liquid in the five-component CaO-MgO-FeO-Al2O3-SiO2 system. This data allows us to identify liquid compositions likely to be negatively or neutrally buoyant in the lower mantle and to form a preliminary description of the dynamics of partial melting of solid lower mantle or initial crystallization of a deep mantle magma ocean. The most robust and surprising feature of all studied liquids, which places very strong constraints on microscopic models for silicate liquid compression behavior, is anomalous increase of the Grüneisen parameter upon compression, with remarkably consistent q = dln γ/dlnV = -1.75 +/- 0.25. Thanks to long-term support by the National Science Foundation.

Composition characteristics and regularities of dissolving of hydroxyapatite materials obtained in water solutions with varied content of silicate ions

NASA Astrophysics Data System (ADS)

Solonenko, A. P.

2018-01-01

Research aimed at developing new bioactive materials for the repair of defects in bone tissues, do not lose relevance due to the strengthening of the regenerative approach in medicine. From this point of view, materials based on calcium phosphates, including silicate ions, consider as one of the most promising group of substances. Methods of synthesis and properties of hydroxyapatite doped with various amounts of SiO4 4- ions are described in literature. In the present work synthesis of a solid phase in the systems Ca(NO3)2 - (NH4)2HPO4 - Na2SiO3 - NH4OH - H2O (Cca/CP = 1.70) performed with a wide range of sodium silicate additive concentration (y = CSi/CP = 0 ÷ 5). It is established that under the studied conditions at y ≥ 0.3 highly dispersed poorly crystallized apatite containing isomorphic impurities of CO3 2- and SiO4 4- precipitates in a mixture with calcium hydrosilicate and SiO2. It is shown that the resulting composites can gradually dissolve in physiological solution and initiate passive formation of the mineral component of hard tissues.

Ignition and growth modeling of detonation reaction zone experiments on single crystals of PETN and HMX

NASA Astrophysics Data System (ADS)

White, Bradley W.; Tarver, Craig M.

2017-01-01

It has long been known that detonating single crystals of solid explosives have much larger failure diameters than those of heterogeneous charges of the same explosive pressed or cast to 98 - 99% theoretical maximum density (TMD). In 1957, Holland et al. demonstrated that PETN single crystals have failure diameters of about 8 mm, whereas heterogeneous PETN charges have failure diameters of less than 0.5 mm. Recently, Fedorov et al. quantitatively determined nanosecond time resolved detonation reaction zone profiles of single crystals of PETN and HMX by measuring the interface particle velocity histories of the detonating crystals and LiF windows using a PDV system. The measured reaction zone time durations for PETN and HMX single crystal detonations were approximately 100 and 260 nanoseconds, respectively. These experiments provided the necessary data to develop Ignition and Growth (I&G) reactive flow model parameters for the single crystal detonation reaction zones. Using these parameters, the calculated unconfined failure diameter of a PETN single crystal was 7.5 +/- 0.5 mm, close to the 8 mm experimental value. The calculated failure diameter of an unconfined HMX single crystal was 15 +/- 1 mm. The unconfined failure diameter of an HMX single crystal has not yet been determined precisely, but Fedorov et al. detonated 14 mm diameter crystals confined by detonating a HMX-based plastic bonded explosive (PBX) without initially overdriving the HMX crystals.

Secondary orientation effects in a single crystal superalloy under mechanical and thermal loads

NASA Technical Reports Server (NTRS)

Kalluri, Sreeramesh; Abdul-Aziz, Ali; Mcgaw, Michael A.

1991-01-01

The nickel-base single crystal superalloy PWA 1480 is a candidate blading material for the advanced turbopump development program of the SSME. In order to improve thermal fatigue resistance of the turbine blades, the single crystal superalloy PWA 1480 is grown along the low modulus zone axes (001) crystal orientation by a directional solidification process. Since cubic single crystal materials such as PWA 1480 exhibit anisotropic elastic behavior, the stresses developed within the single crystal superalloy due to mechanical and thermal loads are likely to be affected by the exact orientation of the secondary crystallographic direction with respect to the geometry of the turbine blade. The effects of secondary crystal orientation on the elastic response of single crystal PWA 1480 superalloy were investigated.

Piezoelectric single crystals for ultrasonic transducers in biomedical applications

PubMed Central

Zhou, Qifa; Lam, Kwok Ho; Zheng, Hairong; Qiu, Weibao; Shung, K. Kirk

2014-01-01

Piezoelectric single crystals, which have excellent piezoelectric properties, have extensively been employed for various sensors and actuators applications. In this paper, the state–of–art in piezoelectric single crystals for ultrasonic transducer applications is reviewed. Firstly, the basic principles and design considerations of piezoelectric ultrasonic transducers will be addressed. Then, the popular piezoelectric single crystals used for ultrasonic transducer applications, including LiNbO3 (LN), PMN–PT and PIN–PMN–PT, will be introduced. After describing the preparation and performance of the single crystals, the recent development of both the single–element and array transducers fabricated using the single crystals will be presented. Finally, various biomedical applications including eye imaging, intravascular imaging, blood flow measurement, photoacoustic imaging, and microbeam applications of the single crystal transducers will be discussed. PMID:25386032

All-into-one strategy to synthesize mesoporous hybrid silicate microspheres from naturally rich red palygorskite clay as high-efficient adsorbents

PubMed Central

Wang, Wenbo; Tian, Guangyan; Wang, Dandan; Zhang, Zhifang; Kang, Yuru; Zong, Li; Wang, Aiqin

2016-01-01

A mesoporous hybrid silicate microsphere with superior adsorption performance has been successfully synthesized by employing an “all-into-one” strategy and a simple one-pot hydrothermal process using naturally abundant low-grade red palygorskite (PAL) clay as raw material in the presence of non-toxic SiO32− and Mg2+ ions. As is expected, both the PAL and associated minerals transformed into a new amorphous mesoporous hybrid silicate microsphere without using any additional pore-forming template. The mesoporous silicate microsphere shows a large pore size of 37.74 nm, high specific surface area of 489.81 m2/g (only 54.67 m2/g for raw PAL) and negative surface potential of −43.3 mV, and its maximum adsorption capabilities for Methylene bule (MB) and Crystal violet (CV) reach 407.95 mg/g and 397.22 mg/g, respectively. Meanwhile, 99.8% of MB (only 53% for raw PAL) and 99.7% of CV (only 43% for raw PAL) were sucessfully removed from 200 mg/L of initial dye solution by only using 1 g/L of the adsorbent. In addition, the spent adsorbent can be easily regenerated and repeatly reused for muptiple cycles. The study on adsorption mechanism revealed that electrostatic attraction, hydrogen bonding and chemical complexing interactions are the main factors contributed to the high dye adsorption. PMID:28000784

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.

Inclusions of Sulphide Immiscible Melts in Primitive Olivine Phenocrysts from Mantle-Derived Magmas; Preliminary Results

NASA Astrophysics Data System (ADS)

Danyushevsky, L.; Ryan, C.; Kamenetsky, V.; Crawford, A.

2001-12-01

Sulphide inclusions have been identified in olivine phenocrysts (and in one case in a spinel phenocryst) in primitive volcanic rocks from mid- ocean ridges, subduction-related island arcs and backarc basins. These inclusions represent droplets of an immiscible sulphide melt and are trapped by olivine crystals growing from silicate melts. Sulphide melt is usually trapped as separate inclusions, however combined inclusions of sulphide and silicate melts have also been observed. Sulphide inclusions have rounded shapes and vary in size from several up to 100 microns in diameter. At room temperature sulphide inclusions consist of several phases. These phases are formed as a result of crystallisation of the sulphide melt after it was trapped. Crystallisation occurs due to decreasing temperature in the magma chamber after trapping and/or when magma ascents from the magma chamber during eruptions. In all studied sulphides three different phases can be identified: a high- Fe, low-Ni, low-Cu phase; a high-Fe, high-Ni, low-Cu phase; and high-Fe, low-Ni, high-Cu phase. Low-Cu phases appear to be monomineralic, whereas the high-Cu phase is usually composed of a fine intergrowth of high- and low-Cu phases, resembling the quench 'spinifex' structure. Fe, Ni and Cu are the major elements in all sulphides studied. The amount of Ni decreases with decreasing forsterite content of the host olivine phenocryst, which is an index of the degree of silicate magma fractionation. Since Ni content of the silicate magma is decreasing during fractionation, this indicates either that the immiscible sulfide melt remains in equilibrium with the silicate melt continuously changing its composition during fractionation, or that the sulfide melt is continuously separated from the silicate melt during fractionation, with later formed droplets having lower Ni content due to the lower Ni content of the evolved, stronger fractionated silicate melt. Trace element contents of the sulfide inclusions have been analysed on the proton microprobe at CSIRO in Sydney. The main trace elements in the sulfide inclusions are Zn, Pb, Ag, and Se. Other trace elements are below detection limits, which are normally at a level of several ppm. Zn concentrations (120 +/- 40 ppm) in sulphides are similar to those in silicate melts. This indicates that separation of the sulfide melt does not affect Zn contents of silicate melts. On the contrary, Ag (30 +/- 10 ppm) and Pb (40 +/- 10 ppm) contents in sulphides are at least in order of magnitude higher than in the silicate melt, and thus separation of the immiscible sulfide melt can significantly decrease Pb and Ag contents of the silicate magma. The widespread occurrence of sulfide inclusions, which were also described in olivine phenocrysts from ocean island basalts, indicates common saturation at low pressure of mantle-derived magmas with reduced sulfur.

Preparation of a Non-Polar ZnO Film on a Single-Crystal NdGaO3 Substrate by the RF Sputtering Method

NASA Astrophysics Data System (ADS)

Kashiwaba, Y.; Tanaka, Y.; Sakuma, M.; Abe, T.; Imai, Y.; Kawasaki, K.; Nakagawa, A.; Niikura, I.; Kashiwaba, Y.; Osada, H.

2018-04-01

Preparation of non-polar ZnO ( 11\\overline{2} 0 ) films on single-crystal NdGaO3 (NGO) (001) substrates was successfully achieved by the radio frequency (RF) sputtering method. Orientation, deposition rate, and surface roughness of ZnO films strongly depend on the working pressure. Characteristics of ZnO films deposited on single-crystal NGO (001) substrates were compared with those of ZnO films deposited on single-crystal sapphire ( 01\\overline{1} 2 ) substrates. An x-ray diffraction peak of the ZnO ( 11\\overline{2} 0 ) plane was observed on ZnO films deposited on single-crystal NGO (001) substrates under working pressure of less than 0.5 Pa. On the other hand, uniaxially oriented ZnO ( 11\\overline{2} 0 ) films on single-crystal sapphire ( 01\\overline{1} 2 ) substrates were observed under working pressure of 0.1 Pa. The mechanism by which the diffraction angle of the ZnO ( 11\\overline{2} 0 ) plane on single-crystal NGO (001) substrates was shifted is discussed on the basis of anisotropic stress of lattice mismatch. The deposition rate of ZnO films decreased with an increase in working pressure, and the deposition rate on single-crystal NGO (001) substrates was larger than that on single-crystal sapphire ( 01\\overline{1} 2 ) substrates. Root mean square (RMS) roughness of ZnO films increased with an increase in working pressure, and RMS roughness of ZnO films on single-crystal NGO (001) substrates was smaller than that of ZnO films on single-crystal sapphire ( 01\\overline{1} 2 ) substrates even though the film thickness on single-crystal NGO (001) substrates was greater than that on sapphire substrates. It is thought that a single-crystal NGO (001) substrate is useful for deposition of non-polar ZnO ( 11\\overline{2} 0 ) films.

Electrical characteristics of organic perylene single-crystal-based field-effect transistors

NASA Astrophysics Data System (ADS)

Lee, Jin-Woo; Kang, Han-Saem; Kim, Min-Ki; Kim, Kihyun; Cho, Mi-Yeon; Kwon, Young-Wan; Joo, Jinsoo; Kim, Jae-Il; Hong, Chang-Seop

2007-12-01

We report on the fabrication of organic field-effect transistors (OFETs) using perylene single crystal as the active material and their electrical characteristics. Perylene single crystals were directly grown from perylene powder in a furnace using a relatively short growth time of 1-3 h. The crystalline structure of the perylene single crystals was characterized by means of a single-crystal x-ray diffractometer. In order to place the perylene single crystal onto the Au electrodes of the field-effect transistor, a polymethlymethacrylate thin layer was spin-coated on top of the crystal surface. The OFETs fabricated using the perylene single crystal showed a typical p-type operating mode. The field-effect mobility of the perylene crystal based OFETs was measured to be ˜9.62×10-4 cm2/V s at room temperature. The anisotropy of the mobility implying the existence of different mobilities when applying currents in different directions was observed for the OFETs, and the existence of traps in the perylene crystal was found through the measurements of the temperature-dependent mobility at various operating drain voltages.

Deformation and failure of single- and multi-phase silicate liquids: seismic precursors and mechanical work

NASA Astrophysics Data System (ADS)

Vasseur, Jeremie; Lavallée, Yan; Hess, Kai-Uwe; Wassermann, Joachim; Dingwell, Donald B.

2013-04-01

Along with many others, volcanic unrest is regarded as a catastrophic material failure phenomenon and is often preceded by diverse precursory signals. Although a volcanic system intrinsically behave in a non-linear and stochastic way, these precursors display systematic evolutionary trends to upcoming eruptions. Seismic signals in particular are in general dramatically increasing prior to an eruption and have been extensively reported to show accelerating rates through time, as well as in the laboratory before failure of rock samples. At the lab-scale, acoustic emissions (AE) are high frequency transient stress waves used to track fracture initiation and propagation inside a rock sample. Synthesized glass samples featuring a range of porosities (0 - 30%) and natural rock samples from volcán de Colima, Mexico, have been failed under high temperature uniaxial compression experiments at constant stresses and strain rates. Using the monitored AEs and the generated mechanical work during deformation, we investigated the evolutionary trends of energy patterns associated to different degrees of heterogeneity. We observed that the failure of dense, poorly porous glasses is achieved by exceeding elevated strength and thus requires a significant accumulation of strain, meaning only pervasive small-scale cracking is occurring. More porous glasses as well as volcanic samples need much lower applied stress and deformation to fail, as fractures are nucleating, propagating and coalescing into localized large-scale cracks, taking the advantage of the existence of numerous defects (voids for glasses, voids and crystals for volcanic rocks). These observations demonstrate that the mechanical work generated through cracking is efficiently distributed inside denser and more homogeneous samples, as underlined by the overall lower AE energy released during experiments. In contrast, the quicker and larger AE energy released during the loading of heterogeneous samples shows that the mechanical work tends to concentrate in specific weak regions facilitating dynamical failure of the material through dissipation of the accumulated strain energy. Applying a statistical Global Linearization Method (GLM) in multi-phase silicate liquids samples leads to a maximum likelihood power-law fit of the accelerating rates of released AEs. The calculated α exponent of the famous empirical Failure Forecast Method (FFM) tends to decrease from 2 towards 1 with increasing porosity, suggesting a shift towards an idealized exponential-like acceleration. Single-phase silicate liquids behave more elastically during deformation without much cracking and suddenly releasing their accumulated strain energy at failure, implying less clear trends in monitored AEs. In a predictive prospective, these results support the fact that failure forecasting power is enhanced by the presence of heterogeneities inside a material.

Exploring the folding pattern of a polymer chain in a single crystal by combining single-molecule force spectroscopy and steered molecular dynamics simulations.

PubMed

Song, Yu; Feng, Wei; Liu, Kai; Yang, Peng; Zhang, Wenke; Zhang, Xi

2013-03-26

Understanding the folding pattern of a single polymer chain within its single crystal will shed light on the mechanism of crystallization. Here, we use the combined techniques of atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) and steered molecular dynamics (SMD) simulations to study the folding pattern of a polyethylene oxide (PEO) chain in its single crystal. Our results show that the folding pattern of a PEO chain in the crystal formed in dilute solution follows the adjacent re-entry folding model. While in the crystal obtained from the melt, the nonadjacent folding with large and irregular loops contributes to big force fluctuations in the force-extension curves. The method established here can offer a novel strategy to directly unravel the chain-folding pattern of polymer single crystals at single-molecule level.

Effect of amaranth dye on the growth and properties of conventional and SR method grown KAP single crystals

NASA Astrophysics Data System (ADS)

Babu Rao, G.; P., Rajesh; Ramasamy, P.

2018-04-01

The 0.1 mol% amaranth added KAP single crystals were grown from aqueous solutions by both slow evaporation solution technique and Sankaranarayanan-Ramasamy method. The single crystal having dimension of 45 mm length and 12 mm diameter was grown with growth rate of 1.5 mm/day using SR method. 87 % transmittance is obtained for SR method grown amaranth added KAP single crystal. The high intense luminescence at 661 nm is obtained from amaranth added conventional and SR method grown KAP single crystal. The amaranth added KAP single crystal possesses good mechanical and laser damage threshold stability.

Hibonite: Crystal Chemistry and Origin of Blue Coloration in Meteoritic Assemblages

NASA Technical Reports Server (NTRS)

Burns, R. G.; Burns, V. M.

1985-01-01

The blue color and optical spectra of hibonite, a common constituent of refractory inclusions in carbonaceous chondrites, are discussed. Because they may be manifestations of exotic cation species stabilized in unusual coordination sites in the hibonite crystalstructure. Hibonite, ideally CaAl12O19, is conducive to atomic substitution of host Ca2+ and Al3+ ions by a variety of lanthanide and first series transition elements. The latter cations are responsible for the colors of many rock-forming minerals as a result of intraelectronic or intervalence transitions. The visible-region spectra of most oxide and silicate minerals are generally well understood. Assignments of absorption bands in meteoritic hibonite optical spectra due to uncertainties of cation valencies and complexities in the crystal structure are examined. The crystal chemistry of hibonite is reviewed, Mossbauer spectral measurements of iron-bearing hibonite and electronic transitions that may be responsible for the blue coloration of meteoritic hibonites are discussed.

Constraints on Ureilite Petrogenesis and Carbon-Metal-Silicate Equilibria on the UPB

NASA Astrophysics Data System (ADS)

Goodrich, C. A.; Holloway, J. R.

1992-07-01

The most important constraints on models of ureilite petrogenesis are 1) Ureilites have lost a basaltic complement (they are ultramafic, extremely depleted in plagiophile elements, enriched in HREE, and have negative Eu anomalies and superchondritic Ca/Al ratios). 2) Ureilites experienced long equilibration times at high T (indicated by coarse grain size, extreme homogeneity of core crystals, correlations between olivine and pyroxene compositions, and metamorphic-like textures), followed by rapid cooling (indicated by structural features of pyroxene and narrow reduction rims on olivine). 3) Ureilites are probably residues (based on mass balance) but partly crystallized from melts. 4) Ureilites are derived from a minimum of six reservoirs that were distinct in oxygen isotopic composition and did not equilibrate with one another (this is consistent with the observation that olivine and pyroxene cores do not show correlations of mg with MnO, Cr2O3, Sm/Eu or Lu/Eu). 5) There is a correlation between oxygen isotopic composition and mg ratio in ureilites. Similar correlations are observed for Allende chondrules and group means of H3-L3-LL3 chondrites (Fig. 1), and are argued to result from nebular processes [1]. 6) If graphite-metal-silicate-CO/CO2 equilibrium was established during melting, then mg ratios of ureilites were determined by depth because CCO redox reactions are strongly pressure-dependent. Cohenite-bearing metallic spherule inclusions in the silicates and euhedral shapes of large graphite crystals in low-shock ureilites have been taken as evidence of equilibrium. Olivine reduction rims, highly variable interstitial metal compositions, and a lack of correlation between mg and metal content argue against equilibrium. 7) Ureilites either lost a low melting-T metal fraction or gained a refractory-rich metal component. (they have high abundances of siderophile elements but show fractionation between [Os, Ir, W, Re] and [Ni, Ga, Ge, Au]). 8) Primordial noble gases were retained in some carbon phases. 9) Ureilites formed at ~4.55 Ga but both Sm-Nd and Rb-Sr isotopic systematics have been subsequently disturbed. Constraints 1-4 are best met if ureilites are partial melt residues produced by ~25% equilibrium partial melting on an oxygen-isotopically heterogeneous parent body in >=6 distinct melting zones. If there was no global magma ocean, km-sized melting zones would not equilibrate oxygen with one another in 10 m.y. Constraints 5 and 6 appear difficult to reconcile. If the UPB inherited a nebular oxygen isotope-mg correlation how could this correlation have survived partial melting? If the melting zones all experienced approximately the same degree of melting (Mn/Mg, Cr/Mg, and HRE provide evidence for this), and silicate equilibria determined mg, then the original correlation may simply have shifted to higher mg, consistent with the position of the ureilite trend relative to the Allende trends (Fig. 1). However, if mg was depth-dependent then it is unlikely that any oxygen isotope-mg correlation would remain. Also, noble gases in carbon would be lost (violating constraint 8) during carbon redox reactions. All constraints would be better met if graphite-metal-silicate-CO/CO2 equilibrium was not established during partial melting. If graphite was primary but a CO/CO2 fluid phase was not present then there would have been no pressure/depth dependence of fO(sub)2. As long as the pressure was sufficiently high (~100-200 bars) to stabilize the most ferroan ureilite (Fo 76) then the more magnesian ureilites would have been stable in the presence of graphite and metal. On the other hand, constraints 7, 8, and 9 could be neatly met if most of the carbon was not primary but a carbon-metal-noble gas assemblage was added as a late component to the ultramafic rocks. The cohenite-bearing metallic spherules are rare and tiny (10-50 micrometers) compared to interstitial metal (mm-sized irregular grains). They appear to have been droplets of immiscible, hypereutectic Fe(Ni)-C liquids that were trapped by crystallizing silicates. In contrast, the interstitial metal and graphite show no evidence of having been a liquid Fe-C alloy and their confinement to grain boundaries and reduction rims is consistent with late addition. Goodrich and Berkley (2) argued that the spherules were carbon-saturated at 1200-1225 degrees C and therefore that the silicate liquid must have contained graphite. However, in the Fe-C system the stable graphite liquidus is much steeper than the metastable cohenite liquidus, and although these alloys were cohenite-saturated, they were not graphite-saturated. Hence, the silicate magma probably did not contain graphite and carbon was not the dominant control on fO(sub)2. Thus, it may be possible to reconcile the main constraints on ureilite petrogenesis without high pressures. [1] R.N. Clayton & T.K. Mayeda (1988] GCA 52, 1313. [2] C.A. Goodrich & J.L. Berkely (1986) GCA 50, 681.

Origins of cryptic variation in the Ediacaran-Fortunian rhyolitic ignimbrites of the Saldanha Bay Volcanic Complex, Western Cape, South Africa

NASA Astrophysics Data System (ADS)

Clemens, J. D.; Stevens, G.; Frei, D.; Joseph, C. S. A.

2017-12-01

The Saldanha eruption centre, on the West Coast of South Africa, consists of 542 Ma, intracaldera, S-type, rhyolite ignimbrites divided into the basal Saldanha Ignimbrite and the partly overlying Jacob's Bay Ignimbrite. Depleted-mantle Nd model ages suggest magma sources younger than the Early Mesoproterozoic, and located within the Neoproterozoic Malmesbury Group and Swartland complex metasedimentary and metavolcanic rocks that form the regional basement. The Sr isotope systematics suggest that the dominant source rocks were metavolcaniclastic rocks and metagreywackes, and that the magmas formed from separate batches extracted from the same heterogeneous source. No apparent magma mixing trends relate the Saldanha to the Jacob's Bay Ignimbrites, or either of these to the magmas that formed the Plankiesbaai or Tsaarsbank Ignimbrites in the neighbouring Postberg eruption centre. The magmas were extracted from their source rocks carrying small but significant proportions of peritectic and restitic accessory minerals. Variations in the content of this entrained crystal cargo were responsible for most of the chemical variations in the magmas. Although we cannot construct a cogent crystal fractionation model to relate these groups of magmas, at least some crystal fractionation occurred, as an overlay on the primary signal due to peritectic assemblage entrainment (PAE). Thus, the causes of the cryptic chemical variation among the ignimbrite magmas of the Saldanha centre are variable, but dominated by the compositions of the parent melts and PAE. The preservation of clear, source-inherited chemical signatures, in individual samples, calls into question the common interpretation of silicic calderas as having been formed in large magma reservoirs, with magma compositions shaped by magma mingling, mixing, and fractional crystallization. The Saldanha rocks suggest a more intimate connection between source and erupted magma, and perhaps indicate that silicic magmas are too viscous to be significantly modified by magma-chamber processes.

Crystal structures of CaSiO3 polymorphs control growth and osteogenic differentiation of human mesenchymal stem cells on bioceramic surfaces.

PubMed

Zhang, Nianli; Molenda, James A; Mankoci, Steven; Zhou, Xianfeng; Murphy, William L; Sahai, Nita

2013-10-01

The repair and replacement of damaged or diseased human bone tissue requires a stable interface between the orthopedic implant and living tissue. The ideal material should be both osteoconductive (promote bonding to bone) and osteoinductive (induce osteogenic differentiation of cells and generate new bone). Partially resorbable bioceramic materials with both properties are developed by expensive trial-and-error methods. Structure-reactivity relationships for predicting the osteoinductive properties of ceramics would significantly increase the efficiency of developing materials for bone tissue engineering. Here we propose the novel hypothesis that the crystal structure of a bioceramic controls the release rates, subsequent surface modifications due to precipitation of new phases, and thus, the concentrations of soluble factors, and ultimately, the attachment, viability and osteogenic differentiation of human Mesenchymal Stem Cells (hMSCs). To illustrate our hypothesis, we used two CaSiO 3 polymorphs, pseudo-wollastonite (psw, β-CaSiO 3 ) and wollastonite (wol, α-CaSiO 3 ) as scaffolds for hMSC culture. Polymorphs are materials which have identical chemical composition and stoichiometry, but different crystal structures. We combined the results of detailed surface characterizations, including environmental Scanning Electron Microscopy (SEM) back-scattered imaging, and spot-analysis and 2D elemental mapping by SEM-Energy Dispersive X-ray (SEM-EDX), High Resolution Transmission Electron Microscopy (HRTEM) and surface roughness analysis; culture medium solution analyses; and molecular/genetic assays from cell culture. Our results confirmed the hypothesis that the psw polymorph, which has a strained silicate ring structure, is more osteoinductive than the wol polymorph, which has a more stable, open silicate chain structure. The observations could be attributed to easier dissolution (resorption) of psw compared to wol, which resulted in concentration profiles that were more osteoinductive for the former. Thus, we showed that crystal structure is a fundamental parameter to be considered in the intelligent design of pro-osteogenic, partially resorbable bioceramics.

Translation effects on vertical Bridgman growth and optical, mechanical and surface analysis of 2-phenylphenol single crystal

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

Sadhasivam, S., E-mail: sadha.phy1@gmail.com; Perumal, Rajesh Narayana

2-phenylphenol optical crystals were grown in cone ampoules using vertical Bridgman technique. Single crystal of 2-phenylphenol with 150 mm length has been grown. The inclination on the conical part of the ampoule reduces the growth defects in the 2-phenylphenol single crystal. The lattice parameters and structure studied using single crystal X-ray diffraction method. 2-phenylphenol single crystal belongs to orthorhombic space group Fdd2. The micro translation rate affects crystal growth of 2-phenylphenol crystal was studied. The translation rate dependent defects present in the crystal were investigated by transmittance, indentation and etching characterizations. The dislocation induced indentation crack lengths variations were studied. Etchmore » pits and striations observed for the selective etchants furnish significant information on growth aspects and degree of defect present in the crystal.« less

The Design and Testing of a High-Temperature Graphite Dilatometer

DTIC Science & Technology

1992-06-24

characterization of its CTE is of little significance. Practical candidates are silica (fused quartz glass), Zerodur -type glass ceramics (5 x 10- 8 C-1 ), and...titanium silicates (< 5 x IO17 *C-1 ). Partially crystallized glasses, such as Zerodur , are limited to about 6006C. Silica can be subjected to almost...electronics, solid-state lasers , optical propagation and communications; cw and pulsed chemical laser development, optical resonators, beam control

The interplay between crystallization, replenishment and hybridization in large felsic magma chambers

NASA Astrophysics Data System (ADS)

Bateman, R.

1995-09-01

While hybridized granitoid magmas are readily identifiable, the mechanisms of hybridization in large crustal magma chambers are so not clearly understood. Characteristic features of hybrid granitoids are (1) both the granitoid and included enclaves are commonly hybrids, as shown by mineralogy, geochemistry and isotopes; (2) mixing seen in zoned plutons and synplutonic dykes and enclaves occurred early; (3) zoned plagioclase phenocrysts commonly show very complex life histories of growth and dissolution; (4) mafic end-members in hybrids are commonly fractionated magmas and (5) stratification in subvolcanic granitoid magma chambers is not uncommon, and stratification has been identified in some deeper level plutons. Hybridization must overcome the tendency to form a stable stratification of dense mafic magma underlying less dense felsic magma. Experimental work with magma analogues and theoretical considerations reveal very severe thermal, rheological and dynamical limitations on mixing: only very similar (composition, temperature) magmas are likely to mix to homogeneity, and only moderately silicic hybrids are likely to be produced. However, "impossibly" silicic hybrids do exist. Synchronous, interactive fractional crystallization and hybridization may provide a mechanism for hybridization of magmas, in the following manner. A mafic magma intrudes into the base of a stratified felsic magma and is cooled against it. Crystallization of the upper boundary layer of the mafic magma yields an eventually buoyant residual melt that overturns and mixes with an adjacent stratum of the felsic magma chamber. Subsequently, melt released by crystallization pf this, now-hybrid zone mixes with adjacent, more felsic zones. Thus, a suite of hybrid magmas are progressively formed. Density inhibitions are overcome by the generation of relatively low density residual melts. As crystallization proceeds, later injections are preserved as dykes and enclaves composed of hybrid magma. In this process, only physically adjacent and dynamically-thermally similar magmas directly interact, and so may mix to homogeneity. Finally, not simply felsic and mafic endmembers mix, but a whole suite of "intermediate" endmembers participate, ranging from relatively mafic through to felsic pairs of magmas. Direct mixing between the primary magmas only occurs at the beginning.

Precise new shock temperatures in forsterite and in silicate liquids: phase transitions and heat capacity at high pressure

NASA Astrophysics Data System (ADS)

Asimow, P. D.; Fat'yanov, O. V.; Su, C.; Ma, X. J.

2017-12-01

Shock temperature measurements in transparent samples provide key constraints on the phase transitions and thermodynamic properties of materials at high pressure and temperature. Such measurements are necessary, for example, to allow equation of state measurements taken along the Hugoniot to be translated to P-V-T space. We have recently completed a detailed study of the accuracy and reproducibility of calibration of our 6-channel fast pyrometer. We have also introduced improved analysis procedures of the time-dependent multi-wavelength radiance signal that avoid the need for a greybody assumption and therefore have better precision than earlier results. This has motivated (a) renewed study of the shock temperature of forsterite in the superheating, partial melting, and complete melting regimes, (b) pre-heated diopside-anorthite glass shock temperature experiments for comparison to pre-heated silicate liquid equation of state results, and (c) new soda-lime glass shock temperature experiments. Single-crystal synthetic forsterite samples were shocked along (100) to pressures between 120 and 210 GPa on the Caltech two-stage light gas gun. Uncertainties on most results are 50 K. Results above the onset of partial melting at 130 GPa are consistent with Lyzenga and Ahrens (1980) data and show a low P-T slope consistent with a partial melting interval. Complete melting may occur, given sufficient time, at about 210 GPa. The experiment at 120-130 GPa is anomalous, showing two-wave structure and time- and wavelength-dependent scattering suggesting a subsolidus phase transition behind the shock front. The amount of super-heating, if any, is far smaller than claimed by Holland and Ahrens (1997). Steady radiation profiles, high emissivity, and consistency from channel to channel provide high precision (±40 K) in diopside-anorthite liquid shocked from just above the glass transition to high pressure. Temperatures are colder than expected for a model with constant heat capacity, providing direct evidence that multicomponent silicate liquids show a major increase in heat capacity in the P-T range appropriate to terrestrial magma oceans (<150 GPa, <5000 K).

VARIATIONS OF THE 10 mum SILICATE FEATURES IN THE ACTIVELY ACCRETING T TAURI STARS: DG Tau AND XZ Tau

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

Bary, Jeffrey S.; Leisenring, Jarron M.; Skrutskie, Michael F., E-mail: jbary@colgate.ed, E-mail: jml2u@virginia.ed, E-mail: mfs4n@virginia.ed

2009-11-20

Using the Infrared Spectrograph aboard the Spitzer Space Telescope, we observed multiple epochs of 11 actively accreting T Tauri stars in the nearby Taurus-Auriga star-forming region. In total, 88 low-resolution mid-infrared spectra were collected over 1.5 years in Cycles 2 and 3. The results of this multi-epoch survey show that the 10 mum silicate complex in the spectra of two sources-DG Tau and XZ Tau-undergoes significant variations with the silicate feature growing both weaker and stronger over month- and year-long timescales. Shorter timescale variations on day- to week-long timescales were not detected within the measured flux errors. The time resolutionmore » coverage of this data set is inadequate for determining if the variations are periodic. Pure emission compositional models of the silicate complex in each epoch of the DG Tau and XZ Tau spectra provide poor fits to the observed silicate features. These results agree with those of previous groups that attempted to fit only single-epoch observations of these sources. Simple two-temperature, two-slab models with similar compositions successfully reproduce the observed variations in the silicate features. These models hint at a self-absorption origin of the diminution of the silicate complex instead of a compositional change in the population of emitting dust grains. We discuss several scenarios for producing such variability including disk shadowing, vertical mixing, variations in disk heating, and disk wind events associated with accretion outbursts.« less

Local crystal/chemical structures at iron sites in amorphous, magnetic, and nanocrystalline materials

NASA Astrophysics Data System (ADS)

Clark, Ted Michael

Order-disorder phenomena have been examined by means of Mossbauer spectroscopy in a variety of materials, including (a) tektites and other silicate glasses, (b) magnetic materials such as natural and synthetic magnetoplumbite, M-type hexagonal ferrites and magnetite, and (c) nanocrystalline zinc ferrite. A methodology has been established for the analysis of the local crystal/chemical structures of iron in tektites and its application has reconfirmed a low ferric/ferrous ratio of approximately 0.10 for tektites. Additionally, a greater degree of submirocscopic heterogeneity has been established for Muong Nong tektites in comparison with splash form tektites. The dynamics of the 2b site in hexagonal ferrites has been studied above and below the Curie temperature for magnetoplumbite and its synthetic analogs, and also for polycrystalline and oriented single-crystals of MeFesb{12}Osb{19} (Me=Ba, Sr, Pb). Cation ordering on this site is shown to be dependent on the thermal history of the material, while the dynamic disorder of the 2b site for the end-member hexagonal ferrites is shown to be influenced by the divalent heavy metal species, Me. The influence of chemical composition on the morphology of magnetite has been shown to depend on the site preference of impurity cations: Substitutional impurities with tetrahedral site preferences are postulated to result in the seldom-observed cubic habit. Based on the cation distributions of bulk and nanocrystalline material it is held that the enhanced magnetic moments and susceptibilities of nanocrystalline zinc ferrite are shown to be consistent with surface phenomena, independent of synthesis methodology, and contrary to claims of special effects resulting from a particular synthesis methodology.

Structure of calcinaksite KNa[Ca(H₂O)][Si₄O₁₀], the first hydrous member of the litidionite group of silicates with [Si₈O₂₀]⁸⁻ tubes.

PubMed

Aksenov, Sergey M; Rastsvetaeva, Ramiza K; Chukanov, Nikita V; Kolitsch, Uwe

2014-08-01

Calcinaksite, KNa[Ca(H2O)][Si4Ol0], a new natural member of the litidionite group, was found in a calcic xenolith from alkaline basalt of the Bellerberg volcano, Eastern Eifel region, Rhineland-Palatinate, Germany. The crystal structure has been studied based on single-crystal X-ray diffraction data. Triclinic unit-cell parameters are: a = 7.021 (2), b = 8.250 (3), c = 10.145 (2) Å, α = 102.23 (2), β = 100.34 (2), γ = 115.09 (3)°, space group P1. The structure model was determined by the `charge-flipping' method and refined to R = 0.0527 in anisotropic approximation using 3057 I > 3σ(I). Calcinaksite is a hydrous calcium-dominant litidionite-group mineral. The crystal structure of calcinaksite (like other litidionite-group minerals and related compounds) is based on a heteropolyhedral framework and is characterized by the presence of several types of channels. Calcium forms distorted CaO5Ø (Ø = H2O) octahedra while Na forms NaO5 square pyramids. Nine-coordinated K atoms are located in a channel extending along [010]. Water molecules occupy a channel running along the [100] direction and are characterized by a rather high equivalent isotropic displacement parameter of 0.053 (2) Å(2). In calcinaksite, there are three short distances between the water molecule and oxygen atoms, Ow...O3 [2.844 (5) Å], Ow...O9 [2.736 (4) Å] and Ow...Ow [2.843 (7) Å]. These distances correspond to three hydrogen bonds detected by IR data (the bands at 3340, 3170 and 3540 cm(-1)).

Pulse energy dependence of refractive index change in lithium niobium silicate glass during femtosecond laser direct writing.

PubMed

Cao, Jing; Poumellec, Bertrand; Brisset, François; Lancry, Matthieu

2018-03-19

Femtosecond laser-induced refractive index changes in lithium niobium silicate glass were explored at high repetition rate (300 fs, 500 kHz) by polarized light microscopy, full-wave retardation plate, quantitative birefringence microscopy, and digital holographic microscopy. We found three regimes on energy increase. The first one corresponds to isotropic negative refractive index change (for pulse energy ranging 0.4-0.8 μJ/pulse, 0.6 NA, 5μm/s, 650μm focusing depth in the glass). The second one (0.8-1.2 μJ/pulse) corresponds to birefringence with well-defined slow axis orientation. The third one (above 1.2 μJ/pulse) is related to birefringence direction fluctuation. Interestingly, these regimes are consistent with crystallization ones. In addition, an asymmetric orientational writing effect has been detected on birefringence. These topics extend the possibility of controlling refractive index change in multi-component glasses.

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.

High-temperature ultrasonic characterization of the mechanical and microstructural behavior of a fibrous composite with a magnesium lithium aluminum silicate glass-ceramic matrix

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

Cutard, T.; Huger, M.; Fargeot, D.

The mechanical behavior and the microstructural modifications of a SiC-fiber-reinforced magnesium lithium aluminum silicate glass-ceramic (SiC/MASL) have been characterized by ultrasonic measurement of uniaxial Young`s modulus at high temperature. Under vacuum, long isothermal agings in the 750--1,000 C temperature range have shown matrix modifications in terms of crystallization of residual glassy phases, and of phase transformations in the Li{sub 2}O-Al{sub 2}O{sub 3}-SiO{sub 2} system. In air, long isothermal agings performed under the same conditions have led to the same matrix transformations but in competition with oxidation mechanisms of the carbon fiber-matrix interphase. All of these matrix and/or interface transformations havemore » been confirmed by X-ray diffraction analysis, scanning electron microscopy, scanning acoustic microscopy, and microindentation tests.« less

Majorite-Garnet Partitioning of the Highly Siderophile Elements: New Results and Application to Mars

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Waeselmann, N.; Humayun, M.

2015-01-01

HSE and Os isotopes are used to constrain processes such as accretion, mantle evolution, crustal recycling, and core-mantle mixing, and to constrain the timing and depth of differentiation of Mars. Although showed that the HSE contents of the martian mantle could have been established by metal-silicate equilibrium in early Mars, the role of a cooling magma ocean and associated crystallization in further fractionating the HSEs is unclear. Garnet is thought to have played an important role in controlling trace element concentrations in the martian mantle reservoirs. However, testing these models, including Os isotopes, has been hindered by a dearth of partitioning data for the HSE in deep mantle phases - majorite, wadsleyite, ringwoodite, akimotoite - that may be present in the martian mantle. We examine the partitioning behavior of HSEs between majorite garnet (gt), olivine (oliv), and silicate liquid (melt).

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

NASA Technical Reports Server (NTRS)

Day, Delbert E.; Ray, Chandra S.

2003-01-01

This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one1 of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on earth (1g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials. The classical theories for nucleation and crystal growth for a glass or melt do not contain any parameter that is directly dependent upon the g-value, so it is not readily apparent why glasses prepared in microgravity should be more resistant to crystallization than equivalent glasses prepared on earth. Similarly, the gravity-driven convection in a fluid melt is believed to be the primary force field that is responsible for melt homogenization on earth. Thus, it is not obvious why a glass prepared in space, where gravity-driven convection is ideally absent, would be more chemically homogeneous than a glass identically prepared on earth. The primary objective of the present research is to obtain experimental data for the nucleation rate and crystal growth rate for a well characterized silicate melt (lithium disilicate) processed entirely in space (low gravity) and compare these rates with the nucleation and crystal growth rates for a similar glass prepared identically on earth (1g).

Ultratough CVD single crystal diamond and three dimensional growth thereof

DOEpatents

Hemley, Russell J [Washington, DC; Mao, Ho-kwang [Washington, DC; Yan, Chih-shiue [Washington, DC

2009-09-29

The invention relates to a single-crystal diamond grown by microwave plasma chemical vapor deposition that has a toughness of at least about 30 MPa m.sup.1/2. The invention also relates to a method of producing a single-crystal diamond with a toughness of at least about 30 MPa m.sup.1/2. The invention further relates to a process for producing a single crystal CVD diamond in three dimensions on a single crystal diamond substrate.

Development of n- and p-type Doped Perovskite Single Crystals Using Solid-State Single Crystal Growth (SSCG) Technique

DTIC Science & Technology

2017-10-09

doped BaTiO3 single crystal) could be also fabricated by using a BaTiO3 ceramics with the same compositional gradient (Fig. 8). This result has...piezoelectric applications. Compositionally PZT ceramics lie near the MPB between the tetragonal and rhombohedral phases and MPB compositions ...single crystal growth) technique are suitable to grow a variety of “n- and p-type doped” perovskite single crystals of complicated compositions . The

Growth of high quality bulk size single crystals of inverted solubility lithium sulphate monohydrate

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

Silambarasan, A.; Rajesh, P., E-mail: rajeshp@ssn.edu.in; Ramasamy, P.

2015-06-24

The paper summarizes the processes of growing large lithium sulfate monohydrate (LSMH) single crystals. We have established a procedure to grow high quality bulk size single crystals of inverted solubility LSMH by a newly developed unidirectional crystallization technique called the Sankeranarayenan - Ramasamy (SR) method. The convective flow of crystal growth processes from solution and the conditions of growing crystals of various aspects were discussed. Good quality LSMH single crystal is grown of the size 20 mmX80 mm without cracks, localized-defects and inclusions. The as-grown crystals are suitable for piezoelectric and nonlinear optical applications.

A new method to evaluate the quality of single crystal Cu by an X-ray diffraction butterfly pattern method

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

Xu Zhenming; Guo Zhenqi; Li Jianguo

2004-12-15

A new method for the evaluation of the quality of an Ohno continuous cast (OCC) Cu single crystal by X-ray diffraction (XRD) butterfly pattern was brought forward. Experimental results show that the growth direction of single crystal Cu is inclined from both sides of the single crystal Cu rod to the axis and is axially symmetric. The degree of deviation from the [100] orientation from the crystal axis is less than 5 deg. with a casting speed 10-40 mm/min. The orientation of single crystal Cu does not have a fixed direction but is in a regular range. Moreover, the orientationmore » of stray grains in the single crystal Cu is random from continuous casting.« less

Apatite sulfur systematics and crystal population in the 1991 Pinatubo magmas

NASA Astrophysics Data System (ADS)

van Hoose, A. E.; Streck, M. J.; Pallister, J. S.

2010-12-01

On June 15, 1991, Mount Pinatubo, Philippines, ejected 20 mega-tonnes of sulfur dioxide into the atmosphere, significantly impacting global climate and stratospheric ozone. Recharging basaltic magma mixed into the 50 km3 dacitic magma reservoir 6 to 11 km beneath Mount Pinatubo, and triggered the 1991 eruption. The result of the magma mixing was a hybrid andesite with quenched basalt inclusions that erupted as a dome between June 7 and June 12. On June 15, approximately 5 km3 of anhydrite bearing magma was erupted from the main phenocryst-rich dacitic reservoir. We are using this extraordinary framework of the 1991 Pinatubo eruption to investigate the systematics of sulfur uptake by apatite in order to further develop apatite as a monitor for magmatic sulfur. In the dacite and hybrid andesite, apatite occurs as individual phenocrysts (up to ~200 μm diameter) or included within anhydrite, hornblende, and plagioclase phenocrysts. In the basaltic magmatic inclusions, apatite is found as acicular microphenocrysts. Electron microprobe data collected on apatite yield low- (<0.3 SO3 wt.%), medium- (0.3-0.7 SO3 wt.%), and high-sulfur (>0.7 SO3 wt.%) apatites in all juvenile products, and show that two distinct populations of apatites exist. Apatites crystallizing from silicic melt have predominantly low- to medium-sulfur contents, but high-sulfur apatites with as much as 1.2-1.6 wt.% SO3 occur sporadically and are always found in close proximity to anhydrite. Except for a few low-sulfur apatites, apatite in the basalt is always sulfur-rich with compositions forming a continuous array between 0.9 to 2.4 wt.% SO3. The population of apatite that crystallized from silicic melt has elevated cerium, fluorine, and chlorine and lower magnesium concentrations (average dacite values in wt.%: 0.22 Ce2O3; 1.4 F; 1.1 Cl, 0.14 MgO ;) relative to the population of apatite from the basalt (average basalt values in wt.%: 0.08 Ce2O3; 0.9 F; 0.9 Cl, 0.20 MgO). These compositional systematics rule out the possibility that sulfur-rich apatite from dacite are inherited from mafic magma. We will evaluate this in further detail with additional LA-ICP-MS data. These data beg the question: which condition led to the crystallization of such high-sulfur apatites in silicic Pinatubo magmas (occurring also elsewhere, e.g., Streck et al., 2007)? Equilibrium crystal-melt partitioning is unlikely the cause because these apatites appear over-enriched in SO3, as they exceed values for apatite of experimental studies with a rhyolitic melt containing 400-700 ppm sulfur at high temperature (≥900 °C) (Parat and Holtz, 2005). Close proximity of sulfur-rich apatite to anhydrite suggests that high sulfur content is a local phenomenon that occurs only where anhydrite has crystallized and may in part be diffusion and/or fluid-controlled. On the other hand, high-sulfur apatite of the basalt likely reflects the high intrinsic sulfur content of the basaltic magma. (Parat, F., Holtz, F. (2005), CMP 150: 643-651; Streck, M., Broderick, C., Halter, W. (2007) GCA 71: A979)

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

USGS Publications Warehouse

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

2012-01-01

Crystal zoning as well as temperature and pressure estimates from phenocryst phase equilibria are used to constrain the architecture of the intermediate-sized magmatic system (some tens of km3) of Volcán Quizapu, Chile, and to document the textural and compositional effects of magma mixing. In contrast to most arc magma systems, where multiple episodes of open-system behavior obscure the evidence of major magma chamber events (e.g. melt extraction, magma mixing), the Quizapu magma system shows limited petrographic complexity in two large historical eruptions (1846–1847 and 1932) that have contrasting eruptive styles. Quizapu magmas and peripheral mafic magmas exhibit a simple binary mixing relationship. At the mafic end, basaltic andesite to andesite recharge magmas complement the record from peripheral cones and show the same limited range of compositions. The silicic end-member composition is almost identical in both eruptions of Quizapu. The effusive 1846–1847 eruption records significant mixing between the mafic and silicic end-members, resulting in hybridized andesites and mingled dacites. These two compositionally simple eruptions at Volcán Quizapu present a rare opportunity to isolate particular aspects of magma evolution—formation of homogeneous dacite magma and late-stage magma mixing—from other magma chamber processes. Crystal zoning, trace element compositions, and crystal-size distributions provide evidence for spatial separation of the mafic and silicic magmas. Dacite-derived plagioclase phenocrysts (i.e. An25–40) show a narrow range in composition and limited zonation, suggesting growth from a compositionally restricted melt. Dacite-derived amphibole phenocrysts show similar restricted compositions and furthermore constrain, together with more mafic amphibole phenocrysts, the architecture of the magmatic system at Volcán Quizapu to be compositionally and thermally zoned, in which an andesitic mush is overlain by a homogeneous dacitic magma that is the source for most of the 1846–1847 and 1932 erupted magmas. Dacite formation is best explained by mineral–melt separation (crystal fractionation) from an andesitic mush, which is inferred to have thermally and compositionally buffered the dacite magma thereby keeping it at relatively low crystallinity (<30 vol. %). The dominant cause of compositional diversity is melt separation. Back-mixing of mush (i.e. crystals with signatures of growth both in the andesitic mush and in the dacite magma) into the overlying dacite magma is rarely observed. Recharge events that increase crystal and magma diversity in the dacite magma are limited to an episode of mafic recharge and mixing just prior to the 1846–1847 eruption, where evidence for magma mixing is present on all scales. Chamber-wide mixing was incomplete (mixing efficiency of ∼0·53–0·85) as flow lobes vary significantly in composition along the proposed mixing array. Estimates of viscosity variations during the course of magma mixing suggest that mixing dynamics and the degree of magma interaction on all scales were established at the beginning of the recharge event.

Spray printing of organic semiconducting single crystals

NASA Astrophysics Data System (ADS)

Rigas, Grigorios-Panagiotis; Payne, Marcia M.; Anthony, John E.; Horton, Peter N.; Castro, Fernando A.; Shkunov, Maxim

2016-11-01

Single-crystal semiconductors have been at the forefront of scientific interest for more than 70 years, serving as the backbone of electronic devices. Inorganic single crystals are typically grown from a melt using time-consuming and energy-intensive processes. Organic semiconductor single crystals, however, can be grown using solution-based methods at room temperature in air, opening up the possibility of large-scale production of inexpensive electronics targeting applications ranging from field-effect transistors and light-emitting diodes to medical X-ray detectors. Here we demonstrate a low-cost, scalable spray-printing process to fabricate high-quality organic single crystals, based on various semiconducting small molecules on virtually any substrate by combining the advantages of antisolvent crystallization and solution shearing. The crystals' size, shape and orientation are controlled by the sheer force generated by the spray droplets' impact onto the antisolvent's surface. This method demonstrates the feasibility of a spray-on single-crystal organic electronics.

Timescales and conditions of crystallization in the Pokai and Chimpanzee Ignimbrites, Taupo Volcanic Zone, New Zealand

NASA Astrophysics Data System (ADS)

Connor, M.; Gualda, G. A.; Gravley, D. M.

2013-12-01

Silicic magmas give rise to explosive eruptions that are both of scientific and societal interest. The central Taupo Volcanic Zone in New Zealand has been volcanically active for 2 Ma and represents the most active volcanic area in the world today. Particularly intense volcanic activity took place as part of a flare-up event that occurred from ~340 to ~240 ka, when 7 large ignimbrite eruptions took place, as well as many smaller eruptions, which erupted a total of at least 3000 km3 of magma. This project seeks to identify the conditions and timescales over which magma bodies that gave rise to these ignimbrite eruptions evolved. We aim to understand how much of the tens of thousands of years between successive eruptions were characterized by the presence of large bodies of silicic magma within the crust, as well the magma distribution within the crust during those times. We focus on the Chimpanzee and Pokai ignimbrites, which together erupted ~150 km3 of magma. The Pokai ignimbrite erupted at ~275 ka, while the Chimpanzee ignimbrite (undated) erupted between ~320 and 275 ka. Pumice clasts from the Chimpanzee and Pokai ignimbrite were collected in the field. Pumice bulk densities were measured using a submersion technique. Quartz and plagioclase crystals were extracted through a crushing, sieving, and winnowing procedure. Whole crystals were hand-picked under a conventional microscope, mounted on epoxy, and polished to expose grain interiors. Grain mounts were analyzed under an SEM using back-scattered electron, cathodoluminescence (CL), and energy-dispersive x-ray (EDX) imaging. Bulk-densities vary from 0.42 to 0.81 g/cm3 for Pokai and between 0.52 and 0.64 g/cm3 for Chimpanzee pumice clasts. Plagioclase is the dominant crystal phase in both units. Several plagioclase crystals have inclusions of orthopyroxene, ilmenite, magnetite, and zircon, which in some cases form clusters. Quartz is rare but is present in pumice from both deposits. Both plagioclase and quartz have glass inclusions. Quantitative EDX analyses under the SEM reveal high-silica rhyolite compositions (~78 wt. % SiO2), consistent with crystallization at shallow crustal levels (~100 MPa). Rhyolite-MELTS barometry confirms this suggestion, with estimated crystallization pressures of 70-110 MPa. Such crystallization depths are characteristic of magma bodies that give rise to ignimbrites in the Taupo Volcanic Zone. CL images of a small number of quartz crystals reveal zoning that is variable in character, from unzoned to distinctly zoned. Zoned crystals have several discrete zones, each one with its own characteristic homogeneous brightness; bright CL rims are observed in these crystals. Contacts between zones can be used to calculate crystallization times using diffusional relaxation assuming that CL intensity variations are due to Ti zonation. We estimate that quartz crystallization took place over decades to a few centuries, with rims crystallizing over months to years at most. These short timescales suggest that magma bodies with eruptible magma are very short-lived, much shorter-lived than the 10s of ka repose periods between eruptions that make up the flare-up event.

Gallium arsenide single crystal solar cell structure and method of making

NASA Technical Reports Server (NTRS)

Stirn, Richard J. (Inventor)

1983-01-01

A production method and structure for a thin-film GaAs crystal for a solar cell on a single-crystal silicon substrate (10) comprising the steps of growing a single-crystal interlayer (12) of material having a closer match in lattice and thermal expansion with single-crystal GaAs than the single-crystal silicon of the substrate, and epitaxially growing a single-crystal film (14) on the interlayer. The material of the interlayer may be germanium or graded germanium-silicon alloy, with low germanium content at the silicon substrate interface, and high germanium content at the upper surface. The surface of the interface layer (12) is annealed for recrystallization by a pulsed beam of energy (laser or electron) prior to growing the interlayer. The solar cell structure may be grown as a single-crystal n.sup.+ /p shallow homojunction film or as a p/n or n/p junction film. A Ga(Al)AS heteroface film may be grown over the GaAs film.

Preparation of fine single crystals of magnetic superconductor RuSr2GdCu2O8-δ by partial melting

NASA Astrophysics Data System (ADS)

Yamaki, Kazuhiro; Bamba, Yoshihiro; Irie, Akinobu

2018-03-01

In this study, fine uniform RuSr2GdCu2O8-δ (RuGd-1212) single crystals have been successfully prepared by partial melting. Synthesis temperature could be lowered to a value not exceeding the decomposition temperature of RuGd-1212 using the Sr-Gd-Cu-O flux. The crystals grown by alumina boats are cubic, which coincides with the result of a previous study of RuGd-1212 single crystals using platinum crucibles. The single crystals were up to 15 × 15 × 15 µm3 in size and their lattice constants were consistent with those of polycrystalline samples reported previously. Although the present size of single crystals is not sufficient for measurements, the partial melting technique will be beneficial for future progress of research using RuGd-1212 single crystals. Appropriate nominal composition, sintering atmosphere, and temperature are essential factors for growing RuGd-1212 single crystals.

Demonstration of single crystal growth via solid-solid transformation of a glass

DOE PAGES

Savytskii, Dmytro; Knorr, Brian; Dierolf, Volkmar; ...

2016-03-18

Many advanced technologies have relied on the availability of single crystals of appropriate material such as silicon for microelectronics or superalloys for turbine blades. Similarly, many promising materials could unleash their full potential if they were available in a single crystal form. However, the current methods are unsuitable for growing single crystals of these oftentimes incongruently melting, unstable or metastable materials. Here we demonstrate a strategy to overcome this hurdle by avoiding the gaseous or liquid phase, and directly converting glass into a single crystal. Specifically, Sb 2S 3 single crystals are grown in Sb-S-I glasses as an example ofmore » this approach. In this first unambiguous demonstration of an all-solid-state glass → crystal transformation, extraneous nucleation is avoided relative to crystal growth via spatially localized laser heating and inclusion of a suitable glass former in the composition. Lastly, the ability to fabricate patterned single-crystal architecture on a glass surface is demonstrated, providing a new class of micro-structured substrate for low cost epitaxial growth, active planar devices, etc.« less

Study of single crystals of metal solid solutions

NASA Technical Reports Server (NTRS)

Doty, J. P.; Reising, J. A.

1973-01-01

The growth of single crystals of relatively high melting point metals such as silver, copper, gold, and their alloys was investigated. The purpose was to develop background information necessary to support a space flight experiment and to generate ground based data for comparison. The ground based data, when compared to the data from space grown crystals, are intended to identify any effects which zero-gravity might have on the basic process of single crystal growth of these metals. The ultimate purposes of the complete investigation are to: (1) determine specific metals and alloys to be investigated; (2) grow single metal crystals in a terrestrial laboratory; (3) determine crystal characteristics, properties, and growth parameters that will be effected by zero-gravity; (4) evaluate terrestrially grown crystals; (5) grow single metal crystals in a space laboratory such as Skylab; (6) evaluate the space grown crystals; (7) compare for zero-gravity effects of crystal characteristics, properties, and parameters; and (8) make a recommendation as to production of these crystals as a routine space manufacturing proceses.

Crystal growth and scintillation properties of Pr-doped SrI2 single crystals

NASA Astrophysics Data System (ADS)

Yokota, Yuui; Ito, Tomoki; Yoshino, Masao; Yamaji, Akihiro; Ohashi, Yuji; Kurosawa, Shunsuke; Kamada, Kei; Yoshikawa, Akira

2018-04-01

Pr-doped SrI2 (Pr:SrI2) single crystals with various Pr concentrations were grown by the halide-micro-pulling-down (H-μ-PD) method, and the scintillation properties were investigated. Pr1%:SrI2 single crystal with high transparency could be grown by the H-μ-PD method while Pr2, 3 and 5%:SrI2 single crystals included some cracks and opaque parts. In the photoluminescence spectrum of the Pr1%:SrI2 single crystal, an emission peak originated from the Pr3+ ion was observed around 435 nm while the radioluminescence spectra showed an emission peak around 535 nm for the undoped SrI2 and Pr:SrI2 single crystals. Light yields of Pr1, 2, 3 and 5%:SrI2 single crystals under γ-ray irradiation were 7700, 8700, 7200 and 6700 photons/MeV, respectively. Decay times of Pr1 and 2%:SrI2 single crystals under γ-ray irradiation were 55.9 and 35.0 ns of the fast decay component, and 435 and 408 ns of the slow decay component, respectively.

Zoning and exsolution in cumulate alkali feldspars from the eruption (12.9 Ka) of Laacher see volcano (Western Germany) as an indicator of time-scales and dynamics of carbonate-silicate unmixing

NASA Astrophysics Data System (ADS)

Sourav Rout, Smruti; Wörner, Gerhard

2017-04-01

Time-scales extracted from the detailed analysis of chemically zoned minerals provide insights into crystal ages, magma storage and compositional evolution, including mixing and unmixing events. This allows having a better understanding of pre-eruptive history of large and potentially dangerous magma chambers. We present a comprehensive study of chemical diffusion across zoning and exsolution patterns of alkali feldspars in carbonatite-bearing cognate syenites from the 6.3 km3 (D.R.E) phonolitic Laacher See Tephra (LST) eruption 12.9 ka ago. The Laacher See volcano is located in the Quaternary East Eifel volcanic field of the Paleozoic Rhenish Massif in Western Germany and has produced a compositionally variable sequence in a single eruption from a magma chamber that was zoned from mafic phonolite at the base to highly evolved, actively degassing phonolite magma at the top. Diffusion chronometry is applied to major and trace element compositions obtained on alkali feldspars from carbonate-bearing syenitic cumulates. Methods used were laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS) in combination with energy-dispersive and wavelength-dispersive electron microprobe analyses (EDS & WDS-EMPA). The grey scale values extracted from multiple accumulations of back-scattered electron images represent the K/Na ratio owing to the extremely low concentrations of Ba and Sr (<30 ppm). The numerical grey scale profiles and the quantitative compositional profiles are anatomized using three different fitting models in MATLAB®, Mathematica® and Origin® to estimate related time-scales with minimized error for a temperature range of 750 deg C to 800 deg C (on the basis of existing experimental data on phase transition and phase separation). A distinctive uphill diffusive analysis is used specifically for the phase separation in the case of exsolution features (comprising of albite- and orthoclase-rich phases) in sanidines. The error values are aggregates of propagated error through calculations and the uncertainty in temperature values. Trace element compositional data of distinct feldspar compositions that are assumed to have grown before and after silicate-carbonate unmixing are used to estimate partition coefficients between carbonate and silicate melt. The resulting values correlate well with available experimental data from the literature. We will present a genetic model based on the compositional data on feldspar zonation for the process and timing of silicate-carbonate unmixing prior to eruption of the host phonolite magma.

Syneruptive deep magma transfer and shallow magma remobilization during the 2011 eruption of Shinmoe-dake, Japan—Constraints from melt inclusions and phase equilibria experiments

NASA Astrophysics Data System (ADS)

Suzuki, Yuki; Yasuda, Atsushi; Hokanishi, Natsumi; Kaneko, Takayuki; Nakada, Setsuya; Fujii, Toshitsugu

2013-05-01

The 2011 Shinmoe-dake eruption started with a phreatomagmatic eruption (Jan 19), followed by climax sub-Plinian events and subsequent explosions (Jan 26-28), lava accumulation in the crater (end of January), and vulcanian eruptions (February-April). We have studied a suite of ejecta to investigate the magmatic system beneath the volcano and remobilization processes in the silicic magma mush. Most of the ejecta, including brown and gray colored pumice clasts (Jan 26-28), ballistically ejected dense lava (Feb 1), and juvenile particles in ash from the phreatomagmatic and vulcanian events are magma mixing products (SiO2 = 57-58 wt.%; 960-980 °C). Mixing occurred between silicic andesite (SA) and basaltic andesite (BA) magmas at a fixed ratio (40%-30% SA and 60%-70% BA). The SA magma had SiO2 = 62-63 wt.% and a temperature of 870 °C, and contains 43 vol.% phenocrysts of pyroxene, plagioclase, and Fe-Ti oxide. The BA magma had SiO2 = 55 wt.% and a temperature of 1030 °C, and contains 9 vol.% phenocrysts of olivine and plagioclase. The SA magma partly erupted without mixing as white parts of pumices and juvenile particles. The two magmatic end-members crystallized at different depths, requiring the presence of two separate magma reservoirs; shallower SA reservoir and deeper BA reservoir. An experimental study reveals that the SA magma had been stored at a pressure of 125 MPa, corresponding to a depth of 5 km. The textures and forms of phenocrysts from the BA magma indicate rapid crystallization directly related to the 2011 eruptive activity. The wide range of H2O contents of olivine melt inclusions (5.5-1.6 wt.%) indicates that rapid crystallization was induced by decompression, with olivine crystallization first (≤ 250 MPa), followed by plagioclase addition. The limited occurrence of olivine melt inclusions trapped at depths of < 5 km is consistent with the proposed magma system model, because olivine crystallization ceased after magma mixing. Our petrological model is consistent with a geophysical model that explains whole crustal deformation as being due to a single source located 7-8 km northwest of the Shinmoe-dake summit. However, even the shallowest estimated source of this deformation (7.5-6.2 km) is deeper than the SA reservoir, which thus requires a contribution of deeper BA magmas to the observed deformation. Remobilization of mush-like SA magma occurred in two stages before the early sub-Plinian event. Firstly, precursor mixing with BA magma and associated heating occurred (925-871 °C; stage-1 of ≥ 350 h), followed by final mixing with BA magma (stage-2). MgO profiles of magnetite phenocrysts define timescales of 0.7-15.2 h from this final mixing to eruption. The mixed and heated magmas, and stagnant mush that existed in the SA reservoir in the precursor stage, were finally erupted together. Magnetite phenocrysts in the Feb 18 ash reveal the occurrence of continuous erosion of the stagnant mush during the course of the 2011 eruptive activity.

Numerical study of slip system activity and crystal lattice rotation under wedge nanoindents in tungsten single crystals

NASA Astrophysics Data System (ADS)

Volz, T.; Schwaiger, R.; Wang, J.; Weygand, S. M.

2018-05-01

Tungsten is a promising material for plasma facing components in future nuclear fusion reactors. In the present work, we numerically investigate the deformation behavior of unirradiated tungsten (a body-centered cubic (bcc) single crystal) underneath nanoindents. A finite element (FE) model is presented to simulate wedge indentation. Crystal plasticity finite element (CPFE) simulations were performed for face-centered and body-centered single crystals accounting for the slip system family {110} <111> in the bcc crystal system and the {111} <110> slip family in the fcc system. The 90° wedge indenter was aligned parallel to the [1 ¯01 ]-direction and indented the crystal in the [0 1 ¯0 ]-direction up to a maximum indentation depth of 2 µm. In both, the fcc and bcc single crystals, the activity of slip systems was investigated and compared. Good agreement with the results from former investigations on fcc single crystals was observed. Furthermore, the in-plane lattice rotation in the material underneath an indent was determined and compared for the fcc and bcc single crystals.

Molecular dynamic simulations of the intergranular films between alumina and silicon nitride crystal grains

NASA Astrophysics Data System (ADS)

Zhang, Shenghong

The intergranular films (IGFs) between the ceramics grains have very important effects on the structure and mechanical properties on the whole ceramics and have been studied for many decades. In the thesis, molecular dynamic (MD) computer simulations were applied to study the IGFs between the alumina and silicon nitride ceramic grains. Preferential adsorption of specific ions from the IGFs to the contacting surfaces of the alumina crystals was observed in the study of calcium-alumino-silicate glassy (CAS) IGFs formed between the combined basal and prism orientations of alpha-Al2O3 crystals. This segregation of specific ions to the interface enables formation of localized, ordered structures between the IGF and the crystals. However, the segregation behavior of the ions is anisotropic, depending on the orientation of the alpha-Al2O 3 crystals. Self-diffusion of calcium ions between these CAS IGFs was also carried out by MD simulations. The results show that the diffusion coefficients adjacent to the interfaces are smaller and the activation energies are much higher than those in the interior of the IGF and in bulk glasses. It was also suggested that Ca transport is mainly though the interior of the IGF and implies that diffusion would be significantly inhibited by sufficiently thin IGFs. The growth of the alumina ceramic grains was simulated in the contacting with IGFs containing high concentrations of aluminum ions. Five different compositions in the IGFs were studied. Results show preferential growth along the [1120] of the (1120) surface in comparison to growth along the [0001] direction on the (0001) surface for compositions near a Ca/Al ratio of 0.5. The simulations also show the mechanism by which Ca ions in the IGF inhibit growth on the basal surface. The simulations provide an atomistic view of attachment onto crystal surfaces, affecting grain growth in alumina. The dissolution of the alumina crystal grains in the silicate melts is another important issue in the application of alumina ceramics. The simulations results showed that alumina grains dissolved into the melts homogeneously at very high temperatures. The orientation of the crystals and the compositions of the melts only take effect at some intermediate temperatures, to make the alumina grains dissolution anisotropic. The fracture phenomena of the pure silica IGFs between the basal silicon nitride crystals were studied by applying the constant tensile strain on the simulated IGF system, as well as for the bulk silica glass for the comparison. The data indicated that the fracture was happened in the interior of the IGFs and the thickness of the IGFs has important effect on the fracture stress/strain relationships.

A preliminary review of organic materials single crystal growth by the Czochralski technique

NASA Astrophysics Data System (ADS)

Penn, B. G.; Shields, A. W.; Frazier, D. O.

1988-09-01

The growth of single crystals of organic compounds by the Czochralski method is reviewed. From the literature it is found that single crystals of benzil, a nonlinear optical material with a d sub 11 value of 11.2 + or - 1.5 x d sub 11 value of alpha quartz, has fewer dislocations than generally contained in Bridgman crystals. More perfect crystals were grown by repeated Czochralski growth. This consists of etching away the defect-containing portion of a Czochralski grown crystal and using it as a seed for further growth. Other compounds used to grow single crystals are benzophenone, 12-tricosanone (laurone), and salol. The physical properties, growth apparatus, and processing conditions presented in the literature are discussed. Moreover, some of the possible advantages of growing single crystals of organic compounds in microgravity to obtain more perfect crystals than on Earth are reviewed.

A preliminary review of organic materials single crystal growth by the Czochralski technique

NASA Technical Reports Server (NTRS)

Penn, B. G.; Shields, A. W.; Frazier, D. O.

1988-01-01

The growth of single crystals of organic compounds by the Czochralski method is reviewed. From the literature it is found that single crystals of benzil, a nonlinear optical material with a d sub 11 value of 11.2 + or - 1.5 x d sub 11 value of alpha quartz, has fewer dislocations than generally contained in Bridgman crystals. More perfect crystals were grown by repeated Czochralski growth. This consists of etching away the defect-containing portion of a Czochralski grown crystal and using it as a seed for further growth. Other compounds used to grow single crystals are benzophenone, 12-tricosanone (laurone), and salol. The physical properties, growth apparatus, and processing conditions presented in the literature are discussed. Moreover, some of the possible advantages of growing single crystals of organic compounds in microgravity to obtain more perfect crystals than on Earth are reviewed.

Mechanochemical Synthesis of Carbon Nanothread Single Crystals.

PubMed

Li, Xiang; Baldini, Maria; Wang, Tao; Chen, Bo; Xu, En-Shi; Vermilyea, Brian; Crespi, Vincent H; Hoffmann, Roald; Molaison, Jamie J; Tulk, Christopher A; Guthrie, Malcolm; Sinogeikin, Stanislav; Badding, John V

2017-11-15

Synthesis of well-ordered reduced dimensional carbon solids with extended bonding remains a challenge. For example, few single-crystal organic monomers react under topochemical control to produce single-crystal extended solids. We report a mechanochemical synthesis in which slow compression at room temperature under uniaxial stress can convert polycrystalline or single-crystal benzene monomer into single-crystalline packings of carbon nanothreads, a one-dimensional sp 3 carbon nanomaterial. The long-range order over hundreds of microns of these crystals allows them to readily exfoliate into fibers. The mechanochemical reaction produces macroscopic single crystals despite large dimensional changes caused by the formation of multiple strong, covalent C-C bonds to each monomer and a lack of reactant single-crystal order. Therefore, it appears not to follow a topochemical pathway, but rather one guided by uniaxial stress, to which the nanothreads consistently align. Slow-compression room-temperature synthesis may allow diverse molecular monomers to form single-crystalline packings of polymers, threads, and higher dimensional carbon networks.

Eruptive history and geochronology of Mount Mazama and the Crater Lake region, Oregon

USGS Publications Warehouse

Bacon, Charles R.; Lanphere, Marvin A.

2006-01-01

Geologic mapping, K-Ar, and 40Ar/39Ar age determinations, supplemented by paleomagnetic measurements and geochemical data, are used to quantify the Quaternary volcanic history of the Crater Lake region in order to define processes and conditions that led to voluminous explosive eruptions. The Cascade arc volcano known as Mount Mazama collapsed during its climactic eruption of ∼50 km3 of mainly rhyodacitic magma ∼7700 yr ago to form Crater Lake caldera. The Mazama edifice was constructed on a Pleistocene silicic lava field, amidst monogenetic and shield volcanoes ranging from basalt to andesite similar to parental magmas for Mount Mazama. Between 420 ka and 35 ka, Mazama produced medium-K andesite and dacite in 2:1 proportion. The edifice was built in many episodes; some of the more voluminous occurred approximately coeval with volcanic pulses in the surrounding region, and some were possibly related to deglaciation following marine oxygen isotope stages (MIS) 12, 10, 8, 6, 5.2, and 2. Magmas as evolved as dacite erupted many times, commonly associated with or following voluminous andesite effusion. Establishment of the climactic magma chamber was under way when the first preclimactic rhyodacites vented ca. 27 ka. The silicic melt volume then grew incrementally at an average rate of 2.5 km3 k.y.−1 for nearly 20 k.y. The climactic eruption exhausted the rhyodacitic magma and brought up crystal-rich andesitic magma, mafic cumulate mush, and wall-rock granodiorite. Postcaldera volcanism produced 4 km3 of andesite during the first 200–500 yr after collapse, followed at ca. 4800 yr B.P. by 0.07 km3 of rhyodacite. The average eruption rate for all Mazama products was ∼0.4 km3 k.y.−1, but major edifice construction episodes had rates of ∼0.8 km3 k.y.−1. The long-term eruption rate for regional monogenetic and shield volcanoes was d∼0.07 km3 k.y.−1, but only ∼0.02 km3 k.y.−1 when the two major shields are excluded. Plutonic xenoliths and evidence for crystallization differentiation imply that the amount of magma intruded beneath Mount Mazama is several times that which has been erupted. The eruptive and intrusive history reflects competition between (1) crystallization driven by degassing and hydrothermal cooling and (2) thermal input from a regional magma flux focused at Mazama. Before ca. 30 ka, relatively small volumes of nonerupted derivative magma crystallized to form a composite pluton because the upper crust had not been heated sufficiently to sustain voluminous convecting crystal-poor melt. Subsequently, and perhaps not coincidentally, during MIS 2, a large volume of eruptible silicic magma accumulated in the climactic chamber, probably because of heating associated with mantle input to the roots of the system as suggested by eruption of unusually primitive magnesian basaltic andesite and tholeiite west of Mazama.

Nd3+-doped soft glass double-clad fibers with a hexagonal inner cladding

NASA Astrophysics Data System (ADS)

Wang, Longfei; He, Dongbing; Hu, Lili; Chen, Danping

2015-04-01

The stack-and-draw technique was used to fabricate Nd3+-doped silicate and phosphate glass double-clad step-index fibers with a non-circular inner cladding. For the silicate fiber, a maximum output power of 7.7 W was obtained from a 94 cm fiber. An output power of 1.25 W was also realized with a short length fiber of 8 cm, confirming the application potential of this fiber in single frequency lasers and pulsed amplifiers where an efficient rare-earth-doped fiber with short length is desirable. For the phosphate fiber, a maximum output power of 2.78 W was obtained from a single-mode fiber with a core diameter of up to 35 μm.

Microstructure and pinning properties of hexagonal-disc shaped single crystalline MgB2

NASA Astrophysics Data System (ADS)

Jung, C. U.; Kim, J. Y.; Chowdhury, P.; Kim, Kijoon H.; Lee, Sung-Ik; Koh, D. S.; Tamura, N.; Caldwell, W. A.; Patel, J. R.

2002-11-01

We synthesized hexagonal-disc-shaped MgB2 single crystals under high-pressure conditions and analyzed the microstructure and pinning properties. The lattice constants and the Laue pattern of the crystals from x-ray micro-diffraction showed the crystal symmetry of MgB2. A thorough crystallographic mapping within a single crystal showed that the edge and c axis of hexagonal-disc shape exactly matched the [101¯0] and the [0001] directions of the MgB2 phase. Thus, these well-shaped single crystals may be the best candidates for studying the direction dependences of the physical properties. The magnetization curve and the magnetic hysteresis curve for these single crystals showed the existence of a wide reversible region and weak pinning properties, which supported our single crystals being very clean.

Simulation of the planetary interior differentiation processes in the laboratory.

PubMed

Fei, Yingwei

2013-11-15

A planetary interior is under high-pressure and high-temperature conditions and it has a layered structure. There are two important processes that led to that layered structure, (1) percolation of liquid metal in a solid silicate matrix by planet differentiation, and (2) inner core crystallization by subsequent planet cooling. We conduct high-pressure and high-temperature experiments to simulate both processes in the laboratory. Formation of percolative planetary core depends on the efficiency of melt percolation, which is controlled by the dihedral (wetting) angle. The percolation simulation includes heating the sample at high pressure to a target temperature at which iron-sulfur alloy is molten while the silicate remains solid, and then determining the true dihedral angle to evaluate the style of liquid migration in a crystalline matrix by 3D visualization. The 3D volume rendering is achieved by slicing the recovered sample with a focused ion beam (FIB) and taking SEM image of each slice with a FIB/SEM crossbeam instrument. The second set of experiments is designed to understand the inner core crystallization and element distribution between the liquid outer core and solid inner core by determining the melting temperature and element partitioning at high pressure. The melting experiments are conducted in the multi-anvil apparatus up to 27 GPa and extended to higher pressure in the diamond-anvil cell with laser-heating. We have developed techniques to recover small heated samples by precision FIB milling and obtain high-resolution images of the laser-heated spot that show melting texture at high pressure. By analyzing the chemical compositions of the coexisting liquid and solid phases, we precisely determine the liquidus curve, providing necessary data to understand the inner core crystallization process.

Simulation of the Planetary Interior Differentiation Processes in the Laboratory

PubMed Central

Fei, Yingwei

2013-01-01

A planetary interior is under high-pressure and high-temperature conditions and it has a layered structure. There are two important processes that led to that layered structure, (1) percolation of liquid metal in a solid silicate matrix by planet differentiation, and (2) inner core crystallization by subsequent planet cooling. We conduct high-pressure and high-temperature experiments to simulate both processes in the laboratory. Formation of percolative planetary core depends on the efficiency of melt percolation, which is controlled by the dihedral (wetting) angle. The percolation simulation includes heating the sample at high pressure to a target temperature at which iron-sulfur alloy is molten while the silicate remains solid, and then determining the true dihedral angle to evaluate the style of liquid migration in a crystalline matrix by 3D visualization. The 3D volume rendering is achieved by slicing the recovered sample with a focused ion beam (FIB) and taking SEM image of each slice with a FIB/SEM crossbeam instrument. The second set of experiments is designed to understand the inner core crystallization and element distribution between the liquid outer core and solid inner core by determining the melting temperature and element partitioning at high pressure. The melting experiments are conducted in the multi-anvil apparatus up to 27 GPa and extended to higher pressure in the diamond-anvil cell with laser-heating. We have developed techniques to recover small heated samples by precision FIB milling and obtain high-resolution images of the laser-heated spot that show melting texture at high pressure. By analyzing the chemical compositions of the coexisting liquid and solid phases, we precisely determine the liquidus curve, providing necessary data to understand the inner core crystallization process. PMID:24326245

Dynamic crystallization of silicate melts

NASA Technical Reports Server (NTRS)

Russell, W. J.

1984-01-01

Two types of furnaces with differing temperature range capabilities were used to provide variations in melt temperatures and cooling rates in a study of the effects of heterogeneous nucleation on crystallization. Materials of chondrule composition were used to further understanding of how the disequilibrium features displayed by minerals in rocks are formed. Results show that the textures of natural chondrules were duplicated. It is concluded that the melt history is dominant over cooling rate and composition in controlling texture. The importance of nuclei, which are most readily derived from preexisting crystalline material, support an origin for natural chondrules based on remelting of crystalline material. This would be compatible with a simple, uniform chondrule forming process having only slight variations in thermal histories resulting in the wide range of textures.

Growth and microtopographic study of CuInSe{sub 2} single crystals

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

Chauhan, Sanjaysinh M.; Chaki, Sunil, E-mail: sunilchaki@yahoo.co.in; Deshpande, M. P.

2016-05-23

The CuInSe{sub 2} single crystals were grown by chemical vapour transport (CVT) technique using iodine as transporting agent. The elemental composition of the as-grown CuInSe{sub 2} single crystals was determined by energy dispersive analysis of X-ray (EDAX). The unit cell crystal structure and lattice parameters were determined by X-ray diffraction (XRD) technique. The surface microtopographic study of the as-grown CuInSe{sub 2} single crystals surfaces were done to study the defects, growth mechanism, etc. of the CVT grown crystals.

Method for the preparation of inorganic single crystal and polycrystalline electronic materials

NASA Technical Reports Server (NTRS)

Groves, W. O. (Inventor)

1969-01-01

Large area, semiconductor crystals selected from group 3-5 compounds and alloys are provided for semiconductor device fabrication by the use of a selective etching operation which completely removes the substrate on which the desired crystal was deposited. The substrate, selected from the same group as the single crystal, has a higher solution rate than the epitaxial single crystal which is essentially unaffected by the etching solution. The preparation of gallium phosphide single crystals using a gallium arsenide substrate and a concentrated nitric acid etching solution is described.

An AMS study of different silicic units from the southern Paraná-Etendeka Magmatic Province in Brazil: Implications for the identification of flow directions and local sources

NASA Astrophysics Data System (ADS)

Guimarães, L. F.; Raposo, M. I. B.; Janasi, V. A.; Cañón-Tapia, E.; Polo, L. A.

2018-04-01

In the Southern portion of the Paraná-Etendeka Magmatic Province in Brazil, extensive silicic (dacite-rhyolite) deposits occur at the top of a sequence of low-Ti pahoehoe to rubbly basalts. The internal architecture of the silicic deposits and their eruptive style, as well as the location of their sources are still unsatisfactorily known. In an attempt to provide independent evidence for flow directions in deposits previously characterized as effusive, and test the hypothesis of local sources, we carried out anisotropy of magnetic susceptibility (AMS) studies on the two main silicic units (Caxias do Sul dacites and Santa Maria Rhyolites) with the best exposures in an area previously mapped in detail. Magnetic anisotropies were determined on oriented cylindrical specimens from a total of 28 sites. Rock magnetism properties indicate that "pseudo-single-domain" magnetite carries the fabrics and the remanence. Magnetic fabrics were determined by applying anisotropy of low-field magnetic susceptibility (AMS) and anisotropy of anhysteretic remanent magnetization (AARM). Both AMS and AARM tensors are coaxial, indicating that the AMS fabric is not affected by the effect of magnetite single-domain grains. Magnetic data from several dacitic coulées (Caxias do Sul unit) indicate flows from SE to NW. The location and spatial distribution of these lavas support the hypothesis of local sources, aligned along a NE-SW trend. These data are in agreement with the alignments of structures (dome-shaped hills) observed in field work and DEM images. On the other hand, magnetic data obtained in Santa Maria rhyolites indicate that flow directions in two different areas are distinct (towards NW/NE and W), suggesting that they derived from different emission centers. So, regarding the silicic volcanism in the studied region, our data do not support the model which classifies the entire silicic volcanism of the province as extensive rheomorphic pyroclastic deposits released from a central conduit. In contrast, we propose the occurrence of local volcanic events, implying in the existence of different sources, possibly characterized by local emission centers.

Can Suspended Iron-Alloy Droplets Explain the Origin, Composition and Properties of Large Low Shear Velocity Provinces?

NASA Astrophysics Data System (ADS)

Zhang, Z.; Dorfman, S. M.; Labidi, J.; Zhang, S.; Manga, M.; Stixrude, L. P.; McDonough, W. F.; Williams, Q. C.

2014-12-01

The enigmatic large low shear velocity provinces (LLSVPs) identified by seismic tomography at the base of the Earth's mantle have been proposed to be reservoirs of primordial mantle composition tapped by hot spot volcanism. The LLSVPs are characterized by anomalously low shear wave speed, VS, slightly elevated bulk sound speed, VB, and high density, ρ, in piles as thick as 1000 km above the core-mantle boundary. This combination of properties could be explained by a few percent dense melt, but the solidus of the lower mantle silicate and oxide assemblage may be too high to produce melt over the large extent of these regions. Iron-rich sulfur-bearing alloy may be molten at the conditions of the LLSVPs and ~1-2% of this component could satisfy both constraints on VS and ρ. An Fe alloy phase in the LLSVPs also has the potential to explain geochemical anomalies associated with hot spot volcanism, and its existence can be constrained by geochemical mass balance. Primordial noble gases such as 3He would be preferentially dissolved in Fe-rich melt rather than crystalline silicates. The reconstructed abundances of the moderately siderophile/chalcophile elements S, Cu and Pb in iron-alloy-bearing LLSVPs do not exceed predicted losses from volatilization, though this depends on the S-content of the alloy. The alloy phase would also be expected to incorporate W, and W isotope anomalies associated with hot spots are thus expected to have important implications for the timing of LLSVP formation. We have developed a model, via CIDER-2014, for the origin and properties of LLSVPs incorporating geochemistry, mineral physics, and fluid dynamic constraints on the generation, capture, and thermoelastic properties of Fe-rich melt droplets. The solidification of a basal magma ocean would produce both solid silicates and metallic melt. The bulk of the alloy generated by this process would sink to merge with the core. However, once the density of the remnant liquid exceeds that of the solid, newly-formed crystals floating at the crystallization front may trap droplets of Fe-rich melt as inclusions or at grain boundaries. We find that a mixture of mantle silicates and ~1-2% molten Fe-rich droplets matches constraints on density and seismic velocities and could host the hidden 3He and other elements of the primordial mantle reservoir.

Partitioning of F and Cl Between Apatite and a Synthetic Shergottite Liquid (QUE 94201) at 4 Gpa from 1300 TO 1500 C

NASA Technical Reports Server (NTRS)

McCubbin, F. M.; Barnes, J. J.; Vander Kaaden, K. E.; Boyce, J. W.

2017-01-01

Apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (Xsite), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to accurately determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multicomponent silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al., recently reported that the exchange coefficients vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing, and McCubbin et al. reported substantial deviations in the Cl-F exchange Kd along the F-Cl apatite join that could be explained by the preferential incorporation of F into apatite. In the present study, we assess the effect of apatite crystal chemistry on F-Cl exchange equilibria between apatite and melt at 4 GPa over the temperature range of 1300-1500 C. The goal of these experiments is to assess the variation in the Ap-melt Cl-F exchange Kd over a broad range of F:Cl ratios in apatite. The results of these experiments could be used to understand at what composition apatite shifts from a hexagonal unit cell with space group P63/m to a unit cell with monoclinic symmetry within space group P21/b. We anticipate that this transition occurs at >70% chlorapatite based on solution calorimetry data.

Cluster self-organization of inorganic crystal-forming systems: Templated nanocluster precursors and self-assembly of framework MT structures of A/B,Zr silicates (A = Na, K; B = Ca, Sr)

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

Ilyushin, G. D., E-mail: ilyushin@ns.crys.ras.ru

The basic concepts that are used to describe crystallization as a phenomenon of the hierarchical (cluster) self-organization of a chemical system are considered. The templation of theoretically possible nan-ocluster precursors composed of M octahedra and T tetrahedra by atoms of (A) alkaline and (B) alkaline earth metals is considered for the first time. A relationship between the A/B,M,T composition of templated nanocluster precursors with the composition of A/B,M silicates is established. The model that is developed is used to search for nanocluster precursors in framework MT structures of A/B,Zr silicates. Computer methods (TOPOS 4.0 program package) were used to performmore » complete 3D reconstruction of the self-assembly of all (four) structural types of A/B,Zr silicates (A = Na, K; B = Ca, Sr) with frameworks of the MT{sub 2}O{sub 7} type: nan-ocluster precursor S{sub 3}{sup 0}-primary chain S{sub 3}{sup 1}-microlayer S{sub 3}{sup 2}-microframework S{sub 3}{sup 3}. The invariant type of mono-cyclic nanocluster precursor M{sub 2}T{sub 4} (with the point symmetries 1-bar and 2), stabilized by one or two template cations (A and B), is determined. Bifurcations of the paths of evolution at the S{sub 3}{sup 1} level (structural branching point) are established for the self-assembly of the following frameworks: MT-1 in CaZrSi{sub 2}O{sub 7} (gittinsite, C2), MT-2 in SrZrSi{sub 2}O{sub 7} (P2{sub 1}/c); MT-3 in Na{sub 2}ZrSi{sub 2}O{sub 7} (parakeldyshite,), K{sub 2}ZrSi{sub 2}O{sub 7} (khibinskite, P2{sub 1}/b), and K{sub 2}ZrGe{sub 2}O{sub 7} (C2/c); and MT-4 in Na{sub 2}ZrSi{sub 2}O{sub 7} (H{sub 2}O)(C2/c), Na{sub 3}ScSi{sub 2}O{sub 7} (Pbnm), and K{sub 3}ScSi{sub 2}O{sub 7} (P6{sub 3}/mmc).« less

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.

Apatite formation on bioactive calcium-silicate cements for dentistry affects surface topography and human marrow stromal cells proliferation.

PubMed

Gandolfi, Maria Giovanna; Ciapetti, Gabriela; Taddei, Paola; Perut, Francesca; Tinti, Anna; Cardoso, Marcio Vivan; Van Meerbeek, Bart; Prati, Carlo

2010-10-01

The effect of ageing in phosphate-containing solution of bioactive calcium-silicate cements on the chemistry, morphology and topography of the surface, as well as on in vitro human marrow stromal cells viability and proliferation was investigated. A calcium-silicate cement (wTC) mainly based on dicalcium-silicate and tricalcium-silicate was prepared. Alpha-TCP was added to wTC to obtain wTC-TCP. Bismuth oxide was inserted in wTC to prepare a radiopaque cement (wTC-Bi). A commercial calcium-silicate cement (ProRoot MTA) was tested as control. Cement disks were aged in DPBS for 5 h ('fresh samples'), 14 and 28 days, and analyzed by ESEM/EDX, SEM/EDX, ATR-FTIR, micro-Raman techniques and scanning white-light interferometry. Proliferation, LDH release, ALP activity and collagen production of human marrow stromal cells (MSC) seeded for 1-28 days on the cements were evaluated. Fresh samples exposed a surface mainly composed of calcium-silicate hydrates CSH (from the hydration of belite and alite), calcium hydroxide, calcium carbonate, and ettringite. Apatite nano-spherulites rapidly precipitated on cement surfaces within 5 h. On wTC-TCP the Ca-P deposits appeared thicker than on the other cements. Aged cements showed an irregular porous calcium-phosphate (Ca-P) coating, formed by aggregated apatite spherulites with interspersed calcite crystals. All the experimental cements exerted no acute toxicity in the cell assay system and allowed cell growth. Using biochemical results, the scores were: fresh cements>aged cements for cell proliferation and ALP activity (except for wTC-Bi), whereas fresh cements

Characterizing Amorphous Silicates in Extraterrestrial Materials

NASA Astrophysics Data System (ADS)

Fu, X.; Wang, A.; Krawczynski, M. J.

2015-12-01

Amorphous silicates are common in extraterrestrial materials. They are seen in the matrix of carbonaceous chondrites as well as in planetary materials. Tagish Lake is one of the most primitive carbonaceous meteorites in which TEM and XRD analyses found evidence for poorly crystalline phyllosilicate-like species; Raman spectra revealed amorphous silicates with variable degree of polymerization and low crystallinity. On Mars, CheMin discovered amorphous phases in all analyzed samples, and poorly crystalline smectite in mudstone samples. These discoveries pose questions on the crystallinity of phyllosilicates found by remote sensing on Mars, which is directly relevant to aqueous alteration during geologic history of Mars. Our goal is to use spectroscopy to better characterize amorphous silicates. We use three approaches: (1) using silicate glasses synthesized with controlled chemistry to study the effects of silicate polymerization and (2) using phyllosilicates synthesized with controlled hydrothermal treatment to study the effect of crystallinity on vibrational spectroscopy, finally (3) to use the developed correlations in above two steps to study amorphous phases in meteorites, and those found in future missions to Mars. In the 1st step, silicate glasses were synthesized from pure oxides in a range of NBO/T ratios (from 0 to 4). Depending on the targeted NBO/T and composition of mixed oxides, temperatures for each experiment fell in a range from 1260 to 1520 °C, run for ~ 4 hrs. The melt was quenched in liquid N2 or water. Homogeneity of glass was checked under optical microscopy. Raman spectra were taken over 100 spots on small chips free of bubbles and crystals. We have observed that accompanying an increase of NBO/T, there is a strengthening and a position shift of the Raman peak near 1000 cm-1 (Si-Onon-bridging stretching mode), and the weakening of broad Raman peaks near 500 cm-1 (ring breathing mode) and 700cm-1 (Si-Obridging-Si mode). We are building the correlation between peak area ratio, A(500+700)/A1000, and NBO/T. In the 2nd step, we are synthesizing Mg-saponite using a sol-gel method. The crystallinity of sol-gel starting materials will be increased by a controlled hydrothermal treatment. The products will be characterized using XRD/TEM/Raman/NIR. The results will be reported at the conference.

Porosity Evolution in a Creeping Single Crystal (Preprint)

DTIC Science & Technology

2012-08-01

1] indicated that the growth of initially present processing induced voids in a nickel based single crystal superalloy played a significant role in...processing induced voids in a nickel based single crystal superalloy played a significant role in limiting creep life. Also, creep tests on single...experimental observations of creep deformation and failure of a nickel based single crystal superalloy, [1, 2]. Metallographic observations have shown that Ni

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

USGS Publications Warehouse

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

2014-01-01

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

On the longevity of silicic magma based on multi-isotope investigation of zircons and modeling their survivals destinies

NASA Astrophysics Data System (ADS)

Bindeman, I. N.; Wotzlaw, J. F.; Melnik, O. E.

2015-12-01

Large volumes of crystal poor, near-liquidus rhyolites are erupted worldwide as tuffs and lavas in rift and hot spots more common previously on early earth, creating temporally very high magma production rates. In this contribution we combine results of IDTIMS dating of zircons with numerical modeling of zircon crystallization. New investigation of zircons in major Yellowstone tuffs: Huckleberry Ridge (Members A,B,C), Mesa Falls, and Lava Creek (A,B) tuffs was done by a combination of in situ measurements of oxygen isotopes followed by ID-TIMS U-Pb dating, Hf isotopes and trace elemental investigation of single crystals. We discover that nearly all zircons are of eruption age, but display significant isotope (O,Hf) diversity and often show decoupled O and Hf isotope systematics. This record rapid (~103yrs) double or triple remelting and sequestration from diverse Archean crust and hydrothermally altered shallow-crustal rocks from previous eruptive cycles, followed by effective mixing of co-existing magma reservoirs with diverse zircons prior to eruptions. Similar results characterize other studied Snake River Plain rhyolites in pre-Yellowstone Heise complex. These results collectively suggest that zircons crystallize after reheating above saturation rejuvenation in isotopically-diverse areas of the crust in the magma plumbing system. Modeling of zircon and quartz dissolution and crystallization trajectories outline conditions of survival (inheritance) vs complete dissolution on conductive timescales, and when combined with a phase diagram, magma T-t paths can be computed. Zircon rejuvenation requires hot, >770-800°C peak temperatures lasting 10-102yrs. We speculate that near liquidus hot and dry Yellowstone rhyolites are kept alive in a multi-batch state by a series of interconnected pods and sills that can rapidly get thermomechanically assembled into large, shallow and eruptable supervolcanoic magma bodies. We suggest that overpressure and roof dynamics and rheology plays a more important role than magma buyoncy. The runaway batch assembly process creates temporally very high magma production rates, orders of magnitude higher than for arc volcanoes. Such views have implication for the state of the magma chamber under Yellowstone and similar supervolcanoes elsewhere.

Disequilibrium growth of olivine in mafic magmas revealed by phosphorus zoning patterns of olivine from mafic-ultramafic intrusions

NASA Astrophysics Data System (ADS)

Xing, Chang-Ming; Wang, Christina Yan; Tan, Wei

2017-12-01

Olivine from mafic-ultramafic intrusions rarely displays growth zoning in major and some minor elements, such as Fe, Mg and Ni, due to fast diffusion of these elements at high temperatures. These elements in olivine are thus not useful in deciphering magma chamber processes, such as magma convection, multiple injection and mixing. High-resolution X-ray elemental intensity mapping reveals distinct P zoning patterns of olivine from two mafic-ultramafic intrusions in SW China. Polyhedral olivine grains from lherzolite and dunite of the Abulangdang intrusion show P-rich dendrites similar to those observed in volcanic rocks. Rounded olivine grains from net-textured Fe-Ti oxide ores of the Baima layered intrusion have irregular P-rich patches/bands crosscut and interlocked by P-poor olivine domains. P-rich patches/bands contain 250 to 612 ppm P, much higher than P-poor olivine domains with 123 to 230 ppm P. In electron backscattered diffraction (EBSD) maps, P-rich patches/bands within a single olivine grain have the same crystallographic orientation, indicating that they were remnants of the same crystal. Thus, both P-rich patches/bands and P-poor olivine domains in the same grain show a disequilibrium texture and clearly record two-stage growth. The P-rich patches/bands are likely the remnants of a polyhedral olivine crystal that formed in the first stage, whereas the P-poor olivine domains containing rounded Ti-rich magnetite and Fe-rich melt inclusions may have formed from an Fe-rich ambient melt in the second stage. The complex P zoning of olivine can be attributed to the dissolution of early polyhedral olivine and re-precipitation from the Fe-rich ambient melt. The early polyhedral olivine was in chemical disequilibrium with the ambient melt that may have been developed by silicate liquid immiscibility in a crystal mush. Our study implies that olivine crystals in igneous cumulates with an equilibrium appearance may have experienced disequilibrium growth processes during slow cooling. Therefore, the crystallization sequence of mafic magmas based on textural relationships should be treated with caution.

Chemical speciation of individual airborne particles by the combined use of quantitative energy-dispersive electron probe X-ray microanalysis and attenuated total reflection Fourier transform-infrared imaging techniques.

PubMed

Song, Young-Chul; Ryu, JiYeon; Malek, Md Abdul; Jung, Hae-Jin; Ro, Chul-Un

2010-10-01

In our previous work, it was demonstrated that the combined use of attenuated total reflectance (ATR) FT-IR imaging and quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA), named low-Z particle EPMA, had the potential for characterization of individual aerosol particles. Additionally, the speciation of individual mineral particles was performed on a single particle level by the combined use of the two techniques, demonstrating that simultaneous use of the two single particle analytical techniques is powerful for the detailed characterization of externally heterogeneous mineral particle samples and has great potential for characterization of atmospheric mineral dust aerosols. These single particle analytical techniques provide complementary information on the physicochemical characteristics of the same individual particles, such as low-Z particle EPMA on morphology and elemental concentrations and the ATR-FT-IR imaging on molecular species, crystal structures, functional groups, and physical states. In this work, this analytical methodology was applied to characterize an atmospheric aerosol sample collected in Incheon, Korea. Overall, 118 individual particles were observed to be primarily NaNO(3)-containing, Ca- and/or Mg-containing, silicate, and carbonaceous particles, although internal mixing states of the individual particles proved complicated. This work demonstrates that more detailed physiochemical properties of individual airborne particles can be obtained using this approach than when either the low-Z particle EPMA or ATR-FT-IR imaging technique is used alone.

Growth and surface topography of WSe{sub 2} single crystal

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

Dixit, Vijay, E-mail: vijdix1@gmail.com; Vyas, Chirag; Pataniya, Pratik

2016-05-06

Tungsten Di-Selenide belongs to the family of TMDCs showing their potential applications in the fields of Optoelectronics and PEC solar cells. Here in the present investigation single crystals of WSe{sub 2} were grown by Direct Vapour Transport Technique in a dual zone furnace having temperature difference of 50 K between the two zones. These single crystals were characterized by EDAX which confirms the stiochiometry of the grown crystals. Surface topography of the crystal was studied by optical micrograph showing the left handed spirals on the surface of WSe{sub 2} crystals. Single crystalline nature of the crystals was confirmed by SAED.

Samples for estimating primary volatiles in Martian magmas and ancient atmospheric pressures on Mars

NASA Technical Reports Server (NTRS)

Anderson, A. T., Jr.

1988-01-01

Inclusions of glass are likely to be present in phenocrysts in volcanic rocks from Mars, because these occur in volcanic rocks from both Earth and Moon. The usefulness of the inclusions depends upon their size and composition. The compositions of tiny inclusions may be modified by diffusion during growth of the enclosing crystal, the modifications increasing with melt viscosity (silica). Slow cooling results in crystallization and possible redistribution of volatiles, the effects increasing with decreasing silica. Primary volatile concentrations are best sought in inclusions larger than about 50 micrometer diameter in olivine or chromite crystals from quickly cooled basaltic scoria. Such crystals may be present in sands, but it would be preferable to extract them from individual rocks which could be dated and compositionally characterized. This would allow eventual understanding of the role of time and place in outgassing and volcanism on Mars. Analyses of volatiles in inclusions of more siliceous glass in non-basaltic rocks will reveal whether deep outgassing occurs and whether surface volatiles are recycled. Most volcanic crystals contain inclusions, but large inclusions can be uncommon. In the case of terrestrial basalts sample masses of several hundred grams are generally sufficient.

The evolution of magma during continental rifting: New constraints from the isotopic and trace element signatures of silicic magmas from Ethiopian volcanoes

NASA Astrophysics Data System (ADS)

Hutchison, William; Mather, Tamsin A.; Pyle, David M.; Boyce, Adrian J.; Gleeson, Matthew L. M.; Yirgu, Gezahegn; Blundy, Jon D.; Ferguson, David J.; Vye-Brown, Charlotte; Millar, Ian L.; Sims, Kenneth W. W.; Finch, Adrian A.

2018-05-01

Magma plays a vital role in the break-up of continental lithosphere. However, significant uncertainty remains about how magma-crust interactions and melt evolution vary during the development of a rift system. Ethiopia captures the transition from continental rifting to incipient sea-floor spreading and has witnessed the eruption of large volumes of silicic volcanic rocks across the region over ∼45 Ma. The petrogenesis of these silicic rocks sheds light on the role of magmatism in rift development, by providing information on crustal interactions, melt fluxes and magmatic differentiation. We report new trace element and Sr-Nd-O isotopic data for volcanic rocks, glasses and minerals along and across active segments of the Main Ethiopian (MER) and Afar Rifts. Most δ18 O data for mineral and glass separates from these active rift zones fall within the bounds of modelled fractional crystallization trajectories from basaltic parent magmas (i.e., 5.5-6.5‰) with scant evidence for assimilation of Pan-African Precambrian crustal material (δ18 O of 7-18‰). Radiogenic isotopes (εNd = 0.92- 6.52; 87Sr/86Sr = 0.7037-0.7072) and incompatible trace element ratios (Rb/Nb <1.5) are consistent with δ18 O data and emphasize limited interaction with Pan-African crust. However, there are important regional variations in melt evolution revealed by incompatible elements (e.g., Th and Zr) and peralkalinity (molar Na2 O +K2 O /Al2O3). The most chemically-evolved peralkaline compositions are associated with the MER volcanoes (Aluto, Gedemsa and Kone) and an off-axis volcano of the Afar Rift (Badi). On-axis silicic volcanoes of the Afar Rift (e.g., Dabbahu) generate less-evolved melts. While at Erta Ale, the most mature rift setting, peralkaline magmas are rare. We find that melt evolution is enhanced in less mature continental rifts (where parental magmas are of transitional rather than tholeiitic composition) and regions of low magma flux (due to reduced mantle melt productivity or where crustal structure inhibits magma ascent). This has important implications for understanding the geotectonic settings that promote extreme melt evolution and, potentially, genesis of economically-valuable mineral deposits in ancient rift-settings. The limited isotopic evidence for assimilation of Pan-African crustal material in Ethiopia suggests that the pre-rift crust beneath the magmatic segments has been substantially modified by rift-related magmatism over the past ∼45 Ma; consistent with geophysical observations. We argue that considerable volumes of crystal cumulate are stored beneath silicic volcanic systems (>100 km3), and estimate that crystal cumulates fill at least 16-30% of the volume generated by crustal extension under the axial volcanoes of the MER and Manda Hararo Rift Segment (MHRS) of Afar. At Erta Ale only ∼1% of the volume generated due to rift extension is filled by cumulates, supporting previous seismic evidence for a greater role of plate stretching in mature rifts at the onset of sea-floor spreading. We infer that ∼45 Ma of magmatism has left little fusible Pan-African material to be assimilated beneath the magmatic segments and the active segments are predominantly composed of magmatic cumulates with δ18 O indistinguishable from mantle-derived melts. We predict that the δ18 O of silicic magmas should converge to mantle values as the rift continues to evolve. Although current data are limited, a comparison with ∼30 Ma ignimbrites (with δ18 O up to 8.9‰) supports this inference, evidencing greater crustal assimilation during initial stages of rifting and at times of heightened magmatic flux.

Ultrathin solution-processed single crystals of thiophene-phenylene co-oligomers for organic field-effect devices

NASA Astrophysics Data System (ADS)

Glushkova, Anastasia V.; Poimanova, Elena Yu.; Bruevich, Vladimir V.; Luponosov, Yuriy N.; Ponomarenko, Sergei A.; Paraschuk, Dmitry Yu.

2017-08-01

Thiophene-phenylene co-oligomers (TPCO) single crystals are promising materials for organic light-emitting devices, e.g., light-emitting transistors (OLETs), due to their ability to combine high luminescence and efficient charge transport. However, optical confinement in platy single crystals strongly decreases light emission from their top surface degrading the device performance. To avoid optical waveguiding, single crystals thinner than 100 nm would be beneficial. Herein, we report on solution-processed ultrathin single crystals of TPCO and study their charge transport properties. As materials we used 1,4-bis(5'-hexyl-2,2'-bithiophene-5-yl)benzene (DH-TTPTT) and 1,4-bis(5'-decyl-2,2'-bithiophene-5-yl)benzene (DD-TTPTT). The ultrathin single crystals were studied by optical polarization, atomic-force, and transmission electron microscopies, and as active layers in organic field effect transistors (OFET). The OFET hole mobility was increased tenfold for the oligomer with longer alkyl substituents (DD-TTPTT) reaching 0.2 cm2/Vs. Our studies of crystal growth indicate that if the substrate is wetted, it has no significant effect on the crystal growth. We conclude that solution-processed ultrathin TPCO single crystals are a promising platform for organic optoelectronic field-effect devices.

Nanoparticles Incorporated inside Single-Crystals: Enhanced Fluorescent Properties

DOE PAGES

Liu, Yujing; Zang, Huidong; Wang, Ling; ...

2016-09-25

Incorporation of guest materials inside single-crystalline hosts leads to single-crystal composites that have become more and more frequently seen in both biogenic and synthetic crystals. The unique composite structure together with long-range ordering promises special properties that are, however, less often demonstrated. In this study, we examine the fluorescent properties of quantum dots (QDs) and polymer dots (Pdots) encapsulated inside the hosts of calcite single-crystals. Two CdTe QDs and two Pdots are incorporated into growing calcite crystals, as the QDs and Pdots are dispersed in the crystallization media of agarose gels. As a result, enhanced fluorescent properties are obtained frommore » the QDs and Pdots inside calcite single-crystals with greatly improved photostability and significantly prolonged fluorescence lifetime, compared to those in solutions and gels. Particularly, the fluorescence lifetime increases by 0.5-1.6 times after the QDs or Pdots are incorporated. The enhanced fluorescent properties indicate the advantages of encapsulation by single-crystal hosts that provide dense shells to isolate the fluorescent nanoparticles from atmosphere. As such, this work has implications for advancing the research of single-crystal composites toward their functional design.« less

Aqueous alteration of the Nakhla meteorite

NASA Technical Reports Server (NTRS)

Gooding, James L.; Zolensky, Michael E.; Wentworth, Susan J.

1991-01-01

Interior samples of three different Nakhla specimens contain an iron-rich silicate 'rust' (which includes a tentatively identified smectite), Ca-carbonate (probably calcite), Ca-sulfate (possibly gypsum or bassanite), Mg-sulfate (possibly epsomite or kieserite), and NaCl (halite); the total abundance of these phases is estimated as less than 0.01 weight percent of the bulk meteorite. Rust veins are truncated and decrepitated by fusion crust and are preserved as faulted segments in partially healed olivine crystals, indicating that the rust is preterrestrial in origin. Because Ca-carbonate and Ca-sulfate are intergrown with the rust, they are also indicated to be of preterrestrial origin. Similar textural evidence regarding origins of the NaCl and Mg-sulfate is lacking. Impure and poorly crystallized sulfates and halides on the fusion crust of the meteorite suggest leaching of interior (preterrestrial) salts from the interior after Makhla arrived on earth, but coincidental addition of these same salts by terrestrial contamination cannot be exluded. At least the clay-like silicate 'rust', Ca-carbonate, and Ca-sulfate were formed by precipitation from water-based solutions on the Nakhla parent planet, although temperature and pressure conditions of aqueous precipitation are unconstrained by currently available data. It is possible that aqueous alteration on the parent body was responsible for the previously observed disturbance of the Rb-Sr geochronometer in Nakhla at or near 1.3 Ga.

Behavior of Colorado Plateau uranium minerals during oxidation

USGS Publications Warehouse

Garrels, Robert Minard; Christ, C.L.

1956-01-01

Uranium occurs as U(VI) and U(IV) in minerals of the Colorado Plateau ores. The number of species containing U(VI) is large, but only two U(IV) minerals are known from the Plateau: uraninite, and oxide, and coffinite, a hydroxy-silicate. These oxidize to yield U(VI) before reacting significantly with other mineral constituents. Crystal-structure analysis has shown that U(VI) invariable occurs as uranyl ion, UO2+2. Uranyl ion may form complex carbonate or sulfate ions with resulting soluble compounds, but only in the absence of quinquevalent vanadium, arsenic, or phosphorous. In the presence of these elements in the +5 valence state, the uranyl ion is fixed in insoluble layer compounds formed by union of uranyl ion with orthovanadate, orthophosphate, or orthoarsenate. Under favorable conditions UO2+2 may react to form the relatively insoluble rutherfordine, UO2CO3, or hydrated uranyl hydroxides. These are rarely found on the Colorado Plateau as opposed to their excellent development in other uraniferous areas, a condition which is apparently related to the semiarid climate and low water table of the Plateau. Uranium may also be fixed as uranyl silicate, but little is known about minerals of this kind. In the present study emphasis has been placed on a detailing of the chemical and crystal structural changes which occur in the oxidation paragenetic sequence.

Optical characteristics of sol-gel derived M3SiO5:Eu3+ (M = Sr, Ca and Mg) nanophosphors for display device technology

NASA Astrophysics Data System (ADS)

Singh, Devender; Sheoran, Suman; Bhagwan, Shri; Kadyan, Sonika

2016-12-01

A series of trivalent europium-doped M3SiO5 (M = Sr, Ca and Mg) phosphors were synthesized using sol-gel process at 950°C. Samples were further reheated at high temperature to study the effect of reheating on crystal structure and optical characteristics. X-ray diffraction measurement of these materials was carried out to know the crystal structure. Diffraction pattern showed monoclinic structure having space group Cm for Ca3SiO5 materials. However, tetragonal phase with space group P4/ncc was observed for Sr3SiO5 materials. Mg3SiO5 material show mixed diffraction peaks at 950 and 1,150°C. Transmission electron microscopic analysis was used to estimate the particle size of silicates. Photoluminescence emission spectra were recorded to check the luminescence properties of prepared materials. These phosphors exhibited a strong orange-red light under excitation at 395 nm. The prepared phosphors exhibited most intense peak in 610-620 nm region due to the 5D0→7F2 transition of europium (III) ion available in lattice. To overcome the deficiency of red silicates, M3SiO5 materials were explored and they might be integrated with ultraviolet LEDs to generate light which may be suitable for display applications.

Syntectic Reactions involving Limestones and Limestone-Derived Carbonatitic Melts in the Generation of some Peralkalic Magmas: Reflections on Reginald Daly's Insights 100 Years Later

NASA Astrophysics Data System (ADS)

Lentz, D.

2017-12-01

The theoretical analysis of how sedimentary limestones and marbles could melt as a result of infiltrative contact metasomatism associated with silicate magmas, enables reconsideration of the limestone syntectic (assimilation) hypothesis for the origin of some peralkalic rocks. Reginald Daly's syntectic model published in detail in early 1918 fell out of favor because experimental evidence from the early 1960's suggested; 1) that limestone assimilation would increase P(CO2) and cause solidification of the silicate intrusion, 2) that there is a thermal barrier between silica-saturated and undersaturated magmas that would inhibit extensive desilication of the magma, and 3) the endothermic decarbonation reactions would require heat via magmatic crystallization of near-solidus magmas. However, these concerns were not as critical for high-T mafic melts relative to more low-T silicic melts, although most subsequent researchers dismissed syntexis as isotopic arguments also seemed robust. However, skarn-related limestone melts can interact much more easily with silicate magma, resulting in calc-silicate-forming (endoskarn-like) limestone syntectic (desilication - calcification-magnesification processes) decarbonation reactions with compositional evolution into the silica-undersaturated field. If mafic in composition originally when syntectically modified, then the CO2-bearing derivative peralkalic melt may subsequently react with the dominant volume magma or fractionate separately into a more evolved composition. As well, an increase in P(CO2) within the modified silicate fraction coupled with compositional evolution to more silica-undersaturated compositions enhances the stability of the immiscible, extremely low viscosity carbonate melt fraction. In addition, dynamic interaction of these co-existing immiscible melts (analogous to the current hypothesis) would partition elements, as well as isotopic signatures, such that they would be virtually unrecognizable as having a crustal level syntectic origin, based on mass-balance principles and Rayleigh decarbonation isotopic equilibria, as they do in many infiltrative skarn systems. Essentially, this partly vindicates the basic premise of Daly's limestone syntectic hypothesis for the origin of some peralkalic igneous rocks.

Thermodynamic Model of the Na-Al-Si-O-F Melts

NASA Astrophysics Data System (ADS)

Dolejs, D.; Baker, D. R.

2004-05-01

Fluorine is a common volatile element in magmatic-hydrothermal systems, but its solution mechanisms in highly polymerized silicate melts are poorly known. We have developed a thermodynamic model for fluorosilicate liquids which links experimentally determined phase equilibria and spectroscopic information on melt structure. The model is applicable to crystallization of fluoride minerals or fluoride-silicate immiscibility in natural felsic melts. Configurational properties of the liquid are defined by mixing of alkali fluoride, polyhedral aluminofluoride and silicofluoride species and non-bridging terminations of the silicate network. Abundances of individual structural species are described by a homogeneous equilibrium, representing melt depolymerization: F- (free) + O0 (bridging) = F0 (terminal) + O- (non-bridging), which is a replacement of one oxygen bridge, Si-O-Si, by two terminations, Si-F | Na-O-Si. In cryolite-bearing systems, the self-dissociation of octahedral aluminofluoride complexes: Na3[AlF6] = Na[AlF4] + 2 NaF, and the short-range order between (O,F)-corners and (Si,NaAl)-centers of tetrahedra: Si-O-Si + 2 [NaAl]-F = [NaAl]-O-[NaAl] + 2 Si-F, represent two additional interaction mechanisms. Portrayal of these equilibria in ternary Thompson reaction space allows to decrease the number of interaction mechanisms by linearly combining melt depolymerization with tetrahedral short-range order. In this formulation, the interaction parameters are incorporated directly in configurational properties, thus the complete melt speciation can be calculated, and the activities of any macroscopic species are readily derived. The model has been applied to subsystems of the Na2O-NaAlO2-SiO2-F2O-1 compositional space. Activity-composition relationships in the villiaumite-sodium silicate binaries require clustering of silicate tetrahedra in fluoride solvent. Phase-equilibria in cryolite-nepheline and cryolite-albite systems illustrate an overall increase of Na3AlF6 self-association in both joins. On the other hand, melt depolymerization by fluorine controls depression of silicate liquidi. The present model is useful for modeling the differentiation of peralkaline fluorine-bearing magmas and provides a starting point for predicting halide, carbonate, sulfide or sulfate saturation in natural melts.

Solar cell structure incorporating a novel single crystal silicon material

DOEpatents

Pankove, Jacques I.; Wu, Chung P.

1983-01-01

A novel hydrogen rich single crystal silicon material having a band gap energy greater than 1.1 eV can be fabricated by forming an amorphous region of graded crystallinity in a body of single crystalline silicon and thereafter contacting the region with atomic hydrogen followed by pulsed laser annealing at a sufficient power and for a sufficient duration to recrystallize the region into single crystal silicon without out-gassing the hydrogen. The new material can be used to fabricate semiconductor devices such as single crystal silicon solar cells with surface window regions having a greater band gap energy than that of single crystal silicon without hydrogen.

Crystal growth, structural, thermal and mechanical behavior of l-arginine 4-nitrophenolate 4-nitrophenol dihydrate (LAPP) single crystals.

PubMed

Mahadevan, M; Ramachandran, K; Anandan, P; Arivanandhan, M; Bhagavannarayana, G; Hayakawa, Y

2014-12-10

Single crystals of l-arginine 4-nitrophenolate 4-nitrophenol dihydrate (LAPP) have been grown successfully from the solution of l-arginine and 4-nitrophenol. Slow evaporation of solvent technique was adopted to grow the bulk single crystals. Single crystal X-ray diffraction analysis confirms the grown crystal has monoclinic crystal system with space group of P21. Powder X-ray diffraction analysis shows the good crystalline nature. The crystalline perfection of the grown single crystals was analyzed by HRXRD by employing a multicrystal X-ray diffractometer. The functional groups were identified from proton NMR spectroscopic analysis. Linear and nonlinear optical properties were determined by UV-Vis spectrophotometer and Kurtz powder technique respectively. It is found that the grown crystal has no absorption in the green wavelength region and the SHG efficiency was found to be 2.66 times that of the standard KDP. The Thermal stability of the crystal was found by obtaining TG/DTA curve. The mechanical behavior of the grown crystal has been studied by Vicker's microhardness method. Copyright © 2014 Elsevier B.V. All rights reserved.

Is Tridymite at Gale Crater Evidence for Silicic Volcanism on Mars?

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Vaniman, David T.; Ming, Douglas W.; Graff, Trevor G.; Downs, Robert T.; Fendrich, Kim; Mertzman, Stanley A.

2016-01-01

The X-ray diffraction (XRD) instrument (CheMin) onboard the MSL rover Curiosity detected 17 wt% of the SiO2 polymorph tridymite (relative to bulk sample) for the Buckskin drill sample (73 wt% SiO2) obtained from sedimentary rock in the Murray formation at Gale Crater, Mars. Other detected crystalline materials are plagioclase, sanidine, cristobalite, cation-deficient magnetite, and anhydrite. XRD amorphous material constitutes approx. 60 wt% of bulk sample, and the position of its broad diffraction peak near approx. 26 deg. 2-theta is consistent with opal-A. Tridymite is a lowpressure, high-temperature mineral (approx. 870 to 1670 deg. C) whose XRD-identified occurrence on the Earth is usually associated with silicic (e.g., rhyolitic) volcanism. High SiO2 deposits have been detected at Gale crater by remote sensing from martian orbit and interpreted as opal-A on the basis H2O and Si-OH spectral features. Proposed opal-A formation pathways include precipitation of silica from lake waters and high-SiO2 residues of acid-sulfate leaching. Tridymite is nominally anhydrous and would not exhibit these spectral features. We have chemically and spectrally analyzed rhyolitic samples from New Mexico and Iwodake volcano (Japan). The glassy (by XRD) NM samples have H2O spectral features similar to opal-A. The Iwodake sample, which has been subjected to high-temperature acid sulfate leaching, also has H2O spectral features similar to opal-A. The Iwodake sample has approx. 98 wt% SiO2 and 1% wt% TiO2 (by XRF), tridymite (>80 wt.% of crystalline material without detectable quartz by XRD), and H2O and Si-OH spectral features. These results open the working hypothesis that the opal-A-like high-SiO2 deposits at Gale crater detected from martian orbit are products of alteration associated with silicic volcanism. The presence or absence of tridymite will depend on lava crystallization temperatures (NM) and post crystallization alteration temperatures (Iwodake).

Geochemical Evidence for a Terrestrial Magma Ocean

NASA Technical Reports Server (NTRS)

Agee, Carl B.

1999-01-01

The aftermath of phase separation and crystal-liquid fractionation in a magma ocean should leave a planet geochemically differentiated. Subsequent convective and other mixing processes may operate over time to obscure geochemical evidence of magma ocean differentiation. On the other hand, core formation is probably the most permanent, irreversible part of planetary differentiation. Hence the geochemical traces of core separation should be the most distinct remnants left behind in the mantle and crust, In the case of the Earth, core formation apparently coincided with a magma ocean that extended to a depth of approximately 1000 km. Evidence for this is found in high pressure element partitioning behavior of Ni and Co between liquid silicate and liquid iron alloy, and with the Ni-Co ratio and the abundance of Ni and Co in the Earth's upper mantle. A terrestrial magma ocean with a depth of 1000 km will solidify from the bottom up and first crystallize in the perovskite stability field. The largest effect of perovskite fractionation on major element distribution is to decrease the Si-Mg ratio in the silicate liquid and increase the Si-Mg ratio in the crystalline cumulate. Therefore, if a magma ocean with perovskite fractionation existed, then one could expect to observe an upper mantle with a lower than chondritic Si-Mg ratio. This is indeed observed in modern upper mantle peridotites. Although more experimental work is needed to fully understand the high-pressure behavior of trace element partitioning, it is likely that Hf is more compatible than Lu in perovskite-silicate liquid pairs. Thus, perovskite fractionation produces a molten mantle with a higher than chondritic Lu-Hf ratio. Arndt and Blichert-Toft measured Hf isotope compositions of Barberton komatiites that seem to require a source region with a long-lived, high Lu-Hf ratio. It is plausible that that these Barberton komatiites were generated within the majorite stability field by remelting a perovskite-depleted part of the upper mantle transition zone.

Thermal influences on the development and evolution of large catastrophic caldera-forming magmatic systems

NASA Astrophysics Data System (ADS)

de Silva, S. L.; Gregg, P. M.; Grocke, S.; Kern, J. M.; Kaiser, J. F.; Iriarte, R.; Burns, D. H.; Tierney, C.; Schmitt, A. K.; Gosnold, W. D.

2012-12-01

Recent work in the community has emphasized the importance of the thermal environment on the development, evolution, and eventual eruption of large silicic magma systems, commonly referred to as "supervolcanic". With particular reference to the Central Andes, our group has focused on three main themes: thermal preparation of the shallow crust; the importance of temperature-dependent rheology of the host rocks; and time scales of magma evolution. Integrated, these themes provide a useful framework in which to understand supervolcanic systems dominated by crystal-rich silicic magmas such as those also seen in the Great Basin and Southern Rocky Mountain Volcanic Field of the North America and Toba in Sumatra. For both regional and individual systems, the key driver is anomalous high mantle to crust fluxes on time scales of several millions of years. These trigger feedbacks between intermediate melt generation in the lower crust, transport of this melt/magma through the crust, thermal evolution of the crust, and eventual growth and stabilization of silicic upper crustal magma systems. Elevation of geotherms in the upper crust results in conditions that promote the development of large eruptible magma volumes. Specifically, incubation and growth of nascent magma systems is enhanced by the permissive thermal environment and ductile rheology of wall rocks. These conditions are, in our view, the critical ingredients to the formation of the largest systems. Subsequent stabilization and growth of these systems at shallow levels (3 to 7 km) over several hundred of thousands of years results in further, local, feedbacks between chamber volume, temperature, wall rock rheology that cause significant surface uplift (~1 km) above the growing magma system, and long crystallization histories. These conditions lead to mechanically unstable "perched" magma bodies that can reach an advanced state of evolution (high crystallinity) before catastrophic eruption and caldera formation.

Magmatic (silicates/saline/sulfur-rich/CO2) immiscibility and zirconium and rare-earth element enrichment from alkaline magma chamber margins : Evidence from Ponza Island, Pontine Archipelago, Italy

USGS Publications Warehouse

Belkin, H.E.; de Vivo, B.; Lima, A.; Torok, K.

1996-01-01

Fluid inclusions were measured from a feldspathoid-bearing syenite xenolith entrained in trachyte from Ponza, one of the islands of the Pontine Archipelago, located in the Gulf of Gaeta, Italy. The feldspathoid-bearing syenite consists mainly of potassium feldspar, clinopyroxene, amphibole, biotite, titanite, manganoan magnetite, apatite with minor nosean, Na-rich feldspar, pyrrhotite, and rare cheralite. Baddeleyite and zirkelite occur associated with manganoan magnetite. Detailed electron-microprobe analysis reveals enrichments in REE, Y, Nb, U, Th as well as Cl and F in appropriate phases. Fluid inclusions observed in potassium feldspar are either silicate-melt or aqueous inclusions. The aqueous inclusions can be further classified as. (1) one-phase vapor, (2) two-phase (V + L) inclusions, vapor-rich inclusions with a small amount of CO2 in most cases; homogenization of the inclusions always occurred in the vapor phase between 359 and 424??C, salinities vary from 2.9 to 8.5 wt. % NaCl equivalent; and. (3) three-phase and multiphase inclusions (hypersaline/sulfur-rich aqueous inclusions sometimes with up to 8 or more solid phases). Daughter minerals dissolve on heating before vapor/liquid homogenization. Standardless quantitative scanning electron microscope X-ray fluorescence analysis has tentatively identified the following chloride and sulfate daughter crystals; halite, sylvite, glauberite. arcanite, anhydrite, and thenardite. Melting of the daughter crystals occurs between 459 and 536??C (54 to 65 wt. % NaCI equivalent) whereas total homogenization is between 640 and 755??C. The occurrence of silicate-melt inclusions and high-temperature, solute-rich aqueous inclusions suggests that the druse or miarolitic texture of the xenolith is late-stage magmatic. The xenolith from Ponza represents a portion of the peripheral magma chamber wall that has recorded the magmatic/hydrothermal transition and the passage of high solute fluids enriched in chlorides, sulfur, and incompatible elements.

On the localization properties of an RPWELL gas-avalanche detector

NASA Astrophysics Data System (ADS)

Moleri, L.; Bhattacharya, P.; Coimbra, A. E. C.; Breskin, A.; Bressler, S.

2017-10-01

A study of the localization properties of a single-element Resistive Plate WELL (RPWELL) detector is presented. The detector comprises of a single-sided THick Gaseous Electron Multiplier (THGEM) coupled to a segmented readout anode through a doped silicate-glass plate of 1010 Ωṡcm bulk resistivity. Operated in ambient \

Microtube-Czochralski technique (μT-CZ):. a novel way of seeding the melt to grow bulk single crystal

NASA Astrophysics Data System (ADS)

Sankaranarayanan, K.; Ramasamy, P.

1998-09-01

A novel microtube seeding has been proposed in the conventional Czochralski pulling technique to grow a bulk single crystal. The versatility of the technique has been shown by adopting this method for the growth of benzil. Benzil single crystals having hexagonal facets are grown by this technique called the microtube-Czochralski technique (μT-CZ). Due to capillary rise, a fine column of melt was crystallized inside the microtube, which leads to the formation of the single crystal nucleation and ends up with hexagonal morphology. The reproducibility for getting single crystal is about 80%. It is evident that this technique is more viable to grow a bulk single crystal from the melt without a pregrown-seed. Further, the proposed μT-CZ technique can also be extended to other newer materials with the proper choice of the microtube.

Microstructure, Chemistry, and Origin of Grain Rims on ilmenite from the Lunar Soil Finest Fraction

NASA Technical Reports Server (NTRS)

Christoffersen, Roy; Keller, Lindsay P.; McKay, David S.

1996-01-01

Analytical transmission electron microscope (TEM) observations reveal that ilmenite grains sampled from the sub-10 micron size fraction of Apollo 11 (10084) and Apollo 16 (61221, 67701) soils have rims 10-300 nm thick that are chemically and microstructurally distinct from the host ilmenite. The rims have a thin outer sublayer 10-50 nm thick that contains the ilmenite-incompatible elements Si, Al, Ca and S. This overlies a relatively thicker (50-250 nm) inner sublayer of nanocrystalline Ti-oxide precipitates in a matrix of single-crystal ilmenite that is structurally continuous with the underlying host grain. Microstructural information, as well as data from x-ray spectrometry (EDS) and electron energy loss spectrometry (EELS) analysis of the inner sublayer, suggest that both the inner and outer sublayer assemblages are reduced and that the inner layer is depleted in Fe relative to the underlying ilmenite. The chemistry of the outer sublayer suggests that it is a surface deposit of sputtered or impact-vaporized components from the bulk lunar soil. The inner sublayer is part of the original host grain that has been physically and chemically processed, but not amorphized, by solar ion irradiation and possibly some subsolidus heating. The fact that the deposited outer sublayer is consistently much thinner than the radiation-altered inner sublayer indicates that only a minor fraction of the total rim volume is a product of vapor or sputter deposition. This finding is in contrast to recent descriptions of thick deposited layers on one-third of regolith silicate grains and indicates that ilmenite and silicate rims as a group are different in the fraction of deposited material that they contain.

Friction and wear of oxide-ceramic sliding against IN-718 nickel base alloy at 25 to 800 C in atmospheric air

NASA Technical Reports Server (NTRS)

Sliney, Harold E.; Deadmore, Daniel L.

1989-01-01

The friction and wear of oxide-ceramics sliding against the nickel base alloy IN-718 at 25 to 800 C were measured. The oxide materials tested were mullite (3Al2O3.2SiO2); lithium aluminum silicate (LiAlSi(x)O(y)); polycrystalline monolithic alpha alumina (alpha-Al2O3); single crystal alpha-Al2O3 (sapphire); zirconia (ZrO2); and silicon carbide (SiC) whisker-reinforced Al2O3 composites. At 25 C the mullite and zirconia had the lowest friction and the polycrystalline monolithic alumina had the lowest wear. At 800 C the Al2O3-8 vol/percent SiC whisker composite had the lowest friction and the Al2O3-25 vol/percent SiC composite had the lowest wear. The friction of the Al2O3-SiC whisker composites increased with increased whisker content while the wear decreased. In general, the wear-resistance of the ceramics improve with their hardness.

Growth and characterization of binary and pseudo-binary 3-5 compounds exhibiting non-linear optical behavior. Undergraduate research opportunities in microgravity science and technology

NASA Technical Reports Server (NTRS)

Witt, August F.

1992-01-01

In line with the specified objectives, a Bridgman-type growth configuration in which unavoidable end effects - conventionally leading to growth interface relocation - are compensated by commensurate input-power changes is developed; the growth rate on a microscale is predictable and unaffected by changes in heat transfer conditions. To permit quantitative characterization of the growth furnace cavity (hot-zone), a 3-D thermal field mapping technique, based on the thermal image, is being tested for temperatures up to 1100 C. Computational NIR absorption analysis was modified to now permit characterization of semi-insulating single crystals. Work on growth and characterization of bismuth-silicate was initiated. Growth of BSO (B12SiO20) for seed material by the Czochralski technique is currently in progress. Undergraduate research currently in progress includes: ground based measurements of the wetting behavior (contact angles) of semiconductor melts on substrates consisting of potential confinement materials for solidification experiments in a reduced gravity environment. Hardware modifications required for execution of the wetting experiments in a KC-135 facility are developed.

Effect of Chain Conformation on the Single-Molecule Melting Force in Polymer Single Crystals: Steered Molecular Dynamics Simulations Study.

PubMed

Feng, Wei; Wang, Zhigang; Zhang, Wenke

2017-02-28

Understanding the relationship between polymer chain conformation as well as the chain composition within the single crystal and the mechanical properties of the corresponding single polymer chain will facilitate the rational design of high performance polymer materials. Here three model systems of polymer single crystals, namely poly(ethylene oxide) (PEO), polyethylene (PE), and nylon-66 (PA66) have been chosen to study the effects of chain conformation, helical (PEO) versus planar zigzag conformation (PE, PA66), and chain composition (PE versus PA66) on the mechanical properties of a single polymer chain. To do that, steered molecular dynamics simulations were performed on those polymer single crystals by pulling individual polymer chains out of the crystals. Our results show that the patterns of force-extension curve as well as the chain moving mode are closely related to the conformation of the polymer chain in the single crystal. In addition, hydrogen bonds can enhance greatly the force required to stretch the polymer chain out of the single crystal. The dynamic breaking and reformation of multivalent hydrogen bonds have been observed for the first time in PA66 at the single molecule level.

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

Patel, J. R.

We synthesized hexagonal-disc-shaped MgB{sub 2} single crystals under high-pressure conditions and analyzed the microstructure and pinning properties. The lattice constants and the Laue pattern of the crystals from X-ray micro-diffraction showed the crystal symmetry of MgB{sub 2}. A thorough crystallographic mapping within a single crystal showed that the edge and c-axis of hexagonal-disc shape exactly matched the (10-10) and the (0001) directions of the MgB{sub 2} phase. Thus, these well-shaped single crystals may be the best candidates for studying the direction dependences of the physical properties. The magnetization curve and the magnetic hysteresis for these single crystals showed the existencemore » of a wide reversible region and weak pinning properties, which supported our single crystals being very clean.« less

Metal/sulfide-silicate intergrowth textures in EL3 meteorites: Origin by impact melting on the EL parent body

NASA Astrophysics Data System (ADS)

van Niekerk, Deon; Keil, Klaus

2011-10-01

We document the petrographic setting and textures of Fe,Ni metal, the mineralogy of metallic assemblages, and the modal mineral abundances in the EL3 meteorites Asuka (A-) 881314, A-882067, Allan Hills 85119, Elephant Moraine (EET) 90299/EET 90992, LaPaz Icefield 03930, MacAlpine Hills (MAC) 02635, MAC 02837/MAC 02839, MAC 88136, Northwest Africa (NWA) 3132, Pecora Escarpment 91020, Queen Alexandra Range (QUE) 93351/QUE 94321, QUE 94594, and higher petrologic type ELs Dar al Gani 1031 (EL4), Sayh al Uhaymir 188 (EL4), MAC 02747 (EL4), QUE 94368 (EL4), and NWA 1222 (EL5). Large metal assemblages (often containing schreibersite and graphite) only occur outside chondrules and are usually intergrown with silicate minerals (euhedral to subhedral enstatite, silica, and feldspar). Sulfides (troilite, daubréelite, and keilite) are also sometimes intergrown with silicates. Numerous authors have shown that metal in enstatite chondrites that are interpreted to have been impact melted contains euhedral crystals of enstatite. We argue that the metal/sulfide-silicate intergrowths in the ELs we studied were also formed during impact melting and that metal in EL3s thus does not retain primitive (i.e., nebular) textures. Likewise, the EL4s are also impact-melt breccias. Modal abundances of metal in the EL3s and EL4s range from approximately 7 to 30 wt%. These abundances overlap or exceed those of EL6s, and this is consistent either with pre-existing heterogeneity in the parent body or with redistribution of metal during impact processes.

Single-crystal silicon optical fiber by direct laser crystallization

DOE PAGES

Ji, Xiaoyu; Lei, Shiming; Yu, Shih -Ying; ...

2016-12-05

Semiconductor core optical fibers with a silica cladding are of great interest in nonlinear photonics and optoelectronics applications. Laser crystallization has been recently demonstrated for crystallizing amorphous silicon fibers into crystalline form. Here we explore the underlying mechanism by which long single-crystal silicon fibers, which are novel platforms for silicon photonics, can be achieved by this process. Using finite element modeling, we construct a laser processing diagram that reveals a parameter space within which single crystals can be grown. Utilizing this diagram, we illustrate the creation of single-crystal silicon core fibers by laser crystallizing amorphous silicon deposited inside silica capillarymore » fibers by high-pressure chemical vapor deposition. The single-crystal fibers, up to 5.1 mm long, have a very welldefined core/cladding interface and a chemically pure silicon core that leads to very low optical losses down to ~0.47-1dB/cm at the standard telecommunication wavelength (1550 nm). Furthermore, tt also exhibits a photosensitivity that is comparable to bulk silicon. Creating such laser processing diagrams can provide a general framework for developing single-crystal fibers in other materials of technological importance.« less

Early Age Carbonation Heat and Products of Tricalcium Silicate Paste Subject to Carbon Dioxide Curing

PubMed Central

Li, Zhen; He, Zhen; Shao, Yixin

2018-01-01

This paper presents a study on the carbonation reaction heat and products of tricalcium silicate (C3S) paste exposed to carbon dioxide (CO2) for rapid curing. Reaction heat was measured using a retrofitted micro-calorimeter. The highest heat flow of a C3S paste subject to carbonation curing was 200 times higher than that by hydration, and the cumulative heat released by carbonation was three times higher. The compressive strength of a C3S paste carbonated for 2 h and 24 h was 27.5 MPa and 62.9 MPa, respectively. The 24-h carbonation strength had exceeded the hydration strength at 28 days. The CO2 uptake of a C3S paste carbonated for 2 h and 24 h was 17% and 26%, respectively. The X-ray diffraction (XRD), transmission electron microscope coupled with energy dispersive spectrometer (TEM-EDS), and 29Si magic angle spinning–nuclear magnetic resonance (29Si MAS-NMR) results showed that the products of a carbonated C3S paste were amorphous silica (SiO2) and calcite crystal. There was no trace of calcium silicate hydrate (C–S–H) or other polymorphs of calcium carbonate (CaCO3) detected. PMID:29734681

Formation of curved micrometer-sized single crystals.

PubMed

Koifman Khristosov, Maria; Kabalah-Amitai, Lee; Burghammer, Manfred; Katsman, Alex; Pokroy, Boaz

2014-05-27

Crystals in nature often demonstrate curved morphologies rather than classical faceted surfaces. Inspired by biogenic curved single crystals, we demonstrate that gold single crystals exhibiting curved surfaces can be grown with no need of any fabrication steps. These single crystals grow from the confined volume of a droplet of a eutectic composition melt that forms via the dewetting of nanometric thin films. We can control their curvature by controlling the environment in which the process is carried out, including several parameters, such as the contact angle and the curvature of the drops, by changing the surface tension of the liquid drop during crystal growth. Here we present an energetic model that explains this phenomenon and predicts why and under what conditions crystals will be forced to grow with the curvature of the microdroplet even though the energetic state of a curved single crystal is very high.

Imaging the Mount St. Helens Magmatic Systems using Magnetotellurics

NASA Astrophysics Data System (ADS)

Hill, G. J.; Caldwell, T. G.; Heise, W.; Bibby, H. M.; Chertkoff, D. G.; Burgess, M. K.; Cull, J. P.; Cas, R. A.

2009-05-01

A detailed magnetotelluric survey of Mount St. Helens shows that a conduit like zone of high electrical conductivity beneath the volcano is connected to a larger zone of high conductivity at 15 km depth that extends eastward to Mount Adams. We interpret this zone to be a region of connected melt that acts as the reservoir for the silicic magma being extruded at the time of the magnetotelluric survey. This interpretation is consistent with a mid-crustal origin for the silicic component of the Mount St. Helens' magmas and provides an elegant explanation for a previously unexplained feature of the seismicity observed at the time of the catastrophic eruption in 1980. This zone of high mid-crustal conductivity extends northwards to near Mount Rainier suggesting a single region of connected melt comparable in size to the largest silicic volcanic systems known.

Capillarity creates single-crystal calcite nanowires from amorphous calcium carbonate.

PubMed

Kim, Yi-Yeoun; Hetherington, Nicola B J; Noel, Elizabeth H; Kröger, Roland; Charnock, John M; Christenson, Hugo K; Meldrum, Fiona C

2011-12-23

Single-crystal calcite nanowires are formed by crystallization of morphologically equivalent amorphous calcium carbonate (ACC) particles within the pores of track etch membranes. The polyaspartic acid stabilized ACC is drawn into the membrane pores by capillary action, and the single-crystal nature of the nanowires is attributed to the limited contact of the intramembrane ACC particle with the bulk solution. The reaction environment then supports transformation to a single-crystal product. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laser radiation frequency doubling in a single-crystal fibre based on a stoichiometric LiNbO3 crystal

NASA Astrophysics Data System (ADS)

Kashin, V. V.; Nikolaev, D. A.; Rusanov, S. Ya; Tsvetkov, V. B.

2015-01-01

We demonstrate the employment of single-crystal optical fibres based on lithium niobate for doubling the laser radiation frequency. The measured characteristics of the fibre confirm its high quality and spatial homogeneity. Parameters of the frequency doublers for neodymium laser radiation (λ = 1 mm) based on fibre and bulk single crystals are compared. Single crystals are grown by the method of laser-heated pedestal growing with heating by radiation of a CO2 laser (LHPG-method).

Effect of L-Valine on the growth and characterization of Sodium Acid Phthalate (SAP) single crystals.

PubMed

Nirmala, L Ruby; Thomas Joseph Prakash, J

2013-06-01

Undoped and amino acid doped good quality single crystals of Sodium Acid Phthalate crystals (SAP) were grown by slow evaporation solution growth technique which are semiorganic in nature. The effect of amino acid (L-Valine) dopant on the growth and the properties of SAP single crystal was investigated. The single crystal X-ray diffraction studies and FT-IR studies were carried out to identify the crystal structure and the presence of functional groups in undoped and L-Valine doped SAP crystals. The transparent nature of the grown crystal was observed using UV-Visible spectrum. The thermal decomposition of the doped SAP crystals was investigated by thermo gravimetric analysis (TGA) and differential thermal analysis (DTA). The enhancement in the NLO property of the undoped and L-Valine doped SAP crystals using KDP crystal as a reference was studied using SHG measurements. Vickers micro hardness measurements are used for the study of mechanical strength of the grown crystals. Copyright © 2013 Elsevier B.V. All rights reserved.

In Situ Density Measurement of Basaltic Melts at High Pressure by X-ray Absorption Method

NASA Astrophysics Data System (ADS)

Ando, R.; Ohtani, E.; Suzuki, A.; Urakawa, S.; Katayama, Y.

2004-12-01

Density of silicate melt at high pressure is one of the most important properties to understand magma migration in the planetary interior. However, because of experimental difficulties, the density of magma at high pressure is poorly known. Katayama et al. (1996) recently developed a new in situ density measurement method for metallic melts, based on the density dependency of X-ray absorption in the sample. In this study, we tried to measure the density of basaltic melt by this absorption method. When X-ray is transmitted to the sample, the intensity of the transmitted X-ray beam (I) is expressed as follows; I=I0exp(-μ ρ t), where I0 is the intensity of incident X-ray beam, μ is the mass absorption coefficient, ρ is the density of the sample, and t is the thickness of the sample. If t and μ are known, we can determine the density of the sample by measuring I and I0. This is the principle of the absorption method for density measurement. In this study, in order to determine t, we used a single crystalline diamond cylinder as a sample capsule, diamond is less compressive and less deformable so that even at high pressure t (thickness of the sample at the point x) is expressed as follows; t = 2*(R02-x2)1/2, R0 is the inner radius of cylinder at the ambient condition, and x is distance from a center of the capsule. And diamond also shows less absorption so that this make it possible to measure the density of silicate melt with smaller absorption coefficient than metallic melts. In order to know the μ of the sample, we measured both densities (ρ ) and absorptions (I/I0) for some glasses and crystals with same composition of the sample at the ambient condition, and calculated as fallows; μ =ln(I/I0)/ρ . Experiments were made at the beamline (BL22XU) of SPring-8. For generation of high pressure and high temperature, we used DIA-type cubic anvil apparatus (SMAP180) there. We used tungsten carbide anvils with the edge-length of 6 mm. The energy of monochromatic X-ray beam was 25 keV and the beam size was reduced to 0.1*0.1 mm2 by two slits. Intensities of X-ray beam were measured by ion chambers. The starting material was a glass with the MORB composition (SiO2-Al2O3-FeO-MgO-CaO-Na2O). Experiments were made from 1 atm to 5GPa, from 300 to 1873 K. We measured the density of basaltic glass, crystals (eclogite) and melt. A density error of this method is less than 2 %. We calculated the bulk modulus of the glass at 773K, crystals at 1273K and melt at 1873 K, and obtained Kglass(773K)=46(4) GPa, Kcrystals(1273K)=100(7) GPa, Kmelt(1873K)=16.5(1.5) GPa assuming K'=4. This Kmelt(1873K) value is consistent with the previous study by the sink-float method (Ohtani and Maeda (2001); K=18.7(2.1) GPa). We can conclude this method is applicable for silicate melts.

Positioning and joining of organic single-crystalline wires

PubMed Central

Wu, Yuchen; Feng, Jiangang; Jiang, Xiangyu; Zhang, Zhen; Wang, Xuedong; Su, Bin; Jiang, Lei

2015-01-01

Organic single-crystal, one-dimensional materials can effectively carry charges and/or excitons due to their highly ordered molecule packing, minimized defects and eliminated grain boundaries. Controlling the alignment/position of organic single-crystal one-dimensional architectures would allow on-demand photon/electron transport, which is a prerequisite in waveguides and other optoelectronic applications. Here we report a guided physical vapour transport technique to control the growth, alignment and positioning of organic single-crystal wires with the guidance of pillar-structured substrates. Submicrometre-wide, hundreds of micrometres long, highly aligned, organic single-crystal wire arrays are generated. Furthermore, these organic single-crystal wires can be joined within controlled angles by varying the pillar geometries. Owing to the controllable growth of organic single-crystal one-dimensional architectures, we can present proof-of-principle demonstrations utilizing joined wires to allow optical waveguide through small radii of curvature (internal angles of ~90–120°). Our methodology may open a route to control the growth of organic single-crystal one-dimensional materials with potential applications in optoelectronics. PMID:25814032

Evolution of asteroid (4) Vesta in the light of Dawn

NASA Astrophysics Data System (ADS)

Thangjam, Guneshwar; Mengel, Kurt; Nathues, Andreas; Schmidt, Kai H.; Hoffmann, Martin

2016-04-01

Asteroid (4) Vesta has been visited by the NASA Dawn spacecraft in 2011/12. The combination of compositional/elemental information from the three onboard instruments with mineralogical information from the howardite-eucrite-diogenite (HED) clan of stony achondrites has shed new light on the surface lithologic heterogeneity and the early evolution. Although petrologic/chemical models have tried to unravel the evolutionary processes, inconsistencies exist for some chemical major element/phase [e.g., 1, 2]. A revised evolutionary model is presented here [3]. The three oxygen isotope signature of HEDs and, thus, of proto-Vesta is best met by a mixture of 80% ordinary plus 20 % CV chondrites. Assuming a 27Al-triggered magma ocean within the first MA after accretion and taking into account the reliable major element data of the silicate fraction of the chondritic mixture results a crystallization sequence that differs from the earlier models [1, 2, 3]. The crystallized phase obtained by 'MELTS' software [4] starts with olivine and continues with minor olivine plus orthopyroxene until the liquid reaches a Kd value (partition coefficient) of 0.31 where the fractionated melt is in equilibrium with the residual liquid [5]. The abundance of minerals and rocks formed in this model are converted in volume proportions assuming a spherical shape of early Vesta (262 km radius) with a core (FeNi, FeNiS) radius of 110 km [6]. Two scenarios are considered to describe the early bulk silicate Vesta. First, the early-crystallized olivine accumulated at the base of the silicate shell is accounted for a dunitic lower mantle having a thickness of 46 km while the later crystallized phases form an orthopyroxenitic upper mantle and a crust of thickness 84 and 22 km, respectively. Second, an olivine-rich lower mantle that gradually changes to orthopyroxene-rich upper mantle is expected having an overall shell thickness of 137 km, with a 15 km thick crust. An important result is that the deep-seated olivine-rich mantle has not been accessible to the deep excavation processes by large impacts such as the Rheasilvia basin formation [7]. This is likely the reason why olivine-rich exposures detected by Dawn are of exogenic origin [8]. Reference: [1] Mandler B. E., Elkins-Tanton L. T. 2013. Meteorit. Planet. Sci. 48, 2333. [2] Toplis M.J., et al., 2013. Meteorit. Planet. Sci. 48, 2300. [3] Thangjam G., PhD thesis, (in publication process). [4] Ghiorso M.S., Sack R.O., 1995. Contributions to Mineralogy and Petrology 119, 197. [5] Takahasi E., Kushiro I., 1983. American Mineralogist. 68, 859. [6] Russell C.T., et al., 2012. Science 336, 684. [7] Clenet H., et al., 2014. Nature 511, 303. [8] Nathues A., et al., 2015. Icarus 258, 467.

Modeling Magma Mixing: Evidence from U-series age dating and Numerical Simulations

NASA Astrophysics Data System (ADS)

Philipp, R.; Cooper, K. M.; Bergantz, G. W.

2007-12-01

Magma mixing and recharge is an ubiquitous process in the shallow crust, which can trigger eruption and cause magma hybridization. Phenocrysts in mixed magmas are recorders for magma mixing and can be studied by in- situ techniques and analyses of bulk mineral separates. To better understand if micro-textural and compositional information reflects local or reservoir-scale events, a physical model for gathering and dispersal of crystals is necessary. We present the results of a combined geochemical and fluid dynamical study of magma mixing processes at Volcan Quizapu, Chile; two large (1846/47 AD and 1932 AD) dacitic eruptions from the same vent area were triggered by andesitic recharge magma and show various degrees of magma mixing. Employing a multiphase numerical fluid dynamic model, we simulated a simple mixing process of vesiculated mafic magma intruded into a crystal-bearing silicic reservoir. This unstable condition leads to overturn and mixing. In a second step we use the velocity field obtained to calculate the flow path of 5000 crystals randomly distributed over the entire system. Those particles mimic the phenocryst response to the convective motion. There is little local relative motion between silicate liquid and crystals due to the high viscosity of the melts and the rapid overturn rate of the system. Of special interest is the crystal dispersal and gathering, which is quantified by comparing the distance at the beginning and end of the simulation for all particle pairs that are initially closer than a length scale chosen between 1 and 10 m. At the start of the simulation, both the resident and new intruding (mafic) magmas have a unique particle population. Depending on the Reynolds number (Re) and the chosen characteristic length scale of different phenocryst-pairs, we statistically describe the heterogeneity of crystal populations on the thin section scale. For large Re (approx. 25) and a short characteristic length scale of particle-pairs, heterogeneity of particle populations is large. After one overturn event, even the "thin section scale" can contain phenocrysts that derive from the entire magmatic system. We combine these results with time scale information from U-series plagioclase age dating. Apparent crystal residence times from the most evolved and therefore least hybridized rocks for the 1846/47 and 1932 eruptions of Volcan Quizapu are about 5000 and about 3000 yrs, respectively. Based on whole rock chemistry as well as textural and crystal-chemical data, both eruptions tapped the same reservoir and therefore should record similar crystal residence times. Instead, the discordance of these two ages can be explained by magma mixing as modeled above, if some young plagioclase derived from the andesitic recharge magma which triggered the 1846/47 AD eruption got mixed into the dacite remaining in the reservoir after eruption, thus lowering the apparent crystal residence time for magma that was evacuated from the reservoir in 1932.

Diagenetically altered fossil micrometeorites suggest cosmic dust is common in the geological record

NASA Astrophysics Data System (ADS)

Suttle, Martin D.; Genge, Matthew J.

2017-10-01

We report the discovery of fossil micrometeorites from Late Cretaceous chalk. Seventy-six cosmic spherules were recovered from Coniacian (87 ± 1 Ma) sediments of the White Chalk Supergroup. Particles vary from pristine silicate and iron-type spherules to pseudomorphic spherules consisting of either single-phase recrystallized magnetite or Fe-silicide. Pristine spherules are readily identified as micrometeorites on the basis of their characteristic mineralogies, textures and compositions. Both magnetite and silicide spherules contain dendritic crystals and spherical morphologies, testifying to rapid crystallisation of high temperature iron-rich metallic and oxide liquids. These particles also contain spherical cavities, representing weathering and removal of metal beads and irregular cavities, representing vesicles formed by trapped gas during crystallization; both features commonly found among modern Antarctic Iron-type (I-type) cosmic spherules. On the basis of textural analysis, the magnetite and Fe-silicide spherules are shown to be I-type cosmic spherules that have experienced complete secondary replacement during diagenesis (fossilization). Our results demonstrate that micrometeorites, preserved in sedimentary rocks, are affected by a suite of complex diagenetic processes, which can result in disparate replacement minerals, even within the same sequence of sedimentary beds. As a result, the identification of fossil micrometeorites requires careful observation of particle textures and comparisons with modern Antarctic collections. Replaced micrometeorites imply that geochemical signatures the extraterrestrial dust are subject to diagenetic remobilisation that limits their stratigraphic resolution. However, this study demonstrates that fossil, pseudomorphic micrometeorites can be recognised and are likely common within the geological record.

Eye-Safe Polycrystalline Lasers

DTIC Science & Technology

2013-03-01

developed novel ceramic and single crystal laser gain media as a platform for power scaling to +100 kW class levels. Hydrothermal techniques were used...order of magnitude improvement in purity. Bulk single crystal growth was demonstrated for scandia and lutetia single crystals , as well as several...exhibited equivalent transparency to that of the single crystal in the near-infrared spectral region and initial lasing results have been successful

Single crystalline hollow metal-organic frameworks: a metal-organic polyhedron single crystal as a sacrificial template.

PubMed

Kim, Hyehyun; Oh, Minhak; Kim, Dongwook; Park, Jeongin; Seong, Junmo; Kwak, Sang Kyu; Lah, Myoung Soo

2015-02-28

Single crystalline hollow metal-organic frameworks (MOFs) with cavity dimensions on the order of several micrometers and hundreds of micrometers were prepared using a metal-organic polyhedron single crystal as a sacrificial hard template. The hollow nature of the MOF crystal was confirmed by scanning electron microscopy of the crystal sliced using a focused ion beam.

Crystal growth, structure analysis and characterisation of 2 - (1, 3 - dioxoisoindolin - 2 - yl) acetic acid single crystal

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

Sankari, R. Siva, E-mail: sivasankari.sh@act.edu.in; Perumal, Rajesh Narayana

2014-04-24

Single crystal of dielectric material 2 - (1, 3 - dioxoisoindolin - 2 - yl) acetic acid has been grown by slow evaporation solution growth method. The grown crystal was harvested in 25 days. The crystal structure was analyzed by Single crystal X - ray diffraction. UV-vis-NIR analysis was performed to examine the optical property of the grown crystal. The thermal property of the grown crystal was studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The dielectric measurements were carried out and the dielectric constant was calculated and plotted at all frequencies.

Crystal-chemical controls on the partitioning of Sr and Ba between plagioclase feldspar, silicate melts, and hydrothermal solutions

NASA Astrophysics Data System (ADS)

Blundy, Jonathan D.; Wood, Bernard J.

1991-01-01

The isothermal (750°C) experiments of LAGACHE and DUJON (1987) reveal that the partitioning of Sr between plagioclase feldspar and hydrothermal solutions is a funtion of the anorthite (An) content of the plagioclase, indicating that crystal chemistry may exert a powerful influence on trace element partitioning. In order to compare these results with those on trace element partitioning between plagioclase and silicate melts we have compiled from the literature a large dataset of experimental and volcanic distribution coefficients ( D's) for Sr (and Ba). These data, which span a compositional range from lunar basalt to high silica rhyolite and a temperature range of over 650°C, show a relationship between DSr (and DBa) and mole fraction An ( XAn) which is similar to that exhibited by the hydrothermal results obtained at constant temperature. Plots of In DSr and In DBa versus XAn are linear with negative slope, indicating that both elements are more compatible in albite than anorthite. In terms of molar distribution coefficients ( D Sr∗) the hydrothermal and silicate melt data display an identical linear relationship between RT In D Sr∗ (where T is the absolute temperature in K and R is the gas constant, 8.314 JK -1 mol -1) and XAn. We conclude therefore that crystal chemistry provides the dominant control on partitioning of Sr and Ba into plagioclase and that the effects of temperature, pressure, and fluid composition are minor. Apparent relationships between DSr (and DBa) and the reciprocal temperature (1/ T) are artefacts of the linear relationships between XAn and 1/ T in the experimental studies. By defining a Henry's law standard state for the silicate melts and hydrothermal solutions, and considering plagioclases to be ternary regular solutions, we are able to relate the observed relationships between RT In D i∗ (where i is Ba or Sr) and XAn to the excess free energies of the trace element partitioning reactions between plagioclase and melt or hydrothermal solution. The interaction parameters are consistent with simple models in which the larger Ba or Sr cations are accommodated by lattice strain in the host plagioclase lattice, which is assumed to be perfectly elastic and isotropic. Thus D i∗ is a function of the Young's modulus of the host crystal and the size mismatch between trace and host cations. The greater elasticity of albite relative to anorthite accounts for the observed preference of Sr and Ba for sodic plagioclases over calcic plagioclases. For geochemical purposes the weight fraction partition coefficient Di is of more value than its molar counterpart. Regression of the Di data versus XAn yields the semi-empirical relationships RTIn DSr = 26,800 - 26,700 · XAnRTIn DBa = 10,200 - 38,200 · XAn. Thus measurement of the An and trace element (Ba, Sr) contents of a magmatic plagioclase enables calculation of the Ba and Sr contents of the coexisting liquid, which can be extremely important in the deciphering of igneous processes. By reference to plagioclase fractionation in the simple An-Ab binary we show that failure to take into account the compositional dependence of DSr can result in erroneous interpretations of geochemical trends. We also consider applications to three natural igneous suites: the Aden Volcanics; the layered Kiglapait Intrusion, Labrador; and the southern Actamello Massif, Italy.