Evolved Gas Measurements Planned for the Lower Layers of the Gale Crater Mound with the Sample Analysis at Mars Instrument Suite

NASA Technical Reports Server (NTRS)

Mahaffy, Paul; Brunner, Anna; McAdam, Amy; Franz, Heather; Conrad, Pamela; Webster, Chris; Cabane, Michel

2009-01-01

The lower mound strata of Gale Crater provide a diverse set of chemical environments for exploration by the varied tools of the Curiosity Rover of the Mars Science Laboratory (MSL) Mission. Orbital imaging and spectroscopy clearly reveal distinct layers of hydrated minerals, sulfates, and clays with abundant evidence of a variety of fluvial processes. The three instruments of the MSL Sample Analysis at aMars (SAM) investigation, the Quadrupole Mass Spectrometer (QMS), the Tunable Laser Spectrometer (TLS), and the Gas Chromatograph (GC) are designed to analyze either atmospheric gases or volatiles thermally evolved or chemically extracted from powdered rock or soil. The presence or absence of organic compounds in these layers is of great interest since such an in situ search for this type of record has not been successfully implemented since the mid-60s Viking GCMS experiments. However, regardless of the outcome of the analysis for organics, the abundance and isotopic composition of thermally evolved inorganic compounds should also provide a rich data set to complement the mineralogical and elemental information provided by other MSL instruments. In addition, these evolved gas analysis (EGA) experiments will help test sedimentary models proposed by Malin and Edgett (2000) and then further developed by Milliken et al (2010) for Gale Crater. In the SAM EGA experiments the evolution temperatures of H2O, CO2, SO2, O2, or other simple compounds as the samples are heated in a helium stream to 1000 C provides information on mineral types and their associations. The isotopic composition of O, H, C, and S can be precisely determined in several evolved compounds and compared with the present day atmosphere. Such SAM results might be able to test mineralogical evidence of changing sedimentary and alteration processes over an extended period of time. For example, Bibring et al (2006) have suggested such a major shift from early nonacidic to later acidic alteration. We will illustrate through a variety of evolved gas experiments implemented under SAM-like gas flow and temperature ramp conditions on terrestrial analog minerals on high fidelity Sam breadboards the type of chemical information we expect SAM to provide.

Molecular abundances and C/O ratios in chemically evolving planet-forming disk midplanes

NASA Astrophysics Data System (ADS)

Eistrup, Christian; Walsh, Catherine; van Dishoeck, Ewine F.

2018-05-01

Context. Exoplanet atmospheres are thought be built up from accretion of gas as well as pebbles and planetesimals in the midplanes of planet-forming disks. The chemical composition of this material is usually assumed to be unchanged during the disk lifetime. However, chemistry can alter the relative abundances of molecules in this planet-building material. Aims: We aim to assess the impact of disk chemistry during the era of planet formation. This is done by investigating the chemical changes to volatile gases and ices in a protoplanetary disk midplane out to 30 AU for up to 7 Myr, considering a variety of different conditions, including a physical midplane structure that is evolving in time, and also considering two disks with different masses. Methods: An extensive kinetic chemistry gas-grain reaction network was utilised to evolve the abundances of chemical species over time. Two disk midplane ionisation levels (low and high) were explored, as well as two different makeups of the initial abundances ("inheritance" or "reset"). Results: Given a high level of ionisation, chemical evolution in protoplanetary disk midplanes becomes significant after a few times 105 yr, and is still ongoing by 7 Myr between the H2O and the O2 icelines. Inside the H2O iceline, and in the outer, colder regions of the disk midplane outside the O2 iceline, the relative abundances of the species reach (close to) steady state by 7 Myr. Importantly, the changes in the abundances of the major elemental carbon and oxygen-bearing molecules imply that the traditional "stepfunction" for the C/O ratios in gas and ice in the disk midplane (as defined by sharp changes at icelines of H2O, CO2 and CO) evolves over time, and cannot be assumed fixed, with the C/O ratio in the gas even becoming smaller than the C/O ratio in the ice. In addition, at lower temperatures (<29 K), gaseous CO colliding with the grains gets converted into CO2 and other more complex ices, lowering the CO gas abundance between the O2 and CO thermal icelines. This effect can mimic a CO iceline at a higher temperature than suggested by its binding energy. Conclusions: Chemistry in the disk midplane is ionisation-driven, and evolves over time. This affects which molecules go into forming planets and their atmospheres. In order to reliably predict the atmospheric compositions of forming planets, as well as to relate observed atmospheric C/O ratios of exoplanets to where and how the atmospheres have formed in a disk midplane, chemical evolution needs to be considered and implemented into planet formation models.

Cenozoic intra-plate magmatism in the Darfur volcanic province: mantle source, phonolite-trachyte genesis and relation to other volcanic provinces in NE Africa

NASA Astrophysics Data System (ADS)

Lucassen, Friedrich; Pudlo, Dieter; Franz, Gerhard; Romer, Rolf L.; Dulski, Peter

2013-01-01

Chemical and Sr, Nd and Pb isotopic compositions of Late Cenozoic to Quaternary small-volume phonolite, trachyte and related mafic rocks from the Darfur volcanic province/NW-Sudan have been investigated. Isotope signatures indicate variable but minor crustal contributions. Some phonolitic and trachytic rocks show the same isotopic composition as their primitive mantle-derived parents, and no crustal contributions are visible in the trace element patterns of these samples. The magmatic evolution of the evolved rocks is dominated by crystal fractionation. The Si-undersaturated strongly alkaline phonolite and the Si-saturated mildly alkaline trachyte can be modelled by fractionation of basanite and basalt, respectively. The suite of basanite-basalt-phonolite-trachyte with characteristic isotope signatures from the Darfur volcanic province fits the compositional features of other Cenozoic intra-plate magmatism scattered in North and Central Africa (e.g., Tibesti, Maghreb, Cameroon line), which evolved on a lithosphere that was reworked or formed during the Neoproterozoic.

A DTA/GC for the in Situ Identification of the Martian Surface Material

NASA Technical Reports Server (NTRS)

Mancinelli, R. L.; White, M. R.; Orenberg, J. B.

1993-01-01

The composition and mineralogy of the Martian surface material remain largely unknown. To determine its composition and mineralogy, several techniques are being considered for in situ analyses of the Martian surface material during missions to Mars. We have successfully developed, constructed, and tested a laboratory DTA/GC. The DTA is a Dupont model 1600 high temperature DTA coupled with a GC equipped with a MID detector. The system is operated by a Sun Sparc 11 workstation. When gas evolves during a thermal chemical event, it is shunted into the GC and the temperature is recorded in association with the specific thermal event. We have used this laboratory instrument to define experimental criteria necessary for determining the composition and mineralogy of the Martian surface in situ (e.g., heating of sample to 1100 C to distinguish clays). Our studies indicate that DTA/GC will provide a broad spectrum of mineralogical and evolved gas data pertinent to exobiology, geochemistry, and geology.

Comprehensive modeling study of ozonolysis of oleic acid aerosol based on real-time, online measurements of aerosol composition

NASA Astrophysics Data System (ADS)

Gallimore, P. J.; Griffiths, P. T.; Pope, F. D.; Reid, J. P.; Kalberer, M.

2017-04-01

The chemical composition of organic aerosols profoundly influences their atmospheric properties, but a detailed understanding of heterogeneous and in-particle reactivity is lacking. We present here a combined experimental and modeling study of the ozonolysis of oleic acid particles. An online mass spectrometry (MS) method, Extractive Electrospray Ionization (EESI), is used to follow the composition of the aerosol at a molecular level in real time; relative changes in the concentrations of both reactants and products are determined during aerosol aging. The results show evidence for multiple non-first-order reactions involving stabilized Criegee intermediates, including the formation of secondary ozonides and other oligomers. Offline liquid chromatography MS is used to confirm the online MS assignment of the monomeric and dimeric products. We explain the observed EESI-MS chemical composition changes, and chemical and physical data from previous studies, using a process-based aerosol chemistry simulation, the Pretty Good Aerosol Model (PG-AM). In particular, we extend previous studies of reactant loss by demonstrating success in reproducing the time dependence of product formation and the evolving particle size. This advance requires a comprehensive chemical scheme coupled to the partitioning of semivolatile products; relevant reaction and evaporation parameters have been refined using our new measurements in combination with PG-AM.

Quantitative composition determination at the atomic level using model-based high-angle annular dark field scanning transmission electron microscopy.

PubMed

Martinez, G T; Rosenauer, A; De Backer, A; Verbeeck, J; Van Aert, S

2014-02-01

High angle annular dark field scanning transmission electron microscopy (HAADF STEM) images provide sample information which is sensitive to the chemical composition. The image intensities indeed scale with the mean atomic number Z. To some extent, chemically different atomic column types can therefore be visually distinguished. However, in order to quantify the atomic column composition with high accuracy and precision, model-based methods are necessary. Therefore, an empirical incoherent parametric imaging model can be used of which the unknown parameters are determined using statistical parameter estimation theory (Van Aert et al., 2009, [1]). In this paper, it will be shown how this method can be combined with frozen lattice multislice simulations in order to evolve from a relative toward an absolute quantification of the composition of single atomic columns with mixed atom types. Furthermore, the validity of the model assumptions are explored and discussed. © 2013 Published by Elsevier B.V. All rights reserved.

Towards a coherent view of mass loss in Betelgeuse from the photosphere to the interstellar medium

NASA Astrophysics Data System (ADS)

Montarges, Miguel; Kervella, Pierre; Perrin, Guy

2013-06-01

Massive evolved stars contribute to the chemical enrichment of the interstellar medium (ISM), the Galaxy and ultimately the Universe through their mass loss. From the photosphere to the ISM, large convective motions, low surface gravity and high brightness combine to trigger an intense stellar wind. The released material evolves chemically as the distance from the star increases, and eventually forms dust particles. The involved physical and chemical processes are central to apprehend the cosmic impact of massive evolved stars, but they are poorly understood: the surface convection remains essentially uncharacterized, as the composition of the wind, and the role of the magnetic field is unknown. Betelgeuse is the closest red supergiant and therefore it stands out as the best candidate to obtain detailed observations of the close circumstellar environment of a massive evolved star. We are currently running a high angular resolution observations program to obtain a multi-wavelength and multi-epoch characterisation of this star. Using the IOTA interferometer, Haubois et al. reconstructed an image of the photosphere of the star. Within 1 to 100 stellar radii, the VLT and VLTI allowed us to probe the compact molecular envelope of Betelgeuse (the MOLsphere) in the near-infrared, and the extended dusty envelope in the thermal infrared domain. They were recently completed with HST/STIS observations of the chromosphere in the UV, whose location is surprisingly coincident with the MOLsphere. We will present a brief review of our recent results and of our ongoing work on Betelgeuse.

On the binary helium star DY Centauri: chemical composition and evolutionary state

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

Pandey, Gajendra; Rao, N. Kameswara; Jeffery, C. Simon

2014-10-01

DY Cen has shown a steady fading of its visual light by about one magnitude in the last 40 yr, suggesting a secular increase in its effective temperature. We have conducted non-local thermodynamic equilibrium (LTE) and LTE abundance analyses to determine the star's effective temperature, surface gravity, and chemical composition using high-resolution spectra obtained over two decades. The derived stellar parameters for three epochs suggest that DY Cen has evolved at a constant luminosity and has become hotter by about 5000 K in 23 yr. We show that the derived abundances remain unchanged for the three epochs. The derived abundancesmore » of the key elements, including F and Ne, are as observed for the extreme helium stars resulting from a merger of a He white dwarf with a C-O white dwarf. Thus DY Cen by chemical composition appears to also be a product of a merger of two white dwarfs. This appearance seems to be at odds with the recent suggestion that DY Cen is a single-lined spectroscopic binary.« less

Time Domain Astrochemistry in Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Cleeves, Lauren Ilsedore

2018-01-01

The chemistry of protoplanetary disks sets the initial composition of newly formed planets and may regulate the efficiency by which planets form. Disk chemical abundances typically evolve over timescales spanning thousands if not millions of years. Consequently, it was a surprise when ALMA observations taken over the course of a single year showed significantly variable emission in H13CO+ relative to the otherwise constant thermal dust emission in the IM Lup protoplanetary disk. HCO+ is a known X-ray sensitive molecule, and by using simple time-evolving chemical models including stellar activity, we demonstrate that stellar X-ray flares are a viable explanation for the observed H13CO+ variability. If this link between chemistry and stellar activity is confirmed, simultaneous observations can provide a new tool to measure (and potentially map) fundamental disk parameters, such as electron density, as the light from X-ray flares propagates across the disk.

Five Years of Analyses of Volatiles, Isotopes and Organics in Gale Crater Materials

NASA Astrophysics Data System (ADS)

McAdam, A.; Mahaffy, P. R.; Andrejkovicova, S. C.; Archer, P. D., Jr.; Atreya, S. K.; Buch, A.; Coll, P. J.; Conrad, P. G.; Eigenbrode, J. L.; Farley, K. A.; Flesch, G.; Franz, H. B.; Freissinet, C.; Glavin, D. P.; Hogancamp, J. V.; House, C. H.; Knudson, C. A.; Lewis, J. M.; Malespin, C.; Martin, P. M.; Millan, M.; Ming, D. W.; Morris, R. V.; Navarro-Gonzalez, R.; Steele, A.; Stern, J. C.; Summons, R. E.; Sutter, B.; Szopa, C.; Teinturier, S.; Trainer, M. G.; Webster, C. R.; Wong, G. M.

2017-12-01

Over the last five years, the Curiosity rover has explored a variety of fluvial, lacustrine and aeolian sedimentary rocks, and soils. The Sample Analysis at Mars (SAM) instrument has analysed 3 soil and 12 rock samples, which exhibit significant chemical and mineralogical diversity in over 200 meters of vertical section. Here we will highlight several key insights enabled by recent measurements of the chemical and isotopic composition of inorganic volatiles and organic compounds detected in Gale Crater materials. Until recently samples have evolved O2 during SAM evolved gas analyses (EGA), attributed to the thermal decomposition of oxychlorine phases. A lack of O2 evolution from recent mudstone samples may indicate a difference in the composition of depositional or diagenetic fluids, and can also have implications for the detection of organic compounds since O2 can combust organics to CO2 in the SAM ovens. Recent mudstone samples have also shown little or no evolution of NO attributable to nitrate salts, possibly also as a result of changes in the chemical composition of fluids [1]. Measurements of the isotopic composition of sulfur, hydrogen, nitrogen, chlorine, and carbon in methane evolved during SAM pyrolysis are providing constraints on the conditions of possible paleoenvironments [e.g., 2, 3]. There is evidence of organic C from both EGA and GCMS measurements of Gale samples [e.g., 4, 5]. Organic sulfur volatiles have been detected in several samples, and the first opportunistic derivatization experiment produced a rich dataset indicating the presence of several organic compounds [6, 7]. A K-Ar age has been obtained from the Mojave mudstone, and the age of secondary materials formed by aqueous alteration is likely <3 Ga [8]. This relatively young formation age suggests fluid interactions after the end of most fluvial activity on the surface of Mars. As these highlights show, SAM measurements of solid samples have made diverse and important contributions to the exploration of Gale's rock records of martian environmental history and habitability. [1] Sutter et al. (2017) LPSC 3009. [2] Franz et al., this mtg. [3] Stern et al., this mtg. [4] Ming et al. (2014) Science 343. [5] Freissinet et al. (2015) JGR 120. [6] Eigenbrode et al. (2016) AGU P21D-08. [7] Freissinet et al. (2017) LPSC 2687. [8] Martin et al. (2017) LPSC 1531.

TEMPORAL EVOLUTION OF SUB-NANOMETER COMPOSITIONAL PROFILES ACROSS THE GAMMA/GAMMA' INTERFACE IN A MODEL Ni-Al-Cr SUPERALLOY

NASA Technical Reports Server (NTRS)

Sudbrack, Chantal K.; Noebe, Ronald D.; Seidman, David N.

2005-01-01

Early-stage phase separation in a Ni-5.2 Al-14.2 Cr at.% superalloy, isothermally decomposing at 873 K, is investigated with atom-probe tomography. Sub-nanometer scale compositional profiles across the gamma/gamma'(L12) interfaces demonstrate that both the gamma-matrix and the gamma'-precipitate compositions evolve with time. Observed chemical gradients of Al depletion and Cr enrichment adjacent to the gamma'-precipitates are transient, consistent with well-established model predictions for diffusion-limited growth, and mark the first detailed observation of this phenomenon. Furthermore, it is shown that Cr atoms are kinetically trapped in the growing precipitates.

Melt Transport and Mantle Assimilation at Atlantis Massif (IODP Site U1309): Evidence from Chemical Profiles along Olivine Crystallographic Axes

NASA Astrophysics Data System (ADS)

Ferrando, C.; Godard, M.; Ildefonse, B.; Rampone, E.

2017-12-01

Olivine-rich troctolites (Ol > 70%, Ol T) indicate that extensive melt impregnation of preexisting Ol rich lithologies participate to the building of slow spread crust. To constrain their origin and their impact on the structure and geochemistry of oceanic crust, we realized a multi-scale petro-structural, geochemical, and numerical modelling study of Ol T drilled at IODP Hole U1309D (Atlantis Massif, Exp. 304/305). Ol T display deformed (high temperature imprint) corroded coarse grained to undeformed fine grained Ol embayed in poikilitic Cpx and Plg. Ol crystallographic preferred orientations show [001] cluster suggesting formation after impregnation and assimilation of a deformed Ol rich matrix at high melt/rock ratios. Ol have variable major and minor element compositions, but similar fractionated REE (DyN/YbN = 0.04 - 0.11). Chemical traverses along principal crystallographic axes of Ol are flat suggesting local equilibrium between Ol and neighboring phases. 3 types of Ol T were distinguished. Ol T 1 - 2 display sharp contacts. Ol T 1 has Ol <75% (single grains) and primitive compositions (Mg# = 85-86; Ni = 1870-2840 ppm, Mn = 1570-1950 ppm; Li = 1.2 - 2.7 ppm). Ol T 2 have high Ol ( > 75%, dominantly aggregates) yet more evolved composition (Mg# = 83-84, Ni = 1790 - 2510 ppm, Mn = 1760 - 1990 ppm, Li = 1.5 - 3.9 ppm) in contrast to modal and composition trends predicted by MORB crystallization. Ol T 3 has diffusive contacts with gabbroic veins, variable modal Ol with the most evolved compositions and record late stages of Ol-T formation. Ol T compositions are best modelled assuming percolation of primitive MORB melts into Hole U1309B harzburgite, triggering Opx dissolution, followed by Ol assimilation and Plg + Cpx crystallization. Modelling shows that Ol Ni variations at constant Mg# in Ol T are mantle inherited. Ol T 1 compositions were fitted assuming higher Ol assimilation (Ma = 0.06 - 0.13) in contrast to Ol T 2 -3 (Ma = 0.01 - 0.02). Ol T 3 was `buffered' by more evolved melts and shows cooling of reacted melts. We interpret the 3 Ol T types as resulting from initial local spatial variations in mantle permeability (pyroxene distribution?) which in turn controlled melt transport and mantle-melt interactions. We expect that such reactive percolation processes will shift MORB compositions to apparent high pressure fractionation.

Making mushy magma chambers in the lower continental crust: Cold storage and compositional bimodality

NASA Astrophysics Data System (ADS)

Jackson, Matthew; Blundy, Jon; Sparks, Steve

2017-04-01

Increasing geological and geophysical evidence suggests that crustal magma reservoirs are normally low melt fraction 'mushes' rather than high melt fraction 'magma chambers'. Yet high melt fractions must form within these mush reservoirs to explain the observed flow and eruption of low crystallinity magmas. In many models, crystallinity is linked directly to temperature, with higher temperature corresponding to lower crystallinity (higher melt fraction). However, increasing temperature yields less evolved (silicic) melt composition for a given starting material. If mobile, low crystallinity magmas require high temperature, it is difficult to explain how they can have evolved composition. Here we use numerical modelling to show that reactive melt flow in a porous and permeable mush reservoir formed by the intrusion of numerous basaltic sills into the lower continental crust produces magma in high melt fraction (> 0.5) layers akin to conventional magma chambers. These magma-chamber-like layers contain evolved (silicic) melt compositions and form at low (close to solidus) temperatures near the top of the mush reservoir. Evolved magma is therefore kept in 'cold storage' at low temperature, but also at low crystallinity so the magma is mobile and can leave the mush reservoir. Buoyancy-driven reactive flow and accumulation of melt in the mush reservoir controls the temperature and composition of magma that can leave the reservoir. The modelling also shows that processes in lower crustal mush reservoirs produce mobile magmas that contain melt of either silicic or mafic composition. Intermediate melt compositions are present but are not within mobile magmas. Silicic melt compositions are found at high melt fraction within the magma-chamber like layers near the top of the mush reservoir. Mafic melt compositions are found at high melt fraction within the cooling sills. Melt elsewhere in the reservoir has intermediate composition, but remains trapped in the reservoir because the local melt fraction is too low to form a mobile magma. The model results are consistent with geochemical data suggesting that lower crustal magma reservoirs supply silicic and mafic melts to arc volcanoes, but intermediate magmas are formed by mixing in shallower reservoirs. We suggest here that lower crustal magma chambers primarily form in response to changes in bulk composition caused by melt migration and chemical reaction in a mush reservoir. This process is different to the conventional and widely applied models of magma chamber formation. Similar processes are likely to operate in shallow mush reservoirs, but will likely be further complicated by the presence of volatile phases, and mixing of different melt compositions sourced from deeper mush reservoirs.

Conspicuous and aposematic spines in the animal kingdom

NASA Astrophysics Data System (ADS)

Inbar, Moshe; Lev-Yadun, Simcha

2005-04-01

Spines serve as a common physical defence mechanism in both the plant and animal kingdoms. Here we argue that as in plants, defensive animal spines are often conspicuous (shape and colour) and should be considered aposematic. Conspicuous spines may evolve as signals or serve as a cue for potential predators. Spine conspicuousness in animals has evolved independently across and within phyla occupying aquatic and terrestrial ecosystems, indicating that this convergent phenomenon is highly adaptive. Still, many spines are cryptic, suggesting that conspicuity is not simply constrained by developmental factors such as differences in the chemical composition of the integument. Aposematism does not preclude the signalling role of conspicuous spines in the sexual arena.

Emergence of life: Physical chemistry changes the paradigm.

PubMed

Spitzer, Jan; Pielak, Gary J; Poolman, Bert

2015-06-10

Origin of life research has been slow to advance not only because of its complex evolutionary nature (Franklin Harold: In Search of Cell History, 2014) but also because of the lack of agreement on fundamental concepts, including the question of 'what is life?'. To re-energize the research and define a new experimental paradigm, we advance four premises to better understand the physicochemical complexities of life's emergence: (1) Chemical and Darwinian (biological) evolutions are distinct, but become continuous with the appearance of heredity. (2) Earth's chemical evolution is driven by energies of cycling (diurnal) disequilibria and by energies of hydrothermal vents. (3) Earth's overall chemical complexity must be high at the origin of life for a subset of (complex) chemicals to phase separate and evolve into living states. (4) Macromolecular crowding in aqueous electrolytes under confined conditions enables evolution of molecular recognition and cellular self-organization. We discuss these premises in relation to current 'constructive' (non-evolutionary) paradigm of origins research - the process of complexification of chemical matter 'from the simple to the complex'. This paradigm artificially avoids planetary chemical complexity and the natural tendency of molecular compositions toward maximum disorder embodied in the second law of thermodynamics. Our four premises suggest an empirical program of experiments involving complex chemical compositions under cycling gradients of temperature, water activity and electromagnetic radiation.

ChemCam at Gale Crater: Highlights and Discoveries from Three Years of Chemical Measurements on Mars

NASA Astrophysics Data System (ADS)

Blaney, Diana L.; Wiens, Roger; Maurice, Sylvestre; Gasnault, Olivier; Anderson, Ryan; Bridges, John; Bridges, Nathan; Clegg, Samuel; Clark, Benton; Ehlmann, Bethany; Dyar, Melinda D.; Fisk, Martin; Francis, Raymond; Fabre, Cecile; Forni, Olivier; Frydenvang, Jens; Johnson, Jeffery; Lanza, Nina; Leveille, Richard; Lasue, Jeremie; Le Deit, Laetitia; Mangold, Nicholas; Melikechi, Noureddine; Nachon, Marion; Newsom, Horton; Payre, Valerie; Rapin, William; Sautter, Violane; Vaniman, David; Grotzinger, John; Vasavad, Ashwin; Crisp, Joy

2015-11-01

ChemCam has undertaken a detailed chemical investigation of the rocks and soils at Gale crater over the last three years with over six thousand separate geochemical measurements. Recent recalibration of the ChemCam data using a new library of >350 geochemical standards has enabled increased elemental accuracies over a wider compositional range. The increased accuracy combined with ChemCam’s small spot size allows for the chemistry of mineral end members including feldspars, high silica, oxide rich grains to be identified. ChemCam has observed both sedimentary and igneous compositions. Igneous compositions are generally present in conglomerates and in float rocks. Compositions show a wide range of igneous chemistry ranging from basaltic to feldspar rich assemblages.Sedimentary rocks have a wide range of compositions reflecting both differences in chemical source regions and in depositional and diagenetic histories. The “Sheepbed” mudstones cluster around Martian average crustal compositions. The “Kimberley” outcrop showed enhanced potassium reaching concentrations up to ~6 wt% K2O. More recent observations in the Murray Formation at the base of Mt. Sharp reveal mudstones that are lower in magnesium and higher in silica and aluminum than the more basaltic mudstones previously investigated. Extremely high silica (75-85 wt%) deposits have also been identified. The high silica observations were associated with increased TiO2, While the Murray mudstones are generally low in magnesium, local enhancements in magnesium have also been noted associated with resistant facies in the outcrop. Chemical trends also indicate that iron oxide phases may also be present as cements. Sandstone facies with a mafic composition are also present. Veins in the unit also show a wide range of compositions indicating fluid chemistries rich in calcium sulfate, fluorine, magnesium and iron were present. Vein chemistry could be the result of distinct fluids migrating through from a distance with a pre-established chemical signature, fluids locally evolved from water rock interactions, or both. Thus the chemical relationships between the Pahrump bedrock and the veins’ chemistry can be used to constrain the origin of the fluids.

Project Hotspot: Temporal Compositional Variation in Basalts of the Kimama Core and Implications for Magma Source Evolution, Snake River Scientific Drilling Project, Idaho

NASA Astrophysics Data System (ADS)

Potter, K. E.; Shervais, J. W.; Champion, D.; Duncan, R. A.; Christiansen, E. H.

2012-12-01

Project Hotspot produced continuous core from three drill sites in the Snake River plain, including 1912 m of core from the Kimama drill site on the axis of the plain. Ongoing major and trace element chemical characterization of the Kimama core and new 40Ar/39Ar and paleomagnetic age data demonstrate temporal variations in the evolution of Snake River Plain volcanism. Cyclic fluctuations in magma chemistry identify over a hundred chemically distinct basalt flow groups (comprising 550 individual lava flows) within 54 periods of volcanic activity, separated by hiatuses of decades to many millennia. From a surface age of 700 ka to a bottom-hole age of 6.5 Ma, the Kimama core records the presence of several nearly coeval but compositionally different lava flows, ranging from highly evolved lavas to non-evolved tholeiites. Determining whether Kimama lavas are genetically unrelated or extreme differentiates of a single magma batch relies upon a combination of detailed chemostratigraphy and absolute and relative age data. Age and geochemical data introduce new ideas on the role of multiple magma sources and/or differentiation processes in the development of central Snake River Plain volcanic systems. The relatively short gestation of evolved liquids is demonstrated throughout the Kimama core, with evidence for cyclic fractionation of mafic lavas at depths of 318 m, 350 m, 547 m, and 1078 m. Here, highly evolved lava flows (FeOT 16.0-18.4 wt %; TiO2 3.43-4.62 wt %) are stratigraphically bounded by more primitive tholeiitic basalts (FeOT 9.9-14.8 wt%; TiO2 1.22-3.56 wt%) within the same inclination range, suggesting that cyclic fractionation is a regular feature of shield volcano development on the central Snake River Plain. Between 1.60 ± 0.13 Ma (453.5 m depth) and 1.54 ± 0.15 Ma (320.0 m depth), Kimama lavas ranged in composition from primitive tholeiite (FeOT 11.7 wt %; TiO2 1.76 wt %) to evolved basalt (FeOT 16.0 wt %; TiO2 4.00 wt %). At depths of 1119 m and 1138 m, evolved lava flows (FeOT 17.2 and 17.0 wt %; TiO2 4.20 and 4.09 wt %, respectively) of negative polarity are stratigraphically bounded by more primitive tholeittic lava flows (FeOT 13.6 and 14.5 wt %; TiO2 2.92 and 3.24 wt %, respectively) of positive polarity, a chronological transition that may represent many millennia and magma source variability. Kimama core stratigraphy as well as paleomagnetic, and radiometric age data demonstrate that mafic volcanism on the central Snake River Plain has been relatively continuous for the last 6.5 Ma. The compositional variability in Kimama basalts introduces broader implications for the timing of cyclic fractionation processes and the development of regional magma sources.

Fahlore and Sphalerite from the Darasun Gold Deposit in the Eastern Transbaikal Region, Russia: I. Mineral Assemblages and Intergrowths, Chemical Composition, and Its Evolution

NASA Astrophysics Data System (ADS)

Lyubimtseva, N. G.; Bortnikov, N. S.; Borisovsky, S. E.; Prokofiev, V. Yu.; Vikent'eva, O. V.

2018-03-01

The mineral assemblages, mode of occurrence, and chemical compositions of coexisting fahlore and sphalerite from the Darasun gold deposit have been described. Three generations of fahlore and three generations of sphalerite have been recognized. The FeS content in sphalerite coexisting with fahlore ranges from 0.8 to 9.4 mol %. The complete solid solution series Fe-tetrahedrite-Zn-tetrahedrite-Fe-tennantite-Zn-tennantite reflected in Sb/(Sb + As) and Fe/(Fe + Zn) ratios ranging from 0 to 0.97 and from 0.07 to 1.00, respectively, with a predominant negative relationship between these ratios has been identified for the first time at the deposit. Stepped, oscillatory, and combined stepped-oscillatory growth zonings within fahlore grains and heterogeneous aggregates of fahlore have been found. Fahlore is enriched in As with respect to Sb, and Zn-tetrahedrite is followed by Fe- and Zn-tennantite from early to late generation; Zn-tetrahedrite is followed by Fe-tennantite in zoned grains and overgrown rims; sphalerite crystallized at decreased temperature and sulfur fugacity. The evolution of the chemical composition of fahlores was caused by the evolving temperature, fluid salinity, and conditions of metal migration.

The chemistry in circumstellar envelopes of evolved stars: following the origin of the elements to the origin of life.

PubMed

Ziurys, Lucy M

2006-08-15

Mass loss from evolved stars results in the formation of unusual chemical laboratories: circumstellar envelopes. Such envelopes are found around carbon- and oxygen-rich asymptotic giant branch stars and red supergiants. As the gaseous material of the envelope flows from the star, the resulting temperature and density gradients create a complex chemical environment involving hot, thermodynamically controlled synthesis, molecule "freeze-out," shock-initiated reactions, and photochemistry governed by radical mechanisms. In the circumstellar envelope of the carbon-rich star IRC+10216, >50 different chemical compounds have been identified, including such exotic species as C(8)H, C(3)S, SiC(3), and AlNC. The chemistry here is dominated by molecules containing long carbon chains, silicon, and metals such as magnesium, sodium, and aluminum, which makes it quite distinct from that found in molecular clouds. The molecular composition of the oxygen-rich counterparts is not nearly as well explored, although recent studies of VY Canis Majoris have resulted in the identification of HCO(+), SO(2), and even NaCl in this object, suggesting chemical complexity here as well. As these envelopes evolve into planetary nebulae with a hot, exposed central star, synthesis of molecular ions becomes important, as indicated by studies of NGC 7027. Numerous species such as HCO(+), HCN, and CCH are found in old planetary nebulae such as the Helix. This "survivor" molecular material may be linked to the variety of compounds found recently in diffuse clouds. Organic molecules in dense interstellar clouds may ultimately be traced back to carbon-rich fragments originally formed in circumstellar shells.

Discovery of meteorites on a blue-ice field near the Frontier Mountains, North Victoria Land, Antarctica

NASA Technical Reports Server (NTRS)

Delisle, G.; Hoefle, H. C.; Thierbach, R.; Schultz, L.

1986-01-01

A high concentration of meteorites were discovered on a blue ice field northeast of the Frontier Mountains. As a result of a systematic search, a total of 42 meteorites were recovered. The current glacial situation has evolved through various stages, which are discussed in relationship to the concentration of meteorites. Ice flow patterns are summarized. The chemical composition and terrestrial ages of the meteorites are discussed.

Hazard assessment of substances produced from the accidental heating of chemical compounds.

PubMed

Lunghi, A; Gigante, L; Cardillo, P; Stefanoni, V; Pulga, G; Rota, R

2004-12-10

Accidental events concerning process industries can affect not only the staff working in, but also the environment and people living next to the factory. For this reason a regulation is imposed by the European Community to prevent accidents that could represent a risk for the population and the environment. In particular, Directive 96/82/CE, the so-called 'Seveso II directive', requests a risk analysis involving also the hazardous materials generated in accidental events. Therefore, it is necessary to develop simple and economic procedure to foresee the hazardous materials that can be produced in the case of major accidents, among which the accidental heating of a chemical due to a fire or a runaway reaction is one of the most frequent. The procedure proposed in this work is based on evolved gas analysis methodology that consists in coupling two instruments: a thermogravimetric analyzer or a flash pyrolyzer, that are employed to simulate accident conditions, and a FTIR spectrometer that can be used to detect the evolved gas composition. More than 40 materials have been examined in various accident scenarios and the obtained data have been statistically analyzed in order to identify meaningful correlations between the presence of a chemical group in the molecule of a chemical and the presence of a given hazardous species in the fume produced.

High heating rate decomposition dynamics of copper oxide by nanocalorimetry-coupled time-of-flight mass spectrometry

NASA Astrophysics Data System (ADS)

Yi, Feng; DeLisio, Jeffery B.; Nguyen, Nam; Zachariah, Michael R.; LaVan, David A.

2017-12-01

The thermodynamics and evolved gases were measured during the rapid decomposition of copper oxide (CuO) thin film at rates exceeding 100,000 K/s. CuO decomposes to release oxygen when heated and serves as an oxidizer in reactive composites and chemical looping combustion. Other instruments have shown either one or two decomposition steps during heating. We have confirmed that CuO decomposes by two steps at both slower and higher heating rates. The decomposition path influences the reaction course in reactive Al/CuO/Al composites, and full understanding is important in designing reactive mixtures and other new reactive materials.

Surface effects on the mechanical elongation of AuCu nanowires: De-alloying and the formation of mixed suspended atomic chains

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

Lagos, M. J.; Laboratório Nacional de Nanotecnologia-LNNANO, 13083-970 Campinas-SP; Autreto, P. A. S.

2015-03-07

We report here an atomistic study of the mechanical deformation of Au{sub x}Cu{sub (1−x)} atomic-size wires (nanowires (NWs)) by means of high resolution transmission electron microscopy experiments. Molecular dynamics simulations were also carried out in order to obtain deeper insights on the dynamical properties of stretched NWs. The mechanical properties are significantly dependent on the chemical composition that evolves in time at the junction; some structures exhibit a remarkable de-alloying behavior. Also, our results represent the first experimental realization of mixed linear atomic chains (LACs) among transition and noble metals; in particular, surface energies induce chemical gradients on NW surfacesmore » that can be exploited to control the relative LAC compositions (different number of gold and copper atoms). The implications of these results for nanocatalysis and spin transport of one-atom-thick metal wires are addressed.« less

Classification and regulatory perspectives of dietary fiber.

PubMed

Dai, Fan-Jhen; Chau, Chi-Fai

2017-01-01

This review discusses the history and evolution of the state of dietary fiber (DF) with account of refinements in extraction methods and legal definitions subsequent to the launch of DF hypothesis. For a long time, defining and regulating DFs relied heavily on their chemical compositions and analytical methods. Although chemical compositions and analytical methods still play an important role in the definition of DF, physiological activity has also been taken into consideration. The precise definition of DF is still evolving, particularly whether oligosaccharides degrees of polymerization (DP) 3-9 should be considered as DF or not. Decades of scientific research have initiated the expansion of the term DF to include indigestible oligosaccharides with their DP between 3 and 9; hence responding to the positive health benefits of DF as well as fulfilling the needs in food labeling regulations. Copyright © 2016. Published by Elsevier B.V.

Is there any pristine gas in nearby starburst galaxies?

NASA Astrophysics Data System (ADS)

Lebouteiller, Vianney; Kunth, Daniel

2008-12-01

We derive the chemical composition of the neutral gas in the blue compact dwarf (BCD) Pox 36 observed with FUSE. Metals (N, O, Ar, and Fe) are underabundant as compared to the ionized gas associated with H ii regions by a factor ~7. The neutral gas, although it is not pristine, is thus probably less chemically evolved than the ionized gas. This could be due to different dispersal and mixing timescales. Results are compared to those of other BCDs observed with FUSE. The metallicity of the neutral gas in BCDs seems to reach a lower threshold of ~1/50 Z⊙ for extremely-metal poor galaxies.

Metal enrichment in the neutral gas of star-forming galaxies

NASA Astrophysics Data System (ADS)

Lebouteiller, V.; Kunth, D.; Désert, J.-M.; Thuan, T. X.

2009-05-01

We derive the chemical composition of the neutral gas in the blue compact dwarf (BCD) Pox 36 observed with FUSE. Metals (N, O, Ar, and Fe) are underabundant as compared to the ionized gas associated with H II regions by a factor ~7. The neutral gas, although it is not pristine, is thus probably less chemically evolved than the ionized gas. This could be due to different dispersal and mixing timescales. Results are compared to those of other BCDs observed with FUSE. The metallicity of the neutral gas in BCDs seems to reach a lower threshold of ~1/50Zsolar for extremely-metal poor galaxies.

Evolved Gas Measurements Planned for the Lower Layers of the Gale Crater Mound with the Sample Analysis at Mars Instrument Suite

NASA Astrophysics Data System (ADS)

Mahaffy, P. R.; Franz, H.; McAdam, A.; Conrad, P. G.; Brunner, A.; Cabane, M.; Webster, C. R.

2011-12-01

The lower mound strata of Gale Crater provide a diverse set of chemical environments for exploration by the varied tools of the Curiosity Rover of the Mars Science Laboratory (MSL) Mission. Orbital imaging and spectroscopy clearly reveal distinct layers of hydrated minerals, sulfates, and clays with abundant evidence of a variety of fluvial processes. The three instruments of the MSL Sample Analysis at Mars (SAM) investigation, the Quadrupole Mass Spectrometer (QMS), the Tunable Laser Spectrometer (TLS), and the Gas Chromatograph (GC) are designed to analyze either atmospheric gases or volatiles thermally evolved or chemically extracted from powdered rock or soil. The presence or absence of organic compounds in these layers is of great interest since such an in situ search for this type of record has not been successfully implemented since the mid-70s Viking GCMS experiments. However, regardless of the outcome of the analysis for organics, the abundance and isotopic composition of thermally evolved inorganic compounds should also provide a rich data set to complement the mineralogical and elemental information provided by other MSL instruments. In addition, these evolved gas analysis (EGA) experiments will help test sedimentary models proposed by Malin and Edgett (2000) and then further developed by Milliken et al (2010) for Gale Crater. In the SAM EGA experiments the evolution temperatures of H2O, CO2, SO2, O2, or other simple compounds as the samples are heated in a helium stream to 1000C provides information on mineral types and their associations. The isotopic composition of O, H, C, and S can be precisely determined in several evolved compounds and compared with the present day atmosphere. Such SAM results might be able to test mineralogical evidence of changing sedimentary and alteration processes over an extended period of time. For example, Bibring et al (2006) have suggested such a major shift from early nonacidic to later acidic alteration. We will illustrate through a variety of evolved gas experiments implemented under SAM-like gas flow and temperature ramp conditions on terrestrial analog minerals on high fidelity SAM breadboards the type of chemical information we expect SAM to provide. Bibring, J.-P., et al. (2006), Global mineralogical and aqueous Mars history derived from OMEGA/Mars Express data, Science, 312, 400-404, doi:10.1126/science.1122659. Malin, M. C., and K. S. Edgett (2000), Sedimentary rocks of early Mars, Science, 290, 1927-1937, doi:10.1126/science.290.5498.1927. Milliken, R. E., J. P. Grotzinger, and B. J. Thomson (2010), Paleoclimate of Mars as captured by the strati- graphic record in Gale Crater, Geophys. Res. Lett., 37, L04201, doi:10.1029/2009GL041870.

Mass Spectrometry Imaging and GC-MS Profiling of the Mammalian Peripheral Sensory-Motor Circuit

NASA Astrophysics Data System (ADS)

Rubakhin, Stanislav S.; Ulanov, Alexander; Sweedler, Jonathan V.

2015-06-01

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) has evolved to become an effective discovery tool in science and clinical diagnostics. Here, chemical imaging approaches are applied to well-defined regions of the mammalian peripheral sensory-motor system, including the dorsal root ganglia (DRG) and adjacent nerves. By combining several MSI approaches, analyte coverage is increased and 195 distinct molecular features are observed. Principal component analysis suggests three chemically different regions within the sensory-motor system, with the DRG and adjacent nerve regions being the most distinct. Investigation of these regions using gas chromatography-mass spectrometry corroborate these findings and reveal important metabolic markers related to the observed differences. The heterogeneity of the structurally, physiologically, and functionally connected regions demonstrates the intricate chemical and spatial regulation of their chemical composition.

Advancing Nucleosynthesis in Core-Collapse Supernovae Models Using 2D CHIMERA Simulations

NASA Astrophysics Data System (ADS)

Harris, J. A.; Hix, W. R.; Chertkow, M. A.; Bruenn, S. W.; Lentz, E. J.; Messer, O. B.; Mezzacappa, A.; Blondin, J. M.; Marronetti, P.; Yakunin, K.

2014-01-01

The deaths of massive stars as core-collapse supernovae (CCSN) serve as a crucial link in understanding galactic chemical evolution since the birth of the universe via the Big Bang. We investigate CCSN in polar axisymmetric simulations using the multidimensional radiation hydrodynamics code CHIMERA. Computational costs have traditionally constrained the evolution of the nuclear composition in CCSN models to, at best, a 14-species α-network. However, the limited capacity of the α-network to accurately evolve detailed composition, the neutronization and the nuclear energy generation rate has fettered the ability of prior CCSN simulations to accurately reproduce the chemical abundances and energy distributions as known from observations. These deficits can be partially ameliorated by "post-processing" with a more realistic network. Lagrangian tracer particles placed throughout the star record the temporal evolution of the initial simulation and enable the extension of the nuclear network evolution by incorporating larger systems in post-processing nucleosynthesis calculations. We present post-processing results of the four ab initio axisymmetric CCSN 2D models of Bruenn et al. (2013) evolved with the smaller α-network, and initiated from stellar metallicity, non-rotating progenitors of mass 12, 15, 20, and 25 M⊙ from Woosley & Heger (2007). As a test of the limitations of post-processing, we provide preliminary results from an ongoing simulation of the 15 M⊙ model evolved with a realistic 150 species nuclear reaction network in situ. With more accurate energy generation rates and an improved determination of the thermodynamic trajectories of the tracer particles, we can better unravel the complicated multidimensional "mass-cut" in CCSN simulations and probe for less energetically significant nuclear processes like the νp-process and the r-process, which require still larger networks.

Crystallisation sequence and magma evolution of the De Beers dyke (Kimberley, South Africa)

NASA Astrophysics Data System (ADS)

Soltys, Ashton; Giuliani, Andrea; Phillips, David

2018-06-01

We present petrographic and mineral chemical data for a suite of samples derived from the De Beers dyke, a contemporaneous, composite intrusion bordering the De Beers pipe (Kimberley, South Africa). Petrographic features and mineral compositions indicate the following stages in the evolution of this dyke: (1) production of antecrystic material by kimberlite-related metasomatism in the mantle (i.e., high Cr-Ti phlogopite); (2) entrainment of wall-rock material during ascent through the lithospheric mantle, including antecrysts; (3) early magmatic crystallisation of olivine (internal zones and subsequently rims), Cr-rich spinel, rutile, and magnesian ilmenite, probably on ascent to the surface; and (4) crystallisation of groundmass phases (i.e., olivine rinds, Fe-Ti-rich spinels, perovskite, apatite, monticellite, calcite micro-phenocrysts, kinoshitalite-phlogopite, barite, and baddeleyite) and the mesostasis (calcite, dolomite, and serpentine) on emplacement in the upper crust. Groundmass and mesostasis crystallisation likely forms a continuous sequence with deuteric/hydrothermal modification. The petrographic features, mineralogy, and mineral compositions of different units within the De Beers dyke are indistinguishable from one another, indicating a common petrogenesis. The compositions of antecrysts (i.e., high Cr-Ti phlogopite) and magmatic phases (e.g., olivine rims, magnesian ilmenite, and spinel) overlap those from the root zone intrusions of the main Kimberley pipes (i.e., Wesselton, De Beers, Bultfontein). However, the composition of these magmatic phases is distinct from those in `evolved' intrusions of the Kimberley cluster (e.g., Benfontein, Wesselton water tunnel sills). Although the effects of syn-emplacement flow processes are evident (e.g., alignment of phases parallel to contacts), there is no evidence that the De Beers dyke has undergone significant pre-emplacement crystal fractionation (e.g., olivine, spinel, ilmenite). This study demonstrates the requirement for detailed petrographic and mineral chemical studies to assess whether individual intrusions are in fact `evolved'; and that dykes are not necessarily produced by differentiated magmas.

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

NASA Technical Reports Server (NTRS)

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

2013-01-01

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

Titan's Interior Chemical Composition: A Thermochemical Assessment*

NASA Astrophysics Data System (ADS)

Howard, Michael; Zaug, J. M.; Khare, B. N.; McKay, C. P.

2007-10-01

We study the interior composition of Titan using thermal chemical equilibrium calculations that are valid to high pressures and temperatures. The equations of state are based on exponential-6 fluid theory and have been validated against experimental data up to a few Mbars in pressure and approximately 20000K in temperature. In addition to CHNO molecules, we account for multi-phases of carbon, water and a variety of metals such as Al and Fe, and their oxides. With these fluid equations of state, chemical equilibrium is calculated for a set of product species. As the temperature and pressure evolves for increasing depth in the interior, the chemical equilibrium shifts. We assume that Titan is initially composed of comet material, which we assume to be solar, except for hydrogen, which we take to be depleted by a factor 1/690. We find that a significant amount of nitrogen is in the form of n2, rather than nh3. Moreover, above 12 kbars, as is the interior pressure of Titan, a significant amount of the carbon is in the form of graphite, rather than co2 and ch4. We discuss the implications of these results for understanding the atmospheric and surface composition of Titan. • This work was performed under the auspices of the U.S. Department of Energy by the University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48.

Titan's Interior Chemical Composition: Possible Important Phase Transitions

NASA Astrophysics Data System (ADS)

Howard, Michael; Fried, L. E.; Khare, B. N.; McKay, C. P.

2008-09-01

We study the interior composition of Titan using thermal chemical equilibrium calculations that are valid to high pressures and temperatures. The equations of state are based on exponential-6 fluid theory and have been validated against experimental data up to a few Mbars in pressure and approximately 20000K in temperature. In addition to CHNO molecules, we account for multi-phases of carbon, water and a variety of metals such as Al and Fe, and their oxides. With these fluid equations of state, chemical equilibrium is calculated for a set of product species. As the temperature and pressure evolves for increasing depth in the interior, the chemical equilibrium shifts. We assume that Titan is initially composed of comet material, which we assume to be solar, except for hydrogen, which we take to be depleted by a factor 1/1000. We find that a significant amount of nitrogen is in the form of N2, rather than NH3. Moreover, above 12 kbars pressure, as is the interior pressure of Titan, a significant amount of the carbon is in the form of graphite, rather than CO2 and CH4. We discuss the implications of these results for understanding the atmospheric and surface composition of Titan. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Adaptive evolution of Saccharomyces cerevisiae with enhanced ethanol tolerance for Chinese rice wine fermentation.

PubMed

Chen, Shuang; Xu, Yan

2014-08-01

High tolerance towards ethanol is a desirable property for the Saccharomyces cerevisiae strains used in the alcoholic beverage industry. To improve the ethanol tolerance of an industrial Chinese rice wine yeast, a sequential batch fermentation strategy was used to adaptively evolve a chemically mutagenized Chinese rice wine G85 strain. The high level of ethanol produced under Chinese rice wine-like fermentation conditions was used as the selective pressure. After adaptive evolution of approximately 200 generations, mutant G85X-8 was isolated and shown to have markedly increased ethanol tolerance. The evolved strain also showed higher osmotic and temperature tolerances than the parental strain. Laboratory Chinese rice wine fermentation showed that the evolved G85X-8 strain was able to catabolize sugars more completely than the parental G85 strain. A higher level of yeast cell activity was found in the fermentation mash produced by the evolved strain, but the aroma profiles were similar between the evolved and parental strains. The improved ethanol tolerance in the evolved strain might be ascribed to the altered fatty acids composition of the cell membrane and higher intracellular trehalose concentrations. These results suggest that adaptive evolution is an efficient approach for the non-recombinant modification of industrial yeast strains.

The Ackley City Batholith, southeastern Newfoundland: Evidence for crystal versus liquid-state fractionation

NASA Astrophysics Data System (ADS)

Whalen, J. B.

1983-08-01

The 345 ± 10 Ma old composite Ackley City Batholith of southeastern Newfoundland, consists largely of very felsic K-feldspar megacrystic granite and alaskite. Spatially related to the southeast contact of the alaskite are younger aplites and pegmatite, intrusive phases which are interpreted to be pan of a tilted, high level roof zone complex to the batholith. The compositions of the alaskite and roof zone complex define major and trace element gradients similar to those in voluminous high-silica eruptive suites; i.e., the alaskite is more chemically evolved (higher in Rb, lower in Ca, Fe, Mn, Ti, P, Sr, Ba and LREE) toward the roof. Apparently these chemical gradients in the batholith are restricted to the top 2 to 3 kms of the former magma chamber. Fractional crystallization is a plausible process for generating the chemical dispersion in the granites, although very high feldspar partition coefficients for Ba, Sr and Eu are required to generate the observed chemical gradients by a reasonable degree of fractional crystallization. Restriction of crystal fractionation to near the roof of the batholith may reflect a decreased viscosity which would facilitate crystal-liquid separation by processes such as filter pressing, flow differentiation or convective fractionation. The chemical gradients in these granites closely resemble those attributed in high-silica volcanics to the process of thermogravitational diffusion (TGD). Compositional gradients in the upper portion of a magma chamber are consistent with the TGD model. This model, although still poorly understood, is, like fractional crystallization, a plausible mechanism to generate the chemical features of the Ackley City granites.

Photochemical Alternation of Phragmites australis Plant Litter: New Insight into the Chemical Evolution of Particulate Organic Matter

NASA Astrophysics Data System (ADS)

Carrasquillo, A. J.; Gelfond, C. E.; Kocar, B. D.

2015-12-01

The photolysis of natural organic matter (NOM) is a potential pathway for the alteration of material that is not easily biodegraded. Irradiation can alter the physical state of organic matter by facilitating the cycling between the particulate (POM) and dissolved (DOM) pools. However, a detailed understanding of the underlying chemical changes to the material in both phases is lacking. Here, we use a suspension of particles derived from Phragmites australis, a common marsh reed with high lignin content, as our model "recalcitrant" POM substrate. The solution was irradiated for three weeks with regular sampling, and the composition of the POM and the photo-produced DOM were measured separately using a suite of mass spectrometric and spectroscopic techniques. The chemical composition of individual molecules was measured by coupling soft ionization techniques (electrospray (ESI) and matrix assisted laser desorption (MALDI) to high-resolution mass spectrometry. Structural information, including the distribution of the major carbon containing functional groups, was obtained using a combination of FTIR for bulk analyses and scanning transmission x-ray microscopy (STXM) for spatially resolved chemistry. Results are discussed in the context of differences in chemical composition and structure with increased irradiation time for both organic matter pools. We observed a general shift in the mass spectra of POM towards lower molecular weight masses and an increase in the abundance of ions in DOM as a function of irradiation time- hence the larger POM matrix is likely fragmenting into smaller species that are more soluble. Spectroscopic measurements indicate that the abundance of acidic and alcohol functionalities increased with irradiation in both carbon pools. These complementary approaches provide new detailed information about how the chemical composition of recalcitrant NOM evolves as it is exposed to sunlight.

Developing a predictive model for the chemical composition of soot nanoparticles

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

Violi, Angela; Michelsen, Hope; Hansen, Nils

In order to provide the scientific foundation to enable technology breakthroughs in transportation fuel, it is important to develop a combustion modeling capability to optimize the operation and design of evolving fuels in advanced engines for transportation applications. The goal of this proposal is to develop a validated predictive model to describe the chemical composition of soot nanoparticles in premixed and diffusion flames. Atomistic studies in conjunction with state-of-the-art experiments are the distinguishing characteristics of this unique interdisciplinary effort. The modeling effort has been conducted at the University of Michigan by Prof. A. Violi. The experimental work has entailed amore » series of studies using different techniques to analyze gas-phase soot precursor chemistry and soot particle production in premixed and diffusion flames. Measurements have provided spatial distributions of polycyclic aromatic hydrocarbons and other gas-phase species and size and composition of incipient soot nanoparticles for comparison with model results. The experimental team includes Dr. N. Hansen and H. Michelsen at Sandia National Labs' Combustion Research Facility, and Dr. K. Wilson as collaborator at Lawrence Berkeley National Lab's Advanced Light Source. Our results show that the chemical and physical properties of nanoparticles affect the coagulation behavior in soot formation, and our results on an experimentally validated, predictive model for the chemical composition of soot nanoparticles will not only enhance our understanding of soot formation since but will also allow the prediction of particle size distributions under combustion conditions. These results provide a novel description of soot formation based on physical and chemical properties of the particles for use in the next generation of soot models and an enhanced capability for facilitating the design of alternative fuels and the engines they will power.« less

The chemistry in circumstellar envelopes of evolved stars: Following the origin of the elements to the origin of life

PubMed Central

Ziurys, Lucy M.

2006-01-01

Mass loss from evolved stars results in the formation of unusual chemical laboratories: circumstellar envelopes. Such envelopes are found around carbon- and oxygen-rich asymptotic giant branch stars and red supergiants. As the gaseous material of the envelope flows from the star, the resulting temperature and density gradients create a complex chemical environment involving hot, thermodynamically controlled synthesis, molecule “freeze-out,” shock-initiated reactions, and photochemistry governed by radical mechanisms. In the circumstellar envelope of the carbon-rich star IRC+10216, >50 different chemical compounds have been identified, including such exotic species as C8H, C3S, SiC3, and AlNC. The chemistry here is dominated by molecules containing long carbon chains, silicon, and metals such as magnesium, sodium, and aluminum, which makes it quite distinct from that found in molecular clouds. The molecular composition of the oxygen-rich counterparts is not nearly as well explored, although recent studies of VY Canis Majoris have resulted in the identification of HCO+, SO2, and even NaCl in this object, suggesting chemical complexity here as well. As these envelopes evolve into planetary nebulae with a hot, exposed central star, synthesis of molecular ions becomes important, as indicated by studies of NGC 7027. Numerous species such as HCO+, HCN, and CCH are found in old planetary nebulae such as the Helix. This “survivor” molecular material may be linked to the variety of compounds found recently in diffuse clouds. Organic molecules in dense interstellar clouds may ultimately be traced back to carbon-rich fragments originally formed in circumstellar shells. PMID:16894164

Interstellar Chemistry Special Feature: The chemistry in circumstellar envelopes of evolved stars: Following the origin of the elements to the origin of life

NASA Astrophysics Data System (ADS)

Ziurys, Lucy M.

2006-08-01

Mass loss from evolved stars results in the formation of unusual chemical laboratories: circumstellar envelopes. Such envelopes are found around carbon- and oxygen-rich asymptotic giant branch stars and red supergiants. As the gaseous material of the envelope flows from the star, the resulting temperature and density gradients create a complex chemical environment involving hot, thermodynamically controlled synthesis, molecule "freeze-out," shock-initiated reactions, and photochemistry governed by radical mechanisms. In the circumstellar envelope of the carbon-rich star IRC+10216, >50 different chemical compounds have been identified, including such exotic species as C8H, C3S, SiC3, and AlNC. The chemistry here is dominated by molecules containing long carbon chains, silicon, and metals such as magnesium, sodium, and aluminum, which makes it quite distinct from that found in molecular clouds. The molecular composition of the oxygen-rich counterparts is not nearly as well explored, although recent studies of VY Canis Majoris have resulted in the identification of HCO+, SO2, and even NaCl in this object, suggesting chemical complexity here as well. As these envelopes evolve into planetary nebulae with a hot, exposed central star, synthesis of molecular ions becomes important, as indicated by studies of NGC 7027. Numerous species such as HCO+, HCN, and CCH are found in old planetary nebulae such as the Helix. This "survivor" molecular material may be linked to the variety of compounds found recently in diffuse clouds. Organic molecules in dense interstellar clouds may ultimately be traced back to carbon-rich fragments originally formed in circumstellar shells.

Origins of GEMS Grains

NASA Technical Reports Server (NTRS)

Messenger, S.; Walker, R. M.

2012-01-01

Interplanetary dust particles (IDPs) collected in the Earth s stratosphere contain high abundances of submicrometer amorphous silicates known as GEMS grains. From their birth as condensates in the outflows of oxygen-rich evolved stars, processing in interstellar space, and incorporation into disks around new stars, amorphous silicates predominate in most astrophysical environments. Amorphous silicates were a major building block of our Solar System and are prominent in infrared spectra of comets. Anhydrous interplanetary dust particles (IDPs) thought to derive from comets contain abundant amorphous silicates known as GEMS (glass with embedded metal and sulfides) grains. GEMS grains have been proposed to be isotopically and chemically homogenized interstellar amorphous silicate dust. We evaluated this hypothesis through coordinated chemical and isotopic analyses of GEMS grains in a suite of IDPs to constrain their origins. GEMS grains show order of magnitude variations in Mg, Fe, Ca, and S abundances. GEMS grains do not match the average element abundances inferred for ISM dust containing on average, too little Mg, Fe, and Ca, and too much S. GEMS grains have complementary compositions to the crystalline components in IDPs suggesting that they formed from the same reservoir. We did not observe any unequivocal microstructural or chemical evidence that GEMS grains experienced prolonged exposure to radiation. We identified four GEMS grains having O isotopic compositions that point to origins in red giant branch or asymptotic giant branch stars and supernovae. Based on their O isotopic compositions, we estimate that 1-6% of GEMS grains are surviving circumstellar grains. The remaining 94-99% of GEMS grains have O isotopic compositions that are indistinguishable from terrestrial materials and carbonaceous chondrites. These isotopically solar GEMS grains either formed in the Solar System or were completely homogenized in the interstellar medium (ISM). However, the chemical compositions of GEMS grains are extremely heterogeneous and seem to rule out this possibility. Based on their solar isotopic compositions and their non-solar elemental compositions we propose that most GEMS grains formed in the nebula as late-stage non-equilibrium condensates.

Modelling of chemical degradation of blended cement-based materials by leaching cycles with Callovo-Oxfordian porewater

NASA Astrophysics Data System (ADS)

Olmeda, Javier; Henocq, Pierre; Giffaut, Eric; Grivé, Mireia

2017-06-01

The present work describes a thermodynamic model based on pore water replacement cycles to simulate the chemical evolution of blended cement (BFS + FA) by interaction with external Callovo-Oxfordian (COx) pore water. In the framework of the radioactive waste management, the characterization of the radionuclide behaviour (solubility/speciation, adsorption) in cementitious materials needs to be done for several chemical degradation states (I to IV). In particular, in the context of the deep geological radioactive waste disposal project (Cigéo), cement-based materials will be chemically evolved with time in contact with the host-rock (COx formation). The objective of this study is to provide an equilibrium solution composition for each degradation state for a CEM-V cement-based material to support the adsorption and diffusion experiments reproducing any state of degradation. Calculations have been performed at 25 °C using the geochemical code PhreeqC and an up-to-date thermodynamic database (ThermoChimie v.9.0.b) coupled to SIT approach for ionic strength correction. The model replicates experimental data with accuracy. The approach followed in this study eases the analysis of the chemical evolution in both aqueous and solid phase to obtain a fast assessment of the geochemical effects associated to an external water intrusion of variable composition on concrete structures.

Origins of water and solutes in and north of the Norris-Mammoth Corridor, Yellowstone National Park

USGS Publications Warehouse

Kharaka, Yousif; Mariner, Robert; Ambats, Gil; Evans, William; White, Lloyd; Bullen, Thomas; Kennedy, B. Mack

1990-01-01

This study was initiated to investigate the impacts of geothermal development in the Corwin Springs Known Geothermal Resources Area (KGRA) on the hydrothermal features of Yellowstone National Park. To determine possible hydrogeochemical connections, we used the diagnostic stable and radioactive isotopes of several elements, and the chemical and gas compositions of thermal and cold waters from the Norris-Mammoth Corridor and areas north of the Park. The investigations were particularly comprehensive in the Mammoth Hot Springs area, Corwin Springs KGRA, and Chico Hot Springs. The geochemical tools used are still subject to uncertainties of 1 - 5%. Preliminary interpretation of the data, especially the ??D and ??18O values of water, 87Sr/86Sr ratios, ??11B values, composition and isotopes of noble gases and several conservative chemical species would indicate that the waters from Mammoth Hot Springs and La Duke Spring area have evolved chemically and isotopically by reactions with different rock types, and are probably not directly connected. These data indicate that a component (<20%) of water in Bear Creek Springs may be derived from the Mammoth system.

Glacial influence on the geochemistry of riverine iron fluxes to the Gulf of Alaska and effects of deglaciation

USGS Publications Warehouse

Schroth, A.W.; Crusius, John; Chever, F.; Bostick, B.C.; Rouxel, O.J.

2011-01-01

Riverine iron (Fe) derived from glacial weathering is a critical micronutrient source to ecosystems of the Gulf of Alaska (GoA). Here we demonstrate that the source and chemical nature of riverine Fe input to the GoA could change dramatically due to the widespread watershed deglaciation that is underway. We examine Fe size partitioning, speciation, and isotopic composition in tributaries of the Copper River which exemplify a long-term GoA watershed evolution from one strongly influenced by glacial weathering to a boreal-forested watershed. Iron fluxes from glacierized tributaries bear high suspended sediment and colloidal Fe loads of mixed valence silicate species, with low concentrations of dissolved Fe and dissolved organic carbon (DOC). Iron isotopic composition is indicative of mechanical weathering as the Fe source. Conversely, Fe fluxes from boreal-forested systems have higher dissolved Fe concentrations corresponding to higher DOC concentrations. Iron colloids and suspended sediment consist of Fe (hydr)oxides and organic complexes. These watersheds have an iron isotopic composition indicative of an internal chemical processing source. We predict that as the GoA watershed evolves due to deglaciation, so will the source, flux, and chemical nature of riverine Fe loads, which could have significant ramifications for Alaskan marine and freshwater ecosystems.

Reactive Monte Carlo sampling with an ab initio potential

NASA Astrophysics Data System (ADS)

Leiding, Jeff; Coe, Joshua D.

2016-05-01

We present the first application of reactive Monte Carlo in a first-principles context. The algorithm samples in a modified NVT ensemble in which the volume, temperature, and total number of atoms of a given type are held fixed, but molecular composition is allowed to evolve through stochastic variation of chemical connectivity. We discuss general features of the method, as well as techniques needed to enhance the efficiency of Boltzmann sampling. Finally, we compare the results of simulation of NH3 to those of ab initio molecular dynamics (AIMD). We find that there are regions of state space for which RxMC sampling is much more efficient than AIMD due to the "rare-event" character of chemical reactions.

Assessment of the Simulated Molecular Composition with the GECKO-A Modeling Tool Using Chamber Observations for α-Pinene.

NASA Astrophysics Data System (ADS)

Aumont, B.; Camredon, M.; Isaacman-VanWertz, G. A.; Karam, C.; Valorso, R.; Madronich, S.; Kroll, J. H.

2016-12-01

Gas phase oxidation of VOC is a gradual process leading to the formation of multifunctional organic compounds, i.e., typically species with higher oxidation state, high water solubility and low volatility. These species contribute to the formation of secondary organic aerosols (SOA) viamultiphase processes involving a myriad of organic species that evolve through thousands of reactions and gas/particle mass exchanges. Explicit chemical mechanisms reflect the understanding of these multigenerational oxidation steps. These mechanisms rely directly on elementary reactions to describe the chemical evolution and track the identity of organic carbon through various phases down to ultimate oxidation products. The development, assessment and improvement of such explicit schemes is a key issue, as major uncertainties remain on the chemical pathways involved during atmospheric oxidation of organic matter. An array of mass spectrometric techniques (CIMS, PTRMS, AMS) was recently used to track the composition of organic species during α-pinene oxidation in the MIT environmental chamber, providing an experimental database to evaluate and improve explicit mechanisms. In this study, the GECKO-A tool (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to generate fully explicit oxidation schemes for α-pinene multiphase oxidation simulating the MIT experiment. The ability of the GECKO-A chemical scheme to explain the organic molecular composition in the gas and the condensed phases is explored. First results of this model/observation comparison at the molecular level will be presented.

The physical and chemical evolution of disks during planet formation

NASA Astrophysics Data System (ADS)

Gorti, Uma

2018-06-01

Protoplanetary disks evolve and disperse rapidly during the early stages of star and planet formation. While disks initially inherit a full complement of interstellar cloud material that is mainly accreted on to the central star, their gas and dust components appear to evolve along distinct pathways. Dust accumulates to form rocky planets, whereas only a small fraction of the available gas may be incorporated into gas giants in a typical exoplanetary system. However, the radial distribution of gas and its chemistry are expected to impact the architecture and composition of formed planets. Recent ALMA results have underscored the importance of ices and grain surface chemistry in disks, and their significance for planet formation. I will describe disk models that aim to probe the physical and chemical processes in the disk at various stages of evolution, and specifically discuss diagnostics of conditions in the innermost regions of disks which will become accessible for the first time with the launch of JWST. Current theoretical modeling is however hindered by many uncertainties in input parameters and poorly known chemical and physical processes. I will highlight some gaps in our current understanding, and discuss how laboratory astrophysics can help in preparing for the JWST era and aid in the interpretation of future line and continuum emission studies.

Spatial and temporal patterns of hydrologic connectivity between upland landscapes and stream networks (Invited)

NASA Astrophysics Data System (ADS)

McGlynn, B. L.; Nippgen, F.; Jencso, K. G.; Emanuel, R. E.

2013-12-01

Congress enacted the Clean Water Act (CWA) 'to restore and maintain the chemical, physical, and biological integrity of the Nation's waters'. A recent Supreme Court decision further described protection for waters with 'a significant nexus to navigable waters" if they are in the same watershed and have an effect on the chemical, physical, or biological integrity of traditional navigable waters or interstate waters that is more than 'speculative or insubstantial.' Evolving interpretation of the CWA and 'significant nexus' (connectivity) requires investigation and understanding of the spatial and temporal patterns of hydrologic connectivity between upland landscapes and stream networks that mediate streamflow magnitude and composition. While hydrologic connectivity is a continuum, strong non-linearities including the shift from unsaturated to saturated flow conditions lead to threshold or transient connectivity behavior and orders of magnitude changes in flow velocities and source water compositions. Here we illustrate the spatial and temporal dynamics of hydrologic connectivity between upland landscapes and stream networks that provide direct and proximate links between streamflow composition and its watershed sources. We suggest that adjacency alone does not determine influence on hydrologic response and streamwater composition and that new understanding and communication of the temporal and spatial dynamics of watershed connectivity are required to address urgent needs at the interface of the CWA, science, and society.

Infrared Spectroscopy as a Chemical Fingerprinting Tool

NASA Technical Reports Server (NTRS)

Huff, Tim; Munafo, Paul M. (Technical Monitor)

2002-01-01

Infrared (IR) spectroscopy is a powerful analytical tool in the chemical fingerprinting of materials. The technique is rapid, reproducible and usually non-invasive. With the appropriate accessories, the technique can be used to examine samples in either a solid, liquid or gas phase. Solid samples of varying sizes and shapes may be used, and with the addition of microscopic IR (microspectroscopy) capabilities, minute materials such as single fibers and threads may be examined. With the addition of appropriate software, microspectroscopy can be used for automated discrete point or compositional surface area mapping, with the latter providing a means to record changes in the chemical composition of a material surface over a defined area. Both aqueous and non-aqueous free-flowing solutions can be analyzed using appropriate IR techniques, as can viscous liquids such as heavy oils and greases. Due to the ability to characterize gaseous samples, IR spectroscopy can also be coupled with thermal processes such as thermogravimetric (TG) analyses to provide both thermal and chemical data in a single run. In this configuration, solids (or liquids) heated in a TG analyzer undergo decomposition, with the evolving gases directed into the IR spectrometer. Thus, information is provided on the thermal properties of a material and the order in which its chemical constituents are broken down during incremental heating. Specific examples of these varied applications will be cited, with data interpretation and method limitations further discussed.

Primordial evolvability: Impasses and challenges.

PubMed

Vasas, Vera; Fernando, Chrisantha; Szilágyi, András; Zachár, István; Santos, Mauro; Szathmáry, Eörs

2015-09-21

While it is generally agreed that some kind of replicating non-living compounds were the precursors of life, there is much debate over their possible chemical nature. Metabolism-first approaches propose that mutually catalytic sets of simple organic molecules could be capable of self-replication and rudimentary chemical evolution. In particular, the graded autocatalysis replication domain (GARD) model, depicting assemblies of amphiphilic molecules, has received considerable interest. The system propagates compositional information across generations and is suggested to be a target of natural selection. However, evolutionary simulations indicate that the system lacks selectability (i.e. selection has negligible effect on the equilibrium concentrations). We elaborate on the lessons learnt from the example of the GARD model and, more widely, on the issue of evolvability, and discuss the implications for similar metabolism-first scenarios. We found that simple incorporation-type chemistry based on non-covalent bonds, as assumed in GARD, is unlikely to result in alternative autocatalytic cycles when catalytic interactions are randomly distributed. An even more serious problem stems from the lognormal distribution of catalytic factors, causing inherent kinetic instability of such loops, due to the dominance of efficiently catalyzed components that fail to return catalytic aid. Accordingly, the dynamics of the GARD model is dominated by strongly catalytic, but not auto-catalytic, molecules. Without effective autocatalysis, stable hereditary propagation is not possible. Many repetitions and different scaling of the model come to no rescue. Despite all attempts to show the contrary, the GARD model is not evolvable, in contrast to reflexively autocatalytic networks, complemented by rare uncatalyzed reactions and compartmentation. The latter networks, resting on the creation and breakage of chemical bonds, can generate novel ('mutant') autocatalytic loops from a given set of environmentally available compounds. Real chemical reactions that make or break covalent bonds, rather than mere incorporation of components, are necessary for open-ended evolvability. The issue of whether or not several concrete chemical systems (rather than singular curiosities) could realize reflexively autocatalytic macromolecular networks will ultimately determine the relevance of metabolism-first approaches to the origin of life, as stepping stones towards true open-endedness that requires the combination of rich combinatorial chemistry controlled by information stored in template replicators. Copyright © 2015 Elsevier Ltd. All rights reserved.

Historical Review of Glasses Used for Parenteral Packaging.

PubMed

Schaut, Robert A; Weeks, W Porter

2017-01-01

Glass has long been used for packaging precious liquids, in particular pharmaceuticals. Its unique combination of hermeticity, transparency, strength, and chemical durability make it the optimal material for such an important role. Today's life-saving drugs are stored in borosilicate glasses, which evolved from applications in microscope optics and thermometers. As the glass compositions improved, so did the methods used to shape them and the tests used to characterize them. While all of these advances improved the quality of the glass container and its ability to protect the contents, problems still exist such as delamination, cracks, and glass particulates. In addition to these issues, we review new developments in glass composition development, performance, and testing in the 21 st century. © PDA, Inc. 2017.

High-resolution EPMA X-ray images of mother liquid inclusions in a Pd2Ga single crystal

NASA Astrophysics Data System (ADS)

Müller, D.; Schwerin, J.; Gille, P.; Fehr, K. T.

2014-03-01

During crystal growth from solution inclusions of different compositions were trapped at the rim of a Pd2Ga single crystal. Their fine-grained (< 5 μm) internal structure demands special requirements for electron microprobe analysis, realized by low-voltage (5 keV) element mapping applying a step size of 0.138 μm for each pixel. It can be shown, that these inclusions represent an isolated chemical system, and that crystallisation upon cooling follows the expected thermodynamic phase relations. Thus the final composition in the centre of the inclusion consists of a small-scale mixture of PdGa and Pd5Ga3 evolved out of a solid-solid decomposition of Pd5Ga4.

Compositional evolution of the zoned calcalkaline magma chamber of Mount Mazama, Crater Lake, Oregon

USGS Publications Warehouse

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

1988-01-01

The climactic eruption of Mount Mazama has long been recognized as a classic example of rapid eruption of a substantial fraction of a zoned magma body. Increased knowledge of eruptive history and new chemical analyses of ???350 wholerock and glass samples of the climactic ejecta, preclimactic rhyodacite flows and their inclusions, postcaldera lavas, and lavas of nearby monogenetic vents are used here to infer processes of chemical evolution of this late Pleistocene - Holocene magmatic system. The 6845??50 BP climactic eruption vented ???50 km3 of magma to form: (1) rhyodacite fall deposit; (2) welded rhyodacite ignimbrite; and (3) lithic breccia and zoned ignimbrite, these during collapse of Crater Lake caldera. Climactic ejecta were dominantly homogeneous rhyodacite (70.4??0.3% SiO2), followed by subordinate andesite and cumulate scoriae (48-61% SiO2). The gap in wholerock composition reflects mainly a step in crystal content because glass compositions are virtually continuous. Two types of scoriae are distinguished by different LREE, Rb, Th, and Zr, but principally by a twofold contrast in Sr content: High-Sr (HSr) and low-Sr (LSr) scoriae. HSr scoriae were erupted first. Trace element abundances indicate that HSr and LSr scoriae had different calcalkaline andesite parents; basalt was parental to some mafic cumulate scoriae. Parental magma compositions reconstructed from scoria wholerock and glass data are similar to those of inclusions in preclimactic rhyodacites and of aphyric lavas of nearby monogenetic vents. Preclimactic rhyodacite flows and their magmatic inclusions give insight into evolution of the climactic chamber. Evolved rhyodacite flows containing LSr andesite inclusions were emplaced between ???30000 and ???25000 BP. At 7015??45 BP, the Llao Rock vent produced a zoned rhyodacite pumice fall, then rhyodacite lava with HSr andesite inclusions. The Cleetwood rhyodacite flow, emplaced immediately before the climactic eruption and compositionally identical to climactic rhyodacite (volatile-free), contains different HSr inclusions from Llao Rock. The change from LSr to HSr inclusions indicates replenishment of the chamber with andesite magma, perhaps several times, in the latest Pleistocene to early Holocene. Modeling calculations and wholerock-glass relations suggest than: (1) magmas were derived mainly by crystallization differentiation of andesite liquid; (2) evolved preclimactic rhyodacite probably was derived from LSr andesite; (3) rhyodacites contain a minor component of partial melt from wall rocks, and (4) climactic and compositionally similar rhyodacites probably formed by mixing of evolved rhyodacite with HSr derivative liquid(s) after replenishment of the chamber with HSr andesite magma. Density considerations permit a model for growth and evolution of the chamber in which andesite recharge magma ponded repeatedly between cumulates and rhyodacite magma. Convective cooling of this andesite resulted in rapid crystallization and upward escape of buoyant derivative liquid which mixed with overlying, convecting rhyodacite. The evolved rhyodacites were erupted early in the chamber's history and(or) near its margins. Postcaldera andesite lavas may be hybrids composed of LSr cumulates mixed with remnant climactic rhyodacite. Younger postcaldera rhyodacite probably formed by fractionation of similar andesite and assimilation of partial melts of wallrocks. Uniformity of climactic rhyodacite suggests homogeneous silicic ejecta from other volcanoes resulted from similar replenishment-driven convective mixing. Calcalkaline pluton compositions and their internal zonation can be interpreted in terms of the Mazama system frozen at various times in its history. ?? 1988 Springer-Verlag.

Origin and emplacement of the andesite of Burroughs Mountain, a zoned, large-volume lava flow at Mount Rainier, Washington, USA

USGS Publications Warehouse

Stockstill, K.R.; Vogel, T.A.; Sisson, T.W.

2002-01-01

Burroughs Mountain, situated at the northeast foot of Mount Rainier, WA, exposes a large-volume (3.4 km3) andesitic lava flow, up to 350 m thick and extending 11 km in length. Two sampling traverses from flow base to eroded top, over vertical sections of 245 and 300 m, show that the flow consists of a felsic lower unit (100 m thick) overlain sharply by a more mafic upper unit. The mafic upper unit is chemically zoned, becoming slightly more evolved upward; the lower unit is heterogeneous and unzoned. The lower unit is also more phenocryst-rich and locally contains inclusions of quenched basaltic andesite magma that are absent from the upper unit. Widespread, vuggy, gabbronorite-to-diorite inclusions may be fragments of shallow cumulates, exhumed from the Mount Rainier magmatic system. Chemically heterogeneous block-and-ash-flow deposits that conformably underlie the lava flow were the earliest products of the eruptive episode. The felsic-mafic-felsic progression in lava composition resulted from partial evacuation of a vertically-zoned magma reservoir, in which either (1) average depth of withdrawal increased, then decreased, during eruption, perhaps due to variations in effusion rate, or (2) magmatic recharge stimulated ascent of a plume that brought less evolved magma to shallow levels at an intermediate stage of the eruption. Pre-eruptive zonation resulted from combined crystallization- differentiation and intrusion(s) of less evolved magma into the partly crystallized resident magma body. The zoned lava flow at Burroughs Mountain shows that, at times, Mount Rainier's magmatic system has developed relatively large, shallow reservoirs that, despite complex recharge events, were capable of developing a felsic-upward compositional zonation similar to that inferred from large ash-flow sheets and other zoned lava flows. ?? 2002 Elsevier Science B.V. All rights reserved.

Laboratory Analysis of Silicate Stardust Grains of Diverse Stellar Origins

NASA Technical Reports Server (NTRS)

Nguyen, Ann N.; Keller, Lindsay P.; Nakamura-Messenger, Keiko

2016-01-01

Silicate dust is ubiquitous in a multitude of environments across the cosmos, including evolved oxygen-rich stars, interstellar space, protoplanetary disks, comets, and asteroids. The identification of bona fide silicate stardust grains in meteorites, interplanetary dust particles, micrometeorites, and dust returned from comet Wild 2 by the Stardust spacecraft has revolutionized the study of stars, interstellar space, and the history of dust in the Galaxy. These stardust grains have exotic isotopic compositions that are records of nucleosynthetic processes that occurred in the depths of their now extinct parent stars. Moreover, the chemical compositions and mineralogies of silicate stardust are consequences of the physical and chemical nature of the stellar condensation environment, as well as secondary alteration processes that can occur in interstellar space, the solar nebula, and on the asteroid or comet parent body in which they were incorporated. In this talk I will discuss our use of advanced nano-scale instrumentation in the laboratory to conduct coordinated isotopic, chemical, and mineralogical analyses of silicate stardust grains from AGB stars, supernovae, and novae. By analyzing the isotopic compositions of multiple elements in individual grains, we have been able to constrain their stellar sources, explore stellar nucleosynthetic and mixing processes, and Galactic chemical evolution. Through our mineralogical studies, we have found these presolar silicate grains to have wide-ranging chemical and mineral characteristics. This diversity is the result of primary condensation characteristics and in some cases secondary features imparted by alteration in space and in our Solar System. The laboratory analysis of actual samples of stars directly complements astronomical observations and astrophysical models and offers an unprecedented level of detail into the lifecycles of dust in the Galaxy.

Summary of Cosmic Ray Spectrum and Composition Below 1018 eV

NASA Astrophysics Data System (ADS)

Chiavassa, Andrea

In this contribution I will review the main results recently obtained in the study of the cosmic ray spectrum and composition below 1018 eV. The interest in this range is growing being related to the search of the knee of the iron component of cosmic ray and to the study of the transition between galactic and extra-galactic primaries. The all particle spectrum measured in this energy range is more structured than previously thought, showing some faint features: a hardening slightly above 1016 eV and a steepening below 1017 eV. The studies of the primary chemical composition are quickly evolving towards the measurements of the primary spectra of different mass groups: light and heavy primaries. A steepening of the heavy primary spectrum and a hardening of the light ones has been claimed. I will review these measurements and I will try to discuss the main sources of systematic errors still affecting them.

Mineralogical Characterization of Fe-Bearing AGB and Supernova Silicate Grains From the Queen Alexandra Range 99177 Meteorite

NASA Technical Reports Server (NTRS)

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

2017-01-01

Spectroscopic observations of the circumstellar envelopes of evolved O-rich stars indicate the dust is mostly amorphous silicate with olivine-like compositions. Spectral modeling suggests these grains are Fe-rich [Mg/(Mg+Fe) 0.5], but it is not known whether the Fe is distributed within the silicate matrix or exists as metal inclusions. In contrast, the crystalline silicates are inferred to be extremely Mg-rich [Mg/(Mg+Fe) > 0.95]. The mineralogies and chemical compositions of dust in supernova (SN) remnants are not as well constrained, but abundant silicates of olivine-like and enstatite-like compositions have been fit to the infrared emission features. Silicates in the interstellar medium (ISM) are >99% amor-phous and Fe-bearing. The dearth of crystalline silicates in the ISM requires that some amorphization or destruction mechanisms process these grains.

Surface Compositions of Red Giant Stars in Globular Clusters

NASA Astrophysics Data System (ADS)

Cheng, Eric; Lau, Marie; Smith, Graeme; Chen, Brian

2018-01-01

Globular clusters (GCs) are excellent “laboratories” to study the formation and evolution of our galaxy. In order to understand, more specifically, the chemical compositions and stellar evolution of the stars in GCs, we ask whether or not deep internal mixing occurs in red giants or if in fact the compositions come from the primordial interstellar medium or previous generations of stars. It has been discovered that as a star evolves up the red giant branch, the surface carbon abundance decreases, which is evidence of deep internal mixing. We questioned whether these processes also affect O or Na abundance as a star evolves. We collected measurement data of red giants from GCs out of academic journals and sorted the data into catalogs. Then, we plotted the catalogs into figures, comparing surface O and Na each with stellar luminosity. Statistical tests were ran to quantify the amount of correlation between the variables. Out of 27 GCs, we concluded that eight show a positive correlation between Na and luminosity, and two show a negative correlation between O and luminosity. Properties of GCs were compared to determine if chemical distribution in stars depends on GCs as the self-enrichment scenario suggests. We created histograms of sodium distribution to test for bimodality to examine if there are separate trends in each GC. In six GCs, two different sequences of red giants appear for Na versus luminosity, suggesting evidence that the depth of mixing may differ among each red giant in a GC. This study has provided new evidence that the changing chemical abundances on the surfaces of red giants can be due to stellar evolutionary effects and deep internal mixing, which may not necessarily depend on the GC and may differ in depth among each red giant. Through this study, we learn more about stellar evolution which will eventually help us understand the origins of our universe. Most of this work was carried out by high school students working under the auspices of the Science Internship Program (SIP) at UC Santa Cruz.

Use of stable sulphur isotopes to monitor directly the behaviour of sulphur in coal during thermal desulphurization

USGS Publications Warehouse

Liu, Chao-Li; Hackley, Keith C.; Coleman, D.D.

1987-01-01

A method has been developed using stable sulphur isotope analyses to monitor the behaviour of sulphur forms in a coal during thermal desulphurization. In this method, the natural stable isotopic composition of the pyritic and organic sulphur in coal is used as a tracer to follow their mobility during the desulphurization process. This tracer method is based on the fact that the isotopic compositions of pyritic and organic sulphur are significantly different in some coals. Isotopic results of pyrolysis experiments at temperatures ranging from 350 to 750 ??C indicate that the sulphur released with the volatiles is predominantly organic sulphur. The pyritic sulphur is evolved in significant quantities only when pyrolysis temperatures exceed 500 ??C. The presence of pyrite seems to have no effect on the amount of organic sulphur evolved during pyrolysis. The chemical and isotopic mass balances achieved from three different samples of the Herrin (No. 6) coal of the Illinois Basin demonstrate that this stable isotope tracer method is quantitative. The main disadvantage of this tracing technique is that not all coals contain isotopically distinct organic and pyritic sulphur. ?? 1987.

Rivers and streams: Physical setting and adapted biota

USGS Publications Warehouse

Wilzbach, Margaret A.; Cummins, K.W.

2008-01-01

Streams and rivers are enormously important, with their ecological, and economic value, greatly outweighing their significance on the landscape. Lotic ecology began in Europe with a focus on the distribution, abundance, and taxonomic composition of aquatic organisms and in North American with a focus on fishery biology. Since 1980, stream/river research has been highly interdisciplinary, involving fishery biologists, aquatic entomologists, algologists, hydrologists, geomorphologists, microbiologists, and terrestrial plant ecologists. Stream and river biota evolved in response to, and in concert with, the physical and chemical setting. Streams/rivers transport water and move sediments to the sea as part of the hydrologic cycle that involves evaporation, plant evapotranspiration, and precipitation. Ephemeral streams flow only in the wettest year, intermittent streams flow predictably every year during capture of surface runoff, and perennial streams flow continuously during wet and dry periods, receiving both stormflow and groundwater baseflow. The lotic biota, for example, algae, macrophytes, benthic invertebrates, and fishes, have evolved adaptations to their running-water setting. Dominant physical features of this setting are current, substrate, and temperature. Key chemical constituents are dissolved gases, dissolved inorganic ions and compounds, particulate inorganic material, particulate organic material, and dissolved organic ions (nitrogen and phosphorus) and compounds.

Evolving and Combining Facial Composites: Between-Witness and Within-Witness Morphs Compared

ERIC Educational Resources Information Center

Valentine, Tim; Davis, Josh P.; Thorner, Kate; Solomon, Chris; Gibson, Stuart

2010-01-01

Student participant-witnesses produced 4 composites of unfamiliar faces with a system that uses a genetic algorithm to evolve appearance of artificial faces. Morphs of 4 composites produced by different witnesses (between-witness morphs) were judged better likenesses (Experiment 1) and were more frequently named (Experiment 2) by participants who…

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Reactive Monte Carlo sampling with an ab initio potential

DOE PAGES

Leiding, Jeff; Coe, Joshua D.

2016-05-04

Here, we present the first application of reactive Monte Carlo in a first-principles context. The algorithm samples in a modified NVT ensemble in which the volume, temperature, and total number of atoms of a given type are held fixed, but molecular composition is allowed to evolve through stochastic variation of chemical connectivity. We also discuss general features of the method, as well as techniques needed to enhance the efficiency of Boltzmann sampling. Finally, we compare the results of simulation of NH 3 to those of ab initio molecular dynamics (AIMD). Furthermore, we find that there are regions of state spacemore » for which RxMC sampling is much more efficient than AIMD due to the “rare-event” character of chemical reactions.« less

Vesper - Venus Chemistry and Dynamics Orbiter - A NASA Discovery Mission Proposal: Submillimeter Investigation of Atmospheric Chemistry and Dynamics

NASA Technical Reports Server (NTRS)

Chin, Gordon

2011-01-01

Vesper conducts a focused investigation of the chemistry and dynamics of the middle atmosphere of our sister planet- from the base of the global cloud cover to the lower thermosphere. The middle atmosphere controls the stability of the Venus climate system. Vesper determines what processes maintain the atmospheric chemical stability, cause observed variability of chemical composition, control the escape of water, and drive the extreme super-rotation. The Vesper science investigation provides a unique perspective on the Earth environment due to the similarities in the middle atmosphere processes of both Venus and the Earth. Understanding key distinctions and similarities between Venus and Earth will increase our knowledge of how terrestrial planets evolve along different paths from nearly identical initial conditions.

β-Ga2O3 versus ε-Ga2O3: Control of the crystal phase composition of gallium oxide thin film prepared by metal-organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Zhuo, Yi; Chen, Zimin; Tu, Wenbin; Ma, Xuejin; Pei, Yanli; Wang, Gang

2017-10-01

Gallium oxide thin films of β and ε phase were grown on c-plane sapphire using metal-organic chemical vapor deposition and the phase compositions were analyzed using X-ray diffraction. The epitaxial phase diagram was constructed as a function of the growth temperature and VI/III ratio. A low growth temperature and low VI/III ratio were beneficial for the formation of hexagonal-type ε-Ga2O3. Further structure analysis revealed that the epitaxial relationship between ε-Ga2O3 and c-plane sapphire is ε-Ga2O3 (0001) || Al2O3 (0001) and ε-Ga2O3 || Al2O3 . The structural evolution of the mixed-phase sample during film thickening was investigated. By reducing the growth rate, the film evolved from a mixed phase to the energetically favored ε phase. Based on these results, a Ga2O3 thin film with a phase-pure ε-Ga2O3 upper layer was successfully obtained.

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

Jo, Yeon Hwa; Kang, Min Soo; Chung, Kyung Won

New lanthanum borate (La{sub 2}O{sub 3}-B{sub 2}O{sub 3}) glasses modified with divalent oxides, such as CaO, MgO and ZnO were investigated as potential low temperature dielectrics by understanding compositional dependence of dielectric properties and chemical leaching resistance. Firing behavior, such as densification and crystallization, depended strongly on the glass composition and is found to influence the resultant dielectric performance. Specifically, the dielectric composition of 20ZnO-20La{sub 2}O{sub 3}-60B{sub 2}O{sub 3} glass with 40 wt% Al{sub 2}O{sub 3} as a filler showed distinct enhancements of dielectric properties, i.e., k {approx} 8.3 and Q {approx} 1091 at the resonant frequency of 17.1 GHz,more » as a result of 850 deg. C firing. The result was believed related to earlier densification and unexpected evolvements of ZnAl{sub 2}O{sub 4} and La(BO{sub 2}){sub 3} phases during firing. The Mg-containing glass sample was most stable in strong acid solutions and did not show any significant changes in microstructure even after 300 min exposure. The Ca-containing glass sample was not regarded as a promising candidate for low temperature dielectrics from the observed low quality factor and weak chemical durability.« less

Unconditionally stable, second-order accurate schemes for solid state phase transformations driven by mechano-chemical spinodal decomposition

DOE PAGES

Sagiyama, Koki; Rudraraju, Shiva; Garikipati, Krishna

2016-09-13

Here, we consider solid state phase transformations that are caused by free energy densities with domains of non-convexity in strain-composition space; we refer to the non-convex domains as mechano-chemical spinodals. The non-convexity with respect to composition and strain causes segregation into phases with different crystal structures. We work on an existing model that couples the classical Cahn-Hilliard model with Toupin’s theory of gradient elasticity at finite strains. Both systems are represented by fourth-order, nonlinear, partial differential equations. The goal of this work is to develop unconditionally stable, second-order accurate time-integration schemes, motivated by the need to carry out large scalemore » computations of dynamically evolving microstructures in three dimensions. We also introduce reduced formulations naturally derived from these proposed schemes for faster computations that are still second-order accurate. Although our method is developed and analyzed here for a specific class of mechano-chemical problems, one can readily apply the same method to develop unconditionally stable, second-order accurate schemes for any problems for which free energy density functions are multivariate polynomials of solution components and component gradients. Apart from an analysis and construction of methods, we present a suite of numerical results that demonstrate the schemes in action.« less

Soil organic matter composition from correlated thermal analysis and nuclear magnetic resonance data in Australian national inventory of agricultural soils

NASA Astrophysics Data System (ADS)

Moore, T. S.; Sanderman, J.; Baldock, J.; Plante, A. F.

2016-12-01

National-scale inventories typically include soil organic carbon (SOC) content, but not chemical composition or biogeochemical stability. Australia's Soil Carbon Research Programme (SCaRP) represents a national inventory of SOC content and composition in agricultural systems. The program used physical fractionation followed by 13C nuclear magnetic resonance (NMR) spectroscopy. While these techniques are highly effective, they are typically too expensive and time consuming for use in large-scale SOC monitoring. We seek to understand if analytical thermal analysis is a viable alternative. Coupled differential scanning calorimetry (DSC) and evolved gas analysis (CO2- and H2O-EGA) yields valuable data on SOC composition and stability via ramped combustion. The technique requires little training to use, and does not require fractionation or other sample pre-treatment. We analyzed 300 agricultural samples collected by SCaRP, divided into four fractions: whole soil, coarse particulates (POM), untreated mineral associated (HUM), and hydrofluoric acid (HF)-treated HUM. All samples were analyzed by DSC-EGA, but only the POM and HF-HUM fractions were analyzed by NMR. Multivariate statistical analyses were used to explore natural clustering in SOC composition and stability based on DSC-EGA data. A partial least-squares regression (PLSR) model was used to explore correlations among the NMR and DSC-EGA data. Correlations demonstrated regions of combustion attributable to specific functional groups, which may relate to SOC stability. We are increasingly challenged with developing an efficient technique to assess SOC composition and stability at large spatial and temporal scales. Correlations between NMR and DSC-EGA may demonstrate the viability of using thermal analysis in lieu of more demanding methods in future large-scale surveys, and may provide data that goes beyond chemical composition to better approach quantification of biogeochemical stability.

Ice-gas interactions during planet formation

NASA Astrophysics Data System (ADS)

Öberg, Karin I.

2016-10-01

Planets form in disks around young stars. In these disks, condensation fronts or snowlines of water, CO2, CO and other abundant molecules regulate the outcome of planet formation. Snowline locations determine how the elemental and molecular compositions of the gaseous and solid building blocks of planets evolve with distance from the central star. Snowlines may also locally increase the planet formation efficiency. Observations of snowlines have only become possible in the past couple of years. This proceeding reviews these observations as well as the theory on the physical and chemical processes in disks that affect snowline locations.

Thermal and chemical evolution in the early solar system as recorded by FUN CAIs: Part I - Petrology, mineral chemistry, and isotopic composition of Allende FUN CAI CMS-1

NASA Astrophysics Data System (ADS)

Williams, C. D.; Ushikubo, T.; Bullock, E. S.; Janney, P. E.; Hines, R. R.; Kita, N. T.; Hervig, R. L.; MacPherson, G. J.; Mendybaev, R. A.; Richter, F. M.; Wadhwa, M.

2017-03-01

Detailed petrologic, geochemical and isotopic analyses of a new FUN CAI from the Allende CV3 meteorite (designated CMS-1) indicate that it formed by extensive melting and evaporation of primitive precursor material(s). The precursor material(s) condensed in a 16O-rich region (δ17O and δ18O ∼ -49‰) of the inner solar nebula dominated by gas of solar composition at total pressures of ∼10-3-10-6 bar. Subsequent melting of the precursor material(s) was accompanied by evaporative loss of magnesium, silicon and oxygen resulting in large mass-dependent isotope fractionations in these elements (δ25Mg = 30.71-39.26‰, δ29Si = 14.98-16.65‰, and δ18O = -41.57 to -15.50‰). This evaporative loss resulted in a bulk composition similar to that of compact Type A and Type B CAIs, but very distinct from the composition of the original precursor condensate(s). Kinetic fractionation factors and the measured mass-dependent fractionation of silicon and magnesium in CMS-1 suggest that ∼80% of the silicon and ∼85% of the magnesium were lost from its precursor material(s) through evaporative processes. These results suggest that the precursor material(s) of normal and FUN CAIs condensed in similar environments, but subsequently evolved under vastly different conditions such as total gas pressure. The chemical and isotopic differences between normal and FUN CAIs could be explained by sorting of early solar system materials into distinct physical and chemical regimes, in conjunction with discrete heating events, within the protoplanetary disk.

Effect of glow DBD modulation on gas and thin film chemical composition: case of Ar/SiH4/NH3 mixture

NASA Astrophysics Data System (ADS)

Vallade, Julien; Bazinette, Remy; Gaudy, Laura; Massines, Françoise

2014-06-01

In recent years, atmospheric pressure plasma-enhanced chemical vapour deposition has been identified as a convenient way to deposit good quality thin films. With this type of process, where the gas mixture is injected on one side of the electrodes, the chemical composition of the gas evolves with the gas residence time in the plasma. The consequence is a possible gradient in the chemical composition over the thickness of in-line coatings. The present work shows that the modulation of the plasma with a square signal significantly reduces this gradient while the drawback of low growth rate is avoided by increasing the discharge power. This study deals with plane/plane glow dielectric barrier discharges (DBDs) in an Ar/NH3/SiH4 gas mixture to make thin films. The 50 kHz discharge power of the glow DBD was varied by increasing voltage and modulating excitation. The impact on (i) the plasma development was observed through emission spectroscopy and (ii) the thin film coating through Fourier transform infrared measurements. It is shown that the modulation significantly decreases the time and the energy needed to achieve stable chemistry, enhances secondary chemistry and limits disturbance induced by impurities because of a slower decrease of SiH4 concentration and thus a higher ratio of SiH4/impurities, all very important points for in-line AP-PECVD development. When the growth rate is limited by diffusion, coating growth continues when the discharge is off, so long as there is a precursor gradient between the surface and the gas bulk. A higher discharge power steepens this gradient, which enhances diffusion from the bulk and thus growth rate.

The amphiboles of the REE-rich A-type peralkaline Strange Lake pluton - fingerprints of magma evolution

NASA Astrophysics Data System (ADS)

Siegel, Karin; Williams-Jones, Anthony E.; van Hinsberg, Vincent J.

2017-09-01

Major and trace element compositions of amphibole in igneous environments commonly reflect evolving magma compositions. In this study, we use the amphibole-group minerals from the Strange Lake, REE-enriched peralkaline granitic pluton to gain insights into the evolution of the magma. This 1240 Ma old pluton consists of two main intrusive facies, an early hypersolvus granite, which occurs as separate northern and southern intrusions, and a more evolved transsolvus granite. In the hypersolvus granite the amphibole is a late interstitial phase, whereas in the transsolvus granite, it is present as phenocrysts. The amphibole compositions vary from calcic-sodic (ferro-ferri-katophorite) in the southern hypersolvus granite to sodic (arfvedsonite, ferro-ferri-leakeite) in the other, more evolved granitic units. High Na, Si, Li, and low Al and Ca concentrations in the amphibole phenocrysts of the transsolvus granite indicate formation from a more evolved magma compared to the hypersolvus granite, despite the fact that these crystals formed early. We interpret the increasing Fe3+/Fe2+ ratios in the amphibole of the hypersolvus granite to reflect crystal chemical effects (Na/Ca-ratio) and increasingly oxidizing conditions in the magma, whereas in the phenocrysts of the transsolvus granite, the increasing ratio was the product of increasing proportions of F- and OH- in the melt. The amphiboles of all the granite units have elevated Nb, Zr, Hf and REE concentrations compared to the bulk rock, suggesting that these elements are compatible in amphibole. By contrast the much lower Ti concentration was due to saturation of the magma in sodium-titanosilicates. The amphibole REE concentrations vary greatly among the granite units. Amphibole of the southern and northern hypersolvus granite contains 0.16 and 0.07 wt.% ∑ REE + Y, on average, respectively, and in the transsolvus granite, the average ∑ REE content is only 0.01 wt.%, despite the more evolved nature of its host transsolvus granite. We intrepret this compositional difference to be due to the fact that the latter represents phenocrysts, which crystallized early, whereas the hypersolvus arfvedsonite is a late interstitial phase. Chondrite-normalized REE profiles emphasise the wide range in LREE-, and the narrow range in HREE-concentrations of the amphiboles. The variations in the LREE-profiles reflect the variable crystallization of primary LREE-bearing phases, including monazite-(Ce), pyrochlore group minerals and gagarinite-(Ce), prior to or contemporaneous with the amphibole, as well as the exsolution of a LREE-rich fluoride melt. The LREE are incompatible in the amphibole structure (apparent D < 0.01) and are preferably accommodated by the octahedral C-site, whereas the HREE occupy the B-site. The chondrite-normalized HREE profiles are steep and display an increasing relative enrichment that culminates in compatible behavior for Yb and Lu (apparent D > 1). Owing to their small ionic radius and their compatibility with the amphibole structure, HREE concentrations were more controlled by partitioning (crystal chemical effects) than by the concentrations in the corresponding magma. Large proportions of the bulk HREE content (up to 70%) reside in the amphibole, and their later release through hydrothermal replacement helps to explain the extreme and unusual HREE enrichment of the Strange Lake pluton.

The temporal evolution of magnesium isotope fractionation during hydromagnesite dissolution, precipitation, and at equilibrium

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Berninger, Ulf-Niklas; Pérez-Fernàndez, Andrea; Chmeleff, Jérôme; Mavromatis, Vasileios

2018-04-01

This study provides experimental evidence of the resetting of the magnesium (Mg) isotope signatures of hydromagnesite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over month-long timescales. All experiments were performed in batch reactors in aqueous sodium carbonate buffer solutions having a pH from 7.8 to 9.2. The fluid phase in all experiments attained bulk chemical equilibrium within analytical uncertainty with hydromagnesite within several days, but the experiments were allowed to continue for up to 575 days. During congruent hydromagnesite dissolution, the fluid first became enriched in isotopically light Mg compared to the dissolving hydromagnesite, but this Mg isotope composition became heavier after the fluid attained chemical equilibrium with the mineral. The δ26Mg composition of the fluid was up to ∼0.35‰ heavier than the initial dissolving hydromagnesite at the end of the dissolution experiments. Hydromagnesite precipitation was provoked during one experiment by increasing the reaction temperature from 4 to 50 °C. The δ26Mg composition of the fluid increased as hydromagnesite precipitated and continued to increase after the fluid attained bulk equilibrium with this phase. These observations are consistent with the hypothesis that mineral-fluid equilibrium is dynamic (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium). Moreover the results presented in this study confirm (1) that the transfer of material from the solid to the fluid phase may not be conservative during stoichiometric dissolution, and (2) that the isotopic compositions of carbonate minerals can evolve even when the mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests that the preservation of isotopic signatures of carbonate minerals in the geological record may require a combination of the isolation of fluid-mineral system from external chemical input and/or the existence of a yet to be defined dissolution/precipitation inhibition mechanism.

Mafic dykes intrusive into Pre-Cambrian rocks of the São Luís cratonic fragment and Gurupi Belt (Parnaíba Province), north-northeastern Brazil: Geochemistry, Sr-Nd-Pb-O isotopes, 40Ar/39Ar geochronology, and relationships to CAMP magmatism

NASA Astrophysics Data System (ADS)

Klein, Evandro L.; Angélica, Rômulo S.; Harris, Chris; Jourdan, Fred; Babinski, Marly

2013-07-01

Dykes of diabase and microgabbro intruded into Pre-Cambrian rocks of the São Luís cratonic fragment and Gurupi Belt, which are tectonic and erosive windows of the Parnaíba Basin in north-northeastern Brazil. Ar-Ar ages were determined, and major, trace element, and Nd-Sr-Pb-O isotopic compositions of these dykes were measured to provide insights into their age, and into the nature of their mantle sources and petrogenetic processes. The data have also been used to compare the chemical and isotopic signatures of the dykes with those of the Central Atlantic Magmatic Province (CAMP). Four chemical groups of mafic dykes have been identified. These comprise two subtypes of high-Ti rocks (i) HTi-1 (TiO2 < 2.3 wt.%; SiO2 > 47 wt.%), (ii) HTi-2 (TiO2 > 2.7 wt.%; SiO2 > 47 wt.%), in addition to (iii) evolved high-Ti (TiO2 > 4 wt.%; SiO2 of ~ 46 wt.%) and (iv) low-Si (TiO2 > 2.2 wt.%; SiO2 < 45 wt.%) rocks. 40Ar/39Ar geochronology of plagioclase returned ages of 201 ± 4 Ma and 193 ± 10 Ma for the HTi-2 subtype, and of 201 ± 2 Ma and 207 ± 9 Ma for the evolved high-Ti group. The HTi-1 and low-Si groups presented highly disturbed age spectra, and did not allow the definition of their emplacement ages. The Argon data indicate an age > 200 Ma for the low-Si group and are dubious with respect to the age of theHTi-1 subtype, if coeval with (i.e., ~ 200 Ma), or older than, the HTi-2 and evolved high-Ti types. All groups present δ18O values of pyroxene that are compatible with uncontaminated mantle-derived magmas. The HTi-1 subtype (average 143Nd/144Nd200 = 0.512644; 87Sr/86Sr200 = 0.7035; 206Pb/204Pb of 17.86) shows the less enriched and less fractionated (more primitive) trace element distribution of all groups. The HTi-2 subtype shows enriched trace element pattern and depleted Nd-Sr signature (143Nd/144Nd200 = 0.512610; 87Sr/86Sr200 = 0.7037) and average 206Pb/204Pb ratios of 17.23. The evolved high-Ti chemical group shows average ratios of 143Nd/144Nd200 = 0.512558, 87Sr/86Sr200 = 0.7035, and 206Pb/204Pb of 16.88, and the more enriched trace-elements signature among the four groups. The chemical and isotopic compositions and trends of the HTi-1/HTi-2/EHTi types are consistent with their derivation from an asthenosphere-derived parental magma further modified by differentiation and minimal crust contamination (higher in the HTi-2 and EHTi types), and by the derivation of one type from another via fractional crystallization. These high- and evolved high-TiO2 types show ages and some chemical and isotopic features that are consistent with those of the CAMP magmatism. Some differences found are ascribed to petrogenetic processes, such as magma differentiation. A combination of warming of the mantle and edge-driven convection beneath the Pangea supercontinent after the closure of the Neoproterozoic (Brasiliano/Pan-African) orogenies in the Ediacaran-Cambrian boundary might have triggered the magmatic event. The low-Si type shows paired Ta-Nb and Zr-Hf depletions, and depleted Sr-Nd (average 143Nd/144Nd200 = 0.512687; 87Sr/86Sr200 = 0.703) and enriched Pb (206Pb/204Pb of 18.66) isotopic compositions that may be interpreted to result either from interaction of a subcontinental lithospheric mantle with products of an earlier subduction or by contamination of the mantle-derived magma during ascent and emplacement in the continental crust. It is hypothesized that these dykes were emplaced in the Ediacaran-Cambrian boundary, after the Neoproterozoic orogeny that built up the Gurupi Belt and in the early extensional stages that preceded the formation of the Parnaíba Basin.

Constraining mechanisms of quartz precipitation in the Archean ocean using silicon isotopes

NASA Astrophysics Data System (ADS)

Brengman, L. A.; Fedo, C.; Martin, W.

2017-12-01

To constrain reservoir values for the Archean silica cycle we measured silicon isotope compositions (δ30Si) of 28 igneous, siliciclastic sedimentary, hydrothermal, and chemical sedimentary rock samples from three Archean greenstone belts representing different times (>3.7 - 2.7 Ga) and tectonic regimes. We posit that silicon isotope compositions of quartz (746 analyses measured in situ by secondary ion mass spectrometry at the NORDSIM facility) are linked to changes in key geochemical parameters that vary within local depositional environments, coupled with a dependency on size and δ30Si composition of the source reservoir. Collectively, siliceous precipitates from even a single basin span a 7‰ range in δ30Si values. Such heterogeneity, regardless of basinal position or presence of Fe-phases demonstrates that δ30Si values of chemical sediments are linked to neither a well-mixed water column representative of a single ocean composition, nor a specific time in Earth history. Combining data from all three greenstone belts we discern that all measured Algoma-type iron formation (IF) and about 50% of associated chert samples possess δ30Si values <0‰, while the majority of silicified volcanic rocks and the remaining 50% of chert samples have δ30Si values >0‰. Negative values of Algoma-type IF can be explained by rate-dependent fractionation during precipitation and/or adsorption to Fe/Al. Combined experimental and natural data for quartz precipitates suggest slow precipitation rates coupled with closed system, Rayleigh type distillation could produce the isotopically heavy values. Such results suggest the quartz-precipitating fluid for these rocks evolves from an open system in disequilibrium, to one that is closed, and in equilibrium with the host rock. In contrast to the static range of values through time for Algoma-type IF, associated cherts and silicified rocks, compiled data for Superior-type IF from 3 - 1.8 Ga record a systematic increasing trend from dominantly 30Si-depleted to 30Si-enriched values over the Archean-Paleoproterozoic transition. Interpreted in the context of our provisional, mass-balance based flux model for the Precambrian silicon cycle, we conclude the 30Si-enrichment to reflect the evolving δ30Si composition of the ocean due to the addition of continentally derived silica.

Structure and physical properties of silkworm cocoons

PubMed Central

Chen, Fujia; Porter, David; Vollrath, Fritz

2012-01-01

Silkworm cocoons have evolved a wide range of different structures and combinations of physical and chemical properties in order to cope with different threats and environmental conditions. We present our observations and measurements on 25 diverse types of cocoons in a first attempt to correlate physical properties with the structure and morphology of the cocoons. These two architectural parameters appear to be far more important than the material properties of the silk fibres themselves. We consider tensile and compressive mechanical properties and gas permeation of the cocoon walls, and in each case identify mechanisms or models that relate these properties to cocoon structure, usually based upon non-woven fibre composites. These properties are of relevance also for synthetic non-woven composite materials and our studies will help formulate bio-inspired design principles for new materials. PMID:22552916

The Composition of the Protosolar Disk and the Formation Conditions for Comets

NASA Astrophysics Data System (ADS)

Willacy, K.; Alexander, C.; Ali-Dib, M.; Ceccarelli, C.; Charnley, S. B.; Doronin, M.; Ellinger, Y.; Gast, P.; Gibb, E.; Milam, S. N.; Mousis, O.; Pauzat, F.; Tornow, C.; Wirström, E. S.; Zicler, E.

2015-12-01

Conditions in the protosolar nebula have left their mark in the composition of cometary volatiles, thought to be some of the most pristine material in the solar system. Cometary compositions represent the end point of processing that began in the parent molecular cloud core and continued through the collapse of that core to form the protosun and the solar nebula, and finally during the evolution of the solar nebula itself as the cometary bodies were accreting. Disentangling the effects of the various epochs on the final composition of a comet is complicated. But comets are not the only source of information about the solar nebula. Protostellar disks around young stars similar to the protosun provide a way of investigating the evolution of disks similar to the solar nebula while they are in the process of evolving to form their own solar systems. In this way we can learn about the physical and chemical conditions under which comets formed, and about the types of dynamical processing that shaped the solar system we see today.

Mechanisms of transport and electron transfer at conductive polymer/liquid interfaces

NASA Astrophysics Data System (ADS)

Ratcliff, Erin

Organic semiconductors (OSCs) have incredible prospects for next-generation, flexible electronic devices including bioelectronics, thermoelectrics, opto-electronics, and energy storage and conversion devices. Yet many fundamental challenges still exist. First, solution processing prohibits definitive control over microstructure, which is fundamental for controlling electrical, ionic, and thermal transport properties. Second, OSCs generally suffer from poor electrical conductivities due to a combination of low carriers and low mobility. Third, polymeric semiconductors have potential-dependent, dynamically evolving electronic and chemical states, leading to complex interfacial charge transfer properties in contact with liquids. This talk will focus on the use of alternative synthetic strategies of oxidative chemical vapor deposition and electrochemical deposition to control physical, electronic, and chemical structure. We couple our synthetic efforts with energy-, time-, and spatially resolved spectroelectrochemical and microscopy techniques to understand the critical interfacial chemistry-microstructure-property relationships: first at the macroscale, and then moving towards the nanoscale. In particular, approaches to better understand electron transfer events at polymer/liquid interfaces as a function of: 1.) chemical composition; 2.) electronic density of states (DOS); and 3.) crystallinity and microstructure will be discussed.

Evolution of Shock Melt Compositions in Lunar Regoliths

NASA Technical Reports Server (NTRS)

Vance, A. M.; Christoffersen, R.; Keller, L. P.; Berger, E. L.; Noble, S. K.

2016-01-01

Space weathering processes - driven primarily by solar wind ion and micrometeorite bombardment, are constantly changing the surface regoliths of airless bodies, such as the Moon. It is essential to study lunar soils in order to fully under-stand the processes of space weathering, and how they alter the optical reflectance spectral properties of the lunar surface relative to bedrock. Lunar agglutinates are aggregates of regolith grains fused together in a glassy matrix of shock melt produced during micrometeorite impacts into the lunar regolith. The formation of the shock melt component in agglutinates involves reduction of Fe in the target material to generate nm-scale spherules of metallic Fe (nanophase Fe0 or npFe0). The ratio of elemental Fe, in the form of npFe0, to FeO in a given bulk soil indicates its maturity, which increases with length of surface exposure as well as being typically higher in the finer-size fraction of soils. The melting and mixing process in agglutinate formation remain poorly understood. This includes incomplete knowledge regarding how the homogeneity and overall compositional trends of the agglutinate glass portions (agglutinitic glass) evolve with maturity. The aim of this study is to use sub-micrometer scale X-ray compositional mapping and image analysis to quantify the chemical homogeneity of agglutinitic glass, correlate its homogeneity to its parent soil maturity, and identify the principal chemical components contributing to the shock melt composition variations. An additional focus is to see if agglutinitic glass contains anomalously high Fe sub-micron scale compositional domains similar to those recently reported in glassy patina coatings on lunar rocks.

Evaluation of Burning Test Rate Method for Flammable Solids to Increase air-Cargo Safety.

PubMed

Lukežič, Marjan; Marinšek, Marjan; Faganeli, Jadran

2010-03-01

This paper deals with a standard classification procedure for readily combustible solids and their assignment to the relevant packing groups according to international air-cargo legislation and regulations. The current International Air Transport Association and United Nations Orange Book regulations were used on chemically similar substances: hexamethylenetetramine and Dancook ignition briquettes, which are both assigned into the same Packing Group III. To critically evaluate the degree of hazard both chemicals present, a standard burning test rate as well as thermogravimetry, differential scanning calorimetry and evolved gas analysis measurements were performed. It was shown that relatively small changes in the chemical composition of the material may have essential influence on the package group determination. Taking into account all the facts collected in the experimental work, it was concluded that ignition briquettes will undergo spontaneous combustion if exposed to elevated temperatures and, from this point of view, represent higher risk than hexamethylenetetramine during air transportation. Therefore, ignition briquettes should be classified into Packing Group II.

Petrology and physical conditions of metamorphism of calcsilicate rocks from low- to high-grade transition area, Dharmapuri District, Tamil Nadu

NASA Technical Reports Server (NTRS)

Narayana, B. L.; Natarajan, R.; Govil, P. K.

1988-01-01

Calc-silicate rocks comprising quartz, plagioclase, diopside, sphene, scapolite, grossularite-andradite and wollastonite occur as lensoid enclaves within the greasy migmatitic and charnockitic gneisses of the Archaean amphibolite- to granulite-facies transition zone in Dharmapuri district, Tamil Nadu. The calc-silicate rocks are characterized by the absence of K-feldspar and primary calcite, presence of large modal quartz and plagioclase and formation of secondary garnet and zoisite rims around scapolite and wollastonite. The mineral distributions suggest compositional layering. The chemical composition and mineralogy of the calc-silicate rocks indicate that they were derived from impure silica-rich calcareous sediments whose composition is similar to that of pelite-limestone mixtures. From the mineral assemblages the temperature, pressure and fluid composition during metamorphism were estimated. The observed mineral reaction sequences require a range of X sub CO2 values demonstrating that an initially CO2-rich metamorphic fluid evolved with time towards considerably more H2O-rich compositions. These variations in fluid composition suggest that there were sources of water-rich fluids external to the calc-silicate rocks and that mixing of these fluids with those of calc-silicate rocks was important in controlling fluid composition in calc-silicate rocks and some adjacent rock types as well.

Explaining intraspecific diversity in plant secondary metabolites in an ecological context.

PubMed

Moore, Ben D; Andrew, Rose L; Külheim, Carsten; Foley, William J

2014-02-01

Plant secondary metabolites (PSMs) are ubiquitous in plants and play many ecological roles. Each compound can vary in presence and/or quantity, and the composition of the mixture of chemicals can vary, such that chemodiversity can be partitioned within and among individuals. Plant ontogeny and environmental and genetic variation are recognized as sources of chemical variation, but recent advances in understanding the molecular basis of variation may allow the future deployment of isogenic mutants to test the specific adaptive function of variation in PSMs. An important consequence of high intraspecific variation is the capacity to evolve rapidly. It is becoming increasingly clear that trait variance linked to both macro- and micro-environmental variation can also evolve and may respond more strongly to selection than mean trait values. This research, which is in its infancy in plants, highlights what could be a missing piece of the picture of PSM evolution. PSM polymorphisms are probably maintained by multiple selective forces acting across many spatial and temporal scales, but convincing examples that recognize the diversity of plant population structures are rare. We describe how diversity can be inherently beneficial for plants and suggest fruitful avenues for future research to untangle the causes and consequences of intraspecific variation. © 2013 The Authors. New Phytologist © 2013 New Phytologist Trust.

Microspectroscopic imaging of solution plasma: How do its physical properties and chemical species evolve in atmospheric-pressure water vapor bubbles?

NASA Astrophysics Data System (ADS)

Yui, Hiroharu; Banno, Motohiro

2018-01-01

In this article, we review the development of scientific instruments for obtaining information on the evolution of physical properties and chemical species of solution plasma (SP). When a pulsed high voltage is applied between electrodes immersed in an aqueous solution, SP is formed in water vapor bubbles transiently generated in the solution under atmospheric pressure. To clarify how SP emerges in water vapor bubbles and is sustained in solutions, an instrument with micrometer spatial resolution and nanosecond temporal resolution is required. To meet these requirements, a microscopic system with a custom-made optical discharge cell was newly developed, where the working distance between the SP and the microscopic objective lens was minimized. A hollow electrode equipped in the discharge cell also enabled us to control the chemical composition in water vapor bubbles. To study the spatial and temporal evolutions of chemical species in micrometer and nano- to microsecond regions, a streak camera with a spectrometer and a CCD detector with a time-gated electronic device were combined with the microscope system. The developed instrument is expected to contribute to providing a new means of developing new schemes for chemical reactions and material syntheses.

Multiple plagioclase crystal populations identified by crystal size distribution and in situ chemical data: Implications for timescales of magma chamber processes associated with the 1915 eruption of Lassen Peak, CA

USGS Publications Warehouse

Salisbury, M.J.; Bohrson, W.A.; Clynne, M.A.; Ramos, F.C.; Hoskin, P.

2008-01-01

Products of the 1915 Lassen Peak eruption reveal evidence for a magma recharge-magma mixing event that may have catalyzed the eruption and from which four compositional members were identified: light dacite, black dacite, andesitic inclusion, and dark andesite. Crystal size distribution, textural, and in situ chemical (major and trace element and Sr isotope) data for plagioclase from these compositional products define three crystal populations that have distinct origins: phenocrysts (long axis > 0??5 mm) that typically have core An contents between 34 and 36 mol %, microphenocrysts (long axis between 0??1 and 0??5 mm) that have core An contents of 66-69, and microlites (long axis < 0??1 mm) with variable An core contents from 64 to 52. Phenocrysts are interpreted to form in an isolated dacitic magma chamber that experienced slow cooling. Based on textural, compositional, and isotopic data for the magma represented by the dacitic component, magma recharge was not an important process until just prior to the 1915 eruption. Average residence times for phenocrysts are in the range of centuries to millennia. Microphenocrysts formed in a hybrid layer that resulted from mixing between end-member reservoir dacite and recharge magma of basaltic andesite composition. High thermal contrast between the two end-member magmas led to relatively high degrees of undercooling, which resulted in faster crystal growth rates and acicular and swallowtail crystal habits. Some plagioclase phenocrysts from the dacitic chamber were incorporated into the hybrid layer and underwent dissolution-precipitation, seen in both crystal textures and rim compositions. Average microphenocryst residence times are of the order of months. Microlites may have formed in response to decompression and/ or syn-eruptive degassing as magma ascended from the chamber through the volcanic conduit. Chemical distinctions in plagioclase microlite An contents reveal that melt of the dark andesite was more mafic than the melt of the other three compositions. We suggest that mixing of an intruding basaltic andesite and reservoir dacite before magma began ascending in the conduit allowed formation of a compositionally distinct microlite population. Melt in the other three products was more evolved because it had undergone differentiation during the months following initial mixing; as a consequence, melt and microlites among these three products have similar compositions. The results of this study highlight the integrated use of crystal size distribution, textural, and in situ chemical data in identifying distinct crystal populations and linking these populations to the thermal and chemical characteristics of complex magma bodies. ?? The Author 2008. Published by Oxford University Press. All rights reserved.

METHOD FOR PRODUCING ISOTOPIC METHANES FROM LITHIUM CARBONATE AND LITHIUM HYDRIDE

DOEpatents

Frazer, J.W.

1959-10-27

A process is descrlbed for the production of methane and for the production of methane containing isotopes of hydrogen and/or carbon. Finely divided lithium hydrlde and litldum carbonate reactants are mixed in intimate contact and subsequently compacted under pressures of from 5000 to 60,000 psl. The compacted lithium hydride and lithium carbenate reactunts are dispised in a gas collecting apparatus. Subsequently, the compact is heated to a temperature in the range 350 to 400 deg C whereupon a solid-solid reaction takes place and gaseous methane is evolved. The evolved methane is contaminated with gaseous hydrogen and a very small amount of CO/sub 2/; however, the desired methane product is separated from sald impurities by well known chemical processes, e.g., condensation in a cold trap. The product methane contalns isotopes of carbon and hydrogen, the Isotopic composition being determined by the carbon isotopes originally present In the lithium carbonate and the hydrogen isotopes originally present in the lithium hydride.

Evolving application of biomimetic nanostructured hydroxyapatite

PubMed Central

Roveri, Norberto; Iafisco, Michele

2010-01-01

By mimicking Nature, we can design and synthesize inorganic smart materials that are reactive to biological tissues. These smart materials can be utilized to design innovative third-generation biomaterials, which are able to not only optimize their interaction with biological tissues and environment, but also mimic biogenic materials in their functionalities. The biomedical applications involve increasing the biomimetic levels from chemical composition, structural organization, morphology, mechanical behavior, nanostructure, and bulk and surface chemical–physical properties until the surface becomes bioreactive and stimulates cellular materials. The chemical–physical characteristics of biogenic hydroxyapatites from bone and tooth have been described, in order to point out the elective sides, which are important to reproduce the design of a new biomimetic synthetic hydroxyapatite. This review outlines the evolving applications of biomimetic synthetic calcium phosphates, details the main characteristics of bone and tooth, where the calcium phosphates are present, and discusses the chemical–physical characteristics of biomimetic calcium phosphates, methods of synthesizing them, and some of their biomedical applications. PMID:24198477

Carbon chemistry of circumstellar envelopes

NASA Technical Reports Server (NTRS)

Bieging, John H.

1990-01-01

The chemical composition of envelopes surrounding cool evolved stars, as determined from microwave spectroscopic observations, is reviewed. Emphasis is placed on recent observations with the new large mm-wavelength telescopes and interferometer arrays, and on new theoretical work, especially concerning ion-molecule chemistry of carbon-bearing in these envelopes. Thermal (as opposed to maser) emission lines are discussed. Much progress has been made in the past few years in the theoretical understanding of these objects. It is already clear, however, that observations with the new generation of mm-telescopes will require substantial improvements in the theoretical models to achieve a thorough understanding of the data now becoming available.

Time-Dependent Changes in a Shampoo Bubble

NASA Astrophysics Data System (ADS)

Chattopadhyay, Arun

2000-10-01

This article demonstrates the fascinating phenomenon of time evolution of a shampoo bubble through experiments that can be performed by undergraduate students. The changes in thickness of the bubble films with time are followed by UV-vis spectroscopy. The change in chemical composition as a bubble film evolves is monitored by FTIR spectroscopy. It is observed that the change in thickness of a typical shampoo bubble film enclosed in a container is gradual and slow, and the hydrocarbon components of the bubble drain from the bubble much more slowly than water. An additional agent, such as acetonitrile, strikingly alters the dynamics of evolution of such a bubble.

Hygroscopic properties of internally mixed particles composed of NaCl and water-soluble organic acids.

PubMed

Ghorai, Suman; Wang, Bingbing; Tivanski, Alexei; Laskin, Alexander

2014-02-18

Atmospheric aging of naturally emitted marine aerosol often leads to formation of internally mixed particles composed of sea salts and water-soluble organic compounds of anthropogenic origin. Mixing of sea salt and organic components has profound effects on the evolving chemical composition and hygroscopic properties of the resulted particles, which are poorly understood. Here, we have studied chemical composition and hygroscopic properties of laboratory generated NaCl particles mixed with malonic acid (MA) and glutaric acid (GA) at different molar ratios using micro-FTIR spectroscopy, atomic force microscopy, and X-ray elemental microanalysis. Hygroscopic properties of internally mixed NaCl and organic acid particles were distinctly different from pure components and varied significantly with the type and amount of organic compound present. Experimental results were in a good agreement with the AIM modeling calculations of gas/liquid/solid partitioning in studied systems. X-ray elemental microanalysis of particles showed that Cl/Na ratio decreased with increasing organic acid component in the particles with MA yielding lower ratios relative to GA. We attribute the depletion of chloride to the formation of sodium malonate and sodium glutarate salts resulted by HCl evaporation from dehydrating particles.

Measurement of the cosmic ray spectrum and chemical composition in the 1015-1018 eV energy range

NASA Astrophysics Data System (ADS)

Chiavassa, Andrea

2018-01-01

Cosmic ray in the 1015-1018 eV energy range can only be detected with ground based experiments, sampling Extensive Air Showers (EAS) particles. The interest in this energetic interval is related to the search of the knee of the iron component of cosmic ray and to the study of the transition between galactic and extra-galactic primaries. The energy and mass calibration of these arrays can only be performed with complete EAS simulations as no sources are available for an absolute calibration. The systematic error on the energy assignment can be estimated around 30 ± 10%. The all particle spectrum measured in this energy range is more structured than previously thought, showing some faint features: a hardening slightly above 1016 eV and a steepening below 1017 eV. The studies of the primary chemical composition are quickly evolving towards the measurements of the primary spectra of different mass groups: up to now we are able to separate (on a event by event basis) light and heavy primaries. Above the knee a steepening of the heavy primary spectrum and a hardening of the light ones have been detected.

Hygroscopic Properties of Internally Mixed Particles Composed of NaCl and Water-Soluble Organic Acids

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

Ghorai, Suman; Wang, Bingbing; Tivanski, Alexei V.

Atmospheric aging of naturally emitted marine aerosol often leads to formation of internally mixed particles composed of sea salts and water soluble organic compounds of anthropogenic origin. Mixing of sea salt and organic components has profound effects on the evolving chemical composition and hygroscopic properties of the resulted particles, which are poorly understood. Here, we have studied chemical composition and hygroscopic properties of laboratory generated NaCl particles mixed with malonic acid (MA) and glutaric acid (GA) at different molar ratios using micro-FTIR spectroscopy and X-ray elemental microanalysis.Hygroscopic properties of inte rnally mixed NaCl and organic acid particles were distinctly differentmore » from pure components and varied significantly with the type and amount of organic compound present. Experimental results were in a good agreement with the AIM modeling calculations of gas/liquid/solid partitioning in studied systems. X-ray elemental microanalysis of particles showed that Cl/Na ratio decreased with increasing organic acid component in the particles with MA yielding lower ratios relative to GA. We attribute the depletion of chloride to the formation of Na-malonate and Na-glutarate salts resulted by HCl evaporation from dehydrating particles.« less

Fast changes in chemical composition and size distribution of fine particles during the near-field transport of industrial plumes.

PubMed

Marris, Hélène; Deboudt, Karine; Augustin, Patrick; Flament, Pascal; Blond, François; Fiani, Emmanuel; Fourmentin, Marc; Delbarre, Hervé

2012-06-15

Aerosol sampling was performed inside the chimneys and in the close environment of a FeMn alloys manufacturing plant. The number size distributions show a higher abundance of ultrafine aerosols (10-100 nm) inside the plume than upwind of the plant, indicating the emissions of nanoparticles by the industrial process. Individual analysis of particles collected inside the plume shows a high proportion of metal bearing particles (Mn-/Fe-) consisting essentially of internally mixed aluminosilicate and metallic compounds. These particles evolve rapidly (in a few minutes) after emission by adsorption of VOC gas and sulfuric acid emitted by the plant but also by agglomeration with pre-existing particles. At the moment, municipalities require a monitoring of industrial emissions inside the chimneys from manufacturers. However those measures are insufficient to report such rapid changes in chemical composition and thus to evaluate the real impact of industrial plumes in the close environment of plants (when those particles leave the industrial site). Consequently, environmental authorities will have to consider such fast evolutions and then to adapt future regulations on air pollution sources. Copyright © 2012 Elsevier B.V. All rights reserved.

Construction and Characterization of an Indoor Smog Chamber for Measuring Chemical and Optical Properties of Biomass Burning Aerosols as a Function of Age

NASA Astrophysics Data System (ADS)

Smith, D. M.; Fiddler, M. N.; Sexton, K.; Bililign, S.; Dowdell, T. M.

2016-12-01

Biomass burning is recognized as one of the largest sources of absorbing aerosols in the atmosphere and significantly influences the radiative properties of the atmosphere. In the atmosphere, aerosols dynamically change in complex ways. The chemical composition and physical properties of particles evolve during their atmospheric lifetime due to condensation, oxidation reactions, etc. Changes in chemical composition due to aging is likely to change the optical properties of these particles as well. We have built a 9.01m3 indoor smog chamber made of FEP Teflon. Wood and other organic samples are burned in a tube furnace with the exhaust going directly into the chamber. The construction, characterization, and calibration of the smog chamber will be presented, along with preliminary measurements of extinction and scattering of biomass burning aerosols measured using a Cavity Ring-down and Integrating Nephelometry system. This system allows us to measure any changes in the optical properties of the soot as it ages. Injections to the chamber can be controlled to simulate various atmospheric conditions. These include clean (dry) air, laboratory (room) air, water vapor, NOX, and various biogenic and anthropogenic VOCs such as aromatic hydrocarbons. These components and some of their oxidation products can also be monitored and characterized during aging. The authors acknowledge the support from the National Science Foundation through Grant Number NSF-AGS-1555479

Elemental geochemistry of sedimentary rocks at Yellowknife Bay, Gale crater, Mars.

PubMed

McLennan, S M; Anderson, R B; Bell, J F; Bridges, J C; Calef, F; Campbell, J L; Clark, B C; Clegg, S; Conrad, P; Cousin, A; Des Marais, D J; Dromart, G; Dyar, M D; Edgar, L A; Ehlmann, B L; Fabre, C; Forni, O; Gasnault, O; Gellert, R; Gordon, S; Grant, J A; Grotzinger, J P; Gupta, S; Herkenhoff, K E; Hurowitz, J A; King, P L; Le Mouélic, S; Leshin, L A; Léveillé, R; Lewis, K W; Mangold, N; Maurice, S; Ming, D W; Morris, R V; Nachon, M; Newsom, H E; Ollila, A M; Perrett, G M; Rice, M S; Schmidt, M E; Schwenzer, S P; Stack, K; Stolper, E M; Sumner, D Y; Treiman, A H; VanBommel, S; Vaniman, D T; Vasavada, A; Wiens, R C; Yingst, R A

2014-01-24

Sedimentary rocks examined by the Curiosity rover at Yellowknife Bay, Mars, were derived from sources that evolved from an approximately average martian crustal composition to one influenced by alkaline basalts. No evidence of chemical weathering is preserved, indicating arid, possibly cold, paleoclimates and rapid erosion and deposition. The absence of predicted geochemical variations indicates that magnetite and phyllosilicates formed by diagenesis under low-temperature, circumneutral pH, rock-dominated aqueous conditions. Analyses of diagenetic features (including concretions, raised ridges, and fractures) at high spatial resolution indicate that they are composed of iron- and halogen-rich components, magnesium-iron-chlorine-rich components, and hydrated calcium sulfates, respectively. Composition of a cross-cutting dike-like feature is consistent with sedimentary intrusion. The geochemistry of these sedimentary rocks provides further evidence for diverse depositional and diagenetic sedimentary environments during the early history of Mars.

The Interaction Between Accretion from the Interstellar Medium and Accretion from the Evolved Binary Component in Barium Stars

NASA Astrophysics Data System (ADS)

Jeong, Yeuncheol; Yushchenko, Alexander V.; Doikov, Dmytry N.

2018-03-01

The reanalysis of the previously published abundance pattern of mild barium star HD202109 (ζ Cyg) and the chemical compositions of 129 thin disk barium stars facilitated the search for possible correlations of different stellar parameters with second ionization potentials of chemical elements. Results show that three valuable correlations exist in the atmospheres of barium stars. The first is the relationship between relative abundances and second ionization potentials. The second is the age dependence of mean correlation coefficients of relative abundances vs. second ionization potentials, and the third one is the changes in correlation coefficients of relative abundances vs. second ionization potentials as a function of stellar spatial velocities and overabundances of s-process elements. These findings demonstrate the possibility of hydrogen and helium accretion from the interstellar medium on the atmospheres of barium stars.

The effect of mechano-chemical treatment on structural properties of the drawn TiNi-based alloy wire

NASA Astrophysics Data System (ADS)

Anikeev, Sergey; Hodorenko, Valentina; Gunther, Victor; Chekalkin, Timofey; Kang, Ji-hoon; Kang, Seung-baik

2018-01-01

The rapid development of biomedical materials with the advanced functional characteristics is a challenging task because of the growing demands for better material properties in-clinically employed. Modern medical devices that can be implanted into humans have evolved steadily by replacing TiNi-based alloys for titanium and stainless steel. In this study, the effect of the mechano-chemical treatment on structural properties of the matrix and surface layer of the drawn TiNi-based alloy wire was assessed. A range of samples have been prepared using different drawing and etching procedures. It is clear from the results obtained that the fabricated samples show a composite structure comprising the complex matrix and textured oxycarbonitride spitted surface layer. The suggested method of surface treatment is a concept to increase the surface roughness for the enhanced bio-performance and better in vivo integration.

Petrographic and Geochemical Investigation of Andesitic Arc Volcanism: Mount Kerinci, Sunda Arc, Indonesia

NASA Astrophysics Data System (ADS)

Tully, M.; Saunders, K.; Troll, V. R.; Jolis, E.; Muir, D. D.; Deegan, F. M.; Budd, D. A.; Astbury, R.; Bromiley, G. D.

2014-12-01

Present knowledge of the chain of dominantly andesitic volcanoes, which span the Sumatran portion of the Sunda Arc is extremely limited. Previous studies have focused on Toba and Krakatau, although over 13 further volcanic edifices are known. Several recent explosive eruptions in Sumatra such as that of Mt. Sinabung, 2014, have highlighted the potential hazard that these volcanoes pose to the local and regional communities. Mount Kerinci, is one of the most active of the volcanoes in this region, yet little is known about the petrogenesis of the magma by which it is fed. Kerinci is located approximately mid-way between Toba in the North and Krakatau in the south. Along arc variations are observed in the major, minor and trace elements of whole rock analyses. However, bulk rock approaches produce an average chemical composition for a sample, potentially masking important chemical signatures. In-situ micro-analytical analysis of individual components of samples such as melt inclusions, crystals and groundmass provides chemical signatures of individual components allowing the evolution of volcanic centres to be deciphered in considerably more detail. Examination of whole rock chemistry indicates its location may be key to unravelling the petrogenesis of the arc as significant chemical changes occur between Kerinci and Kaba, 250 km to the south. Kerinci samples are dominantly porphyritic with large crystals of plagioclase, pyroxene and Fe-Ti oxides, rare olivine crystals are observed. Plagioclase and pyroxene crystals are chemically zoned and host melt inclusions. Multiple plagioclase populations are observed. A combination of in-situ micro-analysis techniques will be used to characterise the chemical composition of melt inclusions and crystals. These data can be used along with extant geothermobarometric models to help determine the magma source, storage conditions and composition of the evolving melt. Integration of the findings from this study with existing data for the volcanic chain will enable along-arc variations in magmatic processes in Sumatra to be assessed more thoroughly, providing fundamental insights into the evolution of not only Kerinci, but magma genesis in Sumatra in general. Keywords: Sunda Arc, andesite, arc volcanism, petrogenesis.

PALOMA : an isotope analyzer using static mass spectrometry, coupled with cryogenic and chemical trapping, for the MSL mission to Mars

NASA Astrophysics Data System (ADS)

Chassefiere, E.; Jambon, A.; Berthelier, J.-J.; Goulpeau, G.; Leblanc, F.; Montmessin, F.; Sarda, P.; Agrinier, P.; Fouchet, T.; Waite, H.

The technique of GCMS analysis has to be completed by static mass spectrometry for precise in-situ measurements of the isotopic composition of planetary atmospheres (noble gases, stable isotopes), and volatile outgassed products from solid sample pyrolysis. Static mass spectrometry, coupled with gas separation by cryo-separation and gettering, is commonly used in the laboratory to study volatiles extracted from terrestrial and meteoritic samples. Such an instrument (PALOMA) is presently developed in our laboratories, and it will be coupled with a Pyr-GCMS analyzer (MACE), built by a US consortium of science laboratories and industrials (University of Michigan, Southwest Research Institute, JPL, Ball Aerospace). The MACE/PALOMA experiment will be proposed on the NASA Mars Science Laboratory mission, planned to be launched in 2009. The scientific objectives of PALOMA, coupled with MACE, may be listed as follows : (i) search for isotopic signatures of past life in atmosphere, rock, dust and ice samples, with emphasis on carbon, nitrogen and hydrogen; (ii) accurately measure isotopic composition of atmospheric noble gases, and stable isotopes, in order to better constrain past escape, surface interaction, outgassing history and climate evolution; (iii) precisely measure diurnal/ seasonal variations of isotopic ratios of H2O, CO2, and N2, for improving our understanding of present and past climate, and of the role of water cycle. Main measurement objectives are : (i) C, H, O, N isotopic composition in both organic evolved samples (provided by MACE pyrolysis system) and atmosphere with high accuracy (a few per mil at 1-s level); (ii) noble gas (He, Ne, Ar, Kr, Xe) and stable (C, H, O, N) isotope composition in atmosphere with high accuracy (a few per mil at 1-s level); (iii) molecular and isotopic composition of inorganic evolved samples (salts, hydrates, nitrates, {ldots}), including ices; (iv) diurnal and seasonal monitoring of D/H in water vapor, and water ice.

Infrared Spectroscopy as a Chemical Fingerprinting Tool

NASA Technical Reports Server (NTRS)

Huff, Timothy L.

2003-01-01

Infrared (IR) spectroscopy is a powerful analytical tool in the chemical fingerprinting of materials. Any sample material that will interact with infrared light produces a spectrum and, although normally associated with organic materials, inorganic compounds may also be infrared active. The technique is rapid, reproducible and usually non-invasive to the sample. That it is non-invasive allows for additional characterization of the original material using other analytical techniques including thermal analysis and RAMAN spectroscopic techniques. With the appropriate accessories, the technique can be used to examine samples in liquid, solid or gas phase. Both aqueous and non-aqueous free-flowing solutions can be analyzed, as can viscous liquids such as heavy oils and greases. Solid samples of varying sizes and shapes may also be examined and with the addition of microscopic IR (microspectroscopy) capabilities, minute materials such as single fibers and threads may be analyzed. With the addition of appropriate software, microspectroscopy can be used for automated discrete point or compositional surface area mapping, with the latter providing a means to record changes in the chemical composition of a material surface over a defined area. Due to the ability to characterize gaseous samples, IR spectroscopy can also be coupled with thermal processes such as thermogravimetric (TG) analyses to provide both thermal and chemical data in a single run. In this configuration, solids (or liquids) heated in a TG analyzer undergo decomposition, with the evolving gases directed into the IR spectrometer. Thus, information is provided on the thermal properties of a material and the order in which its chemical constituents are broken down during incremental heating. Specific examples of these varied applications will be cited, with data interpretation and method limitations further discussed.

The chemically zoned 1949 eruption on La Palma (Canary Islands): Petrologic evolution and magma supply dynamics of a rift zone eruption

NASA Astrophysics Data System (ADS)

Klügel, Andreas; Hoernle, Kaj A.; Schmincke, Hans-Ulrich; White, James D. L.

2000-03-01

The 1949 rift zone eruption along the Cumbre Vieja ridge on La Palma involved three eruptive centers, 3 km spaced apart, and was chemically and mineralogically zoned. Duraznero crater erupted tephrite for 14 days and shut down upon the opening of Llano del Banco, a fissure that issued first tephrite and, after 3 days, basanite. Hoyo Negro crater opened 4 days later and erupted basanite, tephrite, and phonotephrite, while Llano del Banco continued to issue basanite. The eruption ended with Duraznero erupting basanite with abundant crustal and mantle xenoliths. The tephrites and basanites from Duraznero and Llano del Banco show narrow compositional ranges and define a bimodal suite. Each batch ascended and evolved separately without significant intermixing, as did the Hoyo Negro basanite, which formed at lower degrees of melting. The magmas fractionated clinopyroxene +olivine±kaersutite±Ti-magnetite at 600-800 MPa and possibly 800-1100 MPa. Abundant reversely zoned phenocrysts reflect mixing with evolved melts at mantle depths. Probably as early as 1936, Hoyo Negro basanite entered the deep rift system at 200-350 MPa. Some shallower pockets of this basanite evolved to phonotephrite through differentiation and assimilation of wall rock. A few months prior to eruption, a mixing event in the mantle may have triggered the final ascent of the magmas. Most of the erupted tephrite and basanite ascended from mantle depths within hours to days without prolonged storage in crustal reservoirs. The Cumbre Vieja rift zone differs from the rift zones of Kilauea volcano (Hawaii) in lacking a summit caldera or a summit reservoir feeding the rift system and in being smaller and less active with most of the rift magma solidifying between eruptions.

Application of modern online instrumentation for chemical analysis of gas and particulate phases of exhaust at the European Commission heavy-duty vehicle emission laboratory.

PubMed

Adam, T W; Chirico, R; Clairotte, M; Elsasser, M; Manfredi, U; Martini, G; Sklorz, M; Streibel, T; Heringa, M F; Decarlo, P F; Baltensperger, U; De Santi, G; Krasenbrink, A; Zimmermann, R; Prevot, A S H; Astorga, C

2011-01-01

The European Commission recently established a novel test facility for heavy-duty vehicles to enhance more sustainable transport. The facility enables the study of energy efficiency of various fuels/scenarios as well as the chemical composition of evolved exhaust emissions. Sophisticated instrumentation for real-time analysis of the gas and particulate phases of exhaust has been implemented. Thereby, gas-phase characterization was carried out by a Fourier transform infrared spectrometer (FT-IR; carbonyls, nitrogen-containing species, small hydrocarbons) and a resonance-enhanced multiphoton ionization time-of-flight mass spectrometer (REMPI-TOFMS; monocyclic and polycyclic aromatic hydrocarbons). For analysis of the particulate phase, a high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS; organic matter, chloride, nitrate), a condensation particle counter (CPC; particle number), and a multiangle absorption photometer (MAAP; black carbon) were applied. In this paper, the first application of the new facility in combination with the described instruments is presented, whereby a medium-size truck was investigated by applying different driving cycles. The goal was simultaneous chemical characterization of a great variety of gaseous compounds and particulate matter in exhaust on a real-time basis. The time-resolved data allowed new approaches to view the results; for example, emission factors were normalized to time-resolved consumption of fuel and were related to emission factors evolved during high speeds. Compounds could be identified that followed the fuel consumption, others showed very different behavior. In particular, engine cold start, engine ignition (unburned fuel), and high-speed events resulted in unique emission patterns.

Understanding Gas-Phase Ammonia Chemistry in Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Chambers, Lauren; Oberg, Karin I.; Cleeves, Lauren Ilsedore

2017-01-01

Protoplanetary disks are dynamic regions of gas and dust around young stars, the remnants of star formation, that evolve and coagulate over millions of years in order to ultimately form planets. The chemical composition of protoplanetary disks is affected by both the chemical and physical conditions in which they develop, including the initial molecular abundances in the birth cloud, the spectrum and intensity of radiation from the host star and nearby systems, and mixing and turbulence within the disk. A more complete understanding of the chemical evolution of disks enables a more complete understanding of the chemical composition of planets that may form within them, and of their capability to support life. One element known to be essential for life on Earth is nitrogen, which often is present in the form of ammonia (NH3). Recent observations by Salinas et al. (2016) reveal a theoretical discrepancy in the gas-phase and ice-phase ammonia abundances in protoplanetary disks; while observations of comets and protostars estimate the ice-phase NH3/H2O ratio in disks to be 5%, Salinas reports a gas-phase NH3/H2O ratio of ~7-84% in the disk surrounding TW Hydra, a young nearby star. Through computational chemical modeling of the TW Hydra disk using a reaction network of over 5000 chemical reactions, I am investigating the possible sources of excess gas-phase NH3 by determining the primary reaction pathways of NH3 production; the downstream chemical effects of ionization by ultraviolet photons, X-rays, and cosmic rays; and the effects of altering the initial abundances of key molecules such as N and N2. Beyond providing a theoretical explanation for the NH3 ice/gas discrepancy, this new model may lead to fuller understanding of the gas-phase formation processes of all nitrogen hydrides (NHx), and thus fuller understanding of the nitrogen-bearing molecules that are fundamental for life as we know it.

Chemical alarm in the termite Termitogeton planus (Rhinotermitidae).

PubMed

Dolejšová, Klára; Krasulová, Jana; Kutalová, Kateřina; Hanus, Robert

2014-12-01

Effective defense is a common characteristic of insect societies. Indeed, the occurrence of specialized defenders, soldiers, has been the first step toward eusociality in several independent lineages, including termites. Among the multitude of defensive strategies used by termite soldiers, defense by chemicals plays a crucial role. It has evolved with complexity in advanced isopteran lineages, whose soldiers are equipped with a unique defensive organ, the frontal gland. Besides direct defense against predators, competitors, and pathogens, the chemicals emitted by soldiers from the frontal gland are used as signals of alarm. In this study, we investigated the chemical composition of the defensive secretion produced by soldiers of the termite Termitogeton planus (Isoptera: Rhinotermitidae), from West Papua, and the effects of this secretion on the behavior of termite groups. Detailed two-dimensional gas chromatography/mass spectrometry analyses of the soldier defensive secretion revealed the presence of four linear and nine monoterpene hydrocarbons. Soldier head extracts, as well as synthetic mixtures of the monoterpenes found in these extracts, elicited alarm behavior in both soldiers and pseudergates. Our results suggest that the alarm is not triggered by a single monoterpene from the defensive blend, but by a multi-component signal combining quantitatively major and minor compounds.

Use of environmental tracers to study the chemical evolution of shallow ground water in a karst area of northern Florida

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

Katz, B.G.; Plummer, L.N.; Busenberg, E.

1993-03-01

The pathways of shallow ground-water flow in poorly confined aquifer systems of northern FL are influenced by inflow to and outflow from numerous sinkhole lakes that are characteristic of the Sand Hills karst region. Ground-water samples were collected immediately upgradient and downgradient from Lake Barco at depths of 1.6--29 m below the water table from observation wells completed in the surficial aquifer system, the intermediate confining unit (icu), and the Upper Floridan aquifer. Samples were also collected of rainfall, lake water, and ground water at a depth of 4.1 m beneath the lake bottom. The environmental tracers tritium and chlorofluorocarbonsmore » were used to estimate mean residence times of water and rates of chemical mass transfer along flow paths. Water samples collected from wells upgradient of the lake were oxic and had CFC-model recharge dates between 1971 and 1986. The content of delta H-2 and delta O-18 of water from the two aquifer systems and the icu was nearly identical to the isotopic composition of rainfall. Changes in the chemical composition of the ground water with depth were simulated by reacting rainfall with minerals and dissolved gases that exist in the hydrogeologic units. Ground-water samples collected from sites beneath and downgradient of the lake were anoxic, with measured concentrations of hydrogen sulfide and methane ranging from 0.02--0.58 mg/l and 0.30--6.1 mg/l, respectively. CFC-model recharge dates ranged from 1956 to 1983. The data indicated that ground water downgradient of the lake is being recharged by leakage of lake water. The chemical composition of ground water is influenced by the movement of lake water through reducing, organic-rich sediments accumulated at the bottom. Along the downgradient flow paths, the water chemistry evolves from the composition of lake water and is modified by subsequent reactions including reduction of sulfate and ferric iron, methanogenesis, and dissolution and precipitation of minerals.« less

Coupled petrological-geodynamical modeling of a compositionally heterogeneous mantle plume

NASA Astrophysics Data System (ADS)

Rummel, Lisa; Kaus, Boris J. P.; White, Richard W.; Mertz, Dieter F.; Yang, Jianfeng; Baumann, Tobias S.

2018-01-01

Self-consistent geodynamic modeling that includes melting is challenging as the chemistry of the source rocks continuously changes as a result of melt extraction. Here, we describe a new method to study the interaction between physical and chemical processes in an uprising heterogeneous mantle plume by combining a geodynamic code with a thermodynamic modeling approach for magma generation and evolution. We pre-computed hundreds of phase diagrams, each of them for a different chemical system. After melt is extracted, the phase diagram with the closest bulk rock chemistry to the depleted source rock is updated locally. The petrological evolution of rocks is tracked via evolving chemical compositions of source rocks and extracted melts using twelve oxide compositional parameters. As a result, a wide variety of newly generated magmatic rocks can in principle be produced from mantle rocks with different degrees of depletion. The results show that a variable geothermal gradient, the amount of extracted melt and plume excess temperature affect the magma production and chemistry by influencing decompression melting and the depletion of rocks. Decompression melting is facilitated by a shallower lithosphere-asthenosphere boundary and an increase in the amount of extracted magma is induced by a lower critical melt fraction for melt extraction and/or higher plume temperatures. Increasing critical melt fractions activates the extraction of melts triggered by decompression at a later stage and slows down the depletion process from the metasomatized mantle. Melt compositional trends are used to determine melting related processes by focusing on K2O/Na2O ratio as indicator for the rock type that has been molten. Thus, a step-like-profile in K2O/Na2O might be explained by a transition between melting metasomatized and pyrolitic mantle components reproducible through numerical modeling of a heterogeneous asthenospheric mantle source. A potential application of the developed method is shown for the West Eifel volcanic field.

A new approach to assess the chemical composition of powder deposits damaging the stone surfaces of historical monuments.

PubMed

Fermo, Paola; Turrion, Raquel Gonzalez; Rosa, Mario; Omegna, Alessandra

2015-04-01

The issue of conservation of the monumental heritage worldwide is mainly related to atmospheric pollution that causes the degradation of stone surfaces. The powder deposits present on the stone monuments reflect the composition of the aerosol particulate matter (PM) to which the surfaces are exposed, so the chemical characterization of the outermost damaged layers is necessary in order to adopt mitigation measurements to reduce PM emissions. In the present paper, a new analytical approach is proposed to investigate the chemical composition of powder deposits present on Angera stone, a dolomitic rock used in the Richini courtyard, a masterpiece of Lombard Baroque and placed in Milan. Inorganic and organic components present in these deposits have been analyzed by IC (ion chromatography) and a new approach mainly bases on thermal analyses, respectively. Gypsum is the main inorganic constituent indicating a composition similar to that of black crusts, hard black patina covering the degraded building surfaces. Ammonium nitrate present in the powder is able to react with the stone substrate to form magnesium nitrate which can migrate into the porous stone. The carbonaceous fraction powder deposits (i.e. OC = Organic Carbon and EC = Elemental Carbon) have been quantified by a new simple thermal approach based on carbon hydrogen nitrogen (CHN) analysis. The presence of high concentration of EC confirms that the powder deposits are evolving to black crust. Low values of water-soluble organic carbon (WSOC, determined by total organic carbon-TOC), with respect to what is normally found in PM, may indicate a migration process of organic substances into the stone with a worsening of the conservation conditions. The presence of heavy metals of anthropogenic origin and acting as catalysts in the black crust formation process has been highlighted by SEM-EDS (electron microscopy coupled with an energy dispersive spectrometer) as well.

Crystallization and Melt Removal at Arenal Volcano, Polytopic Vector Analysis

NASA Astrophysics Data System (ADS)

Hidalgo, P. J.; Vogel, T. A.; Bolge, L. L.; Ehrlich, R.; Alvarado, G. E.

2007-12-01

Tephra sequences ET3 and ET4 from Arenal volcano in Costa Rica have recently been interpreted to be a product of crystal fractionation by Bolge and coworkers in a series of papers (2004, 2006). The two tephra units are part of a sequence of 22 tephra units that represent a 7000 year span of the Arenal volcano activity. The tephro- stratigraphy has been described extensively by Melson (1982; 1994). The ET3 and ET4 tephras were interpreted (based on major- and trace-element, isotopic analyses of whole rocks and microchemical analyses of individual phases) as clear evidence of crystal separation by gravity settling (Bolge et al., 2004, 2006). The lower ET4 tephra sequence (andesitic and crystal poor) and the upper ET3 tephra (basaltic and crystal rich) represent an inverted snapshot of the magma chamber with contrasting geochemical properties. The ET3 sequence (deeper part of the magma chamber) has nearly constant composition with only a few elements varying stratigraphically (best represented by CaO). This is consistent with gradually decreasing amounts of melt in the upper part of ET3. The lower ET4 tephra (upper part of the magma chamber) contains large chemical gradients in both incompatible and compatible elements. In the present study we use whole-rock geochemical data from the recent tephra sequences ET3 and ET4 as inputs to Polytopic Vector Analysis (PVA) (for a review of this method see Vogel and coworkers, in press). With this method we produce a three end member solution that is consistent with crystallization of Olivine, plagioclase and pyroxene from the most mafic end member (EM1) resulting in a crystal rich mush zone. As crystallization progresses the compositions of the liquids are driven towards an intermediate end member (EM3), which has an intermediate composition liquid. At EM3 composition, rapid depletion of FeO, MgO and TiO2 by crystallization of Fe-Ti oxides, rapidly drives the liquid composition towards the silicic EM1 (incompatible element enriched end member). Using PVA we refine the interpretations of Bolge and coworkers and show that melt from the crystalline rich ET3 tephra was removed and ponded in the magma chamber above the crystalline mush (top part of ET4 unit). Thus when the eruption occurred the most evolved tephra (ET4) were deposited first followed by the least evolved tephra (ET3), which resulted in sampling of a chemically zoned magma chamber. Using PVA on stratigraphically controlled whole-rock analyses of tephra samples, we can unambiguously identify processes and end members that are involved in crystal accumulation and liquid separation processes. Thus PVA is a rigorous analytical tool that uses only whole-rock chemical data to produce robust results that can be used with other analytical techniques to test petrological models.

The metamorphic basement of the southern Sierra de Aconquija, Eastern Sierras Pampeanas: Provenance and tectonic setting of a Neoproterozoic back-arc basin

NASA Astrophysics Data System (ADS)

Cisterna, Clara Eugenia; Altenberger, Uwe; Mon, Ricardo; Günter, Christina; Gutiérrez, Antonio

2018-03-01

The Eastern Sierras Pampeanas are mainly composed of Neoproterozoic-early Palaeozoic metamorphic complexes whose protoliths were sedimentary sequences deposited along the western margin of Gondwana. South of the Sierra de Aconquija, Eastern Sierras Pampeanas, a voluminous metamorphic complex crops out. It is mainly composed of schists, gneisses, marbles, calk-silicate schists, thin layers of amphibolites intercalated with the marbles and granitic veins. The new data correlate the Sierra de Aconquija with others metamorphic units that crop out to the south, at the middle portion of the Sierra de Ancasti. Bulk rock composition reflects originally shales, iron rich shales, wackes, minor litharenites and impure limestones as its protoliths. Moreover, comparisons with the northern Sierra de Aconquija and from La Majada (Sierra de Ancasti) show similar composition. Amphibolites have a basaltic precursor, like those from the La Majada (Sierra de Ancasti) ones. The analyzed metamorphic sequence reflects low to moderate weathering conditions in the sediments source environment and their chemical composition would be mainly controlled by the tectonic setting of the sedimentary basin rather than by the secondary sorting and reworking of older deposits. The sediments composition reveal relatively low maturity, nevertheless the Fe - shale and the litharenite show a tendency of minor maturity among them. The source is related to an acid one for the litharenite protolith and a more basic to intermediate for the other rocks, suggesting a main derivation from intermediate to felsic orogen. The source of the Fe-shales may be related to and admixture of the sediments with basic components. Overall the composition point to an upper continental crust as the dominant sediment source for most of the metasedimentary rocks. The protolith of the amphibolites have basic precursors, related to an evolving back-arc basin. The chemical data in combination with the specific sediment association (wackes, shales, Fe-shales and minor litharenites) are characteristic for turbidity currents deposits along tectonically active region. They are also commonly associated with calcareous clays (marbles), commonly observed in the evolution of basins with slope and shelf derived carbonate turbidites. The amphibolites members are probably derived from lava-flows synchronous with the sedimentation during the basin evolution. The basin was controlled by a continental island arc possible evolving to a back-arc setting, as indicated for the mixed nature of the inferred source. The metasedimentary sequence from the Cuesta de La Chilca have petrographic, structural and strong chemical similarities, building a north-south striking belt from the north of the Sierra de Aconquija and to the south along the Sierra de Ancasti (La Majada area). The observed similarities allow to present this portion of the Eastern Sierras Pampeanas as a crustal block that records the sedimentary sequences developed along the geodynamic context of the southwestern margin of Gondwana during the Neoproterozoic and Early Palaeozoic.

