CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

DOE PAGES

Mei, Yuan; Liu, Weihua; Migdiov, A. A.; ...

2018-05-02

We invesmore » tigated the hydration of the CuCl 0 complex in HCl-bearing water vapor at 350°C and a vapor-like fluid density between 0.02 and 0.09 g/cm 3 using ab initio molecular dynamics (MD) simulations. The simulations reveal that one water molecule is strongly bonded to Cu(I) (first coordination shell), forming a linear [H 2O-Cu-Cl] 0 moiety. The second hydration shell is highly dynamic in nature, and individual configurations have short life-spans in such low-density vapors, resulting in large fluctuations in instantaneous hydration numbers over a timescale of picoseconds. The average hydration number in the second shell (m) increased from ~0.5 to ~3.5 and the calculated number of hydrogen bonds per water molecule increased from 0.09 to 0.25 when fluid density (which is correlated to water activity) increased from 0.02 to 0.09 g/cm 3 ( f H 2O 1.72 to 2.05). These changes of hydration number are qualitatively consistent with previous solubility studies under similar conditions, although the absolute hydration numbers from MD were much lower than the values inferred by correlating experimental Cu fugacity with water fugacity. This could be due to the uncertainties in the MD simulations and uncertainty in the estimation of the fugacity coefficients for these highly nonideal “vapors” in the experiments. Finally, our study provides the first theoretical confirmation that beyond-first-shell hydrated metal complexes play an important role in metal transport in low-density hydrothermal fluids, even if it is highly disordered and dynamic in nature.« less

Evaluation of the Propensity of Niobium to Absorb Hydrogen During Fabrication of Superconducting Radio Frequency Cavities for Particle Accelerators

PubMed Central

Ricker, R. E.; Myneni, G. R.

2010-01-01

During the fabrication of niobium superconducting radio frequency (SRF) particle accelerator cavities procedures are used that chemically or mechanically remove the passivating surface film of niobium pentoxide (Nb2O5). Removal of this film will expose the underlying niobium metal and allow it to react with the processing environment. If these reactions produce hydrogen at sufficient concentrations and rates, then hydrogen will be absorbed and diffuse into the metal. High hydrogen activities could result in supersaturation and the nucleation of hydride phases. If the metal repassivates at the conclusion of the processing step and the passive film blocks hydrogen egress, then the absorbed hydrogen or hydrides could be retained and alter the performance of the metal during subsequent processing steps or in-service. This report examines the feasibility of this hypothesis by first identifying the postulated events, conditions, and reactions and then determining if each is consistent with accepted scientific principles, literature, and data. Established precedent for similar events in other systems was found in the scientific literature and thermodynamic analysis found that the postulated reactions were not only energetically favorable, but produced large driving forces. The hydrogen activity or fugacity required for the reactions to be at equilibrium was determined to indicate the propensity for hydrogen evolution, absorption, and hydride nucleation. The influence of processing conditions and kinetics on the proximity of hydrogen surface coverage to these theoretical values is discussed. This examination found that the hypothesis of hydrogen absorption during SRF processing is consistent with published scientific literature and thermodynamic principles. PMID:27134791

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

NASA Technical Reports Server (NTRS)

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

2015-01-01

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

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

ERIC Educational Resources Information Center

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

2013-01-01

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

Control and monitoring of oxygen fugacity in piston cylinder experiments

NASA Astrophysics Data System (ADS)

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

2015-01-01

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

A simple thermodynamic model useful for calculating gas solubilities in water/brine/hydrocarbon mixtures from 0 to 250 C and 1 to 150 bars

NASA Astrophysics Data System (ADS)

Perez, R. J.; Shevalier, M.; Hutcheon, I.

2004-05-01

Gas solubility is of considerable interest, not only for the theoretical understanding of vapor-liquid equilibria, but also due to extensive applications in combined geochemical, engineering, and environmental problems, such as greenhouse gas sequestration. Reliable models for gas solubility calculations in salt waters and hydrocarbons are also valuable when evaluating fluid inclusions saturated with gas components. We have modeled the solubility of methane, ethane, hydrogen, carbon dioxide, hydrogen sulfide, and five other gases in a water-brine-hydrocarbon system by solving a non-linear system of equations composed by modified Henry's Law Constants (HLC), gas fugacities, and assuming binary mixtures. HLCs are a function of pressure, temperature, brine salinity, and hydrocarbon density. Experimental data of vapor pressures and mutual solubilities of binary mixtures provide the basis for the calibration of the proposed model. It is demonstrated that, by using the Setchenow equation, only a relatively simple modification of the pure water model is required to assess the solubility of gases in brine solutions. Henry's Law constants for gases in hydrocarbons are derived using regular solution theory and Ostwald coefficients available from the literature. We present a set of two-parameter polynomial expressions, which allow simple computation and formulation of the model. Our calculations show that solubility predictions using modified HLCs are acceptable within 0 to 250 C, 1 to 150 bars, salinity up to 5 molar, and gas concentrations up to 4 molar. Our model is currently being used in the IEA Weyburn CO2 monitoring and storage project.

The color of meteoritic hibonite - an indicator of oxygen fugacity

NASA Astrophysics Data System (ADS)

Ihinger, P. D.; Stolper, E.

1986-05-01

Hibonites similar in composition to those found in Ca-Al-rich inclusions change color from blue, to green, to orange, to nearly colorless as oxygen fugacity is increased at high temperature from below the iron-wustite buffer up to air. The development of the blue color is correlated with the growth of an absorption band at 715 nm in the optical spectra of the hibonites as the oxygen fugacity is reduced. The growth of this band is attributed to the increasing concentration of Ti(3+) in these hibonites with decreasing oxygen fugacity. The blue hibonites in meteorites reflect equilibration under reducing conditions based on the intensity of 715 nm band, it is estimated that the hibonite in the Blue Angel inclusion indicates an oxygen fugacity four to five orders of magnitude more oxidizing than that expected in the early solar nebula. This may be due to formation in an anomalously oxidizing region of the nebula or to oxidation during cooling or later alteration. The orange hibonites in Allende reflect oxygen fugacities approximately ten or more orders of magnitude more oxidizing than the expected primitive nebula; this color probably indicates alteration of initially more reduced (blue?) hibonites. The colorless hibonite in the HAL inclusion reflects highly oxidizing conditions and/or its low Ti content.

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

NASA Astrophysics Data System (ADS)

Jakobsson, Sigurdur; Blundy, Jon; Moore, Gordon

2014-06-01

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

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

PubMed

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

2016-08-16

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

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

PubMed

van Noort, Paul C M

2009-06-01

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

Diffusivity of hydrogen in iron-bearing olivine at 3 GPa

NASA Astrophysics Data System (ADS)

Demouchy, Sylvie; Thoraval, Catherine; Bolfan-Casanova, Nathalie; Manthilake, Geeth

2016-11-01

The kinetics of hydrogenation of dry iron-bearing olivine single crystals was determined by performing hydration experiments under hydrothermal conditions at high pressure. The experiments were performed in a multi-anvil press at 3 GPa, for a temperature range between 900 and 1200 °C and for various durations. The oxygen fugacity was buffered along Ni-NiO joint. Polarized Fourier transform infrared spectroscopy and recent empirical calibration were used to quantify the hydroxyl distributions in the samples along crystallographic axes after the experiments. The chemical diffusion coefficients are similar (barely slower) than in olivine hydrated at lower pressure (0.2 and 0.3 GPa) for the same diffusion mechanism. Under the given experimental conditions, the anisotropy of diffusion is the same as for proton-vacancy mechanism, with diffusion along the [0 0 1] axis faster than along the [1 0 0]. However, the anisotropy at 3 GPa is weaker compared to measurements at lower pressures and the analysis of concentration profiles using 3D models shows that an isotropic solution could also be relevant. Fits of the diffusion data to an Arrhenius law yield activation energies for the slightly faster [0 0 1] axis of the crystallographic axes around 198 ± 5 kJ mol-1, a value only slightly lower than the results from previous experimental studies for natural iron-bearing olivine hydrogenated at lower confining pressure. At 3 GPa, hydrogenation can be well approximated by a single mechanism controlled by coupled diffusion of protons and octahedral vacancies (di- and tri-valent ions). The diffusion rates are fast enough to alter hydrogen concentration within olivine in xenoliths ascending from the mantle or experiencing hydrogen-rich metasomatism events, but too slow to permit complete homogenization of hydrogen in olivine-rich rocks at kilometer scale in less than one My.

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

NASA Astrophysics Data System (ADS)

Miyamoto, M.; Mikouchi, T.

1996-08-01

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

Anionic Pt in Silicate Melts at Low Oxygen Fugacity: Speciation, Partitioning and Implications for Core Formation Processes on Asteroids

NASA Technical Reports Server (NTRS)

Medard, E.; Martin, A. M.; Righter, K.; Malouta, A.; Lee, C.-T.

2017-01-01

Most siderophile element concentrations in planetary mantles can be explained by metal/ silicate equilibration at high temperature and pressure during core formation. Highly siderophile elements (HSE = Au, Re, and the Pt-group elements), however, usually have higher mantle abundances than predicted by partitioning models, suggesting that their concentrations have been set by late accretion of material that did not equilibrate with the core. The partitioning of HSE at the low oxygen fugacities relevant for core formation is however poorly constrained due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variables like temperature, pressure, and oxygen fugacity. To better understand the relative roles of metal/silicate partitioning and late accretion, we performed a self-consistent set of experiments that parameterizes the influence of oxygen fugacity, temperature and melt composition on the partitioning of Pt, one of the HSE, between metal and silicate melts. The major outcome of this project is the fact that Pt dissolves in an anionic form in silicate melts, causing a dependence of partitioning on oxygen fugacity opposite to that reported in previous studies.

Redox States of Initial Atmospheres Outgassed on Rocky Planets and Planetesimals

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

Schaefer, Laura; Fegley, Bruce Jr., E-mail: lschaefer@asu.edu

2017-07-10

The Earth and other rocky planets and planetesimals in the solar system formed through the mixing of materials from various radial locations in the solar nebula. This primordial material likely had a range of oxidation states as well as bulk compositions and volatile abundances. We investigate the oxygen fugacity produced by the outgassing of mixtures of solid meteoritic material, which approximate the primitive nebular materials. We find that the gas composition and oxygen fugacity of binary and ternary mixtures of meteoritic materials vary depending on the proportion of reduced versus oxidized material, and also find that mixtures using differentiated materialsmore » do not show the same oxygen fugacity trends as those using similarly reduced but undifferentiated materials. We also find that simply mixing the gases produced by individual meteoritic materials together does not correctly reproduce the gas composition or oxygen fugacity of the binary and ternary mixtures. We provide tabulated fits for the oxygen fugacities of all of the individual materials and binary mixtures that we investigate. These values may be useful in planetary formation models, models of volatile transport on planetesimals or meteorite parent bodies, or models of trace element partitioning during metal-silicate fractionation.« less

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

USGS Publications Warehouse

Sanford, R.F.

1982-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Reports of investigations on: Derivation of an infinite-dilution activity coefficient model and application to two-component vapor/liquid equilibria data: Final report

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

Roper, V.P.; Kobayashi, R.

1988-02-01

Infinite-dilution fugacity coefficients were obtained for the system fluorene/phenanthrene at thirteen temperatures by fitting total pressure across the entire mole fraction range by a computer routine. A thermodynamically consistent routine, that allowed for both positive and negative pressure deviations from the ideal values, was used to correlate data over the full mole fraction range from 0 to 1. The four-suffix Margules activity coefficient model without modification essentially served this purpose since total pressures and total pressure derivatives with respect to mole fraction were negligible compared to pressure measurement precision. The water/ethanol system and binary systems comprised of aniline, chlorobenzene, acetonitrilemore » and other polar compounds were fit for total pressure across the entire mole fraction range for binary Vapor-Liquid-Equilbria (VLE) using the rigorous, thermodynamically consistent Gibbs-Duhem Relation derived by Ibl and Dodge. Data correlation was performed using a computer least squares procedure. Infinite-dilution fugacity coefficients were obtained using a modified Margules activity coefficient model.« less

Fugacity ratio estimations for high-melting rigid aromatic compounds.

PubMed

Van Noort, Paul C M

2004-07-01

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

Speciation and dissolution of hydrogen in the proto-lunar disk

NASA Astrophysics Data System (ADS)

Pahlevan, Kaveh; Karato, Shun-ichiro; Fegley, Bruce

2016-07-01

Despite very high temperatures accompanying lunar origin, indigenous water in the form of OH has been unambiguously observed in Apollo samples in recent years. Such observations have prompted questions about the abundance and distribution of lunar hydrogen. Here, we investigate the related question of the origin of lunar H: is the hydrogen observed a remnant of a much larger initial inventory that was inherited from a ;wet; Earth but partly depleted during the process of origin, or was primordial hydrogen quantitatively lost from the lunar material, with water being delivered to lunar reservoirs via subsequent impacts after the origins sequence? Motivated by recent results pointing to a limited extent of hydrogen escape from the gravity field of the Earth during lunar origin, we apply a newly developed thermodynamic model of liquid-vapor silicates to the proto-lunar disk to interrogate the behavior of H as a trace element in the energetic aftermath of the giant impact. We find that: (1) pre-existing H-bearing molecules are rapidly dissociated at the temperatures considered (3100-4200 K) and vaporized hydrogen predominantly exists as OH(v), H(v) and MgOH(v) for nearly the full range of thermal states encountered in the proto-lunar disk, (2) despite such a diversity in the vapor speciation - which reduces the water fugacity and favors hydrogen exsolution from co-existing liquids - the equilibration of the vapor atmosphere with the disk liquid results in significant dissolution of H into proto-lunar magmas, and (3) equilibrium H isotopic fractionation in this setting is limited to <10 per mil and the ;terrestrial; character of lunar D/H recently inferred should extend to such a precision if liquid-vapor equilibration in the proto-lunar disk is the process that gave rise to lunar hydrogen. Taken together, these results implicate dissolution as the process responsible for establishing lunar H abundances.

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

PubMed

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

2013-01-03

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

Experimental Constraints on the Cr Content, Oxygen Fugacity, and Petrogenesis of EETA79001 Lithology A

NASA Technical Reports Server (NTRS)

Herd, C. D. K.; Jones, J. H.; Papike, J. J.

2000-01-01

Experiments involving the composition of the groundmass of EETA79001 Lithology A constrain the Cr content of the melt and the oxygen fugacity, and suggest that overgrowth of olivine and pyroxene from the groundmass onto xenocrysts has occurred.

Evaluation of triclosan and triclocarban at river basin scale using monitoring and modeling tools: implications for controlling of urban domestic sewage discharge.

PubMed

Zhao, Jian-Liang; Zhang, Qian-Qian; Chen, Feng; Wang, Li; Ying, Guang-Guo; Liu, You-Sheng; Yang, Bin; Zhou, Li-Jun; Liu, Shan; Su, Hao-Chang; Zhang, Rui-Quan

2013-01-01

Triclosan (TCS) and triclocarban (TCC) are two commonly used personal care products. They may enter into aquatic environments after consumption and pose potential risks to aquatic organisms. We investigated the occurrence and fate of TCS and TCC in five large rivers (the Liao River, Hai River, Yellow River, Zhujiang River and Dongjiang River) in China, and compared the monitoring data with the predicted results from Level III fugacity modeling. TCS and TCC were detected in the five large rivers with the detection frequencies of 100% or close to 100% in surface water and sediments of almost every river. TCS and TCC were found at concentrations of up to 478 ng/L and 338 ng/L in surface water, and up to 1329 ng/g and 2723 ng/g in sediments. Cluster analysis indicated that the sites with higher concentrations were usually located in or near urban area. Meanwhile, principal component analysis also suggested that the mass inventories of TCS and TCC in water and sediment were significantly influenced by the factors such as the total or untreated urban domestic sewage discharge at river basin scale. The concentrations and mass inventories from the fugacity modeling were found at the same order of magnitude with the measured values, suggesting that the fugacity modeling can provide a useful tool for evaluating the fate of TCS and TCC in riverine environments. Both monitoring and modeling results indicated that the majority of mass inventories of TCS and TCC were stored into sediment, which could be a potential pollution source for river water. The wide presence of TCS and TCC in these large rivers of China implies that better controlling of urban domestic sewage discharge is needed. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2000-01-01

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

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

USDA-ARS?s Scientific Manuscript database

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

Waiting for O2

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

Hydrogen System Component Validation | Hydrogen and Fuel Cells | NREL

Science.gov Websites

Meeting (June 2017) Hydrogen Component Validation: 2016 Annual Progress Report, Danny Terlip, Excerpt from the 2016 DOE Annual Progress Report (February 2017) Hydrogen Component Validation: 2016 Annual Merit Transportation Decisions, NREL Fact Sheet (June 2016) Hydrogen Component Validation: 2015 Annual Progress Report

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

PubMed

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

2016-06-09

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

The distribution of chromium among orthopyroxene, spinel and silicate liquid at atmospheric pressure

NASA Technical Reports Server (NTRS)

Barnes, S. J.

1986-01-01

The Cr distributions for a synthetic silicate melt equilibrated with bronzitic orthopyroxene and chromite spinel between 1334 and 1151 C over a range of oxygen fugacities between the nickel-nickel oxide and iron-wuestite buffers are studied. The occurrence, chemical composition, and structure of the orthopyroxene-silicate melt and the spinel-silicate melt are described. It is observed that the Cr content between bronzite and the melt increases with falling temperature along a given oxygen buffer and decreases with falling oxygen fugacity at a given temperature; however, the Cr content of the melt in equilibrium with spinel decreases with falling temperature and increases with lower oxygen fugacity.

SNC Oxygen Fugacity Recorded in Pyroxenes and its Implications for the Oxidation State of the Martian Interior: An Experimental and Analytical Study

NASA Technical Reports Server (NTRS)

McCanta, M. C.; Rutherford, M. J.

2003-01-01

Knowledge of the oxidation state of a magma is critical as it is one of the parameters which controls the nature and composition of the resulting crystals. In terrestrial magmatic systems, oxygen fugacity (fo2) is known to vary by over nine orders of magnitude. With variations of this magnitude, understanding the compositional differences, phase changes, and crystallization sequence variations, caused by the magma fo2, is essential in deciphering the origin of all igneous rocks. Magmatic oxidation state is of great importance in that it reflects the degree of oxidation of the source region and can provide insight into magmatic processes, such as metasomatism, degassing, and assimilation, which may have changed them. Carmichael [1991] argues that most magmas are unlikely to have their redox states altered from those of their source region. This assumption allows for estimation of the oxidation state of planetary interiors. Conversely, it is known that the fo2 of the magma can be affected by other processes, which occur outside of the source region and therefore, the oxidation state may record those too. Processes which could overprint source region fugacities include melt dehydrogenation or other volatile loss, water or melt infiltration, or assimilation of oxidized or reduced wallrock. Understanding which of these processes is responsible for the redox state of a magma can provide crucial information regarding igneous processes and other forces active in the region. The composition of the SNC basalts and their widely varying proposed oxidation states raise some interesting questions. Do the SNC meteorites have an oxidized or reduced signature? What was the oxygen fugacity of the SNC source region at the time of melt generation? Is the fugacity calculated for the various SNC samples the fugacity of the magma source region or was it overprinted by later events? Are there different oxidation states in the Martian interior or a single one? This proposal seeks to address all of these questions.

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

ERIC Educational Resources Information Center

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

2006-01-01

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

A Graphical Representation for the Fugacity of a Pure Substance

ERIC Educational Resources Information Center

Book, Neil L.; Sitton, Oliver C.

2010-01-01

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

Fugacity and concentration gradients in a gravity field

NASA Technical Reports Server (NTRS)

May, C. E.

1986-01-01

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

Diffusion of hydrogen in olivine: Implications for water in the mantle

NASA Astrophysics Data System (ADS)

Mackwell, Stephen J.; Kohlstedt, David L.

1990-04-01

To investigate the kinetics of diffusion of hydrogen in olivine, single crystals from San Carlos in Arizona have been annealed at temperatures between 800° and 1000°C under hydrothermal conditions at a confining pressure of 300 MPa. The hydrogen diffusivities were determined for the [100], [010], and [001] directions from concentration profiles for hydroxyl in the samples. These profiles were obtained from infrared spectra taken at 100-μm intervals across a thin slice which was cut from the central portion of each annealed crystal. The rate of diffusion is anisotropic, with fastest transport along the [100] axis and slowest along the [010] axis. The fit of the data to an Arrhenius law for diffusion parallel to [100] yields an activation enthalpy of 130±30 kJ/mol with a preexponential term of (6±3)×10-5 m2 s-1. For diffusion parallel to [001], as there are insufficient data to calculate the activation enthalpy for diffusion, we used the same value as that for diffusion parallel to [100] and determined a preexponential term of (5±4)×10-6 m2 s-1. The diffusion rate parallel to [010] is about 1 order of magnitude slower than along [001]. The measured diffusivities are large enough that the hydrogen content of olivine grains which are millimeters in diameter will adjust to changing environmental conditions in time scales of hours at temperatures as low as 800°C. As xenoliths ascending from the mantle remain at high temperatures (i.e., >1000°C) but experience a rapid decrease in pressure, and hence hydrogen fugacity, olivine grains may dehydrate during ascent. By comparison, slow rates of carbon diffusion (Tingle et al., 1988) suggest that carbon will not be lost from olivine during ascent. Thus, low hydrogen contents within olivine and within fluid inclusions in olivine cannot be taken as support for low water contents in the mantle.

Hydrogen isotope investigation of amphibole and glass in dacite magmas erupted in 1980-1986 and 2005 at Mount St. Helens, Washington

USGS Publications Warehouse

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

2013-01-01

In active, shallow, sub-volcanic magma conduits the extent of the dehydrogenation–oxidation reaction in amphibole phenocrysts is controlled by energetic processes that cause crystal lattice damage or conditions that increase hydrogen diffusivity in magmatic phases. Amphibole phenocrysts separated from dacitic volcanic rocks erupted from 1980 to 1986 and in 2005 at Mount St. Helens (MSH) were analyzed for δD, water content and Fe3+/Fe2+, and fragments of glassy groundmass were analyzed for δD and water content. Changes in amphibole δD values through time are evaluated within the context of carefully observed volcanic eruption behavior and published petrological and geochemical investigations. Driving forces for amphibole dehydrogenation include increase in magma oxygen fugacity, decrease in amphibole hydrogen fugacity, or both. The phenocryst amphibole (δD value c. –57‰ and 2 wt % H2O) in the white fallout pumice of the May 18, 1980 plinian eruptive phase is probably little modified during rapid magma ascent up an ∼7 km conduit. Younger volcanic rocks incorporate some shallowly degassed dacitic magma from earlier pulses, based on amphibole phenocryst populations that exhibit varying degrees of dehydrogenation. Pyroclastic rocks from explosive eruptions in June–October 1980 have elevated abundances of mottled amphibole phenocrysts (peaking in some pyroclastic rocks erupted on July 22, 1980), and extensive amphibole dehydrogenation is linked to crystal damage from vesiculation and pyroclastic fountain collapse that increased effective hydrogen diffusion in amphibole. Multiple amphibole δD populations in many 1980 pyroclastic rocks combined with their groundmass characteristics (e.g. mixed pumice textures) support models of shallow mixing prior to, or during, eruption as new, volatile-rich magma pulses blended with more oxidized, degassed magma. Amphibole dehydrogenation is quenched at the top surface of MSH dacite lava lobes, but the diversity in the δDamph populations in original fresh lava flow surfaces may occur from blending magma domains with different ascent histories in the sub-volcanic environment immediately before eruption. Multi-stage open-system magma degassing operated in each parcel of magma rising toward the surface, whereas the magma below ∼7 km was a relatively closed system, at least to the October 1986 eruption based on the large population of minimally dehydrogenated, rim-free amphibole in the lavas. Magma degassing and possibly H isotope exchange with low-δD fluids around the roof zone may have accompanied the ∼1·5 km upward migration of the 1980 magma body. The low-δDamph (c. –188 to –122‰) oxy-amphibole phenocrysts in lava spines extruded in May 2005 reflect dehydrogenation as ascending viscous magma degassed and crystallized, and fractures that admitted oxygen into the hot solidified lava spine interior facilitated additional iron oxidation.

Ocean Surface Carbon Dioxide Fugacity Observed from Space

NASA Technical Reports Server (NTRS)

Liu, W. Timothy; Xie, Xiaosu

2014-01-01

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

Solubility of copper in silicate melts as function of oxygen and sulfur fugacities, temperature, and silicate composition

NASA Astrophysics Data System (ADS)

Holzheid, A.; Lodders, K.

