Alkali element constraints on Earth-Moon relations

NASA Technical Reports Server (NTRS)

Norman, M. D.; Drake, M. J.; Jones, J. H.

1994-01-01

Given their range of volatilities, alkali elements are potential tracers of temperature-dependent processes during planetary accretion and formation of the Earth-Moon system. Under the giant impact hypothesis, no direct connection between the composition of the Moon and the Earth is required, and proto-lunar material does not necessarily experience high temperatures. Models calling for multiple collisions with smaller planetesimals derive proto-lunar materials mainly from the Earth's mantle and explicitly invoke vaporization, shock melting and volatility-related fractionation. Na/K, K/Rb, and Rb/Cs should all increase in response to thermal volatization, so theories which derive the Moon substantially from Earth's mantle predict these ratios will be higher in the Moon than in the primitive mantle of the Earth. Despite the overall depletion of volatile elements in the Moon, its Na/K and K/Rb are equal to or less than those of Earth. A new model presented here for the composition of Earth's continental crust, a major repository of the alkali elements, suggests the Rb/Cs of the Moon is also less than that of Earth. Fractionation of the alkali elements between Earth and Moon are in the opposite sense to predictions based on the relative volatilities of these elements, if the Moon formed by high-T processing of Earth's mantle. Earth, rather than the Moon, appears to carry a signature of volatility-related fractionation in the alkali elements. This may reflect an early episode of intense heating on Earth with the Moon's alkali budget accreting from cooler material.

Rubidium Isotope Composition of the Earth and the Moon: Evidence for the Origin of Volatile Loss During Planetary Accretion

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.

2016-12-01

The Earth-Moon system has a variety of chemical and isotopic characteristics that provide clues to understanding the mechanism of lunar formation. One important observation is the depletion in moderately volatile elements in the Moon compared to the Earth. This volatile element depletion may be a signature of volatile loss during the Moon-forming Giant Impact. Stable isotopes are powerful tracers of such a process, since volatile loss via evaporation enriches the residue in heavy isotopes. However, early studies searching for the fingerprint of volatile loss failed to find any resolvable variations [1]. Recent work has now revealed heavy isotope enrichments in the Moon relative to the Earth for the moderately volatile elements Zn [2,3] and K [4]. The purely lithophile nature of Rb (in contrast to the chalcophile/lithophile nature of Zn) and the higher volatility of Rb compared to K make Rb an ideal element with which to study the origin of lunar volatile element depletion. We have developed a new method for the high-precision measurement of Rb isotope ratios by MC-ICP-MS. The Rb isotope compositions of terrestrial rocks define a narrow range, indicating that Rb isotope fractionation during igneous differentiation is limited (<30 ppm/amu). There is a clear signature of Rb loss during evaporation in volatile-depleted achondrites and lunar rocks. In particular, eucrites are significantly enriched in 87Rb (up to several per mil) relative to chondrites. Similarly, lunar basalts are enriched in 87Rb compared to terrestrial basalts, by 200 ppm for 87Rb/85Rb. These data are the first measurements of a resolvable difference in Rb isotope composition between the Earth and the Moon. The variations in Rb isotope composition between the Earth and the Moon are consistent with Rb isotope fractionation due to evaporation. References: [1] Humayun & Clayton GCA 1995. [2] Paniello et al. Nature 2012. [3] Kato et al. Nat. Comm. 2015. [4] Wang and Jacobsen Nature in press.

Oxidation/volatilization rates in air for candidate fusion reactor blanket materials, PCA and HT-9

NASA Astrophysics Data System (ADS)

Piet, S. J.; Kraus, H. G.; Neilson, R. M.; Jones, J. L.

1986-11-01

Large uncertainties exist in the quantity of neutron-induced activation products that can be mobilized in potential fusion accidents. The accidental combination of high temperatures and oxidizing conditions might lead to mobilization of a significant amount of activation products from structural materials. Here, the volatilization of constituents of PCA and HT-9 resulting form oxidation in air was investigated. Tests were conducted in flowing air at temperatures from 600 to 1300°C for 1, 5, or 20 h. Elemental volatility was calculated in terms of the weight fraction of the element volatilized from the initial alloy. Molybdenum and manganese were the radiologically significant primary constituents most volatilized, suggesting that molybdenum and manganese should be minimized in fusion steel compositions. Higher chromium content appears beneficial in reducing hazards from mobile activation products. Scanning electron microscopy and energy dispersive spectroscopy were used to study the oxide layer on samples.

Little Chondrules and Giant Impacts

NASA Astrophysics Data System (ADS)

Taylor, G. J.

2005-10-01

Alexander (Sasha) Krot (University of Hawaii), Yuri Amelin (University of Toronto), Pat Cassen (SETI Institute), and Anders Meibom (Museum National d'Histoire Naturelle, Paris) studied and then extracted frozen droplets of molten silicate (chondrules) from unusual meteorites rich in metallic iron-nickel. Called CB (Bencubbin-like) chondrites, these rare but fascinating meteorites contain chondrules with different properties than those in other types of chondrites. Most notably, the chondrules contain very small concentrations of volatile elements and variable concentrations of refractory elements. (Volatile elements condense from a gas at a relatively low temperature, or are boiled out of solids or liquids at relatively low temperature. Refractory elements are the opposite.) Some of the metal grains in CB chondrites are chemically zoned, indicating that they formed by condensation in a vapor cloud. The most intriguing feature of chondrules in CB chondrites is their relatively young age. Lead-lead isotopic dating of chondrules separated from two CB chondrites show that they formed 5 million years after formation of the first solids in the solar system (calcium-aluminum-rich inclusions), which is about at least two million years after formation of other chondrules, and after energetic events in the solar nebula stopped. Krot and his colleagues suggest that the CB chondrules formed as the result of an impact between Moon- to Mars-sized protoplanets. Such impacts were so energetic that huge amounts of material were vaporized and then condensed as chondrules or chemically zoned metal grains. This event enriched refractory elements and depleted volatile elements. Such large impacts appear to play important roles in planet formation, including the formation of the Moon.

Chondritic Mn/Na ratio and limited post-nebular volatile loss of the Earth

NASA Astrophysics Data System (ADS)

Siebert, Julien; Sossi, Paolo A.; Blanchard, Ingrid; Mahan, Brandon; Badro, James; Moynier, Frédéric

2018-03-01

The depletion pattern of volatile elements on Earth and other differentiated terrestrial bodies provides a unique insight as to the nature and origin of planetary building blocks. The processes responsible for the depletion of volatile elements range from the early incomplete condensation in the solar nebula to the late de-volatilization induced by heating and impacting during planetary accretion after the dispersion of the H2-rich nebular gas. Furthermore, as many volatile elements are also siderophile (metal-loving), it is often difficult to deconvolve the effect of volatility from core formation. With the notable exception of the Earth, all the differentiated terrestrial bodies for which we have samples have non-chondritic Mn/Na ratios, taken as a signature of post-nebular volatilization. The bulk silicate Earth (BSE) is unique in that its Mn/Na ratio is chondritic, which points to a nebular origin for the depletion; unless the Mn/Na in the BSE is not that of the bulk Earth (BE), and has been affected by core formation through the partitioning of Mn in Earth's core. Here we quantify the metal-silicate partitioning behavior of Mn at deep magma ocean pressure and temperature conditions directly applicable to core formation. The experiments show that Mn becomes more siderophile with increasing pressure and temperature. Modeling the partitioning of Mn during core formation by combining our results with previous data at lower P-T conditions, we show that the core likely contains a significant fraction (20 to 35%) of Earth's Mn budget. However, we show that the derived Mn/Na value of the bulk Earth still lies on the volatile-depleted end of a trend defined by chondritic meteorites in a Mn/Na vs Mn/Mg plot, which tend to higher Mn/Na with increasing volatile depletion. This suggests that the material that formed the Earth recorded similar chemical fractionation processes for moderately volatile elements as chondrites in the solar nebula, and experienced limited post nebular volatilization.

Uncovering the Chemistry of Earth-like Planets

NASA Astrophysics Data System (ADS)

Zeng, Li; Sasselov, Dimitar; Jacobsen, Stein

2015-08-01

We propose to use the evidence from our solar system to understand exoplanets, and in particular, to predict their surface chemistry and thereby the possibility of life. An Earth-like planet, born from the same nebula as its host star, is composed primarily of silicate rocks and an iron-nickel metal core, and depleted in volatile content in a systematic manner. The more volatile (easier to vaporize or dissociate into gas form) an element is in an Earth-like planet, the more depleted the element is compared to its host star. After depletion, an Earth-like planet would go through the process of core formation due to heat from radioactive decay and collisions. Core formation depletes a planet’s rocky mantle of siderophile (iron-loving) elements, in addition to the volatile depletion. After that, Earth-like planets likely accrete some volatile-rich materials, called “late veneer”. The late veneer could be essential to the origins of life on Earth and Earth-like planets, as it also delivers the volatiles such as nitrogen, sulfur, carbon and water to the planet’s surface, which are crucial for life to occur. Here we build an integrative model of Earth-like planets from the bottom up. Thus the chemical compositions of Earth-like planets could be inferred from their mass-radius relations and their host stars’ elemental abundances, and the origins of volatile contents (especially water) on their surfaces could be understood, and thereby shed light on the origins of life on them. This elemental abundance model could be applied to other rocky exoplanets in exoplanet systems.

Uncovering the Chemistry of Earth-like Planets

NASA Astrophysics Data System (ADS)

Zeng, L.; Jacobsen, S. B.; Sasselov, D. D.

2015-12-01

We propose to use the evidence from our solar system to understand exoplanets, and in particular, to predict their surface chemistry and thereby the possibility of life. An Earth-like planet, born from the same nebula as its host star, is composed primarily of silicate rocks and an iron-nickel metal core, and depleted in volatile content in a systematic manner. The more volatile (easier to vaporize or dissociate into gas form) an element is in an Earth-like planet, the more depleted the element is compared to its host star. After depletion, an Earth-like planet would go through the process of core formation due to heat from radioactive decay and collisions. Core formation depletes a planet's rocky mantle of siderophile (iron-loving) elements, in addition to the volatile depletion. After that, Earth-like planets likely accrete some volatile-rich materials, called "late veneer". The late veneer could be essential to the origins of life on Earth and Earth-like planets, as it also delivers the volatiles such as nitrogen, sulfur, carbon and water to the planet's surface, which are crucial for life to occur. Here we build an integrative model of Earth-like planets from the bottom up. Thus the chemical compositions of Earth-like planets could be inferred from their mass-radius relations and their host stars' elemental abundances, and the origins of volatile contents (especially water) on their surfaces could be understood, and thereby shed light on the origins of life on them. This elemental abundance model could be applied to other rocky exoplanets in exoplanet systems.

REGENERATION OF REACTOR FUEL ELEMENTS

DOEpatents

Lyon, W.L.

1960-04-01

A process is described for concentrating uranium and/or plutonium metal in aluminum alloys in which the actinide content was partially consumed by neutron bombardinent. Two embodiments are claimed: Either the alloy is heated, together with zinc chloride to at least 1000 deg C whereby some aluminum, in the form of aluminum chloride, and any zinc formed volatilize; or else aluminum fluoride is added and reacted at 800 to 1000 deg O and substmospheric pressure whereby pant of the aluminum volatilizes and aluminum subfluoride.

Uncovering the Chemistry of Earth-like Planets

NASA Astrophysics Data System (ADS)

Zeng, Li; Jacobsen, Stein; Sasselov, Dimitar D.

2015-01-01

We propose to use evidence from our solar system to understand exoplanets, and in particular, to predict their surface chemistry and thereby the possibility of life. An Earth-like planet, born from the same nebula as its host star, is composed primarily of silicate rocks and an iron-nickel metal core, and depleted in volatile content in a systematic manner. The more volatile (easier to vaporize or dissociate into gas form) an element is in an Earth-like planet, the more depleted the element is compared to its host star. After depletion, an Earth-like planet would go through the process of core formation due to heat from radioactive decay and collisions. Core formation depletes a planet's rocky mantle of siderophile (iron-loving) elements, in addition to the volatile depletion. After that, Earth-like planets likely accrete some volatile-rich materials, called 'late veneer'. The late veneer could be essential to the origins of life on Earth and Earth-like planets, as it also delivers the volatiles such as nitrogen, sulfur, carbon and water to the planet's surface, which are crucial for life to occur. We plan to build an integrative model of Earth-like planets from the bottom up. We would like to infer their chemical compositions from their mass-radius relations and their host stars' elemental abundances, and understand the origins of volatile contents (especially water) on their surfaces, and thereby shed light on the origins of life on them.

Emission spectrographic determination of volatile trace elements in geologic materials by a carrier distillation technique

USGS Publications Warehouse

Barton, H.N.

1986-01-01

Trace levels of chalcophile elements that form volatile sulfide minerals are determined in stream sediments and in the nonmagnetic fraction of a heavy-mineral concentrate of stream sediments by a carrier distillation emission spectrographic method. Photographically recorded spectra of samples are visually compared with those of synthetic standards for the two sample types. Rock and soil samples may also be analyzed by comparison with the stream-sediment standards. A gallium oxide spectrochemical carrier/buffer enhances the early emission of the volatile elements. Detection limits in parts per million attained are: Sb 5, As 20, Bi 0.1, Cd 1, Cu 1, Pb 2, Ag 0.1, Zn 2, and Sn 0.1. A comparison with other methods of analysis, total-burn emission and atomic absorption spectroscopy, shows good correlation for standard reference for materials and samples from a variety of geologic terranes. ?? 1986.

Geochemistry and petrogenesis of a peralkaline granite complex from the Midian Mountains, Saudi Arabia

NASA Astrophysics Data System (ADS)

Harris, N. B. W.; Marriner, G. F.

1980-10-01

A zoned intrusion with a biotite granodiorite core and arfvedsonite granite rim represents the source magma for an albitised granite plug near its eastern margin and radioactive siliceous veins along its western margin. A study of selected REE and trace elements of samples from this complex reveals that the albitised granite plug has at least a tenfold enrichment in Zr, Hf, Nb, Ta, Y, Th, U and Sr, and a greatly enhanced heavy/light REE ratio compared with the peralkaline granite. The siliceous veins have even stronger enrichment of these trace elements, but a heavy/light REE ratio and negative eu anomaly similar to the peralkaline granite. It is suggested that the veins were formed from acidic volatile activity and the plug from a combination of highly fractionated magma and co-existing alkaline volatile phase. The granodiorite core intrudes the peralkaline granite and has similar trace element geochemistry. The peralkaline granite is probably derived from the partial melting of the lower crust in the presence of halide-rich volatiles, and the granodiorite from further partial melting under volatile-free conditions.

Geochemistry of impact glasses and target rocks from the Zhamanshin impact structure, Kazakhstan: Implications for mixing of target and impactor matter

NASA Astrophysics Data System (ADS)

Jonášová, Šárka; Ackerman, Lukáš; Žák, Karel; Skála, Roman; Ďurišová, Jana; Deutsch, Alexander; Magna, Tomáš

2016-10-01

Internal structure and element chemistry including contents of highly siderophile elements (HSE) and Os isotope ratios have been studied in target rocks and several groups of impact glasses of the Zhamanshin impact structure, Kazakhstan. These include larger irregularly-shaped fragments and blocks of impact glass (zhamanshinites), and three types of tektite-like splash-form glasses, part of fallback ejecta. These glassy objects typically are up to 30 mm large and are shaped as teardrops, irregularly bent and curved glass rods and fibers. They can be subdivided into acidic types (irghizites; typically 69-76 wt.% SiO2), basic splash-forms (typically 53-56 wt.% SiO2), and rarely occurring highly inhomogeneous composites with abundant mineral inclusions. A comparison with the target rocks shows that zhamanshinites and basic splash-forms usually have no detectable admixture of the projectile matter, indicated by major and trace elements as well as highly siderophile element contents, with the exception of one sample containing Fe-, Cr-, Ni- and Ti-enriched particles and elevated HSE contents. In contrast, irghizites exhibit clear admixture of the projectile matter, which was incorporated by complex processes accompanied by strong element fractionations. Microscopic investigations confirm that irghizites were formed mainly by coalescence of smaller molten glass droplets sized typically below 1 mm. Irghizites exhibit significant enrichments in Ni, Co and Cr, whose concentrations are locally elevated in the rims of the original small droplets. A portion of these elements and also part of Fe and Mn and other elements were derived from the impactor, most likely a Ni-rich carbonaceous chondrite. The contents of HSE are low and strongly fractionated, with moderate depletions of Pt and Pd and strong depletions of other HSE with respect to chondritic element ratios. Osmium shows the strongest depletion, likely related to the presence of oxygen in the post-impact atmosphere causing strong Os loss through volatilization. One composite splash-form contains Fe-Ni-S inclusions and exhibits a less fractionated HSE pattern suggesting the lowest degree of melting, volatilization and condensation. The observed structural and microchemical features of irghizites are interpreted to reflect variable proportions of the uppermost target sediments and the projectile matter, with HSE element ratios influenced by evaporation and condensation processes, and differences in volatility of individual HSE elements and/or their compounds. Two possible pathways of incorporation of the projectile matter into the irghizites include either re-condensation of evaporated projectile matter on the surface of glass droplets, or incorporation of less chemically fractionated microparticles dispersed by the explosion.

Origin and timescale of volatile element depletion in crustal and mantle reservoirs

NASA Astrophysics Data System (ADS)

Moynier, Frederic; Day, James M. D.

2014-05-01

Volatile elements play a fundamental role in the evolution of planets. Understanding of how volatile budgets were set in planets, and how and to what extent planetary bodies became volatile-depleted during the earliest stages of Earth and Solar System formation remain poorly understood, however. It has been proposed that the depletion is due to incomplete condensation (volatile elements were not there in the first place, in which case the timing would have to be fast, <1Myr), or that planetary bodies lost volatile elements through evaporation (post-accretion volatilization). Volatilization is known to fractionate isotopes, thus comparing isotope ratios of volatile element between samples is a powerful tool for understanding the origin of volatile element abundance variations. For example, recent work has shown that lunar basalts are enriched in the heavier isotopes of Zn (~1 ‰ for 66Zn/64Zn) compared to chondrites, terrestrial and martian basalts. We will discuss these Zn isotopic data of crustal and mantle rocks, as well as other stable isotopic systems (e.g., Si) in relation with the giant impact theory of lunar origin, as well as the lunar magma ocean and expand to other parent bodies (e.g., angrites). The timescale of depletion in volatile elements of Solar System material is estimated by using radiogenic systems for which the parent and daughter elements have different volatility. Here we focus on the Rb-Sr and Mn-Cr isotopic systems and discuss the timescales and implications for the origin of volatile element depletion (solar nebula stage vs. planetary stage).

Formation of Metal and Silicate Globules in Gujba: A New Bencubbin-like Meteorite Fall

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Kallemeyn, Gregory W.; Wasson, John T.; Clayton, Robert N.; Mayeda, Toshiko; Grady, Monica; Verchovsky, Alexander B.; Eugster, Otto; Lorenzetti, Silvio

2006-01-01

Gujba is a coarse-grained meteorite fall composed of 41 vol% large kamacite globules, 20 vol% large light-colored silicate globules with cryptocrystalline, barred pyroxene and barred olivine textures, 39 vol% dark-colored, silicate-rich matrix, and rare refractory inclusions. Gujba resembles Bencubbin and Weatherford in texture, oxygen-isotopic composition and in having high bulk delta N-15 values (approximately +685%0). The He-3 cosmic-ray exposure age of Gujba (26 +/- 7 Ma) is essentially identical to that of Bencubbin, suggesting that they were both reduced to meter-size fragments in the same parent-body collision. The Gujba metal globules exhibit metal-troilite quench textures and vary in their abundances of troilite and volatile siderophile elements. We suggest that the metal globules formed as liquid droplets either via condensation in an impact-generated vapor plume or by evaporation of preexisting metal particles in a plume. The lower the abundance of volatile elements in the metal globules, the higher the globule quench temperature. We infer that the large silicate globules also formed from completely molten droplets; their low volatile-element abundances indicate that they also formed at high temperatures, probably by processes analogous to those that formed the metal globules. The coarse-grained Bencubbin-Weatherford-Gujba meteorites may represent a depositional component from the vapor cloud enriched in coarse and dense particles. A second class of Bencubbin-like meteorites (represented by Hammadah a1 Hamra 237 and QUE 94411) may be a finer fraction derived from the same vapor cloud

Evaluating Volatility-controlled Isotope Fractionation During Planet Formation: Kinetics versus Equilibrium

NASA Astrophysics Data System (ADS)

Young, E. D.

2017-12-01

Recent advances in our ability to measure stable isotope ratios of light, rock-forming elements, including those for Zn, K, Fe, Si, and Mg, among others, has resulted in an emerging hypothesis that collisions among rocky planetesimals, planetary embryos, and/or proto-planets caused losses of moderately volatile elements (e.g., K) and "common" or moderately refractory elements (e.g., Mg and Si). The primary evidence is in the form of heavy isotope enrichments in rock-forming elements relative to the chondrite groups that are thought to be representative of planetary precursors. Equilibrium volatility-controlled isotope fractionation for planetesimal magma oceans might have occurred for bodies larger than 0.1% of an Earth mass (½ the mass of Pluto) as these bodies had sufficient gravity to overpower the escape velocities of hot gas at 2000K. Both Jean's escape and viscous drag hydrodynamic escape can obviate the escape velocity limit but will fractionate by mass, not by volatility. Equilibrium vapor/melt fractionation is qualitatively consistent with the greater disparity in 29Si/28Si between Earth and chondrites than in 25Mg/24Mg. However, losses of large masses of vapor are required to record the fractionation in the melts. We consider that if Earth was derived from E chondrite-like materials, the bulk composition of the Earth, assuming refractory Ca was retained, requires > 60% loss of Mg. This is a lot of vapor loss for a process relying on at least intermittent equilibrium, although it comports with the isotopic lever-rule requirements. Paradoxically, the alternative of evaporative loss of rock-forming elements requires less total mass loss. For example, the calculated Mg and Si isotopic compositions of residues resulting from evaporation of chondritic melts can fit the Mg and Si isotopic compositions of Earth, Mars, and angrites with varying background pressures and with total mass losses of near 5% or less. These mass losses are closer to, and even lower than, those suggested by Ca concentrations relative to CI chondrite. Equilibrium models achieve greater Si than Mg isotope fractionation by large mass losses while evaporation models produce this effect for small mass losses. Additional constraints involving other isotope systems as well as models for vapor loss can distinguish between the two scenarios.

Resource Prospector: Evaluating the ISRU Potential of the Lunar Poles

NASA Astrophysics Data System (ADS)

Colaprete, A.; Elphic, R. C.; Andrews, D.; Bluethmann, W.; Quinn, J.; Chavers, D. G.

2017-12-01

Resource Prospector (RP) is a lunar volatiles prospecting mission being developed for potential flight in CY2021-2022. The mission includes a rover-borne payload that (1) can locate surface and near-subsurface volatiles, (2) excavate and analyze samples of the volatile-bearing regolith, and (3) demonstrate the form, extractability and usefulness of the materials. The primary mission goal for RP is to evaluate the In-Situ Resource Utilization (ISRU) potential of the lunar poles. While it is now understood that lunar water and other volatiles have a much greater extent of distribution, possible forms, and concentrations than previously believed, to fully understand how viable these volatiles are as a resource to support human exploration of the solar system, the distribution and form needs to be understood at a "human" scale. That is, the "ore body" must be better understood at the scales it would be worked before it can be evaluated as a potential architectural element within any evolvable lunar or Mars campaign. This talk will provide an overview of the RP mission with an emphasis on mission goals and measurements, and will provide an update as to its current status.

A Brief User's Guide to the Excel ® -Based DF Calculator

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

Jubin, Robert T.

2016-06-01

To understand the importance of capturing penetrating forms of iodine as well as the other volatile radionuclides, a calculation tool was developed in the form of an Excel ® spreadsheet to estimate the overall plant decontamination factor (DF). The tool requires the user to estimate splits of the volatile radionuclides within the major portions of the reprocessing plant, speciation of iodine and individual DFs for each off-gas stream within the Used Nuclear Fuel reprocessing plant. The Impact to the overall plant DF for each volatile radionuclide is then calculated by the tool based on the specific user choices. The Excelmore » ® spreadsheet tracks both elemental and penetrating forms of iodine separately and allows changes in the speciation of iodine at each processing step. It also tracks 3H, 14C and 85Kr. This document provides a basic user's guide to the manipulation of this tool.« less

Back-extraction of trace elements from organometallic-halide extracts for determination by flameless atomic absorption spectrometry

USGS Publications Warehouse

Clark, J.R.; Viets, J.G.

1981-01-01

The Methyl isobutyl ketone-Amine synerGistic Iodkte Complex (MAGIC) extraction system offers the advantage that a large number of trace elements can be rapidly determined with a single sample preparation procedure. However, many of the elements extracted by the MAGIC system form volatile organometallic halide salts when the organic extract is heated in the graphite furnace. High concentrations of some elements such as Cu and Zn extracted by the system from anomalous geological samples produce serious interferences when certain other elements are determined by flameless atomic absorption. Stripping systems have been developed using solutions of HNO3, H2SO4, and CH3COOH individually or combined with H2O2 in order to circumvent these problems. With these systems most of the elements in the organic extract can be sequentially stripped into an aqueous phase. Organometallic volatilization and the most serious interelement interferences, therefore, can be eliminated by stripping with various combinations of reagents in a series of steps.

The Earth's missing lead may not be in the core.

PubMed

Lagos, M; Ballhaus, C; Münker, C; Wohlgemuth-Ueberwasser, C; Berndt, J; Kuzmin, Dmitry V

2008-11-06

Relative to the CI chondrite class of meteorites (widely thought to be the 'building blocks' of the terrestrial planets), the Earth is depleted in volatile elements. For most elements this depletion is thought to be a solar nebular signature, as chondrites show depletions qualitatively similar to that of the Earth. On the other hand, as lead is a volatile element, some Pb may also have been lost after accretion. The unique (206)Pb/(204)Pb and (207)Pb/(204)Pb ratios of the Earth's mantle suggest that some lead was lost about 50 to 130 Myr after Solar System formation. This has commonly been explained by lead lost via the segregation of a sulphide melt to the Earth's core, which assumes that lead has an affinity towards sulphide. Some models, however, have reconciled the Earth's lead deficit with volatilization. Whichever model is preferred, the broad coincidence of U-Pb model ages with the age of the Moon suggests that lead loss may be related to the Moon-forming impact. Here we report partitioning experiments in metal-sulphide-silicate systems. We show that lead is neither siderophile nor chalcophile enough to explain the high U/Pb ratio of the Earth's mantle as being a result of lead pumping to the core. The Earth may have accreted from initially volatile-depleted material, some lead may have been lost to degassing following the Moon-forming giant impact, or a hidden reservoir exists in the deep mantle with lead isotope compositions complementary to upper-mantle values; it is unlikely though that the missing lead resides in the core.

Non-volatile copolymer compositions for fabricating gel element microarrays

PubMed Central

Golova, Julia B.; Chernov, Boris K.; Perov, Alexander N.; Reynolds, Jennifer; Linger, Yvonne L.; Kukhtin, Alexander; Chandler, Darrell P.

2011-01-01

By modifying polymer compositions and cross-linking reagents, we have developed a simple yet effective manufacturing strategy for copolymerized three-dimensional gel element arrays. A new gel-forming monomer (2-(hydroxyethyl) methacrylamide; HEMAA) was used that possesses low volatility and improves the stability of copolymerized gel element arrays to on-chip thermal cycling procedures relative to previously used monomers. Probe immobilization efficiency within the new polymer was 55%, equivalent to that obtained with acrylamide (AA) and methacrylamide (MA) monomers. Non-specific binding of single stranded targets was equivalent for all monomers. Increasing cross-linker chain length improved hybridization kinetics and end-point signal intensities relative to N,N-methylenebisacrylamide (Bis). The new copolymer formulation was successfully applied to a model orthopox array. Because HEMAA greatly simplifies gel element array manufacture, we expect it (in combination with new cross-linkers described herein) to find widespread application in microarray science. PMID:22033291

FUEL ELEMENT CONSTRUCTION

DOEpatents

Zumwalt, L.R.

1961-08-01

Fuel elements having a solid core of fissionable material encased in a cladding material are described. A conversion material is provided within the cladding to react with the fission products to form stable, relatively non- volatile compounds thereby minimizing the migration of the fission products into the coolant. The conversion material is preferably a metallic fluoride, such as lead difluoride, and may be in the form of a coating on the fuel core or interior of the cladding, or dispersed within the fuel core. (AEC)

Carbon and sulfur distributions and abundances in lunar fines

NASA Technical Reports Server (NTRS)

Gibson, E. K., Jr.; Moore, G. W.

1973-01-01

Total sulfur abundances have been determined for 20 Apollo 14, 15, and 16 soil samples and one Apollo 14 breccia. Sulfur concentrations range from 474 to 844 microg S/g. Volatilization experiments on selected samples have been carried out using step-wise heating. Sample residues have been analyzed for their total carbon and sulfur abundances to establish the material balance in lunar fines for these two elements. Volatilization experiments have established that between 31 to 54 microg C/g remains in soils which have been heated at 1100 C for 24 hours under vacuum. The residual carbon is believed to be indigenous lunar carbon whereas all forms of carbon lost from samples below 1100 C is extralunar carbon. Total carbon and sulfur abundances taken from the literature have been used to show the depletion of volatile elements with increasing grade for the Apollo 14 breccias.

Volatile elements in Allende inclusions. [Mn, Na and Cl relation to meteorite evolution

NASA Technical Reports Server (NTRS)

Grossman, L.; Ganapathy, R.

1975-01-01

New data are presented on the relatively volatile elements (Mn, Na, and Cl) in coarse- and fine-grained Ca/Al-rich inclusions of different textures and mineralogy in the Allende meteorite. It is shown that the coarse-grained inclusions condensed from the solar nebula at high temperature and contained vanishingly small quantities of volatile elements at that time. Later, volatiles were added to these during the metamorphism of the Allende parent body. The fine-grained inclusions were also affected by the addition of volatiles during this metamorphism but, unlike the coarse-grained ones, they incorporated large amounts of volatiles when they condensed from the solar nebula, accounting for their higher volatile element contents.

Atmospheric Deposition of Mercury

EPA Science Inventory

With the advent of the industrial era, the amount of mercury entering the global environment increased dramatically. Releases of mercury in its elemental form from gold mines and chlor-alkali plants, as sulfides such as mercaptans and agricultural chemicals, and as volatile emiss...

Investigation on the fates of vanadium and nickel during co-gasification of petroleum coke with biomass.

PubMed

Li, Jiazhou; Wang, Xiaoyu; Wang, Bing; Zhao, Jiantao; Fang, Yitian

2018-06-01

This study investigates the volatilization behaviors and mineral transformation of vanadium and nickel during co-gasification of petroleum coke with biomass. Moreover, the evolution of occurrence modes of vanadium and nickel was also determined by the method of sequential chemical extraction. The results show that the volatilities of vanadium and nickel in petroleum coke have a certain level of growth with an increase in the temperature. With the addition of biomass, their volatilities both show an obvious decrease. Organic matter and stable forms are the dominant chemical forms of vanadium and nickel. After gasification, organic-bound vanadium and nickel decompose completely and convert into other chemical forms. The crystalline phases of vanadium trioxide, coulsonite, nickel sulfide, and elemental nickel are clearly present in petroleum coke and biomass gasification ashes. When the addition of biomass reaches 60 wt%, the diffraction peaks of orthovanadate are found while that of vanadium trioxide disappear. Copyright © 2018 Elsevier Ltd. All rights reserved.

Transfer of volatiles and metals from mafic to felsic magmas in composite magma chambers: An experimental study

NASA Astrophysics Data System (ADS)

Guo, Haihao; Audétat, Andreas

2017-02-01

In order to determine the behavior of metals and volatiles during intrusion of mafic magma into the base of silicic, upper crustal magma chambers, fluid-rock partition coefficients (Dfluid/rock) of Li, B, Na, S, Cl, K, Mn, Fe, Rb, Sr, Ba, Ce, Cu, Zn, Ag, Cd, Mo, As, Se, Sb, Te, W, Tl, Pb and Bi were determined experimentally at 2 kbar and 850 °C close to the solidus of mafic magma. In a first step, volatile-bearing mafic glasses were prepared by melting a natural basaltic trachyandesite in the presence of volatile-bearing fluids at 1200 °C/10 kbar in piston cylinder presses. The hydrous glasses were then equilibrated in subsequent experiments at 850 °C/2 kbar in cold-seal pressure vessels, which caused 80-90% of the melt to crystallize. After 0.5-2.0 days of equilibration, the exsolved fluid was trapped by means of in-situ fracturing in the form of synthetic fluid inclusions in quartz. Both the mafic rock residue and the fluid inclusions were subsequently analyzed by laser-ablation ICP-MS for major and trace elements. Reverse experiments were conducted by equilibrating metal-bearing aqueous solutions with rock powder and then trapping the fluid. In two additional experiments, information on relative element mobilities were obtained by reacting fluids that exsolved from crystallizing mafic magma with overlying silicic melts. The combined results suggest that under the studied conditions S, Cl, Cu, Se, Br, Cd and Te are most volatile (Dfluid/rock >10), followed by Li, B, Zn, As, Ag, Sb, Cs, W, Tl, Pb and Bi (Dfluid/rock = 1-10). Less volatile are Na, Mg, K, Ca, Mn, Fe, Rb, Sr, Mo and Rb (Dfluid/rock 0.1-1), and the least fluid-mobile elements are Al, Si, Ti, Zr, Ba and Ce (Dfluid/rock <0.1). This trend is broadly consistent with relative element volatilities determined on natural high-temperature fumarole gases, although some differences exist. Based on the volatility data and measured mineral-melt and sulfide-melt partition coefficients, volatile fluxing in felsic natural samples may be identified by Cu, Se, Te and Cd-enrichment in magmatic sulfides, and by As, Se, Cd and Bi-enrichment in magmatic apatite.

A history of violence: Insights into post-accretionary heating in carbonaceous chondrites from volatile element abundances, Zn isotopes and water contents

NASA Astrophysics Data System (ADS)

Mahan, Brandon; Moynier, Frédéric; Beck, Pierre; Pringle, Emily A.; Siebert, Julien

2018-01-01

Carbonaceous chondrites (CCs) may have been the carriers of water, volatile and moderately volatile elements to Earth. Investigating the abundances of these elements, their relative volatility, and isotopes of state-change tracer elements such as Zn, and linking these observations to water contents, provide vital information on the processes that govern the abundances and isotopic signatures of these species in CCs and other planetary bodies. Here we report Zn isotopic data for 28 CCs (20 CM, 6 CR, 1 C2-ung, and 1 CV3), as well as trace element data for Zn, In, Sn, Tl, Pb, and Bi in 16 samples (8 CM, 6 CR, 1 C2-ung, and 1 CV3), that display a range of elemental abundances from case-normative to intensely depleted. We use these data, water content data from literature and Zn isotopes to investigate volatile depletions and to discern between closed and open system heating. Trace element data have been used to construct relative volatility scales among the elements for the CM and CR chondrites. From least volatile to most, the scale in CM chondrites is Pb-Sn-Bi-In-Zn-Tl, and for CR chondrites it is Tl-Zn-Sn-Pb-Bi-In. These observations suggest that heated CM and CR chondrites underwent volatile loss under different conditions to one another and to that of the solar nebula, e.g. differing oxygen fugacities. Furthermore, the most water and volatile depleted samples are highly enriched in the heavy isotopes of Zn. Taken together, these lines of evidence strongly indicate that heated CM and CR chondrites incurred open system heating, stripping them of water and volatiles concomitantly, during post-accretionary shock impact(s).

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Collisional erosion and the non-chondritic composition of the terrestrial planets.

PubMed

O'Neill, Hugh St C; Palme, Herbert

2008-11-28

The compositional variations among the chondrites inform us about cosmochemical fractionation processes during condensation and aggregation of solid matter from the solar nebula. These fractionations include: (i) variable Mg-Si-RLE ratios (RLE: refractory lithophile element), (ii) depletions in elements more volatile than Mg, (iii) a cosmochemical metal-silicate fractionation, and (iv) variations in oxidation state. Moon- to Mars-sized planetary bodies, formed by rapid accretion of chondrite-like planetesimals in local feeding zones within 106 years, may exhibit some of these chemical variations. However, the next stage of planetary accretion is the growth of the terrestrial planets from approximately 102 embryos sourced across wide heliocentric distances, involving energetic collisions, in which material may be lost from a growing planet as well as gained. While this may result in averaging out of the 'chondritic' fractionations, it introduces two non-chondritic chemical fractionation processes: post-nebular volatilization and preferential collisional erosion. In the latter, geochemically enriched crust formed previously is preferentially lost. That post-nebular volatilization was widespread is demonstrated by the non-chondritic Mn/Na ratio in all the small, differentiated, rocky bodies for which we have basaltic samples, including the Moon and Mars. The bulk silicate Earth (BSE) has chondritic Mn/Na, but shows several other compositional features in its pattern of depletion of volatile elements suggestive of non-chondritic fractionation. The whole-Earth Fe/Mg ratio is 2.1+/-0.1, significantly greater than the solar ratio of 1.9+/-0.1, implying net collisional erosion of approximately 10 per cent silicate relative to metal during the Earth's accretion. If this collisional erosion preferentially removed differentiated crust, the assumption of chondritic ratios among all RLEs in the BSE would not be valid, with the BSE depleted in elements according to their geochemical incompatibility. In the extreme case, the Earth would only have half the chondritic abundances of the highly incompatible, heat-producing elements Th, U and K. Such an Earth model resolves several geochemical paradoxes: the depleted mantle occupies the whole mantle, is completely outgassed in (40)Ar and produces the observed (4)He flux through the ocean basins. But the lower radiogenic heat production exacerbates the discrepancy with heat loss.

Tin in a chondritic interplanetary dust particle

NASA Technical Reports Server (NTRS)

Rietmeijer, Frans J. M.

1989-01-01

Submicron platey Sn-rich grains are present in chondritic porous interplanetary dust particle (IDP) W7029 A and it is the second occurrence of a tin mineral in a stratospheric micrometeorite. Selected Area Electron Diffraction data for the Sn-rich grains match with Sn2O3 and Sn3O4. The oxide(s) may have formed in the solar nebula when tin metal catalytically supported reduction of CO or during flash heating on atmospheric entry of the IDP. The presence of tin is consistent with enrichments for other volatile trace elements in chondritic IDPs and may signal an emerging trend toward nonchondritic volatile element abundances in chondritic IDPs. The observation confirms small-scale mineralogical heterogeneity in fine-grained chondritic porous interplanetary dust.

Phytoremediation of Mercury and Organomercurials in Chloroplast Transgenic Plants: Enhanced Root Uptake, Translocation to Shoots, and Volatilization

PubMed Central

Hussein, Hussein S.; Ruiz, Oscar N.; Terry, Norman; Daniell, Henry

2008-01-01

Transgenic tobacco plants engineered with bacterial merA and merB genes via the chloroplast genome were investigated to study the uptake, translocation of different forms of mercury (Hg) from roots to shoots, and their volatilization. Untransformed plants, regardless of the form of Hg supplied, reached a saturation point at 200 µM of phenylmercuric acetate (PMA) or HgCl2, accumulating Hg concentrations up to 500 µg g−1 with significant reduction in growth. In contrast, chloroplast transgenic lines continued to grow well with Hg concentrations in root tissues up to 2000 µg g−1. Chloroplast transgenic lines accumulated both the organic and inorganic Hg forms to levels surpassing the concentrations found in the soil. The organic-Hg form was absorbed and translocated more efficiently than the inorganic-Hg form in transgenic lines, whereas no such difference was observed in untransformed plants. Chloroplast-transgenic lines showed about 100-fold increase in the efficiency of Hg accumulation in shoots compared to untransformed plants. This is the first report of such high levels of Hg accumulation in green leaves or tissues. Transgenic plants attained a maximum rate of elemental-Hg volatilization in two days when supplied with PMA and in three days when supplied with inorganic-Hg, attaining complete volatilization within a week. The combined expression of merAB via the chloroplast genome enhanced conversion of Hg2+ into Hg,0 conferred tolerance by rapid volatilization and increased uptake of different forms of mercury, surpassing the concentrations found in the soil. These investigations provide novel insights for improvement of plant tolerance and detoxification of mercury. PMID:18200876

Early accretion of water and volatile elements to the inner Solar System: evidence from angrites

NASA Astrophysics Data System (ADS)

Sarafian, Adam R.; Hauri, Erik H.; McCubbin, Francis M.; Lapen, Thomas J.; Berger, Eve L.; Nielsen, Sune G.; Marschall, Horst R.; Gaetani, Glenn A.; Righter, Kevin; Sarafian, Emily

2017-04-01

Inner Solar System bodies are depleted in volatile elements relative to chondrite meteorites, yet the source(s) and mechanism(s) of volatile-element depletion and/or enrichment are poorly constrained. The timing, mechanisms and quantities of volatile elements present in the early inner Solar System have vast implications for diverse processes, from planetary differentiation to the emergence of life. We report major, trace and volatile-element contents of a glass bead derived from the D'Orbigny angrite, the hydrogen isotopic composition of this glass bead and that of coexisting olivine and silicophosphates, and the 207Pb-206Pb age of the silicophosphates, 4568 ± 20 Ma. We use volatile saturation models to demonstrate that the angrite parent body must have been a major body in the early inner Solar System. We further show via mixing calculations that all inner Solar System bodies accreted volatile elements with carbonaceous chondrite H and N isotope signatures extremely early in Solar System history. Only a small portion (if any) of comets and gaseous nebular H species contributed to the volatile content of the inner Solar System bodies. This article is part of the themed issue 'The origin, history and role of water in the evolution of the inner Solar System'.

Early accretion of water and volatile elements to the inner Solar System: evidence from angrites.

PubMed

Sarafian, Adam R; Hauri, Erik H; McCubbin, Francis M; Lapen, Thomas J; Berger, Eve L; Nielsen, Sune G; Marschall, Horst R; Gaetani, Glenn A; Righter, Kevin; Sarafian, Emily

2017-05-28

Inner Solar System bodies are depleted in volatile elements relative to chondrite meteorites, yet the source(s) and mechanism(s) of volatile-element depletion and/or enrichment are poorly constrained. The timing, mechanisms and quantities of volatile elements present in the early inner Solar System have vast implications for diverse processes, from planetary differentiation to the emergence of life. We report major, trace and volatile-element contents of a glass bead derived from the D'Orbigny angrite, the hydrogen isotopic composition of this glass bead and that of coexisting olivine and silicophosphates, and the 207 Pb- 206 Pb age of the silicophosphates, 4568 ± 20 Ma. We use volatile saturation models to demonstrate that the angrite parent body must have been a major body in the early inner Solar System. We further show via mixing calculations that all inner Solar System bodies accreted volatile elements with carbonaceous chondrite H and N isotope signatures extremely early in Solar System history. Only a small portion (if any) of comets and gaseous nebular H species contributed to the volatile content of the inner Solar System bodies.This article is part of the themed issue 'The origin, history and role of water in the evolution of the inner Solar System'. © 2017 The Author(s).

A volatile topic: Parsing out the details of Earth's formation through experimental metal-silicate partitioning of volatile and moderately volatile elements

NASA Astrophysics Data System (ADS)

Mahan, B. M.; Siebert, J.; Blanchard, I.; Badro, J.; Sossi, P.; Moynier, F.

2017-12-01

Volatile and moderately volatile elements display different volatilities and siderophilities, as well as varying sensitivity to thermodynamic controls (X, P, T, fO2) during metal-silicate differentiation. The experimental determination of the metal-silicate partitioning of these elements permits us to evaluate processes controlling the distribution of these elements in Earth. In this work, we have combined metal-silicate partitioning data and results for S, Sn, Zn and Cu, and input these characterizations into Earth formation models. Model parameters such as source material, timing of volatile delivery, fO2 path, and degree of impactor equilibration were varied to encompass an array of possible formation scenarios. These models were then assessed to discern plausible sets of conditions that can produce current observed element-to-element ratios (e.g. S/Zn) in the Earth's present-day mantle, while also satisfying current estimates on the S content of the core, at no more than 2 wt%. The results of our models indicate two modes of accretion that can maintain chondritic element-to-element ratios for the bulk Earth and can arrive at present-day mantle abundances of these elements. The first mode requires the late addition of Earth's entire inventory of these elements (assuming a CI-chondritic composition) and late-stage accretion that is marked by partial equilibration of large impactors. The second, possibly more intuitive mode, requires that Earth accreted - at least initially - from volatile poor material preferentially depleted in S relative to Sn, Zn, and Cu. From a chemical standpoint, this source material is most similar to type I chondrule rich (and S poor) materials (Hewins and Herzberg, 1996; Mahan et al., 2017; Amsellem et al., 2017), such as the metal-bearing carbonaceous chondrites.

MERCURY MEASUREMENTS FOR SOLIDS MADE RAPIDLY, SIMPLY, AND INEXPENSIVELY

EPA Science Inventory

While traditional methods for determining mercury in solid samples involve the use of aggressive chemicals to dissolve the matrix and the use of other chemicals to properly reduce the mercury to the volatile elemental form, pyrolysis-based analyzers can be used by directly weighi...

Composition of the earth's upper mantle. II - Volatile trace elements in ultramafic xenoliths

NASA Technical Reports Server (NTRS)

Morgan, J. W.; Wandless, G. A.; Petrie, R. K.; Irving, A. J.

1980-01-01

Radiochemical neutron activation analysis was used to determine the nine volatile elements Ag, Bi, Cd, In, Sb, Se, Te, Tl, and Zn in 19 ultramafic rocks, consisting mainly of spinel and garnet lherzolites. A sheared garnet lherzolite, PHN 1611, may approximate undepleted mantle material and tends to have a higher volatile element content than the depleted mantle material represented by spinel lherzolites. Comparisons of continental basalts with PHN 1611 and of oceanic ridge basalts with spinel lherzolites show similar basalt: source material partition factors for eight of the nine volatile elements, Sb being the exception. The strong depletion of Te and Se in the mantle, relative to lithophile elements of similar volatility, suggests that 97% of the earth's S, Se and Te may be in the outer core.

ACFER 182/207/214 A Metal-rich, Volatile-poor Chondritic Meteorite, Similar to ALH85085

NASA Astrophysics Data System (ADS)

Palme, H.; Spettel, B.

1992-07-01

The unique Antarctic meteorite ALH85085 was the first chondritic meteorite to contain a significant excess of metallic Fe and associated siderophile elements (e.g., Grossman et al. 1988, Wasson and Kallemeyn 1990). Recently three Sahara meteorites, Acfer 182/207/214, apparently belonging to the same fall, were shown to be chemically and mineralogically very similar to ALHA85085, although minor textural differences appear to exclude a common origin with ALH85085. A mineralogical description and chemical composition of Acfer182/207/214 (henceforth ACFER182) are given in Bischoff et al. (1992). These authors suggested designating ALH85085 and ACFER182 as HH-chondrites reflecting high total Fe and high metal. The Fe/Mg-ratio of ACFER182 is 1.7 times that of CI-chondrites. All metals more refractory than Fe have similar enrichment factors, i.e., non-volatile metals occur in chondritic proportions, except for a slightly lower W enrichment. Metals more volatile than Fe are strongly depleted, with the depletion sequence closely following decreasing condensation temperatures. CI-normalized abundances are: Fe(1.92), Au(1.33), As(1.04), Cu(0.62), Ga(0.38), and the chalcophile Se(0.17). Lithophiles, more refractory than Mg, but including Mg and Cr, also occur in CI-abundance ratios (e.g., Sc/Mg in ACFER182 is 1.05xCI), although their absolute abundances are lower than those of metals. More volatile lithophile elements (Mn, Zn, etc.) decrease in abundance with decreasing condensation temperatures, just as the metals. The parallel (metal and silicate) decrease in moderately volatile element abundances with condensation temperatures suggests a similar nebular history for metal and silicate and is readily understood in a model where nebular gas is continually removed during condensation (Wasson and Chou 1974). Actual mixing of silicate and metal, i.e., agglomeration of silicate and metal grains in non-chondritic proportions (with 70% metal excess) could have occurred at relatively low temperatures, after the chondrule-forming process had transformed silicate grains into chondrules and fine metal grains into coarser metal. Partial loss of volatiles during chondrule formation or reheating of a metal-silicate assemblage with high volatile element abundances are very unlikely to produce the observed depletion sequence as argued by Grossman et al. (1988) for ALH85085. In addition, experiments on artificially heated meteorites produce losses of volatiles that are strongly dependent on fO(sub)2 and are incompatible with the patterns observed in ACFER182 (Wulf and Palme 1991). For example, the observed depletion of Mn in Acfer182 is 0.35 (i.e., 65 % are not condensed). However, Mn loss was never observed in the heating experiments, while large losses of Ga, Se, and Zn were found at temperatures up to 1300 degrees C. At temperatures required for Mn-volatilisation most other moderately volatiles would be quantitatively removed. However, the delicate pattern of moderate volatiles excludes ACFER182 as being a simple mixture of volatile-rich and volatile-poor material. Chemically, ACFER182 and ALHA85085 are related to CR-chondrites. These meteorites follow a trend of increasingly lower contents of volatile elements (e.g., Se, Zn) with decreasing contents of refractory element contents (e.g., Sc), opposite to the major trend in carbonaceous chondrites (from CI to CV). The ACFER182 and ALH85085 meteorites with their low Zn and Se contents and their low Sc abundances appear to form an endmember of this trend. Additional similarities with CR-meteorites in texture, mineralogy, and O, C, and N isotopic compositions (Bischoff et al. 1992; Prinz and Weisberg 1992 and references therein) may indicate that these meteorites are not as unique as originally thought. References: Bischoff A., Palme H., Schultz L., Weber D., Weber H.W. and Spettel B. (submitted to Geochim. Cosmochim. Acta 1992). Grossman J.N., Rubin A.E., MacPherson G.J. (1988) Earth Planet. Sci. Lett. 91, 33-54. Prinz M. and Weisberg M.K. (1992) Lunar. Planet. Sci. (abstract) 23, 1109. Wasson J.T. and Chou C.L. (1974) Meteoritics 9, 69-84. Wasson J.T. and Kallemeyn G.W. (1990) Earth Planet. Sci. Lett. 101, 148-161. Wulf A.-V. and Palme H.(1991) Lunar. Planet. Sci. (abstract) 22, 1527.

The fate of moderately volatile elements during planetary formation in the inner Solar System

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.

2017-12-01

Moderately volatile element abundances are variable among inner Solar System bodies, with differing degrees of depletion compared to chondrites. These variations are a consequence of the processes of planetary formation. The conditions and the specific mechanisms of planetary accretion and differentiation can be investigated by analyzing the stable isotope compositions of terrestrial and extraterrestrial samples. The moderately volatile lithophile elements are particularly useful to distinguish between the effects of accretion and those of core formation. Recent work has shown isotope variations in inner Solar System bodies for the moderately volatile elements Zn and K. The purely lithophile nature of Rb (in contrast to Zn) and the higher volatility of Rb compared to K make Rb an ideal element with which to further study moderately volatile element depletion. We have developed a new method for the high-precision measurement of Rb isotope ratios by MC-ICP-MS. Terrestrial rocks define a narrow range in Rb isotope composition, indicating that Rb isotope fractionation during igneous differentiation is limited (<30 ppm/amu). Larger Rb isotope variations are observed in extraterrestrial materials. Carbonaceous chondrites display a trend toward lighter Rb isotope composition coupled with decreasing Rb/Sr, opposite to the effect expected if their volatile element variations were caused by evaporative loss of Rb. This relationship indicates that the volatile element abundance variations in carbonaceous chondrites are not due to evaporation or condensation, but rather are due to the mixing of chemically and isotopically distinct primordial reservoirs. In contrast, there is a clear signature of Rb loss during evaporation in volatile-depleted achondrites and lunar rocks. Significant heavy isotope enrichments (up to several per mil for 87Rb/85Rb) are found for volatile-depleted planetesimals, including eucrites. In addition, lunar rocks also display heavy Rb isotope enrichments compared to the BSE. The most likely cause of these variations is Rb isotope fractionation due to evaporation during accretion.

TELEPHONIC PRESENTATION: MERCURY MEASUREMENTS FOR SOLIDS MADE RAPIDLY, SIMPLY, AND INEXPENSIVELY

EPA Science Inventory

While traditional methods for determining mercury in solid samples involve the use of aggressive chemicals to dissolve the matrix and the use of other chemicals to properly reduce the mercury to the volatile elemental form, pyrolysis-based analyzers can be used by directly weighi...

Rusty rock 66095 - A paradigm for volatile-element mobility in highland rocks

NASA Astrophysics Data System (ADS)

Hunter, R. H.; Taylor, L. A.

The ultimate goals of Apollo 16 consortia investigations are related to a determination of the nature of the early crust of the moon, taking into account questions regarding the petrogenesis of highland breccias and melt-rocks. In addition to these potential objectives, the consortia study of 66095 has also the goal to provide information for an understanding of the origin of volatile elements. Since 66095 is the most volatile-rich sample returned by the Apollo missions and its elemental ratios mimic those in many Apollo 16 breccias, it was selected as a paradigm for the highland breccias. 66095 is a clast-laden, impact-melt breccia. The volatile-rich nature is manifest in the presence of rust, schreibersite, and minor volatile-bearing compounds, usually in association with native metal and/or troilite. Attention is given to aspects of petrography, mineral chemistry, major element chemistry, the volatile bearing phases, and the history of the volatiles starting with their ultimate origin.

Sources of volatiles in basalts from the Galapagos Archipelago: deep and shallow evidence

NASA Astrophysics Data System (ADS)

Peterson, M. E.; Saal, A. E.; Hauri, E. H.; Werner, R.; Hauff, S. F.; Kurz, M. D.; Geist, D.; Harpp, K. S.

2010-12-01

The study of volatiles (H2O, CO2, F, S, and Cl) is important because volatiles assert a strong influence on mantle melting and magma crystallization, as well as on the viscosity and rheology of the mantle. Despite this importance, there have been a minimal number of volatile studies done on magmas from the four main mantle sources that define the end member compositions of the Galapagos lavas. For this reason, we here present new volatile concentrations of 89 submarine glass chips from dredges collected across the archipelago during the SONNE SO158, PLUM02, AHA-NEMO, and DRIFT04 cruises. All samples, with the exception of six, were collected at depths greater than 1000m. Major elements (E-probe), and volatile and trace elements (SIMS), are analyzed on the same glass chip, using 4 chips per sample, to better represent natural and analytical variation. Trace element contents reveal three main compositional groups: an enriched group typical of OIB, a group with intermediate compositions, and a group with a depleted trace element composition similar to MORB. The absolute ranges of volatile contents for all three compositional groups are .098-1.15wt% for H2O, 10.7-193.7 ppm for CO2, 61.4-806.5 ppm for F, 715.8-1599.2 ppm for S and 3.8-493.3 for Cl. The effect of degassing, sulfide saturation and assimilation of hydrothermally altered material must be understood before using the volatile content of submarine glasses to establish the primary volatile concentration of basalts and their mantle sources. CO2 has a low solubility in basaltic melts causing it to extensively degas. Based on the CO2/Nb ratio, we estimate the extent of degassing for the Galapagos lavas to range from approximately undegassed to 90% degassed. We demonstrate that 98% of the samples are sulfur undersaturated. Therefore, sulfur will behave as a moderately incompatible element during magmatic processes. Finally, we evaluate the effect of assimilation of hydrothermally altered material on the volatile content of the lavas. This process is evident when volatile/refractory element ratios are compared to the trace elements indicative of interaction between melt and the oceanic lithosphere such as a positive Sr anomaly (Sr*) in a primitive mantle normalized diagram. This is indicative of the interaction of basaltic melts with plagioclase cumulates. For the Galapagos depleted submarine glasses, we find a positive correlation between Sr* and all volatile/refractory element ratios suggesting significant volatile input from melt-lithosphere interaction. These samples, due to their low trace element concentrations, readily show the alteration signature, thus making the establishment of their primitive volatile content difficult. As a result, we will present the primary volatile concentrations for the trace element intermediate and enriched groups after careful consideration for degassing, sulfide saturation, and assimilation of hydrothermally altered material.

Lunar volatiles: a clue for understanding the evolution of the Moon and a resource to its exploration

NASA Astrophysics Data System (ADS)

Gerasimov, Mikhail

Introduction: The discovery of noticeable hydrogen concentration (believed to be in the form of water) in the polar regions was among the most exciting recent events in the exploration of the Moon. Concentration of water in polar regolith was estimated at a level of 4-6 wt.% [1,2]. Such high concentration of water in polar regolith on volatiles depleted Moon is probably a result of migration of water molecules from its hot equatorial latitudes to cold traps of the northern and southern polar regions. These depositions of volatiles on one hand contain important information on the evolution of the Moon and on the other hand their utilization can be a bases for the future human exploration. The question about diversity and source of the volatiles is still open. Sources of lunar volatiles: Three main possible sources of the Lunar polar volatiles are: Degassing of the interior. Endogenous source of volatiles is provided by degassing of heated interior of planetary bodies. In this case chemical composition of released gases reflects thermodynamic equilibrium of gases over typical magmas at temperatures around 1000°C. The composition of such gas mixtures is characterized by domination of H2O, CO2, and SO2 over other H, C, and S containing components. CO/CO2 ratio here is typically far below 0.1 level. Hydrocarbons are mainly aromatic hydrocarbons, alkanes, and cycloalkanes. Sulfur containing gases are mainly SO2, H2S, and Sx. Isotopic ratios of volatile elements should be the same as for the bulk Moon. Interaction of solar wind protons with surface rocks. Energetic solar wind protons with the absence of an atmospheric shield can react with oxygen of surface rocks and produce water molecules as end product. Such a mechanism provides a source of mainly water on the Moon with solar hydrogen isotopes and Moon rocks oxygen isotopes. Degassing of impacting meteorites and comets. Volatiles of impacting meteorites and comets are released into transient atmosphere. It was shown experimentally [3] that the forming gases are qualitatively similar for various rocky materials including meteorites of different classes. Such gas mixtures have the following characteristics: the CO/CO2 ratio is ³1, hydrocarbons are presented mainly by alkenes and PAHs, sulfur containing gases are presented by SO2, CS2, H2S, and COS in decreasing sequence, production of HCN, and noticeable release of water. Isotopic composition of volatile elements reflects the projectile to target proportion of their source. Gas-analytic package (GAP) of the Lunar-Resource mission: It is very important to investigate all the inventory of polar volatiles as well as isotopic composition of volatile elements to understand the real source of lunar volatiles and to evaluate their validity as a resource for the Moon exploration. The GAP is aimed on comprehensive investigation of the inventory of volatiles in the regolith of polar regions. It consists of three instruments: 1) Thermal Analyzer; 2) Gas Chromatograph with Tunable Diode Laser Absorption Spectrometer for isotopic measurements of H, O, and C in evolved gases; and 3) Neutral Gas Mass-Spectrometer. References: [1] Mitrofanov, I. G. et al. 2010. Science 330: 483-486. [2] Colaprete, A. et al. 2010. Science 330: 463-468. [3] Gerasimov, M.V. 2002. Geological Society of America Special Paper 356: 705-716. Acknowledgements: This work was supported by P-22 Program of the RAS.

PRESENTED 04/05/2006: MERCURY MEASUREMENTS FOR SOLIDS MADE RAPIDLY, SIMPLY, AND INEXPENSIVELY

EPA Science Inventory

While traditional methods for determining mercury in solid samples involve the use of aggressive chemicals to dissolve the matrix and the use of other chemicals to properly reduce the mercury to the volatile elemental form, pyrolysis-based analyzers can be used by directly weighi...

PRESENTED MAY 10, 2005, MERCURY MEASUREMENTS FOR SOLIDS MADE RAPIDLY, SIMPLY, AND INEXPENSIVELY

EPA Science Inventory

While traditional methods for determining mercury in solid samples involve the use of aggressive chemicals to dissolve the matrix and the use of other chemicals to properly reduce the mercury to the volatile elemental form, pyrolysis-based analyzers can be used by directly weighi...

Gas Phase Chromatography of some Group 4, 5, and 6 Halides

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

Sylwester, Eric Robert

1998-10-01

Gas phase chromatography using The Heavy Element Volatility Instrument (HEVI) and the On Line Gas Apparatus (OLGA III) was used to determine volatilities of ZrBr 4, HfBr 4, RfBr 4, NbBr 5, TaOBr 3, HaCl 5, WBr 6, FrBr, and BiBr 3. Short-lived isotopes of Zr, Hf, Rf, Nb, Ta, Ha, W, and Bi were produced via compound nucleus reactions at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory and transported to the experimental apparatus using a He gas transport system. The isotopes were halogenated, separated from the other reaction products, and their volatilities determined by isothermal gas phase chromatography.more » Adsorption Enthalpy (ΔH a) values for these compounds were calculated using a Monte Carlo simulation program modeling the gas phase chromatography column. All bromides showed lower volatility than molecules of similar molecular structures formed as chlorides, but followed similar trends by central element. Tantalum was observed to form the oxybromide, analogous to the formation of the oxychloride under the same conditions. For the group 4 elements, the following order in volatility and ΔH a was observed: RfBr 4 > ZrBr 4 > HfBr 4. The ΔH a values determined for the group 4, 5, and 6 halides are in general agreement with other experimental data and theoretical predictions. Preliminary experiments were performed on Me-bromides. A new measurement of the half-life of 261Rf was performed. 261Rf was produced via the 248Cm( 18O, 5n) reaction and observed with a half-life of 74 -6 +7 seconds, in excellent agreement with the previous measurement of 78 -6 +11 seconds. We recommend a new half-life of 75±7 seconds for 261Rf based on these two measurements. Preliminary studies in transforming HEVI from an isothermal (constant temperature) gas phase chromatography instrument to a thermochromatographic (variable temperature) instrument have been completed. Thermochromatography is a technique that can be used to study the volatility and ΔH a of longer-lived isotopes off-line, Future work will include a comparison between the two techniques and the use of thermochromatography to study isotopes in a wider range of half-lives and molecular structures.« less

Determination of Trace and Volatile Element Abundance Systematics of Lunar Pyroclastic Glasses 74220 and 15426 Using LA-ICP-MS

NASA Technical Reports Server (NTRS)

McIntosh, E. Carrie; Porrachia, Magali; McCubbin, Francis M.; Day, James M. D.

2017-01-01

Since their recognition as pyroclastic glasses generated by volcanic fire fountaining on the Moon, 74220 and 15426 have garnered significant scientific interest. Early studies recognized that the glasses were particularly enriched in volatile elements on their surfaces. More recently, detailed analyses of the interiors of the glasses, as well as of melt inclusions within olivine grains associated with the 74220 glass beads, have determined high H2O, F, Cl and S contents. Such elevated volatile contents seem at odds with evidence from moderately volatile elements (MVE), such as Zn and K, for a volatile- depleted Moon. In this study, we present initial results from an analytical campaign to study trace element abundances within the pyroclastic glass beads. We report trace element data determined by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for 15426 and 74220.

Volatile elements in and on lunar volcanic glasses: What do they tell us about lunar genesis?

NASA Technical Reports Server (NTRS)

Koeberl, C.

1984-01-01

There are good reasons to believe that lunar volcanic glasses originated from a deep interior source. The presence of a thin layer of surface correlated elements on these glasses may indicate that the Moon has some reservoirs that are enriched in volatiles. Since the glasses themselves do not show similar enrichment, the source should be of limited extent. Three scenarios are advanced for the origin of these elements. The mechanism for lunar volcanism differs from the mechanism for volcanism on Earth since the former produces bubbling and the latter explosive fountaining. From the condensation behavior of the volatile compounds, which leads to heterogeneous condensation, it is concluded that comparing element ratios of surface correlated elements gives little sense. It seems as if the volatile reservoirs are of rather limited extent and that they do not enlarge the volatile content of the bulk Moon significantly.

Metal-Silicate-Sulfide Partitioning of U, Th, and K: Implications for the Budget of Volatile Elements in Mercury

NASA Technical Reports Server (NTRS)

Habermann, M.; Boujibar, A.; Righter, K.; Danielson, L.; Rapp, J.; Righter, M.; Pando, K.; Ross, D. K.; Andreasen, R.

2016-01-01

During formation of the solar system, the Sun produced strong solar winds, which stripped away a portion of the volatile elements from the forming planets. Hence, it was expected that planets closest to the sun, such as Mercury, are more depleted in volatile elements in comparison to other terrestrial planets. However, the MESSENGER mission detected higher than expected K/U and K/Th ratios on Mercury's surface, indicating a volatile content between that of Mars and Earth. Our experiments aim to resolve this discrepancy by experimentally determining the partition coefficients (D(sup met/sil)) of K, U, and Th between metal and silicate at varying pressure (1 to 5 GPa), temperature (1500 to 1900 C), oxygen fugacity (IW-2.5 to IW-6.5) and sulfur-content in the metal (0 to 33 wt%). Our data show that U, Th, and K become more siderophile with decreasing fO2 and increasing sulfur-content, with a stronger effect for U and Th in comparison to K. Using these results, the concentrations of U, Th, and K in the bulk planet were calculated for different scenarios, where the planet equilibrated at a fO2 between IW-4 and IW-7, assuming the existence of a FeS layer, between the core and mantle, with variable thickness. These models show that significant amounts of U and Th are partitioned into Mercury's core. The elevated superficial K/U and K/Th values are therefore only a consequence of the sequestration of U and Th into the core, not evidence of the overall volatile content of Mercury.

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

NASA Technical Reports Server (NTRS)

Righter, Kevin; Pando, K.; Danielson, L.; Nickodem, K.

2014-01-01

Depletions of volatile siderophile elements (VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd) in mantles of Earth and Moon, constrain the origin of volatile elements in these bodies, and the overall depletion of volatile elements in Moon relative to Earth. A satisfactory explanation has remained elusive [1,2]. We examine the depletions of VSE in Earth and Moon and quantify the amount of depletion due to core formation and volatility of potential building blocks. We calculate the composition of the Earth's PUM during continuous accretion scenarios with constant and variable fO2. Results suggest that the VSE can be explained by a rather simple scenario of continuous accretion leading to a high PT metal-silicate equilibrium scenario that establishes the siderophile element content of Earth's PUM near the end of accretion [3]. Core formation models for the Moon explain most VSE, but calculated contents of In, Sn, and Zn (all with Tc < 750 K) are all still too high after core formation, and must therefore require an additional process to explain the depletions in the lunar mantle. We discuss possible processes including magmatic degassing, evaporation, condensation, and vapor-liquid fractionation in the lunar disk.

Resource Prospector, the Decadal Survey and the Scientific Context for the Exploration of the Moon

NASA Technical Reports Server (NTRS)

Elphic, R. C.; Colaprete, A.; Andrews, D. R.

2017-01-01

The Inner Planets Panel of the Planetary Exploration Decadal Survey defined several science questions related to the origins, emplacement, and sequestration of lunar polar volatiles: 1. What is the lateral and vertical distribution of the volatile deposits? 2. What is the chemical composition and variability of polar volatiles? 3. What is the isotopic composition of the volatiles? 4. What is the physical form of the volatiles? 5. What is the rate of the current volatile deposition? A mission concept study, the Lunar Polar Volatiles Explorer (LPVE), defined a approximately $1B New Frontiers mission to address these questions. The NAS/NRC report, 'Scientific Context for the Exploration of the Moon' identified he lunar poles as special environments with important implications. It put forth the following goals: Science Goal 4a-Determine the compositional state (elemental, isotopic, mineralogic) and compositional distribution (lateral and depth) of the volatile component in lunar polar regions. Science Goal 4b-Determine the source(s) for lunar polar volatiles. Science Goal 4c-Understand the transport, retention, alteration, and loss processes that operate on volatile materials at permanently shaded lunar regions. Science Goal 4d-Understand the physical properties of the extremely cold (and possibly volatile rich) polar regolith. Science Goal 4e-Determine what the cold polar regolith reveals about the ancient solar environment.

Sensitive determination of Hg together with Mn, Fe, Cu by combined photochemical vapor generation and pneumatic nebulization in the programmable temperature spray chamber and inductively coupled plasma optical emission spectrometry.

PubMed

Giersz, Jacek; Bartosiak, Magdalena; Jankowski, Krzysztof

2017-05-15

Continuous photo-induced generation of mercury cold vapor has been successfully coupled with conventional pneumatic nebulization in programmable temperature spray chamber (PCVG-PN-PTSC) allowing fast, sensitive and easy multi-element analysis. The applied technique enabled simultaneous determination of non-volatile forming elements (Fe, Cu, Mn) and volatile Hg, while 15% v/v formic acid is present in the sample. PTSC elevated temperature (40°C) causes partial conversion of sample matrix into vapor form, thus improving plasma robustness. The efficiency of Hg vapor generation and its transport to the plasma is close to 100%. Moreover, spray chamber temperature stabilization improved the precision of the measurements (Hg signal RSD below 0.5%). The achieved limit of detection for Hg (90pgmL -1 ) at 194.23nm with no monochromator purge is better by almost two orders of magnitude than that obtained by conventional PN-ICP-OES. On the other hand, LODs for non-vapor forming elements are comparable to those obtained with pneumatic nebulization. The linear dynamic ranges for all examined elements are at least three orders of magnitude up to 1000ngmL -1 . None mutual interference between examined analytes (Hg, Fe, Cu, Mn) has been observed. The method was validated by the analysis of two CRM materials of different matrix composition (waste water ERM CA713 and estuarine sediment ERM CC580) giving satisfactory results. As low as 2 ppb of Hg can he directly determined in waste water. The proposed procedure uses mild reagents and allows for fast multi-element analysis, and matches green chemistry requirements. Copyright © 2017 Elsevier B.V. All rights reserved.

Resource Prospector: A Lunar Volatiles Prospecting and ISRU Demonstration Mission

NASA Technical Reports Server (NTRS)

Colaprete, Anthony

2015-01-01

A variety of recent observations have indicated several possible reservoirs of water and other volatiles. These volatiles, and in particular water, have the potential to be a valuable or enabling resource for future exploration. NASA's Human Exploration and Operations Mission Directorate (HEOMD) Advanced Exploration Systems (AES) is supporting the development of Resource Prospector (RP) to explore the distribution and concentration of lunar volatiles prospecting and to demonstrate In-Situ Resource Utilization (ISRU). The mission includes a NASA developed rover and payload, and a lander will most likely be a contributed element by an international partner or the Lunar Cargo Transportation and Landing by Soft Touchdown (CATALYST) initiative. The RP payload is designed to: (1) locate near-subsurface volatiles, (2) excavate and analyze samples of the volatile-bearing regolith, and (3) demonstrate the form. extractability and usefulness of the materials. RP is being designed with thought given to its extensibility to resource prospecting and ISRU on other airless bodies and Mars. This presentation will describe the Resource Prospector mission, the payload and measurements, and concept of operations

Origin of Volatiles in Earth: Indigenous Versus Exogenous Sources Based on Highly Siderophile, Volatile Siderophile, and Light Volatile Elements

NASA Technical Reports Server (NTRS)

Righter, K.; Danielson, L.; Pando, K. M.; Marin, N.; Nickodem, K.

2015-01-01

Origin of Earth's volatiles has traditionally been ascribed to late accretion of material after major differentiation events - chondrites, comets, ice or other exogenous sources. A competing theory is that the Earth accreted its volatiles as it was built, thus water and other building blocks were present early and during differentiation and core formation (indigenous). Here we discuss geochemical evidence from three groups of elements that suggests Earth's volatiles were acquired during accretion and did not require additional sources after differentiation.

Chemical Composition of Four Shergottites from Northwest Africa (NWA 2800, NWA, 5214, NWA 5990, NWA 6342)

NASA Technical Reports Server (NTRS)

Yang, S.; Humayun, M.; Jefferson, G.; Fields, D.; Righter, K.; Irving, A. J.

2013-01-01

Shergottites represent the majority of recovered Martian meteorites. As basic igneous rocks, they formed from magmas that were emplaced in the Martian crust [1]. Due to the low ambient pressure of the Martian atmosphere, subaerial lavas and shallow magma chambers are expected to outgas volatile metals (e.g., Cd, Te, Re, Bi) [2]. The planetary abundances of the volatile siderophile and chalcophile elements are important at establishing the depth of core formation for Mars, and must be known as a baseline for understanding volcanic outgassing on Mars, particularly the large enrichments of S and Cl observed in modern Martian soils [3]. There is little data on volatile siderophile and chalcophile elements from Martian meteorites, excluding a few well-analyzed samples [2]. Further, a large number of shergottites being recovered from North West Africa are in need of chemical analysis. All of the shergottites are in need of state-of-the art analysis for such ratios as Ge/Si and Ga/Al, which can now be accomplished by LA-ICP-MS [2].

Study on the behavior of heavy metals during thermal treatment of municipal solid waste (MSW) components.

PubMed

Yu, Jie; Sun, Lushi; Wang, Ben; Qiao, Yu; Xiang, Jun; Hu, Song; Yao, Hong

2016-01-01

Laboratory experiments were conducted to investigate the volatilization behavior of heavy metals during pyrolysis and combustion of municipal solid waste (MSW) components at different heating rates and temperatures. The waste fractions comprised waste paper (Paper), disposable chopstick (DC), garbage bag (GB), PVC plastic (PVC), and waste tire (Tire). Generally, the release trend of heavy metals from all MSW fractions in rapid-heating combustion was superior to that in low-heating combustion. Due to the different characteristics of MSW fractions, the behavior of heavy metals varied. Cd exhibited higher volatility than the rest of heavy metals. For Paper, DC, and PVC, the vaporization of Cd can reach as high as 75% at 500 °C in the rapid-heating combustion due to violent combustion, whereas a gradual increase was observed for Tire and GB. Zn and Pb showed a moderate volatilization in rapid-heating combustion, but their volatilities were depressed in slow-heating combustion. During thermal treatment, the additives such as kaolin and calcium can react or adsorb Pb and Zn forming stable metal compounds, thus decreasing their volatilities. The formation of stable compounds can be strengthened in slow-heating combustion. The volatility of Cu was comparatively low in both high and slow-heating combustion partially due to the existence of Al, Si, or Fe in residuals. Generally, in the reducing atmosphere, the volatility of Cd, Pb, and Zn was accelerated for Paper, DC, GB, and Tire due to the formation of elemental metal vapor. TG analysis also showed the reduction of metal oxides by chars forming elemental metal vapor. Cu2S was the dominant Cu species in reducing atmosphere below 900 °C, which was responsible for the low volatility of Cu. The addition of PVC in wastes may enhance the release of heavy metals, while GB and Tire may play an opposite effect. In controlling heavy metal emission, aluminosilicate- and calcium-based sorbents can be co-treated with fuels. Moreover, pyrolysis can be a better choice for treatment of solid waster in terms of controlling heavy metals. PVC and Tire should be separated and treated individually due to high possibility of heavy metal emission. This information may then serve as a guideline for the design of the subsequent gas cleaning plant, necessary to reduce the final emissions to the atmosphere to an acceptable level.

Gallium isotopic evidence for extensive volatile loss from the Moon during its formation

PubMed Central

Kato, Chizu; Moynier, Frédéric

2017-01-01

The distribution and isotopic composition of volatile elements in planetary materials holds a key to the characterization of the early solar system and the Moon’s formation. The Moon and Earth are chemically and isotopically very similar. However, the Moon is highly depleted in volatile elements and the origin of this depletion is still debated. We present gallium isotopic and elemental measurements in a large set of lunar samples to constrain the origin of this volatile depletion. We show that while Ga has a geochemical behavior different from zinc, both elements show a systematic enrichment in the heavier isotopes in lunar mare basalts and Mg-suite rocks compared to the silicate Earth, pointing to a global-scale depletion event. On the other hand, the ferroan anorthosites are isotopically heterogeneous, suggesting a secondary distribution of Ga at the surface of the Moon by volatilization and condensation. The isotopic difference of Ga between Earth and the Moon and the isotopic heterogeneity of the crustal ferroan anorthosites suggest that the volatile depletion occurred following the giant impact and during the lunar magma ocean phase. These results point toward a Moon that has lost its volatile elements during a whole-scale evaporation event and that is now relatively dry compared to Earth. PMID:28782027

Vesicles in Apollo 15 Green Glasses: The Nature of Ancient Lunar Gases

NASA Technical Reports Server (NTRS)

Thomas-Keprta, K. L.; Clemett, S. J.; Berger, E. L.; Rahman, Z.; McKay, D. S.; Gibson, E. K.; Wentworth, S. J.

2014-01-01

Detailed studies of Apollo 15 green glass and related beads have shown they were formed in gas-rich fire fountains.. As the magmatic fluid became super-saturated in volatile gas, bubbles or vesicles formed within the magma. These exsolved gases became trapped within vesicles as the glasses were ejected from the fire-fountain and subsequently quenched. One of the keys to understanding formation processes on the ancient moon includes determining the composition of volatile species and elements, including metals, dissolved in magmatic gases. Here we report the nature of mineral phases spatially associated with vesicles in a green glass bead from Apollo sample 15411,42. The phases reflect the composition of the cooling/degassing magmatic vapors and fluids present at the time of bead formation approx, 3 Ga ago

Venus: Halide cloud condensation and volatile element inventories

NASA Technical Reports Server (NTRS)

Lewis, J. S.; Fegley, B., Jr.

1982-01-01

Several Venus cloud condensates, including A12C16 as well as halides, oxides and sulfides of arsenic and antimony, are assessed for their thermodynamic and geochemical plausibility. Aluminum chloride can confidently be ruled out, and condensation of arsenic sulfides on the surface will cause arsenic compounds to be too rare to produce the observed clouds. Antimony may conceivably be sufficiently volatile, but the expected molecular form is gaseous SbS, not the chloride. Arsenic and antimony compounds in the atmosphere will be regulated at very low levels by sulfide precipitation, irrespective of the planetary inventory of As and Sb. Thus the arguments for a volatile-deficient origin for Venus based on the depletion of water and mercury (relative to Earth) cannot be tested by a search for atmospheric arsenic or antimony.

The isotope composition of selenium in chondrites constrains the depletion mechanism of volatile elements in solar system materials

NASA Astrophysics Data System (ADS)

Vollstaedt, Hauke; Mezger, Klaus; Leya, Ingo

2016-09-01

Solar nebula processes led to a depletion of volatile elements in different chondrite groups when compared to the bulk chemical composition of the solar system deduced from the Sun's photosphere. For moderately-volatile elements, this depletion primarily correlates with the element condensation temperature and is possibly caused by incomplete condensation from a hot solar nebula, evaporative loss from the precursor dust, and/or inherited from the interstellar medium. Element concentrations and interelement ratios of volatile elements do not provide a clear picture about responsible mechanisms. Here, the abundance and stable isotope composition of the moderately- to highly-volatile element Se are investigated in carbonaceous, ordinary, and enstatite chondrites to constrain the mechanism responsible for the depletion of volatile elements in planetary bodies of the inner solar system and to define a δ 82 / 78 Se value for the bulk solar system. The δ 82 / 78 Se of the studied chondrite falls are identical within their measurement uncertainties with a mean of - 0.20 ± 0.26 ‰ (2 s.d., n = 14, relative to NIST SRM 3149) despite Se abundance depletions of up to a factor of 2.5 with respect to the CI group. The absence of resolvable Se isotope fractionation rules out a kinetic Rayleigh-type incomplete condensation of Se from the hot solar nebula or partial kinetic evaporative loss on the precursor material and/or the parent bodies. The Se depletion, if acquired during partial condensation or evaporative loss, therefore must have occurred under near equilibrium conditions to prevent measurable isotope fractionation. Alternatively, the depletion and cooling of the nebula could have occurred simultaneously due to the continuous removal of gas and fine particles by the solar wind accompanied by the quantitative condensation of elements from the pre-depleted gas. In this scenario the condensation of elements does not require equilibrium conditions to avoid isotope fractionation. The results further suggest that the processes causing the high variability of Se concentrations and depletions in ordinary and enstatite chondrites did not involve any measurable isotope fractionation. Different degrees of element depletions and isotope fractionations of the moderately-volatile elements Zn, S, and Se in ordinary and enstatite chondrites indicate that their volatility is controlled by the thermal stabilities of their host phases and not by the condensation temperature under canonical nebular conditions.

Origin of the Martian Moons and Their Volatile Abundances

NASA Astrophysics Data System (ADS)

Nakajima, M.; Canup, R. M.

2017-12-01

The origin of the Martian moons, Phobos and Deimos, has been actively debated. These moons were initially thought to have been gravitationally captured asteroids given that their spectra appeared to be similar to those of D-type asteroids. However, intact capture is difficult to reconcile with their nearly circular, co-planar orbits. Their orbits may be better explained by recent dynamical studies that suggest that the moons may have instead formed from a disk generated by a large impact, as was likely the case for Earth's Moon. Phobos and Deimos' bulk volatile contents, which are currently very uncertain, would also provide key constraints on their origin. If the moons were captured, their bulk compositions may be similar to those of asteroids, and their sub-surfaces could be volatile-rich. We are here exploring the implications of the alternative impact origin on the moon volatile abundances. We perform numerical simulations to estimate the extent of volatile loss from the moon-forming ejecta produced by a large impact with Mars. We find that hydrogen and water vapor escape hydrodynamically from the disk, leading to moons with dry, hydrogen-depleted bulk compositions. It is thus possible that the moons' mode of origin may be determined by knowledge of their volatile contents, because detection of a substantial (non-exogenically delivered) water content would argue strongly against formation by impact. JAXA's Martian Moons eXploration Mission (MMX) will conduct detailed remote sensing of the moons, including a gamma ray and neutron spectrometer that will for the first time probe their sub-surface elemental compositions, and will return samples from Phobos for laboratory analysis. This should allow for characterization of the moon volatile abundances. We also discuss that the inferred high porosities of these moons could be explained if they are rubble piles formed during accretion from impact-produced ejecta.

Distribution of Alkalis (Na, Cs, Rb) Between Silicate and Sulfide: Implications for Planetary Volatile Depletion

NASA Technical Reports Server (NTRS)

Boujibar, A.; Fei, Y.; Righter, K.; Du, Z.; Bullock, E.

2018-01-01

The abundances of volatile elements in the Earth's mantle are correlated with their temperatures of condensation. This depletion can be due to either incomplete condensation of the elements during the nebula condensation or evaporation processes during planetary growth. Elements that have affinities with metals (siderophile) and sulfides (chalcophile) are additionally depleted due to their segregation into the core. Therefore, study of lithophile elements could be useful to isolate processes of volatilization and their effect on the abundance of the elements in the Earth's mantle. However, the correlation of these lithophile elements including alkali elements, with their temperatures of condensation shows a significant scatter, which is difficult to reconcile with a depletion by vaporization or incomplete condensation alone.

Abundances of sodium, sulfur, and potassium in lunar volcanic glasses: Evidence for volatile loss during eruption

NASA Technical Reports Server (NTRS)

Delano, J. W.; Mcguire, J.

1992-01-01

Six varieties of lunar volcanic glass are known to occur within the Apollo 17 sample collection. Investigations have shown that 25 volatile elements are known to be concentrated on the exterior surfaces of individual volcanic glass spheres. Since bulk analyses of volcanic glass provide an integrated abundance of an element on and with the glass spherules, other methods must be relied on to determine the interior abundance of an element. The interior abundance of an element with a volcanic glass sphere establishes the abundance of that element in the melt at the time of quench. The current study is part of a comprehensive attempt to measure the abundance of three volatile elements (Na, S, and K) within representative spheres of the 25 varieties of lunar volcanic glass currently known to exist at the Apollo landing sites. Comparison of the measured abundances of these elements within the interiors of individual glasses with bulk analyses and crystalline mare basalts will furnish new constraints on the geochemical behavior of volatile elements during lunar mare volcanism.

Distribution of 28 elements in size fractions of lunar mare and highlands soils

NASA Technical Reports Server (NTRS)

Boynton, W. V.; Wasson, J. T.

1977-01-01

Four volatile, six siderophile and 18 generally lithophile elements were determined in six sieve fractions of mare soil 15100 (moderately mature) and seven sieve fractions of highlands soil 66080 (highly mature). Previous work (Boynton et al., 1976) showed that the volatile elements in lunar soils were enriched in the finest size fraction relative to the coarsest factors by up to about 20. The present investigation tests Boynton's interpretation that the distribution pattern of the volatiles indicates the presence of two components: a volume-correlated component having volatile concentrations independent of grain size and a surface-correlated component with concentration increasing with decreasing grain size.

Volatile and light lithophile elements in high-anorthite plagioclase-hosted melt inclusions from Iceland

NASA Astrophysics Data System (ADS)

Neave, David A.; Hartley, Margaret E.; Maclennan, John; Edmonds, Marie; Thordarson, Thorvaldur

2017-05-01

Melt inclusions formed during the early stages of magmatic evolution trap primitive melt compositions and enable the volatile contents of primary melts and the mantle to be estimated. However, the syn- and post-entrapment behaviour of volatiles in primitive high-anorthite plagioclase-hosted melt inclusions from oceanic basalts remains poorly constrained. To address this deficit, we present volatile and light lithophile element analyses from a well-characterised suite of nine matrix glasses and 102 melt inclusions from the 10 ka Grímsvötn tephra series (i.e., Saksunarvatn ash) of Iceland's Eastern Volcanic Zone (EVZ). High matrix glass H2O and S contents indicate that eruption-related exsolution was arrested by quenching in a phreatomagmatic setting; Li, B, F and Cl did not exsolve during eruption. The almost uniformly low CO2 content of plagioclase-hosted melt inclusions cannot be explained by either shallow entrapment or the sequestration of CO2 into shrinkage bubbles, suggesting that inclusion CO2 contents were controlled by decrepitation instead. High H2O/Ce values in primitive plagioclase-hosted inclusions (182-823) generally exceed values expected for EVZ primary melts (∼ 180), and can be accounted for by diffusive H2O gain following the entrainment of primitive macrocrysts into evolved and H2O-rich melts a few days before eruption. A strong positive correlation between H2O and Li in plagioclase-hosted inclusions suggests that diffusive Li gain may also have occurred. Extreme F enrichments in primitive plagioclase-hosted inclusions (F/Nd = 51-216 versus ∼15 in matrix glasses) possibly reflect the entrapment of inclusions from high-Al/(Al + Si) melt pools formed by dissolution-crystallisation processes (as indicated by HFSE depletions in some inclusions), and into which F was concentrated by uphill diffusion since F is highly soluble in Al-rich melts. The high S/Dy of primitive inclusions (∼300) indicates that primary melts were S-rich in comparison with most oceanic basalts. Cl and B are unfractionated from similarly compatible trace elements, and preserve records of primary melt heterogeneity. Although primitive plagioclase-hosted melt inclusions from the 10 ka Grímsvötn tephra series record few primary signals in their volatile contents, they nevertheless record information about crustal magma processing that is not captured in olivine-hosted melt inclusions suites.

Volatile Content of the Mid-ocean Ridge Mantle Inferred from Off-axis Seamounts and Intra-transform Lavas

NASA Astrophysics Data System (ADS)

Shimizu, K.; Saal, A. E.; Hauri, E. H.; Nagle, A.; Forsyth, D. W.; Niu, Y.

2011-12-01

Off-axis seamounts and intra-transform lavas provide more direct geochemical information of the mantle than axial lavas. These smaller volumes of melts undergo lower extent of crystal fractionation and mixing compared to basalts erupting within the ridge axis due to a lack of long-lived magma chambers or along axis melt migration. Therefore, their study provide not only a more reliable approach to determine the volatile content of the intrinsic components forming the Earth's upper mantle, but also help constrain mantle convection, heterogeneity, and crustal recycling. Samples from the Quebrada-Discovery-Gofar (QDG) transform fault system (EPR 3°-5°S) and from northern EPR seamounts (5°-15° N) were collected during KN182-13 (R/V Knorr) and RAIT 02 (R/V Thomas Washington) expeditions, respectively. 159 submarine glasses were analyzed for major elements, trace elements, and volatile elements by triplicate analyses, as well as for Sr and Nd isotopes in a subset of samples. The QDG and northern EPR seamounts have similar trace element and isotopic composition that is consistent with melting of two-component mantle common to both regions. The degree of trace element enrichment (e.g. Th/La), isotopic composition, and depth of melt segregation (e.g. Sm/Yb) have a positive correlation and range from ultra depleted to relatively enriched compositions. In order to investigate the primary volatile content of submarine glasses we first considered shallow level processes, such as volatile degassing, sulfide saturation and interaction of melt with hydrothermally altered material. The vapor-melt equilibrium pressure (Dixon et al., 1995) indicates that the majority of the samples were super-saturated in CO2-H2O vapor at the pressure of eruption, which implies rapid magma ascent rate that prevented complete CO2 degassing. Samples that were sulfide saturated (Liu et al., 2007) and contaminated by seawater or seawater derived material (high Cl/K) were filtered out. F/Nd, Cl/K, and H2O/Ce ratios in our samples positively correlate with Th/La, Sm/Yb, and isotope ratios suggesting that the enriched mantle component is also enriched in volatile contents. S/Dy ratios are the exception, with relatively constant values in both enriched, and depleted basalts. Although it has been argued that correlation between Sr, Nd and Pb isotope ratios and fractionation corrected major element in seamount samples indicate different mantle lithologies under the mid-ocean ridges, we will show that such correlation might be an artifact of ignoring the effect of water during the correction for fractional crystallization. [1] Dixon et al. (1995) J. Pet., 36, 1607-1631. [2] Liu et al. (2007) Geochim Cosmochim Ac., 71, 1783-1799.

Trace elements in primitive meteorites—VII Antarctic unequilibrated ordinary chondrites

NASA Astrophysics Data System (ADS)

Wang, Ming-Sheng; Lipschutz, Michael E.

2007-02-01

We report RNAA results for Co, Au, Sb, Ga, Rb, Cs, Se, Ag, Te, Zn, In, Bi, Tl and Cd (in increasing order of metamorphic mobility) in 22 Antarctic unequilibrated ordinary chondrites (UOC). This brings to 38 the number of UOC for which data for highly volatile elements are known. For elements of lesser mobility (Co to Se, omitting Cs) overall variability in UOC are low, relative standard deviations (one sigma) being no more than a factor of two. For Ag, Te and Zn, relative standard deviations are 2-4×, while for Cs and the four most volatile elements, the variabilities are 8-110×. Elemental abundances do not vary with chemical type (H, L and LL) nor with UOC subtype (3.0-3.9). Contents of all elements reach levels up to, even exceeding, cosmic and all but Cd and the two alkalis, seem unaffected by post-accretionary processes. Contents of highly volatile elements are consistent with the idea that source regions producing contemporary falls and older Antarctic UOC differed in thermal histories. The presence or absence of carbide magnetite assemblages (CMA) generally accords with high or low Cd contents, respectively. This relationship accords with the prior suggestion that CMA formed by alteration of Fe-Ni metal by C-O-H-containing fluids at temperatures <700 K, generated by thermal metamorphism in parent body interiors. The absence of CMA in most UOC (and OC), may indicate that they were subsequently destroyed as metamorphic intensity increased. The high, often supercosmic, Rb and Cs levels in UOC may result from their high solubility in liquid water signalling their redistribution by C-O-H-containing fluid while in the liquid water field. Because of its uniquely high mobility, Cd could have been enriched by the C-O-H fluids and should have been lost from parent regions during later, higher temperature anhydrous metamorphism at temperatures in the 500-600 °C range.

Na, Rb and Cs partitioning between metal, silicate and sulfide: Implications for volatile depletion in terrestrial planets

NASA Astrophysics Data System (ADS)

Boujibar, A.; Fei, Y.; Du, Z.; Righter, K.; Bullock, E. S.

2017-12-01

Inner Solar System materials are known for their depletion in volatile elements, including the moderately volatile alkalis: Na, K, Rb, and Cs. The origin of this depletion is still uncertain, as several processes could have been involved, during the nebular condensation or planetary accretion. Volatile depletion is commonly estimated through comparison of alkali concentrations relatively to those of chondrites, assuming they remain in planetary mantles during core segregation. However, experimental studies show that substantial K can partition into metals that are enriched in sulfur and oxygen. Several models have also suggested that sulfides may have played an important role during episodes of sulfide segregation from a crystallizing magma ocean (sulfide matte) or accretion of S-rich planetary embryos. For Mercury, a sulfide layer could be present between core and mantle, due to immiscibility between Si-rich and S-rich metals. Therefore, here we investigate whether alkali elements (Na, Cs and Rb) could be partly sequestered in planetary cores during their differentiation. We conducted experiments at high pressure and temperature (1 to 5 GPa and up to 1900 °C) to determine partition coefficients of Na, Rb and Cs between metal and silicate. Our results show that pressure, temperature, sulfur and oxygen in metals enhance the partitioning of Na, Rb and Cs into metals, as previously found for K. For all three investigated alkalis (Na, Rb and Cs), we found a maximum partition coefficient of 1 between sulfides containing 13 wt% O and silicate melt. Therefore, S-rich cores or sulfide layers formed due to immiscibility in Fe-S-O systems could have acted as important geochemical reservoirs for alkali elements. Using our experimental data and different assumptions on initial bulk abundances, we evaluate volatile depletion in terrestrial planets, by comparing resulting mantle alkali concentrations after core segregation, with actual concentrations in the Earth's mantle.

Trace element partitioning behavior of coal gangue-fired CFB plant: experimental and equilibrium calculation.

PubMed

Zhang, Yingyi; Nakano, Jinichiro; Liu, Lili; Wang, Xidong; Zhang, Zuotai

2015-10-01

Energy recovery is a promising method for coal gangue utilization, during which the prevention of secondary pollution, especially toxic metal emission, is a significant issue in the development of coal gangue utilization. In the present study, investigation into trace element partitioning behavior from a coal gangue-fired power plant in Shanxi province, China, has been conducted. Besides the experimental analysis, thermodynamic equilibrium calculation was also conducted to help the further understanding on the effect of different parameters. Results showed that Hg, As, Be, and Cd were highly volatile elements in the combustion of coal gangue, which were notably enriched in fly ash and may be emitted into the environment via the gas phase. Cr and Mn were mostly non-volatile and were enriched in the bottom ash. Pb, Co, Zn, Cu, and Ni were semi-volatile elements and were enriched in the fly ash to varying degrees. Equilibrium calculations show that the air/fuel ratio and the presence of Cl highly affect the element volatility. The presence of mineral phases, such as aluminosilicates, depresses the volatility of elements by chemical immobilization and competition in Cl. The coal gangue, fly ash, and bottom ash all passed the toxicity characteristic leaching procedure (TCLP), and their alkalinity buffers the acidity of the solution and contributes to the low solubility of the trace elements.

A Novel Inlet System for On-line Chemical Analysis of Semi-Volatile Submicron Particulate Matter

NASA Astrophysics Data System (ADS)

Wisthaler, A.; Eichler, P.; Müller, M.

2015-12-01

Semi-volatile organic molecules bound to particles are difficult to measure, especially if they are reactive in nature. Any technique based on aerosol collection onto a substrate generates sampling artifacts due to surface reactions and ad- and desorption of semi-volatile analytes. On-line sampling without sample pre-collection, as for example implemented in the AMS, has greatly reduced many sampling artifacts. AMS measurements of organics do, however, suffer from the drawback that molecular-level information is, in most cases, lost during hard ionization events. As a consequence, only little speciated and thus mechanistically informative data on organic matter is obtained. PTR-ToF-MS is a well-established on-line measurement technique for gas-phase organics. Soft ionization via gas-phase hydronium ions preserves, to a large extent, molecular-level information and thus allows identifying organic compounds at an elemental composition level. We have recently developed a particle inlet system for PTR-ToF-MS instruments (doi:10.5194/amt-8-1353-2015). The CHARON ("Chemical Analysis of Aerosol On-line") inlet consists of a gas-phase denuder, an aerodynamic lens and a thermodesorption unit. In its latest version, it includes a heatable tube upstream of the denuder to form a thermodenuder. Over the last year, the CHARON PTR-ToF-MS system has been successfully used in a series of measurement campaigns to characterize i) POA emitted from a marine diesel engine, ii) SOA generated from the photo-oxidation of toluene, iii) SOA generated from the photo-oxidation of selected amines, iv) ambient aerosol in two major European cities and v) SOA generated from the photo-oxidation of biogenic VOCs. These measurements have demonstrated that the CHARON PTR-ToF-MS system i) generates on-line and real-time elemental composition information of semi-volatile organics in submicron particles (both POA and SOA), ii) detects 80-100 % of the organic mass as measured by the AMS and iii) generates volatility information of semi-volatile organics at an elemental composition level. Selected application examples will be shown.

The abundance and relative volatility of refractory trace elements in Allende Ca,Al-rich inclusions - Implications for chemical and physical processes in the solar nebula

NASA Technical Reports Server (NTRS)

Kornacki, Alan S.; Fegley, Bruce, Jr.

1986-01-01

The relative volatilities of lithophile refractory trace elements (LRTE) were determined using calculated 50-percent condensation temperatures. Then, the refractory trace-element abundances were measured in about 100 Allende inclusions. The abundance patterns found in Allende Ca,Al-rich inclusions (CAIs) and ultrarefractory inclusions were used to empirically modify the calculated LRTE volatility sequence. In addition, the importance of crystal-chemical effects, diffusion constraints, and grain transport for the origin of the trace-element chemistry of Allende CAIs (which have important implications for chemical and physical processes in the solar nebula) is discussed.

A modification of the U.S. Geological Survey one-sixth order semiquantitative spectrographic method for the analysis of geologic materials that improves limits of determination of some volatile to moderately volatile elements

USGS Publications Warehouse

Detra, D.E.; Cooley, Elmo F.

1988-01-01

A modification of the one-sixth order semi-quantitative emission spectrographic method for the analysis of 30 elements in geologic materials (Grimes and Marranzino 1968) improves the limits of determination of some volatile to moderately volatile elements. The modification uses a compound-pendulum-mounted filter to regulate the amount of emitted light passing into the spectrograph. One hundred percent transmission of emitted light is allowed during the initial 20 seconds of the burn, then continually reduced to 40 percent over the next 32 seconds using the pendulum-mounted filter, and followed by an additional 68 seconds of burn time. The reduction of light transmission during the latter part of the burn decreases spectral background and the line emission of less volatile elements commonly responsible for problem-causing interferences. The sensitivity of the method for some geochemically important trace elements commonly determined in mineral exploration (Ag, As, Au, Be, Bi, Cd, Cr, Cu, Pb, Sb, Sn, and Zn) is improved up to five-fold under ideal conditions without compromising precision or accuracy

Volatile element loss during planetary magma ocean phases

NASA Astrophysics Data System (ADS)

Dhaliwal, Jasmeet K.; Day, James M. D.; Moynier, Frédéric

2018-01-01

Moderately volatile elements (MVE) are key tracers of volatile depletion in planetary bodies. Zinc is an especially useful MVE because of its generally elevated abundances in planetary basalts, relative to other MVE, and limited evidence for mass-dependent isotopic fractionation under high-temperature igneous processes. Compared with terrestrial basalts, which have δ66Zn values (per mille deviation of the 66Zn/64Zn ratio from the JMC-Lyon standard) similar to some chondrite meteorites (∼+0.3‰), lunar mare basalts yield a mean δ66Zn value of +1.4 ± 0.5‰ (2 st. dev.). Furthermore, mare basalts have average Zn concentrations ∼50 times lower than in typical terrestrial basaltic rocks. Late-stage lunar magmatic products, including ferroan anorthosite, Mg- and Alkali-suite rocks have even higher δ66Zn values (+3 to +6‰). Differences in Zn abundance and isotopic compositions between lunar and terrestrial rocks have previously been interpreted to reflect evaporative loss of Zn, either during the Earth-Moon forming Giant Impact, or in a lunar magma ocean (LMO) phase. To explore the mechanisms and processes under which volatile element loss may have occurred during a LMO phase, we developed models of Zn isotopic fractionation that are generally applicable to planetary magma oceans. Our objective was to identify conditions that would yield a δ66Zn signature of ∼+1.4‰ within the lunar mantle. For the sake of simplicity, we neglect possible Zn isotopic fractionation during the Giant Impact, and assumed a starting composition equal to the composition of the present-day terrestrial mantle, assuming both the Earth and Moon had zinc 'consanguinity' following their formation. We developed two models: the first simulates evaporative fractionation of Zn only prior to LMO mixing and crystallization; the second simulates continued evaporative fractionation of Zn that persists until ∼75% LMO crystallization. The first model yields a relatively homogenous bulk solid LMO δ66Zn value, while the second results in a stratification of δ66Zn values within the LMO sequence. Loss and/or isolation mechanisms for volatiles are critical to these models; hydrodynamic escape was not a dominant process, but loss of a nascent lunar atmosphere or separation of condensates into a proto-lunar crust are possible mechanisms by which volatiles could be separated from the lunar interior. The results do not preclude models that suggest a lunar volatile depletion episode related to the Giant Impact. Conversely, LMO models for volatile loss do not require loss of volatiles prior to lunar formation. Outgassing during planetary magma ocean phases likely played a profound role in setting the volatile inventories of planets, particularly for low mass bodies that experienced the greatest volatile loss. In turn, our results suggest that the initial compositions of planets that accreted from smaller, highly differentiated planetesimals were likely to be severely volatile depleted.

Geochemical zoning and early differentiation in the moon

NASA Technical Reports Server (NTRS)

Taylor, S. R.; Jakes, P.

1977-01-01

The volatile elements (e.g., Rb, Pb, Tl, Bi, Cs) seem to have been depleted at the time of lunar accretion. Accordingly, it may be assumed that the moon initially accreted from refractory material. The good correlation between volatile/involatile element ratios (e.g., Cs/U, K/La, K/Zr) in both highland and maria samples means that element distribution in lunar crustal rocks is not governed by volatility differences. This and other evidence encourages the view that the moon was accreted homogeneously. A consequence of homogeneous accretion theories is that very efficient large-scale element fractionation is required to account both for the high near-surface concentrations of refractory elements (e.g., Th, U, REE, Zr, Ba, etc.) and for the Ca-Al-rich crust.

Distribution, movement, and evolution of the volatile elements in the lunar regolith

NASA Technical Reports Server (NTRS)

Gibson, E. K., Jr.

1975-01-01

The abundances and distributions of carbon, nitrogen, and sulfur in lunar soils are reviewed. Carbon and nitrogen have a predominantly extra-lunar origin in lunar soils and breccias, while sulfur is mostly indigeneous to the moon. The lunar processes which effect the movement, distribution, and evolution of carbon, nitrogen, and sulfur, along with the volatile alkali elements sodium, potassium, and rubidium during regolith processes are discussed. Possible mechanisms which may result in the addition to or loss from the moon of these volatile elements are considered.

Zoned chondrules in Semarkona: Evidence for high-and low-temperature processing

USGS Publications Warehouse

Grossman, J.N.; Alexander, C.M. O'D.; Wang, Jingyuan; Brearley, A.J.

2002-01-01

At least 15% of the low-FeO chondrules in Semarkona (LL3.0) have mesostases that are concentrically zoned in Na, with enrichments near the outer margins. We have studied zoned chondrules using electron microprobe methods (x-ray mapping plus quantitative analysis), ion micropobe analysis for trace elements and hydrogen isotopes, cathodoluminescence imaging, and transmission electron microscopy in order to determine what these objects can tell us about the environment in which chondrules formed and evolved. Mesostases in these chondrules are strongly zoned in all moderately volatile elements and H (interpreted as water). Calcium is depleted in areas of volatile enrichment. Titanium and Cr generally decrease toward the chondrule surfaces, whereas Al and Si may either increase or decrease, generally in opposite directions to one another; Mn follows Na in some chondrules but not in others; Fe and Mg are unzoned. D/H ratios increase in the water-rich areas of zoned chondrules. Mesostasis shows cathodoluminescence zoning in most zoned chondrules, with the brightest yellow color near the outside. Mesostasis in zoned chondrules appears to be glassy, with no evidence for devitrification. Systematic variations in zoning patterns among pyroxene- and olivine-rich chondrules may indicate that fractionation of low- and high-Ca pyroxene played some role in Ti, Cr, Mn, Si, Al, and some Ca zoning. But direct condensation of elements into hot chondrules, secondary melting of late condensates into the outer portions of chondrules, and subsolidus diffusion of elements into warm chondrules cannot account for the sub-parallel zoning profiles of many elements, the presence of H2O, or elemental abundance patterns. Zoning of moderately volatile elements and Ca may have been produced by hydration of chondrule glass without devitrification during aqueous alteration on the parent asteroid. This could have induced structural changes in the glass allowing rapid diffusion and exchange of elements between altered glass and surrounding matrix and rim material. Calcium was mainly lost during this process, and other nonvolatile elements may have been mobile as well. Some unzoned, low-FeO chondrules appear to have fully altered mesostasis.

Chemical diffusion during isobaric degassing of magma

NASA Astrophysics Data System (ADS)

von Aulock, Felix W.; Kennedy, Ben M.; Lavallée, Yan; Henton-de Angelis, Sarah; Oze, Christopher; Morgan, Daniel J.; Clesham, Steve

2014-05-01

During ascent of magma, volatiles exsolve and bubbles form. Volatiles can either escape through a permeable network of bubbles in an open system or be trapped in non-connected pores during closed system degassing. Geochemical studies have shown that in most cases both- open system and closed system degassing take place at the same time. During cooling of the melt, diffusion slows down and eventually diffusional gradients get frozen in, preserving a history of degassing and rehydration during bubble growth, bubble collapse and crystal growth. We present data from experiments in which natural obsidian was degassed at atmospheric pressures at 950ºC over timescales of 3-24h. During bubble growth, a skin formed, at the outer edge of the sample, effectively prohibiting any degassing of its interior. Diffusion gradients were measured across the glass surrounding vesicles, and across this impermeable skin. Water contents were analyzed with synchrotron sourced Fourier transform infrared spectroscopy and several major, minor and trace elements were mapped using synchrotron sourced X-ray fluorescence spectroscopy. The samples show a dimpled surface, as well as signs of oxidation and growth of submicroscopic crystals. Water contents around bubbles decrease in simple heating experiments (from ~0.13 wt. % down to ~0.1 wt. %), whereas slight rehydration of the vesicle wall can be observed when a second, cooler step at 850ºC follows the initial 950ºC. Water gradients towards the outside of the sample decrease linearly to a minimum of ~0.045 wt. %, far below the solubility of water in melts at these temperatures. We mapped the distribution of K, Ca, Fe, Ti, Mn, Rb, Sr, Y and Zr. Especially the trace elements show a decrease towards the outside of the sample, whereas K, Fe, Ca and Ti generally do not show significant partitioning between melt and gas/crystal phase. Several effects could attribute to the distribution of these elements, such as the crystal growth and exchange with atmospheric oxygen, and detailed models of the diffusion of these elements will have to verify the mechanisms of elemental partitioning during degassing Our experiments show that even on a small scale, open system and closed system degassing inherently coexist. This manifests itself in different elemental distribution in the quenched glass. Water distribution gradients can be explained with diffusion during exsolution and rehydration during cooling, however, the surface of the sample is undersaturated in water. Some trace elements follow the same pattern, even though they might not be considered as volatile. Therefore we suggest that chemical gradients may be partially induced by the growth of sub-microscopic crystals and by exchange with the atmosphere. Crystal rich, volatile poor outer skins, as produced in the experiments of this study, have locally drastically increased viscosities and can therefore withstand higher pressures during foaming of the interior of the sample. This self sealing of magma could be an important process on different scales of magma degassing, from bread crust bombs to rising magma in conduits.

On volatile element trends in gas-rich meteorites

NASA Technical Reports Server (NTRS)

Bart, G.; Lipschutz, M. E.

1979-01-01

Ten volatile elements (and non-volatile Co) in co-existing light and dark portions of 5 gas-rich chondrites were studied. Patterns of distinct but non-uniform enrichment by dark admixing material are revealed. The dark admixing material is enriched in Cs; Bi and Tl covary in it. It is compositionally unique from known types of primitive materials and is apparently not derived by secondary processes from such materials.

Trace Element Study of H Chondrites: Evidence for Meteoroid Streams.

NASA Astrophysics Data System (ADS)

Wolf, Stephen Frederic

1993-01-01

Multivariate statistical analyses, both linear discriminant analysis and logistic regression, of the volatile trace elemental concentrations in H4-6 chondrites reveal compositionally distinguishable subpopulations. Observed difference in volatile trace element composition between Antarctic and non-Antarctic H4-6 chondrites (Lipschutz and Samuels, 1991) can be explained by a compositionaily distinct subpopulation found in Victoria Land, Antarctica. This population of H4-6 chondrites is compositionally distinct from non-Antarctic H4-6 chondrites and from Antarctic H4 -6 chondrites from Queen Maud Land. Comparisons of Queen Maud Land H4-6 chondrites with non-Antarctic H4-6 chondrites do not give reason to believe that these two populations are distinguishable from each other on the basis of the ten volatile trace element concentrations measured. ANOVA indicates that these differences are not the result of trivial causes such as weathering and analytical bias. Thermoluminescence properties of these populations parallels the results of volatile trace element comparisons. Given the differences in terrestrial age between Victoria Land, Queen Maud Land, and modern H4-6 chondrite falls, these results are consistent with a variation in H4-6 chondrite flux on a 300 ky timescale. This conclusion requires the existence of co-orbital meteoroid streams. Statistical analyses of the volatile trace elemental concentrations in non-Antarctic modern falls of H4-6 chondrites also demonstrate that a group of 13 H4-6 chondrites, Cluster 1, selected exclusively for their distinct fall parameters (Dodd, 1992) is compositionally distinguishable from a control group of 45 non-Antarctic modern H4-6 chondrites on the basis of the ten volatile trace element concentrations measured. Model-independent randomization-simulations based on both linear discriminant analysis and logistic regression verify these results. While ANOVA identifies two possible causes for this difference, analytical bias and group classification, a test validation experiment verifies that group classification is the more significant cause of compositional difference between Cluster 1 and non-Cluster 1 modern H4-6 chondrite falls. Thermoluminescence properties of these populations parallels the results of volatile trace element comparisons. This suggests that these meteorites are fragments of a co-orbital meteorite stream derived from a single parent body.

Angrites: A Volatile-rich Variety of Asteroidal Basalt (Except for Alkalis and Gallium!)

NASA Astrophysics Data System (ADS)

Warren, P. H.; Kallemeyn, G. W.

1995-09-01

Angrites are commonly viewed as extremely volatile-depleted, and a related notion is that they formed by differentiation of a very CAI-rich material [e.g., 1]. Partial melting experiments reportedly reproduce the bulk compositions (although not fassaite-rich mineralogy) of angrites with Allende as starting material [2], but highly CAI-rich parent materials are difficult to reconcile with isotopic and REE data [3,4]. Mittlefehldt and Lindstrom [5] inferred from the low Na/Al ratios of angrites that outgassing, and thus primordial magmatism, was more intense on their parent body than on the eucrite parent asteroid. Of seven elements that (a) have been adequately determined in angrites, and (b) are far more volatile (solar-nebula 50% condensation T [6] = 690-430 K) than the alkalis (1000-910 K), four are enriched, and none is significantly depleted, in average angrite compared to average eucrite or low-Ti mare basalt (Figure). Gallium, which is of intermediate volatility (830 K), is depleted to roughly the same extent as Na and K. Results for A881371 [3] are incomplete (Zn, 6 micrograms/g, is near INAA detection limit), but even based only on AdoR and the two LEW angrites, this pattern seems firmly established. Apparent gas cavities in A881371 [7] also suggest that volatiles are far from uniformly depleted. The only elements known to be depleted, as volatiles, by clearly significant factors in angrites versus eucrites or lunar basalts, are alkalis plus gallium. Besides being moderately volatile, a noteworthy characteristic shared among Ga and alkalis (and not shared with elements such as Br, Se, and Zn) is that these elements probably tend to partition into crustal feldspar during gross differentiation of small (low-pressure) bodies. If gallium + alkalis were depleted by a single process starting from "normal" chondritic material, that process would seem to require selective exposure of a feldspar-enriched region (i.e., crust) to extremely high temperature. Igneous crystallization of the angrites occurred when the solar system was still extremely young, and apparently <=2 Ma after the volatile-depletion process [4]. The data of [4] eliminate 26Al as a potential heat source for magmatism. The angrite volatile pattern may be the product of heating by an intense, short-lived heat source that melted and partially vaporized the crust of an asteroid(s) (not necessarily the final angrite asteroid), without much affecting the deep interior(s), which later (through mixing and/or magmatism) replenished the angritic materials in most volatiles, but not alkalis and Ga. Exogenic heating, as in the often-conjectured (but hard to test) hypothesis that a major early heat source was enhanced solar luminosity (as in FU-Orionis cycles), would seem to be required. LEW 87051 and A881371 are rich in compositionally diverse olivine xenocrysts, and A881371 contains a possible FeS xenocryst [7]. These, and the angrites' great siderophile diversity [3], tend to suggest that magmatism and intensely disruptive cratering (with mixing of precursor materials) were contemporaneous. This scenario is admittedly speculative, but the volatile-depletion pattern is difficult to rationalize with any other model. References: [1] Prinz M. and Weisberg M. (1995) Antarct. Meteorites, XX, 207-210. [2] Jurewicz A. et al. (1993) GCA, 57, 2123-2139. [3] Warren P. et al. (1995) Antarct. Meteorites, XX, 261-264. [4] Lugmair G. and Galer S. 1992) GCA, 56, 1673-1694. [5] Mittlefehldt D. and Lindstrom M. (1990) GCA, 54, 3209-3218. [6] Wasson J. (1985) Meteorites. [7] Warren P. and Davis A. (1995) Antarct. Meteorites, XX, 257-260.

Effect of additives on the volatility of elements in a DC arc during the atomic emission analysis of nickel(II) oxide

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

Zolotareva, N.I.; Kuzyakov, Yu.Ya.; Khlystova, A.D.

1986-10-20

The authors have studied the effect of traditional halogenating additives, AgCl, CdF/sub 2/, PTFE and that of an effective additive they have selected, ZnF/sub 2/, on the volatility of impurity elements, viz. tungsten, molybdenum, titanium, and zirconium from nickel (II) oxide, and determined the constants for the average relative volatility of the elements by the method of Kantor and Pungor. The results have been used to lower the limits of detection of the impurities cited in nickel(II) oxide.

The Chlorine Isotopic Composition Of Lunar UrKREEP

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

2016-01-01

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

Inefficient volatile loss from the Moon-forming disk: Reconciling the giant impact hypothesis and a wet Moon

NASA Astrophysics Data System (ADS)

Nakajima, Miki; Stevenson, David J.

2018-04-01

The Earth's Moon is thought to have formed from a circumterrestrial disk generated by a giant impact between the proto-Earth and an impactor approximately 4.5 billion years ago. Since this impact was energetic, the disk would have been hot (4000-6000 K) and partially vaporized (20-100% by mass). This formation process is thought to be responsible for the geochemical observation that the Moon is depleted in volatiles (e.g., K and Na). To explain this volatile depletion, some studies suggest the Moon-forming disk was rich in hydrogen, which was dissociated from water, and it escaped from the disk as a hydrodynamic wind accompanying heavier volatiles (hydrodynamic escape). This model predicts that the Moon should be significantly depleted in water, but this appears to contradict some of the recently measured lunar water abundances and D/H ratios that suggest that the Moon is more water-rich than previously thought. Alternatively, the Moon could have retained its water if the upper parts (low pressure regions) of the disk were dominated by heavier species because hydrogen would have had to diffuse out from the heavy-element rich disk, and therefore the escape rate would have been limited by this slow diffusion process (diffusion-limited escape). To identify which escape the disk would have experienced and to quantify volatiles loss from the disk, we compute the thermal structure of the Moon-forming disk considering various bulk water abundances (100-1000 ppm) and mid-plane disk temperatures (2500-4000 K). Assuming that the disk consists of silicate (SiO2 or Mg2SiO4) and water and that the disk is in the chemical equilibrium, our calculations show that the upper parts of the Moon-forming disk are dominated by heavy atoms or molecules (SiO and O at Tmid > 2500- 2800 K and H2O at Tmid < 2500- 2800 K) and hydrogen is a minor species. This indicates that hydrogen escape would have been diffusion-limited, and therefore the amount of lost water and hydrogen would have been small compared to the initial abundance assumed. This result indicates that the giant impact hypothesis can be consistent with the water-rich Moon. Furthermore, since the hydrogen wind would have been weak, the other volatiles would not have escaped either. Thus, the observed volatile depletion of the Moon requires another mechanism.

The Origin of Organic Matter in the Solar System: Evidence from Interplanetary Dust Particles

NASA Technical Reports Server (NTRS)

Flynn, G. J.; Keller, L. P.; Jacobsen, C.; Wirick, S.

2001-01-01

The origin of the organic matter in interplanetary materials has not been established. A variety of mechanisms have been proposed, with two extreme cases being a Fisher-Tropsch type process operating in the gas phase of the solar nebula or a Miller-Urey type process, which requires interaction with an aqueous fluid, presumably occurring on an asteroid. In the Fisher-Tropsch case, we might expect similar organic matter in hydrated and anhydrous interplanetary materials. However, aqueous alteration is required in the case of the Miller-Urey process, and we would expect to see organic matter preferentially in interplanetary materials that exhibit evidence of aqueous activity, such as the presence of hydrated silicates. The types and abundance of organic matter in meteorites have been used as an indicator of the origin of organic matter in the Solar System. Indigenous complex organic matter, including amino acids, has been found in hydrated carbonaceous chondrite meteorites, such as Murchison. Much lower amounts of complex organic matter, possibly only terrestrial contamination, have been found in anhydrous carbonaceous chondrite meteorites, such as Allende, that contain most of their carbon in elemental form. These results seem to favor production of the bulk of the organic matter in the Solar System by aqueous processing on parent bodies such as asteroids, a Miller-Urey process. However, the hydrated carbonaceous chondrite meteorites have approximately solar abundances of the moderately volatile elements, while all anhydrous carbonaceous chondrite meteorites have significantly lower contents of these moderately volatile elements. Two mechanisms, incomplete condensation or evaporation, both of which involve processing at approx. 1200 C, have been suggested to explain the lower content of the moderately volatile elements in all anhydrous meteorites. Additional information is contained in the original extended abstract.

Major, Trace, and Volatile (CO2, H2O, S, F, and Cl) Elements from 1000+ Hawaiian Olivine-hosted Melt Inclusions Reveal the Dynamics of Crustal Recycling

NASA Astrophysics Data System (ADS)

Marske, J. P.; Hauri, E. H.; Trusdell, F.; Garcia, M. O.; Pietruszka, A. J.

2015-12-01

Global cycling of volatile elements (H2O, CO2, F, S, Cl) via subduction to deep mantle followed by entrainment and melting within ascending mantle plumes is an enigmatic process that controls key aspects of hot spot volcanism (i.e. melting rate, magma supply, degassing, eruptive style). Variations in radiogenic isotope ratios (e.g.187Os/188Os) at hot spots such as Hawaii reveal magmatic processes within deep-seated mantle plumes (e.g. mantle heterogeneity, lithology, and melt transport). Shield-stage lavas from Hawaii likely originate from a mixed plume source containing peridotite and recycled oceanic crust (pyroxenite) based on variations of radiogenic isotopes. Hawaiian lavas display correlations among isotopes, major and trace elements [1] that might be expected to have an expression in the volatile elements. To investigate this link, we present Os isotopic ratios (n=51), and major, trace, and volatile elements from 1003 olivine-hosted melt inclusions (MI) and their host minerals from tephra from Koolau, Mauna Loa, Hualalai, Kilauea, and Loihi volcanoes. The data show a strong correlation between MI volatile contents and incompatible trace element ratios (La/Yb) with Os isotopes of the same host olivines and reveal large-scale volatile heterogeneity and zonation exists within the Hawaiian plume. 'Loa' chain lavas, which are thought to originate from greater proportions of recycled oceanic crust/pyroxenite, have MIs with lower H2O, S, F, and Cl contents compared to 'Kea' chain lavas that were derived from more peridotite-rich sources. The depletion of volatile elements in the 'Loa' volcano MIs can be explained if they tapped an ancient dehydrated oceanic crust component within the Hawaiian plume. Higher extents of melting beneath 'Loa' volcanoes can also explain these depletions. The presence of dehydrated recycled mafic material in the plume source suggests that subduction effectively devolatilizes part of the oceanic crust. These results are similar to the observed shifts in H2O/Ce ratios near the Easter and Samoan hotspots [2,3]. Thus, it appears that multiple hotspots may record relative H2O depletions and possibly other volatiles. [1] Hauri et al. 1996, Nature 382, 415-419. [2] Dixon et al. 2002, Nature 420:385-89 [3] Workman et al. 2006, EPSL 241:932-51.

SXRF determination of trace elements in chondrule rims in the unequilibrated CO3 chondrite, ALH A77307

NASA Technical Reports Server (NTRS)

Brearley, Adrian J.; Bajt, Sasa; Sutton, Steve R.; Papike, J. J.

1993-01-01

The concentrations of Ni, Cu, Zn, Ga, Ge, and Se in five chondrule rims in the CO3 chondrite ALH A77307 (3.0) using the synchrotron x-ray fluorescence (SXRF) microprobe at Brookhaven National Laboratory were determined. The data show that the trace element chemistry of rims on different chondrules is remarkably similar, consistent with data obtained for the major elements by electron microprobe. These results support the idea that rims are not genetically related to individual chondrules, but all sampled the same reservoir of homogeneously mixed dust. Of the trace elements analyzed Zn and Ga show depletions relative to CI chondrite values, but in comparison with bulk CO chondrites all the elements are enriched by approximately 1.5 to 3.5 x CO. The high concentrations of the highly volatile elements Se and Ga and moderately volatile Zn (1.5 to 2 x CO) in rims show that matrix is the major reservoir of volatile elements in ALH A77307.

Search for naturally occurring superheavy elements

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

Stoughton, R.W.; Halperin, J.; Drury, J.S.

1973-11-12

Several ores, minerals, concentrates and special samples were examined for evidence of superheavy elements using a neutron multiplicity counter. This counter contains 20 /sup 3/He detectors in a paraffin matrix, and enables evaluation of the emitted neutron multiplicity spectrum of large samples with littie or no chemical processing. Such measurements provide an effective tool in the search for superheavy elements, since their decay or the decay of daughter nuclides is expected to proceed by spontaneous fission. In a search for Element 114(ekalead) a massive galena sample and a sample of galena-barite were examined, together with some chalcophilic samples, iron andmore » zinc sulphides, cerussite (PbCO/ sub 3/), and flux dust samples in Cottrell precipitators from the roasting of pentlandite (iron nickel sulphide). Element 114 would be expected to be more volatile than Hg, and intermediate between Pb and Au in nobility, and for this reason a technique was applied which was successfully developed to locate Hg ore bodies. This technique is described. In another attempt to detect possible volatile superheavy elements, such as 118 (ekaradon) or 112 (ekamercury) a sample of silica gel was examined, previously used in a plant for the production of noble gases; a gas mixture of crude Xe from the same plant was also investigated. With regard to Element 110 (ekaplatinum) several ultrabasic rocks were examined. For Element 119 (ekafracium) several potash ores were examined, as well as bittern from the Great Salt Lake, Utah. A sample of native Bi, as well as reagent Bi, were examined for Element 115 (ekabismuth). Several special samples included iron-rich meteorites, samples of biotite in which dwarf haloes had been found, some monazite samples associated with giant haloes, and some haematite and magnetite samples; also manganese nodules, sharks' teeth, and carbonaceous chondrite meteorite samples. The latter were particularly interesting since there is a Xe component in some carbonaceous chondrites that shows a higher /sup 136/Xe/sup 134/Xe ratio than Xe from any known fission source, possibly due to fission of one or more relatively volatile superheavy elements. All the results are summarized in tabular form. None of the samples examined showed evidence of spontaneous fission rates in excess of the detection limit. (UK)« less

Composition of the earth's upper mantle-I. Siderophile trace elements in ultramafic nodules

USGS Publications Warehouse

Morgan, J.W.; Wandless, G.A.; Petrie, R.K.; Irving, A.J.

1981-01-01

Seven siderophile elements (Au, Ge, Ir, Ni, Pd, Os, Re) were determined by radiochemical neutron activation analysis in 19 ultramafic rocks, which are spinel lherzollites-xenoliths from North and Central America, Hawaii and Australia, and garnet Iherzolitexenoliths from Lesotho. Abundances of the platinum metals are very uniform in spinel lherzolites averaging 3.4 ?? 1.2 ppb Os, 3.7 ?? 1.1 ppb Ir, and 4.6 ?? 2.0 ppb Pd. Sheared garnet lherzolite PHN 1611 has similar abundances of these elements, but in 4 granulated garnet lherzolites, abundances are more variable. In all samples, the Pt metals retain cosmic ( Cl-chondrite) ratios. Abundances of Au and Re vary more than those of Pt metals, but the Au/Re ratio remains close to the cosmic value. The fact that higher values of Au and Re approach cosmic proportions with respect to the Pt metals, suggests that Au and Re have been depleted in some ultramafic rocks from an initially chondrite-like pattern equivalent to about 0.01 of Cl chondrite abundances. The relative enrichment of Au and Re in crustal rocks is apparently the result of crust-mantle fractionation and does not require a special circumstance of core-mantle partitioning. Abundances of moderately volatile elements Ni, Co and Ge are very uniform in all rocks, and are much higher than those of the highly siderophile elements Au, Ir, Pd, Os and Re. When normalized to Cl chondrites, abundances of Ni and Co are nearly identical, averaging 0.20 ?? 0.02 and 0.22 ?? 0.02, respectively; but Ge is only 0.027 ?? 0.004. The low abundance of Ge relative to Ni and Co is apparently a reflection of the general depletion of volatile elements in the Earth. The moderately siderophile elements cannot be derived from the same source as the highly siderophile elements because of the marked difference in Cl chondrite-normalized abundances and patterns. We suggest that most of the Ni, Co and Ge were enriched in the silicate by the partial oxidation of pre-existing volatile-poor Fe-Ni, whereas the corresponding highly siderophile elements remained sequestered by the surviving metal. The highly siderophile elements may have been introduced by a population of ~103 large (~1022 g) planetisimals, similar to those forming the lunar mare basins. ?? 1981.

Fractionation of highly siderophile and chalcogen elements in components of EH3 chondrites

NASA Astrophysics Data System (ADS)

Kadlag, Yogita; Becker, Harry

2015-07-01

Abundances of highly siderophile elements (HSE: Re, platinum group elements and Au), chalcogens (Te, Se and S), 187Os/188Os and the major and minor elements Mg, Ca, Mn, Fe, Ni and Co were determined in the components of Sahara 97072 (EH3, find) and Kota Kota (EH3, find) in order to understand the element fractionation processes. In a 187Re-187Os isochron diagram, most magnetic components lie close to the 4.56 Ga IIIA iron meteorite isochron, whereas most other components show deviations from the isochron caused by late redistribution of Re, presumably during terrestrial weathering. Metal- and sulfide rich magnetic fractions and metal-sulfide nodules are responsible for the higher 187Os/188Os in bulk rocks of EH chondrites compared to CI chondrites. The HSE and chalcogens are enriched in magnetic fractions relative to slightly magnetic and nonmagnetic fractions and bulk compositions, indicating that Fe-Ni metal is the main host phase of the HSE in enstatite chondrites. HSE abundance patterns indicate mixing of two components, a CI chondrite like end member and an Au-enriched end member. Because of the decoupled variations of Au from those of Pd or the chalcogens, the enrichment of Au in EH metal cannot be due to metal-sulfide-silicate partitioning processes. Metal and sulfide rich nodules may have formed by melting and reaction of pre-existing refractory element rich material with volatile rich gas. A complex condensation and evaporation history is required to account for the depletion of elements having very different volatility than Au in EH chondrites. The depletions of Te relative to HSE, Se and S in bulk EH chondrites are mainly caused by the depletion of Te in metal. S/Se and S/Mn are lower than in CI chondrites in almost all components and predominantly reflect volatility-controlled loss of sulfur. The latter most likely occurred during thermal processing of dust in the solar nebula (e.g., during chondrule formation), followed by the non-systematic loss of S during terrestrial weathering.

High salinity volatile phases in magmatic Ni-Cu-platinum group element deposits

NASA Astrophysics Data System (ADS)

Hanley, J. J.; Mungall, J. E.

2004-12-01

The role of "deuteric" fluids (exsolved magmatic volatile phases) in the development of Ni-Cu-PGE (platinum group element) deposits in mafic-ultramafic igneous systems is poorly understood. Although considerable field evidence demonstrates unambiguously that fluids modified most large primary Ni-Cu-PGE concentrations, models which hypothesize that fluids alone were largely responsible for the economic concentration of the base and precious metals are not widely accepted. Determination of the trace element composition of magmatic volatile phases in such ore-forming systems can offer considerable insight into the origin of potentially mineralizing fluids in such igneous environments. Laser ablation ICP-MS microanalysis allows researchers to confirm the original metal budget of magmatic volatile phases and quantify the behavior of trace ore metals in the fluid phase in the absence of well-constrained theoretical or experimental predictions of ore metal solubility. In this study, we present new evidence from major deposits (Sudbury, Ontario, Canada; Stillwater Complex, Montana, U.S.A.) that compositionally distinct magmatic brines and halide melt phases were exsolved from crystallizing residual silicate melt and trapped within high-T fluid conduits now comprised of evolved rock compositions (albite-quartz graphic granite, orthoclase-quartz granophyre). Petrographic evidence demonstrates that brines and halide melts coexisted with immiscible carbonic phases at the time of entrapment (light aliphatic hydrocarbons, CO2). Brine and halide melt inclusions are rich in Na, Fe, Mn, K, Pb, Zn, Ba, Sr, Al and Cl, and homogenize by either halite dissolution at high T ( ˜450-700° C) or by melting of the salt phase (700-800° C). LA-ICPMS analyses of single inclusions demonstrate that high salinity volatile phases contained abundant base metals (Cu, Fe, Sn, Bi) and precious metals (Pt, Pd, Au, Ag) at the time of entrapment. Notably, precious metal concentrations in the inclusions are comparable to and often exceed the economic concentrations of the metals within the ores themselves. As a consequence of these results, current genetic models must be revised to consider the role played by hydrous saline melts and magmatic brines in deposit development, and the potential for interaction and competition between sulfide liquids (or PGE-bearing sulfide minerals) and hydrosaline volatiles for available PGE and Au in a crystallizing mafic igneous system must be critically evaluated.

Trace element content of chondritic cosmic dust: Volatile enrichments, thermal alterations, and the possibility of contamination

NASA Technical Reports Server (NTRS)

Flynn, G. J.; Sutton, S. R.; Bajt, S.

1993-01-01

Trace element abundances in 51 chondritic Interplanetary Dust Particles (IDP's) were measured by Synchrotron X-Ray Fluorescence (SXRF). The data allow us to determine an average composition of chondritic IDP's and to examine the questions of volatile loss during the heating pulse experienced on atmospheric entry and possible element addition due to contamination during atmospheric entry, stratospheric residence, and curation.

Volatility in GARCH Models of Business Tendency Index

NASA Astrophysics Data System (ADS)

Wahyuni, Dwi A. S.; Wage, Sutarman; Hartono, Ateng

2018-01-01

This paper aims to obtain a model of business tendency index by considering volatility factor. Volatility factor detected by ARCH (Autoregressive Conditional Heteroscedasticity). The ARCH checking was performed using the Lagrange multiplier test. The modeling is Generalized Autoregressive Conditional Heteroscedasticity (GARCH) are able to overcome volatility problems by incorporating past residual elements and residual variants.

Potassium isotopic evidence for a high-energy giant impact origin of the Moon.

PubMed

Wang, Kun; Jacobsen, Stein B

2016-10-27

The Earth-Moon system has unique chemical and isotopic signatures compared with other planetary bodies; any successful model for the origin of this system therefore has to satisfy these chemical and isotopic constraints. The Moon is substantially depleted in volatile elements such as potassium compared with the Earth and the bulk solar composition, and it has long been thought to be the result of a catastrophic Moon-forming giant impact event. Volatile-element-depleted bodies such as the Moon were expected to be enriched in heavy potassium isotopes during the loss of volatiles; however such enrichment was never found. Here we report new high-precision potassium isotope data for the Earth, the Moon and chondritic meteorites. We found that the lunar rocks are significantly (>2σ) enriched in the heavy isotopes of potassium compared to the Earth and chondrites (by around 0.4 parts per thousand). The enrichment of the heavy isotope of potassium in lunar rocks compared with those of the Earth and chondrites can be best explained as the result of the incomplete condensation of a bulk silicate Earth vapour at an ambient pressure that is higher than 10 bar. We used these coupled constraints of the chemical loss and isotopic fractionation of K to compare two recent dynamic models that were used to explain the identical non-mass-dependent isotope composition of the Earth and the Moon. Our K isotope result is inconsistent with the low-energy disk equilibration model, but supports the high-energy, high-angular-momentum giant impact model for the origin of the Moon. High-precision potassium isotope data can also be used as a 'palaeo-barometer' to reveal the physical conditions during the Moon-forming event.

Halogens in chondritic meteorites and terrestrial accretion

NASA Astrophysics Data System (ADS)

Clay, Patricia L.; Burgess, Ray; Busemann, Henner; Ruzié-Hamilton, Lorraine; Joachim, Bastian; Day, James M. D.; Ballentine, Christopher J.

2017-11-01

Volatile element delivery and retention played a fundamental part in Earth’s formation and subsequent chemical differentiation. The heavy halogens—chlorine (Cl), bromine (Br) and iodine (I)—are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15-37 times lower, respectively, than previously reported and usually accepted estimates. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5 ± 0.2 per cent of Earth’s silicate mass, cannot solely account for present-day terrestrial halogen inventories. It is estimated that 80-90 per cent of heavy halogens are concentrated in Earth’s surface reservoirs and have not undergone the extreme early loss observed in atmosphere-forming elements. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth’s dissolved mantle gases, the efficient extraction of halogen-rich fluids from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track with water, supports this requirement, and is consistent with volatile-rich or water-rich late-stage terrestrial accretion.

Production of sulfur gases and carbon dioxide by synthetic weathering of crushed drill cores from the Santa Cruz porphyry copper deposit near Casa Grande, Pinal County, Arizona

USGS Publications Warehouse

Hinkle, M.E.; Ryder, J.L.; Sutley, S.J.; Botinelly, T.

1990-01-01

Samples of ground drill cores from the southern part of the Santa Cruz porphyry copper deposit, Casa Grande, Arizona, were oxidized in simulated weathering experiments. The samples were also separated into various mineral fractions and analyzed for contents of metals and sulfide minerals. The principal sulfide mineral present was pyrite. Gases produced in the weathering experiments were measured by gas chromatography. Carbon dioxide, oxygen, carbonyl sulfide, sulfur dioxide and carbon disulfide were found in the gases; no hydrogen sulfide, organic sulfides, or mercaptans were detected. Oxygen concentration was very important for production of the volatiles measured; in general, oxygen concentration was more important to gas production than were metallic element content, sulfide mineral content, or mineral fraction (oxide or sulfide) of the sample. The various volatile species also appeared to be interactive; some of the volatiles measured may have been formed through gas reactions. ?? 1990.

Rust and schreibersite in Apollo 16 highland rocks - Manifestations of volatile-element mobility

NASA Technical Reports Server (NTRS)

Hunter, R. H.; Taylor, L. A.

1982-01-01

Rust is a manifestation of halogen and volatile-metal mobility in the lunar environment. Schreibersite is stable as the primary phosphorus-bearing phase in the highland rocks, a consequence of the inherently low oxygen fugacity within impact-generated melts. Apatite and whitlockite are subordinate in these rocks. The partitioning of P into phosphide in impact-generated melts, and the failure of phosphate to crystallize, effects a decoupling of the halogens and phosphorus. Of the Apollo 16 rocks, 63% contain rust, 70% contain schreibersite, and 52% contain both phases, thereby establishing the pervasiveness of volatile-elements throughout the highland rocks. The major portion of these volatile-bearing phases occur in impact melt-rocks or in breccia matrices. Rhabdites of schreibersite in some of the FeNi grains indicate that there is a meteoritic contribution to the phosphorus in these rocks. Cl/P2O5 ratios in lunar highland rocks are a function of secondary effects, with any apparent Cl-P correlations being coincidential. The present observations preclude the validity of models based on such elemental ratios in these rocks. The presence of rust in the clast laden matrices of pristine rocks indicates fugitive element localization. Pristine clasts may have been contaminated. The basis for a pristine volatile chemistry is questioned.

Study of thermal stability and degradation of fire resistant candidate polymers for aircraft interiors

NASA Technical Reports Server (NTRS)

Hsu, M. T. S.

1976-01-01

The thermochemistry of bismaleimide resins and phenolphthalein polycarbonate was studied. Both materials are fire-resistant polymers and may be suitable for aircraft interiors. The chemical composition of the polymers has been determined by nuclear magnetic resonance and infrared spectroscopy and by elemental analysis. Thermal properties of these polymers have been characterized by thermogravimetric analyses. Qualitative evaluation of the volatile products formed in pyrolysis under oxidative and non-oxidative conditions has been made using infrared spectrometry. The residues after pyrolysis were analyzed by elemental analysis. The thermal stability of composite panel and thermoplastic materials for aircraft interiors was studied by thermogravimetric analyses.

Enhancing biogas production from vinasse in sugarcane biorefineries: Effects of urea and trace elements supplementation on process performance and stability.

PubMed

Janke, Leandro; Leite, Athaydes F; Batista, Karla; Silva, Witan; Nikolausz, Marcell; Nelles, Michael; Stinner, Walter

2016-10-01

In this study, the effects of nitrogen, phosphate and trace elements supplementation were investigated in a semi-continuously operated upflow anaerobic sludge blanket system to enhance process stability and biogas production from sugarcane vinasse. Phosphate in form of KH2PO4 induced volatile fatty acids accumulation possibly due to potassium inhibition of the methanogenesis. Although nitrogen in form of urea increased the reactor's alkalinity, the process was overloaded with an organic loading rate of 6.1gCODL(-1)d(-1) and a hydraulic retention time of 3.6days. However, by supplementing urea and trace elements a stable operation even at an organic loading rate of 9.6gCODL(-1)d(-1) and a hydraulic retention time of 2.5days was possible, resulting in 79% higher methane production rate with a stable specific methane production of 239mLgCOD(-1). Copyright © 2016 Elsevier Ltd. All rights reserved.

Geochemistry and genesis of the angrites

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Lindstrom, Marilyn M.

1990-01-01

The major and trace elements were analyzed in samples of LEW86010, LEW87051, and Angra dos Reis angrites were analyzed using INAA and fused-bead EMP techniques. Results suggest that all three angrites originated on a volatile-depleted (Na-poor) but oxidized parent body or on several bodies. The combination of low Na and high FeO/MnO found in these samples suggests that the extreme Na depletion was caused by parent-body outgassing during differentiation, rather than by nebular processes. It was also found that the refractory-element abundances observed in LEW86010 and LEW87051 are related via olivine control; it is suggested that LEW86010 may be a residual melt from a LEW87051-like precursor or that LEW87051 formed from a LEW86010-like precursor via olivine accumulation. On the other hand, the Angra dos Reis displayed an unusual refractory element pattern suggesting that either the angrite parent body was heterogeneous or that Angra dos Reis was formed on a parent body different from that of the other two angrites.

Tellurium in active volcanic environments: Preliminary results

NASA Astrophysics Data System (ADS)

Milazzo, Silvia; Calabrese, Sergio; D'Alessandro, Walter; Brusca, Lorenzo; Bellomo, Sergio; Parello, Francesco

2014-05-01

Tellurium is a toxic metalloid and, according to the Goldschmidt classification, a chalcophile element. In the last years its commercial importance has considerably increased because of its wide use in solar cells, thermoelectric and electronic devices of the last generation. Despite such large use, scientific knowledge about volcanogenic tellurium is very poor. Few previous authors report result of tellurium concentrations in volcanic plume, among with other trace metals. They recognize this element as volatile, concluding that volcanic gases and sulfur deposits are usually enriched with tellurium. Here, we present some results on tellurium concentrations in volcanic emissions (plume, fumaroles, ash leachates) and in environmental matrices (soils and plants) affected by volcanic emissions and/or deposition. Samples were collected at Etna and Vulcano (Italy), Turrialba (Costa Rica), Miyakejima, Aso, Asama (Japan), Mutnovsky (Kamchatka) at the crater rims by using common filtration techniques for aerosols (polytetrafluoroethylene filters). Filters were both eluted with Millipore water and acid microwave digested, and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Volcanic ashes emitted during explosive events on Etna and Copahue (Argentina) were analyzed for tellurium bulk composition and after leaching experiments to evaluate the soluble fraction of tellurium. Soils and leaves of vegetation were also sampled close to active volcanic vents (Etna, Vulcano, Nisyros, Nyiragongo, Turrialba, Gorely and Masaya) and investigated for tellurium contents. Preliminary results showed very high enrichments of tellurium in volcanic emissions comparing with other volatile elements like mercury, arsenic, thallium and bismuth. This suggests a primary transport in the volatile phase, probably in gaseous form (as also suggested by recent studies) and/or as soluble salts (halides and/or sulfates) adsorbed on the surface of particulate particles and ashes. First estimates of volcanic flux of tellurium from Etna range from 1 to 5 tons per year, confirming that this volcano is one of the biggest point sources of trace elements to the atmosphere. Analysis of tellurium in soils and plants close to active vents allowed to highlight the impact of this toxic elements, particularly evident close to the craters. Especially, the leaves of plants used as bioaccumulators of trace metals, showed also high enrichment of tellurium in comparison with other toxic elements.

Volatiles on the surface of Apollo 15 green glass and trace-element distributions among Apollo 15 soils

NASA Technical Reports Server (NTRS)

Chou, C.-L.; Boynton, W. V.; Sundberg, L. L.; Wasson, J. T.

1975-01-01

Zn, Ge, Cd, In, and Au have been detected in surficial deposits on Apollo 15 green-glass spherules, and it is suggested that these deposits are condensates from the magmatic gas phase which was responsible for the pneumatic expulsion of the green glass from the lunar interior. Thermodynamic data indicate that chlorides and fluorides were the dominant forms of the volatile metals. The Ar-40x content of a nongreen-glass soil fraction is greater than that found in green-glass. Mare and low-K Fra Mauro basalts seem to be the most prominent components of Apollo 15 soil. The correlation of Zn with Ar-40x and with Pb-204 is studied, and the distribution of quartz-normative and olivine-normative basalts is considered.

First chemical separation and identification of Seaborgium

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

Tuerler, A.; Eichler, B.; Jost, D.T.

1997-12-31

The chemical properties of element 106 (Seaborgium, Sg) were successfully studied using the On-line Gas Chromatography Apparatus (OLGA III). After chemical separation of Sg in the form of volatile oxichlorides the nuclides {sup 265}Sg and {sup 266}Sg were unambiguously identified and their half-lives were determined for the first time. The Sg nuclides were produced from the {sup 248}Cm({sup 22}Ne, 4,5n){sup 266,265}Sg reaction at the GSI Darmstadt UNILAC accelerator. Simultaneously, short-lived W nuclides were produced from a small admixture of {sup 152}Gd to the Cm target material. As predicted by relativistic calculations and by extrapolations of chemical properties, it was demonstratedmore » that Sg oxichlorides are indeed less volatile than their lighter homologue W- and Mo-oxichlorides.« less

Melt focusing and geochemical evolution at mid-ocean ridges: simulations of reactive two-phase flow

NASA Astrophysics Data System (ADS)

Keller, T.; Katz, R. F.; Hirschmann, M. M.

2017-12-01

The geochemical character of MORB and related off-axis volcanic products reflects the signature of chemical reservoirs in the mantle, the processes of melt transport from source to surface, or both. Focusing of partial melt to the ridge axis controls the proportion of deep, volatile- and incompatible-rich melts that contribute to MORB formation. However, the effect of volatiles, including CO2 and H2O, on melt segregation and focusing remains poorly understood. We investigate this transport using 2-D numerical simulations of reactive two-phase flow. The phases are solid mantle and liquid magma. Major elements and volatiles are represented by a system with 4 or 6 pseudo-components. This captures accepted features of mantle melting with volatiles. The fluid-dynamical model is McKenzie's formulation [1], while melting and reactive transport use the R_DMC method [2,3]. Trace element transport is computed for 5 idealized elements between highly incompatible and compatible behavior. Our results indicate that volatiles cause channelized melt transport, which leads to fluctuations in volume and composition of melt focused to the axis. The volatile-induced expansion of the melting regime at depth, however, has no influence on melt focusing. Up to 50% of deep, volatile-rich melts are not focused to the axis, but are emplaced along the oceanic LAB. There, crystallization of accumulated melt leads to enrichment of volatiles and incompatibles in the deep lithosphere. This has implications for volatile recycling by subduction, seismic properties of the oceanic LAB, and potential sources for seamount volcanism. Results from a suite of simulations, constrained by catalogued observational data [4,5,6], enable prediction of global MORB and volatile output and systematic variations of major, volatile and trace element concentrations as a function of mantle conditions and dynamic properties. REFERENCES[1] McKenzie (1984), doi:10.1093/petrology/25.3.713.[2] Rudge, Bercovici & Spiegelman (2011), doi:10.1111/j.1365-246X.2010.04870.x.[3] Keller & Katz (2016), doi:10.1093/petrology/egw030.[4] Dalton, Langmuir & Gale (2014), doi:10.1126/science.1249466.[5] Gale, Langmuir & Dalton (2014), doi:10.1093/petrology/egu017.[6] White et al. (2001), doi:10.1093/petrology/42.6.1171.

Trace element geochemistry of volcanic gases and particles from 1983-1984 eruptive episodes of Kilauea Volcano

NASA Astrophysics Data System (ADS)

Crowe, Bruce M.; Finnegan, David L.; Zoller, William H.; Boynton, William V.

1987-12-01

Compositional data have been obtained for volcanic gases and particles collected from fume emitted at the Pu'u O'o vent on the east rift zone of Kilauea volcano. The samples were collected by pumping fume through a filter pack system consisting of a front stage particulate filter followed by four base-treated filters (7LiOH). Particles and condensed phases are trapped on the particulate filter, and acidic gases are collected on the treated filters. The filters are analyzed for 30 elements by instrumental neutron activation analysis. Fume samples were collected from the Pu'u O'o vent for two eruptive episodes: (1) 7 days after episode 11 (cooling vent samples) and (2) the waning stage of episode 13 (active vent samples). Additional samples were collected by aircraft from the gas plume released during the lava fountaining phase of episode 17 (aircraft samples). Element concentrations in the vent gases were > 104 μg m-3 for S, Cl, and F. Enrichment factors (EFs) for the volcanic fume versus the source magma were calculated using the volatile element Br as the reference element for normalization and the U.S. Geological Survey standard BHVO-1 as the magma standard. This removes the ash dilution effect obtained by using an ash constituent (Al, Sc, or Mg) as the reference element. Bromine-normalized EFs (× 105) range from 101 to 102 for Na, K, and Cu; 102 to 105 for Zn, W, Sb, In, Ir, Ag, F, and As; and > 105 for Au, Cd, Re, Cl, Se, and S. The highest enrichment factors are for aircraft samples collected during the most gas-rich phase of an eruption cycle. Metal and volatile-element data form two groups: (1) elements showing little or no variation in abundance ratios with sample type (group 1: Cl, Br, and Re) and (2) elements that show significant variation in abundance ratios by sample type (group 2: Zn, W, Sb, In, Ir, Au, and Cd). Bivariate plots of elements of the first group versus elements of the second group separate by sample type. The separation corresponds to samples collected during eruptive activity versus samples collected during repose periods. Monitoring trace metal ratios in volcanic fume could provide an additional tool for predicting volcanic eruptions. The F/Cl ratio of cooling vent samples is higher than those of active vent or aircraft samples, and the ratio is inversely correlated with EFs for most volatile metals.

Universal calibration of Raman spectroscopy for the analysis of volatiles in glasses of variable composition

NASA Astrophysics Data System (ADS)

Schiavi, Federica; Bolfan-Casanova, Nathalie

2017-04-01

The amount and distribution of volatiles (water, carbon dioxide …) in magmas represent key parameters for the understanding of magma processes and dynamics within volcanic plumbing systems. Micro-Raman spectroscopy is an excellent technique for accurate determination of volatile contents in magmas, as it combines several advantages. The technique is non-destructive and requires minimal sample preparation before the analysis. Its high lateral and in-depth spatial resolution is crucial for the study of small objects and samples that are chemically and texturally heterogeneous at the small scale (microns). Moreover, the high confocality allows analysis of sample regions not exposed to the surface and 3D mapping. We present a universal calibration of Raman spectroscopy for quantification of volatiles in silicate glasses. The proposed method is based on internal calibration, i.e., on the correlation between the glass water content and the ratio between the areas of the water and silicate Raman bands. Synthetic glasses with variable major element compositions (basaltic, andesitic, rhyolitic, dacitic ..) bearing different H2O (up to 7 wt%) and CO2 contents are used as standard glasses. Natural silicate glasses, mainly in the form of melt inclusions, are used to test the goodness of the proposed method. In addition to quantification of volatiles in glass, in bubble-bearing melt inclusions we perform micro-Raman spectroscopy investigation of gas-bearing bubbles for accurate determination of total volatile contents in melt inclusions.

Endogenous Lunar Volatiles

NASA Technical Reports Server (NTRS)

McCubbin, F. M.; Liu, Y.; Barnes, J. J.; Boyce, J. W.; Day, J. M. D.; Elardo, S. M.; Hui, H.; Magna, T.; Ni, P.; Tartese, R.;

Determination of refractive and volatile elements in sediment using laser ablation inductively coupled plasma mass spectrometry.

PubMed

Duodu, Godfred Odame; Goonetilleke, Ashantha; Allen, Charlotte; Ayoko, Godwin A

2015-10-22

Wet-milling protocol was employed to produce pressed powder tablets with excellent cohesion and homogeneity suitable for laser ablation (LA) analysis of volatile and refractive elements in sediment. The influence of sample preparation on analytical performance was also investigated, including sample homogeneity, accuracy and limit of detection. Milling in volatile solvent for 40 min ensured sample is well mixed and could reasonably recover both volatile (Hg) and refractive (Zr) elements. With the exception of Cr (-52%) and Nb (+26%) major, minor and trace elements in STSD-1 and MESS-3 could be analysed within ±20% of the certified values. Comparison of the method with total digestion method using HF was tested by analysing 10 different sediment samples. The laser method recovers significantly higher amounts of analytes such as Ag, Cd, Sn and Sn than the total digestion method making it a more robust method for elements across the periodic table. LA-ICP-MS also eliminates the interferences from chemical reagents as well as the health and safety risks associated with digestion processes. Therefore, it can be considered as an enhanced method for the analysis of heterogeneous matrices such as river sediments. Copyright © 2015 Elsevier B.V. All rights reserved.

SNC meteorites and their implications for reservoirs of Martian volatiles

NASA Technical Reports Server (NTRS)

Jones, J. H.

1993-01-01

The SNC meteorites and the measurements of the Viking landers provide our only direct information about the abundance and isotopic composition of Martian volatiles. Indirect measurements include spectroscopic determinations of the D/H ratio of the Martian atmosphere. A personal view of volatile element reservoirs on Mars is presented, largely as inferred from the meteoritic evidence. This view is that the Martian mantle has had several opportunities for dehydration and is most likely dry, although not completely degassed. Consequently, the water contained in SNC meteorites was most likely incorporated during ascent through the crust. Thus, it is possible that water can be decoupled from other volatile/incompatible elements, making the SNC meteorites suspect as indicators of water inventories on Mars.

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.

Application of solid-phase microextraction with gas chromatography and mass spectrometry for the early detection of active moulds on historical woollen objects.

PubMed

Sawoszczuk, Tomasz; Syguła-Cholewińska, Justyna; Del Hoyo-Meléndez, Julio M

2017-02-01

The goal of this work was to determine the microbial volatile organic compounds emitted by moulds growing on wool in search of particular volatiles mentioned in the literature as indicators of active mould growth. The keratinolytically active fungi were inoculated on two types of media: (1) samples of wool placed on broths, and (2) on broths containing amino acids that are elements of the structure of keratin. All samples were prepared inside 20 mL vials (closed system). In the first case (1) the broths did not contain any sources of organic carbon, nitrogen, or sulfur, i.e. wool was the only nutrient for the moulds. A third type of sample was historical wool prepared in a Petri dish without a broth and inoculated with a keratinolytically active mould (open system). The microbial volatiles emitted by moulds were sampled with the headspace solid-phase microextraction method. Volatiles extracted on solid-phase microextraction fibers were analyzed in a gas chromatography with mass spectrometry system. Qualitative and quantitative analyses of chromatograms were carried out in search of indicators of metabolic activity. The results showed that there are three groups of volatiles that can be used for the detection of active forms of moulds on woollen objects. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Case Study: Microbial Ecology and Forensics of Chinese Drywall-Elemental Sulfur Disproportionation as Primary Generator of Hydrogen Sulfide.

PubMed

Tomei Torres, Francisco A

2017-06-21

Drywall manufactured in China released foul odors attributed to volatile sulfur compounds. These included hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Given that calcium sulfate is the main component of drywall, one would suspect bacterial reduction of sulfate to sulfide as the primary culprit. However, when the forensics, i.e., the microbial and chemical signatures left in the drywall, are studied, the evidence suggests that, rather than dissimilatory sulfate reduction, disproportionation of elemental sulfur to hydrogen sulfide and sulfate was actually the primary cause of the malodors. Forensic evidence suggests that the transformation of elemental sulfur went through several abiological and microbial stages: (1) partial volatilization of elemental sulfur during the manufacture of plaster of Paris, (2) partial abiotic disproportionation of elemental sulfur to sulfide and thiosulfate during the manufacture of drywall, (3) microbial disproportionation of elemental sulfur to sulfide and sulfate resulting in neutralization of all alkalinity, and acidification below pH 4, (4) acidophilic microbial disproportionation of elemental sulfur to sulfide and sulfuric acid, and (5) hydrogen sulfide volatilization, coating of copper fixtures resulting in corrosion, and oxidation to sulfur dioxide.

The carbon chemistry of meteorites: Relationships to comets

NASA Technical Reports Server (NTRS)

Chang, S.

1989-01-01

The carbonaceous meteorites exhibiting alteration by liquid water bear a strong relationship to comets. Not only is their elemental composition closer to solar in relative abundances than other meteorites, they are water rich; and they contain isotopic compositions among refractory and volatile elements indicative of presolar components. Some of these isotopic anomalies occur in organic compounds and carbonaceous grains signifying the presence of discrete and identifiable carbon components derived from interstellar and circumstellar matter. Insofar as comets and meteorites are ultimately formed from interstellar gas and dust, and comets have been subjected to considerably less aqueous and thermal evolution than carbonaceous meteorites, the interstellar imprint should be much stronger and better preserved in comets.

Quantification of Methylated Selenium, Sulfur, and Arsenic in the Environment

PubMed Central

Vriens, Bas; Ammann, Adrian A.; Hagendorfer, Harald; Lenz, Markus; Berg, Michael; Winkel, Lenny H. E.

2014-01-01

Biomethylation and volatilization of trace elements may contribute to their redistribution in the environment. However, quantification of volatile, methylated species in the environment is complicated by a lack of straightforward and field-deployable air sampling methods that preserve element speciation. This paper presents a robust and versatile gas trapping method for the simultaneous preconcentration of volatile selenium (Se), sulfur (S), and arsenic (As) species. Using HPLC-HR-ICP-MS and ESI-MS/MS analyses, we demonstrate that volatile Se and S species efficiently transform into specific non-volatile compounds during trapping, which enables the deduction of the original gaseous speciation. With minor adaptations, the presented HPLC-HR-ICP-MS method also allows for the quantification of 13 non-volatile methylated species and oxyanions of Se, S, and As in natural waters. Application of these methods in a peatland indicated that, at the selected sites, fluxes varied between 190–210 ng Se·m−2·d−1, 90–270 ng As·m−2·d−1, and 4–14 µg S·m−2·d−1, and contained at least 70% methylated Se and S species. In the surface water, methylated species were particularly abundant for As (>50% of total As). Our results indicate that methylation plays a significant role in the biogeochemical cycles of these elements. PMID:25047128

Volatile Concentrations and H-Isotope Composition of Unequilibrated Eucrites

NASA Technical Reports Server (NTRS)

Sarafian, Adam R.; Nielsen, Sune G.; Marschall, Horst R.; Gaetani, Glenn A.; Hauri, Erik H.; Righter, Kevin; Berger, Eve L.

2017-01-01

Eucrites are among the oldest and best studied asteroidal basalts (1). They represent magmatism that occurred on their parent asteroid, likely 4-Vesta, starting at 4563 Ma and continuing for approx. 30 Myr. Two hypotheses are debated for the genesis of eucrites, a magma ocean model (2), and a mantle partial melting model. In general, volatiles (H, C, F, Cl) have been ignored for eucrites and 4-Vesta, but solubility of wt% levels of H2O are possible at Vestan interior PT conditions. Targeted measurements on samples could aid our understanding considerably. Recent studies have found evidence of volatile elements in eucrites, but quantifying the abundance of volatiles remains problematic (6). Volatile elements have a disproportionately large effect on melt properties and phase stability, relative to their low abundance. The source of volatile elements can be elucidated by examining the hydrogen isotope ratio (D/H), as different H reservoirs have drastically different H isotope compositions. Recent studies of apatite in eucrites have shown that the D/H of 4-Vesta matches that of Earth and carbonaceous chondrites, however, the D/H of apatites may not represent the D/H of a primitive 4-Vesta melt due to the possibility of degassing prior to the crystallization of apatite. Therefore, the D/H of early crystallizing phases must be measured to determine if the D/H of 4-Vesta is equal to that of the Earth and carbonaceous chondrites.

Diffusive exchange of trace elements between basaltic-andesite and dacitic melt: Insights into potential metal fractionation during magma mixing

NASA Astrophysics Data System (ADS)

Fiege, A.; Ruprecht, P.; Simon, A. C.; Holtz, F.

2017-12-01

Mafic magma recharge is a common process that triggers physical and chemical mixing in magmatic systems and drives their evolution, resulting in, e.g., hybridization and volcanic eruptions. Once magma-magma contact is initiated, rapid heat-flux commonly leads to the formation of a cooling-induced crystal mush on the mafic side of the interface. Here, on a local scale (µm to cm), at the magma-magma interface, melt-melt diffusive exchange is required to approach equilibrium. Significant chemical potential gradients drive a complex, multi-element mass flux between the two systems (Liang, 2010). This diffusive-equilibration often controls crystal dissolution rates within the boundary layers and, thus, the formation of interconnected melt or fluid networks. Such networks provide important pathways for the transport of volatiles and trace metals from the mafic recharge magma to the felsic host magma, where the latter may feed volcanic activities and ore deposits. While major element diffusion in silicate melts is mostly well understood, even in complex systems, the available data for many trace element metals are limited (Liang, 2010; Zhang et al., 2010). Differences in diffusivity in a dynamic, mixing environment can cause trace element fractionation, in particular during crystallization and volatile exsolution and separation. This may affect trace element signatures in phenocrysts and magmatic volatile phases that can form near a magma-magma boundary. As a result, the chemistry of volcanic gases and magmatic-hydrothermal ore deposits may be partially controlled by such mixing phenomena. We performed melt-melt diffusion-couple experiments at 150 MPa, 1100°C, FMQ, FMQ+1 and FMQ+3 (FMQ: fayalite-magnetite-quartz oxygen fugacity buffer). Hydrated, sulfur-bearing cylinders of dacite and basaltic andesite were equilibrated for up to 20 h. Major and trace element gradients were measured by using laser-ablation ICP-MS and electron microprobe analyses. The results we will present will help to fill data gaps for the diffusivity of certain metals in silicate melts (e.g., V, Mo, W). First data analyses indicate a higher diffusivity of V when compared to W . Liang (2010) Rev Mineral Geochem 72, 409-446; Zhang et al. (2010) Rev Mineral Geochem 72, 311-408.

Melt inclusion evidence for a volatile-enriched (H2O, Cl, B) component in parental magmas of Gorgona Island komatiites

NASA Astrophysics Data System (ADS)

Kamenetsky, V.; Sobolev, A.; McDonough, W.

2003-04-01

Late Cretaceous komatiites of Gorgona Island are unambiguous samples of ultra-mafic melts related to a hot and possibly 'wet' mantle plume. Despite significant efforts in studying komatiites, their volatile abundances remain largely unknown because of significant alteration of rocks and lack of fresh glasses. This work presents major, trace and volatile element data for 22 partially homogenised (at 1275oC and 1 bar pressure) melt inclusions in olivine (Fo 90.5-91.5) from a Gorgona Isl. komatiite (# Gor 94-3). Major element compositions (except FeO which is notably lower by up to 5 wt% as a result of post-entrapment re-equilibration) and most lithophile trace elements of melt inclusions are indistinguishable from the whole rock komatiites. With the exception of three inclusions that have low Na, H2O, Cl, F and S (likely compromised and degassed during heating) most compositions are characterised by relatively constant and high volatile abundances (H2O 0.4-0.8 wt%, Cl 0.02-0.03 wt%, B 0.8-1.4 ppm). These are interpreted as representative of original volatiles in parental melts because they correspond to the internal volatile pressure in the closed inclusions significantly exceeding 1 bar pressure of heating experiment. Although H2O is strongly enriched (PM-normalised H2O/Ce 10-17) its concentrations correlate well with many elements (e.g. Yb, Er, Y, Ti, Sr, Be). Other positive anomalies on the overall depleted (La/Sm 0.26-0.33) PM normalized compositional spectra of melt inclusions are shown by B (B/K 2.4-5.4) and Cl (Cl/K 11-16). Compositions of melt inclusions, when corrected for Fe loss and recalculated in equilibrium with host olivine, have high MgO (15.4-16.4 wt%; Mg# of 74) and substantial H2O (0.4-0.6 wt%) contents. This together with the data on other 'enriched' elements argues for the presence of previously unknown volatile-enriched component in the parental melts of Gorgona Isl. komatiites. We discuss contamination of magmas by altered oceanic crust in the plumbing system, the involvement of volatile-rich subduction related component(s) in the mantle source, and the geochemical control from residual garnet during the generation of komatiite primary melts.

Molecular emission characteristics of various fluorides in a low-temperature-hydrogen diffusion flame.

PubMed

Dagnall, R M; Fleet, B; Risby, T H; Deans, D R

1971-02-01

A capillary burner supporting a nitrogen/hydrogen diffusion flame has been evaluated as a possible means of detection for several volatile fluorides after their gas-chromatographic separation. The fluorides of As, B, C, Ge, I, Mo, P, Re, S, Sb, Se, Si, Te and W were formed by the reaction of the element with chlorine trifluoride, and the intense molecular emission given by each was recorded. An attempt was made to identify the emitting species.

Volatile enrichments and composition of carbon-rich giant planets: the case of WASP-12b

NASA Astrophysics Data System (ADS)

Mousis, O.; Madhusudhan, N.; Johnson, T. V.; Lunine, J. I.

2011-10-01

Carbon-rich planets (CRPs) are the exotic new members in the repertoire of extrasolar planets. We define a CRP as a planet with a carbon to oxygen (C/O) ratio ? 1. The first CRP atmosphere was inferred recently for the very hot Jupiter WASP-12b [1]. Here we show that it is not possible to reproduce the C/O ratio ? 1 observed in WASP-12b via the accretion of planetesimals formed in a disk whose gas phase elemental composition is similar to the one of the parent star. In order to reproduce the observed C/O ratio in the planet, one needs to invoke an oxygen abundance which is depleted by a factor of roughly two compared to that of the parent star, with the exact value contingent on the volatile-to-silicate fraction.

Selective Fluorination and Separation of Metals with NF3 for Mass Spectrometry

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

Clark, Richard A.; Barinaga, Charles J.; McNamara, Bruce K.

2016-03-01

We report recent progress on the development of a new methodology based on the generation of volatile metal fluorides through the use of nitrogen trifluoride (NF3), and the separation and measurement of these metal fluorides by electron ionization mass spectrometry. Though unreactive under ambient conditions, NF3 reacts selectively at specified temperatures with various metal-containing species to form volatile metal fluorides. Utilizing these species-dependent traits, elements of a sample may be sequentially produced and thus separated on-line. Metals were reacted inside a thermogravimetric analyzer, the gas outlet of which was directly coupled to a quadrupole mass spectrometer with an electron impactmore » ionization source via a molecular leak valve. We present results of this project including the electron ionization mass spectrum of gaseous tellurium hexafluoride.« less

Reduction, partial evaporation, and spattering - Possible chemical and physical processes in fluid drop chondrule formation

NASA Technical Reports Server (NTRS)

King, E. A.

1983-01-01

The major chemical differences between fluid drop chondrules and their probable parent materials may have resulted from the loss of volatiles such as S, H2O, Fe, and volatile siderophile elements by partial evaporation during the chondrule-forming process. Vertical access solar furnace experiments in vacuum and hydrogen have demonstrated such chemical fractionation trends using standard rock samples. The formation of immiscible iron droplets and spherules by in situ reduction of iron from silicate melt and the subsequent evaporation of the iron have been observed directly. During the time that the main sample bead is molten, many small spatter spherules are thrown off the main bead, thereby producing many additional chondrule-like melt spherules that cool rapidly and generate a population of spherules with size frequency distribution characteristics that closely approximate some populations of fluid drop chondrules in chondrites. It is possible that spatter-produced fluid drop chondrules dominate the meteoritic fluid drop chondrule populations. Such meteoritic chondrule populations should be chemically related by various relative amounts of iron and other volatile loss by vapor fractionation.

A study of the trace sulfide mineral assemblages in the Stillwater Complex, Montana, USA

NASA Astrophysics Data System (ADS)

Aird, Hannah M.; Ferguson, Katherine M.; Lehrer, Malia L.; Boudreau, Alan E.

2017-03-01

The sulfide assemblages of the Stillwater Complex away from the well-studied ore zones are composed mainly of variable proportions of pyrrhotite, chalcopyrite, pentlandite, and ±pyrite. Excluding vein assemblages and those affected by greenschist and lower temperature alteration, the majority can be classified into two broad assemblages, defined here as pristine (multiphase, often globular in shape) or volatile-bearing (multiphase, high-temperature, volatile-rich minerals such as biotite, hornblende, or an unmixed calcite-dolomite assemblage). The volatile-bearing assemblages are mainly found within and below the J-M reef, where native copper and sphalerite are also locally present. Pristine sulfides are found throughout the stratigraphy. Both groups can be affected by apparent S loss in the form of pyrite being converted to magnetite and chalcopyrite to a Cu-Fe-oxide (delafossite), with little to no silicate alteration. An upward trend from pentlandite-rich to pyrrhotite-rich to pyrite-rich assemblages is observed in the footwall rocks in upper GN-I, and the same trend repeats from just below the reef and continues into the overlying N-II and GN-II. Modeling suggests that the sulfide Ni in the Peridotite Zone is largely controlled by silicate Ni. When taken together, observations are most readily explained by the remobilization of selected elements by a high-temperature fluid with the apparent loss of S > Cu > Ni. This could concentrate ore metals by vapor refining, eventually producing a platinum group element-enriched sulfide ore zone, such as the J-M reef.

Trace elements in ocean ridge basalts

NASA Technical Reports Server (NTRS)

Kay, R. W.; Hubbard, N. J.

1978-01-01

A study is made of the trace elements found in ocean ridge basalts. General assumptions regarding melting behavior, trace element fractionation, and alteration effects are presented. Data on the trace elements are grouped according to refractory lithophile elements, refractory siderophile elements, and volatile metals. Variations in ocean ridge basalt chemistry are noted both for regional and temporal characteristics. Ocean ridge basalts are compared to other terrestrial basalts, such as those having La/Yb ratios greater than those of chondrites, and those having La/Yb ratios less than those of chondrites. It is found that (1) as compared to solar or chondrite ratios, ocean ridge basalts have low ratios of large, highly-charged elements to smaller less highly-charged elements, (2) ocean ridge basalts exhibit low ratios of volatile to nonvolatile elements, and (3) the transition metals Cr through Zn in ocean ridge basalts are not fractionated more than a factor of 2 or 3 from the chondritic abundance ratios.

Degassing of metals and metalloids from erupting seamount and mid-ocean ridge volcanoes: Observations and predictions

NASA Astrophysics Data System (ADS)

Rubin, Ken

1997-09-01

Recently, it has been reported that the element polonium degasses from mid-ocean ridge and seamount volcanoes during eruptions. Published and new observations on other volatile metal and metalloid elements can also be interpreted as indicating significant degassing of magmatic vapors during submarine eruptions. This process potentially plays an important role in the net transfer of chemical elements from erupting volcanoes to seawater in addition to that arising from sea floor hydrothermal systems. In this paper, a framework is constructed for predicting and assessing semiquantitatively the potential magnitude and chemical fingerprints in the water column of metal and metalloid degassing using (1) predictions from a summary of element volatilities during mafic subaerial volcanism worldwide and (2) limited data from submarine volcanic effusives. The latter include analyses of polonium and trace metals in near-volcano water masses sampled following a submarine eruption at Loihi seamount, Hawaii (1000 m bsl) in 1996. The element volatility predictions and observations show good agreement, considering the limited dataset. Some of the highest volatility main group and transition element enrichments in seawater over Loihi are predicted by the degassing mass transfer model I present. When expanded to cover all submarine volcanic activity, it is predicted that exit fluxes of these elements are up to 10 2-10 3 greater by degassing than by normal MOR hydrothermalism. In contrast, MOR exit fluxes of low volatility alkali and alkaline earth elements are likely 10 2-10 6 greater from hydrothermal inputs. Degassing inputs to the ocean are probably highly episodic, occurring almost entirely during eruptions; these are times of enhanced and abnormal hydrothermalism as well. Although major hydrothermal and degassing events may not be chemically recognizable in real water masses as wholly distinct entities, it is nevertheless possible to predict to what extent each process flavors the effluents of the other. Degassing at mid-ocean ridges may explain a variety of observations previously ascribed to complexities occurring during hydrothermal venting and/or fluid ascent in the buoyant hydrothermal plumes above ridges.

Characterization of Three Carbon- and Nitrogen-Rich Particles from Comet 81P/WILD

NASA Technical Reports Server (NTRS)

Gallien, J.-P.; Khodja, H.; Herzog, G. F.; Taylor, S.; Koepsell, E.; Daghlian, C. P.; Flynn, G. J.; Sitnitsky, I.; Lanzirotti, A.; Sutton, S. R.;

Volatile element content of the heterogeneous upper mantle

NASA Astrophysics Data System (ADS)

Shimizu, K.; Saal, A. E.; Hauri, E. H.; Forsyth, D. W.; Kamenetsky, V. S.; Niu, Y.

2014-12-01

The physical properties of the asthenosphere (e.g., seismic velocity, viscosity, electrical conductivity) have been attributed to either mineral properties at relevant temperature, pressure, and water content or to the presence of a low melt fraction. We resort to the geochemical studies of MORB to unravel the composition of the asthenosphere. It is important to determine to what extent the geochemical variations in axial MORB do represent a homogeneous mantle composition and variations in the physical conditions of magma generation and transport; or alternatively, they represent mixing of melts from a heterogeneous upper mantle. Lavas from intra-transform faults and off-axis seamounts share a common mantle source with axial MORB, but experience less differentiation and homogenization. Therefore they provide better estimates for the end-member volatile budget of the heterogeneous upper mantle. We present major, trace, and volatile element data (H2O, CO2, Cl, F, S) as well as Sr, Nd, and Pb isotopic compositions [1, 2] of basaltic glasses (MgO > 6.0 wt%) from the NEPR seamounts, Quebrada-Discovery-Gofar transform fault system, and Macquarie Island. The samples range from incompatible trace element (ITE) depleted (DMORB: Th/La<0.035) to enriched (EMORB: Th/La>0.07) spanning the entire range of EPR MORB. The isotopic composition of the samples correlates with the degree of trace element enrichment indicating long-lived mantle heterogeneity. Once shallow-level processes (degassing, crystallization, and crustal assimilation) have been considered, we conducted a two-component (DMORB- and EMORB-) mantle melting-mixing model. Our model reproduces the major, trace and volatile element contents and isotopic composition of our samples and suggests that (1) 90% of the upper mantle is highly depleted in ITE (DMORB source) with only 10% of an enriched component (EMORB source), (2) the EMORB source is peridotitic rather than pyroxenitic, and (3) NMORB do not represent an actual mantle source, but the product of magma mixing between D- and E-MORB. Finally we use the volatile to trace element ratios of our samples to estimate the volatile element budget of the end-member components of the upper mantle. [1] Niu, Y. et al. (2002) EPSL, 199, 327-345. [2] Kamenetsky, V. S. et al. (2000) J. Petrology, 41, 411-430.

Mobility and fluxes of major, minor and trace metals during basalt weathering and groundwater transport at Mt. Etna volcano (Sicily)

NASA Astrophysics Data System (ADS)

Aiuppa, Alessandro; Allard, Patrick; D'Alessandro, Walter; Michel, Agnes; Parello, Francesco; Treuil, Michel; Valenza, Mariano

2000-06-01

The concentrations and fluxes of major, minor and trace metals were determined in 53 samples of groundwaters from around Mt Etna, in order to evaluate the conditions and extent of alkali basalt weathering by waters enriched in magma-derived CO 2 and the contribution of aqueous transport to the overall metal discharge of the volcano. We show that gaseous input of magmatic volatile metals into the Etnean aquifer is small or negligible, being limited by cooling of the rising fluids. Basalt leaching by weakly acidic, CO 2-charged water is the overwhelming source of metals and appears to be more extensive in two sectors of the S-SW (Paternò) and E (Zafferana) volcano flanks, where out flowing groundwaters are the richest in metals and bicarbonate of magmatic origin. Thermodynamic modeling of the results allows to evaluate the relative mobility and chemical speciation of various elements during their partitioning between solid and liquid phases through the weathering process. The facts that rock-forming minerals and groundmass dissolve at different rates and secondary minerals are formed are taken into account. At Mt. Etna, poorly mobile elements (Al, Th, Fe) are preferentially retained in the solid residue of weathering, while alkalis, alkaline earth and oxo-anion-forming elements (As, Se, Sb, Mo) are more mobile and released to the aqueous system. Transition metals display an intermediate behavior and are strongly dependent on either the redox conditions (Mn, Cr, V) or solid surface-related processes (V, Zn, Cu). The fluxes of metals discharged by the volcanic aquifer of Etna range from 7.0 × 10 -3 t/a (Th) to 7.3 × 10 4 t/a (Na). They are comparable in magnitude to the summit crater plume emissions for a series of elements (Na, K, Ca, Mg, U, V, Li) with lithophile affinity, but are minor for volatile elements. Basalt weathering at Mt Etna also consumes about 2.1 × 10 5 t/a of magma-derived carbon dioxide, equivalent to ca. 7% of contemporaneous crater plume emissions. The considerable transport of some metals in Etna's aquifer reflects a particularly high chemical erosion rate, evaluated at 2.3∗10 5 t/a, enhanced by the initial acidity of magmatic CO 2-rich groundwater.

The origin of inner Solar System water

NASA Astrophysics Data System (ADS)

Alexander, Conel M. O'D.

2017-04-01

Of the potential volatile sources for the terrestrial planets, the CI and CM carbonaceous chondrites are closest to the planets' bulk H and N isotopic compositions. For the Earth, the addition of approximately 2-4 wt% of CI/CM material to a volatile-depleted proto-Earth can explain the abundances of many of the most volatile elements, although some solar-like material is also required. Two dynamical models of terrestrial planet formation predict that the carbonaceous chondrites formed either in the asteroid belt (`classical' model) or in the outer Solar System (5-15 AU in the Grand Tack model). To test these models, at present the H isotopes of water are the most promising indicators of formation location because they should have become increasingly D-rich with distance from the Sun. The estimated initial H isotopic compositions of water accreted by the CI, CM, CR and Tagish Lake carbonaceous chondrites were much more D-poor than measured outer Solar System objects. A similar pattern is seen for N isotopes. The D-poor compositions reflect incomplete re-equilibration with H2 in the inner Solar System, which is also consistent with the O isotopes of chondritic water. On balance, it seems that the carbonaceous chondrites and their water did not form very far out in the disc, almost certainly not beyond the orbit of Saturn when its moons formed (approx. 3-7 AU in the Grand Tack model) and possibly close to where they are found today. This article is part of the themed issue 'The origin, history and role of water in the evolution of the inner Solar System'.

Carbon and sulfur budget of the silicate Earth explained by accretion of differentiated planetary embryos

NASA Astrophysics Data System (ADS)

Li, Yuan; Dasgupta, Rajdeep; Tsuno, Kyusei; Monteleone, Brian; Shimizu, Nobumichi

2016-10-01

The abundances of volatile elements in the Earth's mantle have been attributed to the delivery of volatile-rich material after the main phase of accretion. However, no known meteorites could deliver the volatile elements, such as carbon, nitrogen, hydrogen and sulfur, at the relative abundances observed for the silicate Earth. Alternatively, Earth could have acquired its volatile inventory during accretion and differentiation, but the fate of volatile elements during core formation is known only for a limited set of conditions. Here we present constraints from laboratory experiments on the partitioning of carbon and sulfur between metallic cores and silicate mantles under conditions relevant for rocky planetary bodies. We find that carbon remains more siderophile than sulfur over a range of oxygen fugacities; however, our experiments suggest that in reduced or sulfur-rich bodies, carbon is expelled from the segregating core. Combined with previous constraints, we propose that the ratio of carbon to sulfur in the silicate Earth could have been established by differentiation of a planetary embryo that was then accreted to the proto-Earth. We suggest that the accretion of a Mercury-like (reduced) or a sulfur-rich (oxidized) differentiated body--in which carbon has been preferentially partitioned into the mantle--may explain the Earth's carbon and sulfur budgets.

Space-weathering processes and products on volatile-rich asteroids

NASA Astrophysics Data System (ADS)

Britt, D.; Schelling, P.; Consolmagno, G.; Bradley, T.

2014-07-01

Space weathering is a generic term for the effects on atmosphereless solid bodies in the solar system from a range of processes associated with direct exposure to the space environment. These include impact processes (shock, vaporization, fragmentation, heating, melting, and ejecta formation), radiation damage (from galactic and solar cosmic rays), solar-wind effects (irradiation, ion implantation, and sputtering), and the chemical reactions driven by these processes. The classic example of space weathering is the formation of the lunar spectral red slope associated with the production of nanophase Fe (npFe0) in the dusty lunar regolith (C.R. Chapman, 2004, Annual Review of Earth & Planet. Sci. 32, C.M. Pieters, 2000, MAPS 35). Similar npFe0 has been recovered from asteroid (25143) Itokawa and some asteroid classes do exhibit modest spectral red slopes (T. Noguchi, 2011, Science 333). Space weathering can be thought of as driven by a combination of the chemical environment of space (hard vacuum, low oxygen fugacity, solar-wind implantation of hydrogen) along with thermal energy supplied by micrometeorite impacts. The forward modeling of space weathering as thermodynamically-driven decomposition of common rock-forming minerals suggests the production of a range of daughter products: (1) The silicate products typically lose oxygen, other volatile elements (i.e., sulfur and sodium), and metallic cations, producing minerals that are typically more disordered and less optically active than the original parent materials. (2) The decomposed metallic cations form in nano-sized blebs including npFe0, on the surfaces or in condensing rims of mineral grains. This creates a powerful optical component as seen in the lunar red slope. Surfaces with exposed npFe0 are an ideal environment for catalyzing further reactions. (3) The liberated volatile elements and gases (O, S, Na) may form an observable exosphere (e.g., Moon and Mercury) and can either escape from the body or recombine with available solar-wind-implanted hydrogen to form trace amounts of water and OH. Mineral decomposition can be thought of as the first stage of space weathering. It produces weathered surfaces somewhat depleted in volatile elements, creates a predictable set of minor or trace minerals, and leaves the surfaces with catalytic species, primarily npFe0. However, a second stage of further reactions and weathering depends upon the presence of ''feed-stock'' components that can participate in catalyzed chemical reactions on exposed surfaces. For volatile-rich small bodies, the available materials are not only silicates, but a volatile feedstock that can include water, carbon monoxide, ammonia, to name a few. Thermodynamically-driven decomposition of silicates will produce trace amounts of npFe0 which are ideal sites for Fischer-Tropsch type (FTT) catalytic reactions that can produce organics in situ on the asteroids including alkanes, polyaromatic hydrocarbons, and amino acids (J.E. Elsila, 2012, MAPS 47). The mix and range of products depends on the composition and morphology of the mineral surface, energy inputs produced by the micrometeorite impacts or other processes, and the composition of the input volatile feedstock. FFT reactions generate long-chain carbon compounds and amino acids. Secondary reactions that generate more complex carbon compounds and amino acids are likely to occur as the organic material matures. Weathering maturity can be thought of as a function of the abundance and diversity of the weathering products. Since the npFe0 is not destroyed in the reaction, continued micrometeorite bombardment would result in continuing processing and recombination of the existing organic feedstock. More weathering would result in progressively longer-chain carbon compounds as well as more complex and diverse amino acids, and eventually the kerogen-like insoluble-organic matter that forms a large fraction of carbonaceous meteorites. This insight has several major implications for our planetary science and, potentially, the formation of the precursors of life. First, the range of weathering products seen in remotely-sensed data, meteorites, and returned samples are not random, but the predictable outcome of the source region's mineral kinetics and chemical feedstock. Weathering products do not have to be optically active like the npFe0 that produces the lunar red slope; on the contrary, probably most weathering products are spectrally neutral or even suppress an object's near-IR reflectance spectrum. In the case of volatile-rich parent bodies, a major weathering product is a range of carbon-rich compounds. But an additional result of considerable interest is the generation of pre-biotic compounds as a routine and predictable byproduct of common space-weathering processes. Any atmosphereless body around any star with mafic silicate mineral compositions and volatile feedstocks should create amino acids as a standard byproduct of space weathering. The precursors of life are probably abundant in any space-weathered asteroid belt, in any solar system, and only wait being accreted to a hospitable environment.

Interpretations of phenocryst embayments

NASA Astrophysics Data System (ADS)

Rust, Alison; Cashman, Katharine

2017-04-01

Phenocryst embayments in volcanic samples tend to be filled with glass, regardless of the crystallinity and vesicularly of the groundmass surrounding the phenocryst. Embayments are important in volcanology and magma petrology because: 1) they often provide the only areas of matrix glass sufficient for compositional analysis in microlite-rich samples; 2) volatile gradients in embayments are used to constrain rates of magma ascent; 3) with further crystal growth, embayments may develop into melt inclusions, an essential source of data on melt composition evolution. Robust interpretations of data from embayments requires an understanding of why they form and why vesiculation and crystallisation are locally suppressed in these melt channels during ascent. We review instabilities in crystal growth and resorption, considering latent heat, local accumulation of elements, and interaction of the crystal growth front with pre-existing bubbles and other crystals. A survey of textures in volcanic samples from several volcanoes suggests that embayment formation by growth is more common than by resorption. Crystal nucleation suppression in the embayment of a growing phenocryst can be explained by buildup of excluded elements and continued growth (rather than nucleation) of the phenocryst phase. However, the suppression of bubble formation despite the accumulation of excluded volatiles is more difficult to explain but could be related to latent heat and difficulties in bubble formation in a restricted space. Finally, we flag complications in interpretations of embayment composition data due to element accumulation and bubble nucleation suppression.

Mix or un-mix? Trace element segregation from a heterogeneous mantle, simulated.

NASA Astrophysics Data System (ADS)

Katz, R. F.; Keller, T.; Warren, J. M.; Manley, G.

2016-12-01

Incompatible trace-element concentrations vary in mid-ocean ridge lavas and melt inclusions by an order of magnitude or more, even in samples from the same location. This variability has been attributed to channelised melt flow [Spiegelman & Kelemen, 2003], which brings enriched, low-degree melts to the surface in relative isolation from depleted inter-channel melts. We re-examine this hypothesis using a new melting-column model that incorporates mantle volatiles [Keller & Katz 2016]. Volatiles cause a deeper onset of channelisation: their corrosivity is maximum at the base of the silicate melting regime. We consider how source heterogeneity and melt transport shape trace-element concentrations in basaltic lavas. We use both equilibrium and non-equilibrium formulations [Spiegelman 1996]. In particular, we evaluate the effect of melt transport on probability distributions of trace element concentration, comparing the inflow distribution in the mantle with the outflow distribution in the magma. Which features of melt transport preserve, erase or overprint input correlations between elements? To address this we consider various hypotheses about mantle heterogeneity, allowing for spatial structure in major components, volatiles and trace elements. Of interest are the roles of wavelength, amplitude, and correlation of heterogeneity fields. To investigate how different modes of melt transport affect input distributions, we compare melting models that produce either shallow or deep channelisation, or none at all.References:Keller & Katz (2016). The Role of Volatiles in Reactive Melt Transport in the Asthenosphere. Journal of Petrology, http://doi.org/10.1093/petrology/egw030. Spiegelman (1996). Geochemical consequences of melt transport in 2-D: The sensitivity of trace elements to mantle dynamics. Earth and Planetary Science Letters, 139, 115-132. Spiegelman & Kelemen (2003). Extreme chemical variability as a consequence of channelized melt transport. Geochemistry Geophysics Geosystems, http://doi.org/10.1029/2002GC000336

Final Summary of Research Report to the National Aeronautics and Space Administration Origins of Solar Systems Program

NASA Technical Reports Server (NTRS)

O'D. Alexander, Conel

2003-01-01

The chondrites are aggregates of components (e.g. chondrules, chondrule rims and matrix) that formed in the nebula but, at present, there is no consensus on how any of these components formed or whether their formation produced or post dated the chemical fractionations between the chondrites. Chondrites are, at present, the most primitive Solar System objects available for laboratory study and the conditions under which their principle components formed would provide the most direct constraints for models of nebula formation and evolution. The conditions under which chondrules formed is of particular importance because, if their relative abundance in chondrites approximates that in the nebula, they are the products of one of the most energetic and pervasive processes that operated in the early Solar System. The goal of this proposal was to combine theoretical modeling with a comprehensive study of the elemental and isotopic compositions of the major components in unequilibrated ordinary chondrites (UOCs), with the aim of determining the conditions in the nebula at the time of their formation. The isotopes of volatile and moderately volatile elements should be particularly revealing of conditions during chondrule formation, as evaporation under most conditions would lead to isotopic mass fractionation. Modeling of chondrule and matrix formation requires the development of a kinetic model of evaporation and condensation, and calibration of this model against experiments. Cosmic spherules present an opportunity to test our evaporation models under flash heating conditions that would be difficult to simulate experimentally. However, there is surprisingly little known about the isotopic compositions of silicate cosmic spherules, and a number of questions need to be addressed. Is the range of compositions they exhibit due to evaporation? If they are, are the relative volatilities consistent with the models/experiments and are the isotopic fractionations consistent with Rayleigh conditions? For instance, do the alkalis and S evaporate prior to significant melting so that conditions did not meet the Rayleigh criteria of rapid diffusion? If so, their isotopic fractionation might be considerably suppressed. Could this mechanism of K loss apply to chondrule formation? The Fe isotopic fractionation during evaporation of silicates has not been measured, so cosmic spherules might provide a clue to whether FeO diffusion is fast enough to maintain Rayleigh conditions during evaporation. And so on.

Depletion of chlorine into HCl ice in a protostellar core. The CHESS spectral survey of OMC-2 FIR 4

NASA Astrophysics Data System (ADS)

Kama, M.; Caux, E.; López-Sepulcre, A.; Wakelam, V.; Dominik, C.; Ceccarelli, C.; Lanza, M.; Lique, F.; Ochsendorf, B. B.; Lis, D. C.; Caballero, R. N.; Tielens, A. G. G. M.

2015-02-01

Context. The freezeout of gas-phase species onto cold dust grains can drastically alter the chemistry and the heating-cooling balance of protostellar material. In contrast to well-known species such as carbon monoxide (CO), the freezeout of various carriers of elements with abundances <10-5 has not yet been well studied. Aims: Our aim here is to study the depletion of chlorine in the protostellar core, OMC-2 FIR 4. Methods: We observed transitions of HCl and H2Cl+ towards OMC-2 FIR 4 using the Herschel Space Observatory and Caltech Submillimeter Observatory facilities. Our analysis makes use of state of the art chlorine gas-grain chemical models and newly calculated HCl-H2 hyperfine collisional excitation rate coefficients. Results: A narrow emission component in the HCl lines traces the extended envelope, and a broad one traces a more compact central region. The gas-phase HCl abundance in FIR 4 is 9 × 10-11, a factor of only 10-3 that of volatile elemental chlorine. The H2Cl+ lines are detected in absorption and trace a tenuous foreground cloud, where we find no depletion of volatile chlorine. Conclusions: Gas-phase HCl is the tip of the chlorine iceberg in protostellar cores. Using a gas-grain chemical model, we show that the hydrogenation of atomic chlorine on grain surfaces in the dark cloud stage sequesters at least 90% of the volatile chlorine into HCl ice, where it remains in the protostellar stage. About 10% of chlorine is in gaseous atomic form. Gas-phase HCl is a minor, but diagnostically key reservoir, with an abundance of ≲10-10 in most of the protostellar core. We find the [35Cl]/[37Cl] ratio in OMC-2 FIR 4 to be 3.2 ± 0.1, consistent with the solar system value. Appendices are available in electronic form at http://www.aanda.org

Evolution of the protolunar disk: Dynamics, cooling timescale and implantation of volatiles onto the Earth

NASA Astrophysics Data System (ADS)

Charnoz, Sébastien; Michaut, Chloé

2015-11-01

It is thought that the Moon accreted from the protolunar disk that was assembled after the last giant impact on Earth. Due to its high temperature, the protolunar disk may act as a thermochemical reactor in which the material is processed before being incorporated into the Moon. Outstanding issues like devolatilisation and istotopic evolution are tied to the disk evolution, however its lifetime, dynamics and thermodynamics are unknown. Here, we numerically explore the long term viscous evolution of the protolunar disk using a one dimensional model where the different phases (vapor and condensed) are vertically stratified. Viscous heating, radiative cooling, phase transitions and gravitational instability are accounted for whereas Moon's accretion is not considered for the moment. The viscosity of the gas, liquid and solid phases dictates the disk evolution. We find that (1) the vapor condenses into liquid in ∼10 years, (2) a large fraction of the disk mass flows inward forming a hot and compact liquid disk between 1 and 1.7 Earth's radii, a region where the liquid is gravitationally stable and can accumulate, (3) the disk finally solidifies in 103 to 105 years. Viscous heating is never balanced by radiative cooling. If the vapor phase is abnormally viscous, due to magneto-rotational instability for instance, most of the disk volatile components are transported to Earth leaving a disk enriched in refractory elements. This opens a way to form a volatile-depleted Moon and would suggest that the missing Moon's volatiles are buried today into the Earth. The disk cooling timescale may be long enough to allow for planet/disk isotopic equilibration. However large uncertainties on the disk physics remain because of the complexity of its multi-phased structure.

Characteristics of a non-volatile liquid propellant in liquid-fed ablative pulsed plasma thrusters

NASA Astrophysics Data System (ADS)

Ling, William Yeong Liang; Schönherr, Tony; Koizumi, Hiroyuki

2017-02-01

In the past several decades, the use of electric propulsion in spacecraft has experienced tremendous growth. With the increasing adoption of small satellites in the kilogram range, suitable propulsion systems will be necessary in the near future. Pulsed plasma thrusters (PPTs) were the first form of electric propulsion to be deployed in orbit, and are highly suitable for small satellites due to their inherent simplicity. However, their lifetime is limited by disadvantages such as carbon deposition leading to thruster failure, and complicated feeding systems required due to the conventional use of solid propellants (usually polytetrafluoroethylene (PTFE)). A promising alternative to solid propellants has recently emerged in the form of non-volatile liquids that are stable in vacuum. This study presents a broad comparison of the non-volatile liquid perfluoropolyether (PFPE) and solid PTFE as propellants on a PPT with a common design base. We show that liquid PFPE can be successfully used as a propellant, and exhibits similar plasma discharge properties to conventional solid PTFE, but with a mass bit that is an order of magnitude higher for an identical ablation area. We also demonstrate that the liquid PFPE propellant has exceptional resistance to carbon deposition, completely negating one of the major causes of thruster failure, while solid PTFE exhibited considerable carbon build-up. Energy dispersive X-ray spectroscopy was used to examine the elemental compositions of the surface deposition on the electrodes and the ablation area of the propellant (or PFPE encapsulator). The results show that based on its physical characteristics and behavior, non-volatile liquid PFPE is an extremely promising propellant for use in PPTs, with an extensive scope available for future research and development.

Immobilization and bonding scheme of radioactive iodine-129 in silver tellurite glass

NASA Astrophysics Data System (ADS)

Lee, Cheong Won; Pyo, Jae-Young; Park, Hwan-Seo; Yang, Jae Hwan; Heo, Jong

2017-08-01

Silver tellurite glasses with melting temperatures < 700 °C were prepared to immobilize the 129I that normally volatilizes during high-temperature melting. Glasses have densities of 6.31 ± 0.1 g/cm3 and glass transition temperatures of 165 ± 3 °C that provide thermal stability at the disposal site. Iodine waste loading in glasses was as high as 12.64 wt% of all metallic elements and 11.21 wt% including oxygen. Normalized elemental releases obtained from the product consistency test were well below US regulation of 2 g/m2. Iodines are surrounded by four Ag+ ions forming [Ag4I]3+ units that are further connected to tellurite network through bonds with non-bridging oxygens.

Lunar bulk chemical composition: a post-Gravity Recovery and Interior Laboratory reassessment

PubMed Central

Taylor, G. Jeffrey; Wieczorek, Mark A.

2014-01-01

New estimates of the thickness of the lunar highlands crust based on data from the Gravity Recovery and Interior Laboratory mission, allow us to reassess the abundances of refractory elements in the Moon. Previous estimates of the Moon fall into two distinct groups: earthlike and a 50% enrichment in the Moon compared with the Earth. Revised crustal thicknesses and compositional information from remote sensing and lunar samples indicate that the crust contributes 1.13–1.85 wt% Al2O3 to the bulk Moon abundance. Mare basalt Al2O3 concentrations (8–10 wt%) and Al2O3 partitioning behaviour between melt and pyroxene during partial melting indicate mantle Al2O3 concentration in the range 1.3–3.1 wt%, depending on the relative amounts of pyroxene and olivine. Using crustal and mantle mass fractions, we show that that the Moon and the Earth most likely have the same (within 20%) concentrations of refractory elements. This allows us to use correlations between pairs of refractory and volatile elements to confirm that lunar abundances of moderately volatile elements such as K, Rb and Cs are depleted by 75% in the Moon compared with the Earth and that highly volatile elements, such as Tl and Cd, are depleted by 99%. The earthlike refractory abundances and depleted volatile abundances are strong constraints on lunar formation processes. PMID:25114309

Lunar bulk chemical composition: a post-Gravity Recovery and Interior Laboratory reassessment.

PubMed

Taylor, G Jeffrey; Wieczorek, Mark A

2014-09-13

New estimates of the thickness of the lunar highlands crust based on data from the Gravity Recovery and Interior Laboratory mission, allow us to reassess the abundances of refractory elements in the Moon. Previous estimates of the Moon fall into two distinct groups: earthlike and a 50% enrichment in the Moon compared with the Earth. Revised crustal thicknesses and compositional information from remote sensing and lunar samples indicate that the crust contributes 1.13-1.85 wt% Al2O3 to the bulk Moon abundance. Mare basalt Al2O3 concentrations (8-10 wt%) and Al2O3 partitioning behaviour between melt and pyroxene during partial melting indicate mantle Al2O3 concentration in the range 1.3-3.1 wt%, depending on the relative amounts of pyroxene and olivine. Using crustal and mantle mass fractions, we show that that the Moon and the Earth most likely have the same (within 20%) concentrations of refractory elements. This allows us to use correlations between pairs of refractory and volatile elements to confirm that lunar abundances of moderately volatile elements such as K, Rb and Cs are depleted by 75% in the Moon compared with the Earth and that highly volatile elements, such as Tl and Cd, are depleted by 99%. The earthlike refractory abundances and depleted volatile abundances are strong constraints on lunar formation processes. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

Potential health impacts of burning coal beds and waste banks

USGS Publications Warehouse

Finkelman, R.B.

2004-01-01

Uncontrolled release of pollutants from burning coal beds and waste banks presents potential environmental and human health hazards. On a global scale, the emissions of large volumes of greenhouse gases from burning coal beds may contribute to climate change that alters ecosystems and patterns of disease occurrence. On regional and local scales, the emissions from burning coal beds and waste banks of acidic gases, particulates, organic compounds, and trace elements can contribute to a range of respiratory and other human health problems. Although there are few published reports of health problems caused by these emissions, the potential for problems can be significant. In India, large numbers of people have been displaced from their homes because of health problems caused by emissions from burning coal beds. Volatile elements such as arsenic, fluorine, mercury, and selenium are commonly enriched in coal deposits. Burning coal beds can volatilize these elements, which then can be inhaled, or adsorbed on crops and foods, taken up by livestock or bioaccumulated in birds and fish. Some of these elements can condense on dust particles that can be inhaled or ingested. In addition, selenium, arsenic, lead, tin, bismuth, fluorine, and other elements condense where the hot gaseous emissions come in contact with ambient air, forming mats of concentrated efflorescent minerals on the surface of the ground. These mats can be leached by rainwater and washed into local water bodies providing other potential routes of exposure. Although there are little data linking burning coal beds and waste banks to known health problems, a possibly analogous situation exists in rural China where mineralized coal burned in a residential environment has caused widespread and severe health problems such as fluorosis and arseniasis. ?? 2004 Elsevier B.V. All rights reserved.

Petrology of enstatite chondrites and anomalous enstatite achondrites

NASA Astrophysics Data System (ADS)

van Niekerk, Deon

2012-01-01

Chondrites are meteorites that represent unmelted portions of asteroids. The enstatite chondrites are one class of chondrites. They consist of reduced mineral assemblages that formed under low oxygen fugacity in the solar nebula, prior to accretion into asteroids. There are two groups of enstatite chondrites---EH and EL. I studied EL3 meteorites, which are understood to be unmetamorphosed and thus to only preserve primitive nebular products. I show in a petrographic study that the EL3s are in fact melt--breccias in which impact-melting produced new mineral assemblages and textures in portions of the host chondrites, after accretion. I document meta- land sulfide assemblages that are intergrown with silicate minerals (which are often euhedral), and occur outside chondrules; these assemblages probably represent impact-melting products, and are different from those in EH3 chondrites that probably represent nebular products. In situ siderophile trace element compositions of the metal in EL3s, obtained by laser ablation inductively coupled plasma mass spectrometry, are consistent with an impact-melting hypothesis. The trace element concentrations show no clear volatility trend, and are thus probably not the result of volatile-driven petrogenetic processes that operated in the solar nebula. Trace element modeling suggests that the character of the trace element patterns together with deviations from the mean bulk EL metal pattern is consistent with metal that crystallized in a coexisting liquid-solid metal system in which dissolved carbon influenced element partitioning. I also conducted a petrographic and mineral-chemistry study of several anomalous enstatite meteorites. These have igneous textures, but unfractionated mineralogy similar to unmelted chondrites. I show that with the exception of one, the meteorites are related to each other, and probably formed by crystallization from an impact melt instead of metamorphism through the decay of short lived radionuclides. The broad importance of these studies lies in documenting the petrology of extraterrestrial materials that reveal the geological history of the young solar system prior to the existence of planets. Furthermore, they serve to identify which mineral assemblages record nebular processes and which record processes on asteroids, so that future studies may select the correct material to address particular questions.

Asteroidal impacts and the origin of terrestrial and lunar volatiles

NASA Astrophysics Data System (ADS)

Albarede, Francis; Ballhaus, Chris; Blichert-Toft, Janne; Lee, Cin-Ty; Marty, Bernard; Moynier, Frédéric; Yin, Qing-Zhu

2013-01-01

Asteroids impacting the Earth partly volatilize, partly melt (O'Keefe, J.D., Ahrens, T.J. [1977]. Proc. Lunar Sci. Conf. 8, 3357-3374). While metal rapidly segregates out of the melt and sinks into the core, the vaporized material orbits the Earth and eventually rains back onto its surface. The content of the mantle in siderophile elements and their chondritic relative abundances hence is accounted for, not by the impactors themselves, as in the original late-veneer model (Chou, C.L. [1978]. Proc. Lunar Sci. Conf. 9, 219-230; Morgan, J.W. et al. [1981]. Tectonophysics 75, 47-67), but by the vapor resulting from impacts. The impactor's non-siderophile volatiles, notably hydrogen, are added to the mantle and hydrosphere. The addition of late veneer may have lasted for 130 Ma after isolation of the Solar System and probably longer, i.e., well beyond the giant lunar impact. Constraints from the stable isotopes of oxygen and other elements suggest that, contrary to evidence from highly siderophile elements, ˜4% of CI chondrites accreted to the Earth. The amount of water added in this way during the waning stages of accretion, and now dissolved in the deep mantle or used to oxidize Fe in the mantle and the core, may correspond to 10-25 times the mass of the present-day ocean. The Moon is at least 100 times more depleted than the Earth in volatile elements with the exception of some isolated domains, such as the mantle source of 74220 pyroclastic glasses, which appear to contain significantly higher concentrations of water and other volatiles.

Volatiles in melt inclusions from Icelandic magmas

NASA Astrophysics Data System (ADS)

Nichols, A. R.; Wysoczanski, R. J.; Carroll, M. R.

2006-12-01

Melt inclusions hosted in olivine crystals from the glassy rims of subglacially erupted pillow basalts on Iceland have been analysed for volatiles, major elements and trace elements. Volatile measurements were undertaken using Fourier-Transform InfraRed spectroscopy utilising a novel technique which enables unexposed and much smaller inclusions than were previously possible to be analysed. Major elements were measured using electron microprobe and trace elements by laser ablation-inductively coupled plasma-mass spectrometry. Comparison between initial results from the inclusions and the compositions of the bulk glasses show that the inclusions are less evolved and contain more H2O at the same MgO content. In addition many of the inclusions have higher H2O/K2O than their bulk glasses and some even contain CO2 (up to 629 ppm), which is below detection limits in the bulk glasses. This indicates that these inclusions are less affected by degassing. Two inclusions have extreme H2O/K2O (> 10), possibly suggesting that they have assimilated hydrous crustal material. The volatile and major element compositions of the bulk glasses have been used to suggest that the Iceland mantle plume is wet. However, trace element measurements show that enriched Iceland magmas have lower H2O/Ce than the adjacent Reykjanes Ridge. This could reflect syn-eruptive degassing or mixing between undegassed and recycled degassed magmas. Alternatively Iceland magmas could be derived from the EM (enriched mantle) component, which is believed to represent recycled oceanic crust. It is suggested that this material is efficiently dehydrated during the subduction process, so even though it has an enriched character, H2O is relatively depleted. As a result, EM melts have higher absolute H2O contents than mid- ocean ridge basalts (MORB), but lower H2O/Ce (or other H2O-incompatible element ratios), which has led to EM plumes being termed `dampspots'. The inclusion data will be presented in this context. Their compositions will show how the melt has evolved, enabling the relative roles of degassing, crystallisation and assimilation in the volatile systematics to be examined.

CHEMISTRY OF SILICATE ATMOSPHERES OF EVAPORATING SUPER-EARTHS

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

Schaefer, Laura; Fegley, Bruce, E-mail: laura_s@levee.wustl.ed, E-mail: bfegley@levee.wustl.ed

2009-10-01

We model the formation of silicate atmospheres on hot volatile-free super-Earths. Our calculations assume that all volatile elements such as H, C, N, S, and Cl have been lost from the planet. We find that the atmospheres are composed primarily of Na, O{sub 2}, O, and SiO gas, in order of decreasing abundance. The atmospheric composition may be altered by fractional vaporization, cloud condensation, photoionization, and reaction with any residual volatile elements remaining in the atmosphere. Cloud condensation reduces the abundance of all elements in the atmosphere except Na and K. We speculate that large Na and K clouds suchmore » as those observed around Mercury and Io may surround hot super-Earths. These clouds would occult much larger fractions of the parent star than a closely bound atmosphere, and may be observable through currently available methods.« less

The lead isotopic age of the Earth can be explained by core formation alone.

PubMed

Wood, Bernard J; Halliday, Alex N

2010-06-10

The meaning of the age of the Earth defined by lead isotopes has long been unclear. Recently it has been proposed that the age of the Earth deduced from lead isotopes reflects volatile loss to space at the time of the Moon-forming giant impact rather than partitioning into metallic liquids during protracted core formation. Here we show that lead partitioning into liquid iron depends strongly on carbon content and that, given a content of approximately 0.2% carbon, experimental and isotopic data both provide evidence of strong partitioning of lead into the core throughout the Earth's accretion. Earlier conclusions that lead is weakly partitioned into iron arose from the use of carbon-saturated (about 5% C) iron alloys. The lead isotopic age of the Earth is therefore consistent with partitioning into the core and with no significant late losses of moderately volatile elements to space during the giant impact.

Quantitative Analysis of Charge Injection and Discharging of Si Nanocrystals and Arrays by Electrostatic Force Microscopy

NASA Technical Reports Server (NTRS)

Bell, L. D.; Boer, E.; Ostraat, M.; Brongersma, M. L.; Flagan, R. C.; Atwater, H. A.

2000-01-01

NASA requirements for computing and memory for microspacecraft emphasize high density, low power, small size, and radiation hardness. The distributed nature of storage elements in nanocrystal floating-gate memories leads to intrinsic fault tolerance and radiation hardness. Conventional floating-gate non-volatile memories are more susceptible to radiation damage. Nanocrystal-based memories also offer the possibility of faster, lower power operation. In the pursuit of filling these requirements, the following tasks have been accomplished: (1) Si nanocrystal charging has been accomplished with conducting-tip AFM; (2) Both individual nanocrystals on an oxide surface and nanocrystals formed by implantation have been charged; (3) Discharging is consistent with tunneling through a field-lowered oxide barrier; (4) Modeling of the response of the AFM to trapped charge has allowed estimation of the quantity of trapped charge; and (5) Initial attempts to fabricate competitive nanocrystal non-volatile memories have been extremely successful.

Calcium and Titanium Isotope Fractionation in CAIS: Tracers of Condensation and Inheritance in the Early Solar Protoplanetary Disk

NASA Technical Reports Server (NTRS)

Simon, J. I.; Jordan, M. K.; Tappa, M. J.; Kohl, I. E.; Young, E. D.

2016-01-01

The chemical and isotopic compositions of calcium-aluminum-rich inclusions (CAIs) can be used to understand the conditions present in the protoplantary disk where they formed. The isotopic compositions of these early-formed nebular materials are largely controlled by chemical volatility. The isotopic effects of evaporation/sublimation, which are well explained by both theory and experimental work, lead to enrichments of the heavy isotopes that are often exhibited by the moderately refractory elements Mg and Si. Less well understood are the isotopic effects of condensation, which limits our ability to determine whether a CAI is a primary condensate and/or retains any evidence of its primordial formation history.

A volatile rich Earth's core?

NASA Astrophysics Data System (ADS)

Morard, G.; Antonangeli, D.; Andrault, D.; Nakajima, Y.

2017-12-01

The composition of the Earth's core is still an open question. Although mostly composed of iron, it contains impurities that lower its density and melting point with respect to pure Fe. Knowledge of the nature and abundance of light elements (O, S, Si, C or H) in the core has major implications for establishing the bulk composition of the Earth and for building the model of Earth's differentiation. Geochemical models of the Earth's formation point out that its building blocks were depleted in volatile elements compared to the chondritic abundance, therefore light elements such as S, H or C cannot be the major elements alloyed with iron in the Earth's core. However, such models should be compatible with the comparison of seismic properties of the Earth's core and physical properties of iron alloys under extreme conditions, such as sound velocity or density of solid and liquid. The present work will discuss the recent progress for compositional model issued from studies of phase diagrams and elastic properties of iron alloys under core conditions and highlight the compatibility of volatile elements with observed properties of the Earth's core, in potential contradiction with models derived from metal-silicate partitioning experiments.

Genesis of Middle Miocene Yellowstone hotspot-related bonanza epithermal Au-Ag deposits, Northern Great Basin, USA

NASA Astrophysics Data System (ADS)

Saunders, J. A.; Unger, D. L.; Kamenov, G. D.; Fayek, M.; Hames, W. E.; Utterback, W. C.

2008-09-01

Epithermal deposits with bonanza Au-Ag veins in the northern Great Basin (NGB) are spatially and temporally associated with Middle Miocene bimodal volcanism that was related to a mantle plume that has now migrated to the Yellowstone National Park area. The Au-Ag deposits formed between 16.5 and 14 Ma, but exhibit different mineralogical compositions, the latter due to the nature of the country rocks hosting the deposits. Where host rocks were primarily of meta-sedimentary or granitic origin, adularia-rich gold mineralization formed. Where glassy rhyolitic country rocks host veins, colloidal silica textures and precious metal-colloid aggregation textures resulted. Where basalts are the country rocks, clay-rich mineralization (with silica minerals, adularia, and carbonate) developed. Oxygen isotope data from quartz (originally amorphous silica and gels) from super-high-grade banded ores from the Sleeper deposit show that ore-forming solutions had δ 18O values up to 10‰ heavier than mid-Miocene meteoric water. The geochemical signature of the ores (including their Se-rich nature) is interpreted here to reflect a mantle source for the “epithermal suite” elements (Au, Ag, Se, Te, As, Sb, Hg) and that signature is preserved to shallow crustal levels because of the similar volatility and aqueous geochemical behavior of the “epithermal suite” elements. A mantle source for the gold in the deposits is further supported by the Pb isotopic signature of the gold ores. Apparently the host rocks control the mineralization style and gangue mineralogy of ores. However, all deposits are considered to have derived precious metals and metalloids from mafic magmas related to the initial emergence of the Yellowstone hotspot. Basalt-derived volatiles and metal(loid)s are inferred to have been absorbed by meteoric-water-dominated geothermal systems heated by shallow rhyolitic magma chambers. Episodic discharge of volatiles and metal(loid)s from deep basaltic magmas mixed with heated meteoric water to create precious metal ore-forming fluids. Colloidal nanoparticles of Au-Ag alloy (electrum), naumannite (Ag2Se), silica, and adularia, likely nucleated at depth, traveled upward, and deposited where they grew large enough to aggregate along vein walls. Silica and gold colloids have been reported in hot springs from Yellowstone National Park, suggesting that such processes may continue to some extent to the present. However, it is possible that the initial development of the mantle plume led to a major but short-lived “distillation” process which led to the mid-Miocene bonanza ore-forming event.

Metal-Metal Bonds and Metal Carbon Bonds in the Chemistry of Molybdenum and Tungsten Alkoxides.

DTIC Science & Technology

1983-02-07

properties. For example, the lanthanide elements and aluminum form an extensive series of isopropoxides of formula MAI3 (OPr i)12 which are volatile solids or...coordination is imposed. !E 2 RO RO RO-_ 0 1_-OR ROe MV’*’ I ’%OR RO RRO (2) The ethoxides and methoxides of titanium (+4) adopt a tetrameric structure in the...solid state, II, whereby each metal atom achieves an octahedral environment. In benzene solution, the titanium ethoxide dissoci- ates to trimers, while

Siderophile Volatile Element Partitioning during Core Formation.

NASA Astrophysics Data System (ADS)

Loroch, D. C.; Hackler, S.; Rohrbach, A.; Klemme, S.

2017-12-01

Since the nineteen sixties it is known, that the Earth's mantle is depleted relative to CI chondrite in numerous elements as a result of accretion and core-mantle differentiation. Additionally, if we take the chondritic composition as the initial solar nebular element abundances, the Earth lacks 85 % of K and up to 98 % of other volatiles. However one potentially very important group of elements has received considerably less attention in this context and these elements are the siderophile but volatile elements (SVEs). SVEs perhaps provide important information regarding the timing of volatile delivery to Earth. Especially for the SVEs the partitioning between metal melt and silicate melt (Dmetal/silicate) at core formation conditions is poorly constrained, never the less they are very important for most of the core formation models. This study is producing new metal-silicate partitioning data for a wide range of SVEs (S, Se, Te, Tl, Ag, As, Au, Cd, Bi, Pb, Sn, Cu, Ge, Zn, In and Ga) with a focus on the P, T and fO2dependencies. The initial hypothesis that we are aiming to test uses the accretion of major portions of volatile elements while the core formation was still active. The key points of this study are: - What are the effects of P, T and fO2 on SVE metal-silicate partioning? - What is the effect of compositional complexity on SVE metal-silicate partioning? - How can SVE's D-values fit into current models of core formation? The partitioning experiments will be performed using a Walker type multi anvil apparatus in a pressure range between 10 and 20 GPa and temperatures of 1700 up to 2100 °C. To determine the Dmetal/silicate values we are using a field emission high-resolution JEOL JXA-8530F EPMA for major elements and a Photon Machines Analyte G2 Excimer laser (193 nm) ablation system coupled to a Thermo Fisher Element 2 single-collector ICP-MS (LA-ICP-MS) for the trace elements. We recently finished the first sets of experiments and can provide the corresponding datasets. Based on the general understanding of Dmetal/silicate values we expect to depend on the composition, in this particular case this means a variation in sulfur and carbon content of the core composition, and also a change of the redox conditions. The major goal however is to derive a model of core formation on Earth that includes and also explains the SVEs.

Linearization of calibration curves by aerosol carrier effect of CCl 4 vapor in electrothermal vaporization inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Kántor, Tibor; de Loos-Vollebregt, Margaretha T. C.

2005-03-01

Carbon tetrachloride vapor as gaseous phase modifier in a graphite furnace electrothermal vaporizer (GFETV) converts heavy volatile analyte forms to volatile and medium volatile chlorides and produces aerosol carrier effect, the latter being a less generally recognized benefit. However, the possible increase of polyatomic interferences in inductively coupled plasma mass spectrometry (GFETV-ICP-MS) by chlorine and carbon containing species due to CCl 4 vapor introduction has been discouraging with the use of low resolution, quadrupole type MS equipment. Being aware of this possible handicap, it was aimed at to investigate the feasibility of the use of this halogenating agent in ICP-MS with regard of possible hazards to the instrument, and also to explore the advantages under these specific conditions. With sample gas flow (inner gas flow) rate not higher than 900 ml min -1 Ar in the torch and 3 ml min -1 CCl 4 vapor flow rate in the furnace, the long-term stability of the instrument was ensured and the following benefits by the halocarbon were observed. The non-linearity error (defined in the text) of the calibration curves (signal versus mass functions) with matrix-free solution standards was 30-70% without, and 1-5% with CCl 4 vapor introduction, respectively, at 1 ng mass of Cu, Fe, Mn and Pb analytes. The sensitivity for these elements increased by 2-4-fold with chlorination, while the relative standard deviation (RSD) was essentially the same (2-5%) for the two cases in comparison. A vaporization temperature of 2650 °C was required for Cr in Ar atmosphere, while 2200 °C was sufficient in Ar + CCl 4 atmosphere to attain complete vaporization. Improvements in linear response and sensitivity were the highest for this least volatile element. The pyrolytic graphite layer inside the graphite tube was protected by the halocarbon, and tube life time was further increased by using traces of hydrocarbon vapor in the external sheath gas of the graphite furnace. Details of the modification of the gas supply for HGA-600MS furnace and the design of the volatilization device are described.

From Dust to Planets: The Tale Told by Moderately Volatile Element Depletion (MOVED)

NASA Technical Reports Server (NTRS)

Yin, Qing-Zhu

2004-01-01

The pronounced depletion of moderately volatile elements (MOVE, that condense or evaporate at temperatures in the range 1350-650K) relative to the average solar composition is a characteristic feature in most primitive chondrites and bulk terrestrial planets. It differs from the composition of the Sun and from the materials further away from the Sun (CI chondrites). None of the remaining planets or even meteorites shows an enrichment of volatile elements that would balance the depletion in the inner Solar System. Whether this depletion occurred in solar nebular stage or in planetary formation stage has been the subject of long lasting debate. The search for mysterite initiated in 1973 continues today in search of lost planets. Here I show that the MOVED patterns demonstrate a clear connection between the rocky materials of the inner solar system and the interstellar dust. The inheritance of interstellar materials by the solar system is not only documented by the presence of presolar grains, various isotopic anomalies, but also expressed in the chemical element distribution in the inner solar system.

The partitioning behavior of trace element and its distribution in the surrounding soil of a cement plant integrated utilization of hazardous wastes.

PubMed

Yang, Zhenzhou; Chen, Yan; Sun, Yongqi; Liu, Lili; Zhang, Zuotai; Ge, Xinlei

2016-07-01

In the present study, the trace elements partitioning behavior during cement manufacture process were systemically investigated as well as their distribution behaviors in the soil surrounding a cement plant using hazardous waste as raw materials. In addition to the experimental analysis, the thermodynamic equilibrium calculations were simultaneously conducted. The results demonstrate that in the industrial-scale cement manufacture process, the trace elements can be classified into three groups according to their releasing behaviors. Hg is recognized as a highly volatile element, which almost totally partitions into the vapor phase. Co, Cu, Mn, V, and Cr are considered to be non-volatile elements, which are largely incorporated into the clinker. Meanwhile, Cd, Ba, As, Ni, Pb, and Zn can be classified into semi-volatile elements, as they are trapped into clinker to various degrees. Furthermore, the trace elements emitted into the flue gas can be adsorbed onto the fine particles, transport and deposit in the soil, and it is clarified here that the soil around the cement plant is moderately polluted by Cd, slightly polluted by As, Cr, Ba, Zn, yet rarely influenced by Co, Mn, Ni, Cu, Hg, and V elements. It was also estimated that the addition of wastes can efficiently reduce the consumption of raw materials and energy. The deciphered results can thus provide important insights for estimating the environmental impacts of the cement plant on its surroundings by utilizing wastes as raw materials.

The origin of inner Solar System water.

PubMed

Alexander, Conel M O'D

2017-05-28

Of the potential volatile sources for the terrestrial planets, the CI and CM carbonaceous chondrites are closest to the planets' bulk H and N isotopic compositions. For the Earth, the addition of approximately 2-4 wt% of CI/CM material to a volatile-depleted proto-Earth can explain the abundances of many of the most volatile elements, although some solar-like material is also required. Two dynamical models of terrestrial planet formation predict that the carbonaceous chondrites formed either in the asteroid belt ('classical' model) or in the outer Solar System (5-15 AU in the Grand Tack model). To test these models, at present the H isotopes of water are the most promising indicators of formation location because they should have become increasingly D-rich with distance from the Sun. The estimated initial H isotopic compositions of water accreted by the CI, CM, CR and Tagish Lake carbonaceous chondrites were much more D-poor than measured outer Solar System objects. A similar pattern is seen for N isotopes. The D-poor compositions reflect incomplete re-equilibration with H 2 in the inner Solar System, which is also consistent with the O isotopes of chondritic water. On balance, it seems that the carbonaceous chondrites and their water did not form very far out in the disc, almost certainly not beyond the orbit of Saturn when its moons formed (approx. 3-7 AU in the Grand Tack model) and possibly close to where they are found today.This article is part of the themed issue 'The origin, history and role of water in the evolution of the inner Solar System'. © 2017 The Author(s).

Chlorine and Sulfur Volatiles from in Situ Measurements of Martian Surface Materials

NASA Astrophysics Data System (ADS)

Clark, B. C.

2014-12-01

A sentinel discovery by the first in situ measurements on Mars was the high sulfur and chlorine content of global-wide soils. A variety of circumstantial evidence led to the conclusion that soil S is in the form of sulfate, and the Cl is probably chloride. An early hypothesis states that these volatiles are emitted as gases from magmas, and quickly react with dust, soil, and exposed rocks. Subsequent determination that SNC meteorites are also samples of the martian crust revealed a significantly higher S content, as sulfide, than terrestrial igneous rocks but substantially less than in soils. The ensuing wet chemical analyses by the high-latitude Phoenix mission discovered not only chloride but also perchlorate and possibly chlorate. MSL data now also implicate perchlorate at low latitudes. Gaseous interactions may have produced amorphous material on grain surfaces without forming stoichiometric salts. Yet, when exposed to liquid water, Phoenix samples released electrolytes, indicating that the soils have not been leached by rain or fresh groundwater. Sulfate occurrences at many locations on Mars, as well as some chloride enrichments, have now been discovered by remote sensing, Landed missions have discovered Cl-enrichments and ferric, Mg, Ca and more complex sulfates as duricrust, subsurface soil horizons, sandstone evaporites, and rock coatings - most of which cannot be detected from orbit. Salt-forming volatiles affect habitability wherever they are in physical contact: physicochemical parameters (ionic strength, freezing point, water activity); S is an essential element for terrestrial organisms; perchlorate is an oxidant which can degrade some organics but also can be utilized as an energy source; the entire valence range of S-compounds has been exploited by diverse microbiota on Earth. Whether such salt-induced conditions are "extremes" of habitability depends on the relative abundance of liquid H2O.

Isotopic fractionation of volatile species during bubble growth in magmas

NASA Astrophysics Data System (ADS)

Watson, E. B.

2016-12-01

Bubbles grow in decompressing magmas by simple expansion and also by diffusive supply of volatiles to the bubble/melt interface. The latter phenomenon is of significant geochemical interest because diffusion can fractionate isotopes, raising the possibility that the isotopic character of volatile components in bubbles may not reflect that of volatiles dissolved in the host melt over the lifetime of a bubble—even in the complete absence of equilibrium vapor/melt isotopic fractionation. None of the foregoing is conceptually new, but recent experimental studies have established the existence of isotope mass effects on diffusion in silicate melts for several elements (Li, Mg, Ca, Fe), and this finding has now been extended to the volatile (anionic) element chlorine (Fortin et al. 2016; this meeting). Knowledge of isotope mass effects on diffusion of volatile species opens the way for quantitative models of diffusive fractionation during bubble growth. Significantly different effects are anticipated for "passive" volatiles (e.g., noble gases and Cl) that are partitioned into existing bubbles but play little role in nucleation and growth, as opposed to "active" volatiles whose limited solubilities lead to bubble nucleation during magma decompression. Numerical solution of the appropriate diffusion/mass-conservation equations reveals that the isotope effect on passive volatiles partitioned into bubbles growing at a constant rate in a static system depends (predictably) upon R/D, Kd and D1/D2 (R = growth rate; D = diffusivity; Kd = bubble/melt partition coefficient; D1/D2 = diffusivity ratio of the isotopes of interest). Constant R is unrealistic, but other scenarios can be explored by including the solubility and EOS of an "active" volatile (e.g., CO2) in numerical simulations of bubble growth. For plausible decompression paths, R increases exponentially with time—leading, potentially, to larger isotopic fractionation of species partitioned into the growing bubble.

Constraints on Galactic Cosmic-Ray Origins from Elemental and Isotopic Composition Measurements

NASA Technical Reports Server (NTRS)

Binns, W. R.; Christian, E. R.; Cummings, A. C.; deNolfo, G. A.; Israel, M. H.; Leske, R. A.; Mewaldt, R. A,; Stone, E. C.; vonRosevinge, T. T.; Wiedenbeck, M. E.

2013-01-01

The most recent measurements by the Cosmic Ray Isotope Spectrometer (CRIS) aboard the Advanced Composition Explorer (ACE) satellite of ultra-heavy cosmic ray isotopic and elemental abundances will be presented. A range of isotope and element ratios, most importantly Ne-22/Ne-20, Fe-58/Fe-56, and Ga-31/Ge -32 show that the composition is consistent with source material that is a mix of approx 80% ISM (with Solar System abundances) and 20% outflow/ejecta from massive stars. In addition, our data show that the ordering of refractory and volatile elements with atomic mass is greatly improved when compared to an approx 80%/20% mix rather than pure ISM, that the refractory and volatile elements have similar slopes, and that refractory elements are preferentially accelerated by a factor of approx 4. We conclude that these data are consistent with an OB association origin of GCRs.

Semi-volatile organic compounds at the leaf/atmosphere interface: numerical simulation of dispersal and foliar uptake.

PubMed

Riederer, Markus; Daiss, Andreas; Gilbert, Norbert; Köhle, Harald

2002-08-01

The behaviour of (semi-)volatile organic compounds at the interface between the leaf surface and the atmosphere was investigated by finite-element numerical simulation. Three model systems with increasing complexity and closeness to the real situation were studied. The three-dimensional model systems were translated into appropriate grid structures and diffusive and convective transport in the leaf/atmosphere interface was simulated. Fenpropimorph (cis-4-[3-(4-tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine) and Kresoxim-methyl ((E)-methyl-2-methoxyimino-2-[2-(o-tolyloxy-methyl)phenyl] acetate) were used as model compounds. The simulation showed that under still and convective conditions the vapours emitted by a point source rapidly form stationary envelopes around the leaves. Vapour concentrations within these unstirred layers depend on the vapour pressure of the compound in question and on its affinity to the lipoid surface layers of the leaf (cuticular waxes, cutin). The rules deduced from the numerical simulation of organic vapour behaviour in the leaf/atmosphere interface are expected to help in assessing how (semi-)volatile plant products (e.g. hormones, pheromones, secondary metabolites) and xenobiotics (e.g. pesticides, pollutants) perform on plant surfaces.

Reversible capture and release of Cl 2 and Br 2 with a redox-active metal–organic framework

DOE PAGES

Tulchinsky, Yuri; Hendon, Christopher H.; Lomachenko, Kirill A.; ...

2017-03-28

Extreme toxicity, corrosiveness, and volatility pose serious challenges for the safe storage and transportation of elemental chlorine and bromine, which play critical roles in the chemical industry. Solid materials capable of forming stable nonvolatile compounds upon reaction with elemental halogens may partially mitigate these challenges by allowing safe halogen release on demand. Here we demonstrate that elemental halogens quantitatively oxidize coordinatively unsaturated Co(II) ions in a robust azolate metal-organic framework (MOF) to produce stable and safe-to-handle Co(III) materials featuring terminal Co(III)-halogen bonds. Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)-halogen bonds, reduction to Co(II), and concomitantmore » release of elemental halogens. The reversible chemical storage and thermal release of elemental halogens occur with no significant losses of structural integrity, as the parent cobaltous MOF retains its crystallinity and porosity even after three oxidation/reduction cycles. Finally, these results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.« less

A Simulated Chlorine-Saturated Lunar Magmatic System at the Surface and At Depth

NASA Astrophysics Data System (ADS)

DiFrancesco, N.; Nekvasil, H.; Lindsley, D. H.

2016-12-01

Analysis of igneous minerals present in lunar rocks has provided evidence that volatiles such as water, chlorine and fluorine were concentrated in melts present at or near the lunar surface. While at depth, pressure on a magma allows these gases to remain dissolved in a silicate liquid, however as the magma ascends and depressurizes, these components become saturated and begin exsolving. While at pressure, it's possible for these components, specifically Cl, to form complexes in the melt with major cations such as Na, K, and Fe as well as trace elements such as Zn and Li. While dissolved in the melt, it may be possible for the Cl to inhibit the ability for these cations to enter into crystalline phases such as olivine, plagioclase, or pyroxene, potentially altering the composition of minerals associated with the melt. As the magma rises, these compounds are able to boil off from the magma, changing its bulk composition by effectively removing these cations as halides in a vapor phase. The goals of this project are to experimentally ascertain the nature of minerals sublimated by this degassing, and the effects that this process may have on the evolution and liquid line of decent for a cooling lunar magma. This is accomplished by crystallizing volatile-rich synthetic lunar basalts both at high and zero pressure and analyzing both vapor deposits and solidified liquids. Experimental data simulating volatile-rich magma degassing and crystallization at the lunar surface, and within the lunar crust has demonstrated that typical KREEP basalts (potentially rich in Cl) will crystallize more magnesian and calcic phases at high pressure, and subsequently lose alkalis and iron to a vapor phase at low pressure. We see evidence of vapor deposits and volatile element enrichment in returned Apollo samples such as "Rusty Rock", and on the surface of orange glass beads.

C-O-H-S magmatic fluid system in shrinkage bubbles of melt inclusions

NASA Astrophysics Data System (ADS)

Robidoux, P.; Frezzotti, M. L.; Hauri, E. H.; Aiuppa, A.

2016-12-01

Magmatic volatiles include multiple phases in the C-O-H-S system of shrinkage bubbles for which a conceptual model is still unclear during melt inclusion formation [1,2,3,4]. The present study aims to qualitatively explore the evolution of the volatile migration, during and after the formation of the shrinkage bubble in melt inclusions trapped by olivines from Holocene to present at San Cristóbal volcano (Nicaragua), Central American Volcanic Arc (CAVA). Combined scanning electron microscope (SEM) and Raman spectroscopy observations allow to define the mineral-fluid phases inside typical shrinkage bubbles at ambient temperature. The existence of residual liquid water is demonstrated in the shrinkage bubbles of naturally quenched melt inclusion and this water could represents the principal agent for chemical reactions with other dissolved ionic species (SO42-, CO32-, etc.) and major elements (Mg, Fe, Cu, etc.) [4,5]. With the objective of following the cooling story of the bubble-inclusion system, the new methodological approach here estimate the interval of equilibrium temperatures for each SEM-Raman identified mineral phase (carbonates, hydrous carbonates, sulfurs, sulfates, etc.). Finally, two distinct mechanisms are proposed to describe the evolution of this heterogeneous fluid system in bubble samples at San Cristóbal which imply a close re-examination for similar volcanoes in subduction zone settings: (1) bubbles are already contracted and filled by volatiles by diffusion processes from the glass and leading to a C-O-H-S fluid-glass reaction enriched in Mg-Fe-Cu elements (2) bubbles are formed by oversaturation of the volatiles from the magma which is producing an immiscible metal-rich fluid. [1]Moore et al. (2015). Am. Mineral. 100, 806-823 [2]Wallace et al. (2015). Am. Mineral. 100, 787-794 [3]Lowenstern (2015). Am. Mineral. 100, 672-673 [4]Esposito, et al. (2016). Am. Mineral. 101, 1691-1708 [5]Kamenetsky et al. (2001). Earth Planet. Sci. Lett. 184, 685-702

Combustion and leaching behavior of elements in the argonne premium coal samples

USGS Publications Warehouse

Finkelman, R.B.; Palmer, C.A.; Krasnow, M.R.; Aruscavage, P. J.; Sellers, G.A.; Dulong, F.T.

1990-01-01

Eight Argonne Premium Coal samples and two other coal samples were used to observe the effects of combustion and leaching on 30 elements. The results were used to infer the modes of occurrence of these elements. Instrumental neutron activation analysis indicates that the effects of combustion and leaching on many elements varied markedly among the samples. As much as 90% of the selenium and bromine is volatilized from the bituminous coal samples, but substantially less is volatilized from the low-rank coals. We interpret the combustion and leaching behavior of these elements to indicate that they are associated with the organic fraction. Sodium, although nonvolatile, is ion-exchangeable in most samples, particularly in the low-rank coal samples where it is likely to be associated with the organic constituents. Potassium is primarily in an ion-exchangeable form in the Wypdak coal but is in HF-soluble phases (probably silicates) in most other samples. Cesium is in an unidentified HNO3-soluble phase in most samples. Virtually all the strontium and barium in the low-rank coal samples is removed by NH4OAc followed by HCl, indicating that these elements probably occur in both organic and inorganic phases. Most tungsten and tantalum are in insoluble phases, perhaps as oxides or in organic association. Hafnium is generally insoluble, but as much as 65% is HF soluble, perhaps due to the presence of very fine grained or metamict zircon. We interpret the leaching behavior of uranium to indicate its occurrence in chelates and its association with silicates and with zircon. Most of the rare-earth elements (REE) and thorium appear to be associated with phosphates. Differences in textural relationships may account for some of the differences in leaching behavior of the REE among samples. Zinc occurs predominantly in sphalerite. Either the remaining elements occur in several different modes of occurrence (scandium, iron), or the leaching data are equivocal (arsenic, antimony, chromium, cobalt, and nickel). The results of these combustion and leaching experiments indicate that some previously held assumptions concerning modes of occurrence of elements in coal should be reconsidered.

Evidence for a chondritic impactor, evaporation-condensation effects and melting of the Precambrian basement beneath the 'target' Deccan basalts at Lonar crater, India

NASA Astrophysics Data System (ADS)

Das Gupta, Rahul; Banerjee, Anupam; Goderis, Steven; Claeys, Philippe; Vanhaecke, Frank; Chakrabarti, Ramananda

2017-10-01

The ∼1.88 km diameter Lonar impact crater formed ∼570 ka ago and is an almost circular depression hosted entirely in the Poladpur suite of the ∼65 Ma old basalts of the Deccan Traps. To understand the effects of impact cratering on basaltic targets, commonly found on the surfaces of inner Solar System planetary bodies, major and trace element concentrations as well as Nd and Sr isotopic compositions were determined on a suite of selected samples composed of: basalts, a red bole sample, which is a product of basalt alteration, impact breccia, and impact glasses, either in the form of spherules (<1 mm in diameter) or non-spherical impact glasses (>1 mm and <1 cm). These data include the first highly siderophile element (HSE) concentrations for the Lonar spherules. The chemical index of alteration (CIA) values for the basalts and impact breccia (36.4-42.7) are low while the red bole sample shows a high CIA value (55.6 in the acid-leached sample), consistent with its origin by aqueous alteration of the basalts. The Lonar spherules are classified into two main groups based on their CIA values. Most spherules show low CIA values (Group 1: 34.7-40.5) overlapping with the basalts and impact breccia, while seven spherules show significantly higher CIA values (Group 2: >43.0). The Group 1 spherules are further subdivided into Groups 1a and 1b, with Group 1a spherules showing higher Ni and mostly higher Cr compared to the Group 1b spherules. Iridium and Cr concentrations of the spherules are consistent with the admixture of 1-8 wt% of a chondritic impactor to the basaltic target rocks. The impactor contribution is most prominent in the Group 1a and Group 2 spherules, which show higher Ni/Co, Ni/Cr and Cr/Co ratios compared to the target basalts. In contrast, the Group 1b spherules show major and trace element compositions that overlap with those of the impact breccia and are characterized by high EFTh (Enrichment Factor for Th defined as the Nb-normalized concentration of Th relative to that of the average basalt) as well as fractionated La/Sm(N), and higher large ion lithophile element (LILE) concentrations compared to the basalts. The relatively more radiogenic Sr and less radiogenic Nd isotopic composition of the impact breccia and non-spherical impact glasses compared to the target basalts are consistent with melting and mixing of the Precambrian basement beneath the Deccan basalt with up to 15 wt% contribution of the basement to these samples. Variations in the moderately siderophile element (MSE) concentration ratios of the impact breccia as well as all the spherules are best explained by contributions from three components - a chondritic impactor, the basaltic target rocks at Lonar and the basement underlying the Deccan basalts. The large variations in concentrations of volatile elements like Zn and Cu and correlated variations of EFCu-EFZn, EFPb-EFZn, EFK-EFZn and EFNa-EFZn, particularly in the Group 1a spherules, are best explained by evaporation-condensation effects during impact. While most spherules, irrespective of their general major and trace element composition, show a loss in volatile elements (e.g., Zn and Cu) relative to the target basalts, some spherules, mainly of Group 1, display enrichments in these elements that are interpreted to reflect the unique preservation of volatile-rich vapour condensates resulting from geochemical fractionation in a vertical direction within the vapour cloud.

Correlating wine quality indicators to chemical and sensory measurements.

PubMed

Hopfer, Helene; Nelson, Jenny; Ebeler, Susan E; Heymann, Hildegarde

2015-05-12

Twenty-seven commercial Californian Cabernet Sauvignon wines of different quality categories were analyzed with sensory and chemical methods. Correlations between five quality proxies-points awarded during a wine competition, wine expert scores, retail price, vintage, and wine region-were correlated to sensory attributes, volatile compounds, and elemental composition. Wine quality is a multi-faceted construct, incorporating many different layers. Depending on the quality proxy studied, significant correlations between quality and attributes, volatiles and elements were found, some of them previously reported in the literature.

Two-component mantle melting-mixing model for the generation of mid-ocean ridge basalts: Implications for the volatile content of the Pacific upper mantle

NASA Astrophysics Data System (ADS)

Shimizu, Kei; Saal, Alberto E.; Myers, Corinne E.; Nagle, Ashley N.; Hauri, Erik H.; Forsyth, Donald W.; Kamenetsky, Vadim S.; Niu, Yaoling

2016-03-01

We report major, trace, and volatile element (CO2, H2O, F, Cl, S) contents and Sr, Nd, and Pb isotopes of mid-ocean ridge basalt (MORB) glasses from the Northern East Pacific Rise (NEPR) off-axis seamounts, the Quebrada-Discovery-GoFar (QDG) transform fault system, and the Macquarie Island. The incompatible trace element (ITE) contents of the samples range from highly depleted (DMORB, Th/La ⩽ 0.035) to enriched (EMORB, Th/La ⩾ 0.07), and the isotopic composition spans the entire range observed in EPR MORB. Our data suggest that at the time of melt generation, the source that generated the EMORB was essentially peridotitic, and that the composition of NMORB might not represent melting of a single upper mantle source (DMM), but rather mixing of melts from a two-component mantle (depleted and enriched DMM or D-DMM and E-DMM, respectively). After filtering the volatile element data for secondary processes (degassing, sulfide saturation, assimilation of seawater-derived component, and fractional crystallization), we use the volatiles to ITE ratios of our samples and a two-component mantle melting-mixing model to estimate the volatile content of the D-DMM (CO2 = 22 ppm, H2O = 59 ppm, F = 8 ppm, Cl = 0.4 ppm, and S = 100 ppm) and the E-DMM (CO2 = 990 ppm, H2O = 660 ppm, F = 31 ppm, Cl = 22 ppm, and S = 165 ppm). Our two-component mantle melting-mixing model reproduces the kernel density estimates (KDE) of Th/La and 143Nd/144Nd ratios for our samples and for EPR axial MORB compiled from the literature. This model suggests that: (1) 78% of the Pacific upper mantle is highly depleted (D-DMM) while 22% is enriched (E-DMM) in volatile and refractory ITE, (2) the melts produced during variable degrees of melting of the E-DMM controls most of the MORB geochemical variation, and (3) a fraction (∼65% to 80%) of the low degree EMORB melts (produced by ∼1.3% melting) may escape melt aggregation by freezing at the base of the oceanic lithosphere, significantly enriching it in volatile and trace element contents. Our results are consistent with previously proposed geodynamical processes acting at mid-ocean ridges and with the generation of the E-DMM. Our observations indicate that the D-DMM and E-DMM have (1) a relatively constant CO2/Cl ratio of ∼57 ± 8, and (2) volatile and ITE element abundance patterns that can be related by a simple melting event, supporting the hypothesis that the E-DMM is a recycled oceanic lithosphere mantle metasomatized by low degree melts. Our calculation and model give rise to a Pacific upper mantle with volatile content of CO2 = 235 ppm, H2O = 191 ppm, F = 13 ppm, Cl = 5 ppm, and S = 114 ppm.

Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

DOE PAGES

Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.; ...

2015-07-16

We measured a large suite of gas- and particle-phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gas andmore » particle phases, the latter being detected by temperature-programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO–HR-ToF-CIMS are highly correlated with, and explain at least 25–50 % of, the organic aerosol mass measured by an Aerodyne aerosol mass spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from high molecular weight organics and/or oligomers (i.e., multi-phase accretion reaction products). Approximately 50 % of the HR-ToF-CIMS particle-phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption-temperature-based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas-particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of lower volatility components into the detected higher volatility compounds.« less

Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds

DOE PAGES

Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.; ...

2015-02-18

We measured a large suite of gas and particle phase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gasmore » and particle phases, the latter being detected upon temperature programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO HR-ToF-CIMS are highly correlated with, and explain at least 25–50% of, the organic aerosol mass measured by an Aerodyne Aerosol Mass Spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from large molecular weight organics and/or oligomers (i.e. multi-phase accretion reaction products). Approximately 50% of the HR-ToF-CIMS particle phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption temperature based framework for apportionment of thermogram signals into volatility bins. The volatility-based apportionment greatly improves agreement between measured and modeled gas–particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of lower volatility components into the detected higher volatility compounds.« less

Volatile element chemistry in the solar nebula - Na, K, F, Cl, Br, and P

NASA Technical Reports Server (NTRS)

Fegley, B., Jr.; Lewis, J. S.

1980-01-01

The results of the most extensive set to date of thermodynamic calculations on the equilibrium chemistry of several hundred compounds of the elements Na, K, F, Cl, Br, and P in a solar composition system are reported. Two extreme models of accretion are investigated. In one extreme complete chemical equilibrium between condensates and gases is maintained because the time scale for accretion is long compared to the time scale for cooling or dissipation of the nebula. Condensates formed in this homogeneous accretion model include several phases such as whitlockite, alkali feldspars, and apatite minerals which are found in chondrites. In the other extreme complete isolation of newly formed condensates from prior condensates and gases occurs due to a time scale for accretion that is short relative to the time required for nebular cooling or dissipation. The condensates produced in this heterogeneous accretion model include alkali sulfides, ammonium halides, and ammonium phosphates. None of these phases are found in chondrites. Available observations of the Na, K, F, Cl, Br, and P elemental abundances in the terrestrial planets are found to be compatible with the predictions of the homogeneous accretion model.

Effect of Inlet Air Temperature on Auto-Ignition of Fuels with Different Cetane Number and Volatility

DTIC Science & Technology

2011-10-01

IGNITION OF FUELS WITH DIFFERENT CETANE NUMBER AND VOLATILITY Chandrasekharan Jayakumar Wayne State University Detroit, MI, USA. Ziliang Zheng...VOLATILITY 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Eric Sattler; Walter Bryzik; Chandrasekharan Jayakumar ...diagnostics, chemical kinetics, and empirical validation”, SAE 1999-01-0509 8. Nargunde, J., Jayakumar , C., et. al., “Comparison between Combustion

Space exploration and the history of solar-system volatiles

NASA Technical Reports Server (NTRS)

Fanale, F. P.

1976-01-01

The thermochemical history of volatile substances in all solar-system planets, satellites, and planetoids is discussed extensively. The volatiles are viewed as an interface between the abiotic and biotic worlds and as a key to the history of bodies of the solar system. A flowsheet of processes and states is exhibited. Differences in bulk volatiles distribution between the planetary bodies and between the interior, surface, and atmosphere of each body are considered, as well as sinks for volatiles in degassing. The volatiles-rich Jovian and Saturnian satellites, the effect of large-planet magnetosphere sweeps on nearby satellites, volatiles of asteroids and comets, and the crucial importance of seismic, gravity, and libration data are treated. A research program encompassing analysis of the elemental and isotopic composition of rare gas in atmospheres, assay of volatiles-containing phases in regoliths, and examination of present or past atmospheric escape/accretion processes is recommended.

Non-volatile, solid state bistable electrical switch

NASA Technical Reports Server (NTRS)

Williams, Roger M. (Inventor)

1994-01-01

A bistable switching element is made of a material whose electrical resistance reversibly decreases in response to intercalation by positive ions. Flow of positive ions between the bistable switching element and a positive ion source is controlled by means of an electrical potential applied across a thermal switching element. The material of the thermal switching element generates heat in response to electrical current flow therethrough, which in turn causes the material to undergo a thermal phase transition from a high electrical resistance state to a low electrical resistance state as the temperature increases above a predetermined value. Application of the electrical potential in one direction renders the thermal switching element conductive to pass electron current out of the ion source. This causes positive ions to flow from the source into the bistable switching element and intercalate the same to produce a non-volatile, low resistance logic state. Application of the electrical potential in the opposite direction causes reverse current flow which de-intercalates the bistable logic switching element and produces a high resistance logic state.

Methods for detecting the mobility of trace elements during medium-temperature pyrolysis

USGS Publications Warehouse

Shiley, R.H.; Konopka, K.L.; Cahill, R.A.; Hinckley, C.C.; Smith, Gerard V.; Twardowska, H.; Saporoschenko, Mykola

1983-01-01

The mobility (volatility) of trace elements in coal during pyrolysis has been studied for distances of up to 40 cm between the coal and the trace element collector, which was graphite or a baffled solvent trap. Nineteen elements not previously recorded as mobile were detected. ?? 1983.

The formation conditions of chondrules and chondrites

USGS Publications Warehouse

Alexander, C.M. O'D.; Grossman, Jeffrey N.; Ebel, D.S.; Ciesla, F.J.

2008-01-01

Chondrules, which are roughly millimeter-sized silicate-rich spherules, dominate the most primitive meteorites, the chondrites. They formed as molten droplets and, judging from their abundances in chondrites, are the products of one of the most energetic processes that operated in the early inner solar system. The conditions and mechanism of chondrule formation remain poorly understood. Here we show that the abundance of the volatile element sodium remained relatively constant during chondrule formation. Prevention of the evaporation of sodium requires that chondrules formed in regions with much higher solid densities than predicted by known nebular concentration mechanisms. These regions would probably have been self-gravitating. Our model explains many other chemical characteristics of chondrules and also implies that chondrule and planetesimal formation were linked.

Probing the Allende meteorite with a miniature laser-ablation mass analyser for space application

NASA Astrophysics Data System (ADS)

Neuland, M. B.; Meyer, S.; Mezger, K.; Riedo, A.; Tulej, M.; Wurz, P.

2014-10-01

We measured the elemental composition on a sample of Allende meteorite with a miniature laser ablation mass spectrometer. This laser mass spectrometer (LMS) has been designed and built at the University of Bern in the Department of Space Research and Planetary Sciences with the objective of using such an instrument on a space mission. Utilising the meteorite Allende as the test sample in this study, it is demonstrated that the instrument allows the in situ determination of the elemental composition and thus mineralogy and petrology of untreated rocky samples, particularly on planetary surfaces. In total, 138 measurements of elemental compositions have been carried out on an Allende sample. The mass spectrometric data are evaluated and correlated with an optical image. It is demonstrated that by illustrating the measured elements in the form of mineralogical maps, LMS can serve as an element imaging instrument with a very high spatial resolution of μm scale. The detailed analysis also includes a mineralogical evaluation and an investigation of the volatile element content of Allende. All findings are in good agreement with published data and underline the high sensitivity, accuracy and capability of LMS as a mass analyser for space exploration.

Mineralogy and crystallization history of a highly differentiated REE-enriched hypabyssal rhyolite: Round Top laccolith, Trans-Pecos, Texas

NASA Astrophysics Data System (ADS)

O'Neill, L. Christine; Elliott, Brent A.; Kyle, J. Richard

2017-09-01

The Round Top hypabyssal rhyolite laccolith is a highly evolved magmatic system, enriched in incompatible elements including REE [Rare Earth Element(s)], U, Be, and F. The Round Top intrusion is part of a series of Paleogene intrusions emplaced as the Sierra Blanca Complex. These intrusions are situated within long-lived, complex tectonic regimes that have been subjected to regional compression and subduction, punctuated by extensional bimodal volcanism. The enrichment in the rhyolite that comprises Round Top is the result of the prolonged removal of compatible elements from the source magma chamber through the emplacement of earlier magmatic events. With the emplacement of each sequential laccolith, the F-rich source magma became more enriched in incompatible elements, with increasing HREE [Heavy Rare Earth Elements(s)] concentrations. The emplacement of Round Top as a laccolith (versus that of an extrusive rhyolitic flow) facilitated the retention of the volatile-rich vapor phase within the magma, forming ubiquitous REE-bearing minerals, mainly yttrofluorite and yttrocerite. The high temperature mineral-vapor phase alteration of the feldspar groundmass was essential to the formation of REE minerals, where the pervasive open pore space was occupied by the late-crystallizing minerals. These late-forming REE-bearing minerals also occur as crystals associated with other accessory and trace phases, as inclusions within other phases, along grain boundaries, and along fractures and within voids. The rhyolite at Round Top and other laccolith intrusions in the Sierra Blanca Complex represent a new sub-type of magmatic rare earth element hosting system.

Experimental Constraints on Alkali Volatilization during Chondrule Formation: Implications for Early Solar System Heterogeneity

NASA Astrophysics Data System (ADS)

Ustunisik, G. K.; Ebel, D. S.; Nekvasil, H.

2014-12-01

The chemical variability of chondrule volatile element contents provide a wealth of information on the processes that shaped the early solar system and its compositional heterogeneity. An essential observation is that chondrule melts contain very low alkalies and other volatile elements (e.g., Cl). The reason for this depletion is the combined effects of cooling rates (10 to 1000K/h), the small size of chondrules, and their high melting temperatures (~1700 to 2100 K) resulting in extensive loss of volatiles at canonical pressures (e.g., 10-4bar). However, we observe some chondrules with significant concentrations of volatiles (Na, Cl), that differ markedly from chondrules dominated by refractory elements. Could such heterogeneity arise from loss of alkalis and Cl to a gas phase that itself later condenses, thereby yielding variations in volatile enrichments in chondrules? Does Cl enhance volatility of the alkalis to varying extents? Experiments on Cl-bearing and Cl-free melts of equivalent composition for 10 min, 4 h, and 6 h reveal systematic effects of Cl on alkali volatility. Cl-bearing melts lose 48% of initial Na2O, 66% of K2O, 96% of Cl within the first 10 minutes of degassing. Then the amount of alkali loss decreases due to the absence of Cl. Cl-free melts loses only 15% of initial Na2O and 33% K2O. After 4 hours, melts lose 1/3 of initial Na2O and 1/2 of K2O. For both systems, Na2O is more compatible in the melt relative to K2O. Therefore, the vapor given off has a K/Na ratio higher than the melt through time in spite of the much higher initial Na abundance in the melt. Enhanced vaporization of alkalis from Cl-bearing melt suggests that Na and K evaporate more readily as volatile chlorides than as monatomic gases. Cl-free initial melts with normative plagioclase of An50Ab44Or6 evolved into slightly normal zoned ones (An49Ab50Or1) while Cl-bearing initial melts normative to albitic plagioclase (An46Ab50Or4) evolved to reverse zoned ones (An54Ab45Or1). The vapor phase over Cl-bearing chondrule melts may have a bimodal character over time. The heteregeneous volatile contents of chondrules may result from quenching of melt droplets at different stages of repeated heating, chondrule fragment recycling, and recondensation of exsolved volatiles.

Long-term anaerobic digestion of food waste stabilized by trace elements.

PubMed

Zhang, Lei; Jahng, Deokjin

2012-08-01

The purpose of this study was to examine if long-term anaerobic digestion of food waste in a semi-continuous single-stage reactor could be stabilized by supplementing trace elements. Contrary to the failure of anaerobic digestion of food waste alone, stable anaerobic digestion of food waste was achieved for 368 days by supplementing trace elements. Under the conditions of OLR (organic loading rates) of 2.19-6.64 g VS (volatile solid)/L day and 20-30 days of HRT (hydraulic retention time), a high methane yield (352-450 mL CH(4)/g VS(added)) was obtained, and no significant accumulation of volatile fatty acids was observed. The subsequent investigation on effects of individual trace elements (Co, Fe, Mo and Ni) showed that iron was essential for maintaining stable methane production. These results proved that the food waste used in this study was deficient in trace elements. Copyright © 2012. Published by Elsevier Ltd.

Gases and trace elements in soils at the North Silver Bell deposit, Pima County, Arizona

USGS Publications Warehouse

Hinkle, M.E.; Dilbert, C.A.

1984-01-01

Soil samples were collected over the North Silver Bell porphyry copper deposit near Tucson, Arizona. Volatile elements and compounds in gases derived from the soils and metallic elements in the soils were analyzed in order: (1) to see which volatile constituents of the soils might be indicative of the ore body or the alteration zones; and (2) to distinguish the ore and alteration zones by comparison of trace elements in the soil. Plots of analytical data on trace elements in soils indicated a typical distribution pattern for metals around a porphyry copper deposit, with copper, molybdenum, and arsenic concentrations higher over the ore body, and zinc, lead, and silver concentrations higher over the alteration zones. Higher than average concentrations of helium, carbon disulfide, and sulfur dioxide adsorbed on soils were found over the ore body, whereas higher concentrations of carbon dioxide and carbonyl sulfide were found over the alteration zones. ?? 1984.

Passive degassing at Nyiragongo (D.R. Congo) and Etna (Italy) volcanoes: the chemical characterization of the emissions and assessment of their uptake of trace elements emissions on the local environment

NASA Astrophysics Data System (ADS)

Calabrese, Sergio; Scaglione, Sarah; Milazzo, Silvia; D'Alessandro, Walter; Bobrowski, Nicole; Giuffrida, Giovanni; Tedesco, Dario; Parello, Francesco

2014-05-01

Volcanoes are well known as an impressive large natural source of trace elements into the troposphere. Among others, Etna (Italy) and Nyiragongo (D.R. Congo), two noteworthy emitters on Earth, are two stratovolcanoes located in different geological settings, both characterized by persistent passive degassing from their summit craters. Here, we present some results on trace element composition in volcanic plume emissions, atmospheric bulk deposition (rainwater) and their uptake of the surrounding vegetation, with the aim to compare and identify differences and similarities between this these two volcanoes. Volcanic emissions were sampled by using active filter-pack for acid gases (sulfur and halogens) and specific teflon filters for particulates (major and trace elements). The impact of the volcanogenic deposition in the surrounding of the crater rims was investigated by using different sampling techniques: bulk rain collectors gauges were used to collect atmospheric bulk deposition, and biomonitoring technique was carried out to collect gases and particulates by using endemic plant species. Concentrations of major and trace elements of volcanic plume emissions (gases and particulates) were obtained by elution and microwave digestion of the collected filters: sulfur and halogens were determined by ion chromatography and ICP-MS, and untreated filters for particulate were acid digested and analysed by ICP-OES and ICP-MS. Rain water and plant samples were also analysed for major and trace elements by using ICP-OES and ICP-MS. In total 55 elements were determined. The estimates of the trace element fluxes confirm that Etna and Nyiragongo are large sources of metals to the atmosphere, especially considering their persistent state of passive degassing. In general, chemical composition of the volcanic aerosol particles of both volcanoes is characterized by two main components: one is related to the silicic component produced by magma bursting and fragmentation, enriching the plume in Si, Al, Fe, Ti, Mg, Ca, Na, K and other trace elements like Ni, Cr, Co, Th and U; another one components, is dominated by volatile trace elements (As, Bi, Cd, Cu, Hg, Se, Te, Tl) related to the gas volatile phase (H2O, CO2, SO2, HCl, HF) and transported to the atmosphere mainly as hydro-soluble salts and/or in gaseous form in some cases. The large amount of emitted trace elements have a strong impact on the close surrounding of both volcanoes. This is clearly reflected by in the chemical composition of rain water collected at the summit areas both for Etna and Nyiragongo. In fact, rain water samples have low pH values (<2) and high concentrations of dissolved toxic metals. Moreover, the biomonitoring results highlight that bioaccumulation of trace elements is extremely high in the proximity of the crater rim and decreases with the distance from the active craters. In particular, we found a good correlation between volatile elements (Tl, As, Bi, Cd, Se, Cu) concentrations in the leaves of Senecio species collected in on both volcanoes, showing a clear influence of volcanic deposition.

Element variations in rhyolitic magma resulting from gas transport

NASA Astrophysics Data System (ADS)

Berlo, K.; Tuffen, H.; Smith, V. C.; Castro, J. M.; Pyle, D. M.; Mather, T. A.; Geraki, K.

2013-11-01

Tuffisite veins are glass-filled fractures formed when magma fragments during degassing within the conduit. These veins form transient channels through which exsolved gases can escape from magma. The purpose of this study is to determine the extent to which chemical heterogeneity within the melt results from gas transport, and assess how this can be used to study magma degassing. Two tuffisite veins from contrasting rhyolitic eruptions at Torfajökull (Iceland) and Chaitén (Chile) were studied in detail. The tuffisite vein from Torfajökull is from a shallow dissected conduit (∼70 ka) that fed a degassed lava flow, while the sample from Chaitén was a bomb ejected during the waning phases of Plinian activity in May 2008. The results of detailed in situ chemical analyses (synchrotron XRF, FTIR, LA-ICP-MS) show that in both veins larger vesiculated fragments are enriched in volatile elements (Torfajökull: H, Li, Cl; Chaitén: Li, Cl, Cu, Zn, As, Sn, Sb) compared to the host, while the surrounding smaller particles are depleted in the Torfajökull vein (Li, Cl, Zn, Br, Rb, Pb), but enriched in the Chaitén vein (K, Cu, Zn, As, Mo, Sb, Pb). The lifespans of both veins and the fluxes of gas and particles through them can be estimated using diffusion profiles and enrichment factors. The Torfajökull vein had a longer lifespan (∼a day) and low particle velocities (∼cm/s), while the Chaitén vein was shorter lived (<1 h) with a high gas velocity (∼m/s). These differences are consistent with the contrasting eruption mechanisms (effusive vs. explosive). The amount of magma that degassed through the Chaitén vein is more than ten times the volume of the vein itself, requiring the vein to tap into pre-exsolved gas pockets. This study highlights that tuffisite veins are highly efficient gas pathways and thereby impart chemical diversity in volatile elements on the melt.

Reconstructing mantle volatile contents through the veil of degassing

NASA Astrophysics Data System (ADS)

Tucker, J.; Mukhopadhyay, S.; Gonnermann, H. M.

2014-12-01

The abundance of volatile elements in the mantle reveals critical information about the Earth's origin and evolution such as the chemical constituents that built the Earth and material exchange between the mantle and exosphere. However, due to magmatic degassing, volatile element abundances measured in basalts usually do not represent those in undegassed magmas and hence in the mantle source of the basalts. While estimates of average mantle concentrations of some volatile species can be obtained, such as from the 3He flux into the oceans, volatile element variability within the mantle remains poorly constrained. Here, we use CO2-He-Ne-Ar-Xe measurements in basalts and a new degassing model to reconstruct the initial volatile contents of 8 MORBs from the Mid-Atlantic Ridge and Southwest Indian Ridge that span a wide geochemical range from depleted to enriched MORBs. We first show that equilibrium degassing (e.g. Rayleigh degassing), cannot simultaneously fit the measured CO2-He-Ne-Ar-Xe compositions in MORBs and argue that kinetic fractionation between bubbles and melt lowers the dissolved ratios of light to heavy noble gas species in the melt from that expected at equilibrium. We present a degassing model (after Gonnermann and Mukhopadhyay, 2007) that explicitly accounts for diffusive fractionation between melt and bubbles. The model computes the degassed composition based on an initial volatile composition and a diffusive timescale. To reconstruct the undegassed volatile content of a sample, we find the initial composition and degassing timescale which minimize the misfit between predicted and measured degassed compositions. Initial 3He contents calculated for the 8 MORB samples vary by a factor of ~7. We observe a correlation between initial 3He and CO2 contents, indicating relatively constant CO2/3He ratios despite the geochemical diversity and variable gas content in the basalts. Importantly, the gas-rich popping rock from the North Atlantic, as well as the average mantle ratio computed from the ridge 3He flux and independently estimated CO2 content fall along the same correlation. This observation suggests that undegassed CO2 and noble gas concentrations can be reconstructed in individual samples through measurement of noble gases and CO2 in erupted basalts.

Volatile substance misuse : clinical considerations, neuropsychopharmacology and potential role of pharmacotherapy in management.

PubMed

Garland, Eric L; Howard, Matthew O

2012-11-01

Volatile substance misuse is among the most prevalent and toxic forms of psychoactive drug use, and often results in highly deleterious social, psychological and medical consequences. The prevalence of this pernicious form of substance misuse owes in part to the fact that volatile substances of misuse are ubiquitous in the natural environment. Commonly misused commercial products include glue, shoe polish, nail polish remover, butane lighter fluid, gasoline and computer duster spray. National samples of volatile substance misusers tend to exhibit high rates of psychiatric problems and antisocial behaviour. In addition, cognitive impairments and affective dysregulation are often observed among these individuals. Volatile substances exert their complex neuropharmacological effects on dopaminergic, glutamatergic, GABAergic and serotoninergic receptor systems, as well as on cell membranes and ion channels. Concomitantly, pharmacotherapies for volatile substance abuse might profitably target a number of mechanisms, including reward circuitry in the brain, symptoms of craving and withdrawal, neuropsychiatric and emotional impairments that promote volatile substance abuse, and cognitive enhancement to rectify deficits in executive function. This review details the modes of use, subjective effects, epidemiology, adverse consequences, neuropsychopharmacology and drug treatment of volatile substance misuse, and discusses the potential role of novel forms of pharmacological intervention for this oft-overlooked public health threat of epidemic proportions.

Volatile Metabolites

PubMed Central

Rowan, Daryl D.

2011-01-01

Volatile organic compounds (volatiles) comprise a chemically diverse class of low molecular weight organic compounds having an appreciable vapor pressure under ambient conditions. Volatiles produced by plants attract pollinators and seed dispersers, and provide defense against pests and pathogens. For insects, volatiles may act as pheromones directing social behavior or as cues for finding hosts or prey. For humans, volatiles are important as flavorants and as possible disease biomarkers. The marine environment is also a major source of halogenated and sulfur-containing volatiles which participate in the global cycling of these elements. While volatile analysis commonly measures a rather restricted set of analytes, the diverse and extreme physical properties of volatiles provide unique analytical challenges. Volatiles constitute only a small proportion of the total number of metabolites produced by living organisms, however, because of their roles as signaling molecules (semiochemicals) both within and between organisms, accurately measuring and determining the roles of these compounds is crucial to an integrated understanding of living systems. This review summarizes recent developments in volatile research from a metabolomics perspective with a focus on the role of recent technical innovation in developing new areas of volatile research and expanding the range of ecological interactions which may be mediated by volatile organic metabolites. PMID:24957243

Magmas and reservoirs beneath the Rabaul caldera (Papua New Guinea)

NASA Astrophysics Data System (ADS)

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

2013-12-01

The area of Rabaul (Papua New Guinea) consists of at least seven - possibly nine - nested-calderas that have formed over the past 200 ky. The last caldera-forming eruption occurred 1400 y BP, and produced about 10 km3 of crystal-poor, two-pyroxene dacite. Since then, five effusive and explosive eruptive episodes have occurred from volcanic centres along the caldera rim. The most recent of these was preceded by decade-long unrest (starting in 1971) until the simultaneous eruption of Vulcan and Tavurvur, two vents on opposite sides of the caldera in 1994. Most eruptive products are andesitic in composition and show clear signs of mixing/mingling between a basalt and a high-K2O dacite. The hybridization is in the form of banded pumices, quenched mafic enclaves, and hybrid bulk rock compositions. In addition, the 1400 y BP caldera-related products show the presence of a third mixing component; a low-K2O rhyodacitic melt or magma. Geochemical modeling considering major and trace elements and volatile contents shows that the high-K2O dacitic magma can be generated by fractional crystallization of the basaltic magma at shallow depths (~7 km, 200 MPa) and under relatively dry conditions (≤3 wt% H2O). The low-K2O rhyodacitic melt can either be explained by extended crystallization at low temperatures (e.g. in the presence of Sanidine) or the presence of an additional, unrelated magma. Our working model is therefore that basalts ascend to shallow crustal levels before intruding a main silicic reservoir beneath the Rabaul caldera. Storage depths and temperatures estimated from volatile contents, mineral-melt equilibria and rock densities suggest that basalts ascend from ~20 km (~600 MPa) to ~7 km (200 MPa) and cool from ~1150-1100°C before intruding a dacitic magma reservoir at ~950°C. Depending on the state of the reservoir and the volumes of basalt injected, the replenishing magma may either trigger an eruption or cool and crystallize. We use evidence from major and trace element geochemistry, volatile contents, and the comparison of successive eruptions since 1400 y BP to address the question of whether another potentially caldera-forming magma is presently brewing beneath Rabaul. In addition, we apply kinetic modeling of olivine and plagioclase zoning to the recently erupted products to address the prolonged period of seismic and deformational precursory activity. We estimate that at least 20-35 wt% basalt has mixed with the resident silicic magma at time scales that coincide with the main period of unrest (1971 to 1985).

Volatile transfer and recycling at convergent margins: Mass-balance and insights from high-P/T metamorphic rocks

NASA Astrophysics Data System (ADS)

Bebout, Gray E.

The efficiency with which volatiles are deeply subducted is governed by devolatilization histories and the geometries and mechanisms of fluid transport deep in subduction zones. Metamorphism along the forearc slab-mantle interface may prevent the deep subduction of many volatile components (e.g., H2O, Cs, B, N, perhaps As, Sb, and U) and result in their transport in fluids toward shallower reservoirs. The release, by devolatilization, and transport of such components toward the seafloor or into the forearc mantle wedge, could in part explain the imbalances between the estimated amounts of subducted volatiles and the amounts returned to Earth's surface. The proportion of the initially subducted volatile component that is retained in rocks subducted to depths greater than those beneath magmatic arcs (>100 km) is largely unknown, complicating assessments of deep mantle volatile budgets. Isotopic and trace element data and volatile contents for the Catalina Schist, the Franciscan Complex, and eclogite-facies complexes in the Alps (and elsewhere) provide insight into the nature and magnitude of fluid production and transport deep in subduction zones and into the possible effects of metamorphism on the compositions of subducting rocks. Compatibilities of the compositions of the subduction-related rocks and fluids with the isotopic and trace element compositions of various mantle-derived materials (igneous rocks, xenoliths, serpentinite seamounts) indicate the potential to trace the recycling of rock and fluid reservoirs chemically and isotopically fractionated during subduction-zone metamorphism.

Forming chondrules in impact splashes. I. Radiative cooling model

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

Dullemond, Cornelis Petrus; Stammler, Sebastian Markus; Johansen, Anders

2014-10-10

The formation of chondrules is one of the oldest unsolved mysteries in meteoritics and planet formation. Recently an old idea has been revived: the idea that chondrules form as a result of collisions between planetesimals in which the ejected molten material forms small droplets that solidify to become chondrules. Pre-melting of the planetesimals by radioactive decay of {sup 26}Al would help produce sprays of melt even at relatively low impact velocity. In this paper we study the radiative cooling of a ballistically expanding spherical cloud of chondrule droplets ejected from the impact site. We present results from numerical radiative transfermore » models as well as analytic approximate solutions. We find that the temperature after the start of the expansion of the cloud remains constant for a time t {sub cool} and then drops with time t approximately as T ≅ T {sub 0}[(3/5)t/t {sub cool} + 2/5]{sup –5/3} for t > t {sub cool}. The time at which this temperature drop starts t {sub cool} depends via an analytical formula on the mass of the cloud, the expansion velocity, and the size of the chondrule. During the early isothermal expansion phase the density is still so high that we expect the vapor of volatile elements to saturate so that no large volatile losses are expected.« less

[Application characteristics and situation analysis of volatile oils in database of Chinese patent medicine].

PubMed

Wang, Sai-Jun; Wu, Zhen-Feng; Yang, Ming; Wang, Ya-Qi; Hu, Peng-Yi; Jie, Xiao-Lu; Han, Fei; Wang, Fang

2014-09-01

Aromatic traditional Chinese medicines have a long history in China, with wide varieties. Volatile oils are active ingredients extracted from aromatic herbal medicines, which usually contain tens or hundreds of ingredients, with many biological activities. Therefore, volatile oils are often used in combined prescriptions and made into various efficient preparations for oral administration or external use. Based on the sources from the database of Newly Edited National Chinese Traditional Patent Medicines (the second edition), the author selected 266 Chinese patent medicines containing volatile oils in this paper, and then established an information sheet covering such items as name, dosage, dosage form, specification and usage, and main functions. Subsequently, on the basis of the multidisciplinary knowledge of pharmaceutics, traditional Chinese pharmacology and basic theory of traditional Chinese medicine, efforts were also made in the statistics of the dosage form and usage, variety of volatile oils and main functions, as well as the status analysis on volatile oils in terms of the dosage form development, prescription development, drug instruction and quality control, in order to lay a foundation for the further exploration of the market development situations of volatile oils and the future development orientation.

Efficient growth of HTS films with volatile elements

DOEpatents

Siegal, M.P.; Overmyer, D.L.; Dominguez, F.

1998-12-22

A system is disclosed for applying a volatile element-HTS layer, such as Tl-HTS, to a substrate in a multiple zone furnace, said method includes heating at higher temperature, in one zone of the furnace, a substrate and adjacent first source of Tl-HTS material, to sublimate Tl-oxide from the source to the substrate; and heating at lower temperature, in a separate zone of the furnace, a second source of Tl-oxide to replenish the first source of Tl-oxide from the second source. 3 figs.

Regional tectonic analysis of Venus as part of the Pioneer Venus guest investigator project

NASA Technical Reports Server (NTRS)

Williams, David R.

1991-01-01

Over the past year, much of the tectonic analysis of Venus we have done has centered on global properties of the planet, in order to understand fundamental aspects of the dynamics of the mantle and lithosphere of Venus. We have developed convection models of the Earth and Venus. These models assume whole mantle internally-heated convection. The viscosity is temperature, volatile-content, and stress dependent. An initial temperature and volatile content is assumed, and the thermal evolution is tracked for 4.6 billion years. During this time, heating occurs by decay of radiogenic elements in the mantle, and degassing and regassing of volatiles takes place at the surface. For a model assuming plate tectonics as the primary heat loss mechanism, representing the Earth through most of it's history and perhaps Venus' earlier history, degassing of the mantle was found to occur rapidly (approximately 200 My) over a large range of parameters. Even for parameters chosen to represent extreme cases of an initially cool planet, low radiogenic heating, and large initial volatile complement, the mantle water content was degassed to an equilibrium value in about 2 By. These values may be applicable to the early Venus, if a large, Moon-forming impact on Earth resulted in efficient heating and loss of water, leaving Venus with a comparably greater volatile budget and less vigorous early convection. It may therefore be impossible to retain large amounts of water in the interior of Venus until the planet cools down enough for the 'cold-trap' effect to take place. This effect traps crust forming melts within the mantle due to a cusp in the solidus, causing these melts to refreeze at depth into a dense eclogite phase, which will inhibit ascent of this material to the surface. This effect, however, requires a hydrous mantle, so early loss of water might prevent it from taking place. Since without plate tectonics there is no mechanism for regassing volatiles into the mantle, as occurs on Earth at subduction zones, this means the interior of Venus would at present be almost completely dry. We have also calculated argon degassing, and mantle flow velocities. viscosities, and cooling rates in these models, and these values can provide constraints on present day mantle dynamics.

Mercury's Crater-Hosted Hollows: Chalcogenide Pryo-Thermokarst, and Permafrost Analogs on Earth, Mars, and Titan

NASA Astrophysics Data System (ADS)

Kargel, Jeffrey

2013-04-01

MESSENGER has acquired stunning images of pitted, light-toned and variegated light/dark terrains located primarily on the floors—probably impact-melt sheets—of many of Mercury's large craters. Termed "hollows", the pitted terrains are geomorphologically similar to some on Mars formed by sublimation of ice-rich permafrost and to lowland thermokarst on Earth formed by permafrost thaw; to "swiss cheese" terrain forming by sublimation of frozen CO2 at the Martian South Pole; and to suspected hydrocarbon thermokarst at Titan's poles. I shall briefly review some analogs on these other worlds. The most plausible explanation for Mercury's hollows is terrain degradation involving melting or sublimation of heterogeneous chalcogenide and sulfosalt mineral assemblages. I refer to these Mercurian features as pyrothermokarst; the etymological redundancy distinguishes the conditions and mineral agents from the ice-related features on Earth and Mars, though some of the physical processes may be similar. Whereas ice and sulfur have long been suspected and ice recently was discovered in permanently shadowed craters of Mercury's polar regions, the hollows occur down to the equator, where neither ice nor sulfur is plausible. The responsible volatiles must be only slightly volatile on the surface and/or in the upper crust of Mercury's low to middle latitudes at 400-800 K, but they must be capable of either melting or sublimating on geologically long time scales. Under prevailing upper crustal and surface temperatures, chalcophile-rich "permafrost" can undergo either desulfidation or melting reactions that could cause migration or volume changes of the permafrost, and hence lead to collapse and pitting. I propose the initial emplacement of crater-hosted chalcogenides, sulfosalts and related chalcophile materials such as pnictides, in impact-melt pools (involving solid-liquid and silicate-sulfide fractionation) and further differentiation by associated dry or humid fumaroles (solid-vapor and liquid-vapor fractionation and recondensation). Key phase transitions can occur in the temperature range of Mercury's surface and upper crust. Vapor-solid, vapor-liquid, and solid-liquid transitions of the heated materials resulted in migration and loss of volatiles and anatectic liquids, causing collapse pits to form. Seasonal heating near perihelion may work together with geothermal flux or early impact heating to drive off volatiles and produce the pits. In some cases, local recondensation of moderately volatile materials may have occurred on the rims of the pits; some volatiles may have been transported to the polar regions or lost by exospheric escape. Impacts by comets may have caused local oxidation and formation of oxygenated salts and other minerals, whose local recondensation from fumarole gases can explain the light-toned layers and light-toned rims of many pits. Plating of native volatile metals and semi-metals may also account for some light-toned deposits. Large contrasts in thermal conductivity as well as local topographic shading and latitude controls may result in large differences in element mobility and mineral assemblages. Pyrothermokarst on Mercury may be more chemically heterogeneous and complex in its development than any other thermokarst in the Solar System. Validation of this model would require a future mission with high-resolution multispectral imaging and neutral/ion detection.

The origin of volatiles in the Earth's mantle

NASA Astrophysics Data System (ADS)

Hier-Majumder, Saswata; Hirschmann, Marc M.

2017-08-01

The Earth's deep interior contains significant reservoirs of volatiles such as H, C, and N. Due to the incompatible nature of these volatile species, it has been difficult to reconcile their storage in the residual mantle immediately following crystallization of the terrestrial magma ocean (MO). As the magma ocean freezes, it is commonly assumed that very small amounts of melt are retained in the residual mantle, limiting the trapped volatile concentration in the primordial mantle. In this article, we show that inefficient melt drainage out of the freezing front can retain large amounts of volatiles hosted in the trapped melt in the residual mantle while creating a thick early atmosphere. Using a two-phase flow model, we demonstrate that compaction within the moving freezing front is inefficient over time scales characteristic of magma ocean solidification. We employ a scaling relation between the trapped melt fraction, the rate of compaction, and the rate of freezing in our magma ocean evolution model. For cosmochemically plausible fractions of volatiles delivered during the later stages of accretion, our calculations suggest that up to 77% of total H2O and 12% of CO2 could have been trapped in the mantle during magma ocean crystallization. The assumption of a constant trapped melt fraction underestimates the mass of volatiles in the residual mantle by more than an order of magnitude.