Magma feeding system of Kutcharo and Mashu calderas, Hokkaido, Japan: Evidence of a common basaltic magma evolving into two distinct rock series

NASA Astrophysics Data System (ADS)

Miyagi, I.; Itoh, J.; Nguyen, H.

2009-12-01

Kutcharo and its adjacent Mashu volcanoes are located in NE Hokkaido, about 150 km west of the Kurile trench. The latest major activity of Kutcharo was 35 thousand years ago (termed KP I) produced about 50 km3 D.R.E, Mashu meanwhile became active after KP I. To understand the magma feeding system of adjoining but distinct Kutcharo (medium-K) and Mashu (low-K) volcanoes, we examined major and trace element, and Sr, Nd, and Pb isotopic compositions of whole rocks. We also studied phenocryst chemical zoning and chemical compositions of melt inclusions in phenocryst. The chemical results of melt inclusions show no distinction between medium- and low-K as being recognized in bulk rock chemistry of the volcanoes. Instead, the results form a smooth trend between low-K rock series and high-K rhyolitic melt end-member (as high as 5 wt. % K2O). There is no significant difference Sr, Nd and Pb isotopes between basalt and rhyolite suggesting genetic relationship. Moreover, the trace element distribution patterns show enrichment increasing gradually from the basalt to rhyolite via andesite indicating fractional crystallization evolution. Chemical zoning in plagioclase phenocryst in KP I (An 80-40) suggest that basaltic magma injected repeatedly into a voluminous felsic magma chamber of Kutcharo volcano. Chemical compositions of olivine phenocryst show that Kutcharo (Fo 86) was hotter as compared to Mashu (Fo 75). Application of MELTS program (Ghiorso and Sack, 1995) on composition of the basaltic melt end-member suggests that crystallization or subsequent re-melting of the basalt may produce medium- to high-K rhyolite melt, and mixing of the rhyolite with basalt may form the observed medium-K Kutcharo and low-K Mashu rock series. It is estimated that total volume of the basaltic magma supplied intermittently beneath the volcanoes was several folds to 10 times larger than the erupted rhyolite magma. And that the basalt injection may be more intensive beneath Kutcharo, leading to the formation of a thermal structure that has a peak at Kutcharo and lowers gradually toward Mashu. The thermal structure may explain the observed difference in erupted volumes and rock series between two volcanoes. This research project has been conducted under the research contract with Nuclear and Industrial Safety Agency (NISA).

Chemistry of decomposition of freshwater wetland sedimentary organic material during ramped pyrolysis

NASA Astrophysics Data System (ADS)

Williams, E. K.; Rosenheim, B. E.

2011-12-01

Ramped pyrolysis methodology, such as that used in the programmed-temperature pyrolysis/combustion system (PTP/CS), improves radiocarbon analysis of geologic materials devoid of authigenic carbonate compounds and with low concentrations of extractable authochthonous organic molecules. The approach has improved sediment chronology in organic-rich sediments proximal to Antarctic ice shelves (Rosenheim et al., 2008) and constrained the carbon sequestration potential of suspended sediments in the lower Mississippi River (Roe et al., in review). Although ramped pyrolysis allows for separation of sedimentary organic material based upon relative reactivity, chemical information (i.e. chemical composition of pyrolysis products) is lost during the in-line combustion of pyrolysis products. A first order approximation of ramped pyrolysis/combustion system CO2 evolution, employing a simple Gaussian decomposition routine, has been useful (Rosenheim et al., 2008), but improvements may be possible. First, without prior compound-specific extractions, the molecular composition of sedimentary organic matter is unknown and/or unidentifiable. Second, even if determined as constituents of sedimentary organic material, many organic compounds have unknown or variable decomposition temperatures. Third, mixtures of organic compounds may result in significant chemistry within the pyrolysis reactor, prior to introduction of oxygen along the flow path. Gaussian decomposition of the reaction rate may be too simple to fully explain the combination of these factors. To relate both the radiocarbon age over different temperature intervals and the pyrolysis reaction thermograph (temperature (°C) vs. CO2 evolved (μmol)) obtained from PTP/CS to chemical composition of sedimentary organic material, we present a modeling framework developed based upon the ramped pyrolysis decomposition of simple mixtures of organic compounds (i.e. cellulose, lignin, plant fatty acids, etc.) often found in sedimentary organic material to account for changes in thermograph shape. The decompositions will be compositionally verified by 13C NMR analysis of pyrolysis residues from interrupted reactions. This will allow for constraint of decomposition temperatures of individual compounds as well as chemical reactions between volatilized moieties in mixtures of these compounds. We will apply this framework with 13C NMR analysis of interrupted pyrolysis residues and radiocarbon data from PTP/CS analysis of sedimentary organic material from a freshwater marsh wetland in Barataria Bay, Louisiana. We expect to characterize the bulk chemical composition during pyrolysis and as well as diagenetic changes with depth. Most importantly, we expect to constrain the potential and the limitations of this modeling framework for application to other depositional environments.

The role of mantle-hybridization and crustal contamination in the petrogenesis of lithospheric mantle-derived alkaline rocks: constraints from Os and Hf isotopes

NASA Astrophysics Data System (ADS)

Mayer, B.; Jung, S.; Brauns, M.; Münker, C.

2018-06-01

The Rhön area as part of the Central European Volcanic Province (CEVP) hosts an unusual suite of Tertiary 24-Ma old hornblende-bearing alkaline basalts that provide insights into melting and fractionation processes within the lithospheric mantle. These chemically primitive to slightly evolved and isotopically (Sr, Nd, Pb) depleted basalts have slightly lower Hf isotopic compositions than respective other CEVP basalts and Os isotope compositions more radiogenic than commonly observed for continental intraplate alkaline basalts. These highly radiogenic initial 187Os/188Os ratios (0.268-0.892) together with their respective Sr-Nd-Pb isotopic compositions are unlikely to result from crustal contamination alone, although a lack of Os data for lower crustal rocks from the area and limited data for CEVP basalts or mantle xenoliths preclude a detailed evaluation. Similarly, melting of the same metasomatized subcontinental lithospheric mantle as inferred for other CEVP basalts alone is also unlikely, based on only moderately radiogenic Os isotope compositions obtained for upper mantle xenoliths from elsewhere in the province. Another explanation for the combined Nd, Sr and Os isotope data is that the lavas gained their highly radiogenic Os isotope composition through a mantle "hybridization", metasomatism process. This model involves a mafic lithospheric component, such as an intrusion of a sublithospheric primary alkaline melt or a melt derived from subducted oceanic material, sometime in the past into the lithospheric mantle where it metasomatized the ambient mantle. Later at 24 Ma, thermal perturbations during rifting forced the isotopically evolved parts of the mantle together with the peridotitic ambient mantle to melt. This yielded a package of melts with highly correlated Re/Os ratios and radiogenic Os isotope compositions. Subsequent movement through the crust may have further altered the Os isotope composition although this effect is probably minor for the majority of the samples based on radiogenic Nd and unradiogenic Sr isotope composition of the lavas. If the radiogenic Os isotope composition can be explained by a mantle-hybridization and metasomatism model, the isotopic compositions of the hornblende basalts can be satisfied by ca. 5-25% addition of the mafic lithospheric component to an asthenospheric alkaline magma. Although a lack of isotope data for all required endmembers make this model somewhat speculative, the results show that the Re-Os isotope system in continental basalts is able to distinguish between crustal contamination and derivation of continental alkaline lavas from isotopically evolved peridotitic lithosphere that was contaminated by mafic material in the past and later remelted during rifting. The Hf isotopic compositions are slightly less radiogenic than in other alkaline basalts from the province and indicate the derivation of the lavas from low Lu-Hf parts of the lithospheric mantle. The new Os and Hf isotope data constrain a new light of the nature of such metasomatizing agents, at least for these particular rocks, which represent within the particular volcanic complex the first product of the volcanism.

Method of forming a chemical composition

DOEpatents

Bingham, Dennis N.; Wilding, Bruce M.; Klingler, Kerry M.; Zollinger, William T.; Wendt, Kraig M.

2007-10-09

A method of forming a chemical composition such as a chemical hydride is described and which includes the steps of selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of hydrogen; and exposing the selected composition to an amount of ionizing radiation to encourage the changing of the chemical bonds of the selected composition, and chemically reacting the selected composition with the source of hydrogen to facilitate the formation of a chemical hydride.

CHEMICAL/BIOLOGICAL-CAPABLE RPA THREATS AND NATIONAL SECURITY IMPLICATIONS

DTIC Science & Technology

2016-02-07

iv Abstract The technological landscape of the 21st century is evolving at an ever-increasing pace . Autonomous remotely piloted...chemical and biological conventions must occur to address existing coverage gaps in an effort to keep pace with the ongoing advances of science and...21st century is evolving at an ever-increasing pace . Autonomous remotely piloted aircrafts (RPAs) continue to become increasingly sophisticated in

Method and System for Hydrogen Evolution and Storage

DOEpatents

Thorn, David L.; Tumas, William; Hay, P. Jeffrey; Schwarz, Daniel E.; Cameron, Thomas M.

2008-10-21

A method and system for storing and evolving hydrogen employ chemical compounds that can be hydrogenated to store hydrogen and dehydrogenated to evolve hydrogen. A catalyst lowers the energy required for storing and evolving hydrogen. The method and system can provide hydrogen for devices that consume hydrogen as fuel.

Formation mechanism of photo-induced nested wrinkles on siloxane-photomonomer hybrid film

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

Suzuki, Kazumasa; International Laboratory of Materials Science and Nanotechnology; Laboratorio di Scienz

Nested wrinkle structures, hierarchical surface wrinkles of different periodicities of sub-μm and tens-μm, have been fabricated on a siloxane-photomonomer hybrid film via a photo-induced surface polymerization of acrylamide. The formation mechanism of the nested wrinkle structures is examined based on a time-dependent structure observation and chemical composition analyses. In-situ observation of the evolving surface structure showed that sub-μm scale wrinkles first formed, subsequently the tens-μm scale ones did. In-situ FT-IR analysis indicated that the nested wrinkles formation took place along with the development of siloxane network of under layer. A cross sectional observation of the film revealed that the filmmore » was composed of three layers. FT-IR spectra of the film revealed that the surface and interior layers were polyacrylamide rich layer and siloxane-polymer rich layer, respectively. The intermediate layer formed as a diffusion layer by migration of acrylamide from interior to the surface. These three layers have different chemical compositions and therefore different mechanical characteristics, which allows the wrinkle formation. Shrinkage of siloxane-polymer interior layers, as a result of polycondensation of siloxane network, induced mechanical instabilities at interlayers, to form the nested wrinkle structures.« less

Performance of the Linear Ion Trap Mass Spectrometer for the Mars Organic Molecule Analyzer (MOMA) Investigation on the 2018 Exomars Rover

NASA Technical Reports Server (NTRS)

Arevalo, Ricardo, Jr.; Brinckerhoff, William B.; Pinnick, Veronica T.; van Amerom, Friso H. W.; Danell, Ryan M.; Li, Xiang; Getty, Stephanie; Hovmand, Lars; Atanassova, Martina; Mahaffy, Paul R.;

Clastic dikes of the Hatrurim basin (western flank of the Dead Sea) as natural analogues of alkaline concretes: Mineralogy, solution chemistry, and durability

NASA Astrophysics Data System (ADS)

Sokol, E. V.; Gaskova, O. L.; Kozmenko, O. A.; Kokh, S. N.; Vapnik, E. A.; Novikova, S. A.; Nigmatulina, E. N.

2014-11-01

This study shows that the mineral assemblages from clastic dikes in areas adjacent to the Dead Sea graben may be considered as natural analogues of alkaline concretes. The main infilling material of the clastic dikes is composed of well-sorted and well-rounded quartz sand. The cement of these hard rocks contains hydroxylapophyllite, tacharanite, calcium silicate hydrates, opal, calcite, and zeolite-like phases, which is indicative of a similarity of the natural cementation processes and industrial alkaline concrete production from quartz sands and industrial alkaline cements. The quartz grains exhibit a variety of reaction textures reflecting the interaction with alkaline solutions (opal and calcium hydrosilicate overgrowths; full replacement with apophyllite or thomsonite + apophyllite). The physicochemical analysis and reconstruction of the chemical composition of peralkaline Ca, Na, and K solutions that formed these assemblages reveal that the solutions evolved toward a more stable composition of zeolite-like phases, which are more resistant to long-term chemical weathering and atmospheric corrosion. The 40Ar/39Ar age of 6.2 ± 0.7 Ma obtained for apophyllite provides conclusive evidence for the high corrosion resistance of the assemblages consisting of apophyllite and zeolite-like phases.

Chemical Mapping of Vesta

NASA Technical Reports Server (NTRS)

Prettyman, Thomas H.; Mittlefehldt, D. W.; Yamashita, N.; Lawrence, D. J.; Beck, A. W.; McSween, H. Y.; Feldman, W. C.; McCoy, T. J.; Titus, T. N.; Toplis, M. J.;

Melt Inclusions Record Extreme Compositional Variability in Primitive Magmas at Mauna Loa Volcano, Hawaii

NASA Astrophysics Data System (ADS)

Kamenetsky, V. S.; Norman, M. D.; Garcia, M. O.

2002-12-01

Melt inclusions carry potentially unique information about magmatic processes and the compositional evolution of erupted lavas. Major element compositions of olivine-hosted melt inclusions in submarine tholeiitic picrites from the southwest rift zone of Mauna Loa volcano have been studied to examine the compositional variability of primitive magmas feeding the world's largest volcano. Approximately 600 naturally quenched inclusions were examined from 8 samples with 3-25 vol% olivine phenocrysts and 9-22 wt% MgO. Olivine compositions ranged from Fo91-Fo82. The inclusions show a continuous variation in FeO contents from near-magmatic values (9 to 11 wt%) in the most evolved olivines to extremely low values (3.5 to 7.0 wt%) in the most primitive olivines. This appears to reflect a complex magmatic history for these crystals involving extensive re-equlibration of melts trapped by early formed phenocrysts with their host olivine. Extreme compositional variability also characterizes incompatible elements that would not be affected by equilibration with the host olivine. Inclusions trapped in relatively primitive olivines (Fo88-91) show a large range of K2O contents (0.1 to 2.1 wt%), whereas inclusions in more evolved olivines converge on whole rock compositions with 0.3 to 0.4 wt% K2O. Similarly, TiO2/K2O, Na2O/K2O, and K2O/P2O5 ratios of inclusions in primitive olivines span a much larger range than do inclusions hosted by more evolved olivines, with TiO2/K2O ratios extending from enriched to depleted compositions (1.2 to 24.7) in primitive olivines, and converging on whole rock compositions (TiO2/K2O = 6-9) in more evolved host olivine. This points toward extreme compositional variability in melts feeding Mauna Loa, and effective mixing of these melt parcels in the shallower summit reservoir to produce the restricted range of whole rock compositions sampled by erupted lavas. Whole rock compositions, therefore provide an integrated view of melting and high-level mixing processes, whereas melt inclusions provide more detailed information about source characteristics.

Phase equilibria constraints on the chemical and physical evolution of the campanian ignimbrite

USGS Publications Warehouse

Fowler, S.J.; Spera, F.J.; Bohrson, W.A.; Belkin, H.E.; de Vivo, B.

2007-01-01

The Campanian Ignimbrite is a > 200 km3 trachyte-phonolite pyroclastic deposit that erupted at 39.3 ?? 0.1 ka within the Campi Flegrei west of Naples, Italy. Here we test the hypothesis that Campanian Ignimbrite magma was derived by isobaric crystal fractionation of a parental basaltic trachyandesitic melt that reacted and came into local equilibrium with small amounts (5-10 wt%) of crustal rock (skarns and foid-syenites) during crystallization. Comparison of observed crystal and magma compositions with results of phase equilibria assimilation-fractionation simulations (MELTS) is generally very good. Oxygen fugacity was approximately buffered along QFM+1 (where QFM is the quartz-fayalite-magnetite buffer) during isobaric fractionation at 0.15 GPa (???6 km depth). The parental melt, reconstructed from melt inclusion and host clinopyroxene compositions, is found to be basaltic trachyandesite liquid (51.1 wt% SiO2, 9.3 wt% MgO, 3 wt% H2O). A significant feature of phase equilibria simulations is the existence of a pseudo-invariant temperature, ???883??C, at which the fraction of melt remaining in the system decreases abruptly from ???0.5 to < 0.1. Crystallization at the pseudo-invariant point leads to abrupt changes in the composition, properties (density, dissolved water content), and physical state (viscosity, volume fraction fluid) of melt and magma. A dramatic decrease in melt viscosity (from 1700 Pa s to ???200 Pa s), coupled with a change in the volume fraction of water in magma (from ??? 0.1 to 0.8) and a dramatic decrease in melt and magma density acted as a destabilizing eruption trigger. Thermal models suggest a timescale of ??? 200 kyr from the beginning of fractionation until eruption, leading to an apparent rate of evolved magma generation of about 10-3 km3/year. In situ crystallization and crystal settling in density-stratified regions, as well as in convectively mixed, less evolved subjacent magma, operate rapidly enough to match this apparent volumetric rate of evolved magma production. ?? Copyright 2007 Oxford University Press.

Gravitational instabilities in a protosolar-like disc - I. Dynamics and chemistry

NASA Astrophysics Data System (ADS)

Evans, M. G.; Ilee, J. D.; Boley, A. C.; Caselli, P.; Durisen, R. H.; Hartquist, T. W.; Rawlings, J. M. C.

2015-10-01

To date, most simulations of the chemistry in protoplanetary discs have used 1 + 1D or 2D axisymmetric α-disc models to determine chemical compositions within young systems. This assumption is inappropriate for non-axisymmetric, gravitationally unstable discs, which may be a significant stage in early protoplanetary disc evolution. Using 3D radiative hydrodynamics, we have modelled the physical and chemical evolution of a 0.17 M⊙ self-gravitating disc over a period of 2000 yr. The 0.8 M⊙ central protostar is likely to evolve into a solar-like star, and hence this Class 0 or early Class I young stellar object may be analogous to our early Solar system. Shocks driven by gravitational instabilities enhance the desorption rates, which dominate the changes in gas-phase fractional abundances for most species. We find that at the end of the simulation, a number of species distinctly trace the spiral structure of our relatively low-mass disc, particularly CN. We compare our simulation to that of a more massive disc, and conclude that mass differences between gravitationally unstable discs may not have a strong impact on the chemical composition. We find that over the duration of our simulation, successive shock heating has a permanent effect on the abundances of HNO, CN and NH3, which may have significant implications for both simulations and observations. We also find that HCO+ may be a useful tracer of disc mass. We conclude that gravitational instabilities induced in lower mass discs can significantly, and permanently, affect the chemical evolution, and that observations with high-resolution instruments such as Atacama Large Millimeter/submillimeter Array (ALMA) offer a promising means of characterizing gravitational instabilities in protosolar discs.

Numerical modelling of multiphase multicomponent reactive transport in the Earth's interior

NASA Astrophysics Data System (ADS)

Oliveira, Beñat; Afonso, Juan Carlos; Zlotnik, Sergio; Diez, Pedro

2018-01-01

We present a conceptual and numerical approach to model processes in the Earth's interior that involve multiple phases that simultaneously interact thermally, mechanically and chemically. The approach is truly multiphase in the sense that each dynamic phase is explicitly modelled with an individual set of mass, momentum, energy and chemical mass balance equations coupled via interfacial interaction terms. It is also truly multicomponent in the sense that the compositions of the system and its constituent phases are expressed by a full set of fundamental chemical components (e.g. SiO2, Al2O3, MgO, etc.) rather than proxies. These chemical components evolve, react with and partition into different phases according to an internally consistent thermodynamic model. We combine concepts from Ensemble Averaging and Classical Irreversible Thermodynamics to obtain sets of macroscopic balance equations that describe the evolution of systems governed by multiphase multicomponent reactive transport (MPMCRT). Equilibrium mineral assemblages, their compositions and physical properties, and closure relations for the balance equations are obtained via a `dynamic' Gibbs free-energy minimization procedure (i.e. minimizations are performed on-the-fly as needed by the simulation). Surface tension and surface energy contributions to the dynamics and energetics of the system are taken into account. We show how complex rheologies, that is, visco-elasto-plastic, and/or different interfacial models can be incorporated into our MPMCRT ensemble-averaged formulation. The resulting model provides a reliable platform to study the dynamics and nonlinear feedbacks of MPMCRT systems of different nature and scales, as well as to make realistic comparisons with both geophysical and geochemical data sets. Several numerical examples are presented to illustrate the benefits and limitations of the model.

Stratigraphy, composition and form of the Deccan Basalts, Western Ghats, India

NASA Astrophysics Data System (ADS)

Beane, J. E.; Turner, C. A.; Hooper, P. R.; Subbarao, K. V.; Walsh, J. N.

1986-02-01

In the Western Ghats between latitudes 18° 20' N and 19° 15' N, 7000 km2 of Deccan Basalt have been mapped with the primary objective of establishing a flow stratigraphy as a guide to the volcanic history of the flood basalts. Using over 70 measured vertical sections, major and trace element analyses of nearly 1200 samples, and rare-earth and87Sr/86Sr determinations for over 60 samples, we divide the basalt into three subgroups and ten formations. In this paper we describe the seven principal formations in the area and the most prominent individual flows. The Kalsubai Subgroup is formed by the lower five formations, the Jawhar, Igatpuri, Neral, Thakurvadi, and Bhimashankar formations, from botton to top. In these formations amygdaloidal compound flows predominate and have a typically high MgO content, including picrite basalt (> 10% MgO) and picrite (> 18% MgO) with phenocrysts of olivine and clinopyroxene. These flows are separated by others which contain giant plagioclase phenocrysts and have more evolved chamical compositions. The Lonavala Subgroup overlies the Kalsubai and is composed of two formations, the Khandala and the Bushe. Both are readily recognized in the field and by their chemical compositions. The Wai Subgroup includes the upper three formations, the Poladpur, the Ambenali, and the Mahabaleshwar. The whole subgroup is composed of simple flows with well-developed flow tops, small phenocrysts of plagioclase, pyroxene and olivine, and relatively evolved bulk compositions. Distribution and variation in thickness of the straitigraphic units within the Western Ghats provide a first comprehensive view of the development of the Deccan volcanic edifice. The persistent southerly dip and gentle southerly plunging anticlinal form of the flows, the lensoid shape of many of the formations, and nearly randomly oriented feeder-dike system are together interpreted as evidence of a central volcanic edifice formed as the Indian plate drifted northward over a mantle plume or hot spot.

Evolution of sequence-defined highly functionalized nucleic acid polymers

NASA Astrophysics Data System (ADS)

Chen, Zhen; Lichtor, Phillip A.; Berliner, Adrian P.; Chen, Jonathan C.; Liu, David R.

2018-03-01

The evolution of sequence-defined synthetic polymers made of building blocks beyond those compatible with polymerase enzymes or the ribosome has the potential to generate new classes of receptors, catalysts and materials. Here we describe a ligase-mediated DNA-templated polymerization and in vitro selection system to evolve highly functionalized nucleic acid polymers (HFNAPs) made from 32 building blocks that contain eight chemically diverse side chains on a DNA backbone. Through iterated cycles of polymer translation, selection and reverse translation, we discovered HFNAPs that bind proprotein convertase subtilisin/kexin type 9 (PCSK9) and interleukin-6, two protein targets implicated in human diseases. Mutation and reselection of an active PCSK9-binding polymer yielded evolved polymers with high affinity (KD = 3 nM). This evolved polymer potently inhibited the binding between PCSK9 and the low-density lipoprotein receptor. Structure-activity relationship studies revealed that specific side chains at defined positions in the polymers are required for binding to their respective targets. Our findings expand the chemical space of evolvable polymers to include densely functionalized nucleic acids with diverse, researcher-defined chemical repertoires.

Method and system for hydrogen evolution and storage

DOEpatents

Thorn, David L.; Tumas, William; Hay, P. Jeffrey; Schwarz, Daniel E.; Cameron, Thomas M.

2012-12-11

A method and system for storing and evolving hydrogen (H.sub.2) employ chemical compounds that can be hydrogenated to store hydrogen and dehydrogenated to evolve hydrogen. A catalyst lowers the energy required for storing and evolving hydrogen. The method and system can provide hydrogen for devices that consume hydrogen as fuel.

Investigating Evolved Compositions Around Wolf Crater

NASA Technical Reports Server (NTRS)

Greenhagen, B. T.; Cahill, J. T. S.; Jolliff, B. L.; Lawrence, S. J.; Glotch, T. D.

2017-01-01

Wolf crater is an irregularly shaped, approximately 25 km crater in the south-central portion of Mare Nubium on the lunar nearside. While not previously identified as a lunar "red spot", Wolf crater was identified as a Th anomaly by Lawrence and coworkers. We have used data from the Lunar Reconnaissance Orbiter (LRO) to determine the area surrounding Wolf crater has composition more similar to highly evolved, non-mare volcanic structures than typical lunar crustal lithology. In this presentation, we will investigate the geomorphology and composition of the Wolf crater and discuss implications for the origin of the anomalous terrain.

Lavas and Sills in the Ferrar Large Igneous Province: Field and Geochemical Evidence for the Order of Emplacement.

NASA Astrophysics Data System (ADS)

Elliot, D. H.; Fleming, T. H.

2005-12-01

Many large igneous provinces, particularly those associated with Gondwana break-up, include major sill complexes as well as flood basalt fields. In the Ferrar province, radiometric dates of lavas and sills are indistinguishable. Nevertheless, in north Victoria Land (NVL) field evidence suggests the lavas had to have been erupted first in order to create the overburden needed for emplacement at shallow depths of thick sills, lacking vesicles, in a thin (100 m) Upper Triassic sedimentary sequence overlying basement. Elsewhere in the Transantarctic Mountains sills occur almost exclusively in a thick (2-2.5 km) Devonian-Triassic sedimentary sequence (Beacon Supergroup) that was possibly capped by 500+m of lavas before sill emplacement. For south Victoria Land (SVL), Marsh (2004) proposed that the most evolved rocks were erupted first as lavas, and sills were emplaced at progressively greater depth as increasingly more magnesian magmas and crystal mushes were injected into supracrustal and finally basement rocks. In NVL most lavas have MgO between 6-8% with a few as low as 4.5% MgO, whereas analyzed chilled margins of sills range from 3.7-5.6% MgO. In the Prince Albert Mountains (PAM), SVL, lava and sill compositions overlap (3.9-7.3% MgO). In the greater Dry Valleys region (SVL) lavas at Carapace Nunatak range from 3.6-6.7% MgO; chilled margins of Dry Valleys sills range from about 4.2 to 7.2% MgO. In the Queen Alexandra Range, central Transantarctic Mountains (CTM), lavas are predominantly 2.6-5.7% MgO; sills in the region range from 4.5% to 10.7% MgO. In the Otway Massif region (head of the Shackleton Glacier, CTM) most lavas are strongly evolved (2.7-3.4% MgO); sills in the Shackleton Glacier region range from 4.3-7.3% MgO. Nowhere do lavas show unequivocal systematic temporal change in MgO, and notably in CTM the initial flows are the most mafic (7.5-8.0% MgO). Olivine dolerite sills (chilled margins: -9% MgO) tend to occur low in the stratigraphic section. Except for NVL where Beacon strata exposures are limited, sills are thicker (100-200 m) and more regular in lower stratigraphic levels. Sills with orthopyroxene crystal-mush tongues are not known outside the Dry Valleys except perhaps the Warren Range (SVL). No province-wide systematic relationship is apparent between compositions of lavas and sill chilled margins. Nevertheless, in CTM most lavas are significantly more evolved than the sills; within the sills there is no clear relationship between MgO and stratigraphy, and some less evolved compositions occur at relatively high stratigraphic levels. In SVL compositional overlap is almost complete; locally, cross-cutting relations show more mafic sills and sheets cutting less mafic compositions. In NVL the chemical relations between lavas and sills are opposite from those that have been advocated for SVL. Interpretation is compounded by sills that exchange stratigraphic position or climb stratigraphically. Factors affecting magma emplacement include magma density, lithostatic pressure, overpressures required for lateral emplacement, and rock physical properties; when and where the evolving source was tapped may play an equal role in the emplacement order. Further, detailed work on the sills will show whether crystallization might have yielded lower density residual liquids that could have migrated and formed distal fingers of sills or migrated to higher stratigraphic levels.

Structural evolution of detonation carbon in composition B by X-ray scattering

DOE PAGES

Firestone, Millicent A.; Dattelbaum, Dana M.; Podlesak, David W.; ...

2015-01-01

Products evolved during the detonation of high explosives are primarily a collection of molecular gases and solid carbon condensates. Electron microscopy studies have revealed that detonation carbon (soot) can contain a variety of unique carbon particles possessing novel morphologies, such as carbon onions and ribbons. Despite these observations very little is known about the conditions that leads to the production of these novel carbon nanoparticles. A fuller understanding on conditions that generate such nanoparticles would greatly benefit from time-resolved studies that probe particle formation and evolution through and beyond the chemical reaction zone. Herein, we report initial results employing time-resolvedmore » X-ray scattering (TRSAXS) measurements to monitor nanosecond time-scale carbon products formed from detonating Composition B (60% TNT, 40% RDX). These studies were performed at the Dynamic Compression Sector (DCS, Sector 35) at the Advanced Photon Source (Argonne National Laboratory). Lastly, analysis of the collected scattering patterns reveals the presence of fractal multi-layered carbon condensates.« less

Convection induced by thermal gradients on thin reaction fronts

NASA Astrophysics Data System (ADS)

Ruelas Paredes, David R. A.; Vasquez, Desiderio A.

2017-09-01

We present a thin front model for the propagation of chemical reaction fronts in liquids inside a Hele-Shaw cell or porous media. In this model we take into account density gradients due to thermal and compositional changes across a thin interface. The front separating reacted from unreacted fluids evolves following an eikonal relation between the normal speed and the curvature. We carry out a linear stability analysis of convectionless flat fronts confined in a two-dimensional rectangular domain. We find that all fronts are stable to perturbations of short wavelength, but they become unstable for some wavelengths depending on the values of compositional and thermal gradients. If the effects of these gradients oppose each other, we observe a range of wavelengths that make the flat front unstable. Numerical solutions of the nonlinear model show curved fronts of steady shape with convection propagating faster than flat fronts. Exothermic fronts increase the temperature of the fluid as they propagate through the domain. This increment in temperature decreases with increasing speed.

Structural evolution of detonation carbon in composition B by X-ray scattering

NASA Astrophysics Data System (ADS)

Firestone, Millicent A.; Dattelbaum, Dana M.; Podlesak, David W.; Gustavsen, Richard L.; Huber, Rachel C.; Ringstrand, Bryan S.; Watkins, Erik B.; Jensen, Brian; Willey, Trevor; Lauderbauch, Lisa; Hodgin, Ralph; Bagge-Hansen, Michael; van Buuren, Tony; Seifert, Sönke; Graber, Timothy

2017-01-01

Products evolved during the detonation of high explosives are primarily a collection of molecular gases and solid carbon condensates. Electron microscopy studies have revealed that detonation carbon (soot) can contain a variety of unique carbon particles possessing novel morphologies, such as carbon onions and ribbons. Despite these observations very little is known about the conditions that leads to the production of these novel carbon nanoparticles. A fuller understanding on conditions that generate such nanoparticles would greatly benefit from time-resolved studies that probe particle formation and evolution through and beyond the chemical reaction zone. Herein, we report initial results employing time-resolved X-ray scattering (TRSAXS) measurements to monitor nanosecond time-scale carbon products formed from detonating Composition B (60% TNT, 40% RDX). These studies were performed at the Dynamic Compression Sector (DCS, Sector 35) at the Advanced Photon Source (Argonne National Laboratory). Analysis of the collected scattering patterns reveals the presence of fractal multi-layered carbon condensates.

Study of composition change and agglomeration of flue gas cleaning residue from a fluidized bed waste incinerator.

PubMed

Lievens, P; Verbinnen, B; Bollaert, P; Alderweireldt, N; Mertens, G; Elsen, J; Vandecasteele, C

2011-10-01

Blocking of the collection hoppers of the baghouse filters in a fluidized bed incinerator for co-incineration of high calorific industrial solid waste and sludge was observed. The composition of the flue gas cleaning residue (FGCR), both from a blocked hopper and from a normal hopper, was investigated by (differential) thermogravimetric analysis, quantitative X-ray powder diffraction and wet chemical analysis. The lower elemental carbon concentration and the higher calcium carbonate concentration of the agglomerated sample was the result of oxidation of carbon and subsequent reaction of CO2 with CaO. The evolved heat causes a temperature increase, with the decomposition of CaOHCl as a consequence. The formation of calcite and calcium chloride and the evolution of heat caused agglomeration of the FGCR. Activated lignite coke was replaced by another adsorption agent with less carbon, so the auto-ignition temperature increased; since then no further block formation has occurred.

Surface modification of biomaterials using plasma immersion ion implantation and deposition

PubMed Central

Lu, Tao; Qiao, Yuqin; Liu, Xuanyong

2012-01-01

Although remarkable progress has been made on biomaterial research, the ideal biomaterial that satisfies all the technical requirements and biological functions is not available up to now. Surface modification seems to be a more economic and efficient way to adjust existing conventional biomaterials to meet the current and ever-evolving clinical needs. From an industrial perspective, plasma immersion ion implantation and deposition (PIII&D) is an attractive method for biomaterials owing to its capability of treating objects with irregular shapes, as well as the control of coating composition. It is well acknowledged that the physico-chemical characteristics of biomaterials are the decisive factors greatly affecting the biological responses of biomaterials including bioactivity, haemocompatibility and antibacterial activity. Here, we mainly review the recent advances in surface modification of biomaterials via PIII&D technology, especially titanium alloys and polymers used for orthopaedic, dental and cardiovascular implants. Moreover, the variations of biological performances depending on the physico-chemical properties of modified biomaterials will be discussed. PMID:23741609

Robust numerical simulation of porosity evolution in chemical vapor infiltration III: three space dimension

NASA Astrophysics Data System (ADS)

Jin, Shi; Wang, Xuelei

2003-04-01

Chemical vapor infiltration (CVI) process is an important technology to fabricate ceramic matrix composites (CMC's). In this paper, a three-dimension numerical model is presented to describe pore microstructure evolution during the CVI process. We extend the two-dimension model proposed in [S. Jin, X.L. Wang, T.L. Starr, J. Mater. Res. 14 (1999) 3829; S. Jin. X.L. Wang, T.L. Starr, X.F. Chen, J. Comp. Phys. 162 (2000) 467], where the fiber surface is modeled as an evolving interface, to the three space dimension. The 3D method keeps all the virtue of the 2D model: robust numerical capturing of topological changes of the interface such as the merging, and fast detection of the inaccessible pores. For models in the kinetic limit, where the moving speed of the interface is constant, some numerical examples are presented to show that this three-dimension model will effectively track the change of porosity, close-off time, location and shape of all pores.

From Astrochemistry to prebiotic chemistry? An hypothetical approach toward Astrobiology

NASA Astrophysics Data System (ADS)

Le Sergeant d'Hendecourt, L.; Danger, G.

2012-12-01

We present in this paper a general perspective about the evolution of molecular complexity, as observed from an astrophysicist point of view and its possible relation to the problem of the origin of life on Earth. Based on the cosmic abundances of the elements and the molecular composition of our life, we propose that life cannot really be based on other elements. We discuss where the necessary molecular complexity is built-up in astrophysical environments, actually within inter/circumstellar solid state materials known as ``grains''. Considerations based on non-directed laboratory experiments, that must be further extended in the prebiotic domain, lead to the hypothesis that if the chemistry at the origin of life may indeed be a rather universal and deterministic phenomenon, once molecular complexity is installed, the chemical evolution that generated the first prebiotic reactions that involve autoreplication must be treated in a systemic approach because of the strong contingency imposed by the complex local environment(s) and associated processes in which these chemical systems have evolved.

Coronal Elemental Abundances in Solar Emerging Flux Regions

NASA Astrophysics Data System (ADS)

Baker, Deborah; Brooks, David H.; van Driel-Gesztelyi, Lidia; James, Alexander W.; Démoulin, Pascal; Long, David M.; Warren, Harry P.; Williams, David R.

2018-03-01

The chemical composition of solar and stellar atmospheres differs from the composition of their photospheres. Abundances of elements with low first ionization potential (FIP) are enhanced in the corona relative to high-FIP elements with respect to the photosphere. This is known as the FIP effect and it is important for understanding the flow of mass and energy through solar and stellar atmospheres. We used spectroscopic observations from the Extreme-ultraviolet Imaging Spectrometer on board the Hinode observatory to investigate the spatial distribution and temporal evolution of coronal plasma composition within solar emerging flux regions inside a coronal hole. Plasma evolved to values exceeding those of the quiet-Sun corona during the emergence/early-decay phase at a similar rate for two orders of magnitude in magnetic flux, a rate comparable to that observed in large active regions (ARs) containing an order of magnitude more flux. During the late-decay phase, the rate of change was significantly faster than what is observed in large, decaying ARs. Our results suggest that the rate of increase during the emergence/early-decay phase is linked to the fractionation mechanism that leads to the FIP effect, whereas the rate of decrease during the later decay phase depends on the rate of reconnection with the surrounding magnetic field and its plasma composition.

Chemical Evolution in Silicon–Graphite Composite Anodes Investigated by Vibrational Spectroscopy

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

Ruther, Rose E.; Hays, Kevin A.; An, Seong Jin

Silicon–graphite composites are under development for the next generation of high-capacity lithium-ion anodes, and vibrational spectroscopy is a powerful tool to identify the different mechanisms that contribute to performance loss. With alloy anodes, the underlying causes of cell failure are significantly different in half-cells with lithium metal counter electrodes compared to full cells with standard cathodes. However, most studies which take advantage of vibrational spectroscopy have only examined half-cells. In this work, a combination of FTIR and Raman spectroscopy describes several factors that lead to degradation in full pouch cells with LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) cathodes. The spectroscopicmore » signatures evolve after longer term cycling compared to the initial formation cycles. Several side-reactions that consume lithium ions have clear FTIR signatures, and comparison to a library of reference compounds facilitates identification. Raman microspectroscopy combined with mapping shows that the composite anodes are not homogeneous but segregate into graphite-rich and silicon-rich phases. Lithiation does not proceed uniformly either. A basis analysis of Raman maps identifies electrochemically inactive regions of the anodes. In conclusion, the spectroscopic results presented here emphasize the importance of improving electrode processing and SEI stability to enable practical composite anodes with high silicon loadings.« less

Chemical Evolution in Silicon–Graphite Composite Anodes Investigated by Vibrational Spectroscopy

DOE PAGES

Ruther, Rose E.; Hays, Kevin A.; An, Seong Jin; ...

2018-05-24

Silicon–graphite composites are under development for the next generation of high-capacity lithium-ion anodes, and vibrational spectroscopy is a powerful tool to identify the different mechanisms that contribute to performance loss. With alloy anodes, the underlying causes of cell failure are significantly different in half-cells with lithium metal counter electrodes compared to full cells with standard cathodes. However, most studies which take advantage of vibrational spectroscopy have only examined half-cells. In this work, a combination of FTIR and Raman spectroscopy describes several factors that lead to degradation in full pouch cells with LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) cathodes. The spectroscopicmore » signatures evolve after longer term cycling compared to the initial formation cycles. Several side-reactions that consume lithium ions have clear FTIR signatures, and comparison to a library of reference compounds facilitates identification. Raman microspectroscopy combined with mapping shows that the composite anodes are not homogeneous but segregate into graphite-rich and silicon-rich phases. Lithiation does not proceed uniformly either. A basis analysis of Raman maps identifies electrochemically inactive regions of the anodes. In conclusion, the spectroscopic results presented here emphasize the importance of improving electrode processing and SEI stability to enable practical composite anodes with high silicon loadings.« less

Europa's Compositional Evolution and Ocean Salinity

NASA Astrophysics Data System (ADS)

Vance, S.; Glein, C.; Bouquet, A.; Cammarano, F.; McKinnon, W. B.

2017-12-01

Europa's ocean depth and composition have likely evolved through time, in step with the temperature of its mantle, and in concert with the loss of water and hydrogen to space and accretion of water and other chemical species from comets, dust, and Io's volcanism. A key aspect to understanding the consequences of these processes is combining internal structure models with detailed calculations of ocean composition, which to date has not been done. This owes in part to the unavailability of suitable thermodynamic databases for aqueous chemistry above 0.5 GPa. Recent advances in high pressure aqueous chemistry and water-rock interactions allow us to compute the equilibrium ionic conditions and pH everywhere in Europa's interior. In this work, we develop radial structure and composition models for Europa that include self-consistent thermodynamics of all materials, developed using the PlanetProfile software. We will describe the potential hydration states and porosity of the rocky interior, and the partitioning of primordial sulfur between this layer, an underlying metallic core, and the ocean above. We will use these results to compute the ocean's salinity by extraction from the upper part of the rocky layer. In this context, we will also consider the fluxes of reductants from Europa's interior due to high-temperature hydrothermalism, serpentinization, and endogenic radiolysis.

NGC 6067: a young and massive open cluster with high metallicity

NASA Astrophysics Data System (ADS)

Alonso-Santiago, J.; Negueruela, I.; Marco, A.; Tabernero, H. M.; González-Fernández, C.; Castro, N.

2017-08-01

NGC 6067 is a young open cluster hosting the largest population of evolved stars among known Milky Way clusters in the 50-150 Ma age range. It thus represents the best laboratory in our Galaxy to constrain the evolutionary tracks of 5-7 M⊙ stars. We have used high-resolution spectra of a large sample of bright cluster members (45), combined with archival photometry, to obtain accurate parameters for the cluster as well as stellar atmospheric parameters. We derive a distance of 1.78 ± 0.12 kpc, an age of 90 ± 20 Ma and a tidal radius of 14.8^{+6.8}_{-3.2} arcmin. We estimate an initial mass above 5700 M⊙, for a present-day evolved population of two Cepheids, two A supergiants and 12 red giants with masses ≈6 M⊙. We also determine chemical abundances of Li, O, Na, Mg, Si, Ca, Ti, Ni, Rb, Y and Ba for the red clump stars. We find a supersolar metallicity, [Fe/H] = +0.19 ± 0.05, and a homogeneous chemical composition, consistent with the Galactic metallicity gradient. The presence of a Li-rich red giant, star 276 with A(Li) = 2.41, is also detected. An overabundance of Ba is found, supporting the enhanced s-process. The ratio of yellow to red giants is much smaller than 1, in agreement with models with moderate overshooting, but the properties of the cluster Cepheids do not seem consistent with current Padova models for supersolar metallicity.

Compositional variation in minerals of the chevkinite group

USGS Publications Warehouse

Macdonald, R.; Belkin, H.E.

2002-01-01

The composition of chevkinite and perrierite, the most common members of the chevkinite group, is closely expressed by the formula A4BC2D2Si4O22, where A = (La,Ce,Ca,Sr,Th), B = Fe2+, C = (Fe2+,Fe3+,Ti,Al,Zr,Nb) and D = Ti. The A site is dominated by a strong negative correlation between (Ca+Sr) and the REE. Chondrite-normalized REE patterns are very variable, e.g. in LREE/HREE and Eu/Eu*. The C site is dominated by Ti, Al and Fe2+, in very variable proportions. Most chevkinites and perrierites are close to stoichiometric, with cation sums between 12.9 and 13.5, compared to the theoretical 13. There is no single, generally applicable charge balancing substitution scheme in the group; however, the general relationship (Ca+Sr)A + TiC + REEA + M3C+2+ defines a linear array with r2 = 0.91. Chevkinite and perrierite are shown to be compositionally distinct on the basis of CaO, FeO* Al2O3 and Ce2O3 abundances. Chevkinite forms mainly in chemically evolved parageneses, such as syenites, rhyolites and fenites associated with carbonatite complexes. Perrierite is more commonly recorded from igneous rocks of mafic to intermediate composition. The compositional characteristics and possible structural formulae of other members of the chevkinite group are reviewed briefly.

Environmental degradation of composites for marine structures: new materials and new applications

PubMed Central

2016-01-01

This paper describes the influence of seawater ageing on composites used in a range of marine structures, from boats to tidal turbines. Accounting for environmental degradation is an essential element in the multi-scale modelling of composite materials but it requires reliable test data input. The traditional approach to account for ageing effects, based on testing samples after immersion for different periods, is evolving towards coupled studies involving strong interactions between water diffusion and mechanical loading. These can provide a more realistic estimation of long-term behaviour but still require some form of acceleration if useful data, for 20 year lifetimes or more, are to be obtained in a reasonable time. In order to validate extrapolations from short to long times, it is essential to understand the degradation mechanisms, so both physico-chemical and mechanical test data are required. Examples of results from some current studies on more environmentally friendly materials including bio-sourced composites will be described first. Then a case study for renewable marine energy applications will be discussed. In both cases, studies were performed first on coupons at the material level, then during structural testing and analysis of large components, in order to evaluate their long-term behaviour. This article is part of the themed issue ‘Multiscale modelling of the structural integrity of composite materials’. PMID:27242304

Highly evolved rhyolitic glass compositions from the Toba Caldera, Sumatra

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

Chesner, C.A.

1985-01-01

The quartz latite to rhyolitic ash flow tuffs erupted form the Toba Caldera, perhaps the largest caldera on earth (100 by 30 kms), provide the unique opportunity to study a highly differentiated liquid in equilibrium with numerous mineral phases. Not only are the rocks very crystal rich (30-50%), but at present a minimum of 15 co-existing mineral phases have been identified. Both whole-rock and glass analyses were made by XRF techniques providing data on both major and trace elements. Whole rock chemistry of individual pumices from the youngest eruption at Toba (75,000 years ago), are suggestive of the eruption ofmore » two magma compositions across a boundary layer in the magma chamber. Glass chemistry of the pumices also show two distinct liquid compositions. The more silicic pumices, which have the most evolved glass compositions, are similar to the whole rock chemistry of the few aplitic pumices and cognate granitic xenoliths that were collected. This highly evolved composition resulted from the removal of up to 15 mineral phases and may be a fractionation buffered, univariant composition. The glasses from the less silicic pumices are similar to the whole rock chemistry of the more silicic pumice, thus falling nicely on a fractionation trend towards the univariant composition for these rocks. This set of glass compositions allows an independent test for the origin of distal ashes thought to have erupted from Toba and deposited in Malaysia, the Indian Ocean, and as far away as India.« less

SmallSat Spinning Lander with a Raman Spectrometer Payload for Future Ocean Worlds Exploration Missions

NASA Technical Reports Server (NTRS)

Ridenoure, R.; Angel, S. M.; Aslam, S.; Gorius, N.; Hewagama, T.; Nixon, C. A.; Sharma, S.

2017-01-01

We describe an Evolved Expendable Launch Vehicle Secondary Payload Adapter (ESPA)-class SmallSat spinning lander concept for the exploration of Europa or other Ocean World surfaces to ascertain the potential for life. The spinning lander will be ejected from an ESPA ring from an orbiting or flyby spacecraft and will carry on-board a standoff remote Spatial Heterodyne Raman spectrometer (SHRS) and a time resolved laser induced fluorescence spectrograph (TR-LIFS), and once landed and stationary the instruments will make surface chemical measurements. The SHRS and TR-LIFS have no moving parts have minimal mass and power requirements and will be able to characterize the surface and near-surface chemistry, including complex organic chemistry to constrain the ocean composition.

SmallSat Spinning Lander with a Raman Spectrometer Payload for Future Ocean Worlds Exploration Missions

NASA Astrophysics Data System (ADS)

Ridenoure, R.; Angel, S. M.; Aslam, S.; Gorius, N.; Hewagama, T.; Nixon, C. A.; Sharma, S.

2017-09-01

We describe an Evolved Expendable Launch Vehicle Secondary Payload Adapter (ESPA)-class SmallSat spinning lander concept for the exploration of Europa or other Ocean World surfaces to ascertain the potential for life. The spinning lander will be ejected from an ESPA ring from an orbiting or flyby spacecraft and will carry on-board a standoff remote Spatial Heterodyne Raman spectrometer (SHRS) and a time resolved laser induced fluorescence spectrograph (TR-LIFS), and once landed and stationary the instruments will make surface chemical measurements. The SHRS and TR-LIFS have no moving parts have minimal mass and power requirements and will be able to characterize the surface and near-surface chemistry, including complex organic chemistry to constrain the ocean composition.

Molecular Diagnostics of the Interstellar Medium and Star Forming Regions

NASA Astrophysics Data System (ADS)

Hartquist, T. W.; Dalgarno, A.

1996-03-01

Selected examples of the use of observationally inferred molecular level populations and chemical compositions in the diagnosis of interstellar sources and processes important in them (and in other diffuse astrophysical sources) are given. The sources considered include the interclump medium of a giant molecular cloud, dark cores which are the progenitors of star formation, material responding to recent star formation and which may form further stars, and stellar ejecta (including those of supernovae) about to merge with the interstellar medium. The measurement of the microwave background, mixing of material between different nuclear burning zones in evolved stars and turbulent boundary layers (which are present in and influence the structures and evolution of all diffuse astrophysical sources) are treated.

A numerical determination of the evolution of cloud drop spectra due to condensation on natural aerosol particles

NASA Technical Reports Server (NTRS)

Lee, I. Y.; Haenel, G.; Pruppacher, H. R.

1980-01-01

The time variation in size of aerosol particles growing by condensation is studied numerically by means of an air parcel model which allows entrainment of air and aerosol particles. Particles of four types of aerosols typically occurring in atmospheric air masses were considered. The present model circumvents any assumption about the size distribution and chemical composition of the aerosol particles by basing the aerosol particle growth on actually observed size distributions and on observed amounts of water taken up under equilibrium by a deposit of the aerosol particles. Characteristic differences in the drop size distribution, liquid water content and supersaturation were found for the clouds which evolved from the four aerosol types considered.

Container and method for absorbing and reducing hydrogen concentration

DOEpatents

Wicks, George G.; Lee, Myung W.; Heung, Leung K.

2001-01-01

A method for absorbing hydrogen from an enclosed environment comprising providing a vessel; providing a hydrogen storage composition in communication with a vessel, the hydrogen storage composition further comprising a matrix defining a pore size which permits the passage of hydrogen gas while blocking the passage of gaseous poisons; placing a material within the vessel, the material evolving hydrogen gas; sealing the vessel; and absorbing the hydrogen gas released into the vessel by the hydrogen storage composition. A container for absorbing evolved hydrogen gas comprising: a vessel having an interior and adapted for receiving materials which release hydrogen gas; a hydrogen absorbing composition in communication with the interior, the composition defining a matrix surrounding a hydrogen absorber, the matrix permitting the passage of hydrogen gas while excluding gaseous poisons; wherein, when the vessel is sealed, hydrogen gas, which is released into the vessel interior, is absorbed by the hydrogen absorbing composition.

Designing bioinspired composite reinforcement architectures via 3D magnetic printing

NASA Astrophysics Data System (ADS)

Martin, Joshua J.; Fiore, Brad E.; Erb, Randall M.

2015-10-01

Discontinuous fibre composites represent a class of materials that are strong, lightweight and have remarkable fracture toughness. These advantages partially explain the abundance and variety of discontinuous fibre composites that have evolved in the natural world. Many natural structures out-perform the conventional synthetic counterparts due, in part, to the more elaborate reinforcement architectures that occur in natural composites. Here we present an additive manufacturing approach that combines real-time colloidal assembly with existing additive manufacturing technologies to create highly programmable discontinuous fibre composites. This technology, termed as `3D magnetic printing', has enabled us to recreate complex bioinspired reinforcement architectures that deliver enhanced material performance compared with monolithic structures. Further, we demonstrate that we can now design and evolve elaborate reinforcement architectures that are not found in nature, demonstrating a high level of possible customization in discontinuous fibre composites with arbitrary geometries.

Designing bioinspired composite reinforcement architectures via 3D magnetic printing.

PubMed

Martin, Joshua J; Fiore, Brad E; Erb, Randall M

2015-10-23

Discontinuous fibre composites represent a class of materials that are strong, lightweight and have remarkable fracture toughness. These advantages partially explain the abundance and variety of discontinuous fibre composites that have evolved in the natural world. Many natural structures out-perform the conventional synthetic counterparts due, in part, to the more elaborate reinforcement architectures that occur in natural composites. Here we present an additive manufacturing approach that combines real-time colloidal assembly with existing additive manufacturing technologies to create highly programmable discontinuous fibre composites. This technology, termed as '3D magnetic printing', has enabled us to recreate complex bioinspired reinforcement architectures that deliver enhanced material performance compared with monolithic structures. Further, we demonstrate that we can now design and evolve elaborate reinforcement architectures that are not found in nature, demonstrating a high level of possible customization in discontinuous fibre composites with arbitrary geometries.

Molecular Diversity of Sea Spray Aerosol Particles: Impact of Ocean Biology on Particle Composition and Hygroscopicity

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

Cochran, Richard E.; Laskina, Olga; Trueblood, Jonathan V.

The impact of sea spray aerosol (SSA) on climate depends on the size and chemical composition of individual particles that make-up the total SSA ensemble. While the organic fraction of SSA has been characterized from a bulk perspective, there remains a lack of understanding as to the composition of individual particles within the SSA ensemble. To better understand the molecular components within SSA particles and how SSA composition changes with ocean biology, simultaneous measurements of seawater and SSA were made during a month-long mesocosm experiment performed in an ocean-atmosphere facility. Herein, we deconvolute the composition of freshly emitted SSA devoidmore » of anthropogenic and terrestrial influences by characterizing classes of organic compounds as well as specific molecules within individual SSA particles. Analysis of SSA particles show that the diversity of molecules within the organic fraction varies between two size fractions (submicron and supermicron) with contributions from fatty acids, monosaccharides, polysaccharides and siliceous material. Significant changes in the distribution of these compounds within individual particles are observed to coincide with the rise and fall of phytoplankton and bacterial populations within the seawater. Furthermore, water uptake is impacted as shown by hygroscopicity measurements of model systems composed of representative organic compounds. Thus, the how changes in the hygroscopic growth of SSA evolves with composition can be elucidated. Overall, this study provides an important connection between biological processes that control the composition of seawater and changes in single particle composition which will enhances our ability to predict the impact of SSA on climate.« less

Single Particle Analysis by Combined Chemical Imaging to Study Episodic Air Pollution Events in Vienna

NASA Astrophysics Data System (ADS)

Ofner, Johannes; Eitenberger, Elisabeth; Friedbacher, Gernot; Brenner, Florian; Hutter, Herbert; Schauer, Gerhard; Kistler, Magdalena; Greilinger, Marion; Lohninger, Hans; Lendl, Bernhard; Kasper-Giebl, Anne

2017-04-01

The aerosol composition of a city like Vienna is characterized by a complex interaction of local emissions and atmospheric input on a regional and continental scale. The identification of major aerosol constituents for basic source appointment and air quality issues needs a high analytical effort. Exceptional episodic air pollution events strongly change the typical aerosol composition of a city like Vienna on a time-scale of few hours to several days. Analyzing the chemistry of particulate matter from these events is often hampered by the sampling time and related sample amount necessary to apply the full range of bulk analytical methods needed for chemical characterization. Additionally, morphological and single particle features are hardly accessible. Chemical Imaging evolved to a powerful tool for image-based chemical analysis of complex samples. As a complementary technique to bulk analytical methods, chemical imaging can address a new access to study air pollution events by obtaining major aerosol constituents with single particle features at high temporal resolutions and small sample volumes. The analysis of the chemical imaging datasets is assisted by multivariate statistics with the benefit of image-based chemical structure determination for direct aerosol source appointment. A novel approach in chemical imaging is combined chemical imaging or so-called multisensor hyperspectral imaging, involving elemental imaging (electron microscopy-based energy dispersive X-ray imaging), vibrational imaging (Raman micro-spectroscopy) and mass spectrometric imaging (Time-of-Flight Secondary Ion Mass Spectrometry) with subsequent combined multivariate analytics. Combined chemical imaging of precipitated aerosol particles will be demonstrated by the following examples of air pollution events in Vienna: Exceptional episodic events like the transformation of Saharan dust by the impact of the city of Vienna will be discussed and compared to samples obtained at a high alpine background site (Sonnblick Observatory, Saharan Dust Event from April 2016). Further, chemical imaging of biological aerosol constituents of an autumnal pollen breakout in Vienna, with background samples from nearby locations from November 2016 will demonstrate the advantages of the chemical imaging approach. Additionally, the chemical fingerprint of an exceptional air pollution event from a local emission source, caused by the pull down process of a building in Vienna will unravel the needs for multisensor imaging, especially the combinational access. Obtained chemical images will be correlated to bulk analytical results. Benefits of the overall methodical access by combining bulk analytics and combined chemical imaging of exceptional episodic air pollution events will be discussed.

A conceptual review of regional-scale controls on the composition of clastic sediment and the co-evolution of continental blocks and their sedimentary cover.

PubMed

Cox, R; Lowe, D R

1995-01-02

Both sediment recycling and first-cycle input influence the composition of clastic material in sedimentary systems. This paper examines conceptually the roles played by these processes in governing the composition of clastic sediment on a regional scale by outlining the expected effects on sediment composition of protracted sediment recycling and of continuous first-cycle input on a maturing continental block. Generally speaking, long-term recycling tends to enrich sediments in the most chemically and mechanically stable components: quartz in the sand and silt size fractions, and illite among the clay minerals. Sandstones trend towards pure quartz arenites, and mudrocks become more potassic and aluminous. The average grain size of clastic sediment decreases by a combination of progressive attrition of sand grains and ongoing breakdown of primary silicate minerals to finer-grained clay minerals and oxides. Sandstones derived by continuous first-cycle input from an evolving continental crustal source also become increasingly rich in quartz, but in addition become more feldspathic as the proportion of granitic material in the upper continental crust increases during crustal stabilization. Associated mudrocks also become richer in potassium and aluminum, but will have higher K2O/Al2O3 ratios than recycled muds. The average grain size of the sediment may increase with time as the proportion of sand-prone granitic source rocks increases at the expense of more mud-prone volcanic sources. In general, except in instances where chemical weathering is extreme, first-cycle sediments lack the compositional maturity of recycled detritus, and are characterized by the presence of a variety of primary silicate minerals. Sedimentary systems are not usually completely dominated by either recycling or first-cycle detritus. Generally, however, sedimentary systems associated with the earliest phases of formation and accretion of continental crust are characterized by first-cycle input from igneous and metamorphic rocks, whereas those associated with more mature cratons tend to be dominated by recycled sedimentary material.

Additive Manufacturing of Hierarchical Multi-Phase High-Entropy Alloys for Nuclear Component

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

Li, Nan

In recent years, high entropy alloys (HEAs), composed of four or more metallic elements mixed in equal or near equal atomic percent, have attracted significant attention due to their excellent mechanical properties and good corrosion resistance. They show significant promise as candidates for high temperature fission and fusion structural applications. However, the conventional synthesis methods are unlikely to present an industrially suitable route for the production and use of HEAs. Recognizing rapidly evolving additive manufacturing (AM) techniques, the goal of this proposal is to optimize the AM process to fabricate HEAs with predesigned chemical compositions and phase morphologies for nuclearmore » components. For this project, two HEAs FeCrNiMn and FeCrNiMnAl have been successfully synthesized. Correlated mechanical response has been systematically characterized under a variety of laser processing and ion irradiations. Both high entropy alloys are found to present comparable swelling and extraordinary irradiation tolerance (limited voids and stabilized phase structure under high irradiation dose). In addition, the microstructure and radiation-induced hardening can be tailored by laser processing under additive manufacturing. And we have assembled at LANL a unique database of HEAs containing a total of 674 compositions with Phase Stability information. Based on this, the machine learning and Artificial Intelligence capability now are established to predict the microstructure of casted HEAs by given chemical compositions. This unique integration will lead to an optimal AM recipe for fabricating radiation tolerant HEAs. The development of both modeling models and experimental capability will also benefit other programs at LANL.« less

Chemical and microstructural characterization of a 9 cycle Zircaloy-2 cladding using EPMA and FIB tomography

NASA Astrophysics Data System (ADS)

Baris, A.; Restani, R.; Grabherr, R.; Chiu, Y.-L.; Evans, H. E.; Ammon, K.; Limbäck, M.; Abolhassani, S.

2018-06-01

A high burn-up Zircaloy-2 cladding is characterised in order to correlate its microstructure and composition to the change of oxidation and hydrogen uptake behaviour during long term service in the reactor. After 9 cycle of service, the chemical analysis of the cladding segment shows that most secondary phase particles (SPPs) have dissolved into the matrix. Fe and Ni are distributed homogenously in the metal matrix. Cr-containing clusters, remnants of the original Zr(Fe, Cr)2 type precipitates, are still present. Hydrides are observed abundantly in the metal side close to the metal-oxide interface. These hydrides have lower Fe and Ni concentration than that in the metal matrix. The three-dimensional (3D) reconstruction of the oxide and the metal-oxide interface obtained by Focused Ion Beam (FIB) tomography shows how the oxide microstructure has evolved with the number of cycles. The composition and microstructural changes in the oxide and the metal can be correlated to the oxidation kinetics and the H-uptake. It is observed that there is an increase in the oxidation kinetics and in the H-uptake between the third and the fifth cycles, as well as during the last two cycles. At the same time the volume fraction of cracks in the oxide significantly increased. Many fine cracks and pores exist in the oxide formed in the last cycle. Furthermore, the EPMA results confirm that this oxide formed at the last cycle reflects the composition of the metal at the metal-oxide interface after the long residence time in the reactor.

Rapid Shifts in Oxygen and Hydrogen Isotopes, and Chemical Components in Pore Waters During mid-Oligocene in Sediments from IODP 351drilling

NASA Astrophysics Data System (ADS)

Zhang, Z.

2017-12-01

A total of 65 pore water samples were obtained from a sediment sequence in the Amami-Sankaku Basin during the IODP 351 Expedition, which consists of a 160 m thick section of terrestrial origin and underlying 1.3 km thick volcaniclastic section sampled at site U1438. Downcore variations of chemical compositions are characterized by increasing salinity/pH, increasing concentrations of Cl and Ca, and decreasing concentrations of Mg, K and Na, as well as decreasing d18O and dD. The rapid changes in those chemical components and isotopic composition occurred deeper than the lithology boundary between Unit III and Unit II, most likely as a result of substantial difference in extent of alteration above and below this boundary. The strong alterations of volcanicalstic minerals below the boundary not only result in diminishment of K, Mg, Si, and Mn, and an increase of Ca and Cl, but also depleted d18O in pore water. However, hydrogen fractionation factors between pore water and secondary minerals are less 1, and depleted dD values in pore water most likely reflect the signal of paleo-seawater. As a result, samples below the boundary are all plotted on the left side of the meteorite water line (MWL) on the dD vs. d18O plot. Above the boundary, they are placed to the right side of MWL due to substantially weakened alteration, reflecting an evolving trend in sediment setting from the predominance of alterated volcaniclasts to terrestrial pelagic sediments.

Chemical Cues which Include Amino Acids Mediate Species-Specific Feeding Behavior in Invasive Filter-Feeding Bigheaded Carps.

PubMed

Claus, Aaron W; Sorensen, Peter W

2017-04-01

This study tested whether and how dissolved chemicals might assist food recognition in two filter-feeding fishes, the silver (Hypophthalmichthys molitrix) and the bighead carp (H. nobilis). These species evolved in Asia, are now invasive in the Mississippi River, and feed voraciously on microparticles including plankton. The food habits and biology of these carps are broadly similar to many filter-feeding fish, none of whose chemical ecology has been examined. We conducted five experiments. First, we demonstrated that buccal-pharngeal pumping (BPP), a behavior in which fish pump water into their buccal cavities, is responsible for sampling food: BPP activity in both silver and bighead carps was low and increased nearly 25-fold after exposure to a filtrate of a planktonic food mixture (P < 0.01) and over 35-fold when planktonic food was added (P < 0.001). Next, we showed that of nine food filtrates, the one containing chemicals released by spirulina, a type of cyanobacterium, was the most potent planktonic component for both species. The potency of filtrates varied between species in ways that reflected their different chemical compositions. While L-amino acids could explain about half of the activity of food filtrate, other unknown chemical stimuli were also implicated. Finally, occlusion experiments showed the olfactory sense has a very important, but not exclusive, role in bigheaded carp feeding behaviors and this might be exploited in both their control and culture.

An experimental approach to manufacturing technology of historical glass (XIII-XV centuries). Comparison with current glassmaking technology.

NASA Astrophysics Data System (ADS)

Tarrago, Mariona; Gimeno, Domingo; Bazzocchi, Flavia; Garcia-Valles, Maite; Martinez, Salvador

2015-04-01

One of the major and less explored issues in the characterization of historical glasses is the determination of their viscosity as a function of temperature in order to constrain technological aspects of glass production. Until now, assumptions on temperatures have been based on mathematical models based on chemical compositions. Hence, the topic of this work is to explore the technology of stained glass production related to the workability and melting process of the glass by experimental laboratory measurements. This work presents the analysis of viscosity of glasses from different historical sites and chemical compositions: four from Santes Creus (Tarragona, XIII century), two of classical medieval stained glass window from Santa Maria de Pedralbes (Barcelona, mid XIV century), and three of evolved late-medieval type from Santa Maria del Mar (Barcelona first half of XV century), and one sample of soda-lime industrial glass by means of Hot-Stage Microscopy and glass transformation temperature Tg by dilatometry. These data are then compared to the predictions on theoretical viscosity obtained from mathematical models based on chemical composition. These samples are classified according to their major modifier in: Na-rich (12-17% of Na2O, between 65-77% of SiO2 and less than 3 % of K2O); Ca-rich (29% of CaO, 54% of SiO2, 4% of K2O, and 4% of Na2O); K-Ca-rich (17 to 21% of K2O, more than 14% of CaO, 49-55% of SiO2and less than 2% of Na2O); Na-Ca-rich (12-14% of Na2O, 9-15% of CaO, 57-71% of SiO2 and < 6% of K2O). Glass transition temperature (Tg) is correlated to chemical composition: 464-492 °C for Na-rich, 645 °C for Ca-rich, 582-586 °C for K-Ca-rich and 497-542 °C for Na-Ca-rich glasses. Experimental viscosity-temperature curves are traced using Tg and fixed viscosity points measured by Hot-Stage microscopy (according to German standard 51730) in order to provide more accurate insight into the phases of glass production process (melting, working, conditioning and annealing ranges). These results are also compared to mathematical models of glass viscosity based on chemical composition. The annealing range (viscosity between 1013.5 and 1012 Pa-s) is reached at temperatures between 484-633°C (strain point) and 509-664°C (upper limit). The working point (viscosity of 103 Pa-s) has temperature values in the range between 958 and 1097°C.

Model for origin and evolution of water at volcanoes in São Miguel, Azores (Portugal), based on geochemical and isotopic data set

NASA Astrophysics Data System (ADS)

Woitischek, Julia; Dietzel, Martin; Virgílio Cruz, J.; Inguaggiato, Salvatore; Leis, Albrecht; Böttcher, Michael E.

2016-04-01

A conceptual model is presented to better constrain the origin and evolution of discharges at Sete Cidades, Fogo and Furnas Volcano, using geochemical and isotopic analyses of rock and water as well as recalculated gas composition. The evolution of thermal water clearly reveals that Na-HCO3 and Na-SO4 type of springs have their origin in meteoric water as isotope data are close to the local meteoric water line (δ 18OH2O =-3 ± 1 ‰ V-SMOW; δ DH2O= -13 ± 7 ‰ V-SMOW) with exception of a Na-Cl spring named Ferraria, Sete Cidades area (δ 18OH2O = 0.45 ‰ V-SMOW ; δ DH2O= 4.18 ‰ V-SMOW). Analysed solutions are chemical evolved by evaporation, uptake of volcanic gas, leaching of local basaltic rocks, precipitation of solids, partly admixture of sea water and/or biological activity. Following the individual concentrations supports this model e.g.: HCO3 concentration and the recalculated isotopic composition of gaseous CO2 (δ 13CCO_2 = -4 ± 2.5 ‰ V-PDB) reflect evolved magmatic CO2 uptake and the subsequent leaching progress; High SO42- concentration of up to 16.5 mmol L-1 with δ 34SSO4 = 0.35 ± 0.3 ‰ (V-CDT) reflects magmatic origin which mainly control water chemistry of boiling pools of both Fogo and Furnas lake; δ 18OSO4 = 10.5 ‰ (V-SMOW) suggests organic origin and fits together with the observation of stromatolitic structures in the related precipitates; Molar Mg/Caratio (≈ 0.77) of all thermal discharges reflects leaching of analysed local basalt (Mg/Ca≈ 0.78). Furthermore, shallow and evolved outgassing effects can be distinguished. Equilibrium temperatures for various minerals given in SI vs. T plots and further geothermometers (e.g. Na-K, Na-K-Ca geothermometers) were discussed to estimate temperatures of reservoirs.

Interpretation of open system petrogenetic processes: Phase equilibria constraints on magma evolution

NASA Astrophysics Data System (ADS)

Defant, Marc J.; Nielsen, Roger L.

1990-01-01

We have used a computer model (TRACES) to simulate low pressure differentiation of natural basaltic magmas in an attempt to investigate the chemical dynamics of open system magmatic processes. Our results, in the form of simulated liquid lines of descent and the calculated equilibrium mineralogy, were determined for perfect fractional crystallization; fractionation paired with recharge and eruption (PRF); fractionation paired with assimilation (AFC); and fractionation paired with recharge, eruption, and assimilation (FEAR). These simulations were calculated in an attempt to assess the effects of combinations of petrogenetic processes on major and trace element evolution of natural systems and to test techniques that have been used to decipher the relative roles of these processes. If the results of PRF calculations are interpreted in terms of a mass balance based fractionation model (e.g., Bryan et al., 1969), it is possible to generate low residuals even if one assumes that fractional crystallization was the only active process. In effect, the chemical consequences of recharge are invisible to mass balance models. Pearce element ratio analyses, however, can effectively discern the effects of PRF versus simple fractionation. The fractionating mineral proportions, and therefore, bulk distribution coefficients ( D¯) of a differentiating system are dependent on the recharge or assimilation rate. Comparison of the results of simulations assuming constant D¯ with the results calculated by TRACES show that the steady state liquid concentrations of some elements can differ by a factor of 2 to 5. If the PRF simulation is periodic, with episodes of mixing separated by intervals of fractionation, parallel liquidus mineral control lines are produced. Most of these control lines do not project back to the parental composition. This must be an important consideration when attempting to calculate a potential parental magma for any natural suite where magma chamber recharge has occurred. Most basaltic magmas cannot evolve to high silica compositions without magnetite fractionation. Small amounts of rhyolite assimilation (assimilation/fractionation < 0.1), however, can drive evolving basalts to more silica rich compositions. If mass balance models are used to interpret these synthetic AFC data, low residuals are obtained if magnetite is added to the crystallizing assemblage. This approach works even for cases where magnetite was not a fractionating phase. Thus, the mass balance results are mathematically correct, but are geologically irrelevant.

Chemical Risk Assessment

EPA Science Inventory

This course is aimed at providing an overview of the fundamental guiding principles and general methods used in chemical risk assessment. Chemical risk assessment is a complex and ever-evolving process. These principles and methods have been organized by the National Research Cou...

Truth and probability in evolutionary games

NASA Astrophysics Data System (ADS)

Barrett, Jeffrey A.

2017-01-01

This paper concerns two composite Lewis-Skyrms signalling games. Each consists in a base game that evolves a language descriptive of nature and a metagame that coevolves a language descriptive of the base game and its evolving language. The first composite game shows how a pragmatic notion of truth might coevolve with a simple descriptive language. The second shows how a pragmatic notion of probability might similarly coevolve. Each of these pragmatic notions is characterised by the particular game and role that it comes to play in the game.

Adaptive inferential sensors based on evolving fuzzy models.

PubMed

Angelov, Plamen; Kordon, Arthur

2010-04-01

A new technique to the design and use of inferential sensors in the process industry is proposed in this paper, which is based on the recently introduced concept of evolving fuzzy models (EFMs). They address the challenge that the modern process industry faces today, namely, to develop such adaptive and self-calibrating online inferential sensors that reduce the maintenance costs while keeping the high precision and interpretability/transparency. The proposed new methodology makes possible inferential sensors to recalibrate automatically, which reduces significantly the life-cycle efforts for their maintenance. This is achieved by the adaptive and flexible open-structure EFM used. The novelty of this paper lies in the following: (1) the overall concept of inferential sensors with evolving and self-developing structure from the data streams; (2) the new methodology for online automatic selection of input variables that are most relevant for the prediction; (3) the technique to detect automatically a shift in the data pattern using the age of the clusters (and fuzzy rules); (4) the online standardization technique used by the learning procedure of the evolving model; and (5) the application of this innovative approach to several real-life industrial processes from the chemical industry (evolving inferential sensors, namely, eSensors, were used for predicting the chemical properties of different products in The Dow Chemical Company, Freeport, TX). It should be noted, however, that the methodology and conclusions of this paper are valid for the broader area of chemical and process industries in general. The results demonstrate that well-interpretable and with-simple-structure inferential sensors can automatically be designed from the data stream in real time, which predict various process variables of interest. The proposed approach can be used as a basis for the development of a new generation of adaptive and evolving inferential sensors that can address the challenges of the modern advanced process industry.

Progress Towards a Thermo-Mechanical Magma Chamber Forward Model for Eruption Cycles, Applied to the Columbia River Flood Basalts

NASA Astrophysics Data System (ADS)

Karlstrom, L.; Ozimek, C.

2016-12-01

Magma chamber modeling has advanced to the stage where it is now possible to develop self-consistent, predictive models that consider mechanical, thermal, and compositional magma time evolution through multiple eruptive cycles. We have developed such a thermo-mechanical-chemical model for a laterally extensive sill-like chamber beneath free surface, to understand physical controls on eruptive products through time at long-lived magmatic centers. This model predicts the relative importance of recharge, eruption, assimilation and fractional crystallization (REAFC, Lee et al., 2013) on evolving chemical composition as a function of mechanical magma chamber stability regimes. We solve for the time evolution of chamber pressure, temperature, gas volume fraction, volume, elemental concentration in the melt and crustal temperature field that accounts for moving boundary conditions associated with chamber inflation (and the possibility of coupled chambers at different depths). The density, volume fractions of melt and crystals, crustal assimilation and the changing viscosity and crustal properties of the wall rock are also tracked, along with joint solubility of water and CO2. The eventual goal is to develop an efficient forward model to invert for eruptive records at long-lived eruptive centers, where multiple types of data for eruptions are available. As a first step, we apply this model to a new compilation of eruptive data from the Columbia River Flood Basalts (CRFB), which erupted 210,000 km3 from feeder dikes in Washington, Oregon and Idaho between 16.9-6Ma. Data include volumes, timing and geochemical composition of eruptive units, along with seismic surveys and clinopyroxene geobarometry that constrain depth of storage through time. We are in the process of performing a suite of simulations varying model input parameters such as mantle melt rate, emplacement depth, wall rock compositions and rheology, and volatile content to explain volume, eruption timescales, and chemical trace aspects of CRFB eruptions. We are particularly interested in whether the large volume eruptions of the main phase Grande Ronde basalts were made possible due to the development of shallow crustal storage.

Discovery of Carbonate-Rich Outcrops in the Gusev Crater Columbia Hills by the MER Rover Spirit

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Ruff, Steven W.; Gellert, Ralf; Ming, Douglas W.; Arvidson, Raymond E.; Clark, Benton C.; Golden, Dadi C.; Siebach, Kirsten L.; Klingelhoefer, Goestar; Schroeder, Christian;

Composition of early planetary atmospheres - II. Coupled Dust and chemical evolution in protoplanetary discs

NASA Astrophysics Data System (ADS)

Cridland, A. J.; Pudritz, Ralph E.; Birnstiel, Tilman; Cleeves, L. Ilsedore; Bergin, Edwin A.

2017-08-01

We present the next step in a series of papers devoted to connecting the composition of the atmospheres of forming planets with the chemistry of their natal evolving protoplanetary discs. The model presented here computes the coupled chemical and dust evolution of the disc and the formation of three planets per disc model. Our three canonical planet traps produce a Jupiter near 1 AU, a Hot Jupiter and a Super-Earth. We study the dependence of the final orbital radius, mass, and atmospheric chemistry of planets forming in disc models with initial disc masses that vary by 0.02 M⊙ above and below our fiducial model (M_{disc,0} = 0.1 M_{⊙}). We compute C/O and C/N for the atmospheres formed in our three models and find that C/Oplanet ˜ C/O_{disc}, which does not vary strongly between different planets formed in our model. The nitrogen content of atmospheres can vary in planets that grow in different disc models. These differences are related to the formation history of the planet, the time and location that the planet accretes its atmosphere, and are encoded in the bulk abundance of NH3. These results suggest that future observations of atmospheric NH3 and an estimation of the planetary C/O and C/N can inform the formation history of particular planetary systems.

Recycling lower continental crust in the North China craton.

PubMed

Gao, Shan; Rudnick, Roberta L; Yuan, Hong-Ling; Liu, Xiao-Ming; Liu, Yong-Sheng; Xu, Wen-Liang; Ling, Wen-Li; Ayers, John; Wang, Xuan-Che; Wang, Qing-Hai

2004-12-16

Foundering of mafic lower continental crust into underlying convecting mantle has been proposed as one means to explain the unusually evolved chemical composition of Earth's continental crust, yet direct evidence of this process has been scarce. Here we report that Late Jurassic high-magnesium andesites, dacites and adakites (siliceous lavas with high strontium and low heavy-rare-earth element and yttrium contents) from the North China craton have chemical and petrographic features consistent with their origin as partial melts of eclogite that subsequently interacted with mantle peridotite. Similar features observed in adakites and some Archaean sodium-rich granitoids of the tonalite-trondhjemite-granodiorite series have been interpreted to result from interaction of slab melts with the mantle wedge. Unlike their arc-related counterparts, however, the Chinese magmas carry inherited Archaean zircons and have neodymium and strontium isotopic compositions overlapping those of eclogite xenoliths derived from the lower crust of the North China craton. Such features cannot be produced by crustal assimilation of slab melts, given the high Mg#, nickel and chromium contents of the lavas. We infer that the Chinese lavas derive from ancient mafic lower crust that foundered into the convecting mantle and subsequently melted and interacted with peridotite. We suggest that lower crustal foundering occurred within the North China craton during the Late Jurassic, and thus provides constraints on the timing of lithosphere removal beneath the North China craton.

Characterization of Inclusion Populations in Mn-Si Deoxidized Steel

NASA Astrophysics Data System (ADS)

García-Carbajal, Alfonso; Herrera-Trejo, Martín; Castro-Cedeño, Edgar-Ivan; Castro-Román, Manuel; Martinez-Enriquez, Arturo-Isaias

2017-12-01

Four plant heats of Mn-Si deoxidized steel were conducted to follow the evolution of the inclusion population through ladle furnace (LF) treatment and subsequent vacuum treatment (VT). The liquid steel was sampled, and the chemical composition and size distribution of the inclusion populations were characterized. The Gumbel generalized extreme-value (GEV) and generalized Pareto (GP) distributions were used for the statistical analysis of the inclusion size distributions. The inclusions found at the beginning of the LF treatment were mostly fully liquid SiO2-Al2O3-MnO inclusions, which then evolved into fully liquid SiO2-Al2O3-CaO-MgO and partly liquid SiO2-CaO-MgO-(Al2O3-MgO) inclusions detected at the end of the VT. The final fully liquid inclusions had a desirable chemical composition for plastic behavior in subsequent metallurgical operations. The GP distribution was found to be undesirable for statistical analysis. The GEV distribution approach led to shape parameter values different from the zero value hypothesized from the Gumbel distribution. According to the GEV approach, some of the final inclusion size distributions had statistically significant differences, whereas the Gumbel approach predicted no statistically significant differences. The heats were organized according to indicators of inclusion cleanliness and a statistical comparison of the size distributions.

Flowage differentiation in an andesitic dyke of the Motru Dyke Swarm (Southern Carpathians, Romania) inferred from AMS, CSD and geochemistry

NASA Astrophysics Data System (ADS)

Nkono, Collin; Féménias, Olivier; Diot, Hervé; Berza, Tudor; Demaiffe, Daniel

2006-06-01

Two dykes of different thickness (5.5 m for TJ31 and 23 m for TJ34) from the late Pan-African calc-alkaline Motru Dyke Swarm (S. Carpathians, Romania) have been studied by electron microprobe (mineral chemistry), crystal size distribution (CSD), anisotropy of magnetic susceptibility (AMS) and whole-rock geochemistry. All the physical and chemical variations observed across the dyke's width point to concordant results and show that the variations of both modal abundance and size of the amphibole and biotite microphenocrysts inside the dykes (deduced from the classical CSD measurements) are the result of a mechanical segregation of suspended crystals during magmatic transport. Despite a pene-contemporaneous regional tectonic, the flow-induced differentiation in the thicker dyke is characterized by the concentration of pre-existing Ti-rich pargasite-tschermakite, clinopyroxene and plagioclase crystals in the core of the dyke and of the extracted differentiated liquid near the walls. This mechanical differentiation induces a chemical differentiation with a basaltic andesite composition for the core of the dyke whereas the margins are andesitic. Thus the chilled margins appear as a slightly more evolved liquid with a Newtonian behaviour when compared to the average composition of the dyke. The localization of the liquid on both sides of the dyke has certainly facilitated the ascent of the central part of the dyke that behaved as a Binghamian mush.

Rheological Investigation of Cryovolcanic Slurries

NASA Astrophysics Data System (ADS)

Morrison, A. A.; Whittington, A. G.; Zhong, F.; Mitchell, K. L.; Carey, E. M.

2018-06-01

Subliquidus rheological experiments will be conducted for briny cryovolcanic compositions. Understanding how these materials move, deform, and evolve upon crystallizing will help constrain what morphological features can form by various compositions.

Th-REE- and Nb-Ta-accessory minerals in post-collisional Ediacaran felsic rocks from the Katerina Ring Complex (S. Sinai, Egypt): An assessment for the fractionation of Y/Nb, Th/Nb, La/Nb and Ce/Pb in highly evolved A-type granites

NASA Astrophysics Data System (ADS)

Moreno, J. A.; Molina, J. F.; Bea, F.; Abu Anbar, M.; Montero, P.

2016-08-01

The relationships of Y/Nb, Th/Nb, La/Nb and Ce/Pb ratios in A-type felsic rocks from the Ediacaran Katerina Ring Complex, northernmost Arabian-Nubian Shield (ANS; S. Sinai, Egypt), are investigated in this work to understand their behavior during generation of highly evolved granitic magmas and to explore the nature of magma sources. Textural and compositional relationships of cognate Th-REE- and Nb-Ta-accessory minerals in Katerina felsic rocks show that chevkinite-group minerals (CGM), monazite, thorite, allanite and xenotime formed from residual liquids in quartz syenite porphyries, quartz monzonites and peralkaline granites, whereas in aluminous granites, allanite and monazite crystallized early, and thorite and columbite formed from residual liquids. Relationships of Y/Nb, Th/Nb, La/Nb and Ce/Pb ratios with Zr/Hf ratios in the aluminous granites and with Be abundances in the peralkaline granites suggest a decrease in La/Nb and Ce/Pb ratios in the former, and in Y/Nb and La/Nb ratios in the latter with crystallization progress. This contrasts with absence of systematic variations of Th/Nb and Ce/Pb ratios in the peralkaline compositions and of Y/Nb ratio in the aluminous ones. In this latter, Th/Nb ratio can present a significant decrease only in highly evolved compositions. An analysis of Y/Nb, Th/Nb, La/Nb and Ce/Pb relationships in worldwide OIB and subduction-related magmatic suites reveals that A-type felsic rocks with (Th/Nb)N < 1.3, (La/Nb)N < 1.3, and (Ce/Pb)N > 1 may have A1-type affinity, and those with (Th/Nb)N > 2, (La/Nb)N > 2, and (Ce/Pb)N < 1 tend to present A2-type affinity. The crystal fractionation of Th-LREE- and Nb-Ta-accessory minerals and mixing of components derived from the two granite groups may cause deviations from these compositional limits that can be evaluated using constraints imposed by Th/Nb-La/Nb, Ce/Pb-Th/Nb and Ce/Pb-La/Nb relationships in OIB and subduction-related magmatic suites. Three mantle sources might have been involved in the Ediacaran alkaline magmatism from northernmost ANS that are chemically similar to those of (1) OIB suites, (2) subduction-related magmatic suites, and (3) carbonatite-metasomatized peridotites. In addition, compositions characterized by (Y/Nb)N > 0.18, (Th/Nb)N > 2, (La/Nb)N > 2, (Ce/Pb)N < 1, and crustal-like Nb/Ta ratios may point to a significant contribution of crustal sources.

Oxidant activity in hyperarid soils from Atacama Desert in southern Peru, under conditions of the labeled release and thermal evolved gas analysis experiments: Implications for the search of organic matter on Mars

NASA Astrophysics Data System (ADS)

Valdivia-Silva, Julio E.; Navarro-Gonzalez, Rafael; McKay, Chris

Thermal evolved gas analysis (TEGA), one of several instruments on board of the Phoenix Lander, is a combination of a high temperature furnace and a mass spectrometer that was used to analyze Mars soil samples heated at a programmed ramp rate up to 1000 ° C. The evolved gases generated during the process were analyzed with the evolved gas analyzer (a mass spectrometer) in order to determine the composition of gases released as a function of temperature. In other hand, labeled release experiment (LR), one of the Viking biology anal-ysis used on Mars, monitored the radioactive gas evolution after the addition of a 14C-labeled aqueous organic substrate into a sealed test cell that contained a Martian surface sample. This experiment was designed to test Martian surface samples for the presence of life by measuring metabolic activity and distinguishing it from physical or chemical activity. The interpretation of the Viking LR experiment was that the tested soils were chemically reactive and not biolog-ically active, and that at least two oxidative processes with different kinetics were required to explain the observed decomposition of organics, while TEGA experiment of the Phoenix mis-sion apparently didn't detect organic matter on the surface of Mars. Both of these experiments showed little possibility of the presence of organics, and therefore the presence of life. Here we examine the evolved gas properties of hyperarid soils from the Pampas de La Joya, which is considered as a new analogue to Mars, in order to investigate the effect of the soil matrix on the TEGA response, and additionally, we conducted experiments under Viking LR protocol to test the decomposition kinetics of organic compounds in aqueous solution added to these soils. Our TEGA results indicate that native or added organics present in these samples were oxidized to CO2 during thermal process, suggesting the existence in these soils of a thermolabile oxidant which is highly oxidative and other thermostable oxidant which has a minor oxidative activity and that survives the heat-treatment. Interestingly, LR experiment shows that the 13C-labeled formate and DL-alanine were oxidized to 13CO2 when added in aqueous solution to soils collected from the Pampas de La Joya region. The observation of similar 13CO2 initial releasing by soils treated with L-alanine, compared to soils treated D-alanine, indicates the presence of one or more nonbiological chemical decomposition mechanisms similar to Yungay soils and the Viking LR experiment. Thus, the soils from Pampas of La Joya, are potentially excellent analogues of the oxidative processes that occur on Mars, and can be used to study mechanisms of destruction of organics on this planet. The nature of oxidant(s) present in the soils from Pampas de La Joya is still unknown.

Biology, ecology, and biotechnological applications of anaerobic bacteria adapted to environmental stresses in temperature, pH, salinity, or substrates.

PubMed Central

Lowe, S E; Jain, M K; Zeikus, J G

1993-01-01

Anaerobic bacteria include diverse species that can grow at environmental extremes of temperature, pH, salinity, substrate toxicity, or available free energy. The first evolved archaebacterial and eubacterial species appear to have been anaerobes adapted to high temperatures. Thermoanaerobes and their stable enzymes have served as model systems for basic and applied studies of microbial cellulose and starch degradation, methanogenesis, ethanologenesis, acetogenesis, autotrophic CO2 fixation, saccharidases, hydrogenases, and alcohol dehydrogenases. Anaerobes, unlike aerobes, appear to have evolved more energy-conserving mechanisms for physiological adaptation to environmental stresses such as novel enzyme activities and stabilities and novel membrane lipid compositions and functions. Anaerobic syntrophs do not have similar aerobic bacterial counterparts. The metabolic end products of syntrophs are potent thermodynamic inhibitors of energy conservation mechanisms, and they require coordinated consumption by a second partner organism for species growth. Anaerobes adapted to environmental stresses and their enzymes have biotechnological applications in organic waste treatment systems and chemical and fuel production systems based on biomass-derived substrates or syngas. These kinds of anaerobes have only recently been examined by biologists, and considerably more study is required before they are fully appreciated by science and technology. Images PMID:8336675

Chemical compositions, methods of making the chemical compositions, and structures made from the chemical compositions

DOEpatents

Yang, Lei; Cheng, Zhe; Liu, Ze; Liu, Meilin

2015-01-13

Embodiments of the present disclosure include chemical compositions, structures, anodes, cathodes, electrolytes for solid oxide fuel cells, solid oxide fuel cells, fuel cells, fuel cell membranes, separation membranes, catalytic membranes, sensors, coatings for electrolytes, electrodes, membranes, and catalysts, and the like, are disclosed.

The Combustion Experiment on the Sample Analysis at Mars (SAM) Instrument Suite on the Curiosity Rover

NASA Technical Reports Server (NTRS)

Stern, J. C.; Malespin, C. A.; Eigenbrode, J.; Graham, H. V.; Archer, P. D.; Brunner, A.; Freissinet, C.; Franz, H. B.; Fuentes, J.; Glavin, D. P.;

A model for the emergence of cooperation, interdependence, and structure in evolving networks.

PubMed

Jain, S; Krishna, S

2001-01-16

Evolution produces complex and structured networks of interacting components in chemical, biological, and social systems. We describe a simple mathematical model for the evolution of an idealized chemical system to study how a network of cooperative molecular species arises and evolves to become more complex and structured. The network is modeled by a directed weighted graph whose positive and negative links represent "catalytic" and "inhibitory" interactions among the molecular species, and which evolves as the least populated species (typically those that go extinct) are replaced by new ones. A small autocatalytic set, appearing by chance, provides the seed for the spontaneous growth of connectivity and cooperation in the graph. A highly structured chemical organization arises inevitably as the autocatalytic set enlarges and percolates through the network in a short analytically determined timescale. This self organization does not require the presence of self-replicating species. The network also exhibits catastrophes over long timescales triggered by the chance elimination of "keystone" species, followed by recoveries.

A model for the emergence of cooperation, interdependence, and structure in evolving networks

NASA Astrophysics Data System (ADS)

Jain, Sanjay; Krishna, Sandeep

2001-01-01

Evolution produces complex and structured networks of interacting components in chemical, biological, and social systems. We describe a simple mathematical model for the evolution of an idealized chemical system to study how a network of cooperative molecular species arises and evolves to become more complex and structured. The network is modeled by a directed weighted graph whose positive and negative links represent "catalytic" and "inhibitory" interactions among the molecular species, and which evolves as the least populated species (typically those that go extinct) are replaced by new ones. A small autocatalytic set, appearing by chance, provides the seed for the spontaneous growth of connectivity and cooperation in the graph. A highly structured chemical organization arises inevitably as the autocatalytic set enlarges and percolates through the network in a short analytically determined timescale. This self organization does not require the presence of self-replicating species. The network also exhibits catastrophes over long timescales triggered by the chance elimination of "keystone" species, followed by recoveries.

Petrology and geochemistry of lithic fragments separated from the Apollo 15 deep-drill core

NASA Technical Reports Server (NTRS)

Lindstrom, M. M.; Nielsen, R. L.; Drake, M. J.

1977-01-01

Petrological and geochemical analysis of lithic fragments separated from the Apollo 15 deep-drill core showed these fragments to fall into the essentially the same range of rock types as observed in surface soil samples and large rock samples. Three particles are singled out as being of special interest. One sample is a mare basalt containing extremely evolved phases. The particle may represent small-scale imperfect crystal/liquid separation in a lava flow. A green glass particle is not the ultramafic emerald green glass described from the Apollo 15 site, but rather an ANT-like light green color, and has a quite different chemical composition from the ultramafic variety. One mare basalt displays a positive Eu anomaly and is enriched in plagioclase relative to olivine plus pyroxene.

The History of Chemical Engineering and Pedagogy: The Paradox of Tradition and Innovation

ERIC Educational Resources Information Center

Wankat, Phillip C.

2009-01-01

The Massachusetts Institute of Technology started the first US chemical engineering program six score years ago. Since that time, the chemical engineering curriculum has evolved. The latest versions of the curriculum are attempts to broaden chemical engineering to add product engineering, biology and nanotechnology to the traditional process…

The Parent Magmas of the Cumulate Eucrites: A Mass Balance Approach

NASA Technical Reports Server (NTRS)

Treiman, Allan H.

1996-01-01

The cumulate eucrite meteorites are gabbros that are related to the eucrite basalt meteorites. The eucrite basalts are relatively primitive (nearly flat REE patterns with La approx. 8-30 x CI), but the parent magmas of the cumulate eucrites have been inferred as extremely evolved (La to greater than 100 x CI). This inference has been based on mineral/magma partitioning, and on mass balance considering the cumulate eucrites as adcumulates of plagioclase + pigeonite only; both approaches have been criticized as inappropriate. Here, mass balance including magma + equilibrium pigeonite + equilibrium plagiociase is used to test a simple model for the cumulate eucrites: that they formed from known eucritic magma types, that they consisted only of magma + crystals in chemical equilibrium with the magma, and that they were closed to chemical exchange after the accumulation of crystals. This model is tested for major and Rare Earth Elements (REE). The cumulate eucrites Serra de Mage and Moore County are consistent, in both REE and major elements, with formation by this simple model from a eucrite magma with a composition similar to the Nuevo Laredo meteorite: Serra de Mage as 14% magma, 47.5% pigeonite, and 38.5% plagioclase; Moore County as 35% magma, 37.5% pigeonite, and 27.5% plagioclase. These results are insensitive to the choice of mineral/magma partition coefficients. Results for the Moama cumulate eucrite are strongly dependent on choice of partition coefficients; for one reasonable choice, Moama's composition can be modeled as 4% Nuevo Laredo magma, 60% pigeonite, and 36% plagioclase. Selection of parent magma composition relies heavily on major elements; the REE cannot uniquely indicate a parent magma among the eucrite basalts. The major element composition of Y-791195 can be fit adequately as a simple cumulate from any basaltic eucrite composition. However, Y-791195 has LREE abundances and La/Lu too low to be accommodated within the model using any basaltic eucrite composition and any reasonable partition coefficients. Postcumulus loss of incompatible elements seems possible. It is intriguing that Serra de Mage, Moore County, and Moama are consistent with the same parental magma; could they be from the same igneous body on the eucrite parent asteroid (4 Vesta)?

Application of screened Coulomb potential in fitting DBV star PG 0112+104

NASA Astrophysics Data System (ADS)

Chen, Y. H.

2018-03-01

With 78.7 d of observations for PG 0112+104, a pulsating DB star, from Campaign 8 of Kepler 2 mission, Hermes et al. made a detailed mode identification. A reliable mode identification, with 5 l = 1 modes, 3 l = 2 modes, and 3 l = 1 or 2 modes, was identified. Grids of DBV star models are evolved by WDEC with element diffusion effect of pure Coulomb potential and screened Coulomb potential. Fitting the identified modes of PG 0112+104 by the calculated ones, we studied the difference of element diffusion effect between adopting pure Coulomb potential and screened Coulomb potential. Our aim is to reduce the fitting error by studying new input physics. The starting models including their chemical composition profile are from white dwarf models evolved by MESA. They were calculated following the stellar evolution from the main sequence to the start of the white dwarf cooling sequences. The optimal parameters are basically consistent with that of previous spectroscopic and asteroseismological studies. The pure and screened Coulomb potential lead to different composition profiles of the C/O-He interface area. High k modes are very sensitive to the area. However, most of the observed modes for PG 0112+104 are low k modes. The σRMS taking the screened Coulomb potential is reduced by 4 per cent compared with taking the pure Coulomb potential when fitting the identified low k modes of PG 0112+104. Fitting the Kepler 2 data with our models improved the σRMS of the fit by 27 per cent.

Calibration of carbonate composition using micro-Raman analysis: application to planetary surface exploration.

PubMed

Rividi, Nicolas; van Zuilen, Mark; Philippot, Pascal; Ménez, Bénédicte; Godard, Gaston; Poidatz, Emmanuel

2010-04-01

Stromatolite structures in Early Archean carbonate deposits form an important clue for the existence of life in the earliest part of Earth's history. Since Mars is thought to have had similar environmental conditions early in its history, the question arises as to whether such stromatolite structures also evolved there. Here, we explore the capability of Raman spectroscopy to make semiquantitative estimates of solid solutions in the Ca-Mg-Fe(+Mn) carbonate system, and we assess its use as a rover-based technique for stromatolite characterization during future Mars missions. Raman microspectroscopy analysis was performed on a set of carbonate standards (calcite, ankerite, dolomite, siderite, and magnesite) of known composition. We show that Raman band shifts of siderite-magnesite and ankerite-dolomite solid solutions display a well-defined positive correlation (r(2) > 0.9) with the Mg# = 100 x Mg/(Mg + Fe + Mn + Ca) of the carbonate analyzed. Raman shifts calibrated as a function of Mg# were used in turn to evaluate the chemical composition of carbonates. Raman analysis of a suite of carbonates (siderite, sidero-magnesite, ankerite, and dolomite) of hydrothermal and sedimentary origin from the ca. 3.2 Ga old Barite Syncline, Barberton greenstone belt, South Africa, and from the ca. 3.5 Ga old Dresser Formation, Pilbara Craton, Western Australia, show good compositional agreement with electron microprobe analyses. These results indicate that Raman spectroscopy can provide direct information on the composition and structure of carbonates on planetary surfaces.

Technical note: An inverse method to relate organic carbon reactivity to isotope composition from serial oxidation

NASA Astrophysics Data System (ADS)

Hemingway, Jordon D.; Rothman, Daniel H.; Rosengard, Sarah Z.; Galy, Valier V.

2017-11-01

Serial oxidation coupled with stable carbon and radiocarbon analysis of sequentially evolved CO2 is a promising method to characterize the relationship between organic carbon (OC) chemical composition, source, and residence time in the environment. However, observed decay profiles depend on experimental conditions and oxidation pathway. It is therefore necessary to properly assess serial oxidation kinetics before utilizing decay profiles as a measure of OC reactivity. We present a regularized inverse method to estimate the distribution of OC activation energy (E), a proxy for bond strength, using serial oxidation. Here, we apply this method to ramped temperature pyrolysis or oxidation (RPO) analysis but note that this approach is broadly applicable to any serial oxidation technique. RPO analysis directly compares thermal reactivity to isotope composition by determining the E range for OC decaying within each temperature interval over which CO2 is collected. By analyzing a decarbonated test sample at multiple masses and oven ramp rates, we show that OC decay during RPO analysis follows a superposition of parallel first-order kinetics and that resulting E distributions are independent of experimental conditions. We therefore propose the E distribution as a novel proxy to describe OC thermal reactivity and suggest that E vs. isotope relationships can provide new insight into the compositional controls on OC source and residence time.

Chemical Mixtures Health Risk Assessment of Environmental Contaminants: Concepts, Methods, Applications

EPA Science Inventory

This problems-based, introductory workshop focuses on methods to assess health risks posed by exposures to chemical mixtures in the environment. Chemical mixtures health risk assessment methods continue to be developed and evolve to address concerns over health risks from multic...

Chemical Mixtures Health Risk Assessment of Environmental Contaminants: Concepts, Methods, And Applications

EPA Science Inventory

This problems-based, introductory workshop focuses on methods to assess health risks posed by exposures to chemical mixtures in the environment. Chemical mixtures health risk assessment methods continue to be developed and evolve to address concerns over health risks from multic...

Rock-Fluid Interactions Under Stress: How Rock Microstructure Controls The Evolution of Porosity and Permeability

NASA Astrophysics Data System (ADS)

Vanorio, T.

2016-12-01

Monitoring chemo-mechanical processes geophysically — e.g., fluid disposal or storage, thermal and chemical stimulation of reservoirs, or natural fluids simply entering a new system in the subsurface— raises numerous concerns because of the likelihood of fluid-rock chemical interactions and our limited ability to decipher the geophysical signature of coupled processes. One of the missing links is coupling the evolution of porosity, permeability, and velocity of rocks together with reactive transport, since rocks deform and their microstructure evolves, as a result of chemical reactions under stress. This study describes recent advances in rock-physics experiments to understand the effects of dissolution-induced compaction on acoustic velocity, porosity, and permeability. Data observation includes time-lapse experiments and imaging tracking transport and elastic properties, the rock microstructure, and the pH and chemical composition of the fluid permeating the rock. Results show that the removal of high surface area, mineral phases such as microcrystalline calcite and clay appears to be mostly responsible for dissolution-induced compaction. Nevertheless, it is the original rock microstructure and its response to stress that ultimately defines how solution-transfer and rock compaction feed back upon each other. This work has a dual aim: understanding the mechanisms underlying permanent modifications to the rock microstructure and providing a richer set of experimental information to inform the formulation of new simulations and rock modeling.

Photolysis frequency and cloud dynamics during DC3 and SEAC4RS

NASA Astrophysics Data System (ADS)

Hall, S. R.; Ullmann, K.; Madronich, S.; Hair, J. W.; Butler, C. F.; Fenn, M. A.

2013-12-01

Cloud shading plays a critical role in extending the lifetime of short-lived chemical species. During convection, photochemistry is reduced such that short-lived species may be transported from the boundary layer to the upper troposphere/ lower stratosphere. In the anvil outflow, shading continues within and below the cloud. However, near the highly scattering cloud top, the chemistry is greatly accelerated. In this rapidly evolving environment, accurate photolysis frequencies are required to study photochemical evolution of the complex composition. During the Deep Convective Clouds and Chemistry (DC3, 2012) and the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS, 2013) campaigns, photolysis frequencies were determined by measurement of spectrally resolved actinic flux by the Charge-coupled device Actinic Flux Spectroradiometer (CAFS) on the NASA DC-8 and the HIAPER Airborne Radiation Package (HARP) on the NCAR G-V aircraft. Vertical flight profiles allowed in situ characterization of the radiation environment. Input of geometrical cloud characteristics into the Tropospheric Ultraviolet and Visible (TUV) Radiation was used to constrain cloud optical depths for more spatially and temporally stable conditions.

Self-Consistent Hydrodynamical Models For Stellar Winds

NASA Astrophysics Data System (ADS)

Boulangier, Jels; Homan, Ward; van Marle, Allard Jan; Decin, Leen; de Koter, Alex

2016-07-01

The physical and chemical conditions in the atmosphere of pulsating AGB stars are not well understood. In order to properly model this region, which is packed with shocks arisen from the pulsational behaviour of the star, we aim to understand the interplay between spatial and temporal changes in both the chemical composition and the hydro/thermodynamical behaviour inside these regions. Ideal models require the coupling of hydrodynamics, chemistry and radiative transfer, in three dimensions. As this is computationally not yet feasible, we aim to model this zone via a bottom-up approach. At first, we build correct 3D hydrodynamical set-up without any cooling or heating. Omitting cooling hampers the mass-loss of the AGB star within the reasonable confines of a realistic parameter space. Introducing cooling will decrease the temperature gradients in the atmosphere, counteracting the mass-loss even more. However, cooling also ensures the existence of regions where the temperature is low enough for the formation of dust to take place. This dust will absorb the momentum of the impacting photons from the AGB photosphere, accelerate outward and collide with the obstructing gas, dragging it along. Moreover, since chemistry, nucleation and dust formation depend critically on the temperature structure of the circumstellar environment, it is of utmost importance to include all relevant heating/cooling sources. Efforts to include cooling have been undertaken in the last decades, making use of different radiative cooling mechanisms for several chemical species, with some simplified radiative transfer. However, often the chemical composition of these 1D atmosphere models is fixed, implying the very strong assumption of chemical equilibrium, which is not at all true for a pulsating AGB atmosphere. We wish to model these atmospheres making as few assumptions as possible on equilibrium conditions. Therefore, as a first step, we introduce H2 dissociative cooling to the hydrodynamical model, arguing this is the dominant cooling factor. Using dissociative H2 cooling allows the ratio of the H-H2 gas mixture to vary, making the cooling efficiency time and space dependent. This will affect local cooling, in turn affecting the hydrodynamics and chemical composition, hereby introducing a feedback loop. Secondly, most significant radiative heating/cooling sources will be introduced to obtain the most realistic temperature structure. Next, dust acceleration will be introduced in the regions cool enough for dust condensation to exists. Hereby laying the basis of our hydrodynamical chemistry model for stellar winds of evolved stars.

Ultrasound use for body composition and carcass quality assessment in cattle and lambs

USDA-ARS?s Scientific Manuscript database

Genetic evaluation for carcass quality traits has evolved over time, in large part due to introduction of new technology such as ultrasound measures of body composition. Ultrasound measured body composition traits emulate important carcass traits, are very informative for selection purposes, are ac...

Chemical Mixtures Health Risk Assessment of Environmental Contaminants: Concepts, Methods, Applications: Handbook

EPA Science Inventory

This problems-based, half-day, introductory workshop focuses on methods to assess health risks posed by exposures to chemical mixtures in the environment. Chemical mixtures health risk assessment methods continue to be developed and evolve to address concerns over health risks f...

Design Projects of the Future

ERIC Educational Resources Information Center

Shaeiwitz, Joseph A.; Turton, Richard

2006-01-01

The chemical engineering profession is in the midst of a significant evolution, perhaps a revolution. As the profession moves toward product development and design and away from petroleum and chemical process development and design, a new paradigm for chemical engineering education is evolving. Therefore, a new generation of capstone design…

Chemical Heterogeneity on Mercury's Surface Revealed by the MESSENGER X-ray Spectrometer

NASA Technical Reports Server (NTRS)

Weider, Shoshana Z.; Nittler, Larry R.; Starr, Richard D.; McCoy, Timothy J.; Stockstill-Cahill, Karen R.; Byrne, Paul K.; Denevi, Brett W.; Head, James W.; Solomon, Sean C.

2012-01-01

We present the analysis of 205 spatially resolved measurements of the surfacecomposition of Mercury from MESSENGERs X-Ray Spectrometer. The surfacefootprints of these measurements are categorized according to geological terrain. Northernsmooth plains deposits and the plains interior to the Caloris basin differ compositionallyfrom older terrain on Mercury. The older terrain generally has higher MgSi, SSi, andCaSi ratios, and a lower AlSi ratio than the smooth plains. Mercurys surface mineralogyis likely dominated by high-Mg mafic minerals (e.g., enstatite), plagioclase feldspar, andlesser amounts of Ca, Mg, andor Fe sulfides (e.g., oldhamite). The compositionaldifference between the volcanic smooth plains and the older terrain reflects differentabundances of these minerals and points to the crystallization of the smooth plains from amore chemically evolved magma source. High-degree partial melts of enstatite chondritematerial provide a generally good compositional and mineralogical match for much ofthe surface of Mercury. An exception is Fe, for which the low surface abundance onMercury is still higher than that of melts from enstatite chondrites and may indicate anexogenous contribution from meteoroid impacts.

Solar-Powered Plasmon-Enhanced Heterogeneous Catalysis

NASA Astrophysics Data System (ADS)

Naldoni, Alberto; Riboni, Francesca; Guler, Urcan; Boltasseva, Alexandra; Shalaev, Vladimir M.; Kildishev, Alexander V.

2016-06-01

Photocatalysis uses semiconductors to convert sunlight into chemical energy. Recent reports have shown that plasmonic nanostructures can be used to extend semiconductor light absorption or to drive direct photocatalysis with visible light at their surface. In this review, we discuss the fundamental decay pathway of localized surface plasmons in the context of driving solar-powered chemical reactions. We also review different nanophotonic approaches demonstrated for increasing solar-to-hydrogen conversion in photoelectrochemical water splitting, including experimental observations of enhanced reaction selectivity for reactions occurring at the metalsemiconductor interface. The enhanced reaction selectivity is highly dependent on the morphology, electronic properties, and spatial arrangement of composite nanostructures and their elements. In addition, we report on the particular features of photocatalytic reactions evolving at plasmonic metal surfaces and discuss the possibility of manipulating the reaction selectivity through the activation of targeted molecular bonds. Finally, using solar-to-hydrogen conversion techniques as an example, we quantify the efficacy metrics achievable in plasmon-driven photoelectrochemical systems and highlight some of the new directions that could lead to the practical implementation of solar-powered plasmon-based catalytic devices.

X-raying supernova remnants in the Magellanic Clouds

NASA Astrophysics Data System (ADS)

Maggi, P.; Hirschi, R.; Haberl, F.; Vasilopoulos, G.; Pietsch, W.; Greiner, J.; Kavanagh, J. P.; Sasaki, M.; Bozzetto, M. L.; Filipovic, M. D.; Points, S. D.; Chu, Y.-H.; Dickel, J.; Ehle, M.; Williams, R.

2016-06-01

The Magellanic Clouds (MCs) offer an ideal laboratory for the study of the SNR population in star-forming galaxies, since they are relatively nearby and free of large absorption. Both the LMC and SMC have been targeted by large XMM-Newton surveys, which, combined with archival observations, provide the best dataset to systematically study the X-ray emission of their numerous SNRs (˜ 60 in the LMC, ˜ 20 in the SMC). In this talk, I will highlight the results from this homogeneous analysis, which allows for the first time meaningful comparisons of temperature, chemical composition, and luminosity of SNRs in the MCs. The SNRs can be used as probes of their host galaxies: We measured chemical abundances in the hot phase of the LMC, and constrained the ratio of core-collapse to type Ia SN rates. The X-ray luminosity function of SNRs in the MCs are compared to those in other Local Group galaxies with different metallicities and star formation properties. Finally, we present a new population of evolved type Ia SNRs that was discovered recently in the MCs via their iron-rich X-ray emission.

Are X-rays the key to integrated computational materials engineering?

DOE PAGES

Ice, Gene E.

2015-11-01

The ultimate dream of materials science is to predict materials behavior from composition and processing history. Owing to the growing power of computers, this long-time dream has recently found expression through worldwide excitement in a number of computation-based thrusts: integrated computational materials engineering, materials by design, computational materials design, three-dimensional materials physics and mesoscale physics. However, real materials have important crystallographic structures at multiple length scales, which evolve during processing and in service. Moreover, real materials properties can depend on the extreme tails in their structural and chemical distributions. This makes it critical to map structural distributions with sufficient resolutionmore » to resolve small structures and with sufficient statistics to capture the tails of distributions. For two-dimensional materials, there are high-resolution nondestructive probes of surface and near-surface structures with atomic or near-atomic resolution that can provide detailed structural, chemical and functional distributions over important length scales. Furthermore, there are no nondestructive three-dimensional probes with atomic resolution over the multiple length scales needed to understand most materials.« less

An isotopic perspective on growth and differentiation of Proterozoic orogenic crust: From subduction magmatism to cratonization

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

Johnson, Simon P.; Korhonen, Fawna J.; Kirkland, Christopher L.

The in situ chemical differentiation of continental crust ultimately leads to the long-term stability of the continents. This process, more commonly known as ‘cratonization’, is driven by deep crustal melting with the transfer of those melts to shallower regions resulting in a strongly chemically stratified crust, with a refractory, dehydrated lower portion overlain by a complementary enriched upper portion. Since the lower to mid portions of continental crust are rarely exposed, investigation of the cratonization process must be through indirect methods. In this study we use in situ Hf and O isotope compositions of both magmatic and inherited zircons frommore » several felsic magmatic suites in the Capricorn Orogen of Western Australia to highlight the differentiation history (i.e. cratonization) of this portion of late Archean to Proterozoic orogenic crust. The Capricorn Orogen shows a distinct tectonomagmatic history that evolves from an active continental margin through to intracratonic reworking, ultimately leading to thermally stable crust that responds similarly to the bounding Archean Pilbara and Yilgarn Cratons.« less

The mechanism of action of Russian propolis ethanol extracts against two antibiotic-resistant biofilm-forming bacteria.

PubMed

Bryan, J; Redden, P; Traba, C

2016-02-01

The interaction between antibiotic-resistant Staphylococcus aureus and antibiotic-sensitive Escherichia coli biofilm-forming bacteria and Russian propolis ethanol extracts was evaluated. In this study, bacterial cell death occurred when the cell membranes of bacteria interacted specifically with the antibacterial compounds found in propolis. In order to understand the Russian propolis ethanol extract mechanism of action, microscopy and bacterial lysis studies were conducted. Results uncovered from these experiments imply that the mechanism of action of Russian propolis ethanol extracts is structural rather than functional. The results obtained throughout this study demonstrate cell membrane damage, resulting in cell lysis and eventually bacterial death. Most strains of bacteria and subsequently biofilms, have evolved and have altered their chemical composition in an attempt to protect themselves from antibiotics. The resistant nature of bacteria stems from the chemical rather than the physical means of inactivation of antibiotics. The results uncovered in this work demonstrate the potential application of Russian propolis ethanol extracts as a very efficient and effective method for bacterial and biofilm inactivation. © 2015 The Society for Applied Microbiology.

Magma volumes and storage in the middle crust

NASA Astrophysics Data System (ADS)

Memeti, V.; Barnes, C. G.; Paterson, S. R.

2015-12-01

Quantifying magma volumes in magma plumbing systems is mostly done through geophysical means or based on volcanic eruptions. Detailed studies of plutons, however, are useful in revealing depths and evolving volumes of stored magmas over variable lifetimes of magma systems. Knowledge of the location, volume, and longevity of stored magma is critical for understanding where in the crust magmas attain their chemical signature, how these systems physically behave and how source, storage levels, and volcanoes are connected. Detailed field mapping, combined with single mineral geochemistry and geochronology of plutons, allow estimates of size and longevity of melt-interconnected magma batches that existed during the construction of magma storage sites. The Tuolumne intrusive complex (TIC) recorded a 10 myr magmatic history. Detailed maps of the major units in different parts of the TIC indicate overall smaller scale (cm- to <1 km) compositional variation in the oldest, outer Kuna Crest unit and mainly larger scale (>10 km) changes in the younger Half Dome and Cathedral Peak units. Mineral-scale trace element data from hornblende of granodiorites to gabbros from the Kuna Crest lobe show distinct hornblende compositions and zoning patterns. Mixed hornblende populations occur only at the transition to the main TIC. This compositional heterogeneity in the first 1-2 myr points to low volume magmatism resulting in smaller, discrete and not chemically interacting magma bodies. Trace element and Sr- and Pb-isotope data from growth zones of K-feldspar phenocrysts from the two younger granodiorites indicate complex mineral zoning, but general isotopic overlap, suggesting in-situ, inter-unit mixing and fractionation. This is supported by hybrid zones between units, mixing of zircon, hornblende, and K-feldspar populations and late leucogranites. Thus, magma body sizes increased later resulting in overall more homogeneous, but complexly mixing magma mushes that fractionated locally.

Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

NASA Technical Reports Server (NTRS)

Mahaffy, P.; Niemann, Hasso (Technical Monitor)

2001-01-01

Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

Method of producing hydrogen

DOEpatents

Bingham, Dennis N.; Klingler, Kerry M.; Wilding, Bruce M.; Zollinger, William T.

2006-12-26

A method of producing hydrogen is disclosed and which includes providing a first composition; providing a second composition; reacting the first and second compositions together to produce a chemical hydride; providing a liquid and reacting the chemical hydride with the liquid in a manner to produce a high pressure hydrogen gas and a byproduct which includes the first composition; and reusing the first composition formed as a byproduct in a subsequent chemical reaction to form additional chemical hydride.

Crust recycling induced compositional-temporal-spatial variations of Cenozoic basalts in the Trans-North China Orogen

NASA Astrophysics Data System (ADS)

Xu, Rong; Liu, Yongsheng; Wang, Xiaohong; Zong, Keqing; Hu, Zhaochu; Chen, Haihong; Zhou, Lian

2017-03-01

It has been advocated that the stagnant Pacific slab within the mantle transition zone played a critical role in the genesis of the Cenozoic basalts in the eastern part of the North China Craton (NCC); however, it is not clear whether this recycled oceanic crust contributed to the chemical makeup of the Cenozoic basalts in the Trans-North China Orogen (TNCO, the central zone of the NCC). Here, we show that Cenozoic basalts from the TNCO are featured by low CaO contents, high TiO2 and FeOT contents and high Fe/Mn and Zn/Fe ratios, indicating a mantle source of pyroxenite. Temporally, these basalts evolved from alkali basalts of Late Eocene-Oligocene age to coexisting alkali and tholeiitic basalts of Late Miocene-Quaternary age. Spatially, their isotopic and chemical compositions vary symmetrically from the center to both the north and the south sides along the TNCO, i.e., SiO2 contents and 87Sr/86Sr ratios increase, FeOT contents and 143Nd/144Nd, Sm/Yb and Ce/Pb ratios decrease. The estimated average melting pressure of the TNCO tholeiitic basalts ( 3 GPa) agrees well with the present lithosphere thickness beneath the north region of the TNCO ( 90-120 km). The temporal and spatial chemical variations of Cenozoic basalts in the TNCO suggest that the recycled oceanic crust in the mantle of the TNCO is mainly related to the southward subduction of the Paleo-Asian oceanic plate and the northward subduction of the Tethyan ocean plate. The westward subduction of Pacific slab may not have contributed much than previously thought.

The chemical evolution of Kurnub Group palcowater in the Sinai-Negev province - A mass balance approach

USGS Publications Warehouse

Rosenthal, E.; Jones, B.F.; Weinberger, G.

1998-01-01

The chemical evolution of the Kurnub Group paleowater was studied starting from rainwater in recharge areas of the Sinai and along groundwater flowpaths leading to the natural outlets of this regional aquifer. This was achieved by investigating the chemical composition of groundwater, ionic ratios, degrees of saturation with common mineral species, normative analysis of dissolved salts and by modeling of rock/water interaction and mixing processes occurring along groundwater flow paths. The initial groundwater composition used is from the Nakhel well in Sinai. It evolves from desert rainwater percolating through typical Kurnub Group lithology in Sinai. This rainwater dissolves mainly gypsum, halite and dolomite together with smaller amounts of marine aerosol and K-feldspar. At the same time it precipitates calcite, SiO2, smectite and degasses CO2. Between the area of Nakhel and the northern Negev the chemistry of Kurnub Group waters is influenced by dissolution of halite and lesser amounts of gypsum of surficial origin in recharge areas, small amounts of feldspars and of dolomite cement in sandstones eroded from the Arabo-Nubian igneous massif of Sinai and organic degradation-derived CO2. Concomitantly, there is precipitation of calcite, smectite, SiO2 and probably analcime characteristic of sediments in continental closed basins. North of the Negev, the Kurnub Group fluids are diluted and altered by mixing with Judea Group aquifer groundwaters. On the E there is mixing with residual brines from the water body ancestral to the Dead Sea, prior to discharge into the Arava valley. Rock/water interaction indicated by NETPATH and PHREEQC modeling is in agreement with lithology and facies changes previously observed in the Kurnub Group sequence.

Chemical and isotopic equilibrium between CO 2 and CH 4 in fumarolic gas discharges: Generation of CH 4 in arc magmatic-hydrothermal systems

NASA Astrophysics Data System (ADS)

Fiebig, Jens; Chiodini, Giovanni; Caliro, Stefano; Rizzo, Andrea; Spangenberg, Jorge; Hunziker, Johannes C.

2004-05-01

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH 4) within two subduction-related magmatic-hydrothermal environments. Apparent temperatures derived from carbon isotope partitioning between CH 4 and CO 2 of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H 2O-H 2-CO 2-CO-CH 4 geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH 4, CO 2 and H 2O implying that carbon isotope partitioning between CO 2 and CH 4 in both systems is controlled by aquifer temperature. N 2/ 3He and CH 4/ 3He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH 4 may have been primarily generated through the reduction of CO 2 by H 2 in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH 4 and subsequent re-equilibration with co-existing CO 2 cannot be ruled out entirely. CO 2/ 3He ratios and δ 13C CO 2 values imply that the evolved CO 2 either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH 4 during thermometamorphism.

The Main-belt Asteroid and NEO Tour with Imaging and Spectroscopy (MANTIS)

NASA Astrophysics Data System (ADS)

Rivkin, A.; Cohen, B. A.; Barnouin, O. S.; Chabot, N. L.; Ernst, C. M.; Klima, R. L.; Helbert, J.; Sternovsky, Z.

2015-12-01

The asteroids preserve information from the earliest times in solar system history, with compositions in the population reflecting the material in the solar nebula and experiencing a wide range of temperatures. Today they experience ongoing processes, some of which are shared with larger bodies but some of which are unique to their size regime. They are critical to humanity's future as potential threats, resource sites, and targets for human visitation. However, over twenty years since the first spacecraft encounters with asteroids, they remain poorly understood. The mission we propose here, the Main-belt Asteroid and NEO Tour with Imaging and Spectroscopy (MANTIS), explores the diversity of asteroids to understand our solar system's past history, its present processes, and future opportunities and hazards. MANTIS addresses many of NASA's highest priorities as laid out in its 2014 Science Plan and provides additional benefit to the Planetary Defense and Human Exploration communities via a low-risk, cost-effective tour of the near-Earth and inner asteroid belt. MANTIS visits the materials that witnessed solar system formation and its earliest history, addressing the NASA goal of exploring and observing the objects in the solar system to understand how they formed and evolve. MANTIS measures OH, water, and organic materials via several complementary techniques, visiting and sampling objects known to have hydrated minerals and addressing the NASA goal of improving our understanding of the origin and evolution of life on Earth. MANTIS studies the geology and geophysics of nine diverse asteroids, with compositions ranging from water-rich to metallic, representatives of both binary and non-binary asteroids, and sizes covering over two orders of magnitude, providing unique information about the chemical and physical processes shaping the asteroids, addressing the NASA goal of advancing the understanding of how the chemical and physical processes in our solar system operate, interact, and evolve. Finally, the set of measurements carried out by MANTIS at near-Earth and main-belt asteroids will by definition characterize objects in the solar system that pose threats to Earth or offer resources for human exploration, a final goal in the NASA Science Plan.

Characterization of residuals from ice particles and droplets sampled in mid-latitude natural and aviation-influenced cirrus and in tropical deep convective cloud systems during ML-CIRRUS and ACRIDICON

NASA Astrophysics Data System (ADS)

Mertes, Stephan; Kästner, Udo; Schulz, Christiane; Klimach, Thomas; Krüger, Mira; Schneider, Johannes

2015-04-01

Airborne sampling of cloud particles inside different cirrus cloud types and inside deep convective clouds was conducted during the HALO missions ML-CIRRUS over Europe in March/April 2014 and ACRIDICON over Amazonia in September 2014. ML-CIRRUS aims at the investigation of the for-mation, evolution, microphysical state and radiative effects of different natural and aviation-induced cirrus clouds in the mid-latitudes. The main objectives of ACRIDICON are the microphysical vertical profiling, vertical aerosol transport and the cloud processing of aerosol particles (compari-son in- and outflow) of tropical deep convective cloud systems in clean and polluted air masses and over forested and deforested regions. The hydrometeors (drops and ice particles) are sampled by a counterflow virtual impactor (CVI) which has to be installed in the front part of the upper fuselage of the HALO aircraft. Such an intake position implies a size dependent abundance of cloud particles with respect to ambient conditions that was studied by particle trajectory simulations (Katrin Witte, HALO Technical Note 2008-003-A). On the other hand, this sampling location avoids that large ice crystals which could potentially bias the cloud particle sampling by shattering and break-up at the inlet shroud and tip enter the inlet. Both aspects as well as the flight conditions of HALO were taken into account for an optimized CVI design for HALO (HALO-CVI). Interstitial particles are pre-segregated and the condensed phase is evaporated/sublimated by the CVI, such that the residuals from cloud droplets and ice particles (CDR and IPR) can be microphysically and chemically analyzed by respective aerosol sensors located in the cabin. Although an even more comprehensive characterization of CDR and IPR was carried out, we like to report on the following measurements of certain aerosol properties. Particle number concentra-tion and size distribution are measured by a condensation particle counter (CPC) and an ultra-high sensitivity aerosol spectrometer (UHSAS). The absorption coefficient and thus a measure for the black carbon mass concentration is derived from the particle soot absorption photometer (PSAP). In the lower warm parts of the probed convective clouds during the ACRIDICON mission the mean charge of droplets was inferred by means of electrometer measurements. For the determination of the chemical properties of CDR and IPR, the Aircraft-based Laser Ablation Aerosol Mass Spec-trometer (ALABAMA) and a Compact-Time-of-Flight-Aerosol-Mass-Spectrometer (C-ToF-AMS) was operated during ML-CIRRUS and ACRIDICON, respectively, to obtain the mixing state and chemical composition of the cloud particle residues. During ML-CIRRUS, differences in IPR concentration, size distribution, and chemical composition between natural and aviation influenced cirrus clouds could be observed as well as between dif-ferent natural cirrus types and between young and aged contrail cirrus. During ACRIDICON, CDR concentration, size distribution, and chemical composition are found to be different for convective cloud systems evolving from more clean air masses compared to systems evolving from more polluted air masses. Droplet charges change from negative to positive values with height in all vertical cloud profiles. The measured IPR concentration strongly vary in the anvil outflow regions.

A comparison of chemical compositions of reported altered oceanic crusts and global MORB data set: implication for isotopic heterogeneity of recycled materials

NASA Astrophysics Data System (ADS)

Shimoda, G.; Kogiso, T.

2017-12-01

Chemical composition of altered oceanic crust is one of important constraints to delineate chemical heterogeneity of the mantle. Accordingly, many researchers have been studied to determine bulk chemical composition of altered oceanic crust mainly based on chemical compositions of old oceanic crusts at Site 801 and Site 417/418, and young crust at Site 504 (e.g., Staudigel et al., 1996; Bach et al. 2003; Kuo et al., 2016). Their careful estimation provided reliable bulk chemical compositions of these Sites and revealed common geochemical feature of alteration. To assess effect of recycling of altered oceanic crust on chemical evolution of the mantle, it might be meaningful to discuss whether the reported chemical compositions of altered oceanic crusts can represent chemical composition of globally subducted oceanic crusts. Reported chemical compositions of fresh glass or less altered samples from Site 801, 417/418 and 504 were highly depleted compared to that of global MORB reported by Gale et al. (2013), suggesting that there might be sampling bias. Hence, it could be important to consider chemical difference between oceanic crusts of these three Sites and global MORB to discuss effect of recycling of oceanic crust on isotopic heterogeneity of the mantle. It has been suggested that one of controlling factors of chemical variation of oceanic crust is crustal spreading rate because different degree of partial melting affects chemical composition of magmas produced at a mid-ocean ridge. Crustal spreading rate could also affect intensity of alteration. Namely, oceanic crusts produced at slow-spreading ridges may prone to be altered due to existence of larger displacement faults compared to fast spreading ridges which have relatively smooth topography. Thus, it might be significant to evaluate isotopic evolution of oceanic crusts those were produced at different spreading rates. In this presentation, we will provide a possible chemical variation of altered oceanic crusts based on reported bulk chemical compositions of altered oceanic crusts and global data sets of MORB. On the basis of the chemical variation, we will discuss isotopic evolution of altered oceanic crusts to delineate isotopic variation of recycled oceanic crusts.

Lack of evolvability in self-sustaining autocatalytic networks constraints metabolism-first scenarios for the origin of life.

PubMed

Vasas, Vera; Szathmáry, Eörs; Santos, Mauro

2010-01-26

A basic property of life is its capacity to experience Darwinian evolution. The replicator concept is at the core of genetics-first theories of the origin of life, which suggest that self-replicating oligonucleotides or their similar ancestors may have been the first "living" systems and may have led to the evolution of an RNA world. But problems with the nonenzymatic synthesis of biopolymers and the origin of template replication have spurred the alternative metabolism-first scenario, where self-reproducing and evolving proto-metabolic networks are assumed to have predated self-replicating genes. Recent theoretical work shows that "compositional genomes" (i.e., the counts of different molecular species in an assembly) are able to propagate compositional information and can provide a setup on which natural selection acts. Accordingly, if we stick to the notion of replicator as an entity that passes on its structure largely intact in successive replications, those macromolecular aggregates could be dubbed "ensemble replicators" (composomes) and quite different from the more familiar genes and memes. In sharp contrast with template-dependent replication dynamics, we demonstrate here that replication of compositional information is so inaccurate that fitter compositional genomes cannot be maintained by selection and, therefore, the system lacks evolvability (i.e., it cannot substantially depart from the asymptotic steady-state solution already built-in in the dynamical equations). We conclude that this fundamental limitation of ensemble replicators cautions against metabolism-first theories of the origin of life, although ancient metabolic systems could have provided a stable habitat within which polymer replicators later evolved.

Characterizing the Effect of Laser Power on Laser Metal Deposited Titanium Alloy and Boron Carbide

NASA Astrophysics Data System (ADS)

Akinlabi, E. T.; Erinosho, M. F.

2017-11-01

Titanium alloy has gained acceptance in the aerospace, marine, chemical, and other related industries due to its excellent combination of mechanical and corrosion properties. In order to augment its properties, a hard ceramic, boron carbide has been laser cladded with it at varying laser powers between 0.8 and 2.4 kW. This paper presents the effect of laser power on the laser deposited Ti6Al4V-B4C composites through the evolving microstructures and microhardness. The microstructures of the composites exhibit the formation of α-Ti phase and β-Ti phase and were elongated towards the heat affected zone. These phases were terminated at the fusion zone and globular microstructures were found growing epitaxially just immediately after the fusion zone. Good bondings were formed in all the deposited composites. Sample A1 deposited at a laser power of 0.8 kW and scanning speed of 1 m/min exhibits the highest hardness of HV 432 ± 27, while sample A4 deposited at a laser power of 2.0 kW and scanning speed of 1 m/min displays the lowest hardness of HV 360 ± 18. From the hardness results obtained, ceramic B4C has improved the mechanical properties of the primary alloy.

Kinetics of methane hydrate replacement with carbon dioxide and nitrogen gas mixture using in situ NMR spectroscopy.

PubMed

Cha, Minjun; Shin, Kyuchul; Lee, Huen; Moudrakovski, Igor L; Ripmeester, John A; Seo, Yutaek

2015-02-03

In this study, the kinetics of methane replacement with carbon dioxide and nitrogen gas in methane gas hydrate prepared in porous silica gel matrices has been studied by in situ (1)H and (13)C NMR spectroscopy. The replacement process was monitored by in situ (1)H NMR spectra, where about 42 mol % of the methane in the hydrate cages was replaced in 65 h. Large amounts of free water were not observed during the replacement process, indicating a spontaneous replacement reaction upon exposing methane hydrate to carbon dioxide and nitrogen gas mixture. From in situ (13)C NMR spectra, we confirmed that the replacement ratio was slightly higher in small cages, but due to the composition of structure I hydrate, the amount of methane evolved from the large cages was larger than that of the small cages. Compositional analysis of vapor and hydrate phases was also carried out after the replacement reaction ceased. Notably, the composition changes in hydrate phases after the replacement reaction would be affected by the difference in the chemical potential between the vapor phase and hydrate surface rather than a pore size effect. These results suggest that the replacement technique provides methane recovery as well as stabilization of the resulting carbon dioxide hydrate phase without melting.

The Galactic evolution of phosphorus

NASA Astrophysics Data System (ADS)

Caffau, E.; Bonifacio, P.; Faraggiana, R.; Steffen, M.

2011-08-01

Context. As a galaxy evolves, its chemical composition changes and the abundance ratios of different elements are powerful probes of the underlying evolutionary processes. Phosphorous is an element whose evolution has remained quite elusive until now, because it is difficult to detect in cool stars. The infrared weak P i lines of the multiplet 1, at 1050-1082 nm, are the most reliable indicators of the presence of phosphorus. The availability of CRIRES at VLT has permitted access to this wavelength range in stellar spectra. Aims: We attempt to measure the phosphorus abundance of twenty cool stars in the Galactic disk. Methods: The spectra are analysed with one-dimensional model-atmospheres computed in local thermodynamic equilibrium (LTE). The line formation computations are performed assuming LTE. Results: The ratio of phosphorus to iron behaves similarly to sulphur, increasing towards lower metallicity stars. Its ratio with respect to sulphur is roughly constant and slightly larger than solar, [P/S] = 0.10 ± 0.10. Conclusions: We succeed in taking an important step towards the understanding of the chemical evolution of phosphorus in the Galaxy. However, the observed rise in the P/Fe abundance ratio is steeper than predicted by Galactic chemical evolution model developed by Kobayashi and collaborators. Phosphorus appears to evolve differently from the light odd-Z elements sodium and aluminium. The constant value of [P/S] with metallicity implies that P production is insensitive to the neutron excess, thus processes other than neutron captures operate. We suggest that proton captures on 30Si and α captures on 27Al are possibilities to investigate. We see no clear distinction between our results for stars with planets and stars without any detected planet. Based on observations obtained with the CRIRES spectrograph at ESO-VLT Antu 8.2 m telescope at Paranal, Programme 386.D-0130, P.I. E. Caffau.

Chemical Mixtures Health Risk Assessment: Overview of Exposure Assessment, Whole Mixtures Assessments; Basic Concepts

EPA Science Inventory

This problems-based, half-day, introductory workshop focuses on methods to assess health risks posed by exposures to chemical mixtures in the environment. Chemical mixtures health risk assessment methods continue to be developed and evolve to address concerns over health risks f...

Chemical Dependency Regional Needs Assessment: Northeastern Minnesota.

ERIC Educational Resources Information Center

Stone, Marylee

The Minnesota Model of Chemical Dependency Treatment, which evolved from a combination of the grassroots Alcoholics Anonymous movement and the State Mental Health Services in the 1960s has made Minnesota an international leader in chemical dependency treatment efforts. Northeastern Minnesota has shared this reputation with the state. In spite of…

Preservation of overmature, ancient, sedimentary organic matter in carbonate concretions during outcrop weathering.

PubMed

Loyd, S J

2017-01-01

Concretions are preferentially cemented zones within sediments and sedimentary rocks. Cementation can result from relatively early diagenetic processes that include degradation of sedimentary organic compounds or methane as indicated by significantly 13 C-depleted or enriched carbon isotope compositions. As minerals fill pore space, reduced permeability may promote preservation of sediment components from degradation during subsequent diagenesis, burial heating and outcrop weathering. Discrete and macroscopic organic remains, macro and microfossils, magnetic grains, and sedimentary structures can be preferentially preserved within concretions. Here, Cretaceous carbonate concretions of the Holz Shale are shown to contain relatively high carbonate-free total organic carbon (TOC) contents (up to ~18.5 wt%) compared to the surrounding host rock (with <2.1 wt%). TOC increases with total inorganic carbon (TIC) content, a metric of the degree of cementation. Pyrite contents within concretions generally correlate with organic carbon contents. Concretion carbonate carbon isotope compositions (δ 13 C carb ) range from -22.5 to -3.4‰ (VPDB) and do not correlate strongly with TOC. Organic carbon isotope compositions (δ 13 C org ) of concretions and host rock are similar. Thermal maturity data indicate that both host and concretion organic matter are overmature and have evolved beyond the oil window maturity stage. Although the organic matter in general has experienced significant oxidative weathering, concretion interiors exhibit lower oxygen indices relative to the host. These results suggest that carbonate concretions can preferentially preserve overmature, ancient, sedimentary organic matter during outcrop weathering, despite evidence for organic matter degradation genetic mechanisms. As a result, concretions may provide an optimal proxy target for characterization of more primary organic carbon concentrations and chemical compositions. In addition, these findings indicate that concretions can promote delayed oxidative weathering of organic carbon in outcrop and therefore impact local chemical cycling. © 2016 John Wiley & Sons Ltd.

Variability of chemical analysis of reinforcing bar produced in Saudi Arabia

NASA Astrophysics Data System (ADS)

Salman, A.; Djavanroodi, F.

2018-04-01

In view of the importance and demanding roles of steel rebar’s in the reinforced concrete structures, accurate information on the properties of the steels is important at the design stage. In the steelmaking process, production variations in chemical composition are unavoidable. The aim of this work is to study the variability of the chemical composition of reinforcing steel produced throughout the Saudi Arabia and asses the quality of steel rebar’s acoording to ASTM A615. 68 samples of ASTM A615 Grade 60 from different manufacturers were collected and tested using the Spectrometer test to obtain Chemical Compositions. EasyFit (5.6) software is utilized to conducted statistical analysis. Chemical compositions distributions and, control charts are generated for the compositions. Results showed that some compositions are above the upper line of the control chart. Finally, the analyses show that less than 3% of the steel failed to meet minimum ASTM standards for chemical composition.

Analyzing the Formation, Physicochemical, and Optical Properties of Aging Biomass Burning Aerosol Using an Indoor Smog Chamber

NASA Astrophysics Data System (ADS)

Smith, D. M.; Fiddler, M. N.; Bililign, S.; Spann, M.

2017-12-01

Biomass burning (BB) is recognized as one of the largest sources of absorbing aerosols in the atmosphere and significantly influences the radiative properties of the atmosphere. The chemical composition and physical properties of particles evolve during their atmospheric lifetime due to condensation, oxidation reactions, etc., which alters their optical properties. To this end, an indoor smog chamber was constructed to study aging BB aerosol in a laboratory setting. Injections to the chamber, including NOx, O3, and various biogenic and anthropogenic VOCs, can simulate a variety of atmospheric conditions. These components and some of their oxidation products are monitored during the aging process. A tube furnace is used for combustion of biomass to be introduced to the chamber, while size distributions are taken as the aerosol ages. Online measurements of optical properties are determined using a Cavity Ring-down Spectrometry and Integrating Nephelometry system. Chemical properties are measured from samples captured on filters and analyzed using Ultra-Performance Liquid Chromatography coupled in-line to both a Diode Array Detector and High-Resolution Time-of-Flight Mass Spectrometer equipped with electrospray ionization. The measured changes in the optical properties as a function of particle size, aging, and chemical properties are presented for fuel sources used in Africa.

Carbon Isotopic Composition of CO2, Evolved During Perchlorate-Induced Reactions in Mars Analog Materials: Interpreting SAM/MSL Rocknest Data

NASA Technical Reports Server (NTRS)

Stern, J. C.; McAdam, A. C.; Archer, P. D., Jr.; Bower, H.; Buch, A.; Eigenbrode, J.; Freissinet, C.; Franz, H. B.; Glavin, D.; Jones, J. H.;

Introducing Graduate Students to the Chemical Information Landscape: The Ongoing Evolution of a Graduate-Level Chemical Information Course

ERIC Educational Resources Information Center

Currano, Judith N.

2016-01-01

The University of Pennsylvania's doctoral chemistry curriculum has included a required course in chemical information since 1995. Twenty years later, the course has evolved from a loosely associated series of workshops on information resources to a holistic examination of the chemical literature and its place in the general research process. The…

The oligocene Lund Tuff, Great Basin, USA: A very large volume monotonous intermediate

USGS Publications Warehouse

Maughan, L.L.; Christiansen, E.H.; Best, M.G.; Gromme, C.S.; Deino, A.L.; Tingey, D.G.

2002-01-01

Unusual monotonous intermediate ignimbrites consist of phenocryst-rich dacite that occurs as very large volume (> 1000 km3) deposits that lack systematic compositional zonation, comagmatic rhyolite precursors, and underlying plinian beds. They are distinct from countless, usually smaller volume, zoned rhyolite-dacite-andesite deposits that are conventionally believed to have erupted from magma chambers in which thermal and compositional gradients were established because of sidewall crystallization and associated convective fractionation. Despite their great volume, or because of it, monotonous intermediates have received little attention. Documentation of the stratigraphy, composition, and geologic setting of the Lund Tuff - one of four monotonous intermediate tuffs in the middle-Tertiary Great Basin ignimbrite province - provides insight into its unusual origin and, by implication, the origin of other similar monotonous intermediates. The Lund Tuff is a single cooling unit with normal magnetic polarity whose volume likely exceeded 3000 km3. It was emplaced 29.02 ?? 0.04 Ma in and around the coeval White Rock caldera which has an unextended north-south diameter of about 50 km. The tuff is monotonous in that its phenocryst assemblage is virtually uniform throughout the deposit: plagioclase > quartz ??? hornblende > biotite > Fe-Ti oxides ??? sanidine > titanite, zircon, and apatite. However, ratios of phenocrysts vary by as much as an order of magnitude in a manner consistent with progressive crystallization in the pre-eruption chamber. A significant range in whole-rock chemical composition (e.g., 63-71 wt% SiO2) is poorly correlated with phenocryst abundance. These compositional attributes cannot have been caused wholly by winnowing of glass from phenocrysts during eruption, as has been suggested for the monotonous intermediate Fish Canyon Tuff. Pumice fragments are also crystal-rich, and chemically and mineralogically indistinguishable from bulk tuff. We postulate that convective mixing in a sill-like magma chamber precluded development of a zoned chamber with a rhyolitic top or of a zoned pyroclastic deposit. Chemical variations in the Lund Tuff are consistent with equilibrium crystallization of a parental dacitic magma followed by eruptive mixing of compositionally diverse crystals and high-silica rhyolite vitroclasts during evacuation and emplacement. This model contrasts with the more systematic withdrawal from a bottle-shaped chamber in which sidewall crystallization creates a marked vertical compositional gradient and a substantial volume of capping-evolved rhyolite magma. Eruption at exceptionally high discharge rates precluded development of an underlying plinian deposit. The generation of the monotonous intermediate Lund magma and others like it in the middle Tertiary of the western USA reflects an unusually high flux of mantle-derived mafic magma into unusually thick and warm crust above a subducting slab of oceanic lithosphere. ?? 2002 Elsevier Science B.V. All rights reserved.

Bacterial community dynamics in long-term operation of a pilot plant using aerobic granular sludge to treat pig slurry.

PubMed

Fra-Vázquez, A; Morales, N; Figueroa, M; Val Del Río, A; Regueiro, L; Campos, J L; Mosquera-Corral, A

2016-09-01

Aerobic granular sludge represents an interesting approach for simultaneous organic matter and nitrogen removal in wastewater treatment plants. However, the information about microbial communities in aerobic granular systems dealing with industrial wastewater like pig slurry is limited. Herein, bacterial diversity and dynamics were assessed in a pilot scale plant using aerobic granular sludge for organic matter and nitrogen elimination from swine slurry during more than 300 days. Results indicated that bacterial composition evolved throughout the operational period from flocculent activated sludge, used as inoculum, to mature aerobic granules. Bacterial diversity increased at the beginning of the granulation process and then declined due to the application of transient organic matter and nitrogen loads. The operational conditions of the pilot plant and the degree of granulation determined the microbial community of the aerobic granules. Brachymonas, Zoogloea and Thauera were attributed with structural function as they are able to produce extracellular polymeric substances to maintain the granular structure. Nitrogen removal was justified by partial nitrification (Nitrosomonas) and denitrification (Thauera and Zoogloea), while Comamonas was identified as the main organic matter oxidizing bacteria. Overall, clear links between bacterial dynamics and composition with process performance were found and will help to predict their biological functions in wastewater ecosystems improving the future control of the process. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1212-1221, 2016. © 2016 American Institute of Chemical Engineers.

Nanoscale morphogenesis of nylon-sputtered plasma polymer particles

NASA Astrophysics Data System (ADS)

Choukourov, Andrei; Shelemin, Artem; Pleskunov, Pavel; Nikitin, Daniil; Khalakhan, Ivan; Hanuš, Jan

2018-05-01

Sub-micron polymer particles are highly important in various fields including astrophysics, thermonuclear fusion and nanomedicine. Plasma polymerization offers the possibility to produce particles with tailor-made size, crosslink density and chemical composition to meet the requirements of a particular application. However, the mechanism of nucleation and growth of plasma polymer particles as well as diversity of their morphology remain far from being clear. Here, we prepared nitrogen-containing plasma polymer particles by rf magnetron sputtering of nylon in a gas aggregation cluster source with variable length. The method allowed the production of particles with roughly constant chemical composition and number density but with the mean size changing from 80 to 320 nm. Atomic Force Microscopy with super-sharp probes was applied to study the evolution of the particle surface topography as they grow in size. Height–height correlation and power spectral density functions were obtained to quantify the roughness exponent α  =  0.78, the growth exponent β  =  0.35, and the dynamic exponent 1/z  =  0.50. The set of critical exponents indicates that the particle surface evolves in a self-affine mode and the overall particle growth is caused by the accretion of polymer-forming species from the gas phase and not by coagulation. Redistribution of the incoming material over the surface coupled with the inhomogeneous distribution of inner stress is suggested as the main factor that determines the morphogenesis of the plasma polymer particles.

Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction

NASA Astrophysics Data System (ADS)

Minitti, M. P.; Budarz, J. M.; Kirrander, A.; Robinson, J. S.; Ratner, D.; Lane, T. J.; Zhu, D.; Glownia, J. M.; Kozina, M.; Lemke, H. T.; Sikorski, M.; Feng, Y.; Nelson, S.; Saita, K.; Stankus, B.; Northey, T.; Hastings, J. B.; Weber, P. M.

2015-06-01

Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.

Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction.

PubMed

Minitti, M P; Budarz, J M; Kirrander, A; Robinson, J S; Ratner, D; Lane, T J; Zhu, D; Glownia, J M; Kozina, M; Lemke, H T; Sikorski, M; Feng, Y; Nelson, S; Saita, K; Stankus, B; Northey, T; Hastings, J B; Weber, P M

2015-06-26

Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.

Is there a single origin of life?

NASA Astrophysics Data System (ADS)

Soffen, Gerald A.

The emergence of the first life on the earth is now established as an early event, and closely related to the evolving earth. Laboratory experiments examining possible chemical events have revealed a multitude of plausible pathways. Lack of knowledge of the primitive terrestrial conditions contemporary with the evolving prebolic organic chemistry limits reconstruction techniques. The primitive earth's aqueous history is essential to unraveling this problem. Based on our current knowledge of other planets of the solar system, we do not expect close analogues to the early earth. We still do not know if there was a second origin or if only earth has life. This may depend upon the question of the survival of information bearing chemical systems in a dynamic or chaotic environment and the chemical protection afforded within such a system. Water is the central molecule of controversy: the blessing and the curse of the chemist. New and novel chemical mechanisms and systems abound.

Forward selection for multiple resistance across the non-selective glyphosate, glufosinate and oxyfluorfen herbicides in Lolium weed species.

PubMed

Fernández, Pablo; Alcántara, Ricardo; Osuna, María D; Vila-Aiub, Martin M; Prado, Rafael De

2017-05-01

In the Mediterranean area, Lolium species have evolved resistance to glyphosate after decades of continual use without other alternative chemicals in perennial crops (olive, citrus and vineyards). In recent years, oxyfluorfen alone or mixed with glyphosate and glufosinate has been introduced as a chemical option to control dicot and grass weeds. Dose-response studies confirmed that three glyphosate-resistant Lolium weed species (L. rigidum, L. perenne, L. multiflorum) collected from perennial crops in the Iberian Peninsula have also evolved resistance to glufosinate and oxyfluorfen herbicides, despite their recent introduction. Based on the LD 50 resistance parameter, the resistance factor was similar among Lolium species and ranged from 14- to 21-fold and from ten- to 12-fold for oxyfluorfen and glufosinate respectively. Similarly, about 14-fold resistance to both oxyfluorfen and glufosinate was estimated on average for the three Lolium species when growth reduction (GR 50 ) was assessed. This study identified oxyfluorfen resistance in a grass species for the first time. A major threat to sustainability of perennial crops in the Iberian Peninsula is evident, as multiple resistance to non-selective glyphosate, glufosinate and oxyfluorfen herbicides has evolved in L. rigidum, L. perenne and L. multiflorum weeds. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Long-Term Changes in Chemical Weathering in the Himalayan Region from Indus Fan Sediments

NASA Astrophysics Data System (ADS)

Carter, S.; Griffith, E. M.; Scher, H.; Dellapenna, T. M.; Clift, P. D.

2017-12-01

The Asian Monsoon reflects large-scale interactions between the atmosphere, land, and ocean systems. Increasing our understanding of this system, how and why it has evolved through time, is critically important in order to understand how it may evolve in the future. The radiogenic strontium isotopic signature (87Sr/86Sr) of the clay fraction in deep sea sediment cores within submarine fans has been used as a record of riverine 87Sr/86Sr composition to gain information about Himalayan weathering intensity. Strontium exists in clay minerals primarily in interlayer sites or adsorbed onto mineral surfaces. Interlayer cation exchange is thought to be completed within rivers during recrystallization or neoformation of clays. A record of chemical weathering intensity in the Himalayas is presented by analyzing the 87Sr/86Sr signature of the clay fraction in sediments from International Ocean Discovery Program (IODP) Expedition 355 Sites U1456 and U1457, located on the Indus Fan, eastern Arabian Sea. This record will be coupled with additional records of bulk grain size and K/Al ratios of clay as potentially additional indicators of weathering intensity. The Sr isotopes in the interstitial waters at each site have also been measured (Carter et al., in press) to verify that the Sr in the treated clay fraction is not being reset by diagenesis in the sedimentary column. Initial results verify that the 87Sr/86Sr values of the clay are less than those in the bulk sediment, as expected, but are not similar to pore fluid Sr. 87Sr/86Sr values of the clays show trends suggesting fluctuations in chemical weathering intensity through time. However, bulk grain size and K/Al ratios results conflict with the 87Sr/86Sr values. If the additional proxy records continue to show conflicting results for "weathering intensity", together they may reveal more information regarding the sedimentary system. Ultimately, the various records will either agree, providing strong evidence for changes in chemical weathering and the evolution of the monsoon, or disagree, allowing for further investigation into the relationships between chemical weathering, evolution of the flood plain, and sediment deposition in the fan. These new records will aid in the correlation of Himalayan exhumation and monsoon intensity and help to constrain this dynamic system.

Aerosols and Clouds: In Cahoots to Change Climate

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

Berg, Larry

Key knowledge gaps persist despite advances in the scientific understanding of how aerosols and clouds evolve and affect climate. The Two-Column Aerosol Project, or TCAP, was designed to provide a detailed set of observations to tackle this area of unknowns. Led by PNNL atmospheric scientist Larry Berg, ARM's Climate Research Facility was deployed in Cape Cod, Massachusetts for the 12-month duration of TCAP, which came to a close in June 2013. "We are developing new tools to look at particle chemistry, like our mass spectrometer used in TCAP that can tell us the individual chemical composition of an aerosol," saidmore » Berg. "Then, we'll run our models and compare it with the data that we have to make sure we're getting correct answers and make sure our climate models are reflecting the best information."« less

Brine Migration in Heated Salt: Lessons Learned from Field Experiments

NASA Astrophysics Data System (ADS)

Kuhlman, K. L.; Matteo, E. N.; Mills, M.

2017-12-01

We summarize several interesting brine migration related phenomena hinted at in field experiments from field testing related to salt radioactive waste repositories in Germany and the US. Past heater tests in salt have shown 1) thermal-hydrological-mechanical coupling is quite strong during both heating and cooling; 2) chemical composition of brine evolves during heating, and comprises a mix of several water sources; and 3) acid gas (HCl) generation has been observed during past heater tests and may have multiple mechanisms for formation. We present a heated brine migration test design, formulated with these complexities in mind. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525.

Hubble Space Telescope: A cosmic time machine

NASA Technical Reports Server (NTRS)

Westphal, J. A.; Harms, R. J.; Brandt, J. C.; Bless, R. C.; Macchetto, F. D.; Jefferys, W. H.

1991-01-01

The mission of the Hubble Space Telescope (HST) is to explore the expanding and evolving universe. During the 3,000 operating hours every year for the next 15 years or more, the HST will be used to study: galaxies; pulsars; globular clusters; neighboring stars where planets may be forming; binary star systems; condensing gas clouds and their chemical composition; and the rings of Saturn and the swirling ultraviolet clouds of Venus. The major technical achievements - its nearly perfect mirrors, its precise guidance system of rate gyroscopes, reaction wheels, star trackers, and fine guidance sensors are briefly discussed. The scientific instruments on board HST are briefly described. The integration of the equipment and instruments is outlined. The Space Telescope Science Institute (STScI) has approved time for 162 observations from among 556 proposals. The mission operation and data flow are explained.

Aerosols and Clouds: In Cahoots to Change Climate

ScienceCinema

Berg, Larry

2018-01-16

Key knowledge gaps persist despite advances in the scientific understanding of how aerosols and clouds evolve and affect climate. The Two-Column Aerosol Project, or TCAP, was designed to provide a detailed set of observations to tackle this area of unknowns. Led by PNNL atmospheric scientist Larry Berg, ARM's Climate Research Facility was deployed in Cape Cod, Massachusetts for the 12-month duration of TCAP, which came to a close in June 2013. "We are developing new tools to look at particle chemistry, like our mass spectrometer used in TCAP that can tell us the individual chemical composition of an aerosol," said Berg. "Then, we'll run our models and compare it with the data that we have to make sure we're getting correct answers and make sure our climate models are reflecting the best information."

Chemical heterogeneities in the interior of terrestrial bodies

NASA Astrophysics Data System (ADS)

Plesa, Ana-Catalina; Maurice, Maxime; Tosi, Nicola; Breuer, Doris

2016-04-01

Mantle chemical heterogeneities that can strongly influence the interior dynamics have been inferred for all terrestrial bodies of the Solar System and range from local to global scale. Seismic data for the Earth, differences in surface mineral compositions observed in data sets from space missions, and isotopic variations identified in laboratory analyses of meteorites or samples indicate chemically heterogeneous systems. One way to generate large scale geochemical heterogeneities is through the fractional crystallization of a liquid magma ocean. The large amount of energy available in the early stages of planetary evolution can cause melting of a significant part or perhaps even the entire mantle of a terrestrial body resulting in a liquid magma ocean. Assuming fractional crystallization, magma ocean solidification proceeds from the core-mantle boundary to the surface where dense cumulates tend to form due to iron enrichment in the evolving liquid. This process leads to a gravitationally unstable mantle, which is prone to overturn. Following cumulate overturn, a stable stratification may be reached that prevents efficient material transport. As a consequence, mantle reservoirs may be kept separate, possibly for the entire thermo-chemical evolution of a terrestrial body. Scenarios assuming fractional crystallization of a liquid magma ocean have been suggested to explain lavas with distinct composition on Mercury's surface [1], the generation of the Moon's mare basalts by sampling a reservoir consisting of overturned ilmenite-bearing cumulates [2], and the preservation of Mars' geochemical reservoirs as inferred by isotopic analysis of the SNC meteorites [3]. However, recent studies have shown that the style of the overturn as well as the subsequent density stratification are of extreme importance for the subsequent thermo-chemical evolution of a planetary body and may have a major impact on the later surface tectonics and volcanic history. The rapid formation of a stagnant lid that traps the uppermost dense cumulates close to the surface and prevents them from sinking into the mantle or the difficulty to initiate thermal convection because of the stable compositional gradient established after the overturn are difficult to reconcile with observations [4, 5]. More recent results show that the crystallization achieved upon solidification of a liquid magma ocean is considerably more complex than previously assumed. In fact, the onset of solid-state convection prior to complete crystallization of the mantle can efficiently reduce mantle chemical heterogeneities [5]. We thus conclude that mantle mixing may partly or even completely erase the effects of fractional crystallization well before complete solidification. Nevertheless, the subsequent differentiation caused by partial melting, may introduce additional heterogeneities between residual and primitive mantle that could explain compositional differences observed over the surface of terrestrial bodies [6]. References: [1] Charlier et al., 2013, EPSL; [2] Elkins-Tanton et al., 2011, EPSL; [3] Elkins-Tanton et al., 2005, JGR; [4] Tosi et al., 2013, JGR; [5] Plesa et al., 2014, EPSL; [5] Maurice et al, 2015, EGU; [6] Plesa & Breuer, 2014, PSS.

The impact behaviour of silk cocoons.

PubMed

Chen, Fujia; Hesselberg, Thomas; Porter, David; Vollrath, Fritz

2013-07-15

Silk cocoons, constructed by silkmoths (Lepidoptera), are protective structural composites. Some cocoons appear to have evolved towards structural and material optimisation in order to sustain impact strikes from predators and hinder parasite ingress. This study investigates the protective properties of silk cocoons with different morphologies by evaluating their impact resistance and damage tolerance. Finite element analysis was used to analyse empirical observations of the quasi-static impact response of the silk cocoons, and to evaluate the separate benefits of the structures and materials through the deformation and damage mechanism. We use design principles from composite engineering in order to understand the structure-property-function relationship of silkworm cocoons. Understanding the highly evolved survival strategies of the organisms building natural cocoons will hopefully lead to inspiration that in turn could lead to improved composite design.

Basaltic Volcanism and Ancient Planetary Crusts

NASA Technical Reports Server (NTRS)

Shervais, John W.

1993-01-01

The purpose of this project is to decipher the origin of rocks which form the ancient lunar crust. Our goal is to better understand how the moon evolved chemically and, more generally, the processes involved in the chemical fractionation of terrestrial planetoids. This research has implications for other planetary bodies besides the Moon, especially smaller planetoids which evolved early in the history of the solar system and are now thermally stable. The three main areas focused on in our work (lunar mare basalts, KREEP basalts, and plutonic rocks of the lunar highlands) provide complementary information on the lunar interior and the processes that formed it.

Evidence for a homogeneous primary magma at Piton de la Fournaise (La Réunion): A geochemical study of matrix glass, melt inclusions and Pélé's hairs of the 1998-2008 eruptive activity

NASA Astrophysics Data System (ADS)

Villemant, B.; Salaün, A.; Staudacher, T.

2009-07-01

Magmas erupted at Piton de la Fournaise volcano since 0.5 Ma, display a large petrological and chemical range (picrites, 2 types of transitional basalts and differentiated magmas) and low amplitude isotopic heterogeneities. The recent activity (1998-2008) includes all magma types except evolved magmas. Matrix glass compositions from quenched lavas and Pélé's hairs of the whole 1998-2008 period define a single differentiation trend from a common basaltic melt (MgO ~ 9%) for the first time identified in the 2007 magmas. More primitive melt compositions (MgO ~ 12.5%) are only evidenced by olivine crystals with high Fo contents (Fo 85-88.4). Evolutions of major and trace element of glass and mineral compositions are consistently modelled by a unique low pressure crystal fractionation process. The composition range of olivine melt inclusions is distinct from that of matrix glass and Pélé's hair and corresponds to equilibrium crystallisation in closed system of melts trapped from the main differentiation series at high temperature. The range of basaltic types at Piton de la Fournaise is the result of large variations in the differentiation degree (10 to 35% crystallisation) of a single primary basaltic melt and the addition in highly variable amounts (up to 50% in picrites) of co-genetic olivine or gabbroic cumulates. These cumulates may represent the shallow and dense bodies identified by seismic tomography and have likely been produced by the repetitive intrusion and differentiation of basalts along Piton de la Fournaise history. Depending on the shallow transfer paths, ascending magmas may disaggregate and incorporate various types of cumulates, explaining all particular features of basaltic magmas and picrites. These results emphasize the exceptional chemical homogeneity of the primary basaltic melt and of the differentiation process involved in volcanic activity of La Réunion hotspot since 0.5 Ma and the increasingly recognised role of melt-wall rock interactions in compositional and petrological diversity of erupted magmas.

The Deep Crust Magmatic Refinery, Part 2 : The Magmatic Output of Numerical Models.

NASA Astrophysics Data System (ADS)

Bouilhol, P.; Riel, N., Jr.; Van Hunen, J.

2016-12-01

Metamorphic and magmatic processes occurring in the deep crust ultimately control the chemical and physical characteristic of the continental crust. A complex interplay between magma intrusion, crystallization, and reaction with the pre-existing crust provide a wide range of differentiated magma and cumulates (and / or restites) that will feed the upper crustal levels with evolved melt while constructing the lower crust. With growing evidence from field and experimental studies, it becomes clearer that crystallization and melting processes are non-exclusive but should be considered together. Incoming H2O bearing mantle melts will start to fractionate to a certain extent, forming cumulates but also releasing heat and H2O to the intruded host-rock allowing it to melt in saturated conditions. The end-result of such dynamic system is a function of the amount and composition of melt input, and extent of reaction with the host which is itself dependent on the migration mode of the melts. To better constrain lower crust processes, we have built up a numerical model [see Riel et al. associated abstract for methods] to explore different parameters, unravelling the complex interplay between melt percolation / crystallization and degassing / re-melting in a so called "hot zone" model. We simulated the intrusion of water bearing mantle melts at the base of an amphibolitized lower crust during a magmatic event that lasts 5 Ma. We varied several parameters such as Moho depth and melt rock ratio to better constrain what controls the final melt / lower crust composition.. We show the evolution of the chemical characteristics of the melt that escape the system during this magmatic event, as well as the resulting lower crust characteristics. We illustrate how the evolution of melt major elements composition reflects the progressive replacement of the crust towards compositions that are dominated by the mantle melt input. The resulting magmas cover a wide range of composition from tonalite to granite, and the modelled lower crust shows all the petrological characteristic of observed lower arc-crust.

Production waters associated with the Ferron coalbed methane fields, central Utah: Chemical and isotopic composition and volumes

USGS Publications Warehouse

Rice, C.A.

2003-01-01

This study investigated the composition of water co-produced with coalbed methane (CBM) from the Upper Cretaceous Ferron Sandstone Member of the Mancos Shale in east-central Utah to better understand coalbed methane reservoirs. The Ferron coalbed methane play currently has more than 600 wells producing an average of 240 bbl/day/well water. Water samples collected from 28 wellheads in three fields (Buzzards Bench, Drunkards Wash, and Helper State) of the northeast-southwest trending play were analyzed for chemical and stable isotopic composition.Water produced from coalbed methane wells is a Na-Cl-HCO3 type. Water from the Drunkards Wash field has the lowest total dissolved solids (TDS) (6300 mg/l) increasing in value to the southeast and northeast. In the Helper State field, about 6 miles northeast, water has the highest total dissolved solids (43,000 mg/l), and major ion abundance indicates the possible influence of evaporite dissolution or mixing with a saline brine. In the southern Buzzards Bench field, water has variable total dissolved solids that are not correlated with depth or spatial distance. Significant differences in the relative compositions are present between the three fields implying varying origins of solutes and/or different water-rock interactions along multiple flow paths.Stable isotopic values of water from the Ferron range from +0.9??? to -11.4??? ?? 18O and -32??? to -90??? ?? 2H and plot below the global meteoric water line (GMWL) on a line near, but above values of present-day meteoric water. Isotopic values of Ferron water are consistent with modification of meteoric water along a flow path by mixing with an evolved seawater brine and/or interaction with carbonate minerals. Analysis of isotopic values versus chloride (conservative element) and total dissolved solids concentrations indicates that recharge water in the Buzzards Bench area is distinct from recharge water in Drunkards Wash and is about 3 ??C warmer. These variations in isotopes along with compositional variations imply that the Ferron reservoir is heterogeneous and compartmentalized, and that multiple flow paths may exist. ?? 2003 Published by Elsevier B.V. All rights reserved.

Exploring the Structure and Evolution of the Universe: Multi-Band Profiles of the Known Gamma-Ray Pulsars

NASA Technical Reports Server (NTRS)

1998-01-01

As summarized in this pamphlet, some of the far-reaching underlying issues to be addressed include: What is the origin of the universe and its destiny; Why is the universe lumpy; How did the known structures of the universe evolve; How do galaxies evolve; How do massive black holes grow; How did the elemental composition of the universe evolve; What is the structure and behavior of matter in the extreme; and Is Einstein's general relativity theory right.

Environmental and Chemical Aging of Fatty-Acid-Based Vinyl Ester Composites

DTIC Science & Technology

2011-04-01

Environmental and Chemical Aging of Fatty- Acid -Based Vinyl Ester Composites by Steven E. Boyd and John J. La Scala ARL-TR-5523 April...2011 Environmental and Chemical Aging of Fatty- Acid -Based Vinyl Ester Composites Steven E. Boyd and John J. La Scala Weapons and Materials...COVERED (From - To) October 2009–September 2010 4. TITLE AND SUBTITLE Environmental and Chemical Aging of Fatty- Acid -Based Vinyl Ester Composites

An Apollo 15 Mare Basalt Fragment and Lunar Mare Provinces

NASA Technical Reports Server (NTRS)

Ryder, Graham; Burling, Trina Cox

1996-01-01

Lunar sample 15474,4 is a tiny fragment of olivine-augite vitrophyre that is a mare basalt. Although petroraphically distinct from all other Apollo 15 samples, it has been ignored since its first brief description. Our new petrographic and mineral chemical data show that the olivines and pyroxenes are distinct from those in other basalts. The basalt cooled and solidified extremely rapidly; some of the olivine might be cumulate or crystallized prior to extrusion. Bulk-chemical data show that the sample is probably similar to an evolved Apollo 15 olivine-normative basalt in major elements but is distinct in its rare earth element pattern. Its chemical composition and petrography both show that 15474,4 cannot be derived from other Apollo 15 mare basalts by shallow-level crystal fractionation. It represents a distinct extrusion of magma. Nonetheless, the chemical features that 15474,4 has in common with other Apollo 15 mare basalts, including the high FeO/Sc, the general similarity of the rare earth element pattern, and the common (and chondritic) TiO2/Sm ratio, emphasize the concept of a geochemical province at the Apollo 15 site that is distinct from basalts and provinces elsewhere. In making a consistent picture for the derivation of all of the Apollo 15 basalts, both the commonalities and the differences among the basalts must be explained. The Apollo 15 commonalities and differences suggest that the sources must have consisted of major silicate phases with the same composition but with varied amounts of a magma trapped from a contemporary magma ocean. They probably had a high olivine/pyroxene ratio and underwent small and reasonably consistent degrees of partial melting to produce the basalts. These inferences may be inconsistent with models that suggest greatly different depths of melting among basalts, primitive sources for the green glasses, or extensive olivine fractionation during ascent. An integrated approach to lunar mare provinces, of which the Apollo 15 mare basalts constitute only one, offers advances in our understanding of the physical and chemical processes of source formation and mare production but has so far not been utilized.

Spatial Molecular Architecture of the Microbial Community of a Peltigera Lichen.

PubMed

Garg, Neha; Zeng, Yi; Edlund, Anna; Melnik, Alexey V; Sanchez, Laura M; Mohimani, Hosein; Gurevich, Alexey; Miao, Vivian; Schiffler, Stefan; Lim, Yan Wei; Luzzatto-Knaan, Tal; Cai, Shengxin; Rohwer, Forest; Pevzner, Pavel A; Cichewicz, Robert H; Alexandrov, Theodore; Dorrestein, Pieter C

2016-01-01

Microbes are commonly studied as individual species, but they exist as mixed assemblages in nature. At present, we know very little about the spatial organization of the molecules, including natural products that are produced within these microbial networks. Lichens represent a particularly specialized type of symbiotic microbial assemblage in which the component microorganisms exist together. These composite microbial assemblages are typically comprised of several types of microorganisms representing phylogenetically diverse life forms, including fungi, photosymbionts, bacteria, and other microbes. Here, we employed matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) imaging mass spectrometry to characterize the distributions of small molecules within a Peltigera lichen. In order to probe how small molecules are organized and localized within the microbial consortium, analytes were annotated and assigned to their respective producer microorganisms using mass spectrometry-based molecular networking and metagenome sequencing. The spatial analysis of the molecules not only reveals an ordered layering of molecules within the lichen but also supports the compartmentalization of unique functions attributed to various layers. These functions include chemical defense (e.g., antibiotics), light-harvesting functions associated with the cyanobacterial outer layer (e.g., chlorophyll), energy transfer (e.g., sugars) surrounding the sun-exposed cyanobacterial layer, and carbohydrates that may serve a structural or storage function and are observed with higher intensities in the non-sun-exposed areas (e.g., complex carbohydrates). IMPORTANCE Microbial communities have evolved over centuries to live symbiotically. The direct visualization of such communities at the chemical and functional level presents a challenge. Overcoming this challenge may allow one to visualize the spatial distributions of specific molecules involved in symbiosis and to define their functional roles in shaping the community structure. In this study, we examined the diversity of microbial genes and taxa and the presence of biosynthetic gene clusters by metagenomic sequencing and the compartmentalization of organic chemical components within a lichen using mass spectrometry. This approach allowed the identification of chemically distinct sections within this composite organism. Using our multipronged approach, various fungal natural products, not previously reported from lichens, were identified and two different fungal layers were visualized at the chemical level.

Spatial Molecular Architecture of the Microbial Community of a Peltigera Lichen

PubMed Central

Garg, Neha; Zeng, Yi; Edlund, Anna; Melnik, Alexey V.; Mohimani, Hosein; Gurevich, Alexey; Miao, Vivian; Schiffler, Stefan; Lim, Yan Wei; Luzzatto-Knaan, Tal; Cai, Shengxin; Rohwer, Forest; Pevzner, Pavel A.; Cichewicz, Robert H.; Alexandrov, Theodore

2016-01-01

ABSTRACT Microbes are commonly studied as individual species, but they exist as mixed assemblages in nature. At present, we know very little about the spatial organization of the molecules, including natural products that are produced within these microbial networks. Lichens represent a particularly specialized type of symbiotic microbial assemblage in which the component microorganisms exist together. These composite microbial assemblages are typically comprised of several types of microorganisms representing phylogenetically diverse life forms, including fungi, photosymbionts, bacteria, and other microbes. Here, we employed matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) imaging mass spectrometry to characterize the distributions of small molecules within a Peltigera lichen. In order to probe how small molecules are organized and localized within the microbial consortium, analytes were annotated and assigned to their respective producer microorganisms using mass spectrometry-based molecular networking and metagenome sequencing. The spatial analysis of the molecules not only reveals an ordered layering of molecules within the lichen but also supports the compartmentalization of unique functions attributed to various layers. These functions include chemical defense (e.g., antibiotics), light-harvesting functions associated with the cyanobacterial outer layer (e.g., chlorophyll), energy transfer (e.g., sugars) surrounding the sun-exposed cyanobacterial layer, and carbohydrates that may serve a structural or storage function and are observed with higher intensities in the non-sun-exposed areas (e.g., complex carbohydrates). IMPORTANCE Microbial communities have evolved over centuries to live symbiotically. The direct visualization of such communities at the chemical and functional level presents a challenge. Overcoming this challenge may allow one to visualize the spatial distributions of specific molecules involved in symbiosis and to define their functional roles in shaping the community structure. In this study, we examined the diversity of microbial genes and taxa and the presence of biosynthetic gene clusters by metagenomic sequencing and the compartmentalization of organic chemical components within a lichen using mass spectrometry. This approach allowed the identification of chemically distinct sections within this composite organism. Using our multipronged approach, various fungal natural products, not previously reported from lichens, were identified and two different fungal layers were visualized at the chemical level. PMID:28028548

P450 AND METABOLISM IN TOXICOLOGY

EPA Science Inventory

The cytochromes P450 catalyze the initial phase of detoxification of many environmental chemicals, xenobiotic, drugs and the secondary metabolic product of plants. Plant secondary chemicals can be highly toxic, and they evolved in a coevolving plant - animal warfare - the plants ...

The record of mantle heterogeneity preserved in Earth's oceanic crust

NASA Astrophysics Data System (ADS)

Burton, K. W.; Parkinson, I. J.; Schiano, P.; Gannoun, A.; Laubier, M.

2017-12-01

Earth's oceanic crust is produced by melting of the upper mantle where it upwells beneath mid-ocean ridges, and provides a geographically widespread elemental and isotopic `sample' of Earth's mantle. The chemistry of mid-ocean ridge basalts (MORB), therefore, holds key information on the compositional diversity of the upper mantle, but the problem remains that mixing and reaction during melt ascent acts to homogenise the chemical variations they acquire. Nearly all isotope and elemental data obtained thus far are for measurements of MORB glass, and this represents the final melt to crystallise, evolving in an open system. However, the crystals that are present are often not in equilibrium with their glass host. Melts trapped in these minerals indicate that they crystallised from primitive magmas that possess diverse compositions compared to the glass. Therefore, these melt inclusions preserve information on the true extent of the mantle that sources MORB, but are rarely amenable to precise isotope measurement. An alternative approach is to measure the isotope composition of the primitive minerals themselves. Our new isotope data indicates that these minerals crystallised from melts with significantly different isotope compositions to their glass host, pointing to a mantle source that has experienced extreme melt depletion. These primitive minerals largely crystallised in the lower oceanic crust, and our preliminary data for lower crustal rocks and minerals shows that they preserve a remarkable range of isotope compositions. Taken together, these results indicate that the upper mantle sampled by MORB is extremely heterogeneous, reflecting depletion and enrichment over much of Earth's geological history.

Pollinator adaptation and the evolution of floral nectar sugar composition.

PubMed

Abrahamczyk, S; Kessler, M; Hanley, D; Karger, D N; Müller, M P J; Knauer, A C; Keller, F; Schwerdtfeger, M; Humphreys, A M

2017-01-01

A long-standing debate concerns whether nectar sugar composition evolves as an adaptation to pollinator dietary requirements or whether it is 'phylogenetically constrained'. Here, we use a modelling approach to evaluate the hypothesis that nectar sucrose proportion (NSP) is an adaptation to pollinators. We analyse ~ 2100 species of asterids, spanning several plant families and pollinator groups (PGs), and show that the hypothesis of adaptation cannot be rejected: NSP evolves towards two optimal values, high NSP for specialist-pollinated and low NSP for generalist-pollinated plants. However, the inferred adaptive process is weak, suggesting that adaptation to PG only provides a partial explanation for how nectar evolves. Additional factors are therefore needed to fully explain nectar evolution, and we suggest that future studies might incorporate floral shape and size and the abiotic environment into the analytical framework. Further, we show that NSP and PG evolution are correlated - in a manner dictated by pollinator behaviour. This contrasts with the view that a plant necessarily has to adapt its nectar composition to ensure pollination but rather suggests that pollinators adapt their foraging behaviour or dietary requirements to the nectar sugar composition presented by the plants. Finally, we document unexpectedly sucrose-poor nectar in some specialized nectarivorous bird-pollinated plants from the Old World, which might represent an overlooked form of pollinator deception. Thus, our broad study provides several new insights into how nectar evolves and we conclude by discussing why maintaining the conceptual dichotomy between adaptation and constraint might be unhelpful for advancing this field. © 2016 European Society For Evolutionary Biology. Journal of Evolutionary Biology © 2016 European Society For Evolutionary Biology.

Vector diagram of the chemical compositions of tektites and earth lavas

NASA Technical Reports Server (NTRS)

Kvasha, L. G.; Gorshkov, G. S.

1978-01-01

The chemical compositions of tektites and various volcanic glasses, similar in composition to tektites are compared by a petrochemical method. The advantage of the method is that a large number of chemical analyses of igneous rocks can be graphically compared with the help of vectors, plotted in relation to six parameters. These parameters, calculated from ratios of the main oxides given by silicate analysis, reflect the chief characteristics of igneous rock. Material for the study was suppled by data from chemical analysis characterizing tektites of all known locations and data from chemical analyses of obsidians similar in chemical composition to tektites of various petrographical provinces.

Presenting and Mispresenting Students: Constructing an Ethic of Representation in Composition Studies.

ERIC Educational Resources Information Center

Sun, Lulu C. H.

In the last few years, the focus has evolved from considering an "ethic of research" in composition studies to an "ethic of representation" in person-based research. One of the dominant questions that emerged from this shift is how researchers represent their students and their writings in composition research. What does the…

First-Year Composition Teachers' Uses of New Media Technologies in the Composition Class

ERIC Educational Resources Information Center

Mina, Lilian W.

2014-01-01

As new media technologies emerge and evolve rapidly, the need to make informed decisions about using these technologies in teaching writing increases. This dissertation research study aimed at achieving multiple purposes. The first purpose was to catalog the new media technologies writing teachers use in teaching first-year composition classes.…

Adaptive Evolution of Synthetic Cooperating Communities Improves Growth Performance

PubMed Central

Zhang, Xiaolin; Reed, Jennifer L.

2014-01-01

Symbiotic interactions between organisms are important for human health and biotechnological applications. Microbial mutualism is a widespread phenomenon and is important in maintaining natural microbial communities. Although cooperative interactions are prevalent in nature, little is known about the processes that allow their initial establishment, govern population dynamics and affect evolutionary processes. To investigate cooperative interactions between bacteria, we constructed, characterized, and adaptively evolved a synthetic community comprised of leucine and lysine Escherichia coli auxotrophs. The co-culture can grow in glucose minimal medium only if the two auxotrophs exchange essential metabolites — lysine and leucine (or its precursors). Our experiments showed that a viable co-culture using these two auxotrophs could be established and adaptively evolved to increase growth rates (by ∼3 fold) and optical densities. While independently evolved co-cultures achieved similar improvements in growth, they took different evolutionary trajectories leading to different community compositions. Experiments with individual isolates from these evolved co-cultures showed that changes in both the leucine and lysine auxotrophs improved growth of the co-culture. Interestingly, while evolved isolates increased growth of co-cultures, they exhibited decreased growth in mono-culture (in the presence of leucine or lysine). A genome-scale metabolic model of the co-culture was also constructed and used to investigate the effects of amino acid (leucine or lysine) release and uptake rates on growth and composition of the co-culture. When the metabolic model was constrained by the estimated leucine and lysine release rates, the model predictions agreed well with experimental growth rates and composition measurements. While this study and others have focused on cooperative interactions amongst community members, the adaptive evolution of communities with other types of interactions (e.g., commensalism, ammensalism or parasitism) would also be of interest. PMID:25299364

Goldilocks and the three inorganic equilibria: how Earth's chemistry and life coevolve to be nearly in tune.

PubMed

Rickaby, R E M

2015-03-13

Life and the chemical environment are united in an inescapable feedback cycle. The periodic table of the elements essential for life has transformed over Earth's history, but, as today, evolved in tune with the elements available in abundance in the environment. The most revolutionary time in life's history was the advent and proliferation of oxygenic photosynthesis which forced the environment towards a greater degree of oxidation. Consideration of three inorganic chemical equilibria throughout this gradual oxygenation prescribes a phased release of trace metals to the environment, which appear to have coevolved with employment of these new chemicals by life. Evolution towards complexity was chemically constrained, and changes in availability of notably Fe, Zn and Cu paced the systematic development of complex organisms. Evolving life repeatedly catalysed its own chemical challenges via the unwitting release of new and initially toxic chemicals. Ultimately, the harnessing of these allowed life to advance to greater complexity, though the mechanism responsible for translating novel chemistry to heritable use remains elusive. Whether a chemical acts as a poison or a nutrient lies both in the dose and in its environmental history. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

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

Wiegel, Aaron A.; Liu, Matthew J.; Hinsberg, William D.

Multiphase chemical reactions (gas + solid/liquid) involve a complex interplay between bulk and interface chemistry, diffusion, evaporation, and condensation. Reactions of atmospheric aerosols are an important example of this type of chemistry: the rich array of particle phase states and multiphase transformation pathways produce diverse but poorly understood interactions between chemistry and transport. Their chemistry is of intrinsic interest because of their role in controlling climate. Their characteristics also make them useful models for the study of principles of reactivity of condensed materials under confined conditions. Previously, we have reported a computational study of the oxidation chemistry of a liquidmore » aliphatic aerosol. In this study, we extend the calculations to investigate nearly the same reactions at a semisolid gas-aerosol interface. A reaction-diffusion model for heterogeneous oxidation of triacontane by hydroxyl radicals (OH) is described, and its predictions are compared to measurements of aerosol size and composition, which evolve continuously during oxidation. Our results are also explicitly compared to those obtained for the corresponding liquid system, squalane, to pinpoint salient elements controlling reactivity. The diffusive confinement of the free radical intermediates at the interface results in enhanced importance of a few specific chemical processes such as the involvement of aldehydes in fragmentation and evaporation, and a significant role of radical-radical reactions in product formation. The simulations show that under typical laboratory conditions semisolid aerosols have highly oxidized nanometer-scale interfaces that encapsulate an unreacted core and may confer distinct optical properties and enhanced hygroscopicity. This highly oxidized layer dynamically evolves with reaction, which we propose to result in plasticization. The validated model is used to predict chemistry under atmospheric conditions, where the OH radical concentration is much lower. The oxidation reactions are more strongly influenced by diffusion in the particle, resulting in a more liquid-like character.« less

CHEETAH: A fast thermochemical code for detonation

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

Fried, L.E.

1993-11-01

For more than 20 years, TIGER has been the benchmark thermochemical code in the energetic materials community. TIGER has been widely used because it gives good detonation parameters in a very short period of time. Despite its success, TIGER is beginning to show its age. The program`s chemical equilibrium solver frequently crashes, especially when dealing with many chemical species. It often fails to find the C-J point. Finally, there are many inconveniences for the user stemming from the programs roots in pre-modern FORTRAN. These inconveniences often lead to mistakes in preparing input files and thus erroneous results. We are producingmore » a modern version of TIGER, which combines the best features of the old program with new capabilities, better computational algorithms, and improved packaging. The new code, which will evolve out of TIGER in the next few years, will be called ``CHEETAH.`` Many of the capabilities that will be put into CHEETAH are inspired by the thermochemical code CHEQ. The new capabilities of CHEETAH are: calculate trace levels of chemical compounds for environmental analysis; kinetics capability: CHEETAH will predict chemical compositions as a function of time given individual chemical reaction rates. Initial application: carbon condensation; CHEETAH will incorporate partial reactions; CHEETAH will be based on computer-optimized JCZ3 and BKW parameters. These parameters will be fit to over 20 years of data collected at LLNL. We will run CHEETAH thousands of times to determine the best possible parameter sets; CHEETAH will fit C-J data to JWL`s,and also predict full-wall and half-wall cylinder velocities.« less

Surface chemical composition of human maxillary first premolar as assessed by X-ray photoelectron spectroscopy (XPS)

NASA Astrophysics Data System (ADS)

Lou, Leo; Nelson, Alan E.; Heo, Giseon; Major, Paul W.

2008-08-01

The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found ( p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength.

The ultraviolet morphology of evolved populations

NASA Astrophysics Data System (ADS)

Chávez, Miguel

2009-04-01

In this paper I present a summary of the recent investigations we have developed at the Stellar Atmospheres and Populations Research Group (GrAPEs-for its designation in Spanish) at INAOE and collaborators in Italy. These investigations have aimed at providing updated stellar tools for the analysis of the UV spectra of a variety of stellar aggregates, mainly evolved ones. The sequence of material here presented roughly corresponds to the steps we have identified as mandatory to properly establish the applicability of synthetic populations in the analyses of observational data of globular clusters and more complex aged aggregates. The sequence is composed of four main stages, namely, (a) the creation of a theoretical stellar data base that we have called UVBLUE, (b) the comparison of such data base with observational stellar data, (c) the calculation of a set of synthetic spectral energy distributions (SEDs) of simple stellar populations (SSPs) and their validation through a comparison with observations of a sample of galactic globular clusters (GGCs), (d) construction of models for dating local ellipticals and distant red-envelope galaxies. Most of the work relies on the analysis of absorption line spectroscopic indices. The global results are more than satisfactory in the sense that theoretical indices closely follow the overall trends with chemical composition depicted by their empirical counterparts (stars and GGCs).

A Dual-Porosity, In Situ Crystallisation Model For Fast-Spreading Mid-Ocean Ridge Magma Chambers Based Upon Direct Observation From Hess Deep

NASA Astrophysics Data System (ADS)

MacLeod, C. J.; Lissenberg, C. J.

2014-12-01

We propose a revised magma chamber model for fast-spreading mid-ocean ridges based upon a synthesis of new data from a complete section of lower crust from the East Pacific Rise, reconstructed from samples collected from the Hess Deep rift valley during cruise JC21. Our investigation includes detailed sampling across critical transitions in the upper part of the plutonic section, including the inferred axial melt lens (AML) within the dyke-gabbro transition. We find that an overall petrological progression, from troctolite and primitive gabbro at the base up into evolved (oxide) gabbro and gabbronorite at the top of the lower crustal section, is mirrored by a progressive upward chemical fractionation as recorded in bulk rock and mineral compositions. Crystallographic preferred orientations measured using EBSD show that the downward increase in deformation of mush required in crystal subsidence models is not observed. Together these observations are consistent only with a model in which crystallisation of upward migrating evolving melts occurs in situ in the lower crust. Over-enrichment in incompatible trace element concentrations and ratios above that possible by fractional crystallisation is ubiquitous. This implies redistribution of incompatible trace elements in the lower crust by low porosity, near-pervasive reactive porous flow of interstitial melt moving continuously upward through the mush pile. Mass balance calculations reveal a significant proportion of this trace element enriched melt is trapped at mid-crustal levels. Mineral compositions in the upper third to half of the plutonic section are too evolved to represent the crystal residues of MORB. Erupted MORB therefore must be fed from melts sourced in the deeper part of the crystal mush pile, and which must ascend rapidly without significant modification in the upper plutonics or AML. From physical models of mush processes we posit that primitive melts are transported through transient, high porosity channels generated by gravitational instabilities that periodically overturn and drain crystallising melt bodies (sills) from deeper levels of the lower crustal mush. We conclude that magma chambers are characterised by melt delivery to the deep crust, followed by in situ crystallisation of melts transported upwards via a dual-porosity system.

How well will stacked transgenic pest/herbicide resistances delay pests from evolving resistance?

PubMed

Gressel, Jonathan; Gassmann, Aaron J; Owen, Micheal Dk

2017-01-01

Resistance has evolved to single transgenic traits engineered into crops for arthropod and herbicide resistances, and can be expected to evolve to the more recently introduced pathogen resistances. Combining transgenes against the same target pest is being promoted as the solution to the problem. This solution will work if used pre-emptively, but where resistance has evolved to one member of a stack, resistance should easily evolve for the second gene in most cases. We propose and elaborate criteria that could be used to evaluate the value of stacked traits for pest resistance management. Stacked partners must: target the same pest species; be in a tandem construct to preclude segregation; be synchronously expressed in the same tissues; have similar tissue persistence; target pest species that are still susceptible to at least two stacked partners. Additionally, transgene products must not be degraded in the same manner, and there should be a lack of cross-resistance to stacked transgenes or to their products. With stacked herbicide resistance transgenes, both herbicides must be used and have the same persistence. If these criteria are followed, and integrated with other pest management practices, resistance may be considerably delayed. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Chemical abundances and kinematics of 257 G-, K-type field giants. Setting a base for further analysis of giant-planet properties orbiting evolved stars

NASA Astrophysics Data System (ADS)

Adibekyan, V. Zh.; Benamati, L.; Santos, N. C.; Alves, S.; Lovis, C.; Udry, S.; Israelian, G.; Sousa, S. G.; Tsantaki, M.; Mortier, A.; Sozzetti, A.; De Medeiros, J. R.

2015-06-01

We performed a uniform and detailed abundance analysis of 12 refractory elements (Na, Mg, Al, Si, Ca, Ti, Cr, Ni, Co, Sc, Mn, and V) for a sample of 257 G- and K-type evolved stars from the CORALIE planet search programme. To date, only one of these stars is known to harbour a planetary companion. We aimed to characterize this large sample of evolved stars in terms of chemical abundances and kinematics, thus setting a solid base for further analysis of planetary properties around giant stars. This sample, being homogeneously analysed, can be used as a comparison sample for other planet-related studies, as well as for different type of studies related to stellar and Galaxy astrophysics. The abundances of the chemical elements were determined using an local thermodynamic equilibrium (LTE) abundance analysis relative to the Sun, with the spectral synthesis code MOOG and a grid of Kurucz ATLAS9 atmospheres. To separate the Galactic stellar populations, both a purely kinematical approach and a chemical method were applied. We confirm the overabundance of Na in giant stars compared to the field FGK dwarfs. This enhancement might have a stellar evolutionary character, but departures from LTE may also produce a similar enhancement. Our chemical separation of stellar populations also suggests a `gap' in metallicity between the thick-disc and high-α metal-rich stars, as previously observed in dwarfs sample from HARPS. The present sample, as most of the giant star samples, also suffers from the B - V colour cut-off, which excludes low-log g stars with high metallicities, and high-log g star with low [Fe/H]. For future studies of planet occurrence dependence on stellar metallicity around these evolved stars, we suggest to use a subsample of stars in a `cut-rectangle' in the log g-[Fe/H] diagram to overcome the aforementioned issue.

Chemical osmosis, reverse chemical osmosis, and the origin of subsurface brines

NASA Astrophysics Data System (ADS)

Graf, Donald L.

1982-08-01

Calculations using recently-tabulated values of density and osmotic coefficient for NaCl-H 2O indicate that overpressuring is more than adequate to overcome chemical osmosis and drive reverse chemical osmosis in sedimentary sequences. The best-demonstrated overpressuring mechanism is the rapid deposition of fine-grained sediments. The dehydration of gypsum contributes to overpressuring for brief time intervals at shallow depths, whereas water evolved during the protracted conversion of smectite to illite is probably a subordinate, but continuing contributor to overpressuring at greater depth. Occurrences of overpressuring in sedimentary sections older than Cretaceous indicate that post-depositional mechanisms such as tectonic compression and aquathermal pressuring must also operate. The latter may be of major importance in geothermal areas with adequate low-permeability seals, and a nontrivial contributor in areas of normal geothermal gradient because of shales that sharply decrease normal fluid flow. The strongest arguments for the importance to present-day brine compositions of membrane concentration of sea-water solutes are (1) the correlation of δD values of water molecules of pore fluid with those of local meteoric water, (2) the need for major sources of Mg 2+ and Cl - in apparently evaporite-free basins. Even where dissolution of halite is a major contributor of solute, reverse chemical osmosis still operates to leak relatively dilute water. Of the associated diagenetic chemical reactions, that of Mg 2+ with limestone to form dolomite is particularly effective in generating concentrated Cl - brines rich in Ca 2+. It decreases the concentration of Mg 2+, increases that of Ca 2+, and decreases those of both SO 42- and CO 32- by precipitating CaCO 3 and CaSO 4 because of the Ca 2+ common-ion effect.

Students' Ideas about How and Why Chemical Reactions Happen: Mapping the Conceptual Landscape

ERIC Educational Resources Information Center

Yan, Fan; Talanquer, Vicente

2015-01-01

Research in science education has revealed that many students struggle to understand chemical reactions. Improving teaching and learning about chemical processes demands that we develop a clearer understanding of student reasoning in this area and of how this reasoning evolves with training in the domain. Thus, we have carried out a qualitative…

Integrating Chemical Information Instruction into the Chemistry Curriculum on Borrowed Time: The Multiyear Development and Evolution of a Virtual Instructional Tutorial

ERIC Educational Resources Information Center

Jacobs, Danielle L.; Dalal, Heather A.; Dawson, Patricia H.

2016-01-01

The impetus to incorporate instruction on the efficient and responsible practice of chemical information literacy into the undergraduate chemistry curriculum has become exceptionally urgent. At Rider University, Chemical Information Instruction (CII) has accordingly evolved from face-to-face sessions into online modules to embed information…

Observations of nitrogen isotope fractionation in deeply embedded protostars

NASA Astrophysics Data System (ADS)

Wampfler, S. F.; Jørgensen, J. K.; Bizzarro, M.; Bisschop, S. E.

2014-12-01

Context. The terrestrial planets, comets, and meteorites are significantly enriched in 15N compared to the Sun and Jupiter. While the solar and jovian nitrogen isotope ratio is believed to represent the composition of the protosolar nebula, a still unidentified process has caused 15N-enrichment in the solids. Several mechanisms have been proposed to explain the variations, including chemical fractionation. However, observational results that constrain the fractionation models are scarce. While there is evidence of 15N-enrichment in prestellar cores, it is unclear how the signature evolves into the protostellar phases. Aims: The aim of this study is to measure the 14N/15N ratio around three nearby, embedded low- to intermediate-mass protostars. Methods: Isotopologues of HCN and HNC were used to probe the 14N/15N ratio. A selection of J = 3-2 and 4-3 transitions of H13CN, HC15N, HN13C, and H15NC was observed with the Atacama Pathfinder EXperiment telescope (APEX). The 14N/15N ratios were derived from the integrated intensities assuming a standard 12C/13C ratio. The assumption of optically thin emission was verified using radiative transfer modeling and hyperfine structure fitting. Results: Two sources, IRAS 16293A and R CrA IRS7B, show 15N-enrichment by a factor of ~1.5-2.5 in both HCN and HNC with respect to the solar composition. IRAS 16293A falls in the range of typical prestellar core values. Solar composition cannot be excluded for the third source, OMC-3 MMS6. Furthermore, there are indications of a trend toward increasing 14N/15N ratios with increasing outer envelope temperature. Conclusions: The enhanced 15N abundances in HCN and HNC found in two Class 0 sources (14N /15N ~ 160-290) and the tentative trend toward a temperature-dependent 14N/15N ratio are consistent with the chemical fractionation scenario, but 14N/15N ratios from additional tracers are indispensable for testing the models. Spatially resolved observations are needed to distinguish between chemical fractionation and isotope-selective photochemistry. Appendices are available in electronic form at http://www.aanda.org

Understanding the hydrologic and geochemical control of regolith formation on shale in a hilly landscape

NASA Astrophysics Data System (ADS)

Xiao, D.; Brantley, S.; Li, L.

2017-12-01

Chemical weathering transforms rock to soil and determine soil texture, bedrock depth, and soil hydrological properties. At the Shale Hills watershed in central Pennsylvania, field evidence indicated that the regolith depth, hydrologic processes, and chemical depletion are different at the two aspects. Current regolith formation models considering reactive transport processes have a limitation in coupling complex and evolving hydrodynamic conditions. We hypothesize that deeper regolith forms when more water flushes dissolved mass out of the system. The hypothesis is tested by developing a two-dimensional regolith formation model at the hillslope scale using measured mineral composition and hydrologic properties at Shale Hills using CrunchFlow. A 2-D hillslope domain was setup to simulate hydrogeochemical processes at north and south aspects and to understand the evolution of hydrodynamics, rock properties, and extent of chemical reactions. The bedrock has the primary minerals of quartz, illite, chlorite, calcite, and pyrite; goethite and kaolinite precipitated as secondary minerals. The permeability, mass transfer, and groundwater table depth were constrained by field measurement. We implemented different recharge rates on north and south aspects based on the annually averaged fluxes from a current reanalysis using a hydrologic model. The simulation started from a homogeneous bedrock composition at 10,000 years ago. After 10,000 years' weathering, the south facing aspect with small recharge rate has a shallower soil and regolith. The simulation output indicates the formation of a shallow and a deep groundwater, based on the formation of lateral flow that connects to the stream. One is at the interface between high permeability soil zone and low permeability regolith zone, forming a relatively high-velocity perched groundwater layer. The remnant water infiltrates into the deeper low permeability zone and forms the regional groundwater layer. Because of high permeability in perched layer on north facing aspect, the remnant water in regional groundwater layer leads to shallower water table depth on north facing aspect. The model will be used to understand the role fractures, climate, and mineral compositions in affecting regolith formation.

Carbon Characteristics and Biogeochemical Processes of Uranium Accumulating Organic Matter Rich Sediments in the Upper Colorado River Basin

NASA Astrophysics Data System (ADS)

Boye, K.; Noel, V.; Tfaily, M. M.; Dam, W. L.; Bargar, J.; Fendorf, S. E.

2015-12-01

Uranium plume persistence in groundwater aquifers is a problem on several former ore processing sites on floodplains in the upper Colorado River Basin. Earlier observations by our group and others at the Old Rifle Site, CO, have noted that U concentrations are highest in organic rich, fine-grained, and, therefore, diffusion limited sediment material. Due to the constantly evolving depositional environments of floodplains, surficial organic matter may become buried at various stages of decomposition, through sudden events such as overbank flooding and through the slower progression of river meandering. This creates a discontinuous subsurface distribution of organic-rich sediments, which are hotspots for microbial activity and thereby central to the subsurface cycling of contaminants (e.g. U) and biologically relevant elements (e.g. C, N, P, Fe). However, the organic matter itself is poorly characterized. Consequently, little is known about its relevance in driving biogeochemical processes that control U fate and transport in the subsurface. In an investigation of soil/sediment cores from five former uranium ore processing sites on floodplains distributed across the Upper Colorado River Basin we confirmed consistent co-enrichment of U with organic-rich layers in all profiles. However, using C K-edge X-ray Absorption Spectroscopy (XAS) coupled with Fourier-Transformed Ion-Cyclotron-Resonance Mass-Spectroscopy (FT-ICR-MS) on bulk sediments and density-separated organic matter fractions, we did not detect any chemical difference in the organic rich sediments compared to the surrounding coarser-grained aquifer material within the same profile, even though there were differences in organic matter composition between the 5 sites. This suggests that U retention and reduction to U(IV) is independent of C chemical composition on the bulk scale. Instead it appears to be the abundance of organic matter in combination with a limited O2 supply in the fine-grained material that stimulate anaerobic microbial processes responsible for U enrichment. Thus, the chemical composition of organic matter is subordinate to the physical environment and total organic matter content in controlling U reduction and retention processes.

Composition and Chemical Stability of Motor Fuels,

DTIC Science & Technology

Fuels, *Hydrocarbons, Cycloalkanes, Chemical analysis, Gasoline, Diesel fuels, Fuel additives, Chemical reactions, Stability, Jet engine fuels...Aviation gasoline, Aviation fuels, Chemical composition, Aromatic hydrocarbons, Unsaturated hydrocarbons, Storage, USSR, Translations, Fuel systems, Alkanes

Crystal growth and disequilibrium distribution of oxygen isotopes in an igneous Ca-Al-rich inclusion from the Allende carbonaceous chondrite

NASA Astrophysics Data System (ADS)

Kawasaki, Noriyuki; Simon, Steven B.; Grossman, Lawrence; Sakamoto, Naoya; Yurimoto, Hisayoshi

2018-01-01

TS34 is a Type B1 Ca-Al-rich inclusion (CAI) from the Allende CV3 chondrite, consisting of spinel, melilite, Ti-Al-rich clinopyroxene (fassaite) and minor anorthite in an igneous texture. Oxygen and magnesium isotopic compositions were measured by secondary ion mass spectrometry in spots of known chemical composition in all major minerals in TS34. Using the sequence of formation from dynamic crystallization experiments and from chemical compositions of melilite and fassaite, the oxygen isotopic evolution of the CAI melt was established. Oxygen isotopic compositions of the constituent minerals plot along the carbonaceous chondrite anhydrous mineral line. The spinel grains are uniformly 16O-rich (Δ17O = -22.7 ± 1.7‰, 2SD), while the melilite grains are uniformly 16O-poor (Δ17O = -2.8 ± 1.8‰) irrespective of their åkermanite content and thus their relative time of crystallization. The fassaite crystals exhibit growth zoning overprinting poorly-developed sector zoning; they generally grow from Ti-rich to Ti-poor compositions. The fassaite crystals also show continuous variations in Δ17O along the inferred directions of crystal growth, from 16O-poor (Δ17O ∼ -3‰) to 16O-rich (Δ17O ∼ -23‰), covering the full range of oxygen isotopic compositions observed in TS34. The early-crystallized 16O-poor fassaite and the melilite are in oxygen isotope equilibrium and formed simultaneously. The correlation of oxygen isotopic compositions with Ti content in the fassaite imply that the oxygen isotopic composition of the CAI melt evolved from 16O-poor to 16O-rich during fassaite crystallization, presumably due to oxygen isotope exchange with a surrounding 16O-rich nebular gas. Formation of spinel, the liquidus phase in melts of this composition, predates crystallization of all other phases, so its 16O-rich composition is a relic of an earlier stage. Anorthite exhibits oxygen isotopic compositions between Δ17O ∼ -2‰ and -9‰, within the range of those of fassaite, indicating co-crystallization of these two minerals during the earliest to intermediate stage of fassaite growth. The melilite and fassaite yield an 26Al-26Mg mineral isochron with an initial value of (26Al/27Al)0 = (5.003 ± 0.075) × 10-5, corresponding to a relative age of 0.05 ± 0.02 Myr from the canonical Al-Mg age of CAIs. These data demonstrate that both 16O-rich and 16O-poor reservoirs existed in the solar nebula at least ∼0.05 Myr after the birth of the Solar System.

Geochemistry of Pallasite Olivines and the Origin of Main-Group Pallasites

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Rumble, D., III

2006-01-01

Main-group pallasites (PMG) are mixtures of iron-nickel metal and magnesian olivine thought to have been formed at the core-mantle boundary of an asteroid [1]. Some have anomalous metal compositions (PMG-am) and a few have atypically ferroan olivines (PMG-as) [2]. PMG metal is consistent with an origin as a late fractionate of the IIIAB iron core [2]. Most PMG olivines have very similar Fe/Mg ratios, likely due to subsolidus redox reaction with the metal [3]. In contrast, minor and trace elements show substantial variation, which may be explained by either: (i) PMG were formed at a range of depths in the parent asteroid; the element variations reflect variations in igneous evolution with depth, (ii) the pallasite parent asteroid was chemically heterogeneous; the heterogeneity partially survived igneous processing, or (iii) PMG represent the core-mantle boundaries of several distinct parent asteroids [4, 5]. We have continued doing major, minor and trace elements by EMPA and INAA on a wider suite of PMG olivines, and have begun doing precise oxygen isotope analyses to test these hypotheses. Manganese is homologous with Fe(2+), and can be used to distinguish between magmatic and redox processes as causes for Fe/Mg variations. PMG olivines have a range in molar 1000*Mn/Mg of 2.3-4.6 indicating substantial igneous fractionation in olivines with very similar Fe/Mg (0.138-0.148). The Mg-Mn-Fe distributions can be explained by a fractional crystallization-reduction model; higher Mn/Mg ratios reflect more evolved olivines while Fe/Mg is buffered by redox reactions with the metal. There is a positive association between Mn/Mg and Sc content that is consistent with igneous fractionation. However, most PMG olivines fall within a narrow Mn/Mg range (3.0-3.6), but these show a substantial range in Sc (1.00-2.29 micro-g/g). Assuming fractional crystallization, this Sc range could have resulted from approx.65% crystallization of an ultramafic magma. This is inconsistent with formation at the core-mantle boundary of a single asteroid [4]. One alternative is that the PMG are fragments of several asteroids, and these could have had different initial Sc contents, Mn/Mg and differences in igneous history. Our preliminary O isotope data and those of [6, 7] do not support this, although the coverage of PMG olivines is incomplete. The PMG-as Springwater is not easily fit in any scenario. Its olivine has among the highest Mn/Mg suggesting it is one of the most evolved, but the lowest Sc content suggesting it is the least evolved. The O isotopic composition of Springwater olivine is the same as that of other PMG. Thus there is no indication that it represents a distinct parent asteroid. Our preliminary O isotopic data favor a single PMG parent asteroid. In this case, the olivines are more likely melt-residues, and that the parent asteroid was initially heterogeneous in chemical, but not isotopic, composition.

Thermal degradation behaviors and reaction mechanism of carbon fibre-epoxy composite from hydrogen tank by TG-FTIR.

PubMed

Zhang, Zhi; Wang, Changjian; Huang, Gai; Liu, Haoran; Yang, Shenlin; Zhang, Aifeng

2018-05-28

Thermal degradation behaviors and reaction mechanism of Carbon fibre-epoxy composite, obtained from Chinese widely applied hydrogen storage tank, were studied by thermogravimetry combined with Fourier transform infrared spectrometry at varying heating rates. The pyrolysis of carbon fibre-epoxy composite mainly occurs at 550-750 K. The average value of final residue is 72.42%. The calculated activation energies increase exponentially from 206.27 KJ/mol to 412.98 KJ/mol with the average value of 276.6 KJ/mol. The fourth reaction order model is responsible for the pyrolysis of carbon fibre-epoxy composite. The absorption spectra of the evolved gases provided the information that the main evolved products are H 2 O, CO 2 , CO (acid anhydride, ketone or aldehyde), ε- caprolactam, alcohols and phenol. Moreover, CO group > alcohols > phenol > ε- caprolactam > CO 2  > H 2 O. Epoxy is the main pyrolysis crude material in carbon fibre-epoxy composite. Copyright © 2018 Elsevier B.V. All rights reserved.

Plant Species Rather Than Climate Greatly Alters the Temporal Pattern of Litter Chemical Composition During Long-Term Decomposition

NASA Astrophysics Data System (ADS)

Li, Yongfu; Chen, Na; Harmon, Mark E.; Li, Yuan; Cao, Xiaoyan; Chappell, Mark A.; Mao, Jingdong

2015-10-01

A feedback between decomposition and litter chemical composition occurs with decomposition altering composition that in turn influences the decomposition rate. Elucidating the temporal pattern of chemical composition is vital to understand this feedback, but the effects of plant species and climate on chemical changes remain poorly understood, especially over multiple years. In a 10-year decomposition experiment with litter of four species (Acer saccharum, Drypetes glauca, Pinus resinosa, and Thuja plicata) from four sites that range from the arctic to tropics, we determined the abundance of 11 litter chemical constituents that were grouped into waxes, carbohydrates, lignin/tannins, and proteins/peptides using advanced 13C solid-state NMR techniques. Decomposition generally led to an enrichment of waxes and a depletion of carbohydrates, whereas the changes of other chemical constituents were inconsistent. Inconsistent convergence in chemical compositions during decomposition was observed among different litter species across a range of site conditions, whereas one litter species converged under different climate conditions. Our data clearly demonstrate that plant species rather than climate greatly alters the temporal pattern of litter chemical composition, suggesting the decomposition-chemistry feedback varies among different plant species.

Plant Species Rather Than Climate Greatly Alters the Temporal Pattern of Litter Chemical Composition During Long-Term Decomposition

PubMed Central

Li, Yongfu; Chen, Na; Harmon, Mark E.; Li, Yuan; Cao, Xiaoyan; Chappell, Mark A.; Mao, Jingdong

2015-01-01

A feedback between decomposition and litter chemical composition occurs with decomposition altering composition that in turn influences the decomposition rate. Elucidating the temporal pattern of chemical composition is vital to understand this feedback, but the effects of plant species and climate on chemical changes remain poorly understood, especially over multiple years. In a 10-year decomposition experiment with litter of four species (Acer saccharum, Drypetes glauca, Pinus resinosa, and Thuja plicata) from four sites that range from the arctic to tropics, we determined the abundance of 11 litter chemical constituents that were grouped into waxes, carbohydrates, lignin/tannins, and proteins/peptides using advanced 13C solid-state NMR techniques. Decomposition generally led to an enrichment of waxes and a depletion of carbohydrates, whereas the changes of other chemical constituents were inconsistent. Inconsistent convergence in chemical compositions during decomposition was observed among different litter species across a range of site conditions, whereas one litter species converged under different climate conditions. Our data clearly demonstrate that plant species rather than climate greatly alters the temporal pattern of litter chemical composition, suggesting the decomposition-chemistry feedback varies among different plant species. PMID:26515033

A chemical model for lunar non-mare rocks

NASA Technical Reports Server (NTRS)

Hubbard, N. J.; Rhodes, J. M.

1974-01-01

Nearly all rocks returned from the moon are readily divided into three broad categories on the basis of their chemical compositions: (1) mare basalts, (2) non-mare rocks of basaltic composition (KREEP, VHA), and (3) anorthositic rocks. Only mare basalts may unambiguously be considered to have original igneous textures and are widely understood to have an igneous origin. Nearly all other lunar rocks have lost their original textures during metamorphic and impact processes. It is shown that for these rocks one must work primarily with chemical data in order to recognize and define rock groups and their possible modes of origin. Non-mare rocks of basaltic composition have chemical compositions consistent with an origin by partial melting of the lunar interior. The simplest origin for rocks of anorthositic chemical composition is the crystallization and removal of ferromagnesian minerals. It is proposed that the rock groups of anorthositic and non-mare basaltic chemical composition could have been generated from a single series of original but not necessarily primitive lunar materials.

Polypyrrole-MWCNT-Ag composites for electromagnetic shielding: Comparison between chemical deposition and UV-reduction approaches

NASA Astrophysics Data System (ADS)

Ebrahimi, Izadyar; Gashti, Mazeyar Parvinzadeh

2018-07-01

In this study, we focused on the synthesis of polypyrrole-MWCNT-Ag composites and we evaluated their electrical properties to determine the electromagnetic interference shielding performance. We reduced silver nanoparticles in composites using two different in situ methods: UV-reduction and chemical deposition. Composites were characterized using spectroscopic and microscopic tools for evaluation of the chemical, morphological, electrical conductivity and electromagnetic shielding effectiveness. Results from Fourier transform infrared spectroscopy and dispersive Raman microscope showed chemical interactions between silver and the polypyrrole-MWCNT composite due to the charge-transfer within the structure. X-ray diffraction confirmed appearance of two new peaks for silver nanoparticles embedded in polypyrrole-MWCNT independent to reduction method. According to microscopy images, silver nanoparticles were homogenously distributed at the PPy-MWCNTs interfaces by UV reduction, while, chemical reduction resulted to deposition of silver within the PPy matrix. Finally, our results revealed that the polypyrrole-MWCNT-Ag composite produced via UV-reduction has higher electrical conductivity and shielding effectiveness in comparison to chemically reduced one.

A chemical model for lunar non-mare rocks

NASA Technical Reports Server (NTRS)

Hubbard, N. J.; Rhodes, J. M.

1977-01-01

Nearly all rocks returned from the moon are readily divided into three broad categories on the basis of their chemical compositions: (1) mare basalts, (2) non-mare rocks of basaltic composition (KREEP, VHA), and (3) anorthositic rocks. Only mare basalts may unambiguously be considered to have original igneous textures and are widely understood to have an igneous origin. Nearly all other lunar rocks have lost their original textures during metamorphic and impact processes. For these rocks one must work primarily with chemical data in order to recognize and define rock groups and their possible modes of origin. Non-mare rocks of basaltic composition have chemical compositions consistent with an origin by partial melting of the lunar interior. The simplest origin for rocks of anorthositic chemical composition is the crystallization and removal of ferromagnesian minerals. It is proposed that the rock groups of anorthositic and non-mare basaltic chemical composition could have been generated from a single series of original, but not necessarily primitive, lunar materials.

Formation and dynamics of a chemically stratified layer below the Earth's CMB

NASA Astrophysics Data System (ADS)

Bouffard, M.; Labrosse, S.; Choblet, G.; Aubert, J.; Fournier, A.

2017-12-01

Seismological and magnetic observations are compatible with the presence of a stratified layer below the Earth's CMB (Lay and Young, 1990; Tanaka, 2007; Gubbins, 2007; Helffrich and Kaneshima, 2010; Lesur et al., 2015) and the existence of such a layer has also been predicted by several theoretical arguments listed below. The proposed thickness varies from 60 km to several hundreds of kilometers across the literature, but is usually close to 100 km. The layer may be thermally stratified if the CMB heat flow is subadiabatic (Gubbins et al., 1982; Labrosse et al., 1997; Lister and Buffett, 1998; Labrosse, 2015) but the possibility of a stratification of chemical origin has also been evoked. Various mechanisms have been proposed for the formation of a chemically stratified layer and include barodiffusion i.e. diffusion of light elements against the pressure gradient (Fearn and Loper, 1981; Braginsky, 2006; Gubbins and Davies, 2013), chemical plumes and blobs that would be able to reach the CMB where they would accumulate (Loper, 1989; Braginsky, 1994; Moffatt and Loper, 1994; Loper, 2007) or ascending droplets in a Fe-S system kept from mixing by surface tension (Franck, 1982). Layering may also be present if immiscible liquids evolve as the composition changes due to inner core growth (Helffrich and Kaneshima, 2004). To finish, Buffett and Seagle (2010) also studied the possibility that light elements be dissolved from the mantle into the core, forming a lighter layer that could grow by diffusion over long time scales. So far, no numerical simulation of core dynamics has been able to validate any of these potential mechanisms and produce a chemically stratified layer in a self-consistent manner. Using a particle-in-cell method newly implemented in the code PARODY (E. Dormy, J. Aubert) allowing to perform simulations of thermochemical convection in the infinite Lewis number limit (neglecting the compositional diffusivity), I will show that a chemically stratified layer systematically forms in simulations via the accumulation of undiffused plumes and blobs that reach the top boundary. I will discuss the dynamics of such a layer and will present scaling laws of its thickness as a function of the control parameters. Extrapolation to the terrestrial case and the potential implications for core dynamics will also be discussed.

Growth of multi-component alloy films with controlled graded chemical composition on sub-nanometer scale

DOEpatents

Bajt, Sasa; Vernon, Stephen P.

2005-03-15

The chemical composition of thin films is modulated during their growth. A computer code has been developed to design specific processes for producing a desired chemical composition for various deposition geometries. Good agreement between theoretical and experimental results was achieved.

Chemistry of spring and well waters on Kilauea Volcano, Hawaii, and vicinity

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

Janik, C.J.; Nathenson, M.; Scholl, M.A.

1994-12-31

Published and new data for chemical and isotopic samples from wells and springs on Kilauea Volcano and vicinity are presented. These data are used to understand processes that determine the chemistry of dilute meteoric water, mixtures with sea water, and thermal water. Data for well and spring samples of non-thermal water indicate that mixing with sea water and dissolution of rock from weathering are the major processes that determine the composition of dissolved constituents in water. Data from coastal springs demonstrate that there is a large thermal system south of the lower east rift of Kilauea. Samples of thermal watermore » from shallow wells in the lower east rift and vicinity have rather variable chemistry indicating that a number of processes operate in the near surface. Water sampled from the available deep wells is different in composition from the shallow thermal water, indicating that generally there is not a significant component of deep water in the shallow wells. Data for samples from available deep wells show significant gradients in chemistry and steam content of the reservoir fluid. These gradients are interpreted to indicate that the reservoir tapped by the existing wells is an evolving vapor-dominated system.« less

Structural and chemical alteration of crystalline olivine under low energy He+ irradiation

NASA Astrophysics Data System (ADS)

Demyk, K.; Carrez, Ph.; Leroux, H.; Cordier, P.; Jones, A. P.; Borg, J.; Quirico, E.; Raynal, P. I.; d'Hendecourt, L.

2001-03-01

We present the results of irradiation experiments on crystalline olivine with He+ ions at energies of 4 and 10 keV and fluences varying from 5 1016 to 1018 ions/cm2. The aim of these experiments is to simulate ion implantation into interstellar grains in shocks in the ISM. Irradiated samples were analysed by transmission electron microscopy (TEM). The irradiation causes the amorphization of the olivine, at all He+ fluences considered. The thickness of the amorphized region is 40 +/- 15 nm and 90 +/- 10 nm for the 4 keV and 10 keV experiments, respectively. The amorphization of the olivine occurs in conjunction with an increase in the porosity of the material due to the formation of bubbles. In addition, the amorphized layer is deficient in oxygen and magnesium. We find that the O/Si and Mg/Si ratios decrease as the He+ fluence increases. These experiments show that the irradiation of dust in supernova shocks can efficiently alter the dust structure and composition. Our result are consistent with the lack of crystalline silicates in the interstellar medium and also with the compositional evolution observed from olivine-type silicates around evolved stars to pyroxene-type silicates around protostars.

Messages from the Reversing Layer: Clues to Planet Formation in Spectral Abundances

NASA Astrophysics Data System (ADS)

Brewer, John Michael; Fischer, Debra; Basu, Sarbani

2017-01-01

The abundances of elements in the protoplanetary disk evolve over time, but stellar abundances will reflect the initial chemical composition of the disk and this can provide constraints on the range of possible outcomes for planet interiors. Rocky planet habitability depends not just on the availability of liquid water, but also on volcansim and plate tectonics that can stabilize the climate on long timescales. The slow evolution of abundances in stellar photospheres, particularly abundance ratios between elements, makes them ideal laboratories to study primordial disk compositions.In my thesis work, I developed a new spectroscopic analysis procedure that derives gravities consistent with asteroseismology to within 0.05 dex as well as abundances for 15 elements. Using this procedure, we analyzed and published a catalog of accurate stellar parameters and precise abundances for more than 1600 stars and used those to investigate questions of planet formation. The C/O and Mg/Si ratios in the solar neighborhood could affect rocky planet habitability. For lucky cases where planet atmosphereic abundances can be measured, the stellar host C/O and [O/H] ratios carry information about the formation site and migration of hot Jupiters. I will present results on both rocky planet compositions and hot Jupiter migration and discuss how they can help us identify potentially habitable systems and discriminate between different planet formation models.

Modeling the chemistry of complex petroleum mixtures.

PubMed Central

Quann, R J

1998-01-01

Determining the complete molecular composition of petroleum and its refined products is not feasible with current analytical techniques because of the astronomical number of molecular components. Modeling the composition and behavior of such complex mixtures in refinery processes has accordingly evolved along a simplifying concept called lumping. Lumping reduces the complexity of the problem to a manageable form by grouping the entire set of molecular components into a handful of lumps. This traditional approach does not have a molecular basis and therefore excludes important aspects of process chemistry and molecular property fundamentals from the model's formulation. A new approach called structure-oriented lumping has been developed to model the composition and chemistry of complex mixtures at a molecular level. The central concept is to represent an individual molecular or a set of closely related isomers as a mathematical construct of certain specific and repeating structural groups. A complex mixture such as petroleum can then be represented as thousands of distinct molecular components, each having a mathematical identity. This enables the automated construction of large complex reaction networks with tens of thousands of specific reactions for simulating the chemistry of complex mixtures. Further, the method provides a convenient framework for incorporating molecular physical property correlations, existing group contribution methods, molecular thermodynamic properties, and the structure--activity relationships of chemical kinetics in the development of models. PMID:9860903

The Balmat-Edwards zinc-lead deposits-synsedimentary ore from Mississippi valley-type fluids.

USGS Publications Warehouse

Whelan, J.F.; Rye, R.O.; Delorraine, W.

1984-01-01

The Balmat-Edwards Zn-Pb district in New York is in Mid-Proterozoic Grenville marbles. Tabular to podiform, generally conformable massive sphalerite-galena orebodies occur at various horizons in the approx 1 km-thick marbles. Metamorphism obscured or obliterated most primary characteristics, whose reconstruction is attempted through detailed S, C, and O isotope studies of the Fowler orebody, and trace element and S isotope studies of sphalerite concentrates and composite ore samples from 22 orebodies. Sulphur isotope data reflect equilibration at near peak metamorphism with some indication of re-equilibration during retrograde metamorphism. The carbon and oxygen isotope composition of gangue carbonates suggests derivation from the host marbles. The oxygen isotope composition of gangue quartz is compatible with a chert origin or metamorphism-equilibration with other minerals. Sulphur and lead isotopes and sulphide mineralogy suggests that the ore fluids were evolved basin brines, chemically like those responsible for Mississippi Valley-type deposits. The large stratigraphic span (> 600 m) of the Balmat orebodies may be due to basin dewatering of million-year intervals. Stratigraphically increasing 34S values of evaporite-anhydrite are postulated to record hydrothermal events and to imply bacterial sulphate reduction on an unusually large scale. Such a stratigraphic increase may be a general exploration guide where sediment-hosted exhalative deposits or Mississippi Valley-type deposits occur.-G.J.N.

The potential for chemical evolution on Titan

NASA Technical Reports Server (NTRS)

Beauchamp, P. M.; Lunine, J. I.; Welch, C.

2002-01-01

Sampling of organics to determine oxygen content, extent of acetylene polymerization, existence of chiral molecules and enantiomeric excesses, and searches for specific polymer products, would be of interest in assessing how organic chemistry evolves toward biochemistry. Such efforts would require fairly sophisticated chemical analyses from landed missions. This paper examines this chemistry and the potential instruments that could distinguish chemical evolution.

Chemical and isotopic evolution of a layered eastern U.S. snowpack and its relation to stream-water composition

USGS Publications Warehouse

Shanley, J.B.; Kendall, C.; Albert, M.R.; Hardy, J.P.

1995-01-01

The chemical, isotopic, and morphologic evolution of a layered snowpack was investigated during the winter of 1993-94 at Sleepers River Research Watershed in Danville, Vermont. The snowpack was monitored at two small basins: a forested basin at 525 m elevation, and an agricultural basin at 292 m elevation. At each site, the snowpack morphology was characterized and individual layers were sampled seven times during the season. Nitrate and 8d18O profiles in the snowpack remained relatively stable until peak accumulation in mid-March, except near the snow surface, where rain-on-snow events caused water and nitrate movement down to impeding ice layers. Subsequently, water and nitrate moved more readily through the ripening snowpack. As the snowpack evolved, combined processes of preferential ion elution, isotopic fractionation, and infiltration of isotopically heavy rainfall caused the pack to become depleted in solutes and isotopically enriched. The release of nitrate and isotopically depleted water was reflected in patterns of nitrate concentrations and ??18O of meltwater and stream water. Results supported data from the previous year which suggested that streamflow in the forested basin during snowmelt was dominated by groundwater discharge.

Testing of some assumptions about biodegradability in soil as measured by carbon dioxide evolution

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

El-Din Sharabi, N.; Bartha, R.

1993-04-01

The Toxic Substance Control Act calls for a premanufacturing review of novel chemical substances including their biodegradability. Carbon dioxide evolution, using non-labeled carbon or [sup 14]C, is a common method of testing. This study examines assumptions of carbon dioxide evolution testing. Test substances used included: glucose, adipic acid, benzoic acid, and n-hexadecane. Chemical composition other than carbon content appears to influence minimally the percentages conversion to CO[sub 2]. However, that although CO[sub 2] evolution seemed proportional to the carbon content and concentration of the test substance, at least one-half of the evolved net CO[sub 2] did not come directly frommore » the test substance. Conversion to CO[sub 2] in the soil appeared to depend on carbon content only. In experiments of 1 month or longer, the net CO[sub 2] evolution in response to substrate may be above 100% of the added substrate carbon. Whether this applies to all substrate additions remains to be studied. The authors conclude that net CO[sub 2] and [sup 14]CO[sub 2] evolution measurements are useful as a first-tier tests for assessing biodegradability in soil. 11 refs., 6 figs.« less

Meteorites and the Evolution of Our Solar System

NASA Technical Reports Server (NTRS)

Nava, David F.

1999-01-01

The study of meteorites has long been of intense interest ever since these objects were discovered to be of extraterrestrial origin. Meteorite research contributes to unraveling the mysteries in understanding the formation and evolution processes of our solar system. Meteorites, of which there are a variety of widely diverse types of chemical and mineralogical compositions, are the most ancient of solar system objects that can be studied in the laboratory. They preserve a unique historical record of the astronomical and astrophysical events of our solar system. This record is being discerned by a host of ever evolving analytical laboratory methods. Recent discoveries of what are believed to be Martian meteorites, lunar meteorites, a meteorite containing indigenous water, and the recovery from the Cretaceous layer of a small meteorite fragment thought to be from the dinosaur-killing asteroid have fueled additional excitement for studying meteorites.

Controlled disulfonated poly(arylene ether sulfone) multiblock copolymers for direct methanol fuel cells.

PubMed

Li, Qing; Chen, Yu; Rowlett, Jarrett R; McGrath, James E; Mack, Nathan H; Kim, Yu Seung

2014-04-23

Structure-property-performance relationships of disulfonated poly(arylene ether sulfone) multiblock copolymer membranes were investigated for their use in direct methanol fuel cell (DMFC) applications. Multiple series of reactive polysulfone, polyketone, and polynitrile hydrophobic block segments having different block lengths and molecular composition were synthesized and reacted with a disulfonated poly(arylene ether sulfone) hydrophilic block segment by a coupling reaction. Large-scale morphological order of the multiblock copolymers evolved with the increase of block size that gave notable influence on mechanical toughness, water uptake, and proton/methanol transport. Chemical structural changes of the hydrophobic blocks through polar group, fluorination, and bisphenol type allowed further control of the specific properties. DMFC performance was analyzed to elicit the impact of structural variations of the multiblock copolymers. Finally, DMFC performances of selected multiblock copolymers were compared against that of the industrial standard Nafion in the DMFC system.

Blood tolerant laccase by directed evolution.

PubMed

Mate, Diana M; Gonzalez-Perez, David; Falk, Magnus; Kittl, Roman; Pita, Marcos; De Lacey, Antonio L; Ludwig, Roland; Shleev, Sergey; Alcalde, Miguel

2013-02-21

High-redox potential laccases are powerful biocatalysts with a wide range of applications in biotechnology. We have converted a thermostable laccase from a white-rot fungus into a blood tolerant laccase. Adapting the fitness of this laccase to the specific composition of human blood (above neutral pH, high chloride concentration) required several generations of directed evolution in a surrogate complex blood medium. Our evolved laccase was tested in both human plasma and blood, displaying catalytic activity while retaining a high redox potential at the T1 copper site. Mutations introduced in the second coordination sphere of the T1 site shifted the pH activity profile and drastically reduced the inhibitory effect of chloride. This proof of concept that laccases can be adapted to function in extreme conditions opens an array of opportunities for implantable nanobiodevices, chemical syntheses, and detoxification. Copyright © 2013 Elsevier Ltd. All rights reserved.

Chemometric study of Maya Blue from the voltammetry of microparticles approach.

PubMed

Doménech, Antonio; Doménech-Carbó, María Teresa; de Agredos Pascual, María Luisa Vazquez

2007-04-01

The use of the voltammetry of microparticles at paraffin-impregnated graphite electrodes allows for the characterization of different types of Maya Blue (MB) used in wall paintings from different archaeological sites of Campeche and YucatAn (Mexico). Using voltammetric signals for electron-transfer processes involving palygorskite-associated indigo and quinone functionalities generated by scratching the graphite surface, voltammograms provide information on the composition and texture of MB samples. Application of hierarchical cluster analysis and other chemometric methods allows us to characterize samples from different archaeological sites and to distinguish between samples proceeding from different chronological periods. Comparison between microscopic, spectroscopic, and electrochemical examination of genuine MB samples and synthetic specimens indicated that the preparation procedure of the pigment evolved in time via successive steps anticipating modern synthetic procedures, namely, hybrid organic-inorganic synthesis, temperature control of chemical reactivity, and template-like synthesis.

Method of producing a chemical hydride

DOEpatents

Klingler, Kerry M.; Zollinger, William T.; Wilding, Bruce M.; Bingham, Dennis N.; Wendt, Kraig M.

2007-11-13

A method of producing a chemical hydride is described and which includes selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of a hydrocarbon; and reacting the composition with the source of the hydrocarbon to generate a chemical hydride.

Antinociceptive effects, acute toxicity and chemical composition of Vitex agnus-castus essential oil.

PubMed

Khalilzadeh, Emad; Vafaei Saiah, Gholamreza; Hasannejad, Hamideh; Ghaderi, Adel; Ghaderi, Shahla; Hamidian, Gholamreza; Mahmoudi, Razzagh; Eshgi, Davoud; Zangisheh, Mahsa

2015-01-01

Vitex agnus-castus (VAC) and its essential oil have been traditionally used to treat many conditions and symptoms such as premenstrual problems, mastalgia, inflammation, sexual dysfunction, and pain. In this study, the effects of essential oil extracted from Vitex agnus-castus (EOVAC) leaves were investigated in three behavioral models of nociception in adult male Wistar rats. Chemical composition of EOVAC was analyzed using gas chromatography - mass spectrometry (GC-MS) and also its possible toxicity was determined in mice. Analgesic effect of EOVAC was determined using tail immersion test, formalin test, and acetic acid-induced visceral pain in rats. EOVAC (s.c.) and morphine (i.p.) significantly (p<0.05) reduced pain responses in both formalin and tail immersion tests. In the study of evolved mechanisms, pretreatment with naloxone or atropine significantly (p <0.05) reversed the essential oil-induced analgesia in both formalin and tail immersion tests. Moreover, EOVAC and Piroxicam produced significant (p<0.05) inhibition in the acetic acid-induced writhing response. EOVAC did not show any mortality even at high dose (5 g/kg, p.o.) of administration in toxicity test. Moreover, according to GC-MS results, major components of the EOVAC were α-pinene (14.83%), limonene (10.29%), β-caryophyllene (6.9%), sabinene (5.27%), and β-farnesene (5.9%). These results suggest that endogenous opioidergic system as well as muscarinergic receptors of cholinergic system may be involve in the antinociceptive activity of Vitex agnus-castus essential oil in these models of pain in rats.

Antinociceptive effects, acute toxicity and chemical composition of Vitex agnus-castus essential oil

PubMed Central

Khalilzadeh, Emad; Vafaei Saiah, Gholamreza; Hasannejad, Hamideh; Ghaderi, Adel; Ghaderi, Shahla; Hamidian, Gholamreza; Mahmoudi, Razzagh; Eshgi, Davoud; Zangisheh, Mahsa

2015-01-01

Objective: Vitex agnus-castus (VAC) and its essential oil have been traditionally used to treat many conditions and symptoms such as premenstrual problems, mastalgia, inflammation, sexual dysfunction, and pain. In this study, the effects of essential oil extracted from Vitex agnus-castus (EOVAC) leaves were investigated in three behavioral models of nociception in adult male Wistar rats. Materials and methods: Chemical composition of EOVAC was analyzed using gas chromatography – mass spectrometry (GC-MS) and also its possible toxicity was determined in mice. Analgesic effect of EOVAC was determined using tail immersion test, formalin test, and acetic acid-induced visceral pain in rats. Results: EOVAC (s.c.) and morphine (i.p.) significantly (p<0.05) reduced pain responses in both formalin and tail immersion tests. In the study of evolved mechanisms, pretreatment with naloxone or atropine significantly (p <0.05) reversed the essential oil-induced analgesia in both formalin and tail immersion tests. Moreover, EOVAC and Piroxicam produced significant (p<0.05) inhibition in the acetic acid-induced writhing response. EOVAC did not show any mortality even at high dose (5 g/kg, p.o.) of administration in toxicity test. Moreover, according to GC-MS results, major components of the EOVAC were α-pinene (14.83%), limonene (10.29%), β-caryophyllene (6.9%), sabinene (5.27%), and β-farnesene (5.9%). Conclusions: These results suggest that endogenous opioidergic system as well as muscarinergic receptors of cholinergic system may be involve in the antinociceptive activity of Vitex agnus-castus essential oil in these models of pain in rats. PMID:26101755

Chemical Composition and Evaluation of Nicotine, Tobacco Alkaloids, pH and Selected Flavors in e-Cigarette Cartridges and Refill Solutions

PubMed Central

Lisko, Joseph G.; Tran, Hang; Stanfill, Stephen B.; Blount, Benjamin C.; Watson, Clifford H.

2015-01-01

Introduction Electronic cigarette (e-cigarette) use is increasing dramatically in developed countries, but little is known about these rapidly evolving products. This study analyzed and evaluated the chemical composition including nicotine, tobacco alkaloids, pH and flavors in 36 e-liquids brands from four manufacturers. Methods We determined the concentrations of nicotine, alkaloids, and select flavors and measured pH in solutions used in e-cigarettes. E-cigarette products were chosen based upon favorable consumer approval ratings from online review websites. Quantitative analyses were performed using strict quality assurance/quality control (QC) validated methods previously established by our lab for the measurement of nicotine, alkaloids, pH and flavors. Results Three-quarters of the products contained lower measured nicotine levels than the stated label values (6% - 42% by concentration). The pH for e-liquids ranged from 5.1 – 9.1. Minor tobacco alkaloids were found in all samples containing nicotine, and their relative concentrations varied widely among manufacturers. A number of common flavor compounds were analyzed in all e-liquids. Conclusions Free nicotine levels calculated from the measurement of pH correlated with total nicotine content. The direct correlation between the total nicotine concentration and pH suggests that the alkalinity of nicotine drives the pH of e-cigarette solutions. A higher percentage of nicotine exists in the more absorbable free form as total nicotine concentration increases. A number of products contained tobacco alkaloids at concentrations that exceed U.S. Pharmacopeia limits for impurities in nicotine used in pharmaceutical and food products. PMID:25636907

Review on effect of chemical, thermal, additive treatment on mechanical properties of basalt fiber and their composites

NASA Astrophysics Data System (ADS)

Jain, Naman; Singh, Vinay Kumar; Chauhan, Sakshi

2017-12-01

Basalt fiber is emerging out the new reinforcing material for composites. To overcome some of the disadvantages of fibers such as poor bonding to polymers, low thermal stability and high moisture absorption fiber characteristics are modified with chemical, thermal and additive treatments. Chemical treatment corrosive resistance to alkali and acid were investigated which were used to clean and modify the surface of fiber for higher bonding with resins. To improve the thermal stability and reduce moisture uptake thermal treatment such as plasma and non thermal plasma were used which increased the surface roughness and change the chemical composition of surface of basalt fiber. Additive treatment is used to improve the mechanical properties of fibers, in basalt fiber additive treatment was done with SiO2 additive because of its chemical composition which contains major content of SiO2. In present investigation review on the effect of different treatment such as chemical, thermal and additive were studied. Effect of these treatment on chemical composition of the surface of basalt fiber and corrosion to acidic and alkali solution were studied with their effect on mechanical properties of basalt fiber and their composite.

Fast classification and compositional analysis of cornstover fractions using Fourier transform near-infrared techniques.

PubMed

Philip Ye, X; Liu, Lu; Hayes, Douglas; Womac, Alvin; Hong, Kunlun; Sokhansanj, Shahab

2008-10-01

The objectives of this research were to determine the variation of chemical composition across botanical fractions of cornstover, and to probe the potential of Fourier transform near-infrared (FT-NIR) techniques in qualitatively classifying separated cornstover fractions and in quantitatively analyzing chemical compositions of cornstover by developing calibration models to predict chemical compositions of cornstover based on FT-NIR spectra. Large variations of cornstover chemical composition for wide calibration ranges, which is required by a reliable calibration model, were achieved by manually separating the cornstover samples into six botanical fractions, and their chemical compositions were determined by conventional wet chemical analyses, which proved that chemical composition varies significantly among different botanical fractions of cornstover. Different botanic fractions, having total saccharide content in descending order, are husk, sheath, pith, rind, leaf, and node. Based on FT-NIR spectra acquired on the biomass, classification by Soft Independent Modeling of Class Analogy (SIMCA) was employed to conduct qualitative classification of cornstover fractions, and partial least square (PLS) regression was used for quantitative chemical composition analysis. SIMCA was successfully demonstrated in classifying botanical fractions of cornstover. The developed PLS model yielded root mean square error of prediction (RMSEP %w/w) of 0.92, 1.03, 0.17, 0.27, 0.21, 1.12, and 0.57 for glucan, xylan, galactan, arabinan, mannan, lignin, and ash, respectively. The results showed the potential of FT-NIR techniques in combination with multivariate analysis to be utilized by biomass feedstock suppliers, bioethanol manufacturers, and bio-power producers in order to better manage bioenergy feedstocks and enhance bioconversion.

Experimental evaporation of hyperacid brines: Effects on chemical composition and chlorine isotope fractionation

NASA Astrophysics Data System (ADS)

Rodríguez, Alejandro; van Bergen, Manfred J.; Eggenkamp, H. G. M.

2018-02-01

Hyperacid brines from active volcanic lakes are some of the chemically most complex aqueous solutions on Earth. Their compositions provide valuable insights into processes of elemental transfer from a magma body to the surface and interactions with solid rocks and the atmosphere. This paper describes changes in chemical and δ37Cl signatures observed in a 1750 h isothermal evaporation experiment on hyperacid (pH 0.1) sulphate-chloride brine water from the active lake of Kawah Ijen volcano (Indonesia). Although gypsum was the only evaporite mineral identified in the evolving brine, decreasing Si concentrations may ultimately result in amorphous silica precipitation. Geochemical simulations predict the additional formation of elemental sulphur at lower water activities (aH2O ≤ 0.65) that were not reached in the experiment. Absence of other sulphates and halides despite the high load of dissolved elements (initial TDS ca. 100 g/kg) can be attributed to increased solubility of metals, promoted by extensive formation of complexes between the variety of cations and the major anions (HSO4-, Cl-, F-) present. Chlorine deviations from a conservative behaviour point to losses of gaseous hydrogen chloride (HCl(g)) and consequently an increase in Br/Cl ratios. Chlorine isotope fractionation that accompanied the escape of HCl(g) showed a marked change in sign and magnitude in the course of progressive evaporation of the brine. The calculated factor of fractionation between HCl(g) and dissolved Cl for the initial interval (before 500 h) is positive (1000lnαHCl(g)-Cldiss. = + 1.55 ± 0.49‰to + 3.37 ± 1.11‰), indicating that, at first, the escaping HCl(g) was isotopically heavier than the dissolved Cl remaining in the brine. Conversely, fractionation shifted to the opposite direction in the subsequent interval (1000lnαHCl(g)-Cldiss. = 5.67 ± 0.17‰to - 5.64 ± 0.08‰), in agreement with values reported in literature. It is proposed that Cl isotopic fractionation in highly acidic brines is controlled by the distribution of dissolved chlorine species, which changes from Cl- to HClo dominance with the progressive pH decline. The Kawah Ijen lake acquired its extreme composition through influx of sulphur and halogen-rich magmatic gas components and extensive rock dissolution. If hyperacid brines with comparable chemical composition existed on Mars, evaporation processes up to the extent reported here (aH2O = 0.85), were likely accompanied by losses of gaseous HCl. The resulting changes in Cl isotope compositions, Br/Cl, S/Cl and other ratios in the residual brine might be potentially recorded in assemblages of halogen-bearing secondary evaporation minerals. Also, volcanic-hydrothermal brines as these would extend the stability of liquid water on the Martian surface down to a temperature of -90 °C.

Tracking the evolution of a giant magmatic system from assembly to supereruption

NASA Astrophysics Data System (ADS)

Wotzlaw, J. F.; Schaltegger, U.; Frick, D. A.; Dungan, M. A.; Gerdes, A.; Günther, D.

2012-12-01

The chemical and physical characteristics of large magma bodies prior to eruption are closely related consequences of the balance between the rate of magma influx and the rate of cooling. The products of caldera-related silicic supereruptions, and less voluminous associated precursor and post-caldera activity preserve information about the thermal and chemical states of the system at the moment of evacuation of the magma chamber. Numerous studies of the Oligocene Fish Canyon Tuff (5000 km3; Colorado, USA) and related eruptive products of the La Garita caldera have addressed the origin and evolution of large-volume crystal-rich magmas. We use the presence of zircon in all eruptive products of the Fish Canyon magmatic system to gain a high-resolution geochronologic control on the thermal evolution of the magmatic system by using the trace element composition of U-Pb dated zircons as a proxy for magma crystallinity. New analytical protocols permit to obtain age, chemical and isotopic information from the exact same volume of single zircons (Schoene et al., 2010, GCA) allowing us to trace magma crystallinity as a function of time. Zircon U-Pb dates record ~400,000 years of crystallization. Variations in trace element composition in U-Pb dated zircons can be attributed to trace element fractionation imposed by co-crystallization of titanite. Due to the relatively high modal abundance of titanite in Fish Canyon magma and the extreme compatibility of the rare earth elements (REE) in this phase, titanite is the major control on many trace element concentrations and ratios (e.g. Yb/Dy) in coexisting zircons via varying degrees of depletion of these elements in the host melt. Modeling of compositional variations as a result of fractional crystallization suggests that the range of zircon compositions can be explained by 50-70% crystallization of a fractionating assemblage containing 0.4-0.8 vol.% titanite. The period of cooling centered around 28.4 Ma and is marked by an apparent crystallinity that is ~30% higher than at the time of eruption, implying that the Fish Canyon magma was perilously close to complete solidification, hence 'plutonic death', prior to late reheating. We estimate the duration of the reheating event from the age difference of the chemically most evolved (highest Yb/Dy) and the youngest dated zircon to be ~170 ka. This duration for reactivation of the near solidus crystal mush is in excellent agreement with estimates derived from numerical modeling of remelting by upward percolation of a hot gas-phase derived from underplated mafic magma ('gas sparging'; Bachmann and Bergantz, 2003, Geology). This investigation, which is the first in which high resolution U-Pb zircon geochronology has been coupled with geochemical modeling of systematic compositional variations in an accessory mineral, ties together many of the threads which have been developed independently during previous studies of the Fish Canyon magmatic system and places related petrogenetic processes into an absolute time frame.

Fire and season of post-fire defoliation effects on biomass, composition and cover in mixed-grass prairie

USDA-ARS?s Scientific Manuscript database

North American prairies are acknowledged to have evolved with grazing following fire. Given this evolutionary fire-grazing interaction, our objective was to determine whether seasonal timing of defoliation following fire alters subsequent productivity and species composition. Following the April 201...

Chemical composition and digestibility of Trifolium exposed to elevated ozone and carbon dioxide in a free-air (FACE) fumigation system

Treesearch

R.B. Muntifering; A.H. Chappelka; J.C. Lin; D.F. Karnosky; G.L. Somers

2006-01-01

Tropospheric ozone (O3) and carbon dioxide (CO2) are significant drivers of plant growth and chemical composition. We hypothesized that exposure to elevated concentrations of O3 and CO2, singly and in combination, would modify the chemical composition of Trifolium...

An Overview of Recent Development in Composite Catalysts from Porous Materials for Various Reactions and Processes

PubMed Central

Xie, Zaiku; Liu, Zhicheng; Wang, Yangdong; Yang, Qihua; Xu, Longya; Ding, Weiping

2010-01-01

Catalysts are important to the chemical industry and environmental remediation due to their effective conversion of one chemical into another. Among them, composite catalysts have attracted continuous attention during the past decades. Nowadays, composite catalysts are being used more and more to meet the practical catalytic performance requirements in the chemical industry of high activity, high selectivity and good stability. In this paper, we reviewed our recent work on development of composite catalysts, mainly focusing on the composite catalysts obtained from porous materials such as zeolites, mesoporous materials, carbon nanotubes (CNT), etc. Six types of porous composite catalysts are discussed, including amorphous oxide modified zeolite composite catalysts, zeolite composites prepared by co-crystallization or overgrowth, hierarchical porous catalysts, host-guest porous composites, inorganic and organic mesoporous composite catalysts, and polymer/CNT composite catalysts. PMID:20559508

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Fabrication of modified g-C3N4 nanorod/Ag3PO4 nanocomposites for solar-driven photocatalytic oxygen evolution from water splitting

NASA Astrophysics Data System (ADS)

Tian, Lin; Xian, Xiaozhai; Cui, Xingkai; Tang, Hua; Yang, Xiaofei

2018-02-01

Semiconductor-based photocatalysis has been considered as one of the most effective techniques to achieve the conversion of clean and sustainable sunlight to solar fuel, in which the construction of novel solar-driven photocatalytic systems is the key point. Here, we report initially the synthesis of modified graphitic carbon nitride (g-C3N4) nanorods via the calcination of intermediates obtained from the co-polymerization of precursors, and the in-situ hybridization of Ag3PO4 with as-prepared modified g-C3N4 to produce g-C3N4 nanorod/Ag3PO4 composite materials. The diameter of modified rod-like g-C3N4 materials is determined to be around 1 μm. Subsequently the morphological features, crystal and chemical structures of the assembled g-C3N4 nanorod/Ag3PO4 composites were systematically investigated by SEM, XRD, XPS, UV-vis diffuse reflectance spectra (DRS). Furthermore, the use of as-prepared composite materials as the catalyst for photocatalytic oxygen evolution from water splitting was studied. The oxygen-generating results showed that the composite photocatalyst modified with 600 mg rod-like g-C3N4 demonstrates 2.5 times higher efficiency than that of bulk Ag3PO4. The mechanism behind the enhancement in the oxygen-evolving activity is proposed on the basis of in-situ electron spin resonance (ESR) measurement as well as theoretical analysis. The study provides new insights into the design and development of new photocatalytic composite materials for energy and environmental applications.

Origin of reverse compositional and textural zoning in granite plutons by localized thermal overturn of stratified magma chambers

NASA Astrophysics Data System (ADS)

Trubač, Jakub; Janoušek, Vojtěch; Žák, Jiří; Somr, Michael; Kabele, Petr; Švancara, Jan; Gerdes, Axel; Žáčková, Eliška

2017-04-01

This study integrates gravimetry and thermal modelling with petrology, U-Th-Pb monazite and zircon geochronology and whole-rock geochemistry of the early Carboniferous Říčany Pluton, Bohemian Massif, in order to discuss the origin of compositional and textural zoning in granitic plutons and complex histories of horizontally stratified, multiply replenished magma chambers. The pluton consists of two coeval, nested biotite (-muscovite) granite facies: outer one, strongly porphyritic (SPm) and inner one, weakly porphyritic (WPc). Their contact is concealed but is likely gradational over several hundreds of meters. The two facies have nearly identical modal composition, are subaluminous to slightly peraluminous and geochemically evolved. Mafic microgranular enclaves, commonly associated with K-feldspar phenocryst patches, are abundant in the pluton center and indicate a repeated basic magma injection and its multistage interactions with the granitic magma and nearly solidified cumulates. Furthermore, the gravimetric data show that the nested pluton is only a small outcrop of a large anvil-like body reaching the depth of at least 14 km, where the pluton root is expected. Trace-element compositions reveal that the pluton is doubly reversely zoned. On the pluton scale, the outer SRG is geochemically more evolved than the inner WPc. On the scale of individual units, outward whole-rock geochemical variations within each facies (SPm, WPc) are compatible with fractional crystallization dominated by feldspars. The proposed genetic model invokes vertical overturn of a deeper, horizontally stratified anvil-shaped magma chamber. The overturn was driven by reactivation of resident felsic magma from the K-feldspar-rich crystal mush. The energy for the melt remobilization, extraction and subsequent ascent is thought to be provided by a long-lived thermal anomaly above the pluton feeding zone, enhanced by the multiple injections of hot basic magmas. In general, it is concluded that the three-dimensional shape of the granitic bodies exerts a first-order control on their cooling histories and thus also on their physico-chemical evolution. Thicker and longer lived portions of magma chambers are the favourable sites for extensive fractionation and/or, potentially vigorous interaction with the basic magmas. These hot domains are then particularly prone to rejuvenation and subsequent extraction of highly mobile magma leading potentially to volcanic eruptions.

Evolution of atmospheric xenon and other noble gases inferred from Archean to Paleoproterozoic rocks

NASA Astrophysics Data System (ADS)

Avice, G.; Marty, B.; Burgess, R.; Hofmann, A.; Philippot, P.; Zahnle, K.; Zakharov, D.

2018-07-01

We have analyzed ancient atmospheric gases trapped in fluid inclusions contained in minerals of Archean (3.3 Ga) to Paleozoic (404 Ma) rocks in an attempt to document the evolution of the elemental composition and isotopic signature of the atmosphere with time. Doing so, we aimed at understanding how physical and chemical processes acted over geological time to shape the modern atmosphere. Modern atmospheric xenon is enriched in heavy isotopes by 30-40‰ u-1 relative to Solar or Chondritic xenon. Previous studies demonstrated that, 3.3 Ga ago, atmospheric xenon was isotopically fractionated (enriched in the light isotopes) relative to the modern atmosphere, by 12.9 ± 1.2 (1σ) ‰ u-1, whereas krypton was isotopically identical to modern atmospheric Kr. Details about the specific and progressive isotopic fractionation of Xe during the Archean, originally proposed by Pujol et al. (2011), are now well established by this work. Xe isotope fractionation has evolved from 21‰ u-1 at 3.5 Ga to 12.9‰ u-1 at 3.3 Ga. The current dataset provides some evidence for stabilization of the Xe fractionation between 3.3 and 2.7 Ga. However, further studies will be needed to confirm this observation. After 2.7 Ga, the composition kept evolving and reach the modern-like atmospheric Xe composition at around 2.1 Ga ago. Xenon may be the second atmospheric element, after sulfur, to show a secular isotope evolution during the Archean that ended shortly after the Archean-Proterozoic transition. Fractionation of xenon indicates that xenon escaped from Earth, probably as an ion, and that Xe escape stopped when the atmosphere became oxygen-rich. We speculate that the Xe escape was enabled by a vigorous hydrogen escape on the early anoxic Earth. Organic hazes, scavenging isotopically heavy Xe, could also have played a role in the evolution of atmospheric Xe. For 3.3 Ga-old samples, Ar-N2 correlations are consistent with a partial pressure of nitrogen (pN2) in the Archean atmosphere similar to, or lower than, the modern one, thus requiring other processes than a high pN2 to keep the Earth's surface warm despite a fainter Sun. The nitrogen isotope composition of the atmosphere at 3.3 Ga was already modern-like, attesting to inefficient nitrogen escape to space since that time.

Estimation of chemical carcass composition from 8th rib characteristics with Belgian blue double-muscled bulls.

PubMed

De Campeneere, S; Fiems, L O; Van de Voorde, G; Vanacker, J M; Boucque, C V; Demeyer, D I

1999-01-01

Characteristics from the 8th rib cut: chemical composition, tissue composition after dissection, specific gravity (SG) and m. longissimus thoracis (LT) composition, collected on 17 Belgian Blue double-muscled fattening bulls were used to generate equations for predicting chemical carcass composition. Carcass composition was best predicted from chemical analysis of the 8th rib cut and the empty body weight (EBW) of the bull. Carcass chemical fat content (CCF, kg) was predicted from the 8th rib cut fat content (ether extract, 8RF, kg) by the following regression: CCF=1.94+27.37 8RF (R(2)=0.957, RSD =9.89%). A higher coefficient was found for carcass water (CCW, kg) predicted from 8RF and EBW: CCW=-2.26+0.28 EBW-34.28 8RF (R(2)=0.997, RSD=1.48%). No parameter was found to improve the prediction of CCP from EBW solely: CCP=-0.86+0.08 EBW (R(2) =0.992, RSD=2.61%). Prediction equations based solely on LT composition had low R(2) values of between 0.38 and 0.67, whereas no significant equations were found using SG. However, equations based on EBW had R(2) values between 0.78 and 0.99. Chemical components of the 8th rib cut in combination with EBW are most useful in predicting the chemical composition of the carcass of Belgian-Blue double-muscled bulls.

Study of chloride ion transport of composite by using cement and starch as a binder

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

Armynah, Bidayatul; Halide, Halmar; Zahrawani,

This study presents the chemical bonding and the structural properties of composites from accelerator chloride test migration (ACTM). The volume fractions between binder (cement and starch) and charcoal in composites are 20:80 and 60:40. The effect of the binder to the chemical composition, chemical bonding, and structural properties before and after chloride ion passing through the composites was determined by X-ray fluorescence (XRF), by Fourier transform infra-red (FTIR), and x-ray diffraction (XRD), respectively. From the XRD data, XRF data, and the FTIR data shows the amount of chemical composition, the type of binding, and the structure of composites are dependingmore » on the type of binder. The amount of chloride migration using starch as binder is higher than that of cement as a binder due to the density effects.« less

Pulsed plasma chemical synthesis of SixCyOz composite nanopowder

NASA Astrophysics Data System (ADS)

Kholodnaya, G.; Sazonov, R.; Ponomarev, D.; Remnev, G.

2017-05-01

SixCyOz composite nanopowder with an average size of particles about 10-50 nm was produced using the pulsed plasma chemical method. The experiments on the synthesis of nanosized composite were carried out using a TEA-500 pulsed electron accelerator. To produce a composite, SiCl4, O2, and CH4 were used. The major part of experiments was conducted using a plasma chemical reactor (quartz, 140 mm diameter, 6 l volume). The initial reagents were injected into the reactor, then a pulsed electron beam was injected which initiated the chemical reactions whose products were the SixCyOz composite nanopowder. To define the morphology of the particles, the JEOL-II-100 transmission electron microscope (TEM) with an accelerating voltage of 100 kV was used. The substances in the composition of the composite nanopowder were identified using the infrared absorption optical spectrum. To conduct this analysis, the Nicolet 5700 FT-IR spectrometer was used.

Symposium on Current Research in the Chemical Sciences: Third Annual Southern Station Chemical Sciences Meeting

Treesearch

Timothy G. Rials; [Editor

1994-01-01

The original charter for this annual meeting of chemical sciences personnel called for an informal atmosphere for the discussion of common concerns and needs. The years have seen the definition of our "common concern" evolve into a sharing of our efforts in applying the science of chemistry to the resolution of problems faced by our forest resource. I believe...

Pesticide durability and the evolution of resistance: A novel application of survival analysis.

PubMed

Brevik, Kristian; Schoville, Sean D; Mota-Sanchez, David; Chen, Yolanda H

2018-03-01

Arthropod pests are widely perceived to evolve resistance to insecticides at different rates. Although widespread "successful" species are assumed to evolve quickly and minor pests slowly, few studies have utilized published data on resistance events to test for differences among species. Using 532 records from the Arthropod Pesticide Resistance Database covering 20 species, we applied a survival analysis to model the number of generations from insecticide introduction to the first report of arthropod resistance, providing one of the most comprehensive analyses of this question to date. Our approach tested: 1) whether successful pests evolve resistance faster than close relatives, 2) whether species differ significantly in the time to demonstrate resistance, and 3) whether different insecticide classes differ in durability (length of time an insecticide is used before resistance arises). We found that species differed significantly in the amount of time it took for resistance to be reported. Overall, the median duration between the introduction of an insecticide and the first report of resistance was 66 generations (95% c.i. 60-78 generations), and highly-resistant arthropods did not evolve resistance faster than their relatives. Insecticide durability did not differ by the mode of action or year of introduction. Arthropod species significantly varied in how rapidly they evolve resistance to new insecticides, regardless of their chemistry. Visualization of the history of insecticide resistance provides information to be used for understanding how pesticide resistance evolved and how it can best be managed. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

Composite resins in 2013: an update on their progress.

PubMed

Radz, Gary M

2013-01-01

Having steadily evolved and improved over the past several decades, composite resins are providing clinicians with an increased array of options for successfully restoring teeth in a minimally invasive manner. Numerous advances compared to early composite resin systems, such as increased shade availability, reduced polymerization shrinkage, and the development of nanoparticles, have enabled composite resins to offer long-term esthetic solutions for patients. This article summarizes the changes that have occurred, discusses popular applications for the use of composite materials, and presents brief case studies demonstrating their capabilities.

Zoning and exsolution in cumulate alkali feldspars from the eruption (12.9 Ka) of Laacher see volcano (Western Germany) as an indicator of time-scales and dynamics of carbonate-silicate unmixing

NASA Astrophysics Data System (ADS)

Sourav Rout, Smruti; Wörner, Gerhard

2017-04-01

Time-scales extracted from the detailed analysis of chemically zoned minerals provide insights into crystal ages, magma storage and compositional evolution, including mixing and unmixing events. This allows having a better understanding of pre-eruptive history of large and potentially dangerous magma chambers. We present a comprehensive study of chemical diffusion across zoning and exsolution patterns of alkali feldspars in carbonatite-bearing cognate syenites from the 6.3 km3 (D.R.E) phonolitic Laacher See Tephra (LST) eruption 12.9 ka ago. The Laacher See volcano is located in the Quaternary East Eifel volcanic field of the Paleozoic Rhenish Massif in Western Germany and has produced a compositionally variable sequence in a single eruption from a magma chamber that was zoned from mafic phonolite at the base to highly evolved, actively degassing phonolite magma at the top. Diffusion chronometry is applied to major and trace element compositions obtained on alkali feldspars from carbonate-bearing syenitic cumulates. Methods used were laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS) in combination with energy-dispersive and wavelength-dispersive electron microprobe analyses (EDS & WDS-EMPA). The grey scale values extracted from multiple accumulations of back-scattered electron images represent the K/Na ratio owing to the extremely low concentrations of Ba and Sr (<30 ppm). The numerical grey scale profiles and the quantitative compositional profiles are anatomized using three different fitting models in MATLAB®, Mathematica® and Origin® to estimate related time-scales with minimized error for a temperature range of 750 deg C to 800 deg C (on the basis of existing experimental data on phase transition and phase separation). A distinctive uphill diffusive analysis is used specifically for the phase separation in the case of exsolution features (comprising of albite- and orthoclase-rich phases) in sanidines. The error values are aggregates of propagated error through calculations and the uncertainty in temperature values. Trace element compositional data of distinct feldspar compositions that are assumed to have grown before and after silicate-carbonate unmixing are used to estimate partition coefficients between carbonate and silicate melt. The resulting values correlate well with available experimental data from the literature. We will present a genetic model based on the compositional data on feldspar zonation for the process and timing of silicate-carbonate unmixing prior to eruption of the host phonolite magma.

Chemical and physical controls on the transformation of amorphous calcium carbonate into crystalline CaCO3 polymorphs

NASA Astrophysics Data System (ADS)

Blue, C. R.; Giuffre, A.; Mergelsberg, S.; Han, N.; De Yoreo, J. J.; Dove, P. M.

2017-01-01

Calcite and other crystalline polymorphs of CaCO3 can form by pathways involving amorphous calcium carbonate (ACC). Apparent inconsistencies in the literature indicate the relationships between ACC composition, local conditions, and the subsequent crystalline polymorphs are not yet established. This experimental study quantifies the control of solution composition on the transformation of ACC into crystalline polymorphs in the presence of magnesium. Using a mixed flow reactor to control solution chemistry, ACC was synthesized with variable Mg contents by tuning input pH, Mg/Ca, and total carbonate concentration. ACC products were allowed to transform within the output suspension under stirred or quiescent conditions while characterizing the evolving solutions and solids. As the ACC transforms into a crystalline phase, the solutions record a polymorph-specific evolution of pH and Mg/Ca. The data provide a quantitative framework for predicting the initial polymorph that forms from ACC based upon the solution aMg2+/aCa2+ and aCO32-/aCa2+ and stirring versus quiescent conditions. This model reconciles discrepancies among previous studies that report on the nature of the polymorphs produced from ACC and supports the previous claim that monohydrocalcite may be an important, but overlooked, transient phase on the way to forming some aragonite and calcite deposits. By this construct, organic additives and extreme pH are not required to tune the composition and nature of the polymorph that forms. Our measurements show that the Mg content of ACC is recorded in the resulting calcite with a ≈1:1 dependence. By correlating composition of these calcite products with the Mgtot/Catot of the initial solutions, we find a ≈3:1 dependence that is approximately linear and general to whether calcite is formed via an ACC pathway or by the classical step-propagation process. Comparisons to calcite grown in synthetic seawater show a ≈1:1 dependence. The relationships suggest that the local Mg2+/Ca2+ at the time of precipitation determines the calcite composition, independent of whether growth occurs via an amorphous intermediate or classical pathway for a range of supersaturations and pH conditions. The findings reiterate the need to revisit the traditional picture of chemical and physical controls on CaCO3 polymorph selection. Mineralization by pathways involving ACC can lead to the formation of crystalline phases whose polymorphs and compositions are out of equilibrium with local growth media. As such, classical thermodynamic equilibria may not provide a reliable predictor of observed compositions.

RECOMMENDATIONS FOR RESEARCH RELATED TO BIOLOGICAL, CHEMICAL, AND ECOLOGICAL ASPECTS OF SEDIMENT PORE WATER: THE WAY FORWARD

EPA Science Inventory

Toxicity tests are useful and reliable tools for evaluating the adverse effects of chemicals discharged into aquatic ecosystems. The science of sediment toxicology evolved rapidly following the realization that sediments are a sink and a source for contaminants and that they can ...

Evaluating the Impact of Uncertainties in Clearance and Exposure When Prioritizing Chemicals Screened in High-Throughput Assays

EPA Science Inventory

The toxicity-testing paradigm has evolved to include high-throughput (HT) methods for addressing the increasing need to screen hundreds to thousands of chemicals rapidly. Approaches that involve in vitro screening assays, in silico predictions of exposure concentrations, and phar...

Testing and Risk Assessment of Chemicals that Impact Highly Adaptive Biological Systems: The Case of Endocrine Systems

EPA Science Inventory

Animals have evolved a variety of mechanisms for responding to toxic chemicals of both natural and anthropogenic origin. Well-known examples include activation of cellular repair pathways and induction of metabolizing enzymes. From a governmental regulatory perspective, these a...

Impacts of the mixing state and chemical composition on the cloud condensation nuclei (CCN) activity in Beijing during winter, 2016

NASA Astrophysics Data System (ADS)

Ren, J.; Zhang, F.

2017-12-01

Abstract.Understanding aerosol chemical composition and mixing state on CCN activity in polluted urban area is crucial to determine NCCN accurately and thus to quantify aerosol indirect effects. Aerosol hrgroscopicity, size-resolved cloud condensation nuclei (CCN) concentration and chemical composition are measured under polluted and background conditions in Beijing based on the Air Pollution and Human Health (APHH) field campaign in winter 2016. The CCN number concentration (NCCN) is predicted by using κ-Köhler theory from the PNSD and five simplified of the mixing state and chemical composition. The assumption of EIS (sulfate, nitrate and SOA internally mixed, and POA and BC externally mixed with size-resolved chemical composition) shows the best closure to predict NCCN with the ratio of predicted to measured NCCN of 0.96-1.12 both in POL and BG conditions. Under BG conditions, IB (internal mixture with bulk chemical composition) scheme achieves the best CCN closure during any periods of a day. In polluted days, EIS and IS (internal mixture with size-resolved chemical composition) scheme may achieve better closure than IB scheme due to the heterogeneity in particles composition across different size. ES (external mixture with size-resolved chemical composition) and EB (external mixture with bulk chemical composition) scheme markedly underestimate the NCCN with the ratio of predicted to measured NCCN of 0.6-0.8. In addition, we note that assumptions of size-resolved composition (IS or ES) show very limited promotes by comparing with the assumptions of bulk composition (IB or EB), furthermore, the prediction becomes worse by using size-resolved assumption in clean days. The predicted NCCN during eve-rush periods shows the most sensitivity to the five different assumptions, with ratios of the predicted and measured NCCN ranging from 0.5 to 1.4, reflecting great impacts from evening traffic and cooking sources. The result from the sensitivity examination of predict NCCN to particles mixing state and organic volume fractions with the aging of organic particles suggests that the mixing state of particles plays a minor role when the κorg exceeds 0.1. Our study could provide new dataset to evaluate the CCN parameterization in models in those heavily polluted regions with large fraction of POA and BC.

Laboratory Inquiry for Determining the Chemical Composition of a Component in a Daily Use Detergent: Sodium Sesquicarbonate

ERIC Educational Resources Information Center

Koga, Nobuyoshi; Kimura, Tomoyasu; Shigedomi, Kana

2011-01-01

An inquiry-based laboratory activity to determine the chemical composition of a component in alkaline detergents, sodium sesquicarbonate (SSC), is proposed. On the basis of introductory demonstrations by the instructor on the chemical properties and reactions of SSC, students propose the hypothetical composition of SSC and possible quantitative…

Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NOx conditions

NASA Astrophysics Data System (ADS)

D'Ambro, Emma L.; Lee, Ben H.; Liu, Jiumeng; Shilling, John E.; Gaston, Cassandra J.; Lopez-Hilfiker, Felipe D.; Schobesberger, Siegfried; Zaveri, Rahul A.; Mohr, Claudia; Lutz, Anna; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.; Rivera-Rios, Jean C.; Keutsch, Frank N.; Thornton, Joel A.

2017-01-01

We present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO2 and low-NO conditions, highly oxygenated (O : C ≥ 1) C5 compounds were major components (˜ 50 %) of SOA. The SOA composition and effective volatility evolved both as a function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2 h) for some individual components, significant errors in group-contribution methods are revealed. In addition, > 30 % of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled with equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.

Evolved Gas Analyses of the Murray Formation in Gale Crater, Mars: Results of the Curiosity Rover's Sample Analysis at Mars (SAM) Instrument

NASA Technical Reports Server (NTRS)

Sutter, B.; McAdam, A. C.; Rampe, E. B.; Thompson, L. M.; Ming, D. W.; Mahaffy, P. R.; Navarro-Gonzalez, R.; Stern, J. C.; Eigenbrode, J. L.; Archer, P. D.

2017-01-01

The Sample Analysis at Mars (SAM) instrument aboard the Mars Science Laboratory rover has analyzed 13 samples from Gale Crater. All SAM-evolved gas analyses have yielded a multitude of volatiles (e.g., H2O, SO2, H2S, CO2, CO, NO, O2, HCl) [1- 6]. The objectives of this work are to 1) Characterize recent evolved SO2, CO2, O2, and NO gas traces of the Murray formation mudstone, 2) Constrain sediment mineralogy/composition based on SAM evolved gas analysis (SAM-EGA), and 3) Discuss the implications of these results relative to understanding the geological history of Gale Crater.

Petrogenesis of Western Cascades Silicic Volcanics Near Sweet Home, Oregon

NASA Astrophysics Data System (ADS)

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

2002-12-01

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

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

Wood, C.A.

Statistical relations have been determined between geometry, volume, slope, and age for 26 circum-Pacific composite (strato) volcanoes. General trends in eruption characteristics, repose periods, flow lengths and petrology are also documented. Few examples of the earliest stages of composite volcano activity are known, perhaps because these small volcanoes are indistinguishable from cinder cones. If cinder cones evolve into composite volcanoes a fundamental change in morphometry, eruption style, and petrology occurs at a basal diameter of 2 km.

Insights into the chemical composition of the metal-poor Milky Way halo globular cluster NGC 6426

NASA Astrophysics Data System (ADS)

Hanke, M.; Koch, A.; Hansen, C. J.; McWilliam, A.

2017-03-01

We present our detailed spectroscopic analysis of the chemical composition of four red giant stars in the halo globular cluster NGC 6426. We obtained high-resolution spectra using the Magellan2/MIKE spectrograph, from which we derived equivalent widths and subsequently computed abundances of 24 species of 22 chemical elements. For the purpose of measuring equivalent widths, we developed a new semi-automated tool, called EWCODE. We report a mean Fe content of [Fe/H] =-2.34 ± 0.05 dex (stat.) in accordance with previous studies. At a mean α-abundance of [(Mg, Si, Ca)/3 Fe] = 0.39 ± 0.03 dex, NGC 6426 falls on the trend drawn by the Milky Way halo and other globular clusters at comparably low metallicities. The distribution of the lighter α-elements as well as the enhanced ratio [Zn/Fe] = 0.39 dex could originate from hypernova enrichment of the pre-cluster medium. We find tentative evidence for a spread in the elements Mg, Si, and Zn, indicating an enrichment scenario, where ejecta of evolved massive stars of a slightly older population have polluted a newly born younger one. The heavy element abundances in this cluster fit well into the picture of metal-poor globular clusters, which in that respect appear to be remarkably homogeneous. The pattern of the neutron-capture elements heavier than Zn points toward an enrichment history governed by the r-process with little, if any, sign of s-process contributions. This finding is supported by the striking similarity of our program stars to the metal-poor field star HD 108317. This paper includes data gathered with the 6.5-m Magellan Telescopes located at Las Campanas Observatory, Chile.Equivalent widths and full Table 2 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/599/A97

Investigating melting induced mantle heterogeneities in plate driven mantle convection models

NASA Astrophysics Data System (ADS)

Price, M.; Davies, H.; Panton, J.

2017-12-01

Observations from geochemistry and seismology continue to suggest a range of complex heterogeneity in Earth's mantle. In the deep mantle, two large low velocity provinces (LLVPs) have been regularly observed in seismic studies, with their longevity, composition and density compared to the surrounding mantle debated. The cause of these observed LLVPs is equally uncertain, with previous studies advocating either thermal or thermo-chemical causes. There is also evidence that these structures could provide chemically distinct reservoirs within the mantle, with recent studies also suggesting there may be additional reservoirs in the mantle, such as bridgmanite-enriched ancient mantle structures (BEAMS). One way to test these hypotheses is using computational models of the mantle, with models that capture the full 3D system being both complex and computationally expensive. Here we present results from our global mantle model TERRA. Using our model, we can track compositional variations in the convecting mantle that are generated by self-consistent, evolving melting zones. Alongside the melting, we track trace elements and other volatiles which can be partitioned during melting events, and expelled and recycled at the surface. Utilising plate reconstruction models as a boundary condition, the models generate the tectonic features observed at Earth's surface, while also organising the lower mantle into recognisable degree-two structures. This results in our models generating basaltic `oceanic' crusts which are then brought into the mantle at tectonic boundaries, providing additional chemical heterogeneity in the mantle volume. Finally, by utilising thermodynamic lookup tables to convert the final outputs from the model to seismic structures, together with resolution filters for global tomography models, we are able to make direct comparisons between our results and observations. By varying the parameters of the model, we investigate a range of current hypotheses for heterogeneity in the mantle. Our work attempts to reconcile the many proposed current ideas for the deep mantle, giving additional insight from modelling on the latest observations from other Deep Earth disciplines.

Volatile organic compounds in pesticide formulations: Methods to estimate ozone formation potential

NASA Astrophysics Data System (ADS)

Zeinali, Mazyar; McConnell, Laura L.; Hapeman, Cathleen J.; Nguyen, Anh; Schmidt, Walter F.; Howard, Cody J.

2011-05-01

The environmental fate and toxicity of active ingredients in pesticide formulations has been investigated for many decades, but relatively little research has been conducted on the fate of pesticide co-formulants or inerts. Some co-formulants are volatile organic compounds (VOCs) and can contribute to ground-level ozone pollution. Effective product assessment methods are required to reduce emissions of the most reactive VOCs. Six emulsifiable concentrate pesticide products were characterized for percent VOC by thermogravimetric analysis (TGA) and gas chromatography-mass spectrometry (GC-MS). TGA estimates exceeded GC-MS by 10-50% in all but one product, indicating that for some products a fraction of active ingredient is released during TGA or that VOC contribution was underestimated by GC-MS. VOC profiles were examined using TGA-Fourier transform infrared (FTIR) evolved gas analysis and were compared to GC-MS results. The TGA-FTIR method worked best for products with the simplest and most volatile formulations, but could be developed into an effective product screening tool. An ozone formation potential ( OFP) for each product was calculated using the chemical composition from GC-MS and published maximum incremental reactivity ( MIR) values. OFP values ranged from 0.1 to 3.1 g ozone g -1 product. A 24-h VOC emission simulation was developed for each product assuming a constant emission rate calculated from an equation relating maximum flux rate to vapor pressure. Results indicate 100% VOC loss for some products within a few hours, while other products containing less volatile components will remain in the field for several days after application. An alternate method to calculate a product OFP was investigated utilizing the fraction of the total mass of each chemical emitted at the end of the 24-h simulation. The ideal assessment approach will include: 1) unambiguous chemical composition information; 2) flexible simulation models to estimate emissions under different management practices; and 3) accurate reactivity predictions.

Re-evaluating across-axis geochemical variations at the East Pacific Rise and Juan de Fuca Ridge: on- and off-axis melt delivery

NASA Astrophysics Data System (ADS)

Perfit, M. R.; Walters, R. L.

2014-12-01

High spatial density geochemical data sets from the N-EPR and S-JdFR are used to re-evaluate the across-axis geochemical variations in major and trace elements at mid-ocean ridges (MORs). At two axial melt lens (AML) segments, north and south, at the 9-10°N EPR, N-MORB MgO varies across-axis from the most primitive above the AML to more evolved away from the axis. This trend is distinct at the northern (magmatically more robust) segment with an axial MgO range of 8-9 wt% and off-axis (>2km) range of 6.5-8 wt%. This decrease is also reflected in E-MORB MgO variation. There is more variability at the southern segment but, off-axis progression to more evolved MgO is still evident. Interestingly, the Cleft segment, JdFR, displays similar geochemical behavior to the EPR with an axial MgO range of 7-8.5 wt% and off-axis (>2km) range of 6-7.5 wt%. EPR geochemical studies over the past 30 years have described models of upper crustal accumulation ranging from eruptions limited to the axis, to temporal variation in the composition of magma in the AML, to multiple eruption sites across the ridge crest and flanks (<5km). Eruptions limited to the axis, with topographically controlled flow off-axis, cannot reproduce the observed off-axis change to more evolved N-MORB. Time-dependence could explain one instance of evolved lavas off-axis but, similar geochemical behavior is observed at two separate AML segments. Multiple instances of consistent compositional variability at multiple AML segments, and at different ridges, point to a common process of crustal accretion at MORs. In light of recent geophysical discoveries of Off-axis AMLs (OAMLs) at the EPR and JdFR, we propose that the trend of more evolved lavas for the majority of N-MORB lavas with distance from the axis is controlled by thermal distribution in the underlying crystal mush zone (CMZ). Higher magma flux beneath the axis facilitates higher temperatures and high porosity melt pathways, reducing crustal residence times, and erupting more primitive lava compositions. OAMLs at the edges of the CMZ, where it is cooler, feed more evolved off-axis eruptions. Lower magma flux at the edges increases crustal residence time and the extent to which magmas crystallize. OAMLs outside of the CMZ host magmas that may escaped any central mixing and erupt a greater range of compositions.

A Study of Chemical Composition of δ Scuti-Type Stars Based on the Observations with the BTA and RTT-150

NASA Astrophysics Data System (ADS)

Galeev, A. I.; Berdnikova, V. M.; Ivanova, D. V.; Kudryavtsev, D. O.; Shimanskaya, N. N.; Shimansky, V. V.; Balashova, M. O.

2017-06-01

The results of a study of a sample of δ Scuti-type stars obtained from the observations with the BTA and RTT-150 are presented. Based on photometric data, we measured and analyzed the fundamental parameters of all the studied stars. For eight stars (for two of them for the first time), the fundamental parameters of the atmospheres (Teff, log g, [Fe/H]) and the chemical composition for 29 elements in the LTE-approximation are received using spectroscopic observations. The chemical composition analysis demonstrates both the solar abundances of chemical elements and the anomalies of chemical composition typical of Am stars in the studied sample of δ Scuti-type stars.

The use of computer-assisted image analysis in the evaluation of the effect of management systems on changes in the color, chemical composition and texture of m. longissimus dorsi in pigs.

PubMed

Zapotoczny, Piotr; Kozera, Wojciech; Karpiesiuk, Krzysztof; Pawłowski, Rodian

2014-08-01

The effect of management systems on selected physical properties and chemical composition of m. longissimus dorsi was studied in pigs. Muscle texture parameters were determined by computer-assisted image analysis, and the color of muscle samples was evaluated using a spectrophotometer. Highly significant correlations were observed between chemical composition and selected texture variables in the analyzed images. Chemical composition was not correlated with color or spectral distribution. Subject to the applied classification methods and groups of variables included in the classification model, the experimental groups were identified correctly in 35-95%. No significant differences in the chemical composition of m. longissimus dorsi were observed between experimental groups. Significant differences were noted in color lightness (L*) and redness (a*). Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermally emissive sensing materials for chemical spectroscopy analysis

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

Poole, Zsolt; Ohodnicki, Paul R.

A sensor using thermally emissive materials for chemical spectroscopy analysis includes an emissive material, wherein the emissive material includes the thermally emissive materials which emit electromagnetic radiation, wherein the electromagnetic radiation is modified due to chemical composition in an environment; and a detector adapted to detect the electromagnetic radiation, wherein the electromagnetic radiation is indicative of the chemical interaction changes and hence chemical composition and/or chemical composition changes of the environment. The emissive material can be utilized with an optical fiber sensor, with the optical fiber sensor operating without the emissive material probed with a light source external to themore » material.« less

Characterizing the variability in chemical composition of flowback and produced waters - results from lab and field studies

NASA Astrophysics Data System (ADS)

Vieth-Hillebrand, Andrea; Wilke, Franziska D. H.; Schmid, Franziska E.; Zhu, Yaling; Lipińska, Olga; Konieczyńska, Monika

2017-04-01

The huge volumes and unknown composition of flowback and produced waters cause major public concerns about the environmental and social compatibility of hydraulic fracturing and the exploitation of gas from unconventional reservoirs. Flowback and produced waters contain not only residues of fracking additives but also chemical species that are dissolved from the target shales themselves. Shales are a heterogeneous mixture of minerals, organic matter, and formation water and little is actually understood about the fluid-rock interactions occurring during hydraulic fracturing of the shales and their effects on the chemical composition of flowback and produced water. To overcome this knowledge gap, interactions of different shales with different artificial stimulation fluids were studied in lab experiments under ambient and elevated temperature and pressure conditions. These lab experiments showed clearly that fluid-rock interactions change the chemical composition of the initial stimulation fluid and that geochemistry of the fractured shale is relevant for understanding flowback water composition. In addition, flowback water samples were taken after hydraulic fracturing of one horizontal well in Pomeranian region, Poland and investigated for their chemical composition. With this presentation, results from lab and field studies will be presented and compared to decipher possible controls on chemical compositions of flowback and produced water.

Classification of chemical substances, reactions, and interactions: The effect of expertise

NASA Astrophysics Data System (ADS)

Stains, Marilyne Nicole Olivia

2007-12-01

This project explored the strategies that undergraduate and graduate chemistry students engaged in when solving classification tasks involving microscopic (particulate) representations of chemical substances and microscopic and symbolic representations of different chemical reactions. We were specifically interested in characterizing the basic features to which students pay attention while classifying, identifying the patterns of reasoning that they follow, and comparing the performance of students with different levels of preparation in the discipline. In general, our results suggest that advanced levels of expertise in chemical classification do not necessarily evolve in a linear and continuous way with academic training. Novice students had a tendency to reduce the cognitive demand of the task and rely on common-sense reasoning; they had difficulties differentiating concepts (conceptual undifferentiation) and based their classification decisions on only one variable (reduction). These ways of thinking lead them to consider extraneous features, pay more attention to explicit or surface features than implicit features and to overlook important and relevant features. However, unfamiliar levels of representations (microscopic level) seemed to trigger deeper and more meaningful thinking processes. On the other hand, expert students classified entities using a specific set of rules that they applied throughout the classification tasks. They considered a larger variety of implicit features and the unfamiliarity with the microscopic level of representation did not affect their reasoning processes. Consequently, novices created numerous small groups, few of them being chemically meaningful, while experts created few but large chemically meaningful groups. Novices also had difficulties correctly classifying entities in chemically meaningful groups. Finally, expert chemists in our study used classification schemes that are not necessarily traditionally taught in classroom chemistry (e.g. the structure of substances is more relevant to them than their composition when classifying substances as compounds or elements). This result suggests that practice in the field may develop different types of knowledge framework than those usually presented in chemistry textbooks.

Probing Dust Formation Around Evolved Stars with Near-Infrared Interferometry

NASA Astrophysics Data System (ADS)

Sargent, B.; Srinivasan, S.; Riebel, D.; Meixner, M.

2014-09-01

Near-infrared interferometry holds great promise for advancing our understanding of the formation of dust around evolved stars. For example, the Magdalena Ridge Observatory Interferometer (MROI), which will be an optical/near-infrared interferometer with down to submilliarcsecond resolution, includes studying stellar mass loss as being of interest to its Key Science Mission. With facilities like MROI, many questions relating to the formation of dust around evolved stars may be probed. How close to an evolved star such as an asymptotic giant branch (AGB) or red supergiant (RSG) star does a dust grain form? Over what temperature ranges will such dust form? How does dust formation temperature and distance from star change as a function of the dust composition (carbonaceous versus oxygen-rich)? What are the ranges of evolved star dust shell geometries, and does dust shell geometry for AGB and RSG stars correlate with dust composition, similar to the correlation seen for planetary nebula outflows? At what point does the AGB star become a post-AGB star, when dust formation ends and the dust shell detaches? Currently we are conducting studies of evolved star mass loss in the Large Magellanic Cloud using photometry from the Surveying the Agents of a Galaxy's Evolution (SAGE; PI: M. Meixner) Spitzer Space Telescope Legacy program. We model this mass loss using the radiative transfer program 2Dust to create our Grid of Red supergiant and Asymptotic giant branch ModelS (GRAMS). For simplicity, we assume spherical symmetry, but 2Dust does have the capability to model axisymmetric, non-spherically-symmetric dust shell geometries. 2Dust can also generate images of models at specified wavelengths. We discuss possible connections of our GRAMS modeling using 2Dust of SAGE data of evolved stars in the LMC and also other data on evolved stars in the Milky Way's Galactic Bulge to near-infrared interferometric studies of such stars. By understanding the origins of dust around evolved stars, we may learn more about the later parts of the life of stardust; e.g., its residence in the interstellar medium, its time spent in molecular clouds, and its inclusion into solid bodies in future planetary systems.

[Bioinorganic chemical composition of the lens and methods of its investigation].

PubMed

Avetisov, S E; Novikov, I A; Pakhomova, N A; Motalov, V G

2018-01-01

Bioinorganic chemical composition of the lens of human and experimental animals (cows, dogs, rats, rabbits) have been analyzed in various studies. In most cases, the studies employed different methods to determine the gross (total) composition of chemical elements and their concentrations in the examined samples. Less frequently, they included an assessment of the distribution of chemical elements in the lens and correlation of their concentration with its morphological changes. Chemical elements from all groups (series) of the periodic classification system were discovered in the lens substance. Despite similar investigation methods, different authors obtained contradicting results on the chemical composition of the lens. This article presents data suggesting possible correlation between inorganic chemical elements in the lens substance with the development and formation of lenticular opacities. All currently employed methods are known to only analyze limited number of select chemical elements in the tissues and do not consider the whole range of elements that can be analyzed with existing technology; furthermore, the majority of studies are conducted on the animal model lens. Therefore, it is feasible to continue the development of the chemical microanalysis method by increasing the sensitivity of Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM/EDS) with the purpose of assessing the gross chemical composition and distribution of the elements in the lens substance, as well as revealing possible correlation between element concentration and morphological changes in the lens.

Assessment and Interpretation of Body Composition in Physical Education

ERIC Educational Resources Information Center

Vehrs, Pat; Hager, Ron

2006-01-01

The physical educator's role is evolving into that of a teacher who is well educated in the areas of teaching, skill acquisition and development, motor learning, exercise physiology, physical conditioning, weight management, health, and lifestyle management. In an era when childhood obesity is at an all-time high, body composition can be one…

How College Science Students Engage in Note-Taking Strategies

ERIC Educational Resources Information Center

Bonner, Janice M.; Holliday, William G.

2006-01-01

A composite theory of college science student note-taking strategies was derived from a periodic series of five interviews with 23 students and with other variables, including original and final versions of notes analyzed during a semester-long genetics course. This evolving composite theory was later compared with Van Meter, Yokoi, and Pressley's…

Modeling strength loss in wood by chemical composition. Part I, An individual component model for southern pine

Treesearch

J. E. Winandy; P. K. Lebow

2001-01-01

In this study, we develop models for predicting loss in bending strength of clear, straight-grained pine from changes in chemical composition. Although significant work needs to be done before truly universal predictive models are developed, a quantitative fundamental relationship between changes in chemical composition and strength loss for pine was demonstrated. In...

Adsorption behaviour of hydrogarnet for humic acid

NASA Astrophysics Data System (ADS)

Maeda, Hirotaka; Kurosaki, Yuichi; Nakayama, Masanobu; Ishida, Emile Hideki; Kasuga, Toshihiro

2018-04-01

Discharge of humic acid (HA) in aqueous environments is a key health and aesthetic issue. The present work investigates the use of hydrogarnet as a novel adsorbent for HA. Hydrogarnet was hydrothermally synthesized with different solvents to control the chemical composition. Hydrogarnet with three types of chemical compositions had better adsorption properties for HA than hydrogarnet with a single chemical composition. Controlling the chemical composition of hydrogarnet increased the number of hydroxyl groups and the overall binding energy of the system, leading to changes in the zeta potential. The enhancement of these adsorption properties is related to the increased numbers of hydroxyl groups on the surface and their diverse binding energies.

Evaluation of Beef by Electronic Tongue System TS-5000Z: Flavor Assessment, Recognition and Chemical Compositions According to Its Correlation with Flavor.

PubMed

Zhang, Xinzhuang; Zhang, Yawei; Meng, Qingxiang; Li, Ning; Ren, Liping

2015-01-01

The aim of this study was to assess the ability of electronic tongue system TS-5000Z to evaluate meat quality based on flavor assessment, recognition and correlation with the meat chemical composition. Meat was sampled from eighteen beef cattle including 6 Wagyu breed cattle, 6 Angus breed cattle and 6 Simmental breed cattle. Chemical composition including dry matter, crude protein, fat, ash, cholesterol and taurine and flavor of the meat were measured. The results showed that different breed cattle had different chemical compositions and flavor, which contains sourness, umami, saltiness, bitterness, astringency, aftertaste from astringency, aftertaste from bitterness and aftertaste from umami, respectively. A principal component analysis (PCA) showed an easily visible separation between different breeds of cattle and indicated that TS-5000Z made a rapid identification of different breeds of cattle. In addition, TS-5000Z seemed to be used to predict the chemical composition according to its correlation with the flavor. In conclusion, TS-5000Z would be used as a rapid analytical tool to evaluate the beef quality both qualitatively and quantitatively, based on flavor assessment, recognition and chemical composition according to its correlation with flavor.

Cometary coma chemical composition (C4) mission. [Abstract only

NASA Technical Reports Server (NTRS)

Carle, G. C.; Clark, B. C.; Niemann, H. B.; Alexander, M.; Knocke, P. C.; O'Hara, B. J.

1994-01-01

Cometary missions are of enormous fundamental importance for many different space science disciplines, including exobiology. Comets are presumed relics of the earliest, most primitive material in the solar nebula and are related to the planetesimals. They undoubtedly provided a general enrichment of volatiles to the inner solar system (contributing to atmospheres and oceans) and may have been key to the origin of life. A Discovery class, comet rendezvous mission, the Cometary Coma Chemical Composition (C4) Mission, was selected for further study by NASA earlier this year. The C4 Mission is a highly focused and usefully-limited subset of the Cometary Rendezvous Asteroid Flyby (CRAF) Mission, concentrating exclusively on measurements which will lead to an understanding of the chemical composition and make-up of the cometary nucleus. The scientific goals of the Cometary Coma Chemical Composition (C4) Mission are to rendezvous with a short-period comet and (1) to determine the elemental, chemical, and isotopic composition of the nucleus and (2) to characterize the chemical and isotopic nature of its atmosphere. Further, it is a goal to obtain preliminary data on the development of the coma (dust and gas composition) as a function of time and orbital position.

Polarization and studies of evolved star mass loss

NASA Astrophysics Data System (ADS)

Sargent, Benjamin; Srinivasan, Sundar; Riebel, David; Meixner, Margaret

2012-05-01

Polarization studies of astronomical dust have proven very useful in constraining its properties. Such studies are used to constrain the spatial arrangement, shape, composition, and optical properties of astronomical dust grains. Here we explore possible connections between astronomical polarization observations to our studies of mass loss from evolved stars. We are studying evolved star mass loss in the Large Magellanic Cloud (LMC) by using photometry from the Surveying the Agents of a Galaxy's Evolution (SAGE; PI: M. Meixner) Spitzer Space Telescope Legacy program. We use the radiative transfer program 2Dust to create our Grid of Red supergiant and Asymptotic giant branch ModelS (GRAMS), in order to model this mass loss. To model emission of polarized light from evolved stars, however, we appeal to other radiative transfer codes. We probe how polarization observations might be used to constrain the dust shell and dust grain properties of the samples of evolved stars we are studying.

[The characteristics of chemical composition of content of unicameral bone cysts depending on their growth stage].

PubMed

Stogov, M V; Luneva, S N; Mitrofanov, A I; Tkachuk, E A

2012-11-01

The article deals with the results of study of chemical composition of solitary cysts and blood serum of 27 patients. The results demonstrated that qualitative composition of f content of unicameral bone cysts is identical to chemical composition of blood serum. The results of analysis of total proteolysis activity and acid phosphatase activity in content of cysts can be used as criteria to determine the stage of cyst growth and to evaluate the effectiveness of applied treatment.

40 CFR 79.2 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... combustion or other chemical or physical reaction. (d) Fuel manufacturer means any person who, for sale or... the chemical composition of a bulk fuel, or the mixture of chemical compounds in a bulk fuel, by... fuel. (h) Chemical composition means the name and percentage by weight of each compound in an additive...

Prediction of the true digestible amino acid contents from the chemical composition of sorghum grain for poultry.

PubMed

Ebadi, M R; Sedghi, M; Golian, A; Ahmadi, H

2011-10-01

Accurate knowledge of true digestible amino acid (TDAA) contents of feedstuffs is necessary to accurately formulate poultry diets for profitable production. Several experimental approaches that are highly expensive and time consuming have been used to determine available amino acids. Prediction of the nutritive value of a feed ingredient from its chemical composition via regression methodology has been attempted for many years. The artificial neural network (ANN) model is a powerful method that may describe the relationship between digestible amino acid contents and chemical composition. Therefore, multiple linear regressions (MLR) and ANN models were developed for predicting the TDAA contents of sorghum grain based on chemical composition. A precision-fed assay trial using cecectomized roosters was performed to determine the TDAA contents in 48 sorghum samples from 12 sorghum varieties differing in chemical composition. The input variables for both MLR and ANN models were CP, ash, crude fiber, ether extract, and total phenols whereas the output variable was each individual TDAA for every sample. The results of this study revealed that it is possible to satisfactorily estimate the TDAA of sorghum grain through its chemical composition. The chemical composition of sorghum grain seems to highly influence the TDAA contents when considering components such as CP, crude fiber, ether extract, ash and total phenols. It is also possible to estimate the TDAA contents through multiple regression equations with reasonable accuracy depending on composition. However, a more satisfactory prediction may be achieved via ANN for all amino acids. The R(2) values for the ANN model corresponding to testing and training parameters showed a higher accuracy of prediction than equations established by the MLR method. In addition, the current data confirmed that chemical composition, often considered in total amino acid prediction, could be also a useful predictor of true digestible values of selected amino acids for poultry.

Isotopic Composition of Carbon Dioxide Released from Confidence Hills Sediment as Measured by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

NASA Technical Reports Server (NTRS)

Franz, H. B.; Mahaffy, P. R.; Stern, J.; Archer, P., Jr.; Conrad, P.; Eigenbrode, J.; Freissinet, C.; Glavin, D.; Grotzinger, J. P.; Jones, J.;

Effect of alkaline treatment on mechanical properties of kenaf fiber reinforced polyester composites

NASA Astrophysics Data System (ADS)

Reddy, Bijjam Ramgopal; Dhoria, Sneha H.

2018-04-01

This paper focuses on the study of the effect of chemical treatment on mechanical properties such as tensile, flexural and impact properties of kenaf fiber reinforced polyester composites. Adhesion between the fiber and polymer is one of factors affecting the mechanical properties of composites. In order to increase the adhesion, the fibers are chemically treated with 5% of sodium hydroxide (NaOH) solution. The composite specimens are prepared in both untreated and treated forms of kenaf fibers with five levels of fiber volume fractions. The specimens are prepared according to ASTM standards. Mechanical tests such as tensile, flexural and impact are conducted to determine ultimate tensile strength, bending strength and impact strength of composites. The effect of change in volume fraction on the mechanical properties of the composites is studied for both untreated (raw) and chemically treated kenaf fibers. It has been found that the composites made of chemically treated fibers have good mechanical properties compared to untreated fibers.

Bulk chemical compositions of Antarctic meteorites in the NIPR collection

NASA Astrophysics Data System (ADS)

Kimura, M.; Imae, N.; Yamaguchi, A.; Haramura, H.; Kojima, H.

2018-03-01

Bulk chemical compositions of meteorites were traditionally analyzed by wet chemical analysis, and NIPR has data for 1162 meteorites as of September 2017. We discuss the classification of meteorites on the basis of these data. Chondrite data are distributed in an anomalously wide range of compositions on the Urey-Craig diagram. One of the reasons for such wide distribution is terrestrial weathering producing Fe2O3-bearing phases from Fe-Ni metal and sulfides. Another important factor affecting the bulk compositional data is brecciation. Our observations indicate that many brecciated chondrites contain anomalously abundant opaque minerals, or are depleted in them, resulting in unusual compositions. In case of enstatite and some carbonaceous chondrites, the bulk compositions are distributed in wider ranges than reported before. The bulk compositions of HED meteorites are consistent with their mineralogy and classification. Our study suggests that wet chemical data are still significant for the meteorite classification. However, petrographic observation is indispensable for evaluating the bulk chemistry and classification of meteorites.

Geochemistry of the Shuksan greenschists and blueschists, North Cascades, Washington: Variably fractionated and altered metabasalts of oceanic affinity

NASA Astrophysics Data System (ADS)

Dungan, M. A.; Vance, J. A.; Blanchard, D. P.

1983-06-01

The Shuksan schist comprises a structurally coherent, metabasaltic member of the Easton Formation, the uppermost allochthon (Shuksan thrust plate) in the thrust system of the western North Cascades of Washington State. Late Jurassic metamorphism at moderately high P/T produced interlayering of actinolite-bearing greenschist assemblages with blue amphibole-bearing rocks. Major and trace element analyses of twelve greenschist and blueschist samples have been used to establish similarities between the basaltic protolith and moderately to strongly fractionated Type I MORB, to distinguish the effects of seafloor alteration superimposed on the primary igneous chemistry, and to evaluate the origin and nature of the chemical controls which produced the two mineral assemblages. The twelve analyzed samples exhibit moderate to strong LREE depletion, and characteristically low concentrations of other non-labile trace elements such as Nb, Th and Hf. The highly to moderately incompatible elements Ti, P, Nb, Zr, Hf, Y, Sc, and the REE vary by factors of 1.5 to 3.5 within the suite in a systematic pattern, increasing smoothly with increasing total iron. The relative enrichments of these elements are inversely proportional to bulk partition coefficients estimated for fractionation of basaltic magmas. The magnitude of the negative europium anomaly increases with overall incompatible element enrichment. These variations are consistent with the production of a wide spectrum of compositions by different degrees of low pressure fractionation of similar Type I MORB parent magmas. The concentrations of Sr, Rb, Na, and K vary irregularly and do not correlate with the non-labile trace elements. K and Rb are substantially elevated over typical MORB values in most samples and exhibit a consistently lower ratio (K/Rb=400 vs 1000) than fresh MORB. Concentrations of these four elements are believed to have been modified by low temperature seafloor alteration (pre-metamorphic) characterized by the formation of K-rich celadonitic clays, palagonite and minor potassium feldspar. The critical chemical variables that control the occurrence of actinolite and blue amphibole in the Shuksan schists are total iron, Fe2O3-content and Na/Ca (all high in blueschists). The chemical features were largely established by magmatic processes and inherited from the igneous parent rocks; the chemically more evolved samples are blueschists. The Fe2O3-content and Na/Ca, however, may be modified during alteration, rendering initial bulk compositions near the chemical boundary susceptible to changes which may shift rock compositions from one compatibility field to the other. Heterogeneous alteration of pillow lavas and other fragmental deposits, followed by intense flattening during metamorphism, provides a mechanism for generating blueschists and greenschists interlayered on the cm scale.

Evolution of the Craters of the Moon Lavas from primitive Snake River Plain basalts: inferences from plagioclase-melt thermobarometers and whole rock compositions

NASA Astrophysics Data System (ADS)

Vaid, N.; Putirka, K.; Kuntz, M.

2005-12-01

The volcanic rocks of the Craters of the Mon Lava field provide an ideal laboratory for testing models of magma transport and evolution. Their compositions, relative ages and volumes are well known, as are the fractionation processes leading to their evolution (Leeman, 1976). The COM is somewhat distinctive in the Snake River Plain (SRP) region, due to its evolved character, and an apparent compositional segregation from associated SRP basalts. Some have suggested that the high Fe liquids of the COM demand an origin separate from that of SRP basalts, possibly involving an Fe-enriched mantle, while others have suggested that the COM lavas may be derived by fractionation at moderate depths (30 km). In either case, there are important implications in regard to mantle composition and the nature and distribution of thermal energy. We use plagioclase-melt pairs and an analysis of whole rock compositions in attempt to test models of COM magmatic evolution. Plagioclase-melt thermobarometers provide rough estimates of crystallization depths, and show that COM and SRP lavas partially crystallized at similar depths of 14 +/- 6 km. However, plagioclase crystallization temperatures for SRP basalts (1400 +/- 25 K; Kings Bowl, Cerro Grande, North and South Robbers) exceed temperatures for COM lavas (1358 +/- 45 K) by 40 K. Our data also show that fractional crystallization (ol + plag) can explain the evolution of surrounding SRP basalt flows, and that the most evolved SRP basalts approach primitive COM lava compositions. The most primitive of COM magmas appear to be characterized by the appearance of apatite + magnetite as fractionating phases. Our results thus confirm the geochemical model of Leeman (1976) and the physical model of Kuntz (1992), with the added insight that SRP basalts are parental to the more evolved COM lavas, through low-pressure fractional crystallization in the upper crust. The principal differences between SRP and COM magmas appear to relate more to the presence or absence of density contrasts in the crust than differences in composition or temperature of mantle source materials. SRP basalts lie near the axis of the SRP where the granitic upper crust may have been obliterated by earlier volcanic episodes. In contrast, COM lavas, whose vents lie off axis, appear to have been trapped within the upper crust for longer periods, sufficient for further differentiation. Finally, SRP rhyolite compositions lie on the same fractionation trend as COM and SRP lavas, at very low values of MgO. We propose that highly evolved lavas throughout the SRP may form by fractional crystallization mechanisms alone, rather than through the partial melting and remobilization of preexisting felsic crustal materials.

Chemical composition of stars in Ruprecht 106 .

NASA Astrophysics Data System (ADS)

François, P.

High resolution spectra of 9 stars belonging to the globular cluster Rup 106 have been used to determine their chemical composition. The results reveal that Ruprecht 106 exhibits abundance anomalies when compared to galactic globular cluster of similar metallicity. The chemical composition of these stars is similar to what is found in Dwarf spheroidal galaxies favoring the hypothesis that Rup 106 has not been formed in our Galaxy.

Prediction of Combustion Gas Deposit Compositions

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Mcbride, B. J.; Zeleznik, F. J.; Gordon, S.

1985-01-01

Demonstrated procedure used to predict accurately chemical compositions of complicated deposit mixtures. NASA Lewis Research Center's Computer Program for Calculation of Complex Chemical Equilibrium Compositions (CEC) used in conjunction with Computer Program for Calculation of Ideal Gas Thermodynamic Data (PAC) and resulting Thermodynamic Data Base (THDATA) to predict deposit compositions from metal or mineral-seeded combustion processes.

Update on the Chemical Composition Of Crystalline, Smectite, and Amorphous Components for Rocknest Soil and John Klein and Cumberland Mudstone Drill Fines at Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Morris, R. V.; Ming, D. W.; Gellert, R.; Vaniman, D. T.; Bish, D. L.; Blake, D. F.; Chipera, S. J.; Morrison, S. M.; Downs, R. T.; Rampe, E. B.;

Polyimide composites: Application histories

NASA Technical Reports Server (NTRS)

Poveromo, L. M.

1985-01-01

Advanced composite hardware exposed to thermal environments above 127 C (260 F) must be fabricated from materials having resin matrices whose thermal/moisture resistance is superior to that of conventional epoxy-matrix systems. A family of polyimide resins has evolved in the last 10 years that exhibits the thermal-oxidative stability required for high-temperature technology applications. The weight and structural benefits for organic-matrix composites can now be extended by designers and materials engineers to include structures exposed to 316 F (600 F). Polyimide composite materials are now commercially available that can replace metallic or epoxy composite structures in a wide range of aerospace applications.

Evolved Gas Analyses of Sedimentary Materials in Gale Crater, Mars: Results of the Curiosity Rover's Sample Analysis at Mars (SAM) Instrument from Yellowknife Bay to the Stimson Formation

NASA Technical Reports Server (NTRS)

Sutter, B.; McAdam, A. C.; Rampe, E. B.; Ming, D. W.; Mahaffy, P. R.; Navarro-Gonzalez, R.; Stern, J. C.; Eigenbrode, J. L.; Archer, P. D.

2016-01-01

The Sample Analysis at Mars (SAM) instrument aboard the Mars Science Laboratory rover has analyzed 10 samples from Gale Crater. All SAM evolved gas analyses have yielded a multitude of volatiles (e.g, H2O, SO2, H2S, CO2, CO, NO, O2, HC1). The objectives of this work are to 1) Characterize the evolved H2O, SO2, CO2, and O2 gas traces of sediments analyzed by SAM through sol 1178, 2) Constrain sediment mineralogy/composition based on SAM evolved gas analysis (SAM-EGA), and 3) Discuss the implications of these results releative to understanding the geochemical history of Gale Crater.

Searching for Reduced Carbon on the Surface of Mars: The SAM Combustion Experiment

NASA Technical Reports Server (NTRS)

Stern, J. C.; Malespin, C. A.; Mahaffy, P. R.; Webster, C. R.; Eigenbrode, J. L.; Archer, P. D., Jr.; Brunner, A. E.; Freissinet, C.; Franz, H. B.; Glavin, D. P.;

Correlation of rocket propulsion fuel properties with chemical composition using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry followed by partial least squares regression analysis

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

Kehimkar, Benjamin; Hoggard, Jamin C.; Marney, Luke C.

There is an increased need to more fully assess and control the composition of kerosene based rocket propulsion fuels, namely RP-1 and RP-2. In particular, it is crucial to be able to make better quantitative connections between the following three attributes: (a) fuel performance, (b) fuel properties (flash point, density, kinematic viscosity, net heat of combustion, hydrogen content, etc) and (c) the chemical composition of a given fuel (i.e., specific chemical compounds and compound classes present as a result of feedstock blending and processing). Indeed, recent efforts in predicting fuel performance through modeling put greater emphasis on detailed and accuratemore » fuel properties and fuel compositional information. In this regard, advanced distillation curve (ADC) metrology provides improved data relative to classical boiling point and volatility curve techniques. Using ADC metrology, data obtained from RP-1 and RP-2 fuels provides compositional variation information that is directly relevant to predictive modeling of fuel performance. Often, in such studies, one-dimensional gas chromatography (GC) combined with mass spectrometry (MS) is typically employed to provide chemical composition information. Building on approaches using GC-MS, but to glean substantially more chemical composition information from these complex fuels, we have recently studied the use of comprehensive two dimensional gas chromatography combined with time-of-flight mass spectrometry (GC × GC - TOFMS) to provide chemical composition data that is significantly richer than that provided by GC-MS methods. In this report, by applying multivariate data analysis techniques, referred to as chemometrics, we are able to readily model (correlate) the chemical compositional information from RP-1 and RP-2 fuels provided using GC × GC - TOFMS, to the fuel property information such as that provided by the ADC method and other specification properties. We anticipate that this new chemical analysis strategy will have broad implications for the development of high fidelity composition-property models, leading to an optimized approach to fuel formulation and specification for advanced engine cycles.« less

Compositional Variations of Paleogene and Neogene Tephra From the Northern Izu-Bonin-Mariana Arc

NASA Astrophysics Data System (ADS)

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

2014-12-01

A primary objective of IODP Expedition 351 was to evaluate arc initiation processes of the Izu-Bonin-Mariana (IBM) volcanic arc and its compositional evolution through time. To this end, a single thick section of sediment overlying oceanic crust was cored in the Amami Sankaku Basin where a complete sediment record of arc inception and evolution is preserved. This sediment record includes ash and pyroclasts, deposited in fore-arc, arc, and back-arc settings, likely associated with both the ~49-25 Ma emergent IBM volcanic arc and the evolving Ryukyu-Kyushu volcanic arc. Our goal was to assess the major element evolution of the nascent and evolving IBM system using the temporally constrained record of the early and developing system. In all, more than 100 ash and tuff layers, and pyroclastic fragments were selected from temporally resolved portions of the core, and from representative fractions of the overall core ("core catcher"). The samples were prepared to determine major and minor element compositions via electron microprobe analyses. This ash and pyroclast record will allow us to 1) resolve the Paleogene evolutionary history of the northern IBM arc in greater detail; 2) determine compositional variations of this portion of the IBM arc through time; 3) compare the acquired data to an extensive whole rock and tephra dataset from other segments of the IBM arc; 4) test hypotheses of northern IBM arc evolution and the involvement of different source reservoirs; and 5) mark important stratigraphic markers associated with the Neogene volcanic history of the adjacent evolving Ryukyu-Kyushu arc.

Self-repair of cracks in brittle material systems

NASA Astrophysics Data System (ADS)

Dry, Carolyn M.

2016-04-01

One of the most effective uses for self repair is in material systems that crack because the cracks can allow the repair chemical to flow into the crack damage sites in all three dimensions. In order for the repair chemical to stay in the damage site and flow along to all the crack and repair there must be enough chemical to fill the entire crack. The repair chemical must be designed appropriately for the particular crack size and total volume of cracks. In each of the three examples of self repair in crackable brittle systems, the viscosity and chemical makeup and volume of the repair chemicals used is different for each system. Further the chemical delivery system has to be designed for each application also. Test results from self repair of three brittle systems are discussed. In "Self Repair of Concrete Bridges and Infrastructure" two chemicals were used due to different placements in bridges to repair different types of cracks- surface shrinkage and shear cracks, In "Airplane Wings and Fuselage, in Graphite" the composite has very different properties than the concrete bridges. In the graphite for airplane components the chemical also had to survive the high processing temperatures. In this composite the cracks were so definite and deep and thin that the repair chemical could flow easily and repair in all layers of the composite. In "Ceramic/Composite Demonstrating Self Repair" the self repair system not only repaired the broken ceramic but also rebounded the composite to the ceramic layer

Data on the weights, specific gravities and chemical compositions of potato (Solanum tuberosum) tubers for food processing from different areas of Hokkaido, Japan.

PubMed

Sato, Hiroaki; Koizumi, Ryosuke; Nakazawa, Yozo; Yamazaki, Masao; Itoyama, Ryuichi; Ichisawa, Megumi; Negichi, Junko; Sakuma, Rui; Furusho, Tadasu; Sagane, Yoshimasa; Takano, Katsumi

2017-04-01

This data article provides the weights, specific gravities and chemical compositions (moisture, protein, fat, ash, and carbohydrate) of potato tubers, for food processing use, from the Tokachi, Kamikawa and Abashiri areas of Hokkaido, Japan. Potato tubers of four cultivars ('Toyoshiro', 'Kitahime', 'Snowden' and 'Poroshiri') were employed in the current study. The weights and specific gravities of potato tubers from each cultivar, harvested from three areas, were measured, and those of near average weight and specific gravity from each group were analyzed for their chemical composition. In this article, weight, specific gravity, and chemical composition data are provided in tables.

Iron: A Key Element for Understanding the Origin and Evolution of Interstellar Dust

NASA Technical Reports Server (NTRS)

Dwek, Eli

2016-01-01

The origin and depletion of iron differ from all other abundant refractory elements that make up the composition of the interstellar dust. Iron is primarily synthesized in Type Ia supernovae (SNe Ia) and in core collapse supernovae (CCSN), and is present in the outflows from AGB (Asymptotic Giant Branch) stars. Only the latter two are observed to be sources of interstellar dust, since searches for dust in SN Ia have provided strong evidence for the absence of any significant mass of dust in their ejecta. Consequently, more than 65 percent of the iron is injected into the ISM (Inter-Stellar Matter) in gaseous form. Yet, ultraviolet and X-ray observations along many lines of sight in the ISM show that iron is severely depleted in the gas phase compared to expected solar abundances. The missing iron, comprising about 90 percent of the total, is believed to be locked up in interstellar dust. This suggests that most of the missing iron must have precipitated from the ISM gas by cold accretion onto preexisting silicate, carbon, or composite grains. Iron is thus the only element that requires most of its growth to occur outside the traditional stellar condensation sources. This is a robust statement that does not depend on our evolving understanding of the dust destruction efficiency in the ISM. Reconciling the physical, optical, and chemical properties of such composite grains with their many observational manifestations is a major challenge for understanding the nature and origin of interstellar dust.

IRON: A KEY ELEMENT FOR UNDERSTANDING THE ORIGIN AND EVOLUTION OF INTERSTELLAR DUST

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

Dwek, Eli, E-mail: eli.dwek@nasa.gov

The origin and depletion of iron differ from all other abundant refractory elements that make up the composition of interstellar dust. Iron is primarily synthesized in Type Ia supernovae (SNe Ia) and in core collapse supernovae (CCSN), and is present in the outflows from AGB stars. Only the latter two are observed to be sources of interstellar dust since searches for dust in SN Ia have provided strong evidence for the absence of any significant mass of dust in their ejecta. Consequently, more than 65% of the iron is injected into the ISM in gaseous form. Yet ultraviolet and X-raymore » observations along many lines of sight in the ISM show that iron is severely depleted in the gas phase as compared to expected solar abundances. The missing iron, comprising about 90% of the total, is believed to be locked up in interstellar dust. This suggests that most of the missing iron must have precipitated from the ISM gas by a cold accretion onto preexisting silicate, carbon, or composite grains. Iron is thus the only element that requires most of its growth to occur outside the traditional stellar condensation sources. This is a robust statement that does not depend on our evolving understanding of the dust destruction efficiency in the ISM. Reconciling the physical, optical, and chemical properties of such composite grains with their many observational manifestations is a major challenge for understanding the nature and origin of interstellar dust.« less

Turpentine-induced chemical pneumonitis with broncho-pleural fistula.

PubMed

Rodricks, A; Satyanarayana, M; D'Souza, G A; Ramachandran, P

2003-07-01

Turpentine is a volatile hydrocarbon used in polishes, solvents, paints and textile industry. When hydrocarbons are aspirated into the lung, they cause chemical pneumonitis, acute respiratory distress syndrome (ARDS), and rarely pneumatoceles and pneumothorax. We report a 20-year old boy with turpentine-induced chemical pneumonitis that evolved into a bronchopleural fistula. He was treated with oxygen, steroids and intercostal tube drainage. This is the first reported case of turpentine-associated bronchopleural fistula.

(Sub)millimeter emission lines of molecules in born-again stars

NASA Astrophysics Data System (ADS)

Tafoya, D.; Toalá, J. A.; Vlemmings, W. H. T.; Guerrero, M. A.; De Beck, E.; González, M.; Kimeswenger, S.; Zijlstra, A. A.; Sánchez-Monge, Á.; Treviño-Morales, S. P.

2017-04-01

Context. Born-again stars provide a unique possibility to study the evolution of the circumstellar envelope of evolved stars in human timescales. Up until now, most of the observations of the circumstellar material in these stars have been limited to studying the relatively hot gas and dust. In other evolved stars, the emission from rotational transitions of molecules, such as CO, is commonly used to study the cool component of their circumstellar envelopes. Thus, the detection and study of molecular gas in born-again stars is of great importance when attempting to understand their composition and chemical evolution. In addition, the molecular emission is an invaluable tool for exploring the physical conditions, kinematics, and formation of asymmetric structures in the circumstellar envelopes of these evolved stars. However, up until now, all attempts to detect molecular emission from the cool material around born-again stars have failed. Aims: We searched for emission from rotational transitions of molecules in the hydrogen-deficient circumstellar envelopes of born-again stars to explore the chemical composition, kinematics, and physical parameters of the relatively cool gas. Methods: We carried out observations using the APEX and IRAM 30 m telescopes to search for molecular emission toward four well-studied born-again stars, V4334 Sgr, V605 Aql, A30, and A78, that are thought to represent an evolutionary sequence. Results: For the first time, we detected emission from HCN and H13CN molecules toward V4334 Sgr, and CO emission in V605 Aql. No molecular emission was detected above the noise level toward A30 and A78. The detected lines exhibit broad linewidths ≳150 km s-1, which indicates that the emission comes from gas ejected during the born-again event, rather than from the old planetary nebula. A first estimate of the H12CN/H13CN abundance ratio in the circumstellar environment of V4334 Sgr is ≈3, which is similar to the value of the 12C/13C ratio measured from other observations. We derived a rotational temperature of Trot = 13 ± 1 K, and a total column density of NHCN = 1.6 ± 0.1 × 1016 cm-2 for V4334 Sgr. This result sets a lower limit on the amount of hydrogen that was ejected into the wind during the born-again event of this source. For V605 Aql, we obtained a lower limit for the integrated line intensities I12CO/I13CO> 4. This publication is based on data acquired with the Atacama Pathfinder Experiment (APEX) and IRAM 30 m telescopes. APEX is a collaboration between the Max-Planck-Institut für Radioastronomie, the European Southern Observatory, and the Onsala Space Observatory. IRAM is supported by INSU/CNRS (France), MPG (Germany) and IGN (Spain).

Unnatural selection in chemical systems

NASA Technical Reports Server (NTRS)

Orgel, Leslie E.

1995-01-01

The theory of evolution through natural selection was proposed by Darwin and Wallace to explain how the characteristics of populations of animals change with time. An examination of their assumptions shows that the theory has much broader application than they originally envisaged. We now know that in appropriate environments RNA molecules or computer viruses, for example, can evolve. The adventure with which we are concerned is the quest for chemical systems that undergo processes analogous to Darwinian selection in the test tube. The search is not restricted to systems that are closely related to nucleic acids, although most of the available experimental evidence concerns such systems. A population of molecules satisfies all the requirements of the theory is there are different kinds of molecules in the population and if each individual molecule can direct the formation of copies of itself, then a population of molecules will adapt to a varying environment by changing its composition so as to maintain as high as possible a rate of replication. Sol Spiegelman is the inventor of 'unnatural selection'. He showed clearly that populations of RNA molecules evolve when replicated repeatedly by Q beta RNA polymerase under a chosen set of adverse reaction conditions. In the systems that he studied, the initial population was fairly homogeneous and much of the variation was created during the course of the experiment by mutation, that is, error of replication. The term 'unnatural selection' will be used loosely to describe evolution of nucleic acids or other replicatable polymers in vitro. The term 'Natural Selection' will be reserved for the evolution of living organisms and their viruses. Natural Section usually involves the coevolution of nucleic acids and proteins, while 'unnatural selection', as practiced so far, allows replicating nucleic acids to evolve but hold constant the enzymes that catalyze replication. It is widely believed that biology based on DNA, RNA, and proteins was preceded by the biology of an 'RNA world' in which enzymes were composed of RNA alone. The origin of RNA replication is thus the central puzzle of the origins of life. Consequently, RNA-catalyzed RNA replication is presently one of the main goals of experimental work on unnatural selection. However, there is also a more distant goal, namely, to achieve replication and selection in systems unrelated to RNA. These different systems are discussed in this article.

Chemical composition, nutritional value and antioxidant properties of Mediterranean okra genotypes in relation to harvest stage.

PubMed

Petropoulos, Spyridon; Fernandes, Ângela; Barros, Lillian; Ferreira, Isabel C F R

2018-03-01

The aim of the present study was to determine the effect of fruit size on nutritional value, chemical composition and antioxidant properties of Mediterranean okra genotypes. For this purpose, pods from four okra cultivars and local landraces commonly cultivated in Greece, as well as pods from four commercial cultivars from North America were collected at two sizes (3-5 and>7cm). Significant differences were observed between the studied genotypes for both nutritional value and chemical composition parameters. Small fruit had a higher nutritional value, whereas chemical composition differed in a genotype dependent manner with most of the studied cultivars showing better results when harvested in small size. In conclusion, fruit size has a genotype dependent impact on chemical composition and nutritional value of okra pods and the common practice of harvesting okra fruit while they still have a small size helps to increase nutritional value for most of the studied genotypes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Monash Chemical Yields Project (Monχey) Element production in low- and intermediate-mass stars

NASA Astrophysics Data System (ADS)

Doherty, Carolyn; Lattanzio, John; Angelou, George; Campbell, Simon W.; Church, Ross; Constantino, Thomas; Cristallo, Sergio; Gil-Pons, Pilar; Karakas, Amanda; Lugaro, Maria; Stancliffe, Richard

The Monχey project will provide a large and homogeneous set of stellar yields for the low- and intermediate- mass stars and has applications particularly to galactic chemical evolution modelling. We describe our detailed grid of stellar evolutionary models and corresponding nucleosynthetic yields for stars of initial mass 0.8 M⊙ up to the limit for core collapse supernova (CC-SN) ~ 10 M⊙. Our study covers a broad range of metallicities, ranging from the first, primordial stars (Z = 0) to those of super-solar metallicity (Z = 0.04). The models are evolved from the zero-age main-sequence until the end of the asymptotic giant branch (AGB) and the nucleosynthesis calculations include all elements from H to Bi. A major innovation of our work is the first complete grid of heavy element nucleosynthetic predictions for primordial AGB stars as well as the inclusion of extra-mixing processes (in this case thermohaline) during the red giant branch. We provide a broad overview of our results with implications for galactic chemical evolution as well as highlight interesting results such as heavy element production in dredge-out events of super-AGB stars. We briefly introduce our forthcoming web-based database which provides the evolutionary tracks, structural properties, internal/surface nucleosynthetic compositions and stellar yields. Our web interface includes user- driven plotting capabilities with output available in a range of formats. Our nucleosynthetic results will be available for further use in post processing calculations for dust production yields.

Software for analysis of chemical mixtures--composition, occurrence, distribution, and possible toxicity

USGS Publications Warehouse

Scott, Jonathon C.; Skach, Kenneth A.; Toccalino, Patricia L.

2013-01-01

The composition, occurrence, distribution, and possible toxicity of chemical mixtures in the environment are research concerns of the U.S. Geological Survey and others. The presence of specific chemical mixtures may serve as indicators of natural phenomena or human-caused events. Chemical mixtures may also have ecological, industrial, geochemical, or toxicological effects. Chemical-mixture occurrences vary by analyte composition and concentration. Four related computer programs have been developed by the National Water-Quality Assessment Program of the U.S. Geological Survey for research of chemical-mixture compositions, occurrences, distributions, and possible toxicities. The compositions and occurrences are identified for the user-supplied data, and therefore the resultant counts are constrained by the user’s choices for the selection of chemicals, reporting limits for the analytical methods, spatial coverage, and time span for the data supplied. The distribution of chemical mixtures may be spatial, temporal, and (or) related to some other variable, such as chemical usage. Possible toxicities optionally are estimated from user-supplied benchmark data. The software for the analysis of chemical mixtures described in this report is designed to work with chemical-analysis data files retrieved from the U.S. Geological Survey National Water Information System but can also be used with appropriately formatted data from other sources. Installation and usage of the mixture software are documented. This mixture software was designed to function with minimal changes on a variety of computer-operating systems. To obtain the software described herein and other U.S. Geological Survey software, visit http://water.usgs.gov/software/.

Study of the structure and chemical composition of the protective coating of a fist stage gas turbine blade after regenerative heat treatment

NASA Astrophysics Data System (ADS)

Davidov, D. I.; Kazantseva, N. V.; Vinogradova, N. I.; Ezhov, I. V.

2017-12-01

Investigation of the structure and chemical composition of the protective coating of the first stage IN738 gas turbine blade after standard regenerative heat treatment was done. It was found the degradation of microstructure and chemical composition of both the blade feather and its protective coating. Redistribution of the chemical elements decreasing the corrosion resistance was observed inside the protective coating. Cracks on the boundary between the blade feather and the protective coating were found by scanning electron microscopy. The carbide transformation and sigma phase were found in the structure of the blade feather. Based upon the structural and chemical composition studies, it is concluded that the standard regenerative heat treatment of the IN738 operative gas turbine blade does not provide full structure regeneration.

The Genesis solar xenon composition and its relationship to planetary xenon signatures

NASA Astrophysics Data System (ADS)

Crowther, S. A.; Gilmour, J. D.

2013-12-01

The fluence and isotopic composition of solar wind xenon have been determined from silicon collector targets flown on the NASA Genesis mission. A protocol was developed to extract gas quantitatively from samples of ∼9-25 mm2, and xenon measured using the RELAX mass spectrometer. The fluence of implanted solar wind xenon is 1.202(87) × 106 atoms 132Xe cm-2, which equates to a flux of 5.14(21) × 106 atoms 132Xe cm-2 year-1 at the L1 point. This value is in good agreement with those reported in other studies. The isotopic composition of the solar wind is consistent with that extracted from the young lunar regolith and other Genesis collector targets. The more precise xenon isotopic data derived from the Genesis mission confirm models of relationships among planetary xenon signatures. The underlying composition of Xe-Q is mass fractionated solar wind; small, varying contributions of Xe-HL and 129Xe from 129I decay are present in reported meteorite analyses. In contrast, an s-process deficit is apparent in Xe-P3, which appears to have been mass fractionated to the same extent as Xe-Q from a precursor composition, suggesting similar trapping mechanisms. Solar wind xenon later evolved by the addition of ∼1% (at 132Xe) of s-process xenon to this precursor. As an alternative model to a single source reservoir for Xe-P3, we propose that trapping of xenon onto carbonaceous carriers has been an ongoing process across galactic history, and that preparation of the residues in which Xe-P3 has been identified preferentially preserves longer lived host phases; a higher proportion of these sample xenon isotopic compositions from earlier in galactic chemical evolution, allowing the s-process deficit to become apparent. The relationships among SW-Xe, Xe-Q and Xe-P3 predict that the 124Xe/132Xe ratio for the solar wind is 0.00481(6).

9+ Years of CALIPSO PSC Observations: An Evolving Climatology

NASA Technical Reports Server (NTRS)

Pitts, Michael C.; Poole, Lamont R.

2015-01-01

Polar stratospheric clouds (PSCs) play a crucial role in the springtime chemical depletion of ozone at high latitudes. PSC particles (primarily supercooled ternary solution, or STS droplets) provide sites for heterogeneous chemical reactions that transform stable chlorine and bromine reservoir species into highly reactive ozone-destructive forms. Furthermore, large nitric acid trihydrate (NAT) PSC particles can irreversibly redistribute odd nitrogen through gravitational sedimentation (a process commonly known as denitrification), which prolongs the ozone depletion process by slowing the reformation of the stable chlorine reservoirs. Spaceborne observations from the CALIOP (Cloud-Aerosol Lidar with Orthogonal Polarization) lidar on the CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations) satellite are providing a rich new dataset for studying PSCs. CALIPSO is an excellent platform for studying polar processes with CALIOP acquiring, on average, over 300,000 backscatter profiles daily at latitudes between 55o and 82o in both hemispheres. PSCs are detected in the CALIOP backscatter profiles using a successive horizontal averaging scheme that enables detection of strongly scattering PSCs (e.g., ice) at the finest possible spatial resolution (5 km), while enhancing the detection of very tenuous PSCs (e.g., low number density NAT) at larger spatial scales (up to 135 km). CALIOP PSCs are separated into composition classes (STS; liquid/NAT mixtures; and ice) based on the ensemble 532-nm scattering ratio (the ratio of total-to-molecular backscatter) and 532-nm particulate depolarization ratio (which is sensitive to the presence of non-spherical, i.e. NAT and ice particles). In this paper, we will provide an overview of the CALIOP PSC detection and composition classification algorithm and then examine the vertical and spatial distribution of PSCs in the Arctic and Antarctic on vortex-wide scales for entire PSC seasons over the more than nine-year data record from 2006- 2015.

Chemical Composition and Evaluation of Nicotine, Tobacco Alkaloids, pH, and Selected Flavors in E-Cigarette Cartridges and Refill Solutions.

PubMed

Lisko, Joseph G; Tran, Hang; Stanfill, Stephen B; Blount, Benjamin C; Watson, Clifford H

2015-10-01

Electronic cigarette (e-cigarette) use is increasing dramatically in developed countries, but little is known about these rapidly evolving products. This study analyzed and evaluated the chemical composition including nicotine, tobacco alkaloids, pH, and flavors in 36 e-liquids brands from 4 manufacturers. We determined the concentrations of nicotine, alkaloids, and select flavors and measured pH in solutions used in e-cigarettes. E-cigarette products were chosen based upon favorable consumer approval ratings from online review websites. Quantitative analyses were performed using strict quality assurance/quality control validated methods previously established by our lab for the measurement of nicotine, alkaloids, pH, and flavors. Three-quarters of the products contained lower measured nicotine levels than the stated label values (6%-42% by concentration). The pH for e-liquids ranged from 5.1-9.1. Minor tobacco alkaloids were found in all samples containing nicotine, and their relative concentrations varied widely among manufacturers. A number of common flavor compounds were analyzed in all e-liquids. Free nicotine levels calculated from the measurement of pH correlated with total nicotine content. The direct correlation between the total nicotine concentration and pH suggests that the alkalinity of nicotine drives the pH of e-cigarette solutions. A higher percentage of nicotine exists in the more absorbable free form as total nicotine concentration increases. A number of products contained tobacco alkaloids at concentrations that exceed U.S. pharmacopeia limits for impurities in nicotine used in pharmaceutical and food products. © Published by Oxford University Press on behalf of the Society for Research on Nicotine and Tobacco 2015. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Comparative Analysis of Volatile Defensive Secretions of Three Species of Pyrrhocoridae (Insecta: Heteroptera) by Gas Chromatography-Mass Spectrometric Method

PubMed Central

Krajicek, Jan; Havlikova, Martina; Bursova, Miroslava; Ston, Martin; Cabala, Radomir; Exnerova, Alice; Stys, Pavel; Bosakova, Zuzana

2016-01-01

The true bugs (Hemiptera: Heteroptera) have evolved a system of well-developed scent glands that produce diverse and frequently strongly odorous compounds that act mainly as chemical protection against predators. A new method of non-lethal sampling with subsequent separation using gas chromatography with mass spectrometric detection was proposed for analysis of these volatile defensive secretions. Separation was performed on Rtx-200 column containing fluorinated polysiloxane stationary phase. Various mechanical irritation methods (ultrasonics, shaking, pressing bugs with plunger of syringe) were tested for secretion sampling with a special focus on non-lethal irritation. The preconcentration step was performed by sorption on solid phase microextraction (SPME) fibers with different polarity. For optimization of sampling procedure, Pyrrhocoris apterus was selected. The entire multi-parameter optimization procedure of secretion sampling was performed using response surface methodology. The irritation of bugs by pressing them with a plunger of syringe was shown to be the most suitable. The developed method was applied to analysis of secretions produced by adult males and females of Pyrrhocoris apterus, Pyrrhocoris tibialis and Scantius aegyptius (all Heteroptera: Pyrrhocoridae). The chemical composition of secretion, particularly that of alcohols, aldehydes and esters, is species-specific in all three pyrrhocorid species studied. The sexual dimorphism in occurrence of particular compounds is largely limited to alcohols and suggests their epigamic intraspecific function. The phenetic overall similarities in composition of secretion do not reflect either relationship of species or similarities in antipredatory color pattern. The similarities of secretions may be linked with antipredatory strategies. The proposed method requires only a few individuals which remain alive after the procedure. Thus secretions of a number of species including even the rare ones can be analyzed and broadly conceived comparative studies can be carried out. PMID:27997627

Updated Reference Model for Heat Generation in the Lithosphere

NASA Astrophysics Data System (ADS)

Wipperfurth, S. A.; Sramek, O.; Roskovec, B.; Mantovani, F.; McDonough, W. F.

2017-12-01

Models integrating geophysics and geochemistry allow for characterization of the Earth's heat budget and geochemical evolution. Global lithospheric geophysical models are now constrained by surface and body wave data and are classified into several unique tectonic types. Global lithospheric geochemical models have evolved from petrological characterization of layers to a combination of petrologic and seismic constraints. Because of these advances regarding our knowledge of the lithosphere, it is necessary to create an updated chemical and physical reference model. We are developing a global lithospheric reference model based on LITHO1.0 (segmented into 1°lon x 1°lat x 9-layers) and seismological-geochemical relationships. Uncertainty assignments and correlations are assessed for its physical attributes, including layer thickness, Vp and Vs, and density. This approach yields uncertainties for the masses of the crust and lithospheric mantle. Heat producing element abundances (HPE: U, Th, and K) are ascribed to each volume element. These chemical attributes are based upon the composition of subducting sediment (sediment layers), composition of surface rocks (upper crust), a combination of petrologic and seismic correlations (middle and lower crust), and a compilation of xenolith data (lithospheric mantle). The HPE abundances are correlated within each voxel, but not vertically between layers. Efforts to provide correlation of abundances horizontally between each voxel are discussed. These models are used further to critically evaluate the bulk lithosphere heat production in the continents and the oceans. Cross-checks between our model and results from: 1) heat flux (Artemieva, 2006; Davies, 2013; Cammarano and Guerri, 2017), 2) gravity (Reguzzoni and Sampietro, 2015), and 3) geochemical and petrological models (Rudnick and Gao, 2014; Hacker et al. 2015) are performed.

Characteristics and habitat of deep vs. shallow slow slip events

NASA Astrophysics Data System (ADS)

Wipperfurth, S. A.; Sramek, O.; Roskovec, B.; Mantovani, F.; McDonough, W. F.

2016-12-01

Models integrating geophysics and geochemistry allow for characterization of the Earth's heat budget and geochemical evolution. Global lithospheric geophysical models are now constrained by surface and body wave data and are classified into several unique tectonic types. Global lithospheric geochemical models have evolved from petrological characterization of layers to a combination of petrologic and seismic constraints. Because of these advances regarding our knowledge of the lithosphere, it is necessary to create an updated chemical and physical reference model. We are developing a global lithospheric reference model based on LITHO1.0 (segmented into 1°lon x 1°lat x 9-layers) and seismological-geochemical relationships. Uncertainty assignments and correlations are assessed for its physical attributes, including layer thickness, Vp and Vs, and density. This approach yields uncertainties for the masses of the crust and lithospheric mantle. Heat producing element abundances (HPE: U, Th, and K) are ascribed to each volume element. These chemical attributes are based upon the composition of subducting sediment (sediment layers), composition of surface rocks (upper crust), a combination of petrologic and seismic correlations (middle and lower crust), and a compilation of xenolith data (lithospheric mantle). The HPE abundances are correlated within each voxel, but not vertically between layers. Efforts to provide correlation of abundances horizontally between each voxel are discussed. These models are used further to critically evaluate the bulk lithosphere heat production in the continents and the oceans. Cross-checks between our model and results from: 1) heat flux (Artemieva, 2006; Davies, 2013; Cammarano and Guerri, 2017), 2) gravity (Reguzzoni and Sampietro, 2015), and 3) geochemical and petrological models (Rudnick and Gao, 2014; Hacker et al. 2015) are performed.

MOFwich: Sandwiched Metal-Organic Framework-Containing Mixed Matrix Composites for Chemical Warfare Agent Removal.

PubMed

Peterson, Gregory W; Lu, Annie X; Hall, Morgan G; Browe, Matthew A; Tovar, Trenton; Epps, Thomas H

2018-02-28

This work describes a new strategy for fabricating mixed matrix composites containing layered metal-organic framework (MOF)/polymer films as functional barriers for chemical warfare agent protection. Through the use of mechanically robust polymers as the top and bottom encasing layers, a high-MOF-loading, high-performance-core layer can be sandwiched within. We term this multifunctional composite "MOFwich". We found that the use of elastomeric encasing layers enabled core layer reformation after breakage, an important feature for composites and membranes alike. The incorporation of MOFs into the core layer led to enhanced removal of chemical warfare agents while simultaneously promoting moisture vapor transport through the composite, showcasing the promise of these composites for protection applications.

A fully coupled petrological geodynamical model to investigate the evolution of crustal magma chambers

NASA Astrophysics Data System (ADS)

Rummel, Lisa; Kaus, Boris J. P.; White, Richard W.

2017-04-01

The evolution of crustal magma chambers can be considered from a range of different physical and chemical perspectives. Most previous studies focus either on the petrological side (assuming only thermal effects and ignoring mechanics), or on the mechanical evolution (assuming a fixed melt chemistry). Here, we develop a method that fully couples petrological with geodynamic modelling, by combining a finite element code, MVEP2, with a thermodynamic modelling approach (Perple_X) that takes the evolving chemistry into account. The evolution of melt chemistry in a crustal magma chamber is analyzed by focusing on the effects of depth and temperature as well as size and shape of the magma chamber(s). The models show that each of these factors influences the melting behavior of rocks, the magma composition and their effects on the mechanics in the upper lithosphere. Interactions with country rocks (assimilation), ongoing rock depletion (fractional melting) and a possible open system behavior (fractional crystallization) and their effects on magma chemistry are taken into account. The chemical and mineralogical evolution of the melt source, composition (10 oxide component system) of intrusive and extrusive rocks as well as melt fraction and density are tracked on particles using a marker-in-cell-method in the geodynamic code. After each melt extraction event, the employed phase diagram is updated or recalculated based on the residuum chemistry that shifts the solidus to higher temperatures with sequential melt extraction. The resulting wide range in chemical compositions and the volume of intrusive and extrusive rocks are tracked in time and space over the melting region. The newly generated crust employs phase diagrams which are directly computed from the chemistry of extracted melts. Plutons are able to melt again as long as the local temperature is higher in the model than the solidus temperature in the employed phase diagram. As a result, our models make testable predictions on types of erupted lavas. We show an application to the plume-related intracontinental West Eifel volcanism (Germany), where our models explain a sudden change in K2O/Na2O-ratios in the volcanic rocks by a transition between melting a metasomatized and a pyrolitic mantle. We also show initial results from crustal melt extraction in an arc system.

Chemical Mapping of Vesta and Ceres

NASA Technical Reports Server (NTRS)

Prettyman, Thomas H.; Mittlefehldt, David W.; Yamashita, Naoyuki; McSween, Harry Y.; Feldman, William C.; Lawrence, David J.; Beck, Andrew W.; McCoy, Timothy J.; Toplis, Michael J.; Mizzon, Hugau;

The importance of chemistry in creating well-defined nanoscopic embedded therapeutics: devices capable of the dual functions of imaging and therapy.

PubMed

Nyström, Andreas M; Wooley, Karen L

2011-10-18

Nanomedicine is a rapidly evolving field, for which polymer building blocks are proving useful for the construction of sophisticated devices that provide enhanced diagnostic imaging and treatment of disease, known as theranostics. These well-defined nanoscopic objects have high loading capacities, can protect embedded therapeutic cargo, and offer control over the conditions and rates of release. Theranostics also offer external surface area for the conjugation of ligands to impart stealth characteristics and/or direct their interactions with biological receptors and provide a framework for conjugation of imaging agents to track delivery to diseased site(s). The nanoscopic dimensions allow for extensive biological circulation. The incorporation of such multiple functions is complicated, requiring exquisite chemical control during production and rigorous characterization studies to confirm the compositions, structures, properties, and performance. We are particularly interested in the study of nanoscopic objects designed for treatment of lung infections and acute lung injury, urinary tract infections, and cancer. This Account highlights our work over several years to tune the assembly of unique nanostructures. We provide examples of how the composition, structure, dimensions, and morphology of theranostic devices can tune their performance as drug delivery agents for the treatment of infectious diseases and cancer. The evolution of nanostructured materials from relatively simple overall shapes and internal morphologies to those of increasing complexity is driving the development of synthetic methodologies for the preparation of increasingly complex nanomedicine devices. Our nanomedicine devices are derived from macromolecules that have well-defined compositions, structures, and topologies, which provide a framework for their programmed assembly into nanostructures with controlled sizes, shapes, and morphologies. The inclusion of functional units within selective compartments/domains allows us to create (multi)functional materials. We employ combinations of controlled radical and ring-opening polymerizations, chemical transformations, and supramolecular assembly to construct such materials as functional entities. The use of multifunctional monomers with selective polymerization chemistries affords regiochemically functionalized polymers. Further supramolecular assembly processes in water with further chemical transformations provide discrete nanoscopic objects within aqueous solutions. This approach echoes processes in nature, whereby small molecules (amino acids, nucleic acids, saccharides) are linked into polymers (proteins, DNA/RNA, polysaccharides, respectively) and then those polymers fold into three-dimensional conformations that can lead to nanoscopic functional entities.

Carbon and Sulfur Isotopic Composition of Rocknest Soil as Determined with the Sample Analysis at Mars(SAM) Quadrupole Mass Spectrometer

NASA Technical Reports Server (NTRS)

Franz, H. B.; McAdam, C.; Stern, J. C.; Archer, P. D., Jr.; Sutter, B.; Grotzinger, J. P.; Jones, J. H.; Leshin, L. A.; Mahaffy, P. R.; Ming, D. W.;

Regolith Evolved Gas Analyzer

NASA Technical Reports Server (NTRS)

Hoffman, John H.; Hedgecock, Jud; Nienaber, Terry; Cooper, Bonnie; Allen, Carlton; Ming, Doug

2000-01-01

The Regolith Evolved Gas Analyzer (REGA) is a high-temperature furnace and mass spectrometer instrument for determining the mineralogical composition and reactivity of soil samples. REGA provides key mineralogical and reactivity data that is needed to understand the soil chemistry of an asteroid, which then aids in determining in-situ which materials should be selected for return to earth. REGA is capable of conducting a number of direct soil measurements that are unique to this instrument. These experimental measurements include: (1) Mass spectrum analysis of evolved gases from soil samples as they are heated from ambient temperature to 900 C; and (2) Identification of liberated chemicals, e.g., water, oxygen, sulfur, chlorine, and fluorine. REGA would be placed on the surface of a near earth asteroid. It is an autonomous instrument that is controlled from earth but does the analysis of regolith materials automatically. The REGA instrument consists of four primary components: (1) a flight-proven mass spectrometer, (2) a high-temperature furnace, (3) a soil handling system, and (4) a microcontroller. An external arm containing a scoop or drill gathers regolith samples. A sample is placed in the inlet orifice where the finest-grained particles are sifted into a metering volume and subsequently moved into a crucible. A movable arm then places the crucible in the furnace. The furnace is closed, thereby sealing the inner volume to collect the evolved gases for analysis. Owing to the very low g forces on an asteroid compared to Mars or the moon, the sample must be moved from inlet to crucible by mechanical means rather than by gravity. As the soil sample is heated through a programmed pattern, the gases evolved at each temperature are passed through a transfer tube to the mass spectrometer for analysis and identification. Return data from the instrument will lead to new insights and discoveries including: (1) Identification of the molecular masses of all of the gases liberated from heated soil samples; (2) Identification of the asteroid soil mineralogy to aid in the selection process for returned samples; (3) Existence of oxygen in the asteroid soil and the potential for in-situ resource utilization (ISRU); and (4) Existence of water and other volatiles in the asteroid soil. Additional information is contained in the original extended abstract.

Ca isotopic geochemistry of an Antarctic aquatic system

USGS Publications Warehouse

Lyons, W. Berry; Bullen, Thomas D.; Welch, Kathleen A.

2017-01-01

The McMurdo Dry Valleys, Antarctica, are a polar desert ecosystem. The hydrologic system of the dry valleys is linked to climate with ephemeral streams that flow from glacial melt during the austral summer. Past climate variations have strongly influenced the closed-basin, chemically stratified lakes on the valley floor. Results of previous work point to important roles for both in-stream processes (e.g., mineral weathering, precipitation and dissolution of salts) and in-lake processes (e.g., mixing with paleo-seawater and calcite precipitation) in determining the geochemistry of these lakes. These processes have a significant influence on calcium (Ca) biogeochemistry in this aquatic ecosystem, and thus variations in Ca stable isotope compositions of the waters can aid in validating the importance of these processes. We have analyzed the Ca stable isotope compositions of streams and lakes in the McMurdo Dry Valleys. The results validate the important roles of weathering of aluminosilicate minerals and/or CaCO3 in the hyporheic zone of the streams, and mixing of lake surface water with paleo-seawater and precipitation of Ca-salts during cryo-concentration events to form the deep lake waters. The lakes in the McMurdo Dry Valleys evolved following different geochemical pathways, evidenced by their unique, nonsystematic Ca isotope signatures.

Cloud condensation nuclei droplet growth kinetics of ultrafine particles during anthropogenic nucleation events

NASA Astrophysics Data System (ADS)

Shantz, N. C.; Pierce, J. R.; Chang, R. Y.-W.; Vlasenko, A.; Riipinen, I.; Sjostedt, S.; Slowik, J. G.; Wiebe, A.; Liggio, J.; Abbatt, J. P. D.; Leaitch, W. R.

2012-02-01

Evolution of the cloud condensation nucleus (CCN) activity of 36 ± 4 nm diameter anthropogenic aerosol particles at a water supersaturation of 1.0 ± 0.1% is examined for particle nucleation and growth. During the early stages of one event, relatively few of the anthropogenic particles at 36 nm were CCN active and their growth rates by water condensation were delayed relative to ammonium sulphate particles. As the event progressed, the particle size distribution evolved to larger sizes and the relative numbers of particles at 36 nm that were CCN active increased until all the 36 nm particles were activating at the end of the event. Based on the chemistry of larger particles and the results from an aerosol chemical microphysics box model, the increase in CCN activity of the particles was most likely the result of the condensation of sulphate in this case. Despite the increased CCN activity, a delay was observed in the initial growth of these particles into cloud droplets, which persisted even when the aerosol was most CCN active later in the afternoon. Simulations show that the delay in water uptake is explained by a reduction of the mass accommodation coefficient assuming that the composition of the 36 nm particles is the same as the measured composition of the 60-100 nm particles.

Polymer Composite Wrapping and Cathodic Protection System for Reinforced Concrete Piles in Marine Applications

DTIC Science & Technology

2013-06-01

vicinity of new patches. Fiber -reinforced polymer (FRP) composite wrapping systems have been evolving over the last 20 years and are now a viable...material is a woven glass fiber pre-impregnated with moisture-activated resins that cure underwater after being put in place. Figure 4. ICPW...wrap system The FRP composite wrap material that was selected is Aqua Wrap Type G- 05, a woven glass fiber pre-impregnated with moisture-activated

Evolution of stalk/spore ratio in a social amoeba: cell-to-cell interaction via a signaling chemical shaped by cheating risk.

PubMed

Uchinomiya, Kouki; Iwasa, Yoh

2013-11-07

The social amoeba (or cellular slime mold) is a model system for cell cooperation. When food is depleted in the environment, cells aggregate together. Some of these cells become stalks, raising spores to aid in their dispersal. Differentiation-inducing factor-1 (DIF-1) is a signaling chemical produced by prespore cells and decomposed by prestalk cells. It affects the rate of switching between prestalk and prespore cells, thereby achieving a stable stalk/spore ratio. In this study we analyzed the evolution of the stalk/spore ratio. Strains may differ in the production and decomposition rates of the signaling chemical, and in the sensitivity of cells to switch in response to the signaling chemical exposure. When two strains with the same stalk/spore ratio within their own fruiting body are combined into a single fruiting body, one strain may develop into prespores to a greater degree than the other. Direct evolutionary simulations and quantitative genetic dynamics demonstrate that if a fruiting body is always formed by a single strain, the cells evolve to produce less signaling chemical and become more sensitive to the signaling chemical due to the cost of producing the chemical. In contrast, if a fruiting body is formed by multiple strains, the cells evolve to become less sensitive to the signaling chemical and produce more signaling chemical in order to reduce the risk of being exploited. In contrast, the stalk-spore ratio is less likely to be affected by small cheating risk. Copyright © 2013 Elsevier Ltd. All rights reserved.

Composites Based on Polytetrafluoroethylene and Detonation Nanodiamonds: Filler-Matrix Chemical Interaction and Its Effect on a Composite's Properties

NASA Astrophysics Data System (ADS)

Koshcheev, A. P.; Perov, A. A.; Gorokhov, P. V.; Zaripov, N. V.; Tereshenkov, A. V.; Khatipov, S. A.

2018-06-01

Specific properties of PTFE composites filled with ultradisperse detonation diamonds (UDDs) with different surface chemistries are studied. It is found for the first time that filler in the form of UDDs affects not only the rate of PTFE thermal decomposition in vacuum pyrolysis, but also the chemical composition of the products of degradation. The wear resistance of UDD/PTFE composites is shown to depend strongly on the UDD surface chemistry. The presence of UDDs in a PTFE composite is found to result in perfluorocarbon telomeres, released as a readily condensable fraction upon composite pyrolysis. The chemical interaction between PTFE and UDDs, characterized by an increase in the rate of gas evolution and a change in the desorbed gas's composition, is found to occur at temperature as low as 380°C. It is shown that the intensity of this interaction depends on the concentration of oxygen-containing surface groups, the efficiency of UDDs in terms of the composite's wear resistance being reduced due to the presence of these groups. Based on the experimental data, a conclusion is reached about the chemical interaction between UDDs and a PTFE matrix, its dependence on the nanodiamond surface chemistry, and its effect on a composite's tribology.

Uranium and organic matters: use of pyrolysis-gas chromatography, carbon, hydrogen, and uranium contents to characterize the organic matter from sandstone-type deposits

USGS Publications Warehouse

Leventhal, Joel S.

1979-01-01

Organic matter seems to play an important role in the genesis of uranium deposits in sandstones in the western United States. Organic materials associated with ore from the Texas coastal plain, Tertiary basins of Wyoming, Grants mineral belt of New Mexico, and the Uravan mineral belt of Utah and Colorado vary widely in physical appearance and chemical composition. Partial characterization of organic materials is achieved by chemical analyses to determine atomic hydrogen-to-carbon (H/C) ratios and by gas chromatographic analyses to determine the molecular fragments evolved during stepwise pyrolysis. From the pyrolysis experiments the organic materials can be classified and grouped: (a) lignites from Texas and Wyoming and (b) hydrogen poor materials, from Grants and Uravan mineral belts and Wyoming; (c) naphthalene-containing materials from Grants mineral belt and Wyoming; and (d) complex and aromatic materials from Uravan, Grants and Wyoming. The organic materials analyzed have atomic H/C ratios that range from approximately 0.3 to at least 1.5. The samples with higher H/C ratios yield pyrolysis products that contain as many as 30 carbon atoms per molecule. Samples with low H/C ratios are commonly more uraniferous and yield mostly methane and low-molecular-weight gases during pyrolysis.

Characterization of Spirulina biomass for CELSS diet potential

NASA Technical Reports Server (NTRS)

Tadros, Mahasin G.

1993-01-01

Cyanobacteria, Spirulina maxima as a biogenerative photosynthetic and an edible alga for the space craft crew in a CELSS, was evaluated in an effort to increase the growth rate, biomass, yield, and chemical analysis in continuous cultures. The cell characteristics were determined for cultures maintained at steady state with respect to the substrate concentration. The productivity increased in experiments exposed to low light (30 uE m(exp -2)s(exp -1). Oxygen evolved and protein production were higher in cultures exposed to low light intensity. There was a relationship between nitrate concentration and the yield of the culture. Increasing the concentration of nitrate in the growth medium up to 20 mM was enough to produce a culture having the same chemical composition as that of complete medium. High light was inhibiting the yield of the culture. Increasing the concentration of phosphate beyond 1 mM did not improve the yield of the culture. Increasing the concentration of sodium chloride in the growth medium did not affect the growth of the alga up to 0.1 M but beyond that the culture started to be stressed. The response to stress appeared in high production of total carbohydrate on the expense of protein production. The oxygen production was also higher in cultures stressed with sodium chloride.

Electrochemically Active Polyaniline (PANi) Coated Carbon Nanopipes and PANi Nanofibers Containing Composite.

PubMed

Ramana, G Venkata; Kumar, P Sampath; Srikanth, Vadali V S S; Padya, Balaji; Jain, P K

2015-02-01

A composite constituted by carbon nanopipes (CNPs) and polyaniline nanofibers (PANi NFs) is synthesized using in-situ chemical oxidative polymerization. Owing to its electrochemical activity the composite is found to be suitable as a working electrode material in hybrid type supercapacitors. Microstructural and phase analyses of the composite showed that (i) CNP surfaces are coated with PANi and (ii) PANi coated CNPs are distributed among PANi NFs. The composite shows an excellent electrochemical activity and a high specific capacitance of ~224.39 F/g. The electro-chemical activity of the composite is explicated in correlation with crystallinity, intrinsic oxidation state, and doping degree of PANi in the composite. The electro-chemical activity of the composite is also explicated in correlation with BET surface area and ordered meso-porosity pertaining to the composite. Charge/discharge curves indicate that the specific capacitance of the composite is a result of electric double-layer capacitance offered by CNPs and Faradaic pseudo capacitance offered by PANi NFs.

On the evolving open peer review culture for chemical information science.

PubMed

Walters, W Patrick; Bajorath, Jürgen

2015-01-01

Compared to the traditional anonymous peer review process, open post-publication peer review provides additional opportunities -and challenges- for reviewers to judge scientific studies. In this editorial, we comment on the open peer review culture and provide some guidance for reviewers of manuscripts submitted to the Chemical Information Science channel of F1000Research.

Computing Equilibrium Chemical Compositions

NASA Technical Reports Server (NTRS)

Mcbride, Bonnie J.; Gordon, Sanford

1995-01-01

Chemical Equilibrium With Transport Properties, 1993 (CET93) computer program provides data on chemical-equilibrium compositions. Aids calculation of thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93/PC is version of CET93 specifically designed to run within 640K memory limit of MS-DOS operating system. CET93/PC written in FORTRAN.

Geochemical characteristics of igneous rocks associated with epithermal mineral deposits—A review

USGS Publications Warehouse

du Bray, Edward A.

2017-01-01

Newly synthesized data indicate that the geochemistry of igneous rocks associated with epithermal mineral deposits varies extensively and continuously from subalkaline basaltic to rhyolitic compositions. Trace element and isotopic data for these rocks are consistent with subduction-related magmatism and suggest that the primary source magmas were generated by partial melting of the mantle-wedge above subducting oceanic slabs. Broad geochemical and petrographic diversity of individual igneous rock units associated with epithermal deposits indicate that the associated magmas evolved by open-system processes. Following migration to shallow crustal reservoirs, these magmas evolved by assimilation, recharge, and partial homogenization; these processes contribute to arc magmatism worldwide.Although epithermal deposits with the largest Au and Ag production are associated with felsic to intermediate composition igneous rocks, demonstrable relationships between magmas having any particular composition and epithermal deposit genesis are completely absent because the composition of igneous rock units associated with epithermal deposits ranges from basalt to rhyolite. Consequently, igneous rock compositions do not constitute effective exploration criteria with respect to identification of terranes prospective for epithermal deposit formation. However, the close spatial and temporal association of igneous rocks and epithermal deposits does suggest a mutual genetic relationship. Igneous systems likely contribute heat and some of the fluids and metals involved in epithermal deposit formation. Accordingly, deposit formation requires optimization of source metal contents, appropriate fluid compositions and characteristics, structural features conducive to hydrothermal fluid flow and confinement, and receptive host rocks, but not magmas with special compositional characteristics.

Using different assumptions of aerosol mixing state and chemical composition to predict CCN concentrations based on field measurements in urban Beijing

NASA Astrophysics Data System (ADS)

Ren, Jingye; Zhang, Fang; Wang, Yuying; Collins, Don; Fan, Xinxin; Jin, Xiaoai; Xu, Weiqi; Sun, Yele; Cribb, Maureen; Li, Zhanqing

2018-05-01

Understanding the impacts of aerosol chemical composition and mixing state on cloud condensation nuclei (CCN) activity in polluted areas is crucial for accurately predicting CCN number concentrations (NCCN). In this study, we predict NCCN under five assumed schemes of aerosol chemical composition and mixing state based on field measurements in Beijing during the winter of 2016. Our results show that the best closure is achieved with the assumption of size dependent chemical composition for which sulfate, nitrate, secondary organic aerosols, and aged black carbon are internally mixed with each other but externally mixed with primary organic aerosol and fresh black carbon (external-internal size-resolved, abbreviated as EI-SR scheme). The resulting ratios of predicted-to-measured NCCN (RCCN_p/m) were 0.90 - 0.98 under both clean and polluted conditions. Assumption of an internal mixture and bulk chemical composition (INT-BK scheme) shows good closure with RCCN_p/m of 1.0 -1.16 under clean conditions, implying that it is adequate for CCN prediction in continental clean regions. On polluted days, assuming the aerosol is internally mixed and has a chemical composition that is size dependent (INT-SR scheme) achieves better closure than the INT-BK scheme due to the heterogeneity and variation in particle composition at different sizes. The improved closure achieved using the EI-SR and INT-SR assumptions highlight the importance of measuring size-resolved chemical composition for CCN predictions in polluted regions. NCCN is significantly underestimated (with RCCN_p/m of 0.66 - 0.75) when using the schemes of external mixtures with bulk (EXT-BK scheme) or size-resolved composition (EXT-SR scheme), implying that primary particles experience rapid aging and physical mixing processes in urban Beijing. However, our results show that the aerosol mixing state plays a minor role in CCN prediction when the κorg exceeds 0.1.

To measure the chemical composition of a Near Earth Object

NASA Astrophysics Data System (ADS)

Gasnault, 0.; Ball, A.; Biele, J.; D'Uston, C.; Forni, O.; Klingelhofer, G.; Maurice, S.; Ulamec, S.

Introduction. Scenarios for a Near Earth Object (NEO) rendezvous mission were discussed recently in Europe. Such a mission would address scientific questions about the initial conditions and evolutionary history of the solar nebula, as well as mitigation considerations to prevent impact with the Earth. In our opinion the measurement of the elemental composition and the distribution of volatiles in the shallow sub-surface are two of the key observations to be conducted, either from an orbiter or a lander. These measurements are also valuable for documentation (landing site candidates and sample context). This report is limited to the chemical composition, but we assume that remote and/or in-situ observations of physical characteristics, interior, morphology, mineralogy, and organic compounds will also be made as essential complements to achieve the mission scientific objectives. Scientific Interest. The analysis of the bulk composition addresses three fundamental aspects of the scientific mission: (1) the formation of the asteroid or the comet; (2) the evolution of the object; (3) the relation between the parent body and collected meteorites on Earth. Classification of an asteroid/comet can be based on its global composition (abundances of Mg, Si, Fe, Al, Ca, etc. along with its mineralogy), which bears the signature of the feeding zone where it formed. For example the K/U and K/Th ratios seem to increase with distance from the Sun (decreasing temperature). The hydrogen content is another measurable to study the distribution of volatiles in the Solar System. The surface composition is also the result of the degree of evolution of the object and of the interactions with its environment. Building a compositional map of the major elements is necessary to identify and characterize the processes that influenced the asteroid along its history. Finally, knowing the chemical composition will obviously help to relate the parent 1 body to meteorites. Ideally the measurement of specific isotopes, including O, C and those produced by the exposure to the cosmic rays, such as 38 Ar or 21 Ne, can pinpoint to the family of meteorites, but such measurements are challenging with restricted resources. Instrument Payload Options. To define the most appropriate instrument(s) in terms of scientific return and technical constraints, various solutions have been studied. For the orbiter this includes an X-ray spectrometer with a solar monitor, and a gamma-ray spectrometer with a neutron sensor. For a lander, it has been demonstrated that an active X-ray spectrometer gives outstanding results for very low resources. If mass is available in the frame of an ambitious mission, one can consider active experiments such as a laser-induced breakdown spectrometer, a mass spectrometer (needing sample manipulation, a laser ablation system, or an ion source), or evolved gas analyzers. It is very difficult however to baseline the use of active experiments from the orbiter (very close fly-bys) such as those on board the Phobos missions. On the one hand the main constraints on the lander are related to the resources (mass, power, volume) and possibly the need for target contact/manipulation. On the other hand the difficulties from the orbiter are the sensitivity to prioritized chemical elements and the mapping resolution (e.g. of the order of 1/10 of the altitude for X-rays, and equivalent to the altitude for gamma-rays). Remote-sensing experiments have been evaluated from that perspective; It is possible to estimate the accumulation time needed to reach enough precision: of the order of 1 h for X-rays and several hours for gamma-rays above each pixel (defined by the spatial resolution, see above). In a classical orbital mission scenario these numbers translate into several weeks of observations (more than 1 month). Lessons learned from previous missions (Apollo, Lunar Prospector, NEAR, Mars Odyssey, SMART-1) are also taken into account: the difficulty to monitor the solar activity for the X-rays, the low signal to noise ratio for the gamma-rays. Previous experiments were successful when the ratio orbit-radius over body-radius was about 5-7 for X-rays and less than 2 for gamma-rays. All these points put strong constraints on the operations to measure properly the chemical composition of a NEO. 2

Differential effects of conifer and broadleaf litter inputs on soil organic carbon chemical composition through altered soil microbial community composition

PubMed Central

Wang, Hui; Liu, Shi-Rong; Wang, Jing-Xin; Shi, Zuo-Min; Xu, Jia; Hong, Pi-Zheng; Ming, An-Gang; Yu, Hao-Long; Chen, Lin; Lu, Li-Hua; Cai, Dao-Xiong

2016-01-01

A strategic selection of tree species will shift the type and quality of litter input, and subsequently magnitude and composition of the soil organic carbon (SOC) through soil microbial community. We conducted a manipulative experiment in randomized block design with leaf litter inputs of four native subtropical tree species in a Pinus massoniana plantation in southern China and found that the chemical composition of SOC did not differ significantly among treatments until after 28 months of the experiment. Contrasting leaf litter inputs had significant impacts on the amounts of total microbial, Gram-positive bacterial, and actinomycic PLFAs, but not on the amounts of total bacterial, Gram-negative bacterial, and fungal PLFAs. There were significant differences in alkyl/O-alkyl C in soils among the leaf litter input treatments, but no apparent differences in the proportions of chemical compositions (alkyl, O-alkyl, aromatic, and carbonyl C) in SOC. Soil alkyl/O-alkyl C was significantly related to the amounts of total microbial, and Gram-positive bacterial PLFAs, but not to the chemical compositions of leaf litter. Our findings suggest that changes in forest leaf litter inputs could result in changes in chemical stability of SOC through the altered microbial community composition. PMID:27256545

Differential effects of conifer and broadleaf litter inputs on soil organic carbon chemical composition through altered soil microbial community composition.

PubMed

Wang, Hui; Liu, Shi-Rong; Wang, Jing-Xin; Shi, Zuo-Min; Xu, Jia; Hong, Pi-Zheng; Ming, An-Gang; Yu, Hao-Long; Chen, Lin; Lu, Li-Hua; Cai, Dao-Xiong

2016-06-03

A strategic selection of tree species will shift the type and quality of litter input, and subsequently magnitude and composition of the soil organic carbon (SOC) through soil microbial community. We conducted a manipulative experiment in randomized block design with leaf litter inputs of four native subtropical tree species in a Pinus massoniana plantation in southern China and found that the chemical composition of SOC did not differ significantly among treatments until after 28 months of the experiment. Contrasting leaf litter inputs had significant impacts on the amounts of total microbial, Gram-positive bacterial, and actinomycic PLFAs, but not on the amounts of total bacterial, Gram-negative bacterial, and fungal PLFAs. There were significant differences in alkyl/O-alkyl C in soils among the leaf litter input treatments, but no apparent differences in the proportions of chemical compositions (alkyl, O-alkyl, aromatic, and carbonyl C) in SOC. Soil alkyl/O-alkyl C was significantly related to the amounts of total microbial, and Gram-positive bacterial PLFAs, but not to the chemical compositions of leaf litter. Our findings suggest that changes in forest leaf litter inputs could result in changes in chemical stability of SOC through the altered microbial community composition.

Differential effects of conifer and broadleaf litter inputs on soil organic carbon chemical composition through altered soil microbial community composition

NASA Astrophysics Data System (ADS)

Wang, Hui; Liu, Shi-Rong; Wang, Jing-Xin; Shi, Zuo-Min; Xu, Jia; Hong, Pi-Zheng; Ming, An-Gang; Yu, Hao-Long; Chen, Lin; Lu, Li-Hua; Cai, Dao-Xiong

2016-06-01

A strategic selection of tree species will shift the type and quality of litter input, and subsequently magnitude and composition of the soil organic carbon (SOC) through soil microbial community. We conducted a manipulative experiment in randomized block design with leaf litter inputs of four native subtropical tree species in a Pinus massoniana plantation in southern China and found that the chemical composition of SOC did not differ significantly among treatments until after 28 months of the experiment. Contrasting leaf litter inputs had significant impacts on the amounts of total microbial, Gram-positive bacterial, and actinomycic PLFAs, but not on the amounts of total bacterial, Gram-negative bacterial, and fungal PLFAs. There were significant differences in alkyl/O-alkyl C in soils among the leaf litter input treatments, but no apparent differences in the proportions of chemical compositions (alkyl, O-alkyl, aromatic, and carbonyl C) in SOC. Soil alkyl/O-alkyl C was significantly related to the amounts of total microbial, and Gram-positive bacterial PLFAs, but not to the chemical compositions of leaf litter. Our findings suggest that changes in forest leaf litter inputs could result in changes in chemical stability of SOC through the altered microbial community composition.

Feldspars Detected by ChemCam in Gale Crater with Implications for Future Martian Exploration

NASA Astrophysics Data System (ADS)

Gasda, P. J.; Carlson, E.; Wiens, R. C.; Bridges, J.; Sautter, V.; Cousin, A.; Maurice, S.; Gasnault, O.; Clegg, S. M.

2015-12-01

Feldspar is a common igneous mineral that can shed light on parent magma temperatures, pressures, and compositions. During the first 801 sols of the NASA Mars Science Laboratory mission, we have detected 125 possible feldspar grains using the ChemCam LIBS instrument. We analyzed spectra from successive laser shots at the same location and approximate whole rock compositions for each target. Feldspar-containing targets range from tephrite-basanite to trachyandesite. The most common feldspar type is andesine; no targets are >An60. Over 30% are anorthoclase, and ~10% have potassium contents up to Or60. Individual shot measurements in a single spot suggest some feldspars are zoned. Most of these rocks are either float or incorporated into conglomerates, and thus we do not know their provenance. Many of the samples may originate from the Gale crater walls, indicative of Southern Highland ancient crust. Some may also be flung from further away (e.g., emplaced by impact processes). Hence, these rocks may give us a general clue to the variety of evolved igneous materials on Mars. The ubiquity of feldspars at Gale suggests that they have been significantly underestimated for the Southern Highlands, if not for the whole of Mars. For example, significant abundance of andesitic feldspars in both the southern highland and northern lowlands of Mars would imply that Martian volcanism has produced a greater extent of evolved igneous materials to a greater degree than previously thought. Remote sensing instruments are insensitive to plagioclase due to dust cover, lack of exposures, or low feldspar FeO content. However, the Mars 2020 rover will be equipped with 3 new instruments, the arm-mounted SHERLOC Raman, PIXL μXRF, and the mast-mounted SuperCam combined Raman-LIBS instruments, which should help characterize Martian feldspars. Additionally, the SuperCam instrument plans to include three feldspars in its suite of 20+ onboard standards to improve feldspar chemical analysis.

Chemical performance of multi-environment trials in lens (Lens culinaris M.).

PubMed

Karadavut, Ufuk; Palta, Cetin

2010-01-15

Genotype-environment (GE) interaction has been a major effect to determine stable lens (Lens culinaris (Medik.) Merr.) cultivars for chemical composition in Turkey. Utilization of the lines depends on their agronomic traits and stability of the chemical composition in diverse environments. The objectives of this study were: (i) to evaluate the influence of year and location on the chemical composition of lens genotypes; and (ii) to determine which cultivar is the most stable. Genotypes were evaluated over 3 years (2005, 2006 and 2007) at four locations in Turkey. Effects of year had the largest impact on all protein contents. GE interaction was analyzed by using linear regression techniques. Stability was estimated using the Eberhart and Russell method. 'Kişlik Kirmizi51' was the most stable cultivar for grain yield. The highest protein was obtained from 'Kişlik Kirmizi51' (4.6%) across environments. According to stability analysis, 'Firat 87' had the most stable chemical composition. This genotype had a regression coefficient (b(i) = 1) around unity, and deviations from regression values (delta(ij) = 0) around zero. Chemical composition was affected by year in this study. Temperature might have an effect on protein, oil, carbohydrate, fibre and ash. Firat 87 could be recommended for favourable environments. Copyright (c) 2009 Society of Chemical Industry.

Trilateral Design and Test Code for Military Bridging and Gap-Crossing Equipment

DTIC Science & Technology

2005-05-01

Property data should be provided for individual lamina and for the ( laminat - ed) composite . The required lamina properties are identified in...Resistance Welding ....... a Brazing ......................... X Machining ..................... a Chemical Composition : Element... Machining .................. b Chemical Composition : Element % Si .................................. 0.2 max Fe

The Bulk Elemental Composition of any Terrestrial Planets in the Alpha Centauri System

NASA Astrophysics Data System (ADS)

Lineweaver, C. H.; Schonberger, B. F. G.; Robles, J. A.

2010-04-01

Based on the devolatilization patterns in the solar system, and on the differences in the chemical compositions of the Sun and Alpha Centauri, we make estimates of the chemical composition of any Earth-like planets in the Alpha Centauri system.

Effect of chemical treatment of Kevlar fibers on mechanical interfacial properties of composites.

PubMed

Park, Soo-Jin; Seo, Min-Kang; Ma, Tae-Jun; Lee, Douk-Rae

2002-08-01

In this work, the effects of chemical treatment on Kevlar 29 fibers have been studied in a composite system. The surface characteristics of Kevlar 29 fibers were characterized by pH, acid-base value, X-ray photoelectron spectroscopy (XPS), and FT-IR. The mechanical interfacial properties of the final composites were studied by interlaminar shear strength (ILSS), critical stress intensity factor (K(IC)), and specific fracture energy (G(IC)). Also, impact properties of the composites were investigated in the context of differentiating between initiation and propagation energies and ductile index (DI) along with maximum force and total energy. As a result, it was found that chemical treatment with phosphoric acid solution significantly affected the degree of adhesion at interfaces between fibers and resin matrix, resulting in improved mechanical interfacial strength in the composites. This was probably due to the presence of chemical polar groups on Kevlar surfaces, leading to an increment of interfacial binding force between fibers and matrix in a composite system.

Effects of oxygen plasma treatment power on Aramid fiber III/BMI composite humidity resistance properties

NASA Astrophysics Data System (ADS)

Wang, Jing; Shi, Chen; Feng, Jiayue; Long, Xi; Meng, Lingzhi; Ren, Hang

2018-01-01

The effects of oxygen plasma treatment power on Aramid Fiber III chemical structure and its reinforced bismaleimides (BMI) composite humidity resistance properties were investigated in this work. The aramid fiber III chemical structure under different plasma treatment power were measured by FTIR. The composite bending strength and interlinear shear strength with different plasma treatment power before and after absorption water were tested respectively. The composite rupture morphology was observed by SEM. The FTIR results showed that oxygen plasma treatment do not change the fiber bulk chemical structure. The composite humidity resistance of bending strength and interlinear shear strength are similar for untreated and plasma treated samples. The retention rate of composite bending strength and interlinear shear strength are about 75% and 94%, respectively. The composite rupture mode turns to be the fiber failure after water absorption.

Cross-resistance to prosulfocarb + S-metolachlor and pyroxasulfone selected by either herbicide in Lolium rigidum.

PubMed

Busi, Roberto; Powles, Stephen B

2016-09-01

Weeds can be a greater constraint to crop production than animal pests and pathogens. Pre-emergence herbicides are crucial in many cropping systems to control weeds that have evolved resistance to selective post-emergence herbicides. In this study we assessed the potential to evolve resistance to the pre-emergence herbicides prosulfocarb + S-metolachlor or pyroxasulfone in 50 individual field Lolium rigidum populations collected in a random survey in Western Australia prior to commercialisation of these pre-emergence herbicides. This study shows for the first time that in randomly collected L. rigidum field populations the selection with either prosulfocarb + S-metolachlor or pyroxasulfone can result in concomitant evolution of resistance to both prosulfocarb + S-metolachlor and pyroxasulfone after three generations. In the major weed L. rigidum, traits conferring resistance to new herbicides can be present before herbicide commercialisation. Proactive and multidisciplinary research (evolutionary ecology, modelling and molecular biology) is required to detect and analyse resistant populations before they can appear in the field. Several studies show that evolved cross-resistance in weeds is complex and often unpredictable. Thus, long-term management of cross-resistant weeds must be achieved through heterogeneity of selection by effective chemical, cultural and physical weed control strategies that can delay herbicide resistance evolution. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Sequestration and utilization of carbon dioxide by chemical and biological methods for biofuels and biomaterials by chemoautotrophs: Opportunities and challenges.

PubMed

Thakur, Indu Shekhar; Kumar, Manish; Varjani, Sunita J; Wu, Yonghong; Gnansounou, Edgard; Ravindran, Sindhu

2018-05-01

To meet the CO 2 emission reduction targets, carbon dioxide capture and utilization (CCU) comes as an evolve technology. CCU concept is turning into a feedstock and technologies have been developed for transformation of CO 2 into useful organic products. At industrial scale, utilization of CO 2 as raw material is not much significant as compare to its abundance. Mechanisms in nature have evolved for carbon concentration, fixation and utilization. Assimilation and subsequent conversion of CO 2 into complex molecules are performed by the photosynthetic and chemolithotrophic organisms. In the last three decades, substantial research is carry out to discover chemical and biological conversion of CO 2 in various synthetic and biological materials, such as carboxylic acids, esters, lactones, polymer biodiesel, bio-plastics, bio-alcohols, exopolysaccharides. This review presents an over view of catalytic transformation of CO 2 into biofuels and biomaterials by chemical and biological methods. Copyright © 2018 Elsevier Ltd. All rights reserved.

Linking neuroethology to the chemical biology of natural products: interactions between cone snails and their fish prey, a case study.

PubMed

Olivera, Baldomero M; Raghuraman, Shrinivasan; Schmidt, Eric W; Safavi-Hemami, Helena

2017-09-01

From a biological perspective, a natural product can be defined as a compound evolved by an organism for chemical interactions with another organism including prey, predator, competitor, pathogen, symbiont or host. Natural products hold tremendous potential as drug leads and have been extensively studied by chemists and biochemists in the pharmaceutical industry. However, the biological purpose for which a natural product evolved is rarely addressed. By focusing on a well-studied group of natural products-venom components from predatory marine cone snails-this review provides a rationale for why a better understanding of the evolution, biology and biochemistry of natural products will facilitate both neuroscience and the potential for drug leads. The larger goal is to establish a new sub-discipline in the broader field of neuroethology that we refer to as "Chemical Neuroethology", linking the substantial work carried out by chemists on natural products with accelerating advances in neuroethology.

Diffusive confinement of free radical intermediates in the OH radical oxidation of semisolid aerosols

DOE PAGES

Wiegel, Aaron A.; Liu, Matthew J.; Hinsberg, William D.; ...

2017-02-07

Multiphase chemical reactions (gas + solid/liquid) involve a complex interplay between bulk and interface chemistry, diffusion, evaporation, and condensation. Reactions of atmospheric aerosols are an important example of this type of chemistry: the rich array of particle phase states and multiphase transformation pathways produce diverse but poorly understood interactions between chemistry and transport. Their chemistry is of intrinsic interest because of their role in controlling climate. Their characteristics also make them useful models for the study of principles of reactivity of condensed materials under confined conditions. Previously, we have reported a computational study of the oxidation chemistry of a liquidmore » aliphatic aerosol. In this study, we extend the calculations to investigate nearly the same reactions at a semisolid gas-aerosol interface. A reaction-diffusion model for heterogeneous oxidation of triacontane by hydroxyl radicals (OH) is described, and its predictions are compared to measurements of aerosol size and composition, which evolve continuously during oxidation. Our results are also explicitly compared to those obtained for the corresponding liquid system, squalane, to pinpoint salient elements controlling reactivity. The diffusive confinement of the free radical intermediates at the interface results in enhanced importance of a few specific chemical processes such as the involvement of aldehydes in fragmentation and evaporation, and a significant role of radical-radical reactions in product formation. The simulations show that under typical laboratory conditions semisolid aerosols have highly oxidized nanometer-scale interfaces that encapsulate an unreacted core and may confer distinct optical properties and enhanced hygroscopicity. This highly oxidized layer dynamically evolves with reaction, which we propose to result in plasticization. The validated model is used to predict chemistry under atmospheric conditions, where the OH radical concentration is much lower. The oxidation reactions are more strongly influenced by diffusion in the particle, resulting in a more liquid-like character.« less

Evolved stars as complex chemical laboratories - the quest for gaseous chemistry

NASA Astrophysics Data System (ADS)

Katrien Els Decin, Leen

2015-08-01

At the end of their life, most stars lose a large fraction of their mass through a stellar wind. The stellar winds of evolved (super)giant stars are the dominant suppliers for the pristine building blocks of the interstellar medium (ISM). Crucial to the understanding of the chemical life cycle of the ISM is hence a profound insight in the chemical and physical structure governing these stellar winds.These winds are really unique chemical laboratories in which currently more than 70 different molecules and 15 different dust species are detected. Several chemical processes such as neutral-neutral and ion-molecule gas-phase reactions, dust nucleation and growth, and photo-processes determine the chemical content of these winds. However, gas-phase and dust-nucleation chemistry for astronomical environments still faces many challenges. One should realize that only ˜15% of the rate coefficients for gas-phase reactions considered to occur in (inter/circum)stellar regions at temperatures (T) below 300K have been subject to direct laboratory determinations and that the temperature dependence of the rate constants is often not known; only ˜2% have rate constants at T<200K and less than 0.5% at T<100 K. For stellar wind models, an important bottleneck occurs among the reactions involving silicon- and sulfur-bearing species, for which only a few have documented reaction rates. Often, researchers are implementing ‘educated guesses’ for these unknown rates, sometimes forcing the network to yield predictions concurring with (astronomical) observations. Large uncertainties are inherent in this type of ‘optimized’ chemical schemes.Thanks to an ERC-CoG grant, we are now in the position to solve some riddles involved in understanding the gas-phase chemistry in evolved stars. In this presentation, I will demonstrate the need for accurate temperature-dependent gas-phase reaction rate constants and will present our new laboratory equipment built to measure the rate constants for species key in stellar wind chemistry. Specifically, we aim to obtain the rate constants of reactions involving silicon- and sulphur bearing species and HCCO for 30

Evaluating the effect of some mechanical properties for chemically treated various natural fibers reinforced polyester composite

NASA Astrophysics Data System (ADS)

Salih, Wafaa Mahdi; Abdulkader, Niveen Jamal; Salih, Sana Mahdi

2018-05-01

This research were studied the effect of some mechanical properties for composite materials reinforced fiber and prepared from material (polyester with various natural fibers) then studied the effect of chemical treatment on the same fiber immerse in 10% NaOH solution for half an hour and then compared, the results of the same test of composite materials without and with chemical treatment and the results proved that there is a clear effect when treat the fiber compared to non-chemical treatment of the fibers also noted that hemp fibers loaded the stress higher than other fibers for both cases to distinguish them that the hemp fiber has continuous fibers either the other fibers are characterized by the type of cross linking or chopped types in tensile test, and the results of the same test of composite materials without and with chemical treatment and the results proved that the hardness of the fiber composite while the treated fiber composite samples better than the untreated fiber, and from the figures the palm leaf has the highest value than lufa fiber, hemp fiber and the smallest value is in sisal fiber because of the nature of formation fibers materials.

Computing Properties Of Chemical Mixtures At Equilibrium

NASA Technical Reports Server (NTRS)

Mcbride, B. J.; Gordon, S.

1995-01-01

Scientists and engineers need data on chemical equilibrium compositions to calculate theoretical thermodynamic properties of chemical systems. Information essential in design and analysis of such equipment as compressors, turbines, nozzles, engines, shock tubes, heat exchangers, and chemical-processing equipment. CET93 is general program that calculates chemical equilibrium compositions and properties of mixtures for any chemical system for which thermodynamic data are available. Includes thermodynamic data for more than 1,300 gaseous and condensed species and thermal-transport data for 151 gases. Written in FORTRAN 77.

Ceramic composites reinforced with modified silicon carbide whiskers and method for modifying the whiskers

DOEpatents

Tiegs, Terry N.; Lindemer, Terrence B.

1991-01-01

Silicon carbide whisker-reinforced ceramic composites are fabricated in a highly reproducible manner by beneficating the surfaces of the silicon carbide whiskers prior to their usage in the ceramic composites. The silicon carbide whiskers which contain considerable concentrations of surface oxides and other impurities which interact with the ceramic composite material to form a chemical bond are significantly reduced so that only a relatively weak chemical bond is formed between the whisker and the ceramic material. Thus, when the whiskers interact with a crack propagating into the composite the crack is diverted or deflected along the whisker-matrix interface due to the weak chemical bonding so as to deter the crack propagation through the composite. The depletion of the oxygen-containing compounds and other impurities on the whisker surfaces and near surface region is effected by heat treating the whiskers in a suitable oxygen sparaging atmosphere at elevated temperatures. Additionally, a sedimentation technique may be utilized to remove whiskers which suffer structural and physical anomalies which render them undesirable for use in the composite. Also, a layer of carbon may be provided on the surface of the whiskers to further inhibit chemical bonding of the whiskers to the ceramic composite material.

Ceramic composites reinforced with modified silicon carbide whiskers and method for modifying the whiskers

DOEpatents

Tiegs, T.N.; Lindemer, T.B.

1991-02-19

Silicon carbide whisker-reinforced ceramic composites are fabricated in a highly reproducible manner by beneficating the surfaces of the silicon carbide whiskers prior to their usage in the ceramic composites. The silicon carbide whiskers which contain considerable concentrations of surface oxides and other impurities which interact with the ceramic composite material to form a chemical bond are significantly reduced so that only a relatively weak chemical bond is formed between the whisker and the ceramic material. Thus, when the whiskers interact with a crack propagating into the composite the crack is diverted or deflected along the whisker-matrix interface due to the weak chemical bonding so as to deter the crack propagation through the composite. The depletion of the oxygen-containing compounds and other impurities on the whisker surfaces and near surface region is effected by heat treating the whiskers in a suitable oxygen sparging atmosphere at elevated temperatures. Additionally, a sedimentation technique may be utilized to remove whiskers which suffer structural and physical anomalies which render them undesirable for use in the composite. Also, a layer of carbon may be provided on the surface of the whiskers to further inhibit chemical bonding of the whiskers to the ceramic composite material.

Ceramic composites reinforced with modified silicon carbide whiskers

DOEpatents

Tiegs, Terry N.; Lindemer, Terrence B.

1990-01-01

Silicon carbide whisker-reinforced ceramic composites are fabricated in a highly reproducible manner by beneficating the surfaces of the silicon carbide whiskers prior to their usage in the ceramic composites. The silicon carbide whiskers which contain considerable concentrations of surface oxides and other impurities which interact with the ceramic composite material to form a chemical bond are significantly reduced so that only a relatively weak chemical bond is formed between the whisker and the ceramic material. Thus, when the whiskers interact with a crack propagating into the composite the crack is diverted or deflected along the whisker-matrix interface due to the weak chemical bonding so as to deter the crack propagation through the composite. The depletion of the oxygen-containing compounds and other impurities on the whisker surfaces and near surface region is effected by heat treating the whiskers in a suitable oxygen sparaging atmosphere at elevated temperatures. Additionally, a sedimentation technique may be utilized to remove whiskers which suffer structural and physical anomalies which render them undesirable for use in the composite. Also, a layer of carbon may be provided on the surface of the whiskers to further inhibit chemical bonding of the whiskers to the ceramic composite material.

Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NO x conditions

DOE PAGES

D'Ambro, Emma L.; Lee, Ben H.; Liu, Jiumeng; ...

2017-01-04

Here, we present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO 2 and low-NO conditions, highly oxygenated (O : C ≥ 1) C 5 compounds were major components (~50%) of SOA. The SOA composition and effective volatility evolved both as amore » function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2 h) for some individual components, significant errors in group-contribution methods are revealed. In addition, >30% of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled with equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.« less

Formation and Evolution of the Atmosphere on Early Titan

NASA Astrophysics Data System (ADS)

Marounina, N.; Tobie, G.; Carpy, S.; Monteux, J.; Charnay, B.; Grasset, O.

2014-12-01

The mass and composition of Titan's massive atmosphere, which is dominated by N2 and CH4 at present, have probably varied all along its history owing to a combination of exogenous and endogenous processes. In a recent study, we investigated its fate during the Late Heavy Bombardment (LHB) by modeling the competitive loss and supply of volatiles by cometary impacts and their consequences on the atmospheric balance. We examine the emergence of an atmosphere as well as the evolution of a primitive atmosphere of various sizes and compositions. By considering an impactor population characteristic of the LHB, we showed that an atmosphere with a mass equivalent to the present-day one cannot be formed during the LHB era. Our calculations indicated that the high-velocity impacts during the LHB led to a strong atmospheric erosion, so that the pre-LHB atmosphere should be 5 to 7 times more massive than at present (depending mostly on the albedo), in order to sustain an atmosphere equivalent to the present-day one. This implies that either a massive atmosphere was formed on Titan during its accretion or that the nitrogen-rich atmosphere was generated after the LHB.To investigate the primitive atmosphere of the satellite, we consider chemical exchanges of volatils between a global water ocean at Titan's surface, generated by impact heating during the accretion and an atmosphere. We are currently developing a liquid-vapor equilibrium model for various initial oceanic composition to investigate how a massive atmosphere may be generated during the satellite growth and how it may evolve toward a composition dominated by N2. More generally, our model address how atmosphere may be generated in water-rich objects, which may be common around other stars.

Using Ancient Glacial Diamictites to Track the Compositional Evolution of the Upper Continental Crust

NASA Astrophysics Data System (ADS)

Gaschnig, R. M.; Rudnick, R. L.; McDonough, W. F.; Kaufman, A. J.; Valley, J. W.; Hu, Z.; Gao, S.

2014-12-01

V.M. Goldschmidt (1933) first suggested the use of Quaternary glacial till and loess to determine the average composition of the upper continental crust (UCC). We extend this approach back in time through the geochemical study of glacial diamictites from intervals of continental glaciation in the Paleozoic, Neoproterozoic, Paleoproterozoic, and Mesoarchean. The diamictites record fundamental changes in the bulk composition of UCC through time, with the largest change occurring at the end of the Archean. Post-Archean diamictites have progressively lower Eu/Eu* and concentrations of 1st row transition metals (Sc, Cr, V, Ni, Co) and higher Th and U concentrations. δ18O whole-rock values steadily increase through the Precambrian, with average values of 6.0 ± 1.6, 8.3 ± 0.4, 12.3 ± 0.9 per mil for the Mesoarchean, Paleoproterozoic, and Neoproterozoic, respectively. All of these trends are consistent with production of a progressively more evolved UCC, which may reflect changes in the composition of primary crustal melts, as well as a change in the nature of intracrustal differentiation. Subtle increases in Lu/Hf through time imply the continual addition of juvenile crust from an increasingly depleted mantle reservoir, consistent with continuous continental growth rather than an Armstrong-like no-growth model, and suggesting that intracrustal differentiation is unlikely to be the sole driver of the other trends. In addition to these uni-directional trends, Paleoproterozoic diamictites, which are dominated by 2.8 to 2.6 Ga provenance, show unique chemical characteristics (e.g., lowest Nb/Ta and highest La/Lu and Th/Nb). These features may reflect a distinctive geodynamic setting for the Neoarchean period, which was arguably the largest pulse of crustal growth in Earth's history and was also accompanied by widespread cratonization.

Simultaneous iron and nickel isotopic analyses of presolar silicon carbide grains

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

Trappitsch, Reto; Stephan, Thomas; Savina, Michael R.

Aside from recording stellar nucleosynthesis, a few elements in presolar grains can also provide insights into the galactic chemical evolution (GCE) of nuclides. We have studied the carbon, silicon, iron, and nickel isotopic compositions of presolar silicon carbide (SiC) grains from asymptotic giant branch (AGB) stars to better understand GCE. Since only the neutron-rich nuclides in these grains have been heavily in uenced by the parent star, the neutron-poor nuclides serve as GCE proxies. Using CHILI, a new resonance ionization mass spectrometry (RIMS) instrument, we measured 74 presolar SiC grains for all iron and nickel isotopes. With the CHARISMA instrument,more » 13 presolar SiC grains were analyzed for iron isotopes. All grains were also measured by NanoSIMS for their carbon and silicon isotopic compositions. A comparison of the measured neutron-rich isotopes with models for AGB star nucleosynthesis shows that our measurements are consistent with AGB star predictions for low-mass stars between half-solar and solar metallicity. Furthermore, our measurements give an indication on the 22Ne( ,n) 25Mg reaction rate. In terms of GCE, we nd that the GCE-dominated iron and nickel isotope ratios, 54Fe/56Fe and 60Ni/ 58Ni, correlate with their GCE-dominated counterpart in silicon, 29Si/ 28Si. The measured GCE trends include the Solar System composition, showing that the Solar System is not a special case. However, as seen in silicon and titanium, many presolar SiC grains are more evolved for iron and nickel than the Solar System. This con rms prior ndings and agrees with observations of large stellar samples that a simple age-metallicity relationship for GCE cannot explain the composition of the solar neighborhood.« less

Simultaneous iron and nickel isotopic analyses of presolar silicon carbide grains

DOE PAGES

Trappitsch, Reto; Stephan, Thomas; Savina, Michael R.; ...

2018-01-01

Aside from recording stellar nucleosynthesis, a few elements in presolar grains can also provide insights into the galactic chemical evolution (GCE) of nuclides. We have studied the carbon, silicon, iron, and nickel isotopic compositions of presolar silicon carbide (SiC) grains from asymptotic giant branch (AGB) stars to better understand GCE. Since only the neutron-rich nuclides in these grains have been heavily in uenced by the parent star, the neutron-poor nuclides serve as GCE proxies. Using CHILI, a new resonance ionization mass spectrometry (RIMS) instrument, we measured 74 presolar SiC grains for all iron and nickel isotopes. With the CHARISMA instrument,more » 13 presolar SiC grains were analyzed for iron isotopes. All grains were also measured by NanoSIMS for their carbon and silicon isotopic compositions. A comparison of the measured neutron-rich isotopes with models for AGB star nucleosynthesis shows that our measurements are consistent with AGB star predictions for low-mass stars between half-solar and solar metallicity. Furthermore, our measurements give an indication on the 22Ne( ,n) 25Mg reaction rate. In terms of GCE, we nd that the GCE-dominated iron and nickel isotope ratios, 54Fe/56Fe and 60Ni/ 58Ni, correlate with their GCE-dominated counterpart in silicon, 29Si/ 28Si. The measured GCE trends include the Solar System composition, showing that the Solar System is not a special case. However, as seen in silicon and titanium, many presolar SiC grains are more evolved for iron and nickel than the Solar System. This con rms prior ndings and agrees with observations of large stellar samples that a simple age-metallicity relationship for GCE cannot explain the composition of the solar neighborhood.« less

Global two dimensional chemistry model and simulation of atmospheric chemical composition

NASA Astrophysics Data System (ADS)

Zhang, Renjian; Wang, Mingxing; Zeng, Qingcun

2000-03-01

A global two-dimensional zonally averaged chemistry model is developed to study the chemi-cal composition of atmosphere. The region of the model is from 90°S to 90°N and from the ground to the altitude of 20 km with a resolution of 5° x 1 km. The wind field is residual circulation calcu-lated from diabatic rate. 34 species and 104 chemical and photochemical reactions are considered in the model. The sources of CH4, CO and NOx, which are divided into seasonal sources and non-seasonal sources, are parameterized as a function of latitude and time. The chemical composi-tion of atmosphere was simulated with emission level of CH4, CO and NOx in 1990. The results are compared with observations and other model results, showing that the model is successful to simu-late the atmospheric chemical composition and distribution of CH4.

A Statistical Approach for Judging Stability of Whole Mixture Chemical Composition over Time for Highly Complex Disinfection By-Product Mixtures from EPA's Four Lab Study

EPA Science Inventory

Chemical characterization of complex mixtures and assessment of stability over time of the characterized chemicals is crucial both to characterize exposure and to use data from one mixture as a surrogate for other similar mixtures. The chemical composition of test mixtures can va...

Cactus stem (Opuntia ficus-indica Mill): anatomy, physiology and chemical composition with emphasis on its biofunctional properties.

PubMed

Ventura-Aguilar, Rosa Isela; Bosquez-Molina, Elsa; Bautista-Baños, Silvia; Rivera-Cabrera, Fernando

2017-12-01

Cactus stem (Opuntia ficus-indica Mill) is native to Mesoamerica and marketed in different forms such as fresh, frozen or pre-cooked. Worldwide, this vegetable is recognized for its pharmaceutical actions, including its antioxidant, diuretic, anticarcinogenic, anti-inflammatory, anti-diabetic, and anti-hypercholesterolemic properties, as well as their antiviral and antispermatogenic effects. However, not all of these properties have been associated with its chemical composition; therefore, this review aims to present and integrate information available on the physiology and anatomy of cactus stem and its chemical composition, focusing on some of the many factors that determine its biofunctionality. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Chemical evolution of Titan’s aerosol analogues under VUV irradiation

NASA Astrophysics Data System (ADS)

Carrasco, Nathalie; Gavilan, Lisseth; Tigrine, Sarah; Vettier, Ludovic; Nahon, Laurent; Pernot, Pascal

2017-10-01

Since the Cassini-CAPS measurements, organic aerosols are known to be present and formed at high altitudes in the diluted and partially ionized medium that is Titan’s ionosphere [1].After production in the ionosphere, Titan’s aerosols evolve through microphysics during their sedimentation down to Titan’s surface [2]. Starting with a few nanomers size in the upper atmosphere, they reach a fractal structure of a few hundreds nanometers close to the surface [3]. During sedimentation, aerosols are also submitted to solar irradiation. As laboratory analogs of Titan’s atmospheric aerosols (tholins) show a strong UV absorption [4], we suspect that VUV irradiation could also induce a chemical evolution of Titan’s aerosols during their descent in Titan’s atmosphere.The aim of this work ist to simulate the irradiation process occuring on the aerosols in Titan’s atmosphere and to address whether this irradiation impacts the chemical composition of the organic solids. First aerosol analogues were produced in a N2-CH4 plasma discharge as thin organic films of a few hundreds of nanometers thick [5]. Then those were irradiated at Lyman-α wavelength, the strongest VUV line in the solar spectrum, with a high photon flux on a synchrotron VUV beamline. We will present and discuss the significant chemical evolutions observed on the analogues after VUV irradiation by mid-IR absorption spectroscopy.[1] Waite et al. (2009) Science , 316, p. 870[2] Lavvas et al. (2011) Astrophysical Journal, 728:80[3] Tomasko et al. (2008) Planetary and Space Science, 56, p. 669[4] Mahjoub et al. (2012) Icarus 221, P. 670[5] Carrasco et al. (2016) Planetary and Space Science, 128, p. 52

Experimental Approaches to Understanding Surficial Processes on Mars: The Stony Brook Experience 2000-2016

NASA Astrophysics Data System (ADS)

McLennan, S. M.; Dehouck, E.; Hurowitz, J.; Lindsley, D. H.; Schoonen, M. A.; Tosca, N. J.; Zhao, Y. Y. S.

2016-12-01

Starting with Pathfinder and Global Surveyor, recent missions to Mars have provided great opportunity for low-temperature experimental geochemistry investigations of the Martian sedimentary record by providing geochemical and mineralogical data that can be used as meaningful tests for experiments. These missions have documented a long-lived, complex and dynamic sedimentary rock cycle, including "source-to-sink" sedimentary systems and global paleoenvironmental transitions through time. We designed and constructed an experimental facility, beginning in 2000, specifically to evaluate surficial processes on Mars. Our experimental philosophy has been to (1) keep apparatus simple and flexible, and if feasible maintain sample access during experiments; (2) use starting materials (minerals, rocks) close to known Mars compositions (often requiring synthesis); (3) address sedimentary processes supported by geological investigations at Mars; (4) begin with experiments at standard conditions so they are best supported by thermodynamics; (5) support experiments with thermodynamic-kinetic-mass balance modeling in both design and interpretation, and by high quality chemical, mineralogical and textural lab analyses; (6) interpret results in the context of measurements made at Mars. Although eliciting much comment in proposal and manuscript reviews, we have not attempted to slavishly maintain "Mars conditions", doing so only to the degree required by variables being tested in any given experiments. Among the problems we have addressed are (1) Amazonian alteration of rock surfaces; (2) Noachian-Hesperian chemical weathering; (3) epithermal alteration of `evolved' igneous rocks; (4) mineral surface chemical reactivity from aeolian abrasion; (5) evaporation of mafic brines; (6) early diagenesis of sedimentary iron mineralogy; (7) trace element and halogen behavior during chemical weathering and diagenesis; (8) photochemical influences on halogen distribution and speciation; (9) post-depositional stability of sedimentary amorphous materials.

Unravelling the mechanisms for plant survival on gypsum soils: an analysis of the chemical composition of gypsum plants from Turkey.

PubMed

Bolukbasi, A; Kurt, L; Palacio, S

2016-03-01

Depending on their specificity to gypsum, plants can be classified as gypsophiles (gypsum exclusive) and gypsovags (non-exclusive). The former may further be segregated into wide and narrow gypsophiles, depending on the breadth of their distribution area. Narrow gypsum endemics have a putative similar chemical composition to plants non-exclusive to gypsum (i.e. gypsovags), which may indicate their similar ecological strategy as stress-tolerant plant refugees on gypsum. However, this hypothesis awaits testing in different regions of the world. We compared the chemical composition of four narrow gypsum endemics, one widely distributed gypsophile and six gypsovags from Turkey. Further, we explored the plasticity in chemical composition of Turkish gypsovags growing on high- and low-gypsum content soils. Differences were explored with multivariate analyses (RDA) and mixed models (REML). Narrow gypsum endemics segregated from gypsovags in their chemical composition according to RDAs (mainly due to higher K and ash content in the former). Nevertheless, differences were small and disappeared when different nutrients were analysed individually. All the gypsovags studied accumulated more S and ash when growing on high-gypsum than on low-gypsum soils. Similar to narrow gypsum endemics from other regions of the world, most local gypsum endemics from Turkey show a similar chemical composition to gypsovags. This may indicate a shared ecological strategy as stress-tolerant plants not specifically adapted to gypsum. Nevertheless, the narrow gypsum endemic Gypsophila parva showed a chemical composition typical of gypsum specialists, indicating that various strategies are feasible within narrowly distributed gypsophiles. © 2015 German Botanical Society and The Royal Botanical Society of the Netherlands.

Relating the Chemical Composition of Dissolved Organic Matter Draining Permafrost Soils to its Photochemical Degradation in Arctic Surface Waters.

NASA Astrophysics Data System (ADS)

Ward, C.; Cory, R. M.

2015-12-01

Thawing permafrost soils are expected to shift the chemical composition of DOM exported to and degraded in arctic surface waters. While DOM photo-degradation is an important component of the freshwater C cycle in the Arctic, the molecular controls on DOM photo-degradation remain poorly understood, making it difficult to predict how shifting chemical composition may alter DOM photo-degradation in arctic surface waters. To address this knowledge gap, we quantified the susceptibility of DOM draining the shallow organic mat and the deeper permafrost layer to complete photo-oxidation to CO₂ and partial photo-oxidation to compounds that remain in the DOM pool, and investigated changes in DOM chemical composition following sunlight exposure. DOM leached from the organic mat contained higher molecular weight, more oxidized and unsaturated aromatic species compared to permafrost DOM. Despite significant differences in initial chemical composition, permafrost and organic mat DOM had similar susceptibilities to complete photo-oxidation to CO₂. Concurrent losses of carboxyl moieties and shifts in chemical composition during photo-degradation indicated that carboxyl-rich tannin-like compounds in both DOM sources were likely photo-decarboxylated to CO₂. Permafrost DOM had a higher susceptibility to partial photo-oxidation compared to organic mat DOM, potentially due to a lower abundance of phenolic compounds that act as "antioxidants" and slow the oxidation of DOM. These results demonstrated how chemical composition controls the photo-degradation of DOM in arctic surface waters, and that DOM photo-degradation will likely remain an important component of the freshwater C budget in the Arctic with increased export of permafrost DOM to surface waters.

Properties of evolved mass-losing stars in the Milky Way and variations in the interstellar dust composition

NASA Technical Reports Server (NTRS)

Thronson, Harley A., Jr.; Latter, William B.; Black, John H.; Bally, John; Hacking, Perry

1987-01-01

A large sample of evolved carbon-rich and oxygen-rich objects has been studied using data from the IRAS Point Source Catalog. The number density of infrared-emitting 'carbon' stars shows no variation with Galactocentric radius, while the evolved 'oxygen' star volume density can be well fitted by a given law. A law is given for the number of carbon stars; a total is found in the Galaxy of 48,000 highly evolved oxygen stars. The mass-return rate for all evolved stars is found to be 0.35 solar mass/yr, with a small percentage contribution from carbon stars. The mass-loss rates for both types of stars are dominated by the small number of objects with the smallest rates. A mean lifetime of about 200,000 yr is obtained for both carbon and oxygen stars. Main-sequence stars in the mass range of three to five solar masses are the probable precursors of the carbon stars.

Silkworm cocoons inspire models for random fiber and particulate composites

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

Chen Fujia; Porter, David; Vollrath, Fritz

The bioengineering design principles evolved in silkworm cocoons make them ideal natural prototypes and models for structural composites. Cocoons depend for their stiffness and strength on the connectivity of bonding between their constituent materials of silk fibers and sericin binder. Strain-activated mechanisms for loss of bonding connectivity in cocoons can be translated directly into a surprisingly simple yet universal set of physically realistic as well as predictive quantitative structure-property relations for a wide range of technologically important fiber and particulate composite materials.

Silkworm cocoons inspire models for random fiber and particulate composites

NASA Astrophysics Data System (ADS)

Chen, Fujia; Porter, David; Vollrath, Fritz

2010-10-01

The bioengineering design principles evolved in silkworm cocoons make them ideal natural prototypes and models for structural composites. Cocoons depend for their stiffness and strength on the connectivity of bonding between their constituent materials of silk fibers and sericin binder. Strain-activated mechanisms for loss of bonding connectivity in cocoons can be translated directly into a surprisingly simple yet universal set of physically realistic as well as predictive quantitative structure-property relations for a wide range of technologically important fiber and particulate composite materials.

Method for the elucidation of the elemental composition of low molecular mass chemicals using exact masses of product ions and neutral losses: application to environmental chemicals measured by liquid chromatography with hybrid quadrupole/time-of-flight mass spectrometry.

PubMed

Suzuki, Shigeru; Ishii, Tetsuko; Yasuhara, Akio; Sakai, Shinichi

2005-01-01

A method for elucidating the elemental compositions of low molecular weight chemicals, based primarily on mass measurements made using liquid chromatography (LC) with time-of-flight mass spectrometry (TOFMS) and quadrupole/time-of-flight mass spectrometry (LC/QTOFMS), was developed and tested for 113 chemicals of environmental interest with molecular masses up to approximately 400 Da. As the algorithm incorporating the method is not affected by differences in the instrument used, or by the ionization method and other ionization conditions, the method is useful not only for LC/TOFMS, but also for all kinds of mass spectra measured with higher accuracy and precision (uncertainties of a few mDa) employing all ionization methods and on-line separation techniques. The method involves calculating candidate compositions for intact ionized molecules (ionized forms of the sample molecule that have lost or gained no more than a proton, i.e., [M+H](+) or [M-H](-)) as well as for fragment ions and corresponding neutral losses, and eliminating those atomic compositions for the molecules that are inconsistent with the corresponding candidate compositions of fragment ions and neutral losses. Candidate compositions were calculated for the measured masses of the intact ionized molecules and of the fragment ions and corresponding neutral losses, using mass uncertainties of 2 and 5 mDa, respectively. Compositions proposed for the ionized molecule that did not correspond to the sum of the compositions of a candidate fragment ion and its corresponding neutral loss were discarded. One, 2-5, 6-10, 11-20, and >20 candidate compositions were found for 65%, 39%, 1%, 1%, and 0%, respectively, for the 124 ionized molecules formed from the 113 chemicals tested (both positive and negative ions were obtained from 11 of the chemicals). However, no candidate composition was found for 2% of the test cases (i.e., 3 chemicals), for each of which the measured mass of one of the product ions was in error by 5-6.7 mDa.

Bacterial bioluminescence response to long-term exposure to reverse osmosis treated effluents from dye industries.

PubMed

Ravindran, J; Manikandan, B; Shirodkar, P V; Francis, K X; Mani Murali, R; Vethamony, P

2014-10-01

The bacterial bioluminescence assay is one of the novel means for toxicity detection. The bioluminescence response of 2 marine bioluminescent bacteria was tested upon their long-term exposure to 9 different reverse osmosis (RO) rejects with varying chemical composition sampled from various dye industries. Bioluminescent bacteria were cultured in the RO reject samples, at different concentrations, and their growth rate and luminescence was measured for 24 h. The RO reject samples caused sublethal effects upon exposure and retarded the growth of bacteria, confirming their toxic nature. Further, continuation of the exposure showed that the initial luminescence, though reduced, recovered and increased beyond the control cultures irrespective of cell density, and finally decreased once again. The present study emphasizes the need of evolving a long-term exposure assay and shows that the method followed in this study is suitable to evaluate the toxicants that exert delayed toxicity, using lower concentrations of toxicants as well as coloured samples.

Assessing nanoparticle risk poses prodigious challenges.

PubMed

MacPhail, Robert C; Grulke, Eric A; Yokel, Robert A

2013-01-01

Risk assessment is used both formally and informally to estimate the likelihood of an adverse event occurring, for example, as a consequence of exposure to a hazardous chemical, drug, or other agent. Formal risk assessments in government regulatory agencies have a long history of practice. The precision with which risk can be estimated is inevitably constrained, however, by uncertainties arising from the lack of pertinent data. Developing accurate risk assessments for nanoparticles and nanoparticle-containing products may present further challenges because of the unique properties of the particles, uncertainties about their composition and the populations exposed to them, and how these may change throughout the particle's life cycle. This review introduces the evolving practice of risk assessment followed by some of the uncertainties that need to be addressed to improve our understanding of nanoparticle risks. Given the clarion call for life-cycle assessments of nanoparticles, an unprecedented degree of national and international coordination between scientific organizations, regulatory agencies, and stakeholders will be required to achieve this goal. Copyright © 2013 Wiley Periodicals, Inc.

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

PubMed

Pappalardo, Lucia; Mastrolorenzo, Giuseppe

2012-01-01

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

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

PubMed Central

Pappalardo, Lucia; Mastrolorenzo, Giuseppe

2012-01-01

In recent decades, geophysical investigations have detected wide magma reservoirs beneath quiescent calderas. However, the discovery of partially melted horizons inside the crust is not sufficient to put constraints on capability of reservoirs to supply cataclysmic eruptions, which strictly depends on the chemical-physical properties of magmas (composition, viscosity, gas content etc.), and thus on their differentiation histories. In this study, by using geochemical, isotopic and textural records of rocks erupted from the high-risk Campi Flegrei caldera, we show that the alkaline magmas have evolved toward a critical state of explosive behaviour over a time span shorter than the repose time of most volcanic systems and that these magmas have risen rapidly toward the surface. Moreover, similar results on the depth and timescale of magma storage were previously obtained for the neighbouring Somma-Vesuvius volcano. This consistency suggests that there might be a unique long-lived magma pool beneath the whole Neapolitan area. PMID:23050096

Determining the minimum required uranium carbide content for HTGR UCO fuel kernels

DOE PAGES

McMurray, Jacob W.; Lindemer, Terrence B.; Brown, Nicholas R.; ...

2017-03-10

There are three important failure mechanisms that must be controlled in high-temperature gas-cooled reactor (HTGR) fuel for certain higher burnup applications are SiC layer rupture, SiC corrosion by CO, and coating compromise from kernel migration. All are related to high CO pressures stemming from free O generated when uranium present as UO 2 fissions and the O is not subsequently bound by other elements. Furthermore, in the HTGR UCO kernel design, CO buildup from excess O is controlled by the inclusion of additional uranium in the form of a carbide, UC x. An approach for determining the minimum UC xmore » content to ensure negligible CO formation was developed and demonstrated using CALPHAD models and the Serpent 2 reactor physics and depletion analysis tool. Our results are intended to be more accurate than previous estimates by including more nuclear and chemical factors, in particular the effect of transmutation products on the oxygen distribution as the fuel kernel composition evolves with burnup.« less

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

McMurray, Jacob W.; Lindemer, Terrence B.; Brown, Nicholas R.

There are three important failure mechanisms that must be controlled in high-temperature gas-cooled reactor (HTGR) fuel for certain higher burnup applications are SiC layer rupture, SiC corrosion by CO, and coating compromise from kernel migration. All are related to high CO pressures stemming from free O generated when uranium present as UO 2 fissions and the O is not subsequently bound by other elements. Furthermore, in the HTGR UCO kernel design, CO buildup from excess O is controlled by the inclusion of additional uranium in the form of a carbide, UC x. An approach for determining the minimum UC xmore » content to ensure negligible CO formation was developed and demonstrated using CALPHAD models and the Serpent 2 reactor physics and depletion analysis tool. Our results are intended to be more accurate than previous estimates by including more nuclear and chemical factors, in particular the effect of transmutation products on the oxygen distribution as the fuel kernel composition evolves with burnup.« less

Indications of negative evolution for the sources of the highest energy cosmic rays

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

Taylor, Andrew M.; Ahlers, Markus; Hooper, Dan

2015-09-14

Using recent measurements of the spectrum and chemical composition of the highest energy cosmic rays, we consider the sources of these particles. We find that these data strongly prefer models in which the sources of the ultra-high-energy cosmic rays inject predominantly intermediate mass nuclei, with comparatively few protons or heavy nuclei, such as iron or silicon. If the number density of sources per comoving volume does not evolve with redshift, the injected spectrum must be very hard (α≃1) in order to fit the spectrum observed from Earth. Such a hard spectral index would be surprising and difficult to accommodate theoretically.more » In contrast, much softer spectral indices, consistent with the predictions of Fermi acceleration (α≃2), are favored in models with negative source evolution. Furthermore with this theoretical bias, these observations thus favor models in which the sources of the highest energy cosmic rays are preferentially located within the low-redshift universe.« less

Absolute parameters and chemical composition of the binary star OU Gem

NASA Astrophysics Data System (ADS)

Glazunova, L. V.; Mishenina, T. V.; Soubiran, C.; Kovtyukh, V. V.

2014-10-01

The absolute parameters and chemical composition of the BY Dra-type spectroscopic binary OU Gem (HD 45088) were determined on the basis of 10 high-resolution spectra. A new orbital solution of the binary system was determined, the binary ephemerides were specified, and the main physical and atmospheric parameters of the binary components were obtained. The chemical composition of both components was estimated for the first time for the stars of such type.

Pulsed plasma chemical synthesis of carbon-containing titanium and silicon oxide based nanocomposite

NASA Astrophysics Data System (ADS)

Kholodnaya, Galina; Sazonov, Roman; Ponomarev, Denis; Zhirkov, Igor

2018-03-01

The paper presents the results of the experimental investigation of the physical and chemical properties of the TixSiyCzOw composite nanopowders, which were first obtained using a pulsed plasma chemical method. The pulsed plasma chemical synthesis was achieved using a technological electron accelerator (TEA-500). The parameters of the electron beam are as follows: 400-450 keV electron energy, 60 ns half-amplitude pulse duration, up to 200 J pulse energy, and 5 cm beam diameter. The main physical and chemical properties of the obtained composites were studied (morphology, chemical, elemental and phase composition). The morphology of the TixSiyCzOw composites is multiform. There are large round particles, with an average size of above 150 nm. Besides, there are small particles (an average size is in the range of 15-40 nm). The morphology of small particles is in the form of crystallites. In the TixSiyCzOw synthesised composite, the peak with a maximum of 946 cm-1 was registered. The presence of IR radiation in this region of the spectrum is typical for the deformation of atomic oscillations in the Si‒О‒Ti bond, which indicates the formation of the solid solution. The composites consist of two crystal phases - anatase and rutile. The prevailing phase of the crystal structure is rutile.

The simulation method of chemical composition of vermicular graphite iron on the basis of genetic algorithm

NASA Astrophysics Data System (ADS)

Yusupov, L. R.; Klochkova, K. V.; Simonova, L. A.

2017-09-01

The paper presents a methodology of modeling the chemical composition of the composite material via genetic algorithm for optimization of the manufacturing process of products. The paper presents algorithms of methods based on intelligent system of vermicular graphite iron design

Chemical composition of fat and oil products

USDA-ARS?s Scientific Manuscript database

Fats and oils are an important dietary component, and contribute to the nutritional and sensory quality of foods. This chapter focuses on the chemical composition of fats and oils, and how these compositions affect the functional properties of fats and oils in foods. The focus will remain on the mos...

Compositions of micas in peraluminous granitoids of the eastern Arabian shield - Implications for petrogenesis and tectonic setting of highly evolved, rare-metal enriched granites

USGS Publications Warehouse

du Bray, E.A.

1994-01-01

Compositions and pleochroism of micas in fourteen peraluminous alkali-feldspar granites in the eastern part of the Late Proterozoic Arabian Shield are unlike those of micas (principally biotite) in most calc-alkaline granitoid rocks. Compositions of these micas are distinguished by elevated abundances of Li2O, F, and numerous cations and by low MgO abundances. These micas, constituents of highly evolved rare-metal enriched granitoids, represent an iron-lithium substitution series that ranges from lithium-poor siderophyllite to lithium-rich ferroan lepidolite. The eastern Arabian Shield also hosts six epizonal granitoids that contain colorless micas. Compositions of these micas, mostly muscovite, and their host granitoids are distinct from those of the iron-lithium micas and their host granitoids. Compositions of the analyzed micas have a number of petrogenetic implications. The twenty granitoids containing these micas form three compositional groups that reflect genesis in particular tectonic regimes; mica compositions define the same three groups. The presence of magmatic muscovite in six of these shallowly crystallized granitoids conflicts with experimental data indicating muscovite stability at pressures greater than 3 kbar. Muscovite in the Arabian granitoids probably results from its non-ideal composition; the presence of muscovite cannot be used as a pressure indicator. Finally, mineral/matrix partition coefficients are significantly greater than 1.0 for a number of cations, the rare-earth elements in particular, in many of the analyzed iron-lithium micas. Involvement of these types of micas in partial melting or fractionation processes can have a major influence on silicate liquid compositions. ?? 1994 Springer-Verlag.

Dynamics of shearing force and its correlations with chemical compositions and in vitro dry matter digestibility of stylo (Stylosanthes guianensis) stem.

PubMed

Zi, Xuejuan; Li, Mao; Zhou, Hanlin; Tang, Jun; Cai, Yimin

2017-12-01

The study explored the dynamics of shearing force and its correlation with chemical compositions and in vitro dry matter digestibility (IVDMD) of stylo. The shearing force, diameter, linear density, chemical composition, and IVDMD of different height stylo stem were investigated. Linear regression analysis was done to determine the relationships between the shearing force and cut height, diameter, chemical composition, or IVDMD. The results showed that shearing force of stylo stem increased with plant height increasing and the crude protein (CP) content and IVDMD decreased but fiber content increased over time, resulting in decreased forage value. In addition, tall stem had greater shearing force than short stem. Moreover, shearing force is positively correlated with stem diameter, linear density and fiber fraction, but negatively correlated with CP content and IVDMD. Overall, shearing force is an indicator more direct, easier and faster to measure than chemical composition and digestibility for evaluation of forage nutritive value related to animal performance. Therefore, it can be used to evaluate the nutritive value of stylo.

Growth of Infants Fed Formula with Evolving Nutrition Composition: A Single-Arm Non-Inferiority Study

PubMed Central

Spalinger, Johannes; Nydegger, Andreas; Belli, Dominique; Furlano, Raoul I.; Yan, Jian; Tanguy, Jerome; Pecquet, Sophie; Destaillats, Frédéric; Egli, Delphine; Steenhout, Philippe

2017-01-01

The nutritional composition of human milk evolves over the course of lactation, to match the changing needs of infants. This single-arm, non-inferiority study evaluated growth against the WHO standards in the first year of life, in infants consecutively fed four age-based formulas with compositions tailored to infants’ nutritional needs during the 1st, 2nd, 3rd–6th, and 7th–12th months of age. Healthy full-term formula-fed infants (n = 32) were enrolled at ≤14 days of age and exclusively fed study formulas from enrollment, to the age of four months. Powdered study formulas were provided in single-serving capsules that were reconstituted using a dedicated automated preparation system, to ensure precise, hygienic preparation. The primary outcome was the weight-for-age z-score (WAZ) at the age of four months (vs. non-inferiority margin of −0.5 SD). Mean (95% CI) z-scores for the WAZ (0.12 (−0.15, 0.39)), as well as for the length-for-age (0.05 (−0.19, 0.30)), weight-for-length (0.16 (−0.16, 0.48)), BMI-for-age (0.11 (−0.20, 0.43)), and head circumference-for-age (0.41 (0.16, 0.65)) at the age of four months, were non-inferior. Throughout the study, anthropometric z-scores tracked closely against the WHO standards (within ±1 SD). In sum, a four-stage, age-based infant formula system with nutritional compositions tailored to infants’ evolving needs, supports healthy growth consistent with WHO standards, for the first year of life. PMID:28257044

Growth of Infants Fed Formula with Evolving  Nutrition Composition: A Single-Arm Non-Inferiority Study.

PubMed

Spalinger, Johannes; Nydegger, Andreas; Belli, Dominique; Furlano, Raoul I; Yan, Jian; Tanguy, Jerome; Pecquet, Sophie; Destaillats, Frédéric; Egli, Delphine; Steenhout, Philippe

2017-03-01

The nutritional composition of human milk evolves over the course of lactation, to match the changing needs of infants. This single-arm, non-inferiority study evaluated growth against the WHO standards in the first year of life, in infants consecutively fed four age-based formulas with compositions tailored to infants' nutritional needs during the 1st, 2nd, 3rd-6th, and 7th-12th months of age. Healthy full-term formula-fed infants (n = 32) were enrolled at ≤14 days of age and exclusively fed study formulas from enrollment, to the age of four months. Powdered study formulas were provided in single-serving capsules that were reconstituted using a dedicated automated preparation system, to ensure precise, hygienic preparation. The primary outcome was the weight-for-age z-score (WAZ) at the age of four months (vs. non-inferiority margin of -0.5 SD). Mean (95% CI) z-scores for the WAZ (0.12 (-0.15, 0.39)), as well as for the length-for-age (0.05 (-0.19, 0.30)), weight-for-length (0.16 (-0.16, 0.48)), BMI-for-age (0.11 (-0.20, 0.43)), and head circumferencefor-age (0.41 (0.16, 0.65)) at the age of four months, were non-inferior. Throughout the study, anthropometric z-scores tracked closely against the WHO standards (within ±1 SD). In sum, a fourstage, age-based infant formula system with nutritional compositions tailored to infants' evolving needs, supports healthy growth consistent with WHO standards, for the first year of life.

The XRD Amorphous Component in John Klein Drill Fines at Yellowknife Bay, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Ming,, Douglas W.; Blake, David; Vaniman, David; Bish, David L; Chipera, Steve; Downs, Robert; Morrison, Shaunna; Gellert, Ralf; Campbell, Iain;

Chemical similarity and local community assembly in the species rich tropical genus Piper.

PubMed

Salazar, Diego; Jaramillo, M Alejandra; Marquis, Robert J

2016-11-01

Community ecologists have strived to find mechanisms that mediate the assembly of natural communities. Recent evidence suggests that natural enemies could play an important role in the assembly of hyper-diverse tropical plant systems. Classic ecological theory predicts that in order for coexistence to occur, species differences must be maximized across biologically important niche dimensions. For plant-herbivore interactions, it has been recently suggested that, within a particular community, plant species that maximize the difference in chemical defense profiles compared to neighboring taxa will have a relative competitive advantage. Here we tested the hypothesis that plant chemical diversity can affect local community composition in the hyper-diverse genus Piper at a lowland wet forest location in Costa Rica. We first characterized the chemical composition of 27 of the most locally abundant species of Piper. We then tested whether species with different chemical compositions were more likely to coexist. Finally, we assessed the degree to which Piper phylogenetic relationships are related to differences in secondary chemical composition and community assembly. We found that, on average, co-occurring species were more likely to differ in chemical composition than expected by chance. Contrary to expectations, there was no phylogenetic signal for overall secondary chemical composition. In addition we found that species in local communities were, on average, more phylogenetically closely related than expected by chance, suggesting that functional traits other than those measured here also influence local assembly. We propose that selection by herbivores for divergent chemistries between closely related species facilitates the coexistence of a high diversity of congeneric taxa via apparent competition. © 2016 by the Ecological Society of America.

Screening for chemicals that affect hair cell death and survival in the zebrafish lateral line.

PubMed

Ou, Henry; Simon, Julian A; Rubel, Edwin W; Raible, David W

2012-06-01

The zebrafish lateral line is an efficient model system for the evaluation of chemicals that protect and damage hair cells. Located on the surface of the body, lateral line hair cells are accessible for manipulation and visualization. The zebrafish lateral line system allows rapid screens of large chemical libraries, as well as subsequent thorough evaluation of interesting compounds. In this review, we focus on the results of our previous screens and the evolving methodology of our screens for chemicals that protect hair cells, and chemicals that damage hair cells using the zebrafish lateral line. Copyright © 2012 Elsevier B.V. All rights reserved.

The Effect of Chemical Functionalization on Mechanical Properties of Nanotube/Polymer Composites

NASA Technical Reports Server (NTRS)

Odegard, G. M.; Frankland, S. J. V.; Gates, T. S.

2003-01-01

The effects of the chemical functionalization of a carbon nanotube embedded in a nanotube/polyethylene composite on the bulk elastic properties are presented. Constitutive equations are established for both functionalized and non-functionalized nanotube composites systems by using an equivalent-continuum modeling technique. The elastic properties of both composites systems are predicted for various nanotube lengths, volume fractions, and orientations. The results indicate that for the specific composite material considered in this study, most of the elastic stiffness constants of the functionalized composite are either less than or equal to those of the non-functionalized composite.

Rapid, Contactless and Non-Destructive Testing of Chemical Composition of Samples

NASA Astrophysics Data System (ADS)

Ivanov, O.; Vaseashta, A.; Stoychev, L.

Our results demonstrate that a new effect can be induced in each solid in a wide spectral range of electromagnetic irradiation. In the present manuscript we prove experimentally that one of the possible applications of this effect is for an express contactless control of the chemical composition of a series of samples, in this case, coins. The method has wide applicability ranging from defense and homeland security to several applications requiring rapid and nondestructive identification of chemical composition.

ORIGIN: Metal Creation and Evolution From The Cosmic Dawn

NASA Astrophysics Data System (ADS)

Piro, L.; den Herder, J. W.; Ohashi, T.; Hartmann, D. H.; Kouveliotou, C.

2011-08-01

ORIGIN is a mission designed to use Gamma-Ray Bursts as a unique probe to study the cosmic history of baryons and the metal enrichment from the first stars up to the present Universe. Reconstructing the cosmic history of metals, from the first population of stars to the processes involved in the formation of galaxies and clusters of galaxies, is a key observational challenge. Observing any single star in the early Universe is in fact beyond the reach of presently planned mission. By measuring GRB redshifts and abundances in the circumburst medium deep into the era of re-ionization (z>6), ORIGIN will discover when star formation started and how it evolved into the present day structures. ORIGIN will collect 400 GRBs per year covering the full redshift distribution. About twice per month a GRB from the re-ionization era will trigger the instruments. The resulting multi-element abundance patterns derived from high resolution X-ray and IR observations will map the evolving chemical composition of the early Universe, ``fingerprint'' the elusive PopIII stars, and constrain the shape of the Initial Mass Function (IMF) of the first stars. While not observing GRB afterglows, ORIGIN will map element abundances in local structures (z<2) by determining the properties of the hot IGM in clusters and groups of galaxies and the Warm-Hot Intergalactic Medium (WHIM). In this paper we focus on the use of GRB to track the earliest star populations.

Chemical aspects of the formation of the solar system

NASA Technical Reports Server (NTRS)

Arrhenius, G.

1978-01-01

Application of Alfven's theory for the formation of the solar system and the constraints imposed by the chemical composition of space materials are discussed with reference to chemical processes involved in the formation of the solar system. Evidence for the chemical properties of the space medium and the chemical consequences of the postulated physical differentiation processes are outlined, and interpretations based on structure and composition of meteorite material are indicated. A large range of topics, including processes involving chemical differentiation, temperature effects, and isotope fractionation, are examined.

The Acid-Base Properties and Chemical Composition of the Surface of the InSb-ZnTe System

NASA Astrophysics Data System (ADS)

Kirovskaya, I. A.; Shubenkova, E. G.; Timoshenko, O. T.; Filatova, T. N.

2008-04-01

The acid-base properties and chemical composition of the surface of solid solutions and binary components of the InSb-ZnTe system were studied by the hydrolytic adsorption, nonaqueous conductometric titration, mechanochemistry, IR spectroscopy, and mass spectrometry methods. The strength, nature, and concentration of acid centers were determined. Changes in the concentration of acid centers caused by surface exposure to CO and changes in the composition of the system were also studied. The mechanism of acid-base interactions was established. The chemical composition of the surface of system components exposed to air included adsorbed H2O molecules, OH- groups, hydrocarbon and oxocarbon compounds, and the products of surface atom oxidation. After thermal treatment in a vacuum, the composition of the surface approached the stoichiometric composition.

Studies on thermo-mechanical properties of chemically treated jute-polyester composite

NASA Astrophysics Data System (ADS)

Chaudhari, Vikas; Chandekar, Harichandra; Saboo, Jayesh; Mascarenhas, Adlete

2018-03-01

The effect of chemical treatments on jute-polyester composites is studied in this paper. The jute fabrics are chemically treated with NaOH and benzoyl chloride and its tensile and visco-elastic properties are compared with untreated jute composite. The NaOH treated jute-polyester composite show superior tensile strength and modulus compared to other jute-polyester composites. The glass transition temperature obtained from DMA shift to higher temperature for composites in comparison to polyester resin, this is due to restriction of mobility in chains due to introduction of jute reinforcement. The DMA results also show favourable results towards NaOH treatment i.e. higher storage modulus and lower tan δ values relative to untreated jute-polyester composite. The benzoyl treated jute-polyester composite however do not show promising results which may be attributed to the fact that the adhesion properties associated with similar ester functional groups in the benzoyl treated jute fabric and polyester resin were not obtained.

Modified silicon carbide whiskers

DOEpatents

Tiegs, Terry N.; Lindemer, Terrence B.

1991-01-01

Silicon carbide whisker-reinforced ceramic composites are fabricated in a highly reproducible manner by beneficating the surfaces of the silicon carbide whiskers prior to their usage in the ceramic composites. The silicon carbide whiskers which contain considerable concentrations of surface oxides and other impurities which interact with the ceramic composite material to form a chemical bond are significantly reduced so that only a relatively weak chemical bond is formed between the whisker and the ceramic material. Thus, when the whiskers interact with a crack propagating into the composite the crack is diverted or deflected along the whisker-matrix interface due to the weak chemical bonding so as to deter the crack propagation through the composite. The depletion of the oxygen-containing compounds and other impurities on the whisker surfaces and near surface region is effected by heat treating the whiskers in a suitable oxygen sparaging atmosphere at elevated temperatures. Additionally, a sedimentation technique may be utilized to remove whiskers which suffer structural and physical anomalies which render them undesirable for use in the composite. Also, a layer of carbon may be provided on the surface of the whiskers to further inhibit chemical bonding of the whiskers to the ceramic composite material.

Modified silicon carbide whiskers

DOEpatents

Tiegs, T.N.; Lindemer, T.B.

1991-05-21

Silicon carbide whisker-reinforced ceramic composites are fabricated in a highly reproducible manner by beneficating the surfaces of the silicon carbide whiskers prior to their usage in the ceramic composites. The silicon carbide whiskers which contain considerable concentrations of surface oxides and other impurities which interact with the ceramic composite material to form a chemical bond are significantly reduced so that only a relatively weak chemical bond is formed between the whisker and the ceramic material. Thus, when the whiskers interact with a crack propagating into the composite the crack is diverted or deflected along the whisker-matrix interface due to the weak chemical bonding so as to deter the crack propagation through the composite. The depletion of the oxygen-containing compounds and other impurities on the whisker surfaces and near surface region is effected by heat treating the whiskers in a suitable oxygen sparging atmosphere at elevated temperatures. Additionally, a sedimentation technique may be utilized to remove whiskers which suffer structural and physical anomalies which render them undesirable for use in the composite. Also, a layer of carbon may be provided on the surface of the whiskers to further inhibit chemical bonding of the whiskers to the ceramic composite material.

Composite Materials

NASA Technical Reports Server (NTRS)

1988-01-01

Langley Research Center researchers invented an advanced polymer, a chemical compound formed by uniting many small molecules to create a complex molecule with different chemical properties. The material is a thermoplastic polyimide that resists solvents. Other polymers of this generic type are soluble in solvents, thus cannot be used where solvents are present. High Technology Services (HTS), Inc. licensed technology and is engaged in development and manufacture of high performance plastics, resins and composite materials. Techimer Materials Division is using technology for composite matrix resins that offer heat resistance and protection from radiation, electrical and chemical degradation. Applications of new polymer include molding resins, adhesives and matrix resins for fiber reinforced composites.

Elemental Compositions of Comet 81P/Wild 2 Samples Collected by Stardust

NASA Technical Reports Server (NTRS)

Flynn, G. J.; Bleuet, P.; Borg, J.; Bradley, J.; Brenker, F.; Brennan, S.; Bridges, J.; Brownlee, D. E.; Bullock, E.; Clark, B. C.;

Porous multi-component material for the capture and separation of species of interest

DOEpatents

Addleman, Raymond S.; Chouyyok, Wilaiwan; Li, Xiaohong S.; Cinson, Anthony D.; Gerasimenko, Aleksandr A

2016-06-21

A method and porous multi-component material for the capture, separation or chemical reaction of a species of interest is disclosed. The porous multi-component material includes a substrate and a composite thin film. The composite thin film is formed by combining a porous polymer with a nanostructured material. The nanostructured material may include a surface chemistry for the capture of chemicals or particles. The composite thin film is coupled to the support or device surface. The method and material provides a simple, fast, and chemically and physically benign way to integrate nanostructured materials into devices while preserving their chemical activity.

Vegetable fibres from agricultural residues as thermo-mechanical reinforcement in recycled polypropylene-based green foams.

PubMed

Ardanuy, Mònica; Antunes, Marcelo; Velasco, José Ignacio

2012-02-01

Novel lightweight composite foams based on recycled polypropylene reinforced with cellulosic fibres obtained from agricultural residues were prepared and characterized. These composites, initially prepared by melt-mixing recycled polypropylene with variable fibre concentrations (10-25 wt.%), were foamed by high-pressure CO(2) dissolution, a clean process which avoids the use of chemical blowing agents. With the aim of studying the influence of the fibre characteristics on the resultant foams, two chemical treatments were applied to the barley straw in order to increase the α-cellulose content of the fibres. The chemical composition, morphology and thermal stability of the fibres and composites were analyzed. Results indicate that fibre chemical treatment and later foaming of the composites resulted in foams with characteristic closed-cell microcellular structures, their specific storage modulus significantly increasing due to the higher stiffness of the fibres. The addition of the fibres also resulted in an increase in the glass transition temperature of PP in both the solid composites and more significantly in the foams. Copyright © 2011 Elsevier Ltd. All rights reserved.

Experimental Constraints on the Chemical Differentiation of Mercurys Mantle

NASA Technical Reports Server (NTRS)

Boujibar, A.; Righter, K.; Pando, K.; Danielson, L.

2015-01-01

Mercury is known as being the most reduced terrestrial planet with the highest core/mantle ratio. Results from MESSENGER spacecraft have shown that its surface is FeO-poor (2-4 wt%) and S-rich (up to 6-7 wt%), which confirms the reducing nature of its silicate mantle. In addition several features suggest important melting stages of the Mercurian mantle: widespread volcanic deposits on its surface, a high crustal thickness (approximately 10% of the planet's volume) and chemical compositions of its surface suggesting several stages of differentiation and remelting processes. Therefore it is likely that igneous processes like magma ocean crystallization and continuous melting have induced chemical and mineralogical heterogeneities in the Mercurian mantle. The extent and nature of compositional variations produced by partial melting remains poorly constrained for the particular compositions of Mercury (very reducing conditions, low FeO-contents and high sulfur-contents). Melting experiments with bulk Mercury-analogue compositions are scarce and with poorly con-trolled starting compositions. Therefore additional experimental data are needed to better understand the differentiation processes that lead to the observed chemical compositions of Mercury's surface.

Chemical analysis of the moon at the surveyor v landing site.

PubMed

Turkevich, A L; Franzgrote, E J; Patterson, J H

1967-11-03

The chemical composition of the lunar surface material at a maria landing site has been determined by the alpha-scattering technique. Oxygen, silicon, and aluminum have been identified in the preliminary evaluation of the data. The general chemical composition is similar to that of a silicate of a basaltic type.

Chemical structure of wood charcoal by infrared spectroscopy and multivariate analysis

Treesearch

Nicole Labbe; David Harper; Timothy Rials; Thomas Elder

2006-01-01

In this work, the effect of temperature on charcoal structure and chemical composition is investigated for four tree species. Wood charcoal carbonized at various temperatures is analyzed by mid infrared spectroscopy coupled with multivariate analysis and by thermogravimetric analysis to characterize the chemical composition during the carbonization process. The...

Chemical Fingerprinting of Materials Developed Due to Environmental Issues

NASA Technical Reports Server (NTRS)

Smith, Doris A.; McCool, A. (Technical Monitor)

2000-01-01

Instrumental chemical analysis methods are developed and used to chemically fingerprint new and modified External Tank materials made necessary by changing environmental requirements. Chemical fingerprinting can detect and diagnose variations in material composition. To chemically characterize each material, fingerprint methods are selected from an extensive toolbox based on the material's chemistry and the ability of the specific methods to detect the material's critical ingredients. Fingerprint methods have been developed for a variety of materials including Thermal Protection System foams, adhesives, primers, and composites.

Evaluation of composite pavement unbonded overlays : phase III.

DOT National Transportation Integrated Search

2007-08-01

In recent years, thin whitetopping has evolved as a viable rehabilitation technique for deteriorated asphalt cement concrete (ACC) pavements. Numerous projects have been constructed and tested, allowing researchers to identify the important elements ...

National Institute of Diabetes and Digestive and Kidney Diseases

MedlinePlus

... on Human Milk Composition – Biological, Environmental, Nutritional, and Methodological Considerations November 16-17, 2017 | Bethesda, MD Individualizing Treatment for Urinary Incontinence - Evolving Research Questions into Research Plans February 1-2, 2018 | ...

Chemical enrichment in Ultra-Faint Dwarf galaxies

NASA Astrophysics Data System (ADS)

Romano, Donatella

2016-08-01

Our view of the Milky Way's satellite population has radically changed after the discovery, ten years ago, of the first Ultra-Faint Dwarf galaxies (UFDs). These extremely faint, dark-matter dominated, scarcely evolved stellar systems are found in ever-increasing number in our cosmic neighbourhood and constitute a gold-mine for studies of early star formation conditions and early chemical enrichment pathways. Here we show what can be learned from the measurements of chemical abundances in UFD stars read through the lens of chemical evolution studies, point out the limitations of the classic approach, and discuss the way to go to improve the models.

Experimental evolution gone wild.

PubMed

Scheinin, M; Riebesell, U; Rynearson, T A; Lohbeck, K T; Collins, S

2015-05-06

Because of their large population sizes and rapid cell division rates, marine microbes have, or can generate, ample variation to fuel evolution over a few weeks or months, and subsequently have the potential to evolve in response to global change. Here we measure evolution in the marine diatom Skeletonema marinoi evolved in a natural plankton community in CO2-enriched mesocosms deployed in situ. Mesocosm enclosures are typically used to study how the species composition and biogeochemistry of marine communities respond to environmental shifts, but have not been used for experimental evolution to date. Using this approach, we detect a large evolutionary response to CO2 enrichment in a focal marine diatom, where population growth rate increased by 1.3-fold in high CO2-evolved lineages. This study opens an exciting new possibility of carrying out in situ evolution experiments to understand how marine microbial communities evolve in response to environmental change.

Nondestructive characterization of municipal-solid-waste-contaminated surface soil by energy-dispersive X-ray fluorescence and low-Z (atomic number) particle electron probe X-ray microanalysis.

PubMed

Gupta, Dhrubajyoti; Ghosh, Rita; Mitra, Ajoy K; Roy, Subinit; Sarkar, Manoranjan; Chowdhury, Subhajit; Bhowmik, Asit; Mukhopadhyay, Ujjal; Maskey, Shila; Ro, Chul-Un

2011-11-01

The long-term environmental impact of municipal solid waste (MSW) landfilling is still under investigation due to the lack of detailed characterization studies. A MSW landfill site, popularly known as Dhapa, in the eastern fringe of the metropolis of Kolkata, India, is the subject of present study. A vast area of Dhapa, adjoining the current core MSW dump site and evolving from the raw MSW dumping in the past, is presently used for the cultivation of vegetables. The inorganic chemical characteristics of the MSW-contaminated Dhapa surface soil (covering a 2-km stretch of the area) along with a natural composite (geogenic) soil sample (from a small countryside farm), for comparison, were investigated using two complementary nondestructive analytical techniques, energy-dispersive X-ray fluorescence (EDXRF) for bulk analysis and low-Z (atomic number) particle electron probe X-ray microanalysis (low-Z particle EPMA) for single-particle analysis. The bulk concentrations of K, Rb, and Zr remain almost unchanged in all the soil samples. The Dhapa soil is found to be polluted with heavy metals such as Cu, Zn, and Pb (highly elevated) and Ti, Cr, Mn, Fe, Ni, and Sr (moderately elevated), compared to the natural countryside soil. These high bulk concentration levels of heavy metals were compared with the Ecological Soil Screening Levels for these elements (U.S. Environment Protection Agency) to assess the potential risk on the immediate biotic environment. Low-Z particle EPMA results showed that the aluminosilicate-containing particles were the most abundant, followed by SiO2, CaCO3-containing, and carbonaceous particles in the Dhapa samples, whereas in the countryside sample only aluminosilicate-containing and SiO2 particles were observed. The mineral particles encountered in the countryside sample are solely of geogenic origin, whereas those from the Dhapa samples seem to have evolved from a mixture of raw dumped MSW, urban dust, and other contributing factors such as wind, precipitation, weather patterns, farming, and water logging, resulting in their diverse chemical compositions and the abundant observation of carbonaceous species. Particles containing C and P were more abundant in the Dhapa samples than in the countryside soil sample, suggesting that MSW-contaminated soils are more fertile. However, the levels of particles containing potentially toxic heavy metals such as Cr, Mn, Ni, Cu, Zn, and/or Pb in the Dhapa samples were significant, corroborated by their high bulk concentration levels (EDXRF), causing deep concern for the immediate environment and contamination of the food chain through food crops.

Chemostratigraphy of Subduction Initiation: Boninite and Forearc Basalt from IODP Expedition 352

NASA Astrophysics Data System (ADS)

Shervais, John; Haugen, Emily; Godard, Marguerite; Ryan, Jeffrey G.; Prytulak, Julie; Li, Hongyan; Chapman, Timothy; Nelson, Wendy R.; Heaton, Daniel E.; Kirchenbaur, Maria; Shimizu, Kenji; Li, Yibing; Whattam, Scott A.; Almeev, Renat; Sakuyama, Tetsuya; Reagan, Mark K.; Pearce, Julian A.

2017-04-01

The Izu-Bonin forearc has been the focus of several recent IODP (International Ocean Discovery Program) expeditions studying the geophysical, petrologic, and chemical response to subduction initiation and its potential relationship to ophiolite genesis. IODP Expedition 352 cored four holes in the Izu-Bonin forearc near Chichi Jima in order to document the petrologic and chemical evolution of nascent subduction zones. Holes U1440 and U1441, drilled closest to the trench, sampled forearc basalt (FAB). U1439 and U1442, drilled stratigraphically up-section and farther from the trench, sampled boninite, high-Mg andesite, and basalt. FAB are characterized by MORB-like compositions, with relatively constant Ti, Zr, and Ti/Zr. In general, more primitive FAB are found in the lower part of the section. In detail, FAB have lower Na, Ti, P, and Zr, lower Ti/V ratios, and are LREE-depleted relative to MORB. Best fit models for the least evolved FAB and a depleted MORB mantle (DMM) source require extraction of 1% melt in the garnet lherzolite field and 19% melt extraction in the spinel lherzolite field (relative to 8-10% melt of DMM to produce MORB). Three types of boninite were found: high silica boninite (HSB), low silica boninite (LSB), and basaltic boninite (BB), as well as high Mg andesites (HMA). HSB, the youngest unit in both U1439 and U1442, is underlain by LSB-BB-HMA lavas, which often occur in mixed magma zones with evolved boninite and basalt. Boninites are distinguished by co-variations in SiO2-MgO and TiO2-MgO, and by Ti/Zr ratios, which increase from HSB through LSB to BB. HSB, LSB and BB define parallel trends in TiO2-MgO space: a low Ti trend represented by LSB and BB, and a lower Ti trend represented by HSB. All of the boninite suite rocks are slightly LREE-rich relative to MORB. LSB and BB have flat REE patterns relative to primitive mantle, whereas HSB are slightly LREE-rich. These trends require distinct source compositions in HSB relative to LSB/BB. The decrease in Ti/Zr from BB to HSB suggests a slab melt component. Melting models (non-modal, fractional) for boninites require additional partial melting of a residual source more depleted than DMM, and mixing with less depleted melts. The data require a heterogeneous source during subduction initiation, tapping progressively more refractory mantle through time, and showing progressive enrichment in slab components.

Thermal and chemical evolution in the early Solar System as recorded by FUN CAIs: Part II - Laboratory evaporation of potential CMS-1 precursor material

NASA Astrophysics Data System (ADS)

Mendybaev, Ruslan A.; Williams, Curtis D.; Spicuzza, Michael J.; Richter, Frank M.; Valley, John W.; Fedkin, Alexei V.; Wadhwa, Meenakshi

2017-03-01

We present the results of laboratory experiments in which a forsterite-rich melt estimated to be a potential precursor of Allende CMS-1 FUN CAI was evaporated into vacuum for different lengths of time at 1900 °C. The evaporation of this melt resulted in residues that define trajectories in chemical as well as magnesium, silicon and oxygen isotopic composition space and come very close to the measured properties of CMS-1. The isotopic composition of the evaporation residues was also used to determine the kinetic isotopic fractionation factors [α2,1 (vapor-melt) defined as the ratio of isotopes 2 and 1 of a given element in the evaporating gas divided by their ratio in the evaporating source] for evaporation of magnesium (α25,24 for 25Mg/24Mg), silicon (α29,28 for 29Si/28Si) and oxygen (α18,16 for 18O/16O) from the forsterite-rich melt at 1900 °C. The values of α25,24 = 0.98383 ± 0.00033 and α29,28 = 0.99010 ± 0.00038 are essentially independent of change in the melt composition as evaporation proceeds. In contrast, α18,16 changes from 0.9815 ± 0.0016 to ∼0.9911 when the residual melt composition changes from forsteritic to melilitic. Using the determined values of α25,24 and α29,28 and present-day bulk chemical composition of the CMS-1, the composition of the precursor of the inclusion was estimated to be close to the clinopyroxene + spinel + forsterite assemblage condensed from a solar composition gas. The correspondence between the chemical composition and isotopic fractionation of experimental evaporation residues and the present-day bulk chemical and isotopic compositions of CMS-1 is evidence that evaporation played a major role in the chemical evolution of CMS-1.

Characterization and prediction of chemical functions and weight fractions in consumer products.

PubMed

Isaacs, Kristin K; Goldsmith, Michael-Rock; Egeghy, Peter; Phillips, Katherine; Brooks, Raina; Hong, Tao; Wambaugh, John F

2016-01-01

Assessing exposures from the thousands of chemicals in commerce requires quantitative information on the chemical constituents of consumer products. Unfortunately, gaps in available composition data prevent assessment of exposure to chemicals in many products. Here we propose filling these gaps via consideration of chemical functional role. We obtained function information for thousands of chemicals from public sources and used a clustering algorithm to assign chemicals into 35 harmonized function categories (e.g., plasticizers, antimicrobials, solvents). We combined these functions with weight fraction data for 4115 personal care products (PCPs) to characterize the composition of 66 different product categories (e.g., shampoos). We analyzed the combined weight fraction/function dataset using machine learning techniques to develop quantitative structure property relationship (QSPR) classifier models for 22 functions and for weight fraction, based on chemical-specific descriptors (including chemical properties). We applied these classifier models to a library of 10196 data-poor chemicals. Our predictions of chemical function and composition will inform exposure-based screening of chemicals in PCPs for combination with hazard data in risk-based evaluation frameworks. As new information becomes available, this approach can be applied to other classes of products and the chemicals they contain in order to provide essential consumer product data for use in exposure-based chemical prioritization.

Frontiers of stellar evolution

NASA Technical Reports Server (NTRS)

Lambert, David L. (Editor)

1991-01-01

The present conference discusses theoretical and observational views of star formation, spectroscopic constraints on the evolution of massive stars, very low mass stars and brown dwarfs, asteroseismology, globular clusters as tests of stellar evolution, observational tests of stellar evolution, and mass loss from cool evolved giant stars. Also discussed are white dwarfs and hot subdwarfs, neutron stars and black holes, supernovae from single stars, close binaries with evolved components, accretion disks in interacting binaries, supernovae in binary systems, stellar evolution and galactic chemical evolution, and interacting binaries containing compact components.

Designing the Army’s Future Active Duty Weapons of Mass Destruction Response: Is the Defense Chemical, Biological, Radiological, Nuclear and High-Yield Explosives Response Force (DCRF) the Right Force at the Right Time?

DTIC Science & Technology

2013-06-14

ever-evolving contemporary nature of external and internal threats to the safety and security of the American homeland, it becomes increasingly...Major Justin P. Hurt, 146 pages. With the ever-evolving contemporary nature of external and internal threats to the safety and security of the American...HAZMAT Hazardous Materials HRF Homeland Response Force HSPD Homeland Security Presidential Directive JFHQ Joint Force

Temporal Evolution of the Upper Continental Crust: Implications for the Mode of Crustal Growth and the Evolution of the Hydrosphere

NASA Astrophysics Data System (ADS)

Rudnick, R. L.; Gaschnig, R. M.; Li, S.; Tang, M.; Qiu, L.; Valley, J. W.; Zurkowski, C.; McDonough, W. F.

2014-12-01

The upper continental crust (UCC), the interface between the atmosphere and solid Earth, is the site of weathering that produces sedimentary rocks, influences ocean chemistry through runoff of soluble elements, and affects climate through CO2 draw-down. The UCC also contains more than 50% of the crust's highly incompatible element budget (including K, Th, and U). Therefore, understanding its composition and evolution provides insight into how continents have formed, evolved, and interacted with the hydrosphere. New major and trace element compositions of >100 glacial diamictites and >100 Archean shales, plus δ7Li and δ18O for a subset of these samples, combined with data from the literature, show that the average composition of the UCC has changed through time, reflecting both the rise of atmospheric oxygen and its attendant effects on weathering, as well as the mode of crust formation and differentiation. Some changes that occur as a step function near the Archean/Proterozoic boundary (increased Th/U, decreased Mo/Pr, V/Lu) reflect the rise of oxygen at the great oxidation event (GOE) and its influence on chemical weathering signatures in the UCC. Other changes are more gradual with time (e.g., higher Th/Sc and δ18O, lower Ni/Co, La/Nb, Eu/Eu* and transition metal abundances) and reflect an UCC that has transitioned from a more mafic to a more felsic bulk composition, and which experienced increased interaction with the hydrosphere with time. The gradual nature of these compositional changes likely reflects the waning heat production of the Earth, rather than an abrupt change in tectonics or style of crust formation. These more gradual changes in crust composition, which contrast with the abrupt changes associated with the GOE, suggest that a fundamental change in the nature of crust differentiation is unlikely to be responsible for the rise of atmospheric oxygen (cf. Keller and Schoene, 2012). Indeed, it appears that the opposite may be true: that the rise of oxygen has influenced crust composition (and possibly differentiation).

Relation of asphalt chemistry to physical properties and specifications.

DOT National Transportation Integrated Search

1984-01-01

This report constitutes a synthesis of published information concerning the chemical composition and characteristics of asphalt cements used in highway construction. The general relations between chemical composition and physical properties and speci...

CARBON AND OXYGEN ISOTOPIC RATIOS FOR NEARBY MIRAS

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

Hinkle, Kenneth H.; Lebzelter, Thomas; Straniero, Oscar, E-mail: khinkle@noao.edu, E-mail: thomas.lebzelter@univie.ac.at, E-mail: straniero@oa-teramo.inaf.it

2016-07-01

Carbon and oxygen isotopic ratios are reported for a sample of 46 Mira and SRa-type variable asymptotic giant branch (AGB) stars. Vibration–rotation first and second-overtone CO lines in 1.5–2.5 μ m spectra were measured to derive isotopic ratios for {sup 12}C/{sup 13}C, {sup 16}O/{sup 17}O, and {sup 16}O/{sup 18}O. Comparisons with previous measurements for individual stars and with various samples of evolved stars, as available in the extant literature, are discussed. Models for solar composition AGB stars of different initial masses are used to interpret our results. We find that the majority of M-stars have main sequence masses ≤2 Mmore » {sub ⊙} and have not experienced sizable third dredge-up (TDU) episodes. The progenitors of the four S-type stars in our sample are slightly more massive. Of the six C-stars in the sample three have clear evidence relating their origin to the occurrence of TDU. Comparisons with O-rich presolar grains from AGB stars that lived before the formation of the solar system reveal variations in the interstellar medium chemical composition. The present generation of low-mass AGB stars, as represented by our sample of long period variables (LPVs), shows a large spread of {sup 16}O/{sup 17}O ratios, similar to that of group 1 presolar grains and in agreement with theoretical expectations for the composition of mass 1.2–2 M {sub ⊙} stars after the first dredge-up. In contrast, the {sup 16}O/{sup 18}O ratios of present-day LPVs are definitely smaller than those of group 1 grains. This is most probably a consequence of the the decrease with time of the {sup 16}O/{sup 18}O ratio in the interstellar medium due to the chemical evolution of the Milky Way. One star in our sample has an O composition similar to that of group 2 presolar grains originating in an AGB star undergoing extra-mixing. This may indicate that the extra-mixing process is hampered at high metallicity, or, equivalently, favored at low metallicity. Similarly to O-rich grains, no star in our sample shows evidence of hot bottom burning, which is expected for massive AGB stars.« less

Residual glasses and melt inclusions in basalts from DSDP Legs 45 and 46 - Evidence for magma mixing. [Deep Sea Drilling Project

NASA Technical Reports Server (NTRS)

Dungan, M. A.; Rhodes, J. M.

1978-01-01

Microprobe analyses of natural glasses in basalts recovered by Legs 45 and 46 of the Deep Sea Drilling Project are reported and interpreted in the context of other geochemical, petrographic and experimental data on the same rocks (Rhodes et al., 1978). Residual glass compositions in the moderately evolved aphyritic and abundantly phyric basalts within each site indicate that none of the units is related to any other or to a common parent by simple fractional crystallization. The compositional trends, extensive disequilibrium textures in the plagioclase phenocrysts and the presence in evolved lavas of refractory plagioclase and olivine phenocrysts bearing primitive melt inclusions provide evidence that magma mixing had a major role in the genesis of the Leg 45 and 46 basalts. The magma parental to these basalts was most likely characterized by high Mg/(Mg + Fe/+2/), CaO/Al2O3, CaO/Na2O and low lithophile concentrations. A mixing model involving incremental enrichment of magmaphile elements by repeated episodes of mixing of relatively primitive and moderately evolved magmas, followed by a small amount of fractionation is consistent with the characteristics of the basalts studied.

PHILIS (PORTABLE HIGH-THROUGHPUT INTEGRATED LABORATORY IDENTIFICATION SYSTEM)

EPA Pesticide Factsheets

These mobile laboratory assets, for the on-site analysis of chemical warfare agent (CWA) and toxic industrial compound (TIC) contaminated environmental samples, are part of the evolving Environmental Response Laboratory Network (ERLN).

Adaptive Correction from Virtually Complex Dynamic Libraries: The Role of Noncovalent Interactions in Structural Selection and Folding.

PubMed

Lafuente, Maria; Atcher, Joan; Solà, Jordi; Alfonso, Ignacio

2015-11-16

The hierarchical self-assembling of complex molecular systems is dictated by the chemical and structural information stored in their components. This information can be expressed through an adaptive process that determines the structurally fittest assembly under given environmental conditions. We have set up complex disulfide-based dynamic covalent libraries of chemically and topologically diverse pseudopeptidic compounds. We show how the reaction evolves from very complex mixtures at short reaction times to the almost exclusive formation of a major compound, through the establishment of intramolecular noncovalent interactions. Our experiments demonstrate that the systems evolve through error-check and error-correction processes. The nature of these interactions, the importance of the folding and the effects of the environment are also discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The use of kerogen data in understanding the properties and evolution of interstellar carbonaceous dust

NASA Astrophysics Data System (ADS)

Papoular, R.

2001-11-01

A number of authors have, in the past decade, pointed to the similarity of the 3.4-mu m band of kerogen with that of the Galactic Centre (GC). Kerogen is a family of solid terrestrial sedimentary materials essentially made of C, H and O interlocked in a disordered, more or less aliphatic, structure. Here, the most recent results of the astronomical literature and the rich quantitative geochemical literature are tapped with two purposes in mind: extend the analogy to the mid-IR bands and, based on these new constraints, quantitatively assess the properties of the carrier dust. It is shown that the great diversity of IR astronomical IS (interstellar) dust is paralleled by the changes in kerogen spectra as the material spontaneously and continuously evolves (aromatizes) in the earth. Since the composition and structure of kerogen are known all along its evolution, it is possible, by spectral analogy, to estimate these properties for the corresponding astronomical carriers. The Galactic Centre 3.4 mu m feature is thus found to correspond to an early stage of evolution, for which the composition in C, H and O and the structure of the corresponding kerogen are known and reported here. The role of oxygen in the subsequent evolution and its contribution to different bands are stressed. The above provides new arguments in favour of the 3.4-mu m band, as well as the observed accompanying mid-IR bands, being carried by kerogen-like dust born in CS (circumstellar) envelopes, mostly of AGB (asymptotic giant branch) objects. Subsequent dust evolution in composition and structure (aromatization) is fast enough that the unidentified infrared bands can already show up in well-developed planetary nebulae (PNe), as observed. A fraction of incompletely evolved dust can escape into the diffuse IS medium and molecular clouds. As a consequence, aliphatic and aromatic features can both be detected in the sky, in emission (Proto-PNe, PNe and PDRs (photo-dissociation regions)) as well as in absorption (dense molecular clouds and diffuse ISM). Changes in wavelength and band width with line of sight are explained by changes in the nature and number of chemical functional groups composing the carrier material. Predictions of the kerogen model in the UV and far IR are proposed for testing.

The Exobiological Role of Interstellar Polycyclic Aromatic Hydrocarbons and Ices

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; DeVincenzi, Donald (Technical Monitor)

2002-01-01

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Before this time, the composition of interstellar dust was largely guessed-at, the presence of ices in interstellar clouds ignored, and the notion that large, gas phase, carbon rich molecules might be abundant and widespread throughout the interstellar medium (ISM) considered impossible. Today, the composition of dust in the ISM is reasonably well constrained to micron-sized cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. Shrouded within the protective confines of cold, opaque molecular clouds--the birthplace of stars and planets--these cold dust particles secrete mantles of mixed molecular ices whose compositions are also well constrained. Finally, amidst the molecular inventory of these ice mantles are likely to be found polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by the standards of interstellar chemistry, the telltale infrared spectral signature of which is now recognized throughout the Universe. In the first part of this talk, we will review the spectroscopic evidence that forms the basis for the currently accepted abundance and ubiquity of PANs in the ISM. We will then look at a few specific examples which illustrate how experimental and theoretical data can be applied to interpret the interstellar spectra and track how the PAN population evolves as it passes from its formation site in the circumstellar outflows of dying stars, through the various phases of the ISM, and into forniing planetary systems. Nevertheless, despite the fact that PANs likely represent the single largest molecular reservoir of organic carbon in evolving planetary systems, they are not what would be considered "biogenic" molecules. Although interesting from a chemical and astrophysical standpoint, in the absence of a mechanism by which this population can be dislodged from the precipitous thermodynamic well afforded by their extensive aromatic networks, they are of little Astrobiological significance. Consequently, for the remainder of the talk, we will consider the photochemical evolution of PANS under conditions similar to those found in the ISM and in proto-planetary systems with an eye toward means by which this rich repository of pre-biotic organic "ore" might be converted into materials of greater importance to Astrobiology.

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

USGS Publications Warehouse

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

2016-01-01

Despite claims to the contrary, the compositions of magnetite and ilmenite in the Bishop Tuff correctly record the changing conditions of T and fO2 in the magma reservoir. In relatively reduced (∆NNO < 1) siliceous magmas (e.g., Bishop Tuff, Taupo units), Ti behaves compatibly (DTi ≈ 2-3.5), leading to a decrease in TiO2 activity in the melt with cooling and fractionation. In contrast, FeTi-oxides are poorer in TiO2 in more oxidized magmas (∆NNO > 1, e.g., Fish Canyon Tuff, Pinatubo), and the d(aTiO2)/dT slope can be negative. Biotite, FeTi-oxides, liquid, and possibly plagioclase largely maintained equilibrium in the Bishop Tuff magma (unlike the pyroxenes, and cores of quartz, sanidine, and zircon) prior ro and during a mixing event triggered by a deeper recharge, which, based on elemental diffusion profiles in minerals, took place at least several decades before eruption. Equilibrating phases and pumice compositions show evolving chemical variations that correlate well with mutually consistent temperatures based on the FeTi-oxides, sanidine-plagioclase, and ∆18O quartz-magnetite pairs. Early Bishop Tuff (EBT) temperatures are lower (700 to ~780‎°C) than temperatures (780 to >820°C) registered in Late Bishop Tuff (LBT), the latter defined here not strictly stratigraphically, but by the presence of orthopyroxene and reverse-zoned rims on quartz and sanidine. The claimed similarity in compositions, Zr-saturation temperatures and thermodynamically calculated temperatures (730-740°C) between EBT and less evolved LBT reflect the use of glass inclusions in quartz cores in LBT that were inherited from the low temperature rhyolitic part of the reservoir characteristic of the EBT. LBT temperatures as high as 820°C, the preservation of orthopyroxene, and the presence of reverse-zoned minerals (quartz, sanidine, zircons) are consistent with magma recharge at the base of the zoned reservoir, heating the cooler rhyolitic melt, partly remelting cumulate mush, and introducing enough CO2 (0.4-1.4 wt%, mostly contained in the exsolved fluid phase) to significantly lower H2O-activity in the system.

Petrogenesis of KREEP

NASA Technical Reports Server (NTRS)

Mckay, G. A.; Weill, D. F.

1975-01-01

Solid/liquid distribution coefficients (weight basis) were experimentally determined for a number of trace elements for olivine, orthopyroxene, plagioclase and ilmenite. Values of distribution coefficients were measured at 1200 C and a f sub O2 of 10 to the -13.0 power for liquids similar in composition to the olivine-opx-plagioclase peritectic in the pseudoternary system (Fe,Mg)2SiO4-CaAl2Si2O8-SiO2. Values were also measured at 1140 C and a f sub O2 of 10 to the -12.8 power for liquids similar in composition to high-Ti mare basalts. Major and trace element partitioning and relevant phase equilibria were used to investigate possible parent-daughter relationships between a number of highland samples and highly evolved KREEP-rich materials. Out of about 80 highlands samples tested, 33 were found to be possible parents to the KREEP-rich materials. The average composition of these samples is very similar to that of the Low-K Fra Mauro basalt (LKFM). A model is proposed to explain the production of LKFM-type material and more evolved members of the KREEP suite.

Adaptive strain prompting a pseudo-morphotropic phase boundary in ferroelectric (1-x ) Na0.5Bi0.5TiO3-x BaTiO3

NASA Astrophysics Data System (ADS)

Datta, K.; Neder, R. B.; Richter, A.; Göbbels, M.; Neuefeind, J. C.; Mihailova, B.

2018-05-01

The understanding of the atomistic origin of the morphotropic phase boundary (MPB) occurring in composition-temperature phase diagrams of ferroelectric solid solutions is a key topic in material science because materials often exhibit anomalous properties at the MPB. Here we reveal mesoscopic-scale structural correlations for a leading Pb-free ferroelectric system, (1 -x ) Na0.5Bi0.5TiO3-x BaTiO3 (NBT-x BT ), by examining atomic pair distribution functions and Raman scattering data at ambient conditions. We demonstrate that the amplification of the piezoelectric properties of NBT-x BT at the MPB are predominantly driven by an easy switchability resulting from a progressive decoupling between strain and polarization as the Ba content increases from zero to the critical MPB composition. It was observed that as Ba content increases towards MPB, competing local correlations, such as A-site chemical order, antiferrodistortive correlations of correlated BO6 tilts, and antipolar Bi shifts, are reduced, which in turn renders favorable conditions for easy switching of local dipoles under external fields. In addition, the evolving characteristics of the atomic dynamics as a function of composition suggest that the local potential functions of the cations are not completely flat at the MPB. Altogether, our results reveal atomistic mechanisms responsible for the observed elevated MPB properties in the case of NBT-x BT which imply that the so-called MPB of NBT-x BT should not be categorized as originally introduced for Pb-containing solid solutions.

Insights into the evolution of an alkaline magmatic system: An in situ trace element study of clinopyroxenes from the Ditrău Alkaline Massif, Romania

NASA Astrophysics Data System (ADS)

Batki, Anikó; Pál-Molnár, Elemér; Jankovics, M. Éva; Kerr, Andrew C.; Kiss, Balázs; Markl, Gregor; Heincz, Adrián; Harangi, Szabolcs

2018-02-01

Clinopyroxene is a major constituent in most igneous rock types (hornblendite, diorite, syenite, nepheline syenite, camptonite, tinguaite and ijolite) of the Ditrău Alkaline Massif, Eastern Carpathians, Romania. Phenocryst and antecryst populations have been distinguished based on mineral zoning patterns and geochemical characteristics. Major and trace element compositions of clinopyroxenes reflect three dominant pyroxene types including primitive high-Cr Fe-diopside, intermediate Na-diopside-hedenbergite and evolved high-Zr aegirine-augite. Clinopyroxenes record two major magma sources as well as distinct magma evolution trends. The primitive diopside population is derived from an early camptonitic magma related to basanitic parental melts, whilst the intermediate diopside-hedenbergite crystals represent a Na-, Nb- and Zr-rich magma source recognised for the first time in the Ditrău magmatic system. This magma fractionated towards ijolitic and later phonolitic compositions. Field observations, petrography and clinopyroxene-melt equilibrium calculations reveal magma recharge and mingling, pyroxene recycling, fractional crystallisation and accumulation. Repeated recharge events of the two principal magmas resulted in multiple interactions between more primitive and more fractionated co-existing magma batches. Magma mingling occurred between mafic and felsic magmas by injection of ijolitic magma into fissures (dykes) containing phonolitic (tinguaite) magma. This study shows that antecryst recycling, also described for the first time in Ditrău, is a significant process during magma recharge and demonstrates that incorporated crystals can crucially affect the host magma composition and so whole-rock chemical data should be interpreted with great care.

Rotation and magnetism in intermediate-mass stars

NASA Astrophysics Data System (ADS)

Quentin, Léo G.; Tout, Christopher A.

2018-06-01

Rotation and magnetism are increasingly recognized as important phenomena in stellar evolution. Surface magnetic fields from a few to 20 000 G have been observed and models have suggested that magnetohydrodynamic transport of angular momentum and chemical composition could explain the peculiar composition of some stars. Stellar remnants such as white dwarfs have been observed with fields from a few to more than 109 G. We investigate the origin of and the evolution, on thermal and nuclear rather than dynamical time-scales, of an averaged large-scale magnetic field throughout a star's life and its coupling to stellar rotation. Large-scale magnetic fields sustained until late stages of stellar evolution with conservation of magnetic flux could explain the very high fields observed in white dwarfs. We include these effects in the Cambridge stellar evolution code using three time-dependant advection-diffusion equations coupled to the structural and composition equations of stars to model the evolution of angular momentum and the two components of the magnetic field. We present the evolution in various cases for a 3 M_{⊙} star from the beginning to the late stages of its life. Our particular model assumes that turbulent motions, including convection, favour small-scale field at the expense of large-scale field. As a result, the large-scale field concentrates in radiative zones of the star and so is exchanged between the core and the envelope of the star as it evolves. The field is sustained until the end of the asymptotic giant branch, when it concentrates in the degenerate core.

Nanopatterning dynamics on Si(100) during oblique 40-keV Ar+ erosion with metal codeposition: Morphological and compositional correlation

NASA Astrophysics Data System (ADS)

Redondo-Cubero, A.; Gago, R.; Palomares, F. J.; Mücklich, A.; Vinnichenko, M.; Vázquez, L.

2012-08-01

The formation and dynamics of nanopatterns produced on Si(100) surfaces by 40-keV Ar+ oblique (α = 60°) bombardment with concurrent Fe codeposition have been studied. Morphological and chemical analysis has been performed by ex situ atomic force microscopy, Rutherford backscattering spectrometry, x-ray photoelectron spectroscopy, and scanning and transmission electron microscopies. During irradiation, Fe atoms incorporated into the target surface react with Si to form silicides, a process enhanced at this medium-ion energy range. The silicides segregate at the nanoscale from the early irradiation stages. As the irradiation proceeds, a ripple pattern is formed without any correlation with silicide segregation. From the comparison with the pattern dynamics reported previously for metal-free conditions, it is demonstrated that the metal incorporation alters both the pattern dynamics and the morphology. Although the pattern formation and dynamics are delayed for decreasing metal content, once ripples emerge, the same qualitative pattern of morphological evolution is observed for different metal content, resulting in an asymptotic saw-tooth-like facetted surface pattern. Despite the medium ion energy employed, the nanopatterning process with concurrent Fe deposition can be explained by those mechanisms proposed for low-ion energy irradiations such as shadowing, height fluctuations, silicide formation and segregation, ensuing composition dependent sputter rate, and ion sculpting effects. In particular, the interplay between the ion irradiation and metal flux geometries, differences in sputtering rates, and the surface pattern morphology produces a dynamic compositional patterning correlated with the evolving morphological one.

A Neutral Particle Analyser Proposed On Board Bepicolombo Planetary Orbiter: Serena (searching For Exospheric Refilling and Emitted Neutral Abundances)

NASA Astrophysics Data System (ADS)

Orsini, S.; Npa-Serena Team

The Neutral Particle Analyser SERENA, proposed on board the BepiColombo Mer- cury Planetary Orbiter (MPO), has the purpose of investigating the Hermean exo- spheric and energetic neutral populations. Local and detailed analysis of the exo- spheric composition will be performed by a ram-pointing sensor (MAIA), while en- ergetic neutrals produced through sputtering and charge-exchange processes will be collected by two nadir-pointing sensors (L-ENA, MH-ENA). A central problem in the understanding of the evolution of solar system bodies is the role played by the so- lar wind, solar radiation and micro-meteorite bombardment in controlling mass losses. The direct in situ detection of the Hermean exosphere, the gas evolving from the planet as a product of the different physical processes acting onto the surface, is of crucial importance to understand the past and present evolution of the crust. Current knowl- edge of the origin and evolution of the solar system is based on detailed measurement of chemical, elemental, and isotopic composition of matter. The proposed instrument suite is unique in its capability to perform quantitative analysis and resolve exospheric gas composition under all these three aspects. The value of neutral particles mea- surements for getting a comprehensive picture of the solar wind-planets interaction has been appreciated since the late eighties. Comparison of the measurements in the Mercury environment with those achieved by neutral particle imagers already flying around Earth (IMAGE), Mars (Mars Express), Jupiter and Saturn (Cassini) will allow comparative investigations of evolution and dynamics of planetary magnetospheres.

First determination of dissolved volatiles in magmas of Mt Garet (Vanuatu arc). Origin of sulfur emissions

NASA Astrophysics Data System (ADS)

Floury, P.; Metrich, N.; Bertagnini, A.; Garaebiti, E.; Hidalgo, S.; Beaumais, A.; Neuville, D.

2012-12-01

Mt Garet, on Gaua island, is one of the active volcanoes of the Vanuatu arc in the Southwest Pacific. This 360 m high cone emerges from the lake Letas in the summit caldera of a composite volcano. Since 1962, Mt Garet produced ash and gas plumes recurrently, the last explosive events being documented in 2009 - 2010. Airborne measurements of SO2 emission rates, the only data set presently available for this volcano, were realized in 2009 and revealed a high SO2 flux of, on average, 2955 tons per day [1]. We report here the very first data on the geochemistry of the scoriae emitted in January 2010, together with analyses of major elements and volatiles (H2O, Cl, S) in crystal-hosted melt inclusions and a detailed mineralogy of the samples. The 2010 scoriae are basaltic-andesites and are more evolved that the pre-1962 basaltic lava flows of Mt Garet. Their major and trace element evolution cannot be reconciled with a single process of fractional crystallization, but suggest mixing between a pre-1962 like basalt and an evolved trachydacitic end-member. This observation strongly suggests the recent development of a small reservoir beneath Mt Garet. The plagioclases (An89-73) and clinopyroxenes (Fs5-16) display a significant chemical range but do not clearly evidence reverse zoning. The paragenesis is complemented by Fe-Ti oxides (USP39-40) and scarce olivines (Fo72.7). Some crystals are obviously inherited (e.g., An-poor plagioclase). The melt inclusions are ubiquitous but of small size in each mineral phase. Their H2O content was specifically determined using micro-Raman spectroscopy (IPGP), with a series of basaltic glass standards previously developed for Raman calibration [2]. Data and spectrum are treated following [3]. As a whole melt inclusion compositions cover the whole chemical spectrum from basalt to trachydacite. Their contents in H2O (2.7-0.8 wt%), S (1570 - <100 ppm), and Cl (2800-950 ppm) widely vary. Volatile-rich basaltic inclusions are found in clinopyroxenes whereas plagioclases preserved only strongly degassed residual melts with the composition of the glassy matrices. Combining all the data on bulk rocks, minerals and their melt inclusions we propose that the high SO2 fluxes in 2009 testify to the degassing of basaltic magma batches which repeatedly invaded the shallow reservoir. This basaltic magma mixed with the residual trachydacite, in proportions ~ 80:20, to produce the hybrid basaltic andesite which was erupted. This scenario would require a multi-step degassing, with exsolution of an early gas phase rich in H2O and S. The 2010 scoriae illustrate very dynamic processes of degassing and crystallization. [1] Bani et al., (2012), Journal of Volcanology and Geothermal Research, 211-212, 36-46 [2] Mercier et al., (2009) and (2010), Geochimica et Cosmochimica Acta 73, 197-21; and 74, 5461-5656 [3] Le Losq et al (2012), American Mineralogist 97, 779-790

Sampling and physico-chemical analysis of precipitation: a review.

PubMed

Krupa, Sagar V

2002-01-01

Wet deposition is one of two processes governing the transfer of beneficial and toxic chemicals from the atmosphere on to surfaces. Since the early 1970s, numerous investigators have sampled and analyzed precipitation for their chemical constituents, in the context of "acidic rain" and related atmospheric processes. Since then, significant advances have been made in our understanding of how to sample rain, cloud and fog water to preserve their physico-chemical integrity prior to analyses. Since the 1970s large-scale precipitation sampling networks have been in operation to broadly address regional and multi-regional issues. However, in examining the results from such efforts at a site-specific level, concerns have been raised about the accuracy and precision of the information gathered. There is mounting evidence to demonstrate the instability of precipitation samples (e.g. with N species) that have been subjected to prolonged ambient or field conditions. At the present time precipitation sampling procedures allow unrefrigerated or refrigerated collection of wet deposition from individual events, sequential fractions within events, in situ continuous chemical analyses in the field and even sampling of single or individual rain, cloud and fog droplets. Similarly analytical procedures of precipitation composition have advanced from time-consuming methods to rapid and simultaneous analyses of major anions and cations, from bulk samples to single droplets. For example, analytical techniques have evolved from colorimetry to ion chromatography to capillary electrophoresis. Overall, these advances allow a better understanding of heterogeneous reactions and atmospheric pollutant scavenging processes by precipitation. In addition, from an environmental perspective, these advances allow better quantification of semi-labile (e.g. NH4+, frequently its deposition values are underestimated) or labile species [e.g. S (IV)] in precipitation and measurements of toxic chemicals such as Hg and PCBs (polychlorinated biphenyls). Similarly, methods now exist for source-receptor studies, using for example, the characterization of reduced elemental states and/or the use of stable isotopes in precipitation as tracers. Future studies on the relationship between atmospheric deposition and environmental impacts must exploit these advances. This review provides a comprehensive and comparative treatment of the state of the art sampling methods of precipitation and its physico-chemical analysis.