2001-06-01

The solubility of Cu in silicate melts coexisting with liquid Cu(Fe) metal and liquid Cu(Fe) sulfide was determined experimentally at oxygen fugacities ranging from 10 -9.1 to 10 -13.6 bar and sulfur fugacities ranging from 10 -2.5 to 10 -6.3 bar at 1300°C. An iron oxide-free silicate of anorthite-diopside eutectic composition and a synthetic MgO-rich basaltic silicate (FeO-bearing) were used in the partitioning experiments. In S-containing systems, some of the metal reacted to metal sulfide. The silicates in the four systems investigated (Fe-free and S-free; Fe-containing and S-free; Fe-free and S-containing; Fe-containing and S-containing) had different colors depending on the dissolved Cu species and the presence of iron and/or sulfur. Irrespective of the presence of sulfur, the solubility of Cu in the silicate increases with increasing oxygen fugacity and metal/silicate partition coefficients for Cu decrease. Increasing the temperature from 1300°C to 1514°C increases the Cu solubility (decreases the metal/silicate partition coefficient) at an oxygen fugacity 0.5 log units below the iron-wüstite (IW) equilibrium in the Fe-free, S-free and Fe-containing, S-free systems. We infer the presence of monovalent Cu + ("CuO 0.5") in the silicate melt on the basis of the solubility of Cu as function of oxygen fugacity. Experiments containing iron yield a formal valence of ˜0.5 for Cu at very low oxygen fugacities, which is not observed in Fe-free systems. The low formal valence is explained by redox reactions between iron and copper in the silicate melts. There is no evidence for sulfidic dissolution of Cu in the silicates but sulfur has indirect effects on Cu partitioning. Iron metal/silicate partition coefficients depend on oxygen fugacity and on sulfur fugacity. Sulfidic dissolution of iron and oxide-sulfide exchange reactions with Cu cause a small increase in Cu metal/silicate partition coefficients. We derive an activity coefficient (γ CuO 0.5) of 10 ± 1 for liquid CuO 0.5 at 1300°C for the silicate melts used here. A comparison with literature data shows that log γ CuO 0.5 increases in proportion to the mass percentages [CaO +(Al 2O 3)/2] in silicate melts. We recommend the following equations for Cu metal/silicate and sulfide/silicate partitioning for geochemical and cosmochemical modeling if silicate composition and the activity of Cu in the metal or sulfide is known: log D met/sil = -0.48 - 0.25 · log fO 2 - log γ Cu metal + 0.02 · [CaO + (Al 2O 3)/2; wt%] silicate logD sul/sil=+0.76-0.25 · logfO 2+0.25logfS 2-logγ CS 0.5,sulfide +0.02 · [CaO+Al 2O 3/2;wt%] silicate. The derived Cu metal/silicate and metal/sulfide partition coefficients are applied to core formation in the Earth and Mars. The observed Cu abundances in the Earth cannot be easily explained by simple core-mantle equilibrium, but the observed Cu abundances for Mars are consistent with core-mantle equilibrium at low pressure and temperatures.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

A long-standing puzzle in the evolution of the Earth is that while the present day upper mantle has an oxygen fugacity close to the QFM buffer, core formation during accretion would have occurred at much lower oxygen fugacities close to IW. We present a new model based on experimental evidence that normal solidification and differentiation processes in the terrestrial magma ocean may explain both core formation and the current oxygen fugacity of the mantle without resorting to a change in source material or process. A commonly made assumption is that ferric iron (Fe3+) is negligible at such low oxygen fugacities [1]. However, recent work on Fe3+/Fe2+ ratios in molten silicates [2-4] suggests that the Fe3+ content should increase at high pressure for a given oxygen fugacity. While disproportionation was not observed in these experiments, it may nonetheless be occurring in the melt at high pressure [5]. Therefore, there may be non-negligible amounts of Fe3+ formed through metal-silicate equilibration at high pressures within the magma ocean. Homogenization of the mantle and further partitioning of Fe2+/Fe3+ as the magma ocean crystallizes may explain the oxygen fugacity of the Earth's mantle without requiring additional oxidation mechanisms. We present here models using different parameterizations for the Fe2+/Fe3+ thermodynamic relationships in silicate melts to constrain the evolution of the redox state of the magma ocean as it crystallizes. The model begins with metal-silicate partitioning at high pressure to form the core and set the initial Fe3+ abundance. Combined with previous work on oxygen absorption by magma oceans due to escape of H from H2O [6], we show that the upper layers of solidifying magma oceans should be more oxidized than the lower mantle. This model also suggests that large terrestrial planets should have more oxidized mantles than small planets. From a redox perspective, no change in the composition of the Earth's accreting material needs to be invoked to explain mantle oxygen fugacity, although implications for trace elements in the Earth's core and mantle are still being explored. [1] Ringwood, AE (1979) [2] Armstrong, K et al (2016) LPSC, 2580 [3] Armstrong, K et al (2017) ACCRETE workshop [4] Zhang, HL et al (2017) GCA, 204, 83 [5] Frost, DJ et al (2004) Nature, 428, 409 [6] Schaefer, L et al (2016) ApJ, 829, 63

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

NASA Astrophysics Data System (ADS)

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

2005-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Coating for components requiring hydrogen peroxide compatibility

NASA Technical Reports Server (NTRS)

Yousefiani, Ali (Inventor)

2010-01-01

The present invention provides a heretofore-unknown use for zirconium nitride as a hydrogen peroxide compatible protective coating that was discovered to be useful to protect components that catalyze the decomposition of hydrogen peroxide or corrode when exposed to hydrogen peroxide. A zirconium nitride coating of the invention may be applied to a variety of substrates (e.g., metals) using art-recognized techniques, such as plasma vapor deposition. The present invention further provides components and articles of manufacture having hydrogen peroxide compatibility, particularly components for use in aerospace and industrial manufacturing applications. The zirconium nitride barrier coating of the invention provides protection from corrosion by reaction with hydrogen peroxide, as well as prevention of hydrogen peroxide decomposition.

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

NASA Technical Reports Server (NTRS)

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

2016-01-01

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

Mapping out the QCD phase transition in multiparticle production

NASA Astrophysics Data System (ADS)

Kabana, Sonja; Minkowski, Peter

2001-04-01

We analyse multiparticle production in a thermal framework for seven central nucleus + nucleus collisions, e+ + e- annihilation into hadrons on the Z resonance and four hadronic reactions p + p and p + pbar with partial centrality selection), with centre of mass energies ranging from √(s) = 2.6 GeV (per nucleon pair) to 1.8 TeV. Thermodynamic parameters at chemical freeze-out (temperature and baryon and strangeness fugacities) are obtained from appropriate fits, generally improving in quality for reactions subjected to centrality cuts. All systems with non-vanishing fugacities are extrapolated along trajectories of equal energy density, density and entropy density to zero fugacities. The so-obtained temperatures extrapolated to zero fugacities as a function of initial energy density ɛin universally show a strong rise followed by a saturating limit of Tlim = 155 +/- 6 +/- 20 MeV. We interpret this behaviour as mapping out the boundary between quark gluon plasma and hadronic phases. The ratio of strange antiquarks to light ones as a function of the initial energy density ɛin shows the same behaviour as the temperature, saturating at a value of 0.365 +/- 0.033 +/- 0.07. No distinctive feature of `strangeness enhancement' is seen for heavy ion collisions relative to hadronic and leptonic reactions, when compared at the same initial energy density.

Nickel-hydrogen component development

NASA Technical Reports Server (NTRS)

Charleston, J. A.

1983-01-01

Light weight energy storage systems for future space missions are investigated. One of the systems being studied is the nickel hydrogen battery. This battery is designed to achieve longer life, improve performance, and higher energy densities for space applications. The nickel hydrogen component development is discussed. Test data from polarization measurements of the hydrogen electrode component is presented.

Modeling of a complex, polar system with a modified Soave-Redlich-Kwong equation

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

Sturnfield, E.A.; Matherne, J.L.

1988-01-01

It is computationally feasible to use a simple equation of state (like a Redlich-Kwong) to calculate liquid fugacity but the simpler equations work well only for moderately non-ideal systems. More complex equations (like Ghemling-Lui-Prausnitz) predict system behavior more accurately but are much more complicated to use and can require fitting many parameters to data. This paper illustrates success in using a modified Redlich-Kwong to model a complex system including water, hydrogen, sub and supercritical ammonia, and amines. The binary interaction parameter ({Kappa}/sub ij/) of the Soave-Redlich-Kwong equation has been modified to be both asymmetric and temperature dependent. Further, the aimore » constant was determined by fitting vapor pressure data. Predicted model results are compared to literature (example 1) or plant data (examples 2-4) for four systems: 1. The ammonia-water binary over a wide range of pressure and temperature including ammonia above its critical. 2. A multicomponent Vapor-Liquid equilibrium flash tank and condenser containg hydrogen, amonia, water, and other heavier compounds. 3. A multicomponent vapor-liquid equilibrium flash tank containing water, heavier mines, and the amine salts. 4. A Liquid-Liquid-Vapor equilibrium decanter system containing water, ammonia, and an organic chloride.« less

Oxygen fugacities directly measured in magmatic gases.

PubMed

Sato, M; Wright, T L

1966-09-02

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

A fugacity-based indoor residential pesticide fate model

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

Bennett, Deborah H.; Furtaw, Edward J.; McKone, Thomas E.

Dermal and non-dietary pathways are potentially significant exposure pathways to pesticides used in residences. Exposure pathways include dermal contact with residues on surfaces, ingestion from hand- and object-to-mouth activities, and absorption of pesticides into food. A limited amount of data has been collected on pesticide concentrations in various residential compartments following an application. But models are needed to interpret this data and make predictions about other pesticides based on chemical properties. In this paper, we propose a mass-balance compartment model based on fugacity principles. We include air (both gas phase and aerosols), carpet, smooth flooring, and walls as model compartments.more » Pesticide concentrations on furniture and toys, and in food, are being added to the model as data becomes available. We determine the compartmental fugacity capacity and mass transfer-rate coefficient for wallboard as an example. We also present the framework and equations needed for a dynamic mass-balance model.« less

Steady-State Plant Model to Predict Hydroden Levels in Power Plant Components

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

Glatzmaier, Greg C.; Cable, Robert; Newmarker, Marc

The National Renewable Energy Laboratory (NREL) and Acciona Energy North America developed a full-plant steady-state computational model that estimates levels of hydrogen in parabolic trough power plant components. The model estimated dissolved hydrogen concentrations in the circulating heat transfer fluid (HTF), and corresponding partial pressures within each component. Additionally for collector field receivers, the model estimated hydrogen pressure in the receiver annuli. The model was developed to estimate long-term equilibrium hydrogen levels in power plant components, and to predict the benefit of hydrogen mitigation strategies for commercial power plants. Specifically, the model predicted reductions in hydrogen levels within the circulatingmore » HTF that result from purging hydrogen from the power plant expansion tanks at a specified target rate. Our model predicted hydrogen partial pressures from 8.3 mbar to 9.6 mbar in the power plant components when no mitigation treatment was employed at the expansion tanks. Hydrogen pressures in the receiver annuli were 8.3 to 8.4 mbar. When hydrogen partial pressure was reduced to 0.001 mbar in the expansion tanks, hydrogen pressures in the receiver annuli fell to a range of 0.001 mbar to 0.02 mbar. When hydrogen partial pressure was reduced to 0.3 mbar in the expansion tanks, hydrogen pressures in the receiver annuli fell to a range of 0.25 mbar to 0.28 mbar. Our results show that controlling hydrogen partial pressure in the expansion tanks allows us to reduce and maintain hydrogen pressures in the receiver annuli to any practical level.« less

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

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2004-01-01

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

Guide for Hydrogen Hazards Analysis on Components and Systems

NASA Technical Reports Server (NTRS)

Beeson, Harold; Woods, Stephen

2003-01-01

The physical and combustion properties of hydrogen give rise to hazards that must be considered when designing and operating a hydrogen system. One of the major concerns in the use of hydrogen is that of fire or detonation because of hydrogen's wide flammability range, low ignition energy, and flame speed. Other concerns include the contact and interaction of hydrogen with materials, such as the hydrogen embrittlement of materials and the formation of hydrogen hydrides. The low temperature of liquid and slush hydrogen bring other concerns related to material compatibility and pressure control; this is especially important when dissimilar, adjoining materials are involved. The potential hazards arising from these properties and design features necessitate a proper hydrogen hazards analysis before introducing a material, component, or system into hydrogen service. The objective of this guide is to describe the NASA Johnson Space Center White Sands Test Facility hydrogen hazards analysis method that should be performed before hydrogen is used in components and/or systems. The method is consistent with standard practices for analyzing hazards. It is recommended that this analysis be made before implementing a hydrogen component qualification procedure. A hydrogen hazards analysis is a useful tool for hydrogen-system designers, system and safety engineers, and facility managers. A hydrogen hazards analysis can identify problem areas before hydrogen is introduced into a system-preventing damage to hardware, delay or loss of mission or objective, and possible injury or loss of life.

Precipitation of Excess Hydrogen in Olivine During Cooling Under Pressures: An Experimental Study

NASA Astrophysics Data System (ADS)

Borinski, S.; Karato, S.

2007-12-01

Water (hydrogen) content in olivine transported from the upper mantle is used to infer the water content in the upper mantle (e.g., Bell and Rossman 1992). However, since hydrogen diffusion is known to be fast, processes of hydrogen loss need to be examined. In many literature, diffusion loss (or gain) of hydrogen is usually considered, but in addition to diffusion loss, hydrogen could also precipitate inside of olivine as small inclusions. Consider an upward transport of olivine-bearing rock that originally contained a large amount of hydrogen in the deep interior. As this rock is transported to the shallow region, the solubility limit of hydrogen will decrease because of the reduction of pressure (and temperature) (Kohlstedt et al. 1996, Zhao et al 2004). Consequently, excess hydrogen will precipitate to form water bubbles and/or hydrous minerals as inclusions. Frequently observed submicron-scale inclusions of hydrous minerals (Khisina and Wirth 2002, Kitamura et al. 1987) may correspond to these precipitation products. If that is the case, hydrogen content corresponding to these minerals should not be excluded when estimating the hydrogen content of a sample in the Earth's upper mantle. However, kinetics of precipitation of hydrogen from olivine have not been investigated in the laboratory. We have conducted a series of experimental study in which we annealed hydrogen-saturated olivine single crystals in two different P- T conditions. The starting material was an olivine crystal in which ~1,135 H/106Si (70 wt ppm H2O) was dissolved at P= 3.5 GPa and T=1,573 K. A small piece of this crystal (0.5 mm3) was placed in a multianvil at P=3.5 GPa and either at T= 873K or 1,173K with oxygen fugacity, fO2, buffered by the Ni-NiO solid-state reaction and silica activity, aSiO2, buffered by the presence of orthopyroxene powder in contact with the crystal. Annealing experiments were conducted up to 72 hours. Hydroxyl concentrations were determined from infrared spectra obtained from polished thin sections from crack-free regions of 100 x 100 μm. The hydroxyl concentration at the OH-stretching region around 3678 cm-1 increases systematically with increasing time at 873 K, whereas this band is not detected in samples annealed at 1,173 K. The peak(s) at 3678 cm-1 corresponds to the OH-stretching vibration in hydrous minerals such as serpentine (Mellini et al. 2002, Hofmeister and Bowey 2006). We conclude that the water in the upper mantle not only diffuse out and disappear during the ascent (cooling and depressurization), but also is bounded in hydrous minerals (e.g. serpentine).

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

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

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

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

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

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

Third Bose fugacity coefficient in one dimension, as a function of asymptotic quantities

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

Amaya-Tapia, A., E-mail: jano@fis.unam.mx; Larsen, S.Y.; Lassaut, M.

2011-02-15

In one of the very few exact quantum mechanical calculations of fugacity coefficients, [L.R. Dodd, A.M. Gibbs. J. Math. Phys. 15 (1974) 41] obtained b{sub 2} and b{sub 3} for a one dimensional Bose gas, subject to repulsive delta-function interactions, by direct integration of the wave functions. For b{sub 2}, we have shown [A. Amaya-Tapia, S.Y. Larsen, M. Lassaut. Mol. Phys. 103 (2005) 1301-1306. < (arXiv:physics/0405150)>] that Dodd and Gibbs' result can be obtained from a phase shift formalism, if one also includes the contribution of oscillating terms, usually contributing only in one dimension. Now, we develop an exact expressionmore » for b{sub 3}-b{sub 3}{sup 0} (where b{sub 3}{sup 0} is the free particle fugacity coefficient) in terms of sums and differences of three-body eigenphase shifts. Further, we show that if we obtain these eigenphase shifts in a Distorted-Born approximation, then, to first order, we reproduce the leading low temperature behaviour, obtained from an expansion of the twofold integral of Dodd and Gibbs. The contributions of the oscillating terms cancel. The formalism that we propose is not limited to one dimension, but seeks to provide a general method to obtain virial coefficients, fugacity coefficients, in terms of asymptotic quantities. The exact one dimensional results allow us to confirm the validity of our approach in this domain.« less

Assessing the Behavior of Typically Lithophile Elements Under Highly Reducing Conditions Relevant to the Planet Mercury

NASA Technical Reports Server (NTRS)

Rowland, Rick, II; Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Danielson, Lisa R.

2017-01-01

With the data returned from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) mission, there are now numerous constraints on the physical and chemical properties of Mercury, including its surface composition (e.g., Evans et al. 2012; Nittler et al. 201 l; Peplowski et al. 2012; Weider et al. 2012). The high Sand low FeO contents observed from MESSENGER on the planet's surface suggests a low oxygen fugacity of the present planetary materials. Estimates of the oxygen fugacity for Mercurian magmas are approximately 3- 7 log units below the Iron-Wiistite (Fe-FeO) oxygen buffer (McCubbin et al. 2012; Zolotov et al. 2013), several orders of magnitude more reducing than other terrestrial bodies we have data from such as the Earth, Moon, or Mars (Herd 2008; Sharp, McCubbin, and Shearer 2013; Wadhwa 2008). Most of our understanding of elemental partitioning behavior comes from observations made on terrestrial rocks, but Mercury's oxygen fugacity is far outside the conditions of those samples. With limited oxygen available, lithophile elements may instead exhibit chalcophile, halophile, or siderophile behaviors. Furthermore, very few natural samples of rocks that formed under reducing conditions are available in our collections (e.g., enstatite chondrites, achondrites, aubrites). The goal of this study is to conduct experiments at high pressure and temperature conditions to determine the elemental partitioning behavior of typically lithophile elements as a function of decreasing oxygen fugacity.

Combustion of LOX with H2(sub g) under subcritical, critical, and supercritical conditions and experimental observation of dense spray and mixing of impinging jets

NASA Technical Reports Server (NTRS)

Kuo, Kenneth K.; Hsieh, W. H.; Yang, A. S.; Brown, J. J.; Cheung, F. B.; Woodward, R. D.; Kline, M. C.

1992-01-01

Progress made during the period of February 1 to October 15, 1992 is reported. The overall objective of Task 1 of the investigation is to achieve a better understanding of the combustion processes of liquid oxygen and gaseous hydrogen under subcritical, critical, and supercritical conditions. Specific objectives of the research program are: (1) to determine the evaporation- and burning-rate characteristics of LOX in hydrogen/helium environments under broad ranges of operating conditions; (2) to measure species concentration profile and surface temperature of LOX employing the gas chromatography and fine-wire thermocouples under non-reacting flow situations; (3) to perform a fugacity-based multicomponent thermodynamic phase equilibrium analysis for examining the high-pressure vapor-liquid equilibrium behavior at the liquid surface of LOX; (4) to formulate and solve a theoretical model for simulating the evaporation and combustion processes in a LOX/H2/He system; and (5) to validate the theoretical model with the measured experimental data. Task 2 of the investigation is described. Observation of a like-on-like injector element in the near-injector region performed in the previous phase of this project has identified the existence of a high Reynolds number regime in which the pre-impingement jets are fully turbulent and undergoing surface breakup. The new spray regime, which has not been observed by previous investigators, is characterized by the presence of many fine droplets and the disappearance of the well-defined liquid breakup wave pattern in the post-impingement region. It is speculated that a cavitating region may be present within the orifice so that it could induce strong turbulence, leading to an onset of atomization of the jets prior to impingement. To further investigate the dense spray behavior of the impinging jets in the high Reynolds number region, experiments were conducted using Plexiglas injector components for direct internal flow observation. The main objective is to determine under what conditions a cavitating region would form and whether or not the cavitation is reponsible for the development of the high Reynolds number spray regime. The procedure and major findings of the injector cavitation study are described.

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

USGS Publications Warehouse

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

2017-01-01

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

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

USGS Publications Warehouse

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

1984-01-01

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

Experimental calibration of a new oxybarometer for silicic magmas based on the partitioning of vanadium between magnetite and silicate melt

NASA Astrophysics Data System (ADS)

Arató, Róbert; Audétat, Andreas

2016-04-01

Oxygen fugacity is an important parameter in magmatic systems that affects the stability of mineral phases and fluid species. However, there is no well-established method to reconstruct the oxygen fugacity of slowly cooled magmas such as granite, for example, because existing oxybarometers (e.g., magnetite-ilmenite method) are susceptible to re-equilibration processes during slow cooling and thus lead to erroneous results when applied for granitic rocks. In this study, we aim at developing an oxybarometer that is based on the partitioning of vanadium (a redox-sensitive element) between magnetite inclusions and silicate melt inclusions preserved in quartz phenocrysts, where they were protected from subsolidus alteration and can be measured as entities by LA-ICP-MS. In the first - experimental - part of this study we investigated the effects of temperature (800-950 ° C), pressure (1-2 kbar), oxygen fugacity (from ΔFMQ+0.7 to ΔFMQ+4.0), magnetite composition, and melt composition on the partition coefficient of vanadium between magnetite and melt (DVmgt-melt). The experiments were carried out in cold-seal pressure vessels and the starting material was a mixture of V-doped haplogranite glasses or natural obsidian powder with variable aluminum saturation index (ASI), and synthetic, V-free magnetite of 10-20 μm grain size. The vanadium partition coefficient was found to depend strongly on oxygen fugacity, and to lesser (but still considerable) degrees on melt composition and temperature. A more than 1.5 log unit decrease in DVmgt-melt values with increasing oxygen fugacity can be explained by a change of the dominant valence state of V in the silicate melt. For a given oxygen fugacity buffer DVmgt-melt decreases with increasing temperature, but this reflects mostly the change in absolute fO2 values while the net temperature effect is in fact positive. DVmgt-melt depends significantly on melt composition, resulting in higher D-values with increasing aluminum saturation index (ASI). This seems to reflect less favorable incorporation of V into peraluminous melts compared to depolymerized, peralkaline melts. Changing pressure from 1 to 2 kbar had an effect only at NNO, causing 0.3 log unit increase in D, whereas the Ti-content of magnetite turned out to have negligible effect on the V partitioning. In summary, the dependence of DVmgt-melt on temperature, ASI and oxygen fugacity can be described by the following regression equation: logD(V)mgt/melt=-1.22+0.31*10^5/T(° K) +1.73*ASI -0.49*ΔFMQ First tests of the equation on natural samples were carried out on rapidly cooled tuffs and vitrophyres from variable tectonic settings, for which fO2 could be constrained independently by the magnetite-ilmenite method. All calculated fO2 values fall within ± 0.75 log unit within those suggested by the Fe-Ti oxybarometer, whereas 12 out of 16 samples agree within 0.5 log units .

Water abundance and accretion history of terrestrial planets

NASA Technical Reports Server (NTRS)

Waenke, H.; Dreibus, G.

1994-01-01

According to a widespread believe, Earth's water was either added in form of a late volatile-rich veneer or as we have argued repeatedly that of all the water which was added to the Earth only that portion remained which was added towards the end of accretion when the mean oxygen fugacity of the accreting material became so high that metallic iron could not exist any longer. Prior to this moment, all the water in the latter scenario would have been used up for the oxidation of iron. Fe + H2O yields FeO + H2. Huge quantities of hydrogen would continuously be produced in this scenario which escaped. In the same moment the hydrogen on its way to the surface would lead to an efficient degassing of the growing Earth's mantle. The fact that - assuming C1 abundances - the amount of iridium in the Earth's mantle agrees, within a factor of two with the total water inventory of the Earth's mantle and crust is taken as evidence for the validity of such a scenario. In both scenarios, the Earth's mantle would remain dry and devoid of other volatiles. Some species soluble in metallic iron like carbon and hydrogen will probably partly enter the core in some portions. It is generally assumed that today a considerable portion of the earth's total water inventory resides in the mantle. It is also clear that over the history of the Earth the water of the Earth's oceans has been recycled many times through the mantle. This is the consequence of plate subduction. In a similar way mantle convection was probably responsible to being water into the originally dry mantle. As a consequence, today the Earth is wet both inside and outside.

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

NASA Astrophysics Data System (ADS)

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

1988-12-01

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

Design and fabrication of miniaturized PEM fuel cell combined microreactor with self-regulated hydrogen mechanism

NASA Astrophysics Data System (ADS)

Balakrishnan, A.; Frei, M.; Kerzenmacher, S.; Reinecke, H.; Mueller, C.

2015-12-01

In this work we present the design and fabrication of the miniaturized PEM fuel cell combined microreactor system with hydrogen regulation mechanism and testing of prototype microreactor. The system consists of two components (i) fuel cell component and (ii) microreactor component. The fuel cell component represents the miniaturized PEM fuel cell system (combination of screen printed fuel cell assembly and an on-board hydrogen storage medium). Hydrogen production based on catalytic hydrolysis of chemical hydride takes place in the microreactor component. The self-regulated hydrogen mechanism based on the gaseous hydrogen produced from the catalytic hydrolysis of sodium borohydride (NaBH4) gets accumulated as bubbles at the vicinity of the hydrophobic coated hydrogen exhaust holes. When the built up hydrogen bubbles pressure exceeds the burst pressure at the hydrogen exhaust holes the bubble collapses. This collapse causes a surge of fresh NaBH4 solution onto the catalyst surface leading to the removal of the reaction by-products formed at the active sites of the catalyst. The catalyst used in the system is platinum deposited on a base substrate. Nickel foam, carbon porous medium (CPM) and ceramic plate were selected as candidates for base substrate for developing a robust catalyst surface. For the first time the platinum layer fabricated by pulsed electrodeposition and dealloying (EPDD) technique is used for hydrolysis of NaBH4. The major advantages of such platinum catalyst layers are its high surface area and their mechanical stability. Prototype microreactor system with self-regulated hydrogen mechanism is demonstrated.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Investigation of low-latitude hydrogen emission in terms of a two-component interstellar gas model

NASA Technical Reports Server (NTRS)

Baker, P. L.; Burton, W. B.

1975-01-01

High-resolution 21-cm hydrogen line observations at low galactic latitude are analyzed to determine the large-scale distribution of galactic hydrogen. Distribution parameters are found by model fitting, optical depth effects are computed using a two-component gas model suggested by the observations, and calculations are made for a one-component uniform spin-temperature gas model to show the systematic departures between this model and data obtained by incorrect treatment of the optical depth effects. Synthetic 21-cm line profiles are computed from the two-component model, and the large-scale trends of the observed emission profiles are reproduced together with the magnitude of the small-scale emission irregularities. Values are determined for the thickness of the galactic hydrogen disk between half density points, the total observed neutral hydrogen mass of the galaxy, and the central number density of the intercloud hydrogen atoms. It is shown that typical hydrogen clouds must be between 1 and 13 pc in diameter and that optical thinness exists on large-scale despite the presence of optically thin gas.

Characteristics of trophic transfer of polychlorinated biphenyls in marine organisms in Incheon North Harbor, Korea.

PubMed

Kim, Seung Kyu; Lee, Dong Soo; Oh, Jae Ryong

2002-04-01

The trophic transfer of polychlorinated biphenyls (PCBs) was characterized for zooplankton (primarily Paracalanus spp. and Acartia spp.), pacific oyster (Crassostrea gigas), shore crab (Hemigrapsus penicillatus), and goby (Acanthogobius hasta) in the aquatic system of Incheon North Harbor, Korea. The congener pattern in the species was clearly divided by the main PCB uptake route. Compared with zooplankton and oyster, the fraction of heavier homologues increased in crab and goby that take PCBs from food. Linear relationships were observed between log (fugacity in lipid/fugacity in seawater) and log Kow for all the species. For zooplankton and oyster, such an observation should not be regarded as a true absence of superhydrophobicity, because establishment of equilibrium with seawater was not evident. For crab and goby, the absence of superhydrophobicity was evidenced by the trophic transfer factor that continuously increased with Kow up to 10(7.8). These results suggest that superhydrophobicity might be species specific. The trophic transfer factors and the fugacity levels in the lipid phase indicated that bioaccumulation in crab and goby advanced beyond the level in equilibrium with seawater in the harbor basin.

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

NASA Technical Reports Server (NTRS)

Carroll, Michael R.; Rutherford, Malcolm J.

1988-01-01

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

The wet solidus of silica: predictions from the scaled particle theory and polarized continuum model.

PubMed

Ottonello, G; Richet, P; Vetuschi Zuccolini, M

2015-02-07

We present an application of the Scaling Particle Theory (SPT) coupled with an ab initio assessment of the electronic, dispersive, and repulsive energy terms based on the Polarized Continuum Model (PCM) aimed at reproducing the observed solubility behavior of OH2 over the entire compositional range from pure molten silica to pure water and wide pressure and temperature regimes. It is shown that the solution energy is dominated by cavitation terms, mainly entropic in nature, which cause a large negative solution entropy and a consequent marked increase of gas phase fugacity with increasing temperatures. Besides, the solution enthalpy is negative and dominated by electrostatic terms which depict a pseudopotential well whose minimum occurs at a low water fraction (XH2O) of about 6 mol. %. The fine tuning of the solute-solvent interaction is achieved through very limited adjustments of the electrostatic scaling factor γel which, in pure water, is slightly higher than the nominal value (i.e., γel  =  1.224 against 1.2), it attains its minimum at low H2O content (γel = 0.9958) and then rises again at infinite dilution (γel   =  1.0945). The complex solution behavior is interpreted as due to the formation of energetically efficient hydrogen bonding when OH functionals are in appropriate amount and relative positioning with respect to the discrete OH2 molecules, reinforcing in this way the nominal solute-solvent inductive interaction. The interaction energy derived from the SPT-PCM calculations is then recast in terms of a sub-regular Redlich-Kister expansion of appropriate order whereas the thermodynamic properties of the H2O component at its standard state (1-molal solution referred to infinite dilution) are calculated from partial differentiation of the solution energy over the intensive variables.

In Situ High Pressure Hydrogen Tribological Testing of Common Polymer Materials Used in the Hydrogen Delivery Infrastructure.

PubMed

Duranty, Edward R; Roosendaal, Timothy J; Pitman, Stan G; Tucker, Joseph C; Owsley, Stanley L; Suter, Jonathan D; Alvine, Kyle James

2018-03-31

High pressure hydrogen gas is known to adversely affect metallic components of compressors, valves, hoses, and actuators. However, relatively little is known about the effects of high pressure hydrogen on the polymer sealing and barrier materials also found within these components. More study is required in order to determine the compatibility of common polymer materials found in the components of the hydrogen fuel delivery infrastructure with high pressure hydrogen. As a result, it is important to consider the changes in physical properties such as friction and wear in situ while the polymer is exposed to high pressure hydrogen. In this protocol, we present a method for testing the friction and wear properties of ethylene propylene diene monomer (EPDM) elastomer samples in a 28 MPa high pressure hydrogen environment using a custom-built in situ pin-on-flat linear reciprocating tribometer. Representative results from this testing are presented which indicate that the coefficient of friction between the EPDM sample coupon and steel counter surface is increased in high pressure hydrogen as compared to the coefficient of friction similarly measured in ambient air.

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

USGS Publications Warehouse

Gerlach, T.M.

1993-01-01

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

Water sensitivity of the seismic properties of upper-mantle olivine

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Experimental Determination of Fe-Mg Interdiffusion Coefficients in Orthopyroxene Using Pulsed Laser Ablation and Nanoscale Thin Films

NASA Astrophysics Data System (ADS)

Ter Heege, J. H.; Dohmen, R.; Becker, H.; Chakraborty, S.

2006-12-01

Fe-Mg interdiffusion in silicate minerals is of interest in petrological studies for determining the closure temperature of geothermometers and for determining cooling rates from compositional profiles. It is also relevant for studies of the physical properties of silicates, such as rheology or electrical conductivity, because knowledge of its dependence on oxygen fugacity can aid in the understanding of point defect chemistry. Compositionally zoned orthopyroxenes are common in meteorites, mantle rocks, lower crustal rocks and a variety of plutonic and volcanic igneous rocks. However, experimental difficulties have precluded direct determination of Fe-Mg diffusion rates in orthopyroxenes so far and the available information comes from (1) Mg tracer diffusion coefficients obtained from isotope tracer studies using enriched ^{25}MgO films [1], (2) calculations of interdiffusion rates based on the (diffusion-controlled) order-disorder kinetics measured in orthopyroxene [2], and (3) indirect estimates from the comparison of diffusion widths in coexisting garnets and olivines, in which Fe-Mg diffusion rates are relatively well known [e.g., 3]. We have directly measured Fe-Mg interdiffusion coefficients parallel to the [001] direction in two natural orthopyroxene single crystals (approximately En95Fs5 and En90Fs10) using diffusion couples consisting of an olivine thin film (Fo30Fa70, typically 20 - 50 nm thick) deposited under vacuum on pre-heated, polished and oriented pyroxene single crystals using a pulsed laser ablation deposition technique. Samples were annealed for 4 - 337 hours at 800 - 1100 °C under atmospheric pressure in a continuous flow of CO + CO2 to control the oxygen fugacity between 10-16 and 10^{-12} bar within the stability field of pyroxene. Film thickness and compositional profiles were measured using Rutherford backscattering Spectroscopy (RBS) on reference and annealed samples, and Fe concentration depth profiles were extracted from the RBS spectra and fitted numerically. At an oxygen fugacity of 10-16 bar, Fe-Mg interdiffusion coefficients in the Fs richer orthopyroxene vary between 4.10^{-22} m2/s and 2.10^{-20} m2/s for temperatures between 800 and 1000°C. Diffusion coefficients decrease by a factor of ~ 4 with decreasing oxygen fugacity between 10^{-12} and 10-16 bar at 1000 °C. Comparison of our data with other Fe-Mg diffusion data shows that these diffusion coefficients are (1) similar to Mg tracer diffusion coefficients measured in orthopyroxene at somewhat more reducing (e.g. fO2 = 10-16 to 10^{-19} bar) conditions at the same temperatures [1], (2) similar to Mg tracer diffusion in garnets measured at higher pressures of 10 kbar at an oxygen fugacity corresponding to the C-O equilibrium in graphite present systems [4], and (3) slower than Fe-Mg diffusion rates in olivine by a factor of ~10 at the same oxygen fugacities [5]. Further experiments to quantify the dependence on composition, temperature and oxygen fugacity are in progress. References: [1] Schwandt et al. (1998), Contr. Mineral. Petrol. 130: 390-396; [2] Ganguly and Tazzoli (1994), Am. Mineral. 79: 930-937; [3] Smith and Barron (1991), Am. Mineral. 76: 1950-1963; [4] Ganguly et al. (1998), Contr. Mineral. Petrol. 131: 171-180; [5] Chakraborty (1997), J. Geoph. Res. 102: 12317-12331.

Modeling the influence of climate change on the mass balance of polychlorinated biphenyls in the Adriatic Sea.

PubMed

Lamon, Lara; MacLeod, Matthew; Marcomini, Antonio; Hungerbühler, Konrad

2012-05-01

Climate forcing is forecasted to influence the Adriatic Sea region in a variety of ways, including increasing temperature, and affecting wind speeds, marine currents, precipitation and water salinity. The Adriatic Sea is intensively developed with agriculture, industry, and port activities that introduce pollutants to the environment. Here, we developed and applied a Level III fugacity model for the Adriatic Sea to estimate the current mass balance of polychlorinated biphenyls in the Sea, and to examine the effects of a climate change scenario on the distribution of these pollutants. The model's performance was evaluated for three PCB congeners against measured concentrations in the region using environmental parameters estimated from the 20th century climate scenario described in the Special Report on Emission Scenarios (SRES) by the IPCC, and using Monte Carlo uncertainty analysis. We find that modeled fugacities of PCBs in air, water and sediment of the Adriatic are in good agreement with observations. The model indicates that PCBs in the Adriatic Sea are closely coupled with the atmosphere, which acts as a net source to the water column. We used model experiments to assess the influence of changes in temperature, wind speed, precipitation, marine currents, particulate organic carbon and air inflow concentrations forecast in the IPCC A1B climate change scenario on the mass balance of PCBs in the Sea. Assuming an identical PCBs' emission profile (e.g. use pattern, treatment/disposal of stockpiles, mode of entry), modeled fugacities of PCBs in the Adriatic Sea under the A1B climate scenario are higher because higher temperatures reduce the fugacity capacity of air, water and sediments, and because diffusive sources to the air are stronger. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

1980-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-08-01

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

Hydrogen-bromine fuel cell advance component development

NASA Technical Reports Server (NTRS)

Charleston, Joann; Reed, James

1988-01-01

Advanced cell component development is performed by NASA Lewis to achieve improved performance and longer life for the hydrogen-bromine fuel cells system. The state-of-the-art hydrogen-bromine system utilizes the solid polymer electrolyte (SPE) technology, similar to the SPE technology developed for the hydrogen-oxygen fuel cell system. These studies are directed at exploring the potential for this system by assessing and evaluating various types of materials for cell parts and electrode materials for Bromine-hydrogen bromine environment and fabricating experimental membrane/electrode-catalysts by chemical deposition.

Higher order Stark effect and transition probabilities on hyperfine structure components of hydrogen like atoms

NASA Astrophysics Data System (ADS)

Pal'Chikov, V. G.

2000-08-01

A quantum-electrodynamical (QED) perturbation theory is developed for hydrogen and hydrogen-like atomic systems with interaction between bound electrons and radiative field being treated as the perturbation. The dependence of the perturbed energy of levels on hyperfine structure (hfs) effects and on the higher-order Stark effect is investigated. Numerical results have been obtained for the transition probability between the hfs components of hydrogen-like bismuth.

Influence of indigenous minor components on fat crystal network of fully hydrogenated palm kernel oil and fully hydrogenated coconut oil.

PubMed

Chai, Xiu-Hang; Meng, Zong; Cao, Pei-Rang; Liang, Xin-Yu; Piatko, Michael; Campbell, Shawn; Koon Lo, Seong; Liu, Yuan-Fa

2018-07-30

Purification of triglycerides from fully hydrogenated palm kernel oil (FHPKO) and fully hydrogenated coconut oil (FHCNO) was performed by a chromatographic method. Lipid composition, thermal properties, polymorphism, isothermal crystallization behaviour, nanostructure and microstructure of FHPKO, FHPKO-triacylglycerol (TAG), FHCNO and FHCNO-TAG were evaluated. Removal of minor components had no effect on triglycerides composition. However, the presence of the minor components did increase the slip melting point and promote onset of crystallization. Furthermore, the thickness of the nanoscale crystals increased, and polymorphic transformation from β' to β occurred in FHPKO after the removal of minor components, and from α to β' in FHCNO. Sharp changes in the values of the Avrami constant K and exponent n suggested that the presence of minor components changed the crystal growth mechanism. The PLM results indicated that a coarser crystal structure with lower fractal dimension appeared after the removal of minor components from both FHPKO and FHCNO. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hydrogen Permeability of Incoloy 800H, Inconel 617, and Haynes 230 Alloys

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

Pattrick Calderoni

A potential issue in the design of the NGNP reactor and high-temperature components is the permeation of fission generated tritium and hydrogen product from downstream hydrogen generation through high-temperature components. Such permeation can result in the loss of fission-generated tritium to the environment and the potential contamination of the helium coolant by permeation of product hydrogen into the coolant system. The issue will be addressed in the engineering design phase, and requires knowledge of permeation characteristics of the candidate alloys. Of three potential candidates for high-temperature components of the NGNP reactor design, the hydrogen permeability has been documented well onlymore » for Incoloy 800H, but at relatively high partial pressures of hydrogen. Hydrogen permeability data have been published for Inconel 617, but only in two literature reports and for partial pressures of hydrogen greater than one atmosphere, far higher than anticipated in the NGNP reactor. The hydrogen permeability of Haynes 230 has not been published. To support engineering design of the NGNP reactor components, the hydrogen permeability of Inconel 617 and Haynes 230 were determined using a measurement system designed and fabricated at the Idaho National Laboratory. The performance of the system was validated using Incoloy 800H as reference material, for which the permeability has been published in several journal articles. The permeability of Incoloy 800H, Inconel 617 and Haynes 230 was measured in the temperature range 650 to 950 °C and at hydrogen partial pressures of 10-3 and 10-2 atm, substantially lower pressures than used in the published reports. The measured hydrogen permeability of Incoloy 800H and Inconel 617 were in good agreement with published values obtained at higher partial pressures of hydrogen. The hydrogen permeability of Inconel 617 and Haynes 230 were similar, about 50% greater than for Incoloy 800H and with similar temperature dependence.« less

Coal liquefaction process wherein jet fuel, diesel fuel and/or ASTM No. 2 fuel oil is recovered

DOEpatents

Bauman, Richard F.; Ryan, Daniel F.

1982-01-01

An improved process for the liquefaction of coal and similar solid carbonaceous materials wherein a hydrogen donor solvent or diluent derived from the solid carbonaceous material is used to form a slurry of the solid carbonaceous material and wherein the naphthenic components from the solvent or diluent fraction are separated and used as jet fuel components. The extraction increases the relative concentration of hydroaromatic (hydrogen donor) components and as a result reduces the gas yield during liquefaction and decreases hydrogen consumption during said liquefaction. The hydrogenation severity can be controlled to increase the yield of naphthenic components and hence the yield of jet fuel and in a preferred embodiment jet fuel yield is maximized while at the same time maintaining solvent balance.

Theoretical estimation of Photons flow rate Production in quark gluon interaction at high energies

NASA Astrophysics Data System (ADS)

Al-Agealy, Hadi J. M.; Hamza Hussein, Hyder; Mustafa Hussein, Saba

2018-05-01

photons emitted from higher energetic collisions in quark-gluon system have been theoretical studied depending on color quantum theory. A simple model for photons emission at quark-gluon system have been investigated. In this model, we use a quantum consideration which enhances to describing the quark system. The photons current rate are estimation for two system at different fugacity coefficient. We discussion the behavior of photons rate and quark gluon system properties in different photons energies with Boltzmann model. The photons rate depending on anisotropic coefficient : strong constant, photons energy, color number, fugacity parameter, thermal energy and critical energy of system are also discussed.

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

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

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

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

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

NASA Technical Reports Server (NTRS)

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

2000-01-01

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

The principal phenolic and alcoholic components of wine protect human lymphocytes against hydrogen peroxide- and ionizing radiation-induced DNA damage in vitro.

PubMed

Greenrod, William; Fenech, Michael

2003-03-01

We have tested the hypothesis that the alcoholic and phenolic components of wine are protective against the DNA-damaging and cytotoxic effects of hydrogen peroxide and gamma-radiation in vitro. The components of wine tested were ethanol, glycerol, a mixture of the phenolic compounds catechin and caffeic acid and tartaric acid, all at concentrations that were 2.5 or 10.0% of the concentration in a typical Australian white wine (Riesling). These components were tested individually or combined as a mixture and compared to a white wine stripped of polyphenols, as well as a Hanks balanced salt solution control, which was the diluent for the wine components. The effect of the components was tested in lymphocytes, using the cytokinesis-block micronucleus assay, after 30 min incubation in plasma or whole blood for the hydrogen peroxide or gamma-radiation challenge, respectively. The results obtained showed that ethanol, glycerol, the catechin-caffeic acid mixture, the mixture of all components and the stripped white wine significantly reduced the DNA-damaging effects of hydrogen peroxide and gamma-radiation (P = 0.043-0.001, ANOVA). The strongest protective effect against DNA damage by gamma-irradiation was observed for the catechin-caffeic acid mixture and the mixture of all components (30 and 32% reduction, respectively). These two treatments as well as ethanol produced the strongest protective effects against DNA damage by hydrogen peroxide (24, 25 and 18%, respectively). The protection provided by the mixture did not account for the expected additive protective effects of the individual components. Ethanol was the only component that significantly increased baseline DNA damage rate, however, this effect was negated in the mixture. In conclusion, our results suggest that the main phenolic and alcoholic components of wine can reduce the DNA-damaging effects of two important oxidants, i.e. hydrogen peroxide and ionizing radiation, in this physiologically relevant in vitro system.

FirefOx Design Reference fO2 Sensor for Hot, Deep Atmospheres

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Fuel Cell and Hydrogen Technology Validation | Hydrogen and Fuel Cells |

Science.gov Websites

NREL Fuel Cell and Hydrogen Technology Validation Fuel Cell and Hydrogen Technology Validation The NREL technology validation team works on validating hydrogen fuel cell electric vehicles; hydrogen fueling infrastructure; hydrogen system components; and fuel cell use in early market applications such as

Application of a level IV fugacity model to simulate the long-term fate of hexachlorocyclohexane isomers in the lower reach of Yellow River basin, China.

PubMed

Ao, Jiangting; Chen, Jingwen; Tian, Fulin; Cai, Xiyun

2009-01-01

A level IV multimedia fugacity model was established to simulate the fate and transfer of hexachlorocyclohexane (HCH) isomers in the lower reach of the Yellow River basin, China, during 1952-2010. The predicted concentrations of HCHs are in good agreement with the observed ones, as indicated by the residual errors being generally lower than 0.5 logarithmic units. The effects of extensive agricultural application and subsequent prohibition of HCHs are reflected by the temporal variation of HCHs predicted by the model. It is predicted that only 1.8 tons of HCHs will be left in 2010, less than 0.06% of the highest contents (in 1983) in the study area, and about 99% of HCHs remain in soil. The proportions of HCH isomers in the environment also changed with time due to their different physicochemical properties. Although beta-HCH is not the main component of the technical HCHs, it has become the most abundant isomer in the environment because of its persistence. The dominant transfer processes between the adjacent compartments were deposition from air to soil, air diffusion through the air-water interface and runoff from soil to water. Sensitivity analysis showed that degradation rate in soil, parameters related to major sources, and thickness of soils had the strongest influence on the model result. Results of Monte Carlo simulation indicated the overall uncertainty of model predictions, and the coefficients of variation of the estimated concentrations of HCHs in all the compartments ranged from 0.5 to 5.8.

Control method for high-pressure hydrogen vehicle fueling station dispensers

DOEpatents

Kountz, Kenneth John; Kriha, Kenneth Robert; Liss, William E.

2006-06-13

A method for quick filling a vehicle hydrogen storage vessel with hydrogen, the key component of which is an algorithm used to control the fill process, which interacts with the hydrogen dispensing apparatus to determine the vehicle hydrogen storage vessel capacity.

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

USGS Publications Warehouse

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

1996-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

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

NASA Technical Reports Server (NTRS)

Williams, R. J.; Mullins, O.

1976-01-01

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

Partial melting of the Allende (CV3) meteorite - Implications for origins of basaltic meteorites

NASA Technical Reports Server (NTRS)

Jurewicz, A. J. G.; Mittlefehldt, D. W.; Jones, J. H.

1991-01-01

Eucrites and angrites are distinct types of basaltic meteorites whose origins are poorly known. Experiments in which samples of the Allende (CV3) carbonaceous chondrite were partially melted indicate that partial melts can resemble either eucrites or angrites, depending only on the oxygen fugacity. Melts are eucritic if this variable is below that of the iron-wuestite buffer or angritic if above it. With changing pressure, the graphite-oxygen redox reaction can produce oxygen fugacities that are above or below those of the iron-wuestite buffer. Therefore, a single, homogeneous, carbonaceous planetoid greater than 110 kilometers in radius could produce melts of drastically different composition, depending on the depth of melting.

Development of vapor phase hydrogen peroxide sterilization process for spacecraft applications

NASA Technical Reports Server (NTRS)

Rohatgi, N.; Schubert, W.; Knight, J.; Quigley, M.; Forsberg, G.; Ganapathi, G.; Yarbrough, C.; Koukol, R.

2001-01-01

This paper will present test data and discussion on the work we are conducting at JPL to address the following issues: 1) efficacy of sterilization process; 2) diffusion of hydrogen peroxide under sterilization process conditions into hard to reach places; 3) materials and components compatibility with the sterilization process and 4) development of methodology to protect sensitive components from hydrogen peroxide vapor.

Isotopic composition of hydrogen in insoluble organic matter from cherts

NASA Technical Reports Server (NTRS)

Krishnamurthy, R. V.; Epstein, S.

1991-01-01

Robert (1989) reported the presence of unusually enriched hydrogen in the insoluble HF-HCl residue extracted from two chert samples of Eocene and Pliocene ages. Since the presence of heavy hydrogen might be due to the incorporation of extraterrestrial materials, we desired to reexamine the same samples to isolate the D-rich components. Our experiments did not reveal any D-rich components, but the hydrogen isotope composition of the insoluble residue of the two chert samples was well within the range expected for terrestrial organic matter. We also describe a protocol that needs to be followed in the hydrogen isotope analysis of any insoluble organic matter.

A Low Cost, Self Acting, Liquid Hydrogen Boil-Off Recovery System

NASA Technical Reports Server (NTRS)

Pelfrey, Joy W.; Sharp, Kirk V. (Technical Monitor)

2001-01-01

The purpose of this research was to develop a prototype liquid hydrogen boll-off recovery system. Perform analyses to finalize recovery system cycle, design detail components, fabricate hardware, and conduct sub-component, component, and system level tests leading to the delivery of a prototype system. The design point and off-design analyses identified cycle improvements to increase the robustness of the system by adding a by-pass heat exchanger. Based on the design, analysis, and testing conducted, the recovery system will liquefy 31% of the gaseous boil off from a liquid hydrogen storage tank. All components, including a high speed, miniature turbocompressor, were designed and manufacturing drawings were created. All hardware was fabricated and tests were conducted in air, helium, and hydrogen. Testing validated the design, except for the turbocompressor. A rotor-to-stator clearance issue was discovered as a result of a concentricity tolerance stack-up.

Nonlinear partitioning of OH between Ca-rich plagioclase and arc basaltic melt

NASA Astrophysics Data System (ADS)

Hamada, M.; Ushioda, M.; Takahashi, E.

2011-12-01

The hydrogen in nominally anhydrous minerals (NAMs) is becoming a new proxy for dissolved H2O in silicate melts. Plagioclase is one of the NAMs which accommodates hydrogen as OH. Here, we report experimental results on the partitioning of OH between Ca-rich plagioclase and arc basaltic melt. We carried out hydrous melting experiments of arc basaltic magma at 350 MPa using an internally-heated pressure vessel. Starting material was hydrous glass (0.8 wt.%≦H2O≦4.5 wt.%) of an undifferentiated rock from Miyakejima volcano, a frontal-arc volcano in Izu-arc (MTL rock: 50.5% SiO2, 18.1% Al2O3, 4.9% MgO). A grain of Ca-rich plagioclase (≈ 1 mg, about An95, FeOt ≈ 0.5 wt.%) and ≈ 10 mg of powdered glasses were sealed in Au80Pd20 alloy capsule and kept at around the liquidus temperature. Liquidus phase of MTL rock at 350 MPa is always plagioclase with 0 to 4.5 wt.% H2O in melt, and therefore, a grain of plagioclase and hydrous melt are nearly in equilibrium. Oxygen fugacity during the melting experiments was not controlled; the estimated oxygen fugacity was 3 log unit above Ni-NiO buffer. Experiments were quenched after 24-48 hours. Concentrations of H2O in melt and concentration of OH in plagioclase were analyzed by infrared spectroscopy. Obtained correlation between H2O concentration in melt and OH concentration in plagioclase is nonlinear; partition coefficient in molar basis is ≈ 0.01 with low H2O in melt (≤ 1 wt.%), while it decreases down to ≈ 0.005 with increasing H2O in melt (Fig.1). The OH concentration of Ca-rich plagioclase (about An90) from the 1986 summit eruption of Izu-Oshima volcano, also a frontal-arc volcano in Izu arc, shows variation ranging from <50 ppm H2O through 300 ppm H2O as a result of polybaric degassing (Hamada et al. 2011, EPSL 308, 259-266). Melting experiments of hydrous basalts constrained that An90 plagioclase crystallizes form H2O-rich melt (up to 6 wt.% H2O). In consistent with previous studies, our experiments demonstrate that plagioclase with 300 ppm of OH can be in equilibrium with H2O-rich melt dissolving 5-6 wt.% H2O (Fig.1). Plagioclase from the 1986 summit eruption of Izu-Oshima volcano records polybaric degassing history of magma from 5-6 wt.% H2O in melt (300 ppm of OH in plagioclase) to almost dry melt (50 ppm of OH in plagioclase).

Ultrafine hydrogen storage powders

DOEpatents

Anderson, Iver E.; Ellis, Timothy W.; Pecharsky, Vitalij K.; Ting, Jason; Terpstra, Robert; Bowman, Robert C.; Witham, Charles K.; Fultz, Brent T.; Bugga, Ratnakumar V.

2000-06-13

A method of making hydrogen storage powder resistant to fracture in service involves forming a melt having the appropriate composition for the hydrogen storage material, such, for example, LaNi.sub.5 and other AB.sub.5 type materials and AB.sub.5+x materials, where x is from about -2.5 to about +2.5, including x=0, and the melt is gas atomized under conditions of melt temperature and atomizing gas pressure to form generally spherical powder particles. The hydrogen storage powder exhibits improved chemcial homogeneity as a result of rapid solidfication from the melt and small particle size that is more resistant to microcracking during hydrogen absorption/desorption cycling. A hydrogen storage component, such as an electrode for a battery or electrochemical fuel cell, made from the gas atomized hydrogen storage material is resistant to hydrogen degradation upon hydrogen absorption/desorption that occurs for example, during charging/discharging of a battery. Such hydrogen storage components can be made by consolidating and optionally sintering the gas atomized hydrogen storage powder or alternately by shaping the gas atomized powder and a suitable binder to a desired configuration in a mold or die.

Fugacity analysis of polycyclic aromatic hydrocarbons between microplastics and seawater

NASA Astrophysics Data System (ADS)

Lee, Hwang; Chang, Sein; Kim, Seung-Kyu; Kwon, Jung-Hwan

2017-03-01

Recently, the accumulation of plastic debris in the marine environment has become a great concern worldwide. Although plastics are biologically and chemically inert, plastic debris has been suspected of causing adverse effects on ecosystems due to the increase in reactivity by size reduction and/or micropollutants associated with plastics. Because of the high sorption capacity of microplastics toward organic micropollutants, it is suspected that microplastics may play roles in the distribution and fate of micropollutants. In order to quantitatively evaluate the "net flow" of environmental contaminants in water-plastic-organism systems, a fugacity analysis was conducted using concentrations of polycyclic aromatic hydrocarbons (PAHs) in open oceans and in polyethylene as a representative material of plastic debris. Ratio of fugacity in polyethylene to that in seawater showed a decreasing trend with increasing partition coefficient between polyethylene and seawater (KPE/sw). This indicates that phase equilibrium between polyethylene and seawater is not attained for higher molecular weight PAHs. Disequilibrium of high molecular weight PAHs suggests that transfer from seawater to plastic debris is thermodynamically driven and the role of plastic debris as a vector to transfer them to living organisms would be minimal. However, additives may slowly migrate from plastics into the environment causing potentially serious effects on ecosystems.

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

NASA Technical Reports Server (NTRS)

Szumila, Ian; Danielson, Lisa; Trail, Dustin

2017-01-01

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

Integrated fate modeling for exposure assessment of produced water on the Sable Island Bank (Scotian shelf, Canada).

PubMed

Berry, Jody A; Wells, Peter G

2004-10-01

Produced water is the largest waste discharge from the production phase of oil and gas wells. Produced water is a mixture of reservoir formation water and production chemicals from the separation process. This creates a chemical mixture that has several components of toxic concern, ranging from heavy metals to soluble hydrocarbons. Analysis of potential environmental effects from produced water in the Sable Island Bank region (NS, Canada) was conducted using an integrated modeling approach according to the ecological risk assessment framework. A hydrodynamic dispersion model was used to describe the wastewater plume. A second fugacity-based model was used to describe the likely plume partitioning in the local environmental media of water, suspended sediment, biota, and sediment. Results from the integrated modeling showed that the soluble benzene and naphthalene components reach chronic no-effect concentration levels at a distance of 1.0 m from the discharge point. The partition modeling indicated that low persistence was expected because of advection forces caused by tidal currents for the Sable Island Bank system. The exposure assessment for the two soluble hydrocarbon components suggests that the risks of adverse environmental effects from produced water on Sable Island Bank are low.

Potential structural material problems in a hydrogen energy system

NASA Technical Reports Server (NTRS)

Gray, H. R.; Nelson, H. G.; Johnson, R. E.; Mcpherson, B.; Howard, F. S.; Swisher, J. H.

1975-01-01

Potential structural material problems that may be encountered in the three components of a hydrogen energy system - production, transmission/storage, and utilization - were identified. Hydrogen embrittlement, corrosion, oxidation, and erosion may occur during the production of hydrogen. Hydrogen embrittlement is of major concern during both transmission and utilization of hydrogen. Specific materials research and development programs necessary to support a hydrogen energy system are described.

Chromatographic Assessment of Hydrogen-Bond Donating Ability

DTIC Science & Technology

1993-04-22

hydrogen-bond donors used in cocrystallizations . Hydrogen-bond donor solutes are chromatographed on a poly(vinylpyridine-divinylbenzene) column under...provides an a priori measure of the hydrogen- bond acidity of a potential cocrystal component. 20 DISTRIBUTION /AVAILABILITY OF ABSTRACT 21 ABSTRACT...general heuristic principle that has guided our cocrystallization studies is "the best hydrogen-bond donor hydrogen bonds to the best hydrogen-bond acceptor

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

NASA Astrophysics Data System (ADS)

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

1996-04-01

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

Assessing the Behavior of Typically Lithophile Elements Under Highly Reducing Conditions Relevant to the Planet Mercury

NASA Technical Reports Server (NTRS)

Rowland, Rick, II; Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Danielson, Lisa R.

2017-01-01

With the data returned from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (lvtESSENGER) mission, there are now numerous constraints on the physical and chemical properties of Mercury, including its surface composition. The high S and low FeO contents observed from MESSENGER suggest a low oxygen fugacity of the present materials on the planet's surface. Most of our understanding of elemental partitioning behavior comes from observations made on terrestrial rocks, but Mercury's oxygen fugacity is far outside the conditions of those samples, estimated at approximately 3-7 log units below the Iron-Wustite (lW) oxygen buffer, several orders of magnitude more reducing than other terrestrial bodies we have data from. With limited oxygen available, lithophile elements may instead exhibit chalcophile, halophile, or siderophile behaviors. Furthermore, very few natural samples of rocks that formed under reducing conditions (e.g., enstatite chondrites, achondrites, aubrites) are available in our collections for examination of this change in geochemical affinity. Our goal is to determine the elemental partitioning behavior of typically lithophile elements at lower oxygen fugacity as a function of temperature and pressure. Experiments were conducted at I GPa in a 13 mm QUICKpress piston cylinder and at 4 GPa in an 880-ton multi-anvil press, at temperatures up to 1850 C. The composition of starting materials for the experiments were designed so the final run products contained metal, silicate melt, and sulfide melt phases. Oxygen fugacity was controlled in the experiments by adding silicon metal to the samples, in order to utilize the Si-Si02 buffer, which is approx. 5 log units more reducing than the IW buffer at our temperatures of interest. The target silicate melt composition was diopside (CaMgSi206) because measured surface compositions indicate partial melting of a pyroxene-rich mantle. The results of our experiments will aid in our understanding of the fate of elements during the differentiation and thermal evolution of Mercury and other highly reducing planetary bodies.

Assessing the Behavior of Typically Lithophile Elements Under Highly Reducing Conditions Relevant to the Planet Mercury

NASA Technical Reports Server (NTRS)

Rowland, Rick, II; Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Danielson, Lisa R.

2017-01-01

With the data returned from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) mission, there are now numerous constraints on the physical and chemical properties of Mercury, including its surface composition. The high Sand low FeO contents observed from MESSENGER suggest a low oxygen fugacity of the present materials on the planet's surface. Most of our understanding of elemental partitioning behavior comes from observations made on terrestrial rocks, but Mercury's oxygen fugacity is far outside the conditions of those samples, estimated at approximately 3-7 log units below the Iron-Wtistite (lW) oxygen buffer, several orders of magnitude more reducing than other terrestrial bodies we have data from. With limited oxygen available, lithophile elements may instead exhibit chalcophile, halophile, or siderophile behaviors. Furthermore, very few natural samples of rocks that formed under reducing conditions (e.g., enstatite chondrites, achondrites, aubrites) are available in our collections for examination of this change in geochemical affinity. Our goal is to determine the elemental partitioning behavior of typically lithophile elements at lower oxygen fugacity as a function of temperature and pressure. Experiments were conducted at I GPa in a 13 mm QUICKpress piston cylinder and at 4 GPa in an 880-ton multianvil press, at temperatures up to 1850degC. The composition of starting materials for the experiments were designed so the final run products contained metal, silicate melt, and sulfide melt phases. Oxygen fugacity was controlled in the experiments by adding silicon metal to the samples, in order to utilize the Si-Si02 buffer, which is approximately 5 log units more reducing than the IW buffer at our temperatures of interest. The target silicate melt composition was diopside (CaMgSi206) because measured surface compositions indicate partial melting of a pyroxene-rich mantle. The results of our experiments will aid in our understanding of the fate of elements during the differentiation and thermal evolution of Mercury and other highly reducing planetary bodies.

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

NASA Astrophysics Data System (ADS)

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

2003-12-01

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

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

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

Highly Reducing Partitioning Experiments Relevant to the Planet Mercury

NASA Technical Reports Server (NTRS)

Rowland, Rick, II; Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Danielson, Lisa R.

2017-01-01

With the data returned from the MErcury Surface Space ENvironment GEochemistry and Ranging (MESSENGER) mission, there are now numerous constraints on the physical and chemical properties of Mercury, including its surface composition. The high S and low FeO contents observed from MESSENGER on the planet's surface suggests a low oxygen fugacity of the present planetary materials. Estimates of the oxygen fugacity for Mercurian magmas are approximately 3-7 log units below the Iron-Wüstite (Fe-FeO) oxygen buffer, several orders of magnitude more reducing than other terrestrial bodies we have data from such as the Earth, Moon, or Mars. Most of our understanding of elemental partitioning behavior comes from observations made on terrestrial rocks, but Mercury's oxygen fugacity is far outside the conditions of those samples. With limited oxygen available, lithophile elements may instead exhibit chalcophile, halophile, or siderophile behaviors. Furthermore, very few natural samples of rocks that formed under reducing conditions are available in our collections (e.g., enstatite chondrites, achondrites, aubrites). With this limited amount of material, we must perform experiments to determine the elemental partitioning behavior of typically lithophile elements as a function of decreasing oxygen fugacity. Experiments are being conducted at 4 GPa in an 880-ton multi-anvil press, at temperatures up to 1850degC. The composition of starting materials for the experiments were selected for the final run products to contain metal, silicate melt, and sulfide melt phases. Oxygen fugacity is controlled in the experiments by adding silicon metal to the samples, using the Si-SiO2 oxygen buffer, which is approximately 5 log units more reducing than the Fe-FeO oxygen buffer at our temperatures of interest. The target silicate melt compositional is diopside (CaMgSi2O6) because measured surface compositions indicate partial melting of a pyroxene-rich mantle. Elements detected on Mercury's surface by MESSENGER (K, Na, Fe, Ti, Cl, Al, Cr, Mn, U, Th) and other geochemically relevant elements (P, F, H, N, C, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb) are added to the starting composition at trace abundances (approximately 500 ppm) so that they are close enough to infinite dilution to follow Henry's law of trace elements, and their partitioning behavior can be measured between the metal, silicate, and sulfide phases. The results of these experiments will allow us to assess the thermal and magmatic evolution of the planet Mercury from a geochemical standpoint.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Hydrogen Incorporation into Olivine at 9-15 GPa: Implication for Water Dynamics near the 410-km Seismic Discontinuity

NASA Astrophysics Data System (ADS)

Litasov, K.; Ohtani, E.; Kagi, H.; Shatskiy, A.; Ghosh, S.; Lakshtanov, D.; Bass, J.; Matveev, S.

2006-12-01

The hydrogen solubility and hydrogen incorporation mechanism into (Mg,Fe)2SiO4 olivine have been studied at pressures of 9-15 GPa and temperatures of 1100-2000°C. Samples were synthesized using a multianvil apparatus from Fo90 + 4-15 wt.% H2O mixture without controlling oxygen fugacity. Also, pure forsterite crystals were synthesized in KHCO3-Mg(OH)2 flux. Samples were studied by Fourier Transform Infrared spectroscopy (FTIR) and H (H2O) contents were calculated from IR spectra using the calibration by Bell et al. (2003). The hydrogen solubility increases with pressure, but the temperature dependence is complex. The hydrogen solubility increases from 1100-1400°C and then decreases at 1400-2000°C. Maximum hydrogen solubility, equivalent to 1.15 wt.% H2O, was determined in olivine at 13.5 GPa and 1400°C. At temperatures of 1800-2000°C the H2O contents of olivine are very low (280-590 ppm). Hydrogen solubility in Fo90 is consistent with that in pure forsterite studied by Lemaire et al. (2004) and Smyth et al. (2006) indicating minor influence of Fe on hydrogen incorporation. The IR spectra of olivines are composed of several OH absorption bands at 3300-3613 cm-1. IR spectra with the E-field vector parallel to the a-axis show the strongest absorbance, dominated by peaks at 3613 and 3579 cm-1. Although structural calculations are consistent with hydrogen incorporation into octahedral vacancies in olivine (e.g. Smyth et al., 2006; Kudoh et al., 2006) we strongly suggest that majority of observed peaks (at 3533, 3548, 3566, 3579, and 3613 cm-1) are due to hydrogen associated with Si- vacancies. This is consistent with microprobe analyses of the samples, which show a clear deficit of Si in olivines at the highest H2O-contents. Minor bands at 3300-3400 cm-1 may be due to Fe3+ substitution and those at 3400-3500 cm-1 due to vacancies in Mg structural positions. The peak at 3598 cm-1 previously attributed to Mg-vacancies should be addressed to Si-vacancies. The strongest peaks corresponding to Mg vacancies (or OH interstitials) at 3160 and 3220 cm-1 are absent. These conclusions are consistent with molecular dynamic calculations (e.g. Brodholt and Refson, 2000) and IR observations of olivines synthesized under controlled SiO2 and MgO activities (Matveev et al., 2001; 2005; Lemaire et al., 2004; Berry et al., 2005). Significant hydrogen incorporation on Si-site vacancies in olivine is important for hydrogen diffusion models for olivine, which have been studied only for the case where hydrogen incorporation into Mg-Fe-vacancies dominates. A revision of structural refinements of hydrous olivine might be necessary. Discrimination of IR absorption bands between Si- and Mg-vacancies in the olivine structure has an important implication for natural olivines in kimberlites, to determine the style of mantle metasomatism (e.g. silicate melt metasomatism, with high SiO2 activity, versus carbonatitic, with high activity of MgO), relation to their depth of origin, oxidation state, and geodynamic settings.

The hydrogen coma of Comet P/Halley observed in Lyman-alpha using sounding rockets

NASA Technical Reports Server (NTRS)

Mccoy, R. P.; Meier, R. R.; Keller, H. U.; Opal, C. B.; Carruthers, G. R.

1992-01-01

Hydrogen Lyman-alpha (121.6 nm) images of Comet P/Halley were obtained using sounding rockets launched from White Sands Missile Range on 24.5 February and 13.5 March 1986. The second rocket was launched 13 hours before the fly-by of the Giotto spacecraft. An electrographic camera on both flights provided Lyman-alpha images covering a 20 field of view with 3 arcmin resolution. The data from both flights have been compared with a time-dependent model of hydrogen kinetics. To match the measured isophote contours, hydrogen sources with velocity components of 8 km/s and 20 km/s (from OH and H2O respectively) as well as a low velocity component (about 2 km/s) are required. This low velocity component is thought to result from thermalization of fast hydrogen atoms within the collision zone, providing an important diagnostic of temperature and density near the nucleus. Hydrogen production rates of 3.8 x 10 exp 30/s and 1.7 x 10 exp 30/s have been obtained for the two observations.

The solubility of gold in hydrogen sulfide gas: An experimental study

NASA Astrophysics Data System (ADS)

Zezin, Denis Yu.; Migdisov, Artashes A.; Williams-Jones, Anthony E.

2007-06-01

The solubility of gold in H 2S gas has been investigated at temperatures of 300, 350 and 400 °C and pressures up to 230 bars. Experimentally determined values of the solubility of Au are 0.4-1.4 ppb at 300 °C, 1-8 ppb at 350 °C and 8.6-95 ppb at 400 °C. Owing to a positive dependence of the logarithm of the fugacity of gold on the logarithm of the fugacity of H 2S, it is proposed that the solubility of Au can be attributed to formation of a solvated gaseous sulfide or bisulfide complex through reactions of the type: Au(s)+(n+1)·HS(g)=AuS·(HS)n(g)+H(g) or Au(g)+(n+1)·HS(g)=AuHS·(HS)n(g)+{1}/{2}H(g) which are f-dependent; n is a statistical solvation number. If the redox potential is buffered by S/H 2S (the case in our study), the corresponding reactions are: Au(s)+n·HS(g)+S(l)=AuS·(HS)n(g) or Au(s)+(n+{1}/{2})·HS(g)+{1}/{2}S(l)=AuHS·(HS)n(g) Values of n for these latter reactions were calculated to be 1.8 and 1.2 at 300 °C, 1.7 and 1.0 at 350 °C, 2.2 and 1.7 at 400 °C, respectively. The equilibrium constants for reactions 3 and D increase with temperature and have values of log K = -11.1 ± 0.2 at 300 °C (both reactions), -10.7 ± 0.3 and -10.5 ± 0.3 at 350 °C, and -10.6 ± 0.2 and -10.4 ± 0.2 at 400 °C, respectively. At the conditions of this study, the solubility of gold in H 2S gas is relatively high, and the results obtained provide strong evidence that H 2S can play an important role in the vapor transport of gold and the formation of hydrothermal gold deposits.

Cold weather hydrogen generation system and method of operation

DOEpatents

Dreier, Ken Wayne; Kowalski, Michael Thomas; Porter, Stephen Charles; Chow, Oscar Ken; Borland, Nicholas Paul; Goyette, Stephen Arthur

2010-12-14

A system for providing hydrogen gas is provided. The system includes a hydrogen generator that produces gas from water. One or more heat generation devices are arranged to provide heating of the enclosure during different modes of operation to prevent freezing of components. A plurality of temperature sensors are arranged and coupled to a controller to selectively activate a heat source if the temperature of the component is less than a predetermined temperature.

Evaluation of RTV as a Moldable Matrix When Combined With Molecular Sieve and Organic Hydrogen Getter

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

Knight, J. A.

2011-12-01

This work was undertaken in an effort to develop a combined RTV 615/3Å molecular sieve/DEB molded component. A molded RTV 615/3Å molecular sieve component is currently in production, and an RTV 615/DEB component was produced in the past. However, all three materials have never before been combined in a single production part, and this is an opportunity to create a new component capable of being molded to shape, performing desiccation, and hydrogen gettering. This analysis looked at weapons system parameters and how they might influence part design. It also looked at material processing and how it related to mixing, activatingmore » a dessicant, and hydrogen uptake testing.« less

The Derivation Of A CO2 Fugacity Climatology From SOCAT's Global In SITU Data

NASA Astrophysics Data System (ADS)

Goddijn-Murphy, L. M.; Woolf, D. K.; Land, P. E.; Shutler, J. D.

2013-12-01

The Surface Ocean CO2 Atlas (SOCAT) has made millions of global underway sea surface measurements of CO2 publicly available, all in a uniform format and presented as fugacity, fCO2. However, these fCO2 values are valid strictly only for the instantaneous temperature at measurement and are not ideal for climatology. We recomputed these fCO2 values for the measurement month to be applicable to climatological sea surface temperatures, extrapolated to reference year 2010. The data were then spatially interpolated on a 1°×1° grid of the global oceans to produce 12 monthly fCO2 distributions. Our climatology data will be shared with the science community.

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

USGS Publications Warehouse

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

1977-01-01

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

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

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

Brounce, Maryjo; Stolper, Edward; Eiler, John

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

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

PubMed

Brounce, Maryjo; Stolper, Edward; Eiler, John

2017-08-22

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

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

PubMed Central

Stolper, Edward; Eiler, John

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

Brounce, Maryjo; Stolper, Edward; Eiler, John

2017-08-01

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

Design of a nickel-hydrogen battery simulator for the NASA EOS testbed

NASA Technical Reports Server (NTRS)

Gur, Zvi; Mang, Xuesi; Patil, Ashok R.; Sable, Dan M.; Cho, Bo H.; Lee, Fred C.

1992-01-01

The hardware and software design of a nickel-hydrogen (Ni-H2) battery simulator (BS) with application to the NASA Earth Observation System (EOS) satellite is presented. The battery simulator is developed as a part of a complete testbed for the EOS satellite power system. The battery simulator involves both hardware and software components. The hardware component includes the capability of sourcing and sinking current at a constant programmable voltage. The software component includes the capability of monitoring the battery's ampere-hours (Ah) and programming the battery voltage according to an empirical model of the nickel-hydrogen battery stored in a computer.

Electrochemical sensor for monitoring electrochemical potentials of fuel cell components

DOEpatents

Kunz, Harold R.; Breault, Richard D.

1993-01-01

An electrochemical sensor comprised of wires, a sheath, and a conduit can be utilized to monitor fuel cell component electric potentials during fuel cell shut down or steady state. The electrochemical sensor contacts an electrolyte reservoir plate such that the conduit wicks electrolyte through capillary action to the wires to provide water necessary for the electrolysis reaction which occurs thereon. A voltage is applied across the wires of the electrochemical sensor until hydrogen evolution occurs at the surface of one of the wires, thereby forming a hydrogen reference electrode. The voltage of the fuel cell component is then determined with relation to the hydrogen reference electrode.

Fe-Distribution and Hydrogen Generation During Serpentinization

NASA Astrophysics Data System (ADS)

Klein, F.; Bach, W.; Jöns, N.; McCollom, T.; Berquó, T.; Moskowitz, B.

2009-04-01

Serpentinization of peridotite generates large amounts of dihydrogen (H2,aq), indicated by the presence of Ni-Fe alloys and low-sulfur-fugacity sulfides, e. g. awaruite and pentlandite, in serpentinites. Hydrogen is produced when ferrous iron in olivine is oxidized by water to ferric iron in secondary magnetite and serpentine. This process is strongly dependent on bulk rock composition, water-to-rock ratio and temperature. These relations were examined in thermodynamic reaction path models (using the EQ3/6 computer code) with dunitic and harzburgitic rock compositions. The model results were compared with electron microprobe analyses, bulk magnetization measurements, and Mößbauer spectroscopy of partially to fully serpentinized dunites and harzburgites from Ocean Drilling Program Leg 209, Hole 1274A, Mid-Atlantic Ridge 15 °N. These samples have mesh rims that reveal a distinct in-to-out zoning, starting with brucite (Mg# 80) at the interface with olivine, then a zone of serpentine (Mg# 95) + brucite ± magnetite, and finally serpentine + magnetite in the outermost mesh rim. The composition of co-existing serpentine and brucite in pseudomorphic mesh rims is virtually constant in most samples from 32 to 147 meters below seafloor, suggesting similar alteration conditions of olivine downhole. Bulk magnetization measurements of microdrilled mesh rims in combination with thin section petrography revealed a positive correlation of magnetite content with extent of serpentinization. Where relic olivine is present, the magnetite content is significantly lower then in fully serpentinized rocks. In these domains with sparse magnetite, Mößbauer spectra revealed Fe3+/‘ Fe values between 0.30 and 0.48 for paramagnetic minerals in the mesh rims (i. e., secondary hydrous phases). In heavily to completely serpentinized rocks with abundant magnetite, Fe3+/‘ Fe values of the paramagnetic phases are consistently higher and range from 0.53 to 0.68. In the EQ3/6 runs, a serpentine solid solution model that includes greenalite and hisingerite (Fe2Si2O5(OH)4) was used in investigating the distribution of iron between serpentine and magnetite and its oxidation state in serpentine. Our model computations predict that above 330 °C and water activities near unity, the dissolution of olivine and coeval formation of serpentine, magnetite and dihydrogen is significantly obstructed by the dearth of silica. At these temperatures, hydrogen fugacities are too low for awaruite and pentlandite to be stable. When temperatures drop below 320-330 °C, brucite becomes stable and hydrogen generation is facilitated, because the reaction of olivine to serpentine, magnetite and brucite requires no external silica. The MgO-FeO-Fe2O3-SiO2-H2O and Fe-Ni-Co-O-S phase relations observed in the mesh rims suggest that serpentine and brucite from Hole 1274A likely formed at temperatures between 150 and 250 °C and water-to-rock ratios (w/r) between 5 and 0.1. However, formation of awaruite must have taken place during main stage serpentinization at temperatures between 200-250 °C and w/r < 1, when alteration conditions were sufficiently reducing. Likewise, the model predicts the Fe3+/‘ Fe ratios of mesh-rim serpentine/brucite observed in incompletely serpentinized rocks of serpentine (0.3 to 0.5) at low w/r ratios and T < 250 °C. The calculation results furthermore indicate that elevated Fe3+/‘ Fe ratios (0.5 to 0.7) measured in fully serpentinized rocks appear to correspond to higher w/r ratios and less reducing conditions. Our study indicates that unprecedented details about the reaction sequences during serpentinization may be obtained from merging careful petrographic, magnetic, and spectroscopic analyses with comprehensive thermodynamic modeling.

The stationary non-equilibrium plasma of cosmic-ray electrons and positrons

NASA Astrophysics Data System (ADS)

Tomaschitz, Roman

2016-06-01

The statistical properties of the two-component plasma of cosmic-ray electrons and positrons measured by the AMS-02 experiment on the International Space Station and the HESS array of imaging atmospheric Cherenkov telescopes are analyzed. Stationary non-equilibrium distributions defining the relativistic electron-positron plasma are derived semi-empirically by performing spectral fits to the flux data and reconstructing the spectral number densities of the electronic and positronic components in phase space. These distributions are relativistic power-law densities with exponential cutoff, admitting an extensive entropy variable and converging to the Maxwell-Boltzmann or Fermi-Dirac distributions in the non-relativistic limit. Cosmic-ray electrons and positrons constitute a classical (low-density high-temperature) plasma due to the low fugacity in the quantized partition function. The positron fraction is assembled from the flux densities inferred from least-squares fits to the electron and positron spectra and is subjected to test by comparing with the AMS-02 flux ratio measured in the GeV interval. The calculated positron fraction extends to TeV energies, predicting a broad spectral peak at about 1 TeV followed by exponential decay.

Modeling of composite hydrogen storage cylinders using finite element analysis

DOT National Transportation Integrated Search

2008-02-01

Pressurized hydrogen storage cylinders are critical components of hydrogen transportation systems. Composite cylinders have pressure/thermal relief devices that are activated in case of an emergency. The difficulty in accurately analyzing the behavio...

Hydrogen Infrastructure Testing and Research Facility Video (Text Version)

Science.gov Websites

grid integration, continuous code improvement, fuel cell vehicle operation, and renewable hydrogen stations. NRELs research on hydrogen safety provides guidance for safe operation, handling, and use of standards and testing fuel cell and hydrogen components for operation and safety. Building on NRELs Wind-to

The growth of zinc selenide single crystals by physical vapor transport in microgravity

NASA Technical Reports Server (NTRS)

Anderson, Elmer E.; Rosenberger, Franz E.; Cheng, Hai-Yuin

1990-01-01

Growth and characterization studies will be performed on zinc selenide single crystals. The high temperature outgassing behavior of the silica ampoule material will be studied in order to develop a cleaning and bake-out procedure that will minimize the amount of impurities introduced into the vapor from the ampoule materials and in particular during the seal-off procedure. The outgassing behavior of the ZnSe starting material will be studied during high vacuum refinement at elevated temperatures in order to develop a temperature pressure program that will optimize the removal of impurities while minimizing a shift in stoichiometry due to preferred evaporation of the higher fugacity component. The mass spectrometer system was completed, and after calibration, will be used to perform the above tasks. The system and its operation is described in detail.

Development of Press Hardening Steel with High Resistance to Hydrogen Embrittlement

NASA Astrophysics Data System (ADS)

Bian, Jian; Mohrbacher, Hardy; Lu, Hongzhou; Wang, Wenjun

Press hardening has become the state-of-art technology in the car body manufacturing to enhance safety standard and to reduce CO2 emission of new vehicles. However the delayed cracking due to hydrogen embrittlement remains to be a critical issue. Generally press hardening steel is susceptible to hydrogen embrittlement due to ultra-high strength and martensitic microstructure. The hydrogen charging tests clearly demonstrate that only a few ppm of diffusible hydrogen is sufficient to cause such embrittlement. Currently the hydrogen embrittlement cannot be detected in the press hardened components and the embitteled components could collapse in the crash situation with fatal consequences arisen through dramatic loss in both strength and ductility. This paper introduces a new metallurgical solution to increase the resistance to hydrogen embrittlement of conventional press hardening steel based on 22MnB5 by Nb microalloying. In the hydrogen embrittlement and permeation tests the impact of Nb microalloying on the hydrogen embrittlement behavior was investigated under different hydrogen charging conditions and constant load. The test results revealed that Nb addition increases the resistance to hydrogen embrittlement due to reduced hydrogen diffusivity. The focus of this paper is to investigate the precipitation behavior of microalloying elements by using TEM and STEM and to find out the mechanisms leading to higher performance against hydrogen embrittlement of Nb alloyed steels.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

The wet solidus of silica: Predictions from the scaled particle theory and polarized continuum model

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

Ottonello, G., E-mail: giotto@dipteris.unige.it; Vetuschi Zuccolini, M.; Richet, P.

2015-02-07

We present an application of the Scaling Particle Theory (SPT) coupled with an ab initio assessment of the electronic, dispersive, and repulsive energy terms based on the Polarized Continuum Model (PCM) aimed at reproducing the observed solubility behavior of OH{sub 2} over the entire compositional range from pure molten silica to pure water and wide pressure and temperature regimes. It is shown that the solution energy is dominated by cavitation terms, mainly entropic in nature, which cause a large negative solution entropy and a consequent marked increase of gas phase fugacity with increasing temperatures. Besides, the solution enthalpy is negativemore » and dominated by electrostatic terms which depict a pseudopotential well whose minimum occurs at a low water fraction (X{sub H{sub 2O}}) of about 6 mol. %. The fine tuning of the solute-solvent interaction is achieved through very limited adjustments of the electrostatic scaling factor γ{sub el} which, in pure water, is slightly higher than the nominal value (i.e., γ{sub el}  =  1.224 against 1.2), it attains its minimum at low H{sub 2}O content (γ{sub el} = 0.9958) and then rises again at infinite dilution (γ{sub el}   =  1.0945). The complex solution behavior is interpreted as due to the formation of energetically efficient hydrogen bonding when OH functionals are in appropriate amount and relative positioning with respect to the discrete OH{sub 2} molecules, reinforcing in this way the nominal solute-solvent inductive interaction. The interaction energy derived from the SPT-PCM calculations is then recast in terms of a sub-regular Redlich-Kister expansion of appropriate order whereas the thermodynamic properties of the H{sub 2}O component at its standard state (1-molal solution referred to infinite dilution) are calculated from partial differentiation of the solution energy over the intensive variables.« less

N(4)-Methyl-N(4)-(2-methylphenyl)-1H-pyrazolo[3,4-d]pyrimidine-4,6-diamine-ethanol-hydrazine (1/0.865/0.135): hydrogen-bonded ribbons containing four independent ring types.

PubMed

Trilleras, Jorge; Quiroga, Jairo; Cobo, Justo; Glidewell, Christopher

2009-06-01

N(4)-Methyl-N(4)-(2-methylphenyl)-1H-pyrazolo[3,4-d]pyrimidine-4,6-diamine crystallizes from ethanol as a mixed solvate, C(13)H(14)N(6).0.865C(2)H(6)O.0.135N(2)H(4), (I), where the hydrazine has been carried through from the initial preparation. Within the heterocyclic component, the 2-methylphenyl substituent is disordered over two sets of sites. There is an intramolecular C-H...pi(arene) hydrogen bond, which may control the molecular conformation of the heterocycle. The heterocyclic molecules are linked by two independent N-H...N hydrogen bonds in a chain containing two types of R(2)(2)(8) ring. The ethanol component is linked to this chain by a combination of O-H...N and N-H...O hydrogen bonds and the hydrazine component by two N-H...N hydrogen bonds, so generating two R(3)(3)(9) rings and thus forming a ribbon containing four distinct ring types.

Two-component Fermi-liquid theory - Equilibrium properties of liquid metallic hydrogen

NASA Technical Reports Server (NTRS)

Oliva, J.; Ashcroft, N. W.

1981-01-01

It is reported that the transition of condensed hydrogen from an insulating molecular crystal phase to a metallic liquid phase, at zero temperature and high pressure, appears possible. Liquid metallic hydrogen (LMH), comprising interpenetrating proton and electron fluids, would constitute a two-component Fermi liquid with both a very high component-mass ratio and long-range, species-dependent bare interactions. The low-temperature equilibrium properties of LMH are examined by means of a generalization to the case of two components of the phenomenological Landau Fermi-liquid theory, and the low-temperature specific heat, compressibility, thermal expansion coefficient and spin susceptibility are given. It is found that the specific heat and the thermal expansion coefficient are vastly greater in the liquid than in the corresponding solid, due to the presence of proton quasiparticle excitations in the liquid.

Hydrogen concentration in plagioclaes as a hygrometer of magmas: Approaches from melt inclusion analyses and hydrous melting experiments

NASA Astrophysics Data System (ADS)

Hamada, M.; Ushioda, M.; Fujii, T.; Takahashi, E.

2012-12-01

Plagioclase is one of the nominally anhydrous minerals (NAMs) which accommodates hundreds wt. ppm of hydrogen. Hydrogen in igneous plagioclase (OH) can act as a proxy of dissolved H2O in silicate melt. In order to use it as a practical hygrometer of magmas, we studied partitioning of hydrogen between plagioclase and basaltic melt dis-solving H2O (0.3˜5.5 wt.%) by two approaches: analyses of plagioclase-hosted melt inclusions (H2O≈0.3 wt.%) from mid-ocean ridge basalt (MORB) and hydrogen partitioning experiments between An96 plagioclase and hydrous basaltic melt (0.8 wt.%≦H2O≦5.5 wt.%) at 0.35 GPa. Concentration hydrogen in plagioclase and concentration of H2O in basaltic glasses were analyzed by infrared spectroscopy. As a first series of this study, plagioclase-hosted melt inclusions in MORB (50.5% SiO2, 15.1% Al2O3, 7.4% MgO) from the Rodriguez triple junction in the Indian Ocean were analyzed. The hydrogen concentration of plagioclase is less than 50 wt. ppm water, and no correlation between hydrogen concentration and anorthite content is recognized. Average H2O concentrations in melt inclusions is 0.3 wt.%. Therefore, apparent partition coefficient of hydrogen between plagioclase and melt is ≈ 0.01 in molar basis. As a second series of this study, hydrous melting experiments of arc basaltic magma were performed at 350 MPa using internally-heated pressure vessel. Starting material was hydrous glass (0.8 wt.%≦H2O≦5.5 wt.%) of an undifferentiated rock from Miyakejima volcano, a frontal-arc volcano in Izu-arc (MTL rock: 50.5% SiO2, 18.1% Al2O3, 4.9% MgO). A grain of Ca-rich plagioclase (≈1 mg, about An96) and 10 mg of powdered glasses were sealed in Au80Pd20 alloy capsule, and then kept at temperature at around the liquidus. Liquidus phase of MTL rock at 350 MPa is always plagioclase with 0 to 5.5 wt.% H2O in melt, and therefore, a grain of plagioclase and hydrous melt were nearly in equilibrium. Oxygen fugacity (fO2) during the melting experiments was not controlled, which was estimated to be 3 log unit above Ni-NiO buffer. Experiments were quenched after 24 hours, long enough to attain equi-librium partitioning of hydrogen between plagioclase and melt. Combining two series of study, we formulated empirical equation to correlate hydrogen concentration in plagioclase and H2O concentration in melt as: Hydrogen in plagioclase (wt. ppm water) ≈ 94.3×√(H2O in melt, wt.%). We also determined partition coefficient of hydrogen between plagioclase and basaltic melt to be 0.01±0.005 under H2O-poor conditions (≤150 wt. ppm water in plagioclase, ≤2 wt.% H2O in melt) and to be 0.008±0.002 under H2O-rich conditions (≥150 wt. ppm water in plagioclase, ≥2 wt.% H2O in melt). Slight decrease in hydrogen partitioning with increasing H2O can be related to change in hydrogen site in crystal structure of plagioclase (possibly tetrahedral sites). Peak position of infrared absorbance spectra lies at 3200-3400 cm-1 under H2O-poor condition and at 3600 cm-1 under H2O-rich condition, suggesting expansion of O-H…O bond length with increasing H2O.

Assessing the Behavior of Typically Lithophile Elements Under Highly Reducing Conditions Relevant to the Planet Mercury

NASA Astrophysics Data System (ADS)

Rowland, R. L., II; Vander Kaaden, K. E.; McCubbin, F. M.; Danielson, L. R.

2017-12-01

With the data returned from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) mission, there are now numerous constraints on the physical and chemical properties of Mercury, including its surface composition. The high S and low FeO contents observed from MESSENGER suggest a low oxygen fugacity of the present materials on the planet's surface. Most of our understanding of elemental partitioning behavior comes from observations made on terrestrial rocks, but Mercury's oxygen fugacity is far outside the conditions of those samples, estimated at approximately 3-7 log units below the Iron-Wüstite (IW) oxygen buffer, several orders of magnitude more reducing than other terrestrial bodies we have data from. With limited oxygen available, lithophile elements may instead exhibit chalcophile, halophile, or siderophile behaviors. Furthermore, very few natural samples of rocks that formed under reducing conditions (e.g., enstatite chondrites, achondrites, aubrites) are available in our collections for examination of this change in geochemical affinity. Our goal is to determine the elemental partitioning behavior of typically lithophile elements at lower oxygen fugacity as a function of temperature and pressure. Experiments were conducted at 1 GPa in a 13 mm QUICKpress piston cylinder and at 4 GPa in an 880-ton multi-anvil press, at temperatures up to 1850°C. The composition of starting materials for the experiments were designed so the final run products contained metal, silicate melt, and sulfide melt phases. Oxygen fugacity was controlled in the experiments by adding silicon metal to the samples, in order to utilize the Si-SiO2 buffer, which is 5 log units more reducing than the IW buffer at our temperatures of interest. The target silicate melt composition was diopside (CaMgSi2O6) because measured surface compositions indicate partial melting of a pyroxene-rich mantle. The results of our experiments will aid in our understanding of the fate of elements during the differentiation and thermal evolution of Mercury and other highly reducing planetary bodies.

Hydrogen and Storage Initiatives at the NASA JSC White Sands Test Facility

NASA Technical Reports Server (NTRS)

Maes, Miguel; Woods, Stephen S.

2006-01-01

NASA WSTF Hydrogen Activities: a) Aerospace Test; b) System Certification & Verification; c) Component, System, & Facility Hazard Assessment; d) Safety Training Technical Transfer: a) Development of Voluntary Consensus Standards and Practices; b) Support of National Hydrogen Infrastructure Development.

Janus dendrimersomes coassembled from fluorinated, hydrogenated, and hybrid Janus dendrimers as models for cell fusion and fission.

PubMed

Xiao, Qi; Sherman, Samuel E; Wilner, Samantha E; Zhou, Xuhao; Dazen, Cody; Baumgart, Tobias; Reed, Ellen H; Hammer, Daniel A; Shinoda, Wataru; Klein, Michael L; Percec, Virgil

2017-08-22

A three-component system of Janus dendrimers (JDs) including hydrogenated, fluorinated, and hybrid hydrogenated-fluorinated JDs are reported to coassemble by film hydration at specific ratios into an unprecedented class of supramolecular Janus particles (JPs) denoted Janus dendrimersomes (JDSs). They consist of a dumbbell-shaped structure composed of an onion-like hydrogenated vesicle and an onion-like fluorinated vesicle tethered together. The synthesis of dye-tagged analogs of each JD component enabled characterization of JDS architectures with confocal fluorescence microscopy. Additionally, a simple injection method was used to prepare submicron JDSs, which were imaged with cryogenic transmission electron microscopy (cryo-TEM). As reported previously, different ratios of the same three-component system yielded a variety of structures including homogenous onion-like vesicles, core-shell structures, and completely self-sorted hydrogenated and fluorinated vesicles. Taken together with the JDSs reported herein, a self-sorting pathway is revealed as a function of the relative concentration of the hybrid JD, which may serve to stabilize the interface between hydrogenated and fluorinated bilayers. The fission-like pathway suggests the possibility of fusion and fission processes in biological systems that do not require the assistance of proteins but instead may result from alterations in the ratios of membrane composition.

Iron titanium manganase alloy hydrogen storage

DOEpatents

Reilly, James J.; Wiswall, Jr., Richard H.

1979-01-01

A three component alloy capable of reversible sorption of hydrogen having the chemical formula TiFe.sub.1-x Mn.sub.x where x is in the range of about 0.02 to 0.5 and the method of storing hydrogen using said alloy.

Neutrons Provide the First Nanoscale Look at a Living Cell Membrane

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

None

Neutron scattering is a valuable technique for studying cell membranes, but signals from the cell’s other components such as proteins, RNA, DNA and carbohydrates can get in the way. An ORNL team made these other components practically invisible to neutrons by combining specific levels of heavy hydrogen (deuterium) with normal hydrogen within the cell.

Component variations and their effects on bipolar nickel-hydrogen cell performance

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.; Gahn, Randall F.; Gonzalez-Sanabria, Olga D.; Cataldo, Robert L.; Gemeiner, Russel P.

1987-01-01

A 50 cell bipolar nickel-hydrogen battery was assembled to demonstrate the feasibility of constructing a high voltage stack of cells. Various component combinations were tested in this battery. The battery had approximately 1 ampere-hour of capacity and was constructed from components with an active area of 2 x 2 inches. The components were parametrically varied to give a comparison of nickel electrodes, hydrogen electrodes, separators, fill procedures and electrolyte reservoir plate thicknesses. Groups of five cells were constructed using the same components; ten combinations were tested in all. The battery was thoroughly characterized at various change and discharge rates as well as with various pulse patterns and rates. Over a period of 1400 40-percent DOD LEO cycles some of the groups began to exhibit performance differences. In general, only separator variations had a significant effect on cell performance. It also appears that shunt currents may have been operating within the stack, resulting in electrolyte transfer from one cell to another, thus contributing to cell performance variations.

Component variations and their effects on bipolar nickel-hydrogen cell performance

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.; Gahn, Randall F.; Gonzalez-Sanabria, Olga D.; Cataldo, Robert L.; Gemeiner, Russel P.

1987-01-01

A 50 cell bipolar nickel-hydrogen battery was assembled to demonstrate the feasibility of constructing a high voltage stack of cells. Various component combinations were tested in this battery. The battery had approximately 1 ampere-hour of capacity and was constructed from components with an active area of 2" X 2". The components were parametrically varied to give a comparison of nickel electrodes, hydrogen electrodes, separators, fill procedures and electrolyte reservoir plate thicknesses. Groups of five cells were constructed using the same components; ten combinations were tested in all. The battery was thoroughly characterized at various change and discharge rates as well as with various pulse patterns and rates. Over a period of 1400 40% DOD LEO cycles some of the groups began to exhibit performance differences. In general, only separator variations had a significant effect on cell performance. It also appears that shunt currents may have been operating within the stack, resulting in electrolyte transfer from one cell to another, thus contributing to cell performance variations.

Spectral chemistry of green glass-bearing 15426 regolith

NASA Technical Reports Server (NTRS)

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

1983-01-01

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

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

PubMed

Righter, Kevin

2015-09-01

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

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

NASA Technical Reports Server (NTRS)

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

2016-01-01

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

PCB and organochlorine pesticides in northern fulmars (Fulmarus glacialis) from a High Arctic colony: chemical exposure, fate, and transfer to predators.

PubMed

Foster, Karen L; Mallory, Mark L; Hill, Laura; Blais, Jules M

2011-09-01

Organochlorine contaminant concentrations, associated fugacities, and stable isotopes of nitrogen (δ(15) N) are reported for liver, whole body homogenate, and opportunistically collected samples of prey (amphipods), stomach oils, digestive tract contents, and guano for northern fulmars (Fulmarus glacialis) collected at Cape Vera, Devon Island in the Canadian High Arctic. Liver concentrations of polychlorinated biphenyls (ΣPCB) and ΣDDT were on average 49.9 ± 35.4 ng g(-1) and 29.9 ± 25.2 ng g(-1) wet weight, respectively. Whole body homogenate concentrations of ΣPCB and ΣDDT were 637 ± 293 ng g(-1) and 365 ± 212 ng g(-1) wet weight, respectively. A mass and energy balance showed that whole body contaminant concentrations, which are seldom reported for Arctic seabirds, are critical in determining contaminant exposure and associated risk to predators such as the Arctic fox (Alopex lagopus). Biomagnification in the fulmars is evident, because concentrations and fugacities of contaminants were generally one to three orders of magnitude higher than those of likely prey items. The fate of diet-derived contaminants along the digestive tract is discussed, in particular with respect to stomach oils, which are used to feed chicks and for defensive purposes. The benefits of considering both concentrations and fugacities are demonstrated and provide information on the absorption and distribution of chemicals within the fulmars and contaminant transfer to offspring and predators. Copyright © 2011 SETAC.

Initial H2O content and conditions of parent magma origin for Gorely volcano (Southern Kamchatka) estimated by trace element thermobarometry

NASA Astrophysics Data System (ADS)

Nazarova, D. P.; Portnyagin, M. V.; Krasheninnikov, S. P.; Mironov, N. L.; Sobolev, A. V.

2017-01-01

The formation conditions of the parental magmas of Gorely volcano, which is located behind a volcanic front in Southern Kamchatka, have been evaluated using the modern methods of micro-element thermobarometry. These magmas contained 1.7 ± 0.8 (2σ) wt % of H2O, the majority (82%) of which has been lost from inclusions. They crystallized at 1121 ± 17°C and an oxygen fugacity of ΔQFM 1.2 ± 0.2, and could have been produced by about 11% melting of an enriched MORB source (E-DMM) at a temperature of about 1270°C, and a pressure of about 1.5 GPa. A distinctive feature of Gorely volcano, compared with frontal volcanoes of Kamchatka, is the unusually high temperature (925 ± 20°C) of formation of the subduction component corresponding to the region of existence of water-bearing melts.

Hydrogen-bonded structures from adamantane-based catechols

NASA Astrophysics Data System (ADS)

Kawahata, Masatoshi; Matsuura, Miku; Tominaga, Masahide; Katagiri, Kosuke; Yamaguchi, Kentaro

2018-07-01

Adamantane-based bis- and tris-catechols were synthesized to examine the effect of hydrogen bonds on the arrangement and packing of the components in the crystalline state. Single-crystal X-ray crystallographic analysis revealed that hydrogen bonds formed by the hydroxyl groups of catechol groups play essential roles in the production of various types of unique structures. 1,3-Bis(3,4-dihydroxyphenyl)adamantane (1) provided hydrogen-bonded network structures composed of helical chains in crystal from chloroform/methanol, and layer structures in crystal from ethyl acetate/hexane. The complexation of 1 with 1,3,5-trinitrobenzene or 1,2,4,5-tetracyanobenzene resulted in the formation of co-crystals, respectively. One-dimensional hydrogen-bonded structures were constructed from the adamantane-based molecules, which participated in charge-transfer interactions with guests. 1,3,5-Tris(3,4-dihydroxyphenyl)adamantane also afforded crystal, and the components were assembled into infinite polymers.

IUE observations of neutral hydrogen and deuterium in the local interstellar medium

NASA Technical Reports Server (NTRS)

Landsman, W. B.; Murthy, J.; Henry, R. C.; Moos, H. W.; Linsky, J. L.

1986-01-01

Small-aperture, high-dispersion IUE spectra have been obtained of seven late-type stars that, in general, confirm previous Copernicus results concerning the distribution of hydrogen and deuterium in the local interstellar medium. In addition, the IUE Ly Alpha spectra of Altair, and of the Alpha Cen components, suggest that multiple velocity components exist in these two directions.

Isothermal Calorimetric Observations of the Effect of Welding on Compatibility of Stainless Steels with High-Test Hydrogen Peroxide Propellant

NASA Technical Reports Server (NTRS)

Gostowski, Rudy

2003-01-01

High-Test Hydrogen Peroxide (HTP) is receiving renewed interest as a monopropellant and as the oxidizer for bipropellant systems. HTP is hydrogen peroxide having concentrations ranging from 70 to 98%. In these applications the energy and oxygen released during decomposition of HTP is used for propulsion. In propulsion systems components must be fabricated and connected using available joining processes. Welding is a common joining method for metallic components. The goal of this study was to compare the HTP compatibility of welded vs. unwelded stainless steel.

Influence of high pressure hydrogen environment on creep deformation of Mo-Re, Haynes 188, and NARloy-Z alloys

NASA Technical Reports Server (NTRS)

Sastry, S. M. L.; Yang, Charles C.; Ouyang, Shewang; Jerina, K. L.; Schwartz, D. S.

1994-01-01

The present study focuses on the investigation of the influence of hydrogen on the mechanical properties of three types of alloys at elevated temperatures. The reasons for the consideration of hydrogen effects are the potential use of hydrogen as a coolant in gas-cooled reactors and fuel in advanced hypersonic vehicles. The materials used in hydrogen atmosphere must not be embrittled by hydrogen at ambient temperature and should have good strength in hydrogen atmosphere at elevated temperature. The paucity of information concerning the mechanical performance in hydrogen atmosphere at elevated temperature has been a limiting factor in the selection and design of structural components for operation in hydrogen environment.

On fast solid-body rotation of the solar core and differential (liquid-like) rotation of the solar surface

NASA Astrophysics Data System (ADS)

Pashitskii, E. A.

2017-07-01

On the basis of a two-component (two-fluid) hydrodynamic model, it is shown that the probable phenomenon of solar core rotation with a velocity higher than the average velocity of global rotation of the Sun, discovered by the SOHO mission, can be related to fast solid-body rotation of the light hydrogen component of the solar plasma, which is caused by thermonuclear fusion of hydrogen into helium inside the hot dense solar core. Thermonuclear fusion of four protons into a helium nucleus (α-particle) creates a large free specific volume per unit particle due to the large difference between the densities of the solar plasma and nuclear matter. As a result, an efficient volumetric sink of one of the components of the solar substance—hydrogen—forms inside the solar core. Therefore, a steady-state radial proton flux converging to the center should exist inside the Sun, which maintains a constant concentration of hydrogen as it burns out in the solar core. It is demonstrated that such a converging flux of hydrogen plasma with the radial velocity v r ( r) = -β r creates a convective, v r ∂ v φ/∂ r, and a local Coriolis, v r v φ/ r,φ nonlinear hydrodynamic forces in the solar plasma, rotating with the azimuthal velocity v φ. In the absence of dissipation, these forces should cause an exponential growth of the solid-body rotation velocity of the hydrogen component inside the solar core. However, friction between the hydrogen and helium components of the solar plasma due to Coulomb collisions of protons with α-particles results in a steady-state regime of rotation of the hydrogen component in the solar core with an angular velocity substantially exceeding the global rotational velocity of the Sun. It is suggested that the observed differential (liquid-like) rotation of the visible surface of the Sun (photosphere) with the maximum angular velocity at the equator is caused by sold-body rotation of the solar plasma in the radiation zone and strong turbulence in the tachocline layer, where the turbulent viscosity reaches its maximum value at the equator. There, the tachocline layer exerts the most efficient drag on the less dense outer layers of the solar plasma, which are slowed down due to the interaction with the ambient space plasma (solar wind).

The effect of compression on individual pressure vessel nickel/hydrogen components

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.; Perez-Davis, Marla E.

1988-01-01

Compression tests were performed on representative Individual Pressure Vessel (IPV) Nickel/Hydrogen cell components in an effort to better understand the effects of force on component compression and the interactions of components under compression. It appears that the separator is the most easily compressed of all of the stack components. It will typically partially compress before any of the other components begin to compress. The compression characteristics of the cell components in assembly differed considerably from what would be predicted based on individual compression characteristics. Component interactions played a significant role in the stack response to compression. The results of the compression tests were factored into the design and selection of Belleville washers added to the cell stack to accommodate nickel electrode expansion while keeping the pressure on the stack within a reasonable range of the original preset.

THE INDOOR FUGACITY MODEL

EPA Science Inventory

Dermal and non-dietary pathways are potentially significant exposure pathways to pesticides used in the home. The exposure pathways include dermal contact through the hands and skin, ingestion from hand to mouth activities, ingestion through contact with toys and other items, ...

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

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

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

PubMed

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

2008-04-01

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

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

NASA Astrophysics Data System (ADS)

Hao, Xi-Luo; Li, Yi-Liang

2013-01-01

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

Electrostatics determine vibrational frequency shifts in hydrogen bonded complexes.

PubMed

Dey, Arghya; Mondal, Sohidul Islam; Sen, Saumik; Ghosh, Debashree; Patwari, G Naresh

2014-12-14

The red-shifts in the acetylenic C-H stretching vibration of C-H∙∙∙X (X = O, N) hydrogen-bonded complexes increase with an increase in the basicity of the Lewis base. Analysis of various components of stabilization energy suggests that the observed red-shifts are correlated with the electrostatic component of the stabilization energy, while the dispersion modulates the stabilization energy.

Method and means of reducing erosion of components of plasma devices exposed to helium and hydrogen isotope radiation

DOEpatents

Kaminsky, Manfred S.; Das, Santosh K.; Rossing, Thomas D.

1977-01-25

Surfaces of components of plasma devices exposed to radiation by atoms or ions of helium or isotopes of hydrogen can be protected from damage due to blistering by shielding the surfaces with a structure formed by sintering a powder of aluminum or beryllium and its oxide or by coating the surfaces with such a sintered metal powder.

High temperature electrolysis for syngas production

DOEpatents

Stoots, Carl M [Idaho Falls, ID; O'Brien, James E [Idaho Falls, ID; Herring, James Stephen [Idaho Falls, ID; Lessing, Paul A [Idaho Falls, ID; Hawkes, Grant L [Sugar City, ID; Hartvigsen, Joseph J [Kaysville, UT

2011-05-31

Syngas components hydrogen and carbon monoxide may be formed by the decomposition of carbon dioxide and water or steam by a solid-oxide electrolysis cell to form carbon monoxide and hydrogen, a portion of which may be reacted with carbon dioxide to form carbon monoxide. One or more of the components for the process, such as steam, energy, or electricity, may be provided using a nuclear power source.

Environmentally induced crack propagation in Inconel alloys 600 and 690 under hydrogen supersaturated steam

NASA Astrophysics Data System (ADS)

Ali, Mehboob Muzzammil

Intergranular stress corrosion cracking (IGSCC) of Inconel alloys 600 and 690 was investigated by exposing them to 300--400°C in deaerated hydrogen supersaturated steam. Crack growth rates were measured in-situ for the above alloys using modified wedge-opening-loaded (M-WOL) linear elastic fracture specimens under constant displacement conditions. The applied stress intensity factors (K) used varied from 29--90 MPam1/2. An activation energy of 120 kJ/mol was found for crack growth rates as a function of temperature. This activation energy is close to the one corresponding to grain boundary self diffusion of nickel. In addition, it was found that the apparent crack growth rates (da/dt) exhibited a linear dependence with KI, given by (da/dt) = A.KIn, where n = 1 in our case. Microstructurally, crack propagation in both the alloys was predominantly along the grain boundaries. It is suggested that high fugacity hydrogen was generated at the tip of the crack, as a result of the reaction of H2O with Cr2O3 on the fracture surface leading to IGSCC. It was found that the rates of crack propagation in both alloys 600 and 690 are very similar. Moreover, under the applied KIs, both alloys 600 and 690 show a similar tendency to crack intergranularly in a direction perpendicular to the applied stress. Crack branching was also exhibited by both the alloys 600 as well as 690. The difference in the crack growth rates of alloys 600 and 690 was found to be only about 2%, which indicates that the crack growth rates in these alloys is independent of the alloy chromium content and that, possibly very similar crack growth mechanisms are active in both the alloys 600 and 690 under similar conditions of KI and temperature. HREM images at the crack tip of alloy 690 exhibit two distinct regions---a crystalline region, and an adjacent amorphous region, which is likely to be either a hydroxide or an amorphous oxide layer. This layer is expected to result from passivation reactions as the crack surface is exposed to the corrosive environment.

Multiscale modelling and experimentation of hydrogen embrittlement in aerospace materials

NASA Astrophysics Data System (ADS)

Jothi, Sathiskumar

Pulse plated nickel and nickel based superalloys have been used extensively in the Ariane 5 space launcher engines. Large structural Ariane 5 space launcher engine components such as combustion chambers with complex microstructures have usually been manufactured using electrodeposited nickel with advanced pulse plating techniques with smaller parts made of nickel based superalloys joined or welded to the structure to fabricate Ariane 5 space launcher engines. One of the major challenges in manufacturing these space launcher components using newly developed materials is a fundamental understanding of how different materials and microstructures react with hydrogen during welding which can lead to hydrogen induced cracking. The main objective of this research has been to examine and interpret the effects of microstructure on hydrogen diffusion and hydrogen embrittlement in (i) nickel based superalloy 718, (ii) established and (iii) newly developed grades of pulse plated nickel used in the Ariane 5 space launcher engine combustion chamber. Also, the effect of microstructures on hydrogen induced hot and cold cracking and weldability of three different grades of pulse plated nickel were investigated. Multiscale modelling and experimental methods have been used throughout. The effect of microstructure on hydrogen embrittlement was explored using an original multiscale numerical model (exploiting synthetic and real microstructures) and a wide range of material characterization techniques including scanning electron microscopy, 2D and 3D electron back scattering diffraction, in-situ and ex-situ hydrogen charged slow strain rate tests, thermal spectroscopy analysis and the Varestraint weldability test. This research shows that combined multiscale modelling and experimentation is required for a fundamental understanding of microstructural effects in hydrogen embrittlement in these materials. Methods to control the susceptibility to hydrogen induced hot and cold cracking and to improve the resistance to hydrogen embrittlement in aerospace materials are also suggested. This knowledge can play an important role in the development of new hydrogen embrittlement resistant materials. A novel micro/macro-scale coupled finite element method incorporating multi-scale experimental data is presented with which it is possible to perform full scale component analyses in order to investigate hydrogen embrittlement at the design stage. Finally, some preliminary and very encouraging results of grain boundary engineering based techniques to develop alloys that are resistant to hydrogen induced failure are presented. Keywords: Hydrogen embrittlement; Aerospace materials; Ariane 5 combustion chamber; Pulse plated nickel; Nickel based super alloy 718; SSRT test; Weldability test; TDA; SEM/EBSD; Hydrogen induced hot and cold cracking; Multiscale modelling and experimental methods.

The effect of copper on the estimation of sulfur fugacity from the composition of pyrrhotite: an experimental evaluation

NASA Astrophysics Data System (ADS)

Mengason, M. J.; Piccoli, P. M.; Candela, P. A.

2009-12-01

Sulfur fugacity is a critical intensive variable, important to the study of volcanic and plutonic rocks, and experimental systems. In a pioneering study, Toulmin and Barton (1964; GCA 28, 641) derived an equation, based on experimental data, for the relationship between fS2, temperature, and the composition of pyrrhotite (po), a common magmatic sulfide. The binary po solid solution (FeS-S2) was the object of their study; however, po frequently contains in excess of 1 wt. % Cu, and therefore further work has been required to account for the effect of additional phase components in po on the estimation of fS2 by this technique. In order to have consistent results from both Cu-free, and Cu-bearing po, one must properly formulate the Cu-bearing phase component of the po. Toward this end, we have designed a novel series of experiments that allow us to evaluate the relationship between the composition of Cu-Fe sulfides and fS2. Results of these experiments have been used to develop a simple method for the determination of the fS2 from Cu-bearing po and the equations of Toulmin and Barton. The experiments were performed in evacuated sealed silica tubes. Starting materials included pairs of separated reference (Cu-free), and Cu-bearing po in the presence of a common S2 gas phase (and therefore the same fS2). Experiments consisted of silica tubes loaded with mixtures of synthetic po and bornite separated by ~ 1mm thick silica discs, creating vertically stacked chambers. The chambers prevent contact of the separate condensed phase charges, but allow for gas transfer. Samples were heated in a vertical quench furnace at 1050°C for 16 to 24 hours followed by 5 days at 1000°C, concluding with a drop quench into a water bath. The experiments spanned 4 log units (bar) fS2 and the Cu-bearing po had Cu concentrations that ranged from 4.5 to 7.3 wt. %. The data were processed using three methods for incorporating Cu into the calculation, with effectiveness evaluated by deviations in calculated fugacity between pairs of Cu-bearing and Cu-free po. In method 1, the Cu concentration was omitted from the calculation and XFeS (FeS-S2) alone was input into the equation of Toulmin and Barton. In method 2, ideal mixing was assumed and the sum of XCuS + XFeS (FeS-CuS-S2) was substituted for XFeS in the equation of Toulmin and Barton. In method 3, XCuS0.5+ XFeS (FeS-CuS0.5-S2) was substituted for XFeS. Method 1 resulted in overestimates ranging from 1.1 to 1.6 log units fS2; method 2 resulted in underestimates ranging from 0.4 to 1.7; and method 3 performed best, with deviations ranging from -0.02 to 0.4. The results of these experiments suggest that incorporating Cu into the model of Toulmin and Barton as CuS0.5 is appropriate in producing accurate estimates of fS2 in igneous and experimental systems.

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

NASA Technical Reports Server (NTRS)

Righter, K.; Neff, K. E.

2007-01-01

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

Crystal-liquid Fugacity Ratio as a Surrogate Parameter for Intestinal Permeability.

PubMed

Zakeri-Milani, Parvin; Fasihi, Zohreh; Akbari, Jafar; Jannatabadi, Ensieh; Barzegar-Jalali, Mohammad; Loebenberg, Raimar; Valizadeh, Hadi

We assessed the feasibility of using crystal-liquid fugacity ratio (CLFR) as an alternative parameter for intestinal permeability in the biopharmaceutical classification (BCS) of passively absorbed drugs. Dose number, fraction of dose absorbed, intestinal permeability, and intrinsic dissolution rate were used as the input parameters. CLFR was determined using thermodynamic parameters i.e., melting point, molar fusion enthalpy, and entropy of drug molecules obtained using differential scanning calorimetry. The CLFR values were in the range of 0.06-41.76 mole percent. There was a close relationship between CLFR and in vivo intestinal permeability (r > 0.8). CLFR values of greater than 2 mole percent corresponded to complete intestinal absorption. Applying CLFR versus dose number or intrinsic dissolution rate, more than 92% of tested drugs were correctly classified with respect to the reported classification system on the basis of human intestinal permeability and solubility. This investigation revealed that the CLFR might be an appropriate parameter for quantitative biopharmaceutical classification. This could be attributed to the fact that CLFR could be a measure of solubility of compounds in lipid bilayer which was found in this study to be directly proportional to the intestinal permeability of compounds. This classification enables researchers to define characteristics for intestinal absorption of all four BCS drug classes using suitable cutoff points for both intrinsic dissolution rate and crystal-liquid fugacity ratio. Therefore, it may be used as a surrogate for permeability studies. This article is open to POST-PUBLICATION REVIEW. Registered readers (see "For Readers") may comment by clicking on ABSTRACT on the issue's contents page.

Hydrogen molecules and hydrogen-related defects in crystalline silicon

NASA Astrophysics Data System (ADS)

Fukata, N.; Sasaki, S.; Murakami, K.; Ishioka, K.; Nakamura, K. G.; Kitajima, M.; Fujimura, S.; Kikuchi, J.; Haneda, H.

1997-09-01

We have found that hydrogen exists in molecular form in crystalline silicon treated with hydrogen atoms in the downstream of a hydrogen plasma. The vibrational Raman line of hydrogen molecules is observed at 4158 cm-1 for silicon samples hydrogenated between 180 and 500 °C. The assignment of the Raman line is confirmed by its isotope shift to 2990 cm-1 for silicon treated with deuterium atoms. The Raman intensity has a maximum for hydrogenation at 400 °C. The vibrational Raman line of the hydrogen molecules is broad and asymmetric. It consists of at least two components, possibly arising from hydrogen molecules in different occupation sites in crystalline silicon. The rotational Raman line of hydrogen molecules is observed at 590 cm-1. The Raman band of Si-H stretching is observed for hydrogenation temperatures between 100 and 500 °C and the intensity has a maximum for hydrogenation at 250 °C.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Constitutive and damage material modeling in a high pressure hydrogen environment

NASA Technical Reports Server (NTRS)

Russell, D. A.; Fritzemeier, L. G.

1991-01-01

Numerous components in reusable space propulsion systems such as the SSME are exposed to high pressure gaseous hydrogen environments. Flow areas and passages in the fuel turbopump, fuel and oxidizer preburners, main combustion chamber, and injector assembly contain high pressure hydrogen either high in purity or as hydrogen rich steam. Accurate constitutive and damage material models applicable to high pressure hydrogen environments are therefore needed for engine design and analysis. Existing constitutive and cyclic crack initiation models were evaluated only for conditions of oxidizing environments. The main objective is to evaluate these models for applicability to high pressure hydrogen environments.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Untangling the History of Oceanic Peridotites Using Spinel Oxybarometry

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Complications in Determining Oxygen Fugacities From Olivine-Melt Equilibrium Illustrated by the Pu'u'O'o Lavas, Hawaii

NASA Astrophysics Data System (ADS)

McCann, V. E.; Barton, M.; Thornber, C. R.

2005-12-01

We have shown previously that oxygen fugacities calculated from olivine-melt equilibrium using rim compositions agree well with those calculated from analyzed Fe3+/σFe for MORB and for Icelandic OIB (MORB - average ΔFMQ -0.72 versus -0.70, Iceland average ΔFMQ -0.49 versus -0.58). The agreement between oxygen fugacities calculated from Ol-melt equilibrium and those calculated from analyzed Fe3+/σFe is excellent for individual samples of MORB from the FAMOUS region and Blanco Trough ( difference in calculated ΔFMQ < 0.30). Published analyses of Fe3+/σFe yield oxygen fugacilties of ΔFMQ= -0.72±0.43 for lavas from Kilauea and Mauna Loa, and ΔFMQ=0.91±0.72 for Loihi, very close to those for MORB. Oxygen fugacities determined using carefully selected Ol-melt analyses (ΔFMQ= -0.43±0.32) are in reasonable agreement with those determined from Fe3+/σFe for Kilauea and Mauna Loa, and agreement between fO2 calculated from Ol-melt equilibrium (ΔFMQ= -0.26) and that calculated from Fe3+/σFe (ΔFMQ= -0.64) is excellent for one sample from Kilauea. However, olivine-melt pairs from some samples, including those from the Pu'u'O'o lavas, yield anomalously high or low estimates of fO2 (average ΔFMQ =-0.6907, range -4.07 to +0.34). We suggest that these anomalous values reflect the complex history of olivines in these lavas, in particular the effects of magma mixing. Some olivines in the Pu'u'O'o lavas clearly have rims that are anomalously rich in Fa, whereas others have rims that are anomalously rich in Fo and do not appear to have equilibrium compositions. Given the dependence of olivine composition on melt Fe3+/σFe, there is no simple method to determine the equilibrium composition of olivine for a particular melt. However, detailed zoning profiles and analyses of microphenocrysts allow probable equilibrium compositions to be identified. We suggest that the average fO2 of Hawaiian lavas lies close to (ΔFMQ= -1) based on published results using spinel-melt equilibrium and Fe-Ni exchange between olivine and sulfide liquid. Olivine-glass inclusion data for Koolau samples also suggest (ΔFMQ= ~-1).

Hydrogen-Oxygen PEM Regenerative Fuel Cell at NASA Glenn Research Center

NASA Technical Reports Server (NTRS)

Bents, David J.

2004-01-01

The NASA Glenn Research Center has constructed a closed-cycle hydrogen-oxygen PEM regenerative fuel cell (RFC) to explore its potential use as an energy storage device for a high altitude solar electric aircraft. Built up over the last 2 years from specialized hardware and off the shelf components the Glenn RFC is a complete "brassboard" energy storage system which includes all the equipment required to (1) absorb electrical power from an outside source and store it as pressurized hydrogen and oxygen and (2) make electrical power from the stored gases, saving the product water for re-use during the next cycle. It consists of a dedicated hydrogen-oxygen fuel cell stack and an electrolyzer stack, the interconnecting plumbing and valves, cooling pumps, water transfer pumps, gas recirculation pumps, phase separators, storage tanks for oxygen (O2) and hydrogen (H2), heat exchangers, isolation valves, pressure regulators, nitrogen purge provisions, instrumentation, and other components. It specific developmental functions include: (1) Test fuel cells and fuel cell components under repeated closed-cycle operation (nothing escapes; everything is used over and over again). (2) Simulate diurnal charge-discharge cycles (3) Observe long-term system performance and identify degradation and loss mechanisms. (4) Develop safe and convenient operation and control strategies leading to the successful development of mission-capable, flight-weight RFC's.

A general mixture equation of state for double bonding carboxylic acids with ≥2 association sites

NASA Astrophysics Data System (ADS)

Marshall, Bennett D.

2018-05-01

In this paper, we obtain the first general multi-component solution to Wertheim's thermodynamic perturbation theory for the case that molecules can participate in cyclic double bonds. In contrast to previous authors, we do not restrict double bonding molecules to a 2-site association scheme. Each molecule in a multi-component mixture can have an arbitrary number of donor and acceptor association sites. The one restriction on the theory is that molecules can have at most one pair of double bonding sites. We also incorporate the effect of hydrogen bond cooperativity in cyclic double bonds. We then apply this new association theory to 2-site and 3-site models for carboxylic acids within the polar perturbed chain statistical associating fluid theory equation of state. We demonstrate the accuracy of the approach by comparison to both pure and multi-component phase equilibria data. It is demonstrated that the 3-site association model gives substantially a different hydrogen bonding structure than a 2-site approach. We also demonstrate that inclusion of hydrogen bond cooperativity has a substantial effect on a liquid phase hydrogen bonding structure.

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

(Di­methyl­phosphor­yl)methanaminium hydrogen oxalate–oxalic acid (2/1)

PubMed Central

Bialek, Sebastian; Clemens, Rebecca; Reiss, Guido J.

2014-01-01

The reaction of (di­methyl­phosphor­yl)methanamine (dpma) with oxalic acid in ethanol yielded the title solvated salt, C3H11NOP+·C2HO4 −·0.5C2H2O4. Its asymmetric unit consists of one dpmaH+ cation, one hydrogen oxalate anion and a half-mol­ecule of oxalic acid located around a twofold rotation axis. The H atom of the hydrogen oxalate anion is statistically disordered over two positions that are trans to each other. The hydrogen oxalate monoanion is not planar (bend angle ∼16°) whereas the oxalic acid molecule shows a significantly smaller bend angle (∼7°). In the crystal, the components are connected by strong O—H⋯O and much weaker N—H⋯O hydrogen bonds, leading to the formation of layers extending parallel to (001). The structure was refined from a racemically twinned crystal with twin components in an approximate 1:1 ratio. PMID:24765013

Hydrogenated TiO2 Branches Coated Mn3O4 Nanorods as an Advanced Anode Material for Lithium Ion Batteries.

PubMed

Wang, Nana; Yue, Jie; Chen, Liang; Qian, Yitai; Yang, Jian

2015-05-20

Rational design and delicate control on the component, structure, and surface of electrodes in lithium ion batteries are highly important to their performances in practical applications. Compared with various components and structures for electrodes, the choices for their surface are quite limited. The most widespread surface for numerous electrodes, a carbon shell, has its own issues, which stimulates the desire to find another alternative surface. Here, hydrogenated TiO2 is exemplified as an appealing surface for advanced anodes by the growth of ultrathin hydrogenated TiO2 branches on Mn3O4 nanorods. High theoretical capacity of Mn3O4 is well matched with low volume variation (∼4%), enhanced electrical conductivity, good cycling stability, and rate capability of hydrogenated TiO2, as demonstrated in their electrochemical performances. The proof-of-concept reveals the promising potential of hydrogenated TiO2 as a next-generation material for the surface in high-performance hybrid electrodes.

The development of hydrogen sensor technology at NASA Lewis Research Center

NASA Technical Reports Server (NTRS)

Hunter, Gary W.; Neudeck, Philip G.; Jefferson, G. D.; Madzsar, G. C.; Liu, C. C.; Wu, Q. H.

1993-01-01

The detection of hydrogen leaks in aerospace applications, especially those involving hydrogen fuel propulsion systems, is of extreme importance for reasons of reliability, safety, and economy. Motivated by leaks occurring in liquid hydrogen lines supplying the main engine of the Space Shuttle, NASA Lewis has initiated a program to develop point-contact hydrogen sensors which address the needs of aerospace applications. Several different approaches are being explored. They include the fabrication of PdAg Schottky diode structures, the characterization of PdCr as a hydrogen sensitive alloy, and the use of SiC as a semiconductor for hydrogen sensors. This paper discusses the motivation behind and present status of each of the major components of the NASA LeRC hydrogen sensor program.

Catalytic dehydrogenation of amine borane complexes

NASA Technical Reports Server (NTRS)

Mohajeri, Nahid (Inventor); Tabatabaie-Raissi, Ali (Inventor)

2007-01-01

A method of generating hydrogen includes the steps of providing an amine borane (AB) complex, at least one hydrogen generation catalyst, and a solvent, and mixing these components. Hydrogen is generated. The hydrogen produced is high purity hydrogen suitable for PEM fuel cells. A hydrolytic in-situ hydrogen generator includes a first compartment that contains an amine borane (AB) complex, a second container including at least one hydrogen generation catalyst, wherein the first or second compartment includes water or other hydroxyl group containing solvent. A connecting network permits mixing contents in the first compartment with contents in the second compartment, wherein high purity hydrogen is generated upon mixing. At least one flow controller is provided for controlling a flow rate of the catalyst or AB complex.

Catalytic dehydrogenation of amine borane complexes

NASA Technical Reports Server (NTRS)

Tabatabaie-Raissi, Ali (Inventor); Mohajeri, Nahid (Inventor); Bokerman, Gary (Inventor)

2009-01-01

A method of generating hydrogen includes the steps of providing an amine borane (AB) complex, at least one hydrogen generation catalyst, and a solvent, and mixing these components Hydrogen is generated. The hydrogen produced is high purity hydrogen suitable for PEM fuel cells. A hydrolytic in-situ hydrogen generator includes a first compartment that contains an amine borane (AB) complex, a second container including at least one hydrogen generation catalyst, wherein the first or second compartment includes water or other hydroxyl group containing solvent. A connecting network permits mixing contents in the first compartment with contents in the second compartment, wherein high purity hydrogen is generated upon mixing. At least one flow controller is provided for controlling a flow rate of the catalyst or AB complex.

FUGACITY-BASED INDOOR RESIDENTIAL PESTICIDE FATE MODEL

EPA Science Inventory

Dermal and non-dietary pathways are possibly important for exposure to pesticides used in residences. Limited data have been collected on pesticide concentrations in residential air and surfaces following application. Models may be useful for interpreting these data and to make...

A FUGACITY-BASED INDOOR RESIDENTIAL PESTICIDE FATE MODEL

EPA Science Inventory

Dermal and non-dietary pathways are potentially significant exposure pathways to pesticides used in the home. Exposure pathways include dermal contact of pesticide residues with the hands and skin, ingestion from hand-to-mouth activities, ingestion through contact with toys an...

A THREE-DIMENSIONAL MODEL ASSESSMENT OF THE GLOBAL DISTRIBUTION OF HEXACHLOROBENZENE

EPA Science Inventory

The distributions of persistent organic pollutants (POPs) in the global environment have been studied typically with box/fugacity models with simplified treatments of atmospheric transport processes1. Such models are incapable of simulating the complex three-dimensional mechanis...

Supercomputer modeling of hydrogen combustion in rocket engines

NASA Astrophysics Data System (ADS)

Betelin, V. B.; Nikitin, V. F.; Altukhov, D. I.; Dushin, V. R.; Koo, Jaye

2013-08-01

Hydrogen being an ecological fuel is very attractive now for rocket engines designers. However, peculiarities of hydrogen combustion kinetics, the presence of zones of inverse dependence of reaction rate on pressure, etc. prevents from using hydrogen engines in all stages not being supported by other types of engines, which often brings the ecological gains back to zero from using hydrogen. Computer aided design of new effective and clean hydrogen engines needs mathematical tools for supercomputer modeling of hydrogen-oxygen components mixing and combustion in rocket engines. The paper presents the results of developing verification and validation of mathematical model making it possible to simulate unsteady processes of ignition and combustion in rocket engines.

Constraints on Biogenic Emplacement of Crystalline Calcium Carbonate and Dolomite

NASA Astrophysics Data System (ADS)

Colas, B.; Clark, S. M.; Jacob, D. E.

2015-12-01

Amorphous calcium carbonate (ACC) is a biogenic precursor of calcium carbonates forming shells and skeletons of marine organisms, which are key components of the whole marine environment. Understanding carbonate formation is an essential prerequisite to quantify the effect climate change and pollution have on marine population. Water is a critical component of the structure of ACC and the key component controlling the stability of the amorphous state. Addition of small amounts of magnesium (1-5% of the calcium content) is known to promote the stability of ACC presumably through stabilization of the hydrogen bonding network. Understanding the hydrogen bonding network in ACC is fundamental to understand the stability of ACC. Our approach is to use Monte-Carlo simulations constrained by X-ray and neutron scattering data to determine hydrogen bonding networks in ACC as a function of magnesium doping. We have already successfully developed a synthesis protocol to make ACC, and have collected X-ray data, which is suitable for determining Ca, Mg and O correlations, and have collected neutron data, which gives information on the hydrogen/deuterium (as the interaction of X-rays with hydrogen is too low for us to be able to constrain hydrogen atom positions with only X-rays). The X-ray and neutron data are used to constrain reverse Monte-Carlo modelling of the ACC structure using the Empirical Potential Structure Refinement program, in order to yield a complete structural model for ACC including water molecule positions. We will present details of our sample synthesis and characterization methods, X-ray and neutron scattering data, and reverse Monte-Carlo simulations results, together with a discussion of the role of hydrogen bonding in ACC stability.

Highly hydrogen-sensitive thermal desorption spectroscopy system for quantitative analysis of low hydrogen concentration (˜1 × 1016 atoms/cm3) in thin-film samples

NASA Astrophysics Data System (ADS)

Hanna, Taku; Hiramatsu, Hidenori; Sakaguchi, Isao; Hosono, Hideo

2017-05-01

We developed a highly hydrogen-sensitive thermal desorption spectroscopy (HHS-TDS) system to detect and quantitatively analyze low hydrogen concentrations in thin films. The system was connected to an in situ sample-transfer chamber system, manipulators, and an rf magnetron sputtering thin-film deposition chamber under an ultra-high-vacuum (UHV) atmosphere of ˜10-8 Pa. The following key requirements were proposed in developing the HHS-TDS: (i) a low hydrogen residual partial pressure, (ii) a low hydrogen exhaust velocity, and (iii) minimization of hydrogen thermal desorption except from the bulk region of the thin films. To satisfy these requirements, appropriate materials and components were selected, and the system was constructed to extract the maximum performance from each component. Consequently, ˜2000 times higher sensitivity to hydrogen than that of a commercially available UHV-TDS system was achieved using H+-implanted Si samples. Quantitative analysis of an amorphous oxide semiconductor InGaZnO4 thin film (1 cm × 1 cm × 1 μm thickness, hydrogen concentration of 4.5 × 1017 atoms/cm3) was demonstrated using the HHS-TDS system. This concentration level cannot be detected using UHV-TDS or secondary ion mass spectroscopy (SIMS) systems. The hydrogen detection limit of the HHS-TDS system was estimated to be ˜1 × 1016 atoms/cm3, which implies ˜2 orders of magnitude higher sensitivity than that of SIMS and resonance nuclear reaction systems (˜1018 atoms/cm3).

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Hydrogen, helium, and other solar-wind components in lunar soil - Abundances and predictions

NASA Technical Reports Server (NTRS)

Taylor, Lawrence A.

1990-01-01

The lack of a shielding atmosphere on the moon permits solar-wind particles to impinge upon the lunar soil and become implanted into the various phases which comprise the soil. Relatively large quantities of solar-wind implanted hydrogen (50-100 ppm) and helium (10-50 ppm) are present. The measured parameter of I(s)FeO, a direct indicator of maturity and exposure age, can be used as a first approximation to predict the abundances of many solar-wind components in the soils. However, because ilmenite acts as a 'sponge' for the retention of certain elements, the TiO2 content of the soil is a better indicator for hydrogen and helium contents.

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

Rivkin, C.; Blake, C.; Burgess, R.

This report explains the Regulations, Codes, and Standards (RCS) requirements for hydrogen dispensing stations in the State of California. The reports shows the basic components of a hydrogen dispensing station in a simple schematic drawing; the permits and approvals that would typically be required for the construction and operation of a hydrogen dispensing station; and a basic permit that might be employed by an Authority Having Jurisdiction (AHJ).

Economics

NASA Technical Reports Server (NTRS)

1975-01-01

Tables covering the selling price of hydrogen as a function of each process temperature studied are presented. Estimated selling price, based on capital costs and operating and maintenance costs, is included. In all cases, no credit was given for the methane component of hydrogen.

New insights into the folding of a β-sheet miniprotein in a reduced space of collective hydrogen bond variables: application to a hydrodynamic analysis of the folding flow.

PubMed

Kalgin, Igor V; Caflisch, Amedeo; Chekmarev, Sergei F; Karplus, Martin

2013-05-23

A new analysis of the 20 μs equilibrium folding/unfolding molecular dynamics simulations of the three-stranded antiparallel β-sheet miniprotein (beta3s) in implicit solvent is presented. The conformation space is reduced in dimensionality by introduction of linear combinations of hydrogen bond distances as the collective variables making use of a specially adapted principal component analysis (PCA); i.e., to make structured conformations more pronounced, only the formed bonds are included in determining the principal components. It is shown that a three-dimensional (3D) subspace gives a meaningful representation of the folding behavior. The first component, to which eight native hydrogen bonds make the major contribution (four in each beta hairpin), is found to play the role of the reaction coordinate for the overall folding process, while the second and third components distinguish the structured conformations. The representative points of the trajectory in the 3D space are grouped into conformational clusters that correspond to locally stable conformations of beta3s identified in earlier work. A simplified kinetic network based on the three components is constructed, and it is complemented by a hydrodynamic analysis. The latter, making use of "passive tracers" in 3D space, indicates that the folding flow is much more complex than suggested by the kinetic network. A 2D representation of streamlines shows there are vortices which correspond to repeated local rearrangement, not only around minima of the free energy surface but also in flat regions between minima. The vortices revealed by the hydrodynamic analysis are apparently not evident in folding pathways generated by transition-path sampling. Making use of the fact that the values of the collective hydrogen bond variables are linearly related to the Cartesian coordinate space, the RMSD between clusters is determined. Interestingly, the transition rates show an approximate exponential correlation with distance in the hydrogen bond subspace. Comparison with the many published studies shows good agreement with the present analysis for the parts that can be compared, supporting the robust character of our understanding of this "hydrogen atom" of protein folding.

Dynamical core-hole screening in the x-ray absorption spectra of hydrogenated carbon nanotubes and graphene

NASA Astrophysics Data System (ADS)

Wessely, O.; Katsnelson, M. I.; Nilsson, A.; Nikitin, A.; Ogasawara, H.; Odelius, M.; Sanyal, B.; Eriksson, O.

2007-10-01

We have calculated the electronic structure and the x-ray absorption (XA) spectrum of a hydrogenated single graphite plane, in order to simulate recent experimental results on hydrogenated single wall carbon nanotubes (SWCNT) as well as hydrogenated graphene. We find that the presence of H induces a substantial component of sp3 bonding and as a result the π and π* components to the electronic structure vanish. We have calculated a theoretical x-ray absorption spectrum using a multiband version of the Mahan-Nozières-De Dominicis theory. By making a fitting of the XA signal of C atoms that have H attached to them and C atoms without H in the vicinity we obtain a good representation of the experimental data and we can draw the conclusion that in the experiments [A. Nikitin , Phys. Rev. Lett. 95, 225507 (2005)] some 35-50 % H have been absorbed in the SWCNT.

Photoelectrochemical water splitting in separate oxygen and hydrogen cells

NASA Astrophysics Data System (ADS)

Landman, Avigail; Dotan, Hen; Shter, Gennady E.; Wullenkord, Michael; Houaijia, Anis; Maljusch, Artjom; Grader, Gideon S.; Rothschild, Avner

2017-06-01

Solar water splitting provides a promising path for sustainable hydrogen production and solar energy storage. One of the greatest challenges towards large-scale utilization of this technology is reducing the hydrogen production cost. The conventional electrolyser architecture, where hydrogen and oxygen are co-produced in the same cell, gives rise to critical challenges in photoelectrochemical water splitting cells that directly convert solar energy and water to hydrogen. Here we overcome these challenges by separating the hydrogen and oxygen cells. The ion exchange in our cells is mediated by auxiliary electrodes, and the cells are connected to each other only by metal wires, enabling centralized hydrogen production. We demonstrate hydrogen generation in separate cells with solar-to-hydrogen conversion efficiency of 7.5%, which can readily surpass 10% using standard commercial components. A basic cost comparison shows that our approach is competitive with conventional photoelectrochemical systems, enabling safe and potentially affordable solar hydrogen production.

Hydrogen peroxide as a new defensive compound in "benzoyl cyanide" producing polydesmid millipedes

NASA Astrophysics Data System (ADS)

Kuwahara, Yasumasa; Yamaguchi, Takuya; Ichiki, Yayoi; Tanabe, Tsutomu; Asano, Yasuhisa

2017-04-01

Hydrogen peroxide was newly and simultaneously demonstrated with well-known hydrogen cyanide as a component of defensive secretions of "benzoyl cyanide" producing polydesmid millipedes. Presence of hydrogen peroxide was successively evidenced by Trinder reagent's spray with colorless as well as oily smears of defensive secretions containing benzoyl cyanide and hydrogen cyanide by alkaline picrate paper treatment. Linear correlation was demonstrated between quantities of hydrogen peroxide and benzoyl cyanide. By qualitative assay, seven benzoyl cyanide containing polydesmidans (six species of adults and one species of a nymph at stadium I) tested positive to Trinder reagent, indicative of the presence of hydrogen peroxide (together with hydrogen cyanide), while two cyanogenic species without benzoyl cyanide exhibited negative responses to the reagent. Two types of millipedes were elucidated as species of cyanogenic Polydesmida.

Hydrogen peroxide as a new defensive compound in "benzoyl cyanide" producing polydesmid millipedes.

PubMed

Kuwahara, Yasumasa; Yamaguchi, Takuya; Ichiki, Yayoi; Tanabe, Tsutomu; Asano, Yasuhisa

2017-04-01

Hydrogen peroxide was newly and simultaneously demonstrated with well-known hydrogen cyanide as a component of defensive secretions of "benzoyl cyanide" producing polydesmid millipedes. Presence of hydrogen peroxide was successively evidenced by Trinder reagent's spray with colorless as well as oily smears of defensive secretions containing benzoyl cyanide and hydrogen cyanide by alkaline picrate paper treatment. Linear correlation was demonstrated between quantities of hydrogen peroxide and benzoyl cyanide. By qualitative assay, seven benzoyl cyanide containing polydesmidans (six species of adults and one species of a nymph at stadium I) tested positive to Trinder reagent, indicative of the presence of hydrogen peroxide (together with hydrogen cyanide), while two cyanogenic species without benzoyl cyanide exhibited negative responses to the reagent. Two types of millipedes were elucidated as species of cyanogenic Polydesmida.

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

NASA Astrophysics Data System (ADS)

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

1997-08-01

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

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

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

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

2004-05-25

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

Advanced hydrogen electrode for hydrogen-bromide battery

NASA Technical Reports Server (NTRS)

Kosek, Jack A.; Laconti, Anthony B.

1987-01-01

Binary platinum alloys are being developed as hydrogen electrocatalysts for use in a hydrogen bromide battery system. These alloys were varied in terms of alloy component mole ratio and heat treatment temperature. Electrocatalyst evaluation, performed in the absence and presence of bromide ion, includes floating half cell polarization studies, electrochemical surface area measurements, X ray diffraction analysis, scanning electron microscopy analysis and corrosion measurements. Results obtained to date indicate a platinum rich alloy has the best tolerance to bromide ion poisoning.

In vitro hydrogen production--using energy from the sun.

PubMed

Krassen, Henning; Ott, Sascha; Heberle, Joachim

2011-01-07

Using solar energy to produce molecular hydrogen is a promising way to supply the civilization with clean energy. Nature provides the key components to collect solar energy as well as to reduce protons, scientists have developed mimics of these enzymatic centers and also found new ways to catalyze the same reactions. This perspective article surveys the different components and in particular the various coupling possibilities of a light sensitizer and catalyst. Pros and cons are discussed.

A simple hydrogen-bonded chain in (3Z)-3-{1-[(5-phenyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3H)-one, and a hydrogen-bonded ribbon of centrosymmetric rings in the self-assembled adduct (3Z)-3-{1-[(5-methyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3H)-one-6-(2-hydroxyethyl)-2,5-dimethylpyrazolo[1,5-a]pyrimidin-7(4H)-one (1/1).

PubMed

Quiroga, Jairo; Portilla, Jaime; Cobo, Justo; Glidewell, Christopher

2010-01-01

(3Z)-3-{1-[(5-Phenyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3H)-one, C(15)H(15)N(3)O(2), (I), and the stoichiometric adduct (3Z)-3-{1-[(5-methyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3H)-one-6-(2-hydroxyethyl)-2,5-dimethylpyrazolo[1,5-a]pyrimidin-7(4H)-one (1/1), C(10)H(13)N(3)O(2).C(10)H(13)N(3)O(2), (II), in which the two components have the same composition but different constitutions, are formed in the reactions of 2-acetyl-4-butyrolactone with 5-amino-3-phenyl-1H-pyrazole and 5-amino-3-methyl-1H-pyrazole, respectively. In each compound, the furanone component contains an intramolecular N-H...O hydrogen bond. The molecules of (I) are linked into a chain by a single intermolecular N-H...O hydrogen bond, while in (II), a combination of one O-H...N hydrogen bond, within the selected asymmetric unit, and two N-H...O hydrogen bonds link the molecular components into a ribbon containing alternating centrosymmetric R(4)(4)(20) and R(6)(6)(22) rings.

Certification of vapor phase hydrogen peroxide sterilization process for spacecraft application

NASA Technical Reports Server (NTRS)

Rohatgi, N.; Schubert, W.; Koukol, R.; Foster, T. L.; Stabekis, P. D.

2002-01-01

This paper describes the selection process and research activities JPL is planning to conduct for certification of hydrogen peroxide as a NASA approved technique for sterilization of various spacecraft parts/components and entire modern spacecraft.

Comparison and Evaluation of Laboratory and Field Measured Bioaccumulation Endpoints

EPA Science Inventory

Evaluation of bioaccumulation endpoints on a fugacity basis allows provides a framework to assess the biomagnification potential of a chemical and assess data deficiencies, i.e., uncertainties and lack of data. In addition, it is suggested that additional guidance is needed in o...

Indoor Residence Times of Semivolatile Organic Compounds: Model Estimation and Field Evaluation

EPA Science Inventory

Indoor residence times of semivolatile organic compounds (SVOCs) are a major and mostly unavailable input for residential exposure assessment. We calculated residence times for a suite of SVOCs using a fugacity model applied to residential environments. Residence times depend on...

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

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

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

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

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

Gerlach, T.M.

1993-02-01

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

Water and the oxidation state of subduction zone magmas.

PubMed

Kelley, Katherine A; Cottrell, Elizabeth

2009-07-31

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

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

NASA Astrophysics Data System (ADS)

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

1990-12-01

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

Metal/Silicate Partitioning of P, Ga, and W at High Pressures and Temperatures: Dependence on Silicate Melt Composition

NASA Technical Reports Server (NTRS)

Bailey, Edward; Drake, Michael J.

2004-01-01

The distinctive pattern of element concentrations in the upper mantle provides essential evidence in our attempts to understand the accretion and differentiation of the Earth (e.g., Drake and Righter, 2002; Jones and Drake, 1986; Righter et al., 1997; Wanke 1981). Core formation is best investigated through use of metal/silicate partition coefficients for siderophile elements. The variables influencing partition coefficients are temperature, pressure, the major element compositions of the silicate and metal phases, and oxygen fugacity. Examples of studies investigating the effects of these variables on partitioning behavior are: composition of the metal phase by Capobianco et al. (1999) and Righter et al. (1997); silicate melt composition by Watson (1976), Walter and Thibault (1995), Hillgren et al. (1996), Jana and Walker (1997), and Jaeger and Drake (2000); and oxygen fugacity by Capobianco et al. (1999), and Walter and Thibault (1995). Here we address the relative influences of silicate melt composition, pressure and temperature.

Vapor-liquid equilibria for R-22, R-134a, R-125, and R-32/125 with a polyol ester lubricant: Measurements and departure from ideality

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

Martz, W.L.; Burton, C.M.; Jacobi, A.M.

1996-11-01

The effect of a polyol ester lubricant on equilibrium pressure, liquid density, and viscosity is presented for R-22, R-125, and R-134a at varying temperatures and concentrations. Preliminary vapor-liquid equilibrium (VLE) data and miscibility observations are also presented for an R-32/R-125 blend (50%/50%) with the ISO 68 polyol ester (POE). Real-gas behavior is modeled using the vapor-phase fugacity, and vapor pressure effects on liquid fugacities are taken into account with the Poynting effect. Positive, negative, and mixed deviations form the Lewis-Randall rule are observed in the activity coefficient behavior. Departures from ideality are related to molecular size differences, intermolecular forces inmore » the mixture, and other factors. The data are discussed in the context of previous results for other refrigerants and thermodynamic modeling of refrigerant and oil mixtures.« less

Seasonal variation in diffusive exchange of polycyclic aromatic hydrocarbons across the air-seawater interface in coastal urban area.

PubMed

Kim, Seung-Kyu; Chae, Doo Hyun

2016-08-15

Concentrations of 15 polycyclic aromatic hydrocarbons (PAHs) in air-seawater interface were measured over 1year in the coastal region of Incheon, South Korea. Most individual PAHs and total PAHs in air displayed statistically significant negative correlations with temperature, but not significant in seawater. Less hydrophobic compounds with three rings were at or near equilibrium in summer, while PAHs with four to six rings were in disequilibrium in all seasons, with higher fugacity gradients in colder seasons and for more hydrophobic compounds. Differently from fugacity gradients, the highest net fluxes occurred for some three- and four-ring PAHs showing the highest atmospheric concentrations. Net gaseous exchange, which was higher in winter, occurred from air to seawater with an annual cumulative flux of 2075μg/m(2)/year (for Σ15PAHs), indicating that atmospheric PAHs in this region, originating from coal/biomass combustion, can deteriorate the quality of seawater and sediment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Opaque Assemblages in CK and CV Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Neff, K. E.; Righter, K.

2006-01-01

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

Photoinduced Intramolecular Bifurcate Hydrogen Bond: Unusual Mutual Influence of the Components.

PubMed

Sigalov, Mark V; Shainyan, Bagrat A; Sterkhova, Irina V

2017-09-01

A series of 7-hydroxy-2-methylidene-2,3-dihydro-1H-inden-1-ones with 2-pyrrolyl (3), 4-dimethylaminophenyl (4), 4-nitrophenyl (5), and carboxyl group (6) as substituents at the exocyclic double bond was synthesized in the form of the E-isomers (4-6) or predominantly as the Z-isomer (3) which in solution is converted to the E-isomer. The synthesized compounds and their model analogues were studied by NMR spectroscopy, X-ray analysis, and MP2 theoretical calculations. The E-isomers having intramolecular O-H···O═C hydrogen bond are converted by UV irradiation to the Z-isomers having bifurcated O-H···O···H-X hydrogen bond. Unexpected shortening (and, thus, strengthening) of the O-H···O═C component of the bifurcated hydrogen bond upon the formation of the C═O···H-X hydrogen bond was found experimentally, proved theoretically (MP2), and explained by a roundabout interaction of the H-donor (HX) and H-acceptor (C═O) via the system of conjugated bonds.

A preliminary systems-engineering study of an advanced nuclear-electrolytic hydrogen-production facility

NASA Technical Reports Server (NTRS)

Escher, W. J. D.; Donakowski, T. D.; Tison, R. R.

1975-01-01

An advanced nuclear-electrolytic hydrogen-production facility concept was synthesized at a conceptual level with the objective of minimizing estimated hydrogen-production costs. The concept is a closely-integrated, fully-dedicated (only hydrogen energy is produced) system whose components and subsystems are predicted on ''1985 technology.'' The principal components are: (1) a high-temperature gas-cooled reactor (HTGR) operating a helium-Brayton/ammonia-Rankine binary cycle with a helium reactor-core exit temperature of 980 C, (2) acyclic d-c generators, (3) high-pressure, high-current-density electrolyzers based on solid-polymer electrolyte technology. Based on an assumed 3,000 MWt HTGR the facility is capable of producing 8.7 million std cu m/day of hydrogen at pipeline conditions, 6,900 kPa. Coproduct oxygen is also available at pipeline conditions at one-half this volume. It has further been shown that the incorporation of advanced technology provides an overall efficiency of about 43 percent, as compared with 25 percent for a contemporary nuclear-electric plant powering close-coupled contemporary industrial electrolyzers.

Method and apparatus for the selective separation of gaseous coal gasification products by pressure swing adsorption

DOEpatents

Ghate, Madhav R.; Yang, Ralph T.

1987-01-01

Bulk separation of the gaseous components of multi-component gases provided by the gasification of coal including hydrogen, carbon monoxide, methane, and acid gases (carbon dioxide plus hydrogen sulfide) are selectively adsorbed by a pressure swing adsorption technique using activated carbon, zeolite or a combination thereof as the adsorbent. By charging a column containing the adsorbent with a gas mixture and pressurizing the column to a pressure sufficient to cause the adsorption of the gases and then reducing the partial pressure of the contents of the column, the gases are selectively and sequentially desorbed. Hydrogen, the least absorbable gas of the gaseous mixture, is the first gas to be desorbed and is removed from the column in a co-current direction followed by the carbon monoxide, hydrogen and methane. With the pressure in the column reduced to about atmospheric pressure the column is evacuated in a countercurrent direction to remove the acid gases from the column. The present invention is particularly advantageous as a producer of high parity hydrogen from gaseous products of coal gasification and as an acid gas scrubber.

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

NASA Technical Reports Server (NTRS)

Haggerty, S. E.

1983-01-01

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

Stability of ternesite and the production at scale of ternesite-based clinkers

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

Hanein, Theodore; Galan, Isabel; Glasser, Fredrik P.

A method to synthesize high-purity ternesite is presented and the importance of reaction volume is highlighted; a brief description of the product morphology is also presented. Thermodynamic data for ternesite are derived and the limits of ternesite stability are then explored. An upper temperature stability limit of ≈ 1290 °C at 1 atm is determined; however, this temperature is dependent on the fugacity of the volatile components in the atmosphere. Thermodynamic predictions confirm that belite and ternesite rich calcium sulfoaluminate clinkers can be readily produced in a single stage process at temperatures above 1200 °C provided the atmosphere and temperaturemore » are controlled. To demonstrate this control at larger scales, a conventional 7.4-meter rotary kiln has been used to produce ≈ 20 kg of ternesite-containing clinkers. This demonstrates the usefulness of thermodynamic modelling as it has enabled ternesite-based clinkers to be readily produced at scale in a single-stage process using existing equipment without major modifications.« less

Hydrogen storage in Pd nanocrystals covered with a metal-organic framework

NASA Astrophysics Data System (ADS)

Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M.; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Toh, Shoichi; Matsumura, Syo; Kitagawa, Hiroshi

2014-08-01

Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating.

Energy - Sandia National Laboratories

Science.gov Websites

; Components Compatibility Hydrogen Behavior Quantitative Risk Assessment Technical Reference for Hydrogen Combustion jbei Facilities Algae Testbed Battery Abuse Testing Laboratory Center for Infrastructure Research and Innovation Combustion Research Facility Joint BioEnergy Institute Close Energy Research Programs

Earth Science - Sandia Energy

Science.gov Websites

; Components Compatibility Hydrogen Behavior Quantitative Risk Assessment Technical Reference for Hydrogen Combustion jbei Facilities Algae Testbed Battery Abuse Testing Laboratory Center for Infrastructure Research and Innovation Combustion Research Facility Joint BioEnergy Institute Close Energy Research Programs

Stationary Power - Sandia Energy

Science.gov Websites

; Components Compatibility Hydrogen Behavior Quantitative Risk Assessment Technical Reference for Hydrogen Combustion jbei Facilities Algae Testbed Battery Abuse Testing Laboratory Center for Infrastructure Research and Innovation Combustion Research Facility Joint BioEnergy Institute Close Energy Research Programs

Transportation Energy - Sandia Energy

Science.gov Websites

; Components Compatibility Hydrogen Behavior Quantitative Risk Assessment Technical Reference for Hydrogen Combustion jbei Facilities Algae Testbed Battery Abuse Testing Laboratory Center for Infrastructure Research and Innovation Combustion Research Facility Joint BioEnergy Institute Close Energy Research Programs

Grid Modernization - Sandia Energy

Science.gov Websites

; Components Compatibility Hydrogen Behavior Quantitative Risk Assessment Technical Reference for Hydrogen Combustion jbei Facilities Algae Testbed Battery Abuse Testing Laboratory Center for Infrastructure Research and Innovation Combustion Research Facility Joint BioEnergy Institute Close Energy Research Programs

Ethane-1,1,2-trisphosphonic acid hemihydrate.

PubMed

Delain-Bioton, Lise; Lohier, Jean François; Villemin, Didier; Sopková-de Oliveira Santos, Jana; Hix, Gary; Jaffrès, Paul Alain

2008-02-01

Ethane-1,1,2-trisphosphonic acid crystallizes as a hemihydrate, C(2)H(9)O(9)P(3).0.5H(2)O, in which the water O atom lies on an inversion centre in the space group P2(1)/c. The acid component, which contains a short but noncentred O-H...O hydrogen bond, adopts a gauche conformation. The acid components are linked by an extensive series of O-H...O hydrogen bonds to form layers, which are linked into pairs by the water molecules.

Biological components and bioelectronic interfaces of water splitting photoelectrodes for solar hydrogen production.

PubMed

Braun, Artur; Boudoire, Florent; Bora, Debajeet K; Faccio, Greta; Hu, Yelin; Kroll, Alexandra; Mun, Bongjin S; Wilson, Samuel T

2015-03-09

Artificial photosynthesis (AP) is inspired by photosynthesis in nature. In AP, solar hydrogen can be produced by water splitting in photoelectrochemical cells (PEC). The necessary photoelectrodes are inorganic semiconductors. Light-harvesting proteins and biocatalysts can be coupled with these photoelectrodes and thus form bioelectronic interfaces. We expand this concept toward PEC devices with vital bio-organic components and interfaces, and their integration into the built environment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

System Evaluation and Life-Cycle Cost Analysis of a Commercial-Scale High-Temperature Electrolysis Hydrogen Production Plant

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

Edwin A. Harvego; James E. O'Brien; Michael G. McKellar

2012-11-01

Results of a system evaluation and lifecycle cost analysis are presented for a commercial-scale high-temperature electrolysis (HTE) central hydrogen production plant. The plant design relies on grid electricity to power the electrolysis process and system components, and industrial natural gas to provide process heat. The HYSYS process analysis software was used to evaluate the reference central plant design capable of producing 50,000 kg/day of hydrogen. The HYSYS software performs mass and energy balances across all components to allow optimization of the design using a detailed process flow sheet and realistic operating conditions specified by the analyst. The lifecycle cost analysismore » was performed using the H2A analysis methodology developed by the Department of Energy (DOE) Hydrogen Program. This methodology utilizes Microsoft Excel spreadsheet analysis tools that require detailed plant performance information (obtained from HYSYS), along with financial and cost information to calculate lifecycle costs. The results of the lifecycle analyses indicate that for a 10% internal rate of return, a large central commercial-scale hydrogen production plant can produce 50,000 kg/day of hydrogen at an average cost of $2.68/kg. When the cost of carbon sequestration is taken into account, the average cost of hydrogen production increases by $0.40/kg to $3.08/kg.« less

Using Fugacity Ratios to Compare Laboratory and Field Measured Bioaccumulation Endpoint Metrics

EPA Science Inventory

Bioconcentration (BCF) testing provides useful insights into the behavior of chemicals in the aquatic ecosystem that are useful for modeling and other applications. BCFs are also often used for chemical hazard screening and risk assessment. The question arises how well can we ext...

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Equations for calculating hydrogeochemical reactions of minerals and gases such as CO2 at high pressures and temperatures

USGS Publications Warehouse

Appelo, C.A.J.; Parkhurst, David L.; Post, V.E.A.

2014-01-01

Calculating the solubility of gases and minerals at the high pressures of carbon capture and storage in geological reservoirs requires an accurate description of the molar volumes of aqueous species and the fugacity coefficients of gases. Existing methods for calculating the molar volumes of aqueous species are limited to a specific concentration matrix (often seawater), have been fit for a limited temperature (below 60 °C) or pressure range, apply only at infinite dilution, or are defined for salts instead of individual ions. A more general and reliable calculation of apparent molar volumes of single ions is presented, based on a modified Redlich–Rosenfeld equation. The modifications consist of (1) using the Born equation to calculate the temperature dependence of the intrinsic volumes, following Helgeson–Kirkham–Flowers (HKF), but with Bradley and Pitzer’s expression for the dielectric permittivity of water, (2) using the pressure dependence of the extended Debye–Hückel equation to constrain the limiting slope of the molar volume with ionic strength, and (3) adopting the convention that the proton has zero volume at all ionic strengths, temperatures and pressures. The modifications substantially reduce the number of fitting parameters, while maintaining or even extending the range of temperature and pressure over which molar volumes can be accurately estimated. The coefficients in the HKF-modified-Redlich–Rosenfeld equation were fitted by least-squares on measured solution densities.The limiting volume and attraction factor in the Van der Waals equation of state can be estimated with the Peng–Robinson approach from the critical temperature, pressure, and acentric factor of a gas. The Van der Waals equation can then be used to determine the fugacity coefficients for pure gases and gases in a mixture, and the solubility of the gas can be calculated from the fugacity, the molar volume in aqueous solution, and the equilibrium constant. The coefficients for the Peng–Robinson equations are readily available in the literature.The required equations have been implemented in PHREEQC, version 3, and the parameters for calculating the partial molar volumes and fugacity coefficients have been added to the databases that are distributed with PHREEQC. The ease of use and power of the formulation are illustrated by calculating the solubility of CO2 at high pressures and temperatures, and comparing with well-known examples from the geochemical literature. The equations and parameterizations are suitable for wide application in hydrogeochemical systems, especially in the field of carbon capture and storage.

OH in Rutile: an Oxygen and Water Barometer

NASA Astrophysics Data System (ADS)

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

2005-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2003-04-01

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

Equations for calculating hydrogeochemical reactions of minerals and gases such as CO2 at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Appelo, C. A. J.; Parkhurst, D. L.; Post, V. E. A.

2014-01-01

Calculating the solubility of gases and minerals at the high pressures of carbon capture and storage in geological reservoirs requires an accurate description of the molar volumes of aqueous species and the fugacity coefficients of gases. Existing methods for calculating the molar volumes of aqueous species are limited to a specific concentration matrix (often seawater), have been fit for a limited temperature (below 60 °C) or pressure range, apply only at infinite dilution, or are defined for salts instead of individual ions. A more general and reliable calculation of apparent molar volumes of single ions is presented, based on a modified Redlich-Rosenfeld equation. The modifications consist of (1) using the Born equation to calculate the temperature dependence of the intrinsic volumes, following Helgeson-Kirkham-Flowers (HKF), but with Bradley and Pitzer’s expression for the dielectric permittivity of water, (2) using the pressure dependence of the extended Debye-Hückel equation to constrain the limiting slope of the molar volume with ionic strength, and (3) adopting the convention that the proton has zero volume at all ionic strengths, temperatures and pressures. The modifications substantially reduce the number of fitting parameters, while maintaining or even extending the range of temperature and pressure over which molar volumes can be accurately estimated. The coefficients in the HKF-modified-Redlich-Rosenfeld equation were fitted by least-squares on measured solution densities. The limiting volume and attraction factor in the Van der Waals equation of state can be estimated with the Peng-Robinson approach from the critical temperature, pressure, and acentric factor of a gas. The Van der Waals equation can then be used to determine the fugacity coefficients for pure gases and gases in a mixture, and the solubility of the gas can be calculated from the fugacity, the molar volume in aqueous solution, and the equilibrium constant. The coefficients for the Peng-Robinson equations are readily available in the literature. The required equations have been implemented in PHREEQC, version 3, and the parameters for calculating the partial molar volumes and fugacity coefficients have been added to the databases that are distributed with PHREEQC. The ease of use and power of the formulation are illustrated by calculating the solubility of CO2 at high pressures and temperatures, and comparing with well-known examples from the geochemical literature. The equations and parameterizations are suitable for wide application in hydrogeochemical systems, especially in the field of carbon capture and storage.

Turbulent Burning Velocities of Two-Component Fuel Mixtures of Methane, Propane and Hydrogen

NASA Astrophysics Data System (ADS)

Kido, Hiroyuki; Nakahara, Masaya; Hashimoto, Jun; Barat, Dilmurat

In order to clarify the turbulent burning velocity of multi-component fuel mixtures, both lean and rich two-component fuel mixtures, in which methane, propane and hydrogen were used as fuels, were prepared while maintaining the laminar burning velocity approximately constant. A distinct difference in the measured turbulent burning velocity at the same turbulence intensity is observed for two-component fuel mixtures having different addition rates of fuel, even the laminar burning velocities are approximately the same. The burning velocities of lean mixtures change almost constantly as the rate of addition changes, whereas the burning velocities of the rich mixtures show no such tendency. This trend can be explained qualitatively based on the mean local burning velocity, which is estimated by taking into account the preferential diffusion effect for each fuel component. In addition, a model of turbulent burning velocity proposed for single-component fuel mixtures may be applied to two-component fuel mixtures by considering the estimated mean local burning velocity of each fuel.

The path to achieving molecular dispersion in an extremely dense reactive mixture

NASA Astrophysics Data System (ADS)

Patel, Jigneshkumar; Xiang, Zou; Hsu, Shaw; Schoch, Andrew

2015-03-01

In any multicomponent reactive system, a uniform and continuous dispersion of reactants is necessary to achieve a complete reaction. In this study, we have examined the role of one additional component to disperse two seemingly unlikely reactants, including a highly crystalline hexamethylenetetramine (hexa) and strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to decipher the role of specific intermolecular interactions in order for this additional component to dissolve the highly crystalline hexa and to plasticize the phenol formaldehyde resin in this crosslinking reaction. It is clear that the presence of the third component increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of hexa. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to understand the miscibility behavior of this multicomponent system. By designing the additional component to form a hydrogen bond with one or more N of the highly symmetric hexamethylenetetramine, it is then possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. The understanding of this system is applicable to a broad range of reactive systems.

Energy Fact Sheets - Sandia Energy

Science.gov Websites

; Components Compatibility Hydrogen Behavior Quantitative Risk Assessment Technical Reference for Hydrogen Combustion jbei Facilities Algae Testbed Battery Abuse Testing Laboratory Center for Infrastructure Research and Innovation Combustion Research Facility Joint BioEnergy Institute Close Energy Research Programs

Water Hydrogen-Bonding Network Structure and Dynamics at Phospholipid Multibilayer Surface: Femtosecond Mid-IR Pump-Probe Spectroscopy.

PubMed

Kundu, Achintya; Błasiak, Bartosz; Lim, Joon-Hyung; Kwak, Kyungwon; Cho, Minhaeng

2016-03-03

The water hydrogen-bonding network at a lipid bilayer surface is crucial to understanding membrane structures and its functional activities. With a phospholipid multibilayer mimicking a biological membrane, we study the temperature dependence of water hydrogen-bonding structure, distribution, and dynamics at a lipid multibilayer surface using femtosecond mid-IR pump-probe spectroscopy. We observe two distinguished vibrational lifetime components. The fast component (0.6 ps) is associated with water interacting with a phosphate part, whereas the slow component (1.9 ps) is with bulk-like choline-associated water. With increasing temperature, the vibrational lifetime of phosphate-associated water remains constant though its relative fraction dramatically increases. The OD stretch vibrational lifetime of choline-bound water slows down in a sigmoidal fashion with respect to temperature, indicating a noticeable change of the water environment upon the phase transition. The water structure and dynamics are thus shown to be in quantitative correlation with the structural change of liquid multibilayer upon the gel-to-liquid crystal phase transition.

Hydrogen-enhanced fatigue crack growth in steels and its frequency dependence

NASA Astrophysics Data System (ADS)

Matsunaga, Hisao; Takakuwa, Osamu; Yamabe, Junichiro; Matsuoka, Saburo

2017-06-01

In the context of the fatigue life design of components, particularly those destined for use in hydrogen refuelling stations and fuel cell vehicles, it is important to understand the hydrogen-induced, fatigue crack growth (FCG) acceleration in steels. As such, the mechanisms for acceleration and its influencing factors are reviewed and discussed in this paper, with a special focus on the peculiar frequency dependence of the hydrogen-induced FCG acceleration. Further, this frequency dependence is debated by introducing some potentially responsible elements, along with new experimental data obtained by the authors. This article is part of the themed issue 'The challenges of hydrogen and metals'.

Hydrogen Compressor Reliability Investigation and Improvement. Cooperative Research and Development Final Report, CRADA Number CRD-13-514

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

Terlip, Danny

2016-03-28

Diaphragm compressors have become the primary source of on-site hydrogen compression for hydrogen fueling stations around the world. NREL and PDC have undertaken two studies aimed at improving hydrogen compressor operation and reducing the cost contribution to dispensed fuel. The first study identified the failure mechanisms associated with mechanical compression to reduce the maintenance and down-time. The second study will investigate novel station configurations to maximize hydrogen usage and compressor lifetime. This partnership will allow for the simulation of operations in the field and a thorough analysis of the component failure to improve the reliability of diaphragm compression.

Upper mantle oxygen fugacity recorded by peridotite xenoliths from oceanic islands

NASA Astrophysics Data System (ADS)

Davis, F. A.; Wall, K. T.; Cottrell, E.

2017-12-01

Oxygen fugacity (fO2) in Earth's mantle is a key variable influencing mineral and fluid stability, the onset of melting, and mantle rheology; but fO2 is not uniform across mantle spatial domains. Peridotite xenoliths erupted in oceanic island basalts (OIB) potentially record fO2 of their lithospheric source - the convecting upper mantle. Many of these xenoliths have reacted with OIB as they transited the lithosphere. These xenoliths may record fO2 of the OIB source, potentially recording fO2 heterogeneity within the upper mantle. We investigate fO2heterogeneity by analyzing coexisting olivine, opx, and spinel in 41 peridotite xenoliths from islands associated with four different hotspots: Oahu (Hawaii), Savai'i (Samoa), Tubuai (Austral), and Tahiti (Society). Elevated spinel TiO2 concentrations (TiO2 >0.2 wt.%) in xenoliths from Oahu, Tubuai, and Tahiti may indicate interaction with OIB magmas [1]. Such assemblages record higher fO2 on average (QFM+0.4 to QFM+1.0) than peridotites and lavas from mid-ocean ridges (QFM-2 to QFM) [2,3,4]. This suggests that Hawaiian, Society, and Austral basalts with fO2 ≥ QFM+0.4 are more oxidized than MORB. (None of the Samoan xenoliths have spinel TiO2 >0.05 wt.%). Xenoliths with TiO2 <0.2 wt.% that have not reacted with OIB show a great degree of fO2 heterogeneity (QFM-1.5 to QFM+1.0) reflective of heterogeneity in lithospheric fO2. Although some heterogeneity may indicate spatial variability in bulk mantle chemistry, it is likely that it is partly driven by metamorphic reactions as lithosphere cools or is reheated by a mantle plume. Increased temperature causes the (Mg,Fe)Al2O4 component of spinel to dissolve into pyroxene; this concentrates the magnetite component in spinel and increases fO2 [5]. We observed evidence of this reaction at the grain-scale. Spinels in spinel-cpx symplectites and rims of equant spinels are >1 log unit more oxidized and have lower Al2O3 concentrations than interiors of the equant spinels. These results indicate that fO2 of the oceanic lithosphere is affected by subsolidus metamorphic reactions, which must be considered when relating fO2 of peridotites to fO2 of the convecting upper mantle. [1] Pearce et al. 2000, CMP; [2] Bryndzia and Wood 1990, AJS; [3] Bézos and Humler 2005, GCA; [4] Cottrell and Kelley 2011, EPSL; [5] Canil and O'Neill 1996, JPet

Detectability of Noble Gases in Jovian Atmospheres Utilizing Dimer Spectral Structures

NASA Astrophysics Data System (ADS)

Kim, S. J.; Min, Y.; Kim, Y.; Lee, Y.; Trafton, L.; Miller, S.; McKellar, A. R. W.

1997-07-01

The detection of jovian hydrogen-hydrogen dimers through the clear telluric 2-micron window (Kim et al. 1995; Trafton et al. 1997) suggests possibility to detect noble gases in the form of dimer with hydrogen in jovian atmospheres. Since noble gases do not have spectral structures in the infrared, it has been difficult to derive their abundances in the atmospheres of jovian planets. If there is a significant component of noble gases other than helium in the jovian atmospheres, it might be detected through its dimer spectrum with hydrogen molecule. The relatively sharp spectral structures of hydrogen-argon and hydrogen-neon dimers compared with those of hydrogen-hydrogen dimers are useful for the detection, if adequate S/N is obtained. However, these dimer structures should be much weaker than the nearby hydrogen-hydrogen features because noble gases are expected to be minor constituents of these atmospheres. We will discuss the detectability of these dimers based on laboratory measurements (McKellar, 1994; 1996), and current technology of infrared observations.

Hydrogen generation in CSP plants and maintenance of DPO/BP heat transfer fluids - A simulation approach

NASA Astrophysics Data System (ADS)

Kuckelkorn, Thomas; Jung, Christian; Gnädig, Tim; Lang, Christoph; Schall, Christina

2016-05-01

The ageing of diphenyl oxide/ biphenyl (DPO/BP) Heat Transfer Fluids (HTFs) implies challenging tasks for operators of parabolic trough power plants in order to find the economic optimum between plant performance and O&M costs. Focusing on the generation of hydrogen, which is effecting from the HTF ageing process, the balance of hydrogen pressure in the HTF is simulated for different operation scenarios. Accelerated build-up of hydrogen pressure in the HTF is causing increased permeation into the annular vacuum space of the installed receivers and must be avoided in order to maintain the performance of these components. Therefore, the effective hydrogen partial pressure in the HTF has to be controlled and limited according to the specified values so that the vacuum lifetime of the receivers and the overall plant performance can be ensured. In order to simulate and visualize the hydrogen balance of a typical parabolic trough plant, initially a simple model is used to calculate the balance of hydrogen in the system and this is described. As input data for the simulation, extrapolated hydrogen generation rates have been used, which were calculated from results of lab tests performed by DLR in Cologne, Germany. Hourly weather data, surface temperatures of the tubing system calculated by using the simulation tool from NREL, and hydrogen permeation rates for stainless steel and carbon steel grades taken from literature have been added to the model. In a first step the effect of HTF ageing, build-up of hydrogen pressure in the HTF and hydrogen loss rates through piping and receiver components have been modeled. In a second step a selective hydrogen removal process has been added to the model. The simulation results are confirming the need of active monitoring and controlling the effective hydrogen partial pressure in parabolic trough solar thermal power plants with DPO/BP HTF. Following the results of the simulation, the expected plant performance can only be achieved over lifetime, if the hydrogen partial pressure is actively controlled and limited.

New potentials for conventional aircraft when powered by hydrogen-enriched gasoline

NASA Technical Reports Server (NTRS)

Menard, W. A.; Moynihan, P. I.; Rupe, J. H.

1976-01-01

Overall system efficiency and performance of a Beech Model 20 Duke aircraft was studied to provide analytical representations of an aircraft piston engine system, including all essential components required for onboard hydrogen generation. Lower emission levels and a 20% reduction in fuel consumption may be obtained by using a catalytic hydrogen generator, incorporated as part of the air induction system, to generate hydrogen by breaking down small amounts of the aviation gasoline used in the normal propulsion system. This hydrogen is then mixed with gasoline and compressed air from the turbocharger before entering the engine combustion chamber. The special properties of the hydrogen-enriched gasoline allow the engine to operate at ultra lean fuel/air ratios, resulting in higher efficiencies.

Low water contents in diamond mineral inclusions: Proto-genetic origin in a dry cratonic lithosphere

NASA Astrophysics Data System (ADS)

Taylor, Lawrence A.; Logvinova, Alla M.; Howarth, Geoffrey H.; Liu, Yang; Peslier, Anne H.; Rossman, George R.; Guan, Yunbin; Chen, Yang; Sobolev, Nikolay V.

2016-01-01

The mantle is the major reservoir of Earth's water, hosted within Nominally Anhydrous Minerals (NAMs) (e.g., Bell and Rossman, 1992; Peslier et al., 2010; Peslier, 2010; Nestola and Smyth, 2015), in the form of hydrogen bonded to the silicate's structural oxygen. From whence cometh this water? Is the water in these minerals representative of the Earth's primitive upper mantle or did it come from melting events linked to crustal formation or to more recent metasomatic/re-fertilization events? During diamond formation, NAMs are encapsulated at hundreds of kilometers depth within the mantle, thereby possibly shielding and preserving their pristine water contents from re-equilibrating with fluids and melts percolating through the lithospheric mantle. Here we show that the NAMs included in diamonds from six locales on the Siberian Craton contain measurable and variable H2O concentrations from 2 to 34 parts per million by weight (ppmw) in olivine, 7 to 276 ppmw in clinopyroxene, and 11-17 ppmw in garnets. Our results suggest that if the inclusions were in equilibrium with the diamond-forming fluid, the water fugacity would have been unrealistically low. Instead, we consider the H2O contents of the inclusions, shielded by diamonds, as pristine representatives of the residual mantle prior to encapsulation, and indicative of a protogenetic origin for the inclusions. Hydrogen diffusion in the diamond does not appear to have modified these values significantly. The H2O contents of NAMs in mantle xenoliths may represent some later metasomatic event(s), and are not always representative of most of the continental lithospheric mantle. Results from the present study also support the conclusions of Peslier et al. (2010) and Novella et al. (2015) that the dry nature of the SCLM of a craton may provide stabilization of its thickened continental roots.

Exploring the Use of Multimedia Fate and Bioaccumulation Models to Calculate Trophic Magnification Factors (TMFs)

EPA Science Inventory

The trophic magnification factor (TMF) is considered to be a key metric for assessing the bioaccumulation potential of organic chemicals in food webs. Fugacity is an equilibrium criterion and thus reflects the relative thermodynamic status of a chemical in the environment and in ...

Four-component numerical simulation model of radiative convective interactions in large-scale oxygen-hydrogen turbulent fire balls

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

Surzhikov, S.T.

1996-12-31

Two-dimensional radiative gas dynamics model for numerical simulation of oxygen-hydrogen fire ball which may be generated by an explosion of a launch vehicle with cryogenic (LO{sub 2}-LH{sub 2}) fuel components is presented. The following physical-chemical processes are taken into account in the numerical model: and effective chemical reaction between the gaseous components (O{sub 2}-H{sub 2}) of the propellant, turbulent mixing and diffusion of the components, and radiative heat transfer. The results of numerical investigations of the following problems are presented: The influence of radiative heat transfer on fire ball gas dynamics during the first 13 sec after explosion, the effectmore » of the fuel gaseous components afterburning on fire ball gas dynamics, and the effect of turbulence on fire ball gas dynamics (in a framework of algebraic model of turbulent mixing).« less

Development Of A Centrifugal Hydrogen Pipeline Gas Compressor

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

Di Bella, Francis A.

2015-04-16

Concepts NREC (CN) has completed a Department of Energy (DOE) sponsored project to analyze, design, and fabricate a pipeline capacity hydrogen compressor. The pipeline compressor is a critical component in the DOE strategy to provide sufficient quantities of hydrogen to support the expected shift in transportation fuels from liquid and natural gas to hydrogen. The hydrogen would be generated by renewable energy (solar, wind, and perhaps even tidal or ocean), and would be electrolyzed from water. The hydrogen would then be transported to the population centers in the U.S., where fuel-cell vehicles are expected to become popular and necessary tomore » relieve dependency on fossil fuels. The specifications for the required pipeline hydrogen compressor indicates a need for a small package that is efficient, less costly, and more reliable than what is available in the form of a multi-cylinder, reciprocating (positive displacement) compressor for compressing hydrogen in the gas industry.« less

The 2:1 salt-type adduct formed between 6-amino-3-methyl-5-nitrosopyrimidine-2,4(1H,3H)-dione and piperidine: sheets containing 20 independent hydrogen bonds.

PubMed

Orozco, Fabián; Insuasty, Braulio; Cobo, Justo; Glidewell, Christopher

2009-05-01

The title compound, piperidinium 6-amino-3-methyl-5-nitroso-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ide 6-amino-3-methyl-5-nitrosopyrimidine-2,4(1H,3H)-dione, C(5)H(12)N(+).C(5)H(5)N(4)O(3)(-).C(5)H(6)N(4)O(3), (I), crystallizes with Z' = 2 in the space group P1. There is an intramolecular N-H...O hydrogen bond in each pyrimidine unit and within the selected asymmetric unit the six independent components are linked by 11 hydrogen bonds, seven of the N-H...O type and four of the N-H...N type. These six-component aggregates are linked into sheets by five further hydrogen bonds, three of the N-H...O type and one each of the N-H...N and C-H...O types.

Dynamical Core-Hole Screening in the X-Ray Absorption Spectra of Hydrogenated Carbon Nanotubes And Graphene

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

Wessely, O.; /Uppsala U. /Imperial Coll., London; Katsnelson, M.I.

2009-04-30

We have calculated the electronic structure and the x-ray absorption (XA) spectrum of a hydrogenated single graphite plane, in order to simulate recent experimental results on hydrogenated single wall carbon nanotubes (SWCNT) as well as hydrogenated graphene. We find that the presence of H induces a substantial component of sp{sup 3} bonding and as a result the {pi} and {pi}* components to the electronic structure vanish. We have calculated a theoretical x-ray absorption spectrum using a multiband version of the Mahan-Nozieres-De Dominicis theory. By making a fitting of the XA signal of C atoms that have H attached to themmore » and C atoms without H in the vicinity we obtain a good representation of the experimental data and we can draw the conclusion that in the experiments [A. Nikitin et al., Phys. Rev. Lett. 95, 225507 (2005)] some 35-50 % H have been absorbed in the SWCNT.« less

Molecular dynamics of acetamide based ionic deep eutectic solvents

NASA Astrophysics Data System (ADS)

Srinivasan, H.; Dubey, P. S.; Sharma, V. K.; Biswas, R.; Mitra, S.; Mukhopadhyay, R.

2018-04-01

Deep eutectic solvents are multi-component mixtures that have freezing point lower than their individual components. Mixture of acetamide+ lithium nitrate in the molar ratio 78:22 and acetamide+ lithium perchlorate in the molar ratio 81:19 are found to form deep eutectic solvents with melting point lower than the room temperature. It is known that the depression in freezing point is due to the hydrogen bond breaking ability of anions in the system. Quasielastic neutron scattering experiments on these systems were carried out to study the dynamics of acetamide molecules which may be influenced by this hydrogen bond breaking phenomena. The motion of acetamide molecules is modeled using jump diffusion mechanism to demonstrate continuous breaking and reforming hydrogen bonds in the solvent. Using the jump diffusion model, it is inferred that the jump lengths of acetamide molecules are better approximated by a Gaussian distribution. The shorter residence time of acetamide in presence of perchlorate ions suggest that the perchlorate ions have a higher hydrogen bond breaking ability compared to nitrate ions.

The effect of the charge exchange source on the velocity and 'temperature' distributions and their anisotropies in the earth's exosphere

NASA Technical Reports Server (NTRS)

Hodges, R. R., Jr.; Rohrbaugh, R. P.; Tinsley, B. A.

1981-01-01

The velocity distribution of atomic hydrogen in the earth's exosphere is calculated as a function of altitude and direction taking into account both the classic exobase source and the higher-altitude plasmaspheric charge exchange source. Calculations are performed on the basis of a Monte Carlo technique in which random ballistic trajectories of individual atoms are traced through a three-dimensional grid of audit zones, at which relative concentrations and momentum or energy fluxes are obtained. In the case of the classical exobase source alone, the slope of the velocity distribution is constant only for the upward radial velocity component and increases dramatically with altitude for the incoming radial and transverse velocity components, resulting in a temperature decrease. The charge exchange source, which produces the satellite hydrogen component and the hot ballistic and escape components of the exosphere, is found to enhance the wings of the velocity distributions, however this effect is not sufficient to overcome the temperature decreases at altitudes above one earth radius. The resulting global model of the hydrogen exosphere may be used as a realistic basis for radiative transfer calculations.

New Insights into the Folding of a β-Sheet Miniprotein in a Reduced Space of Collective Hydrogen Bond Variables: Application to a Hydrodynamic Analysis of the Folding Flow

PubMed Central

Kalgin, Igor V.; Caflisch, Amedeo; Chekmarev, Sergei F.; Karplus, Martin

2013-01-01

A new analysis of the 20 μs equilibrium folding/unfolding molecular dynamics simulations of the three-stranded antiparallel β-sheet miniprotein (beta3s) in implicit solvent is presented. The conformation space is reduced in dimensionality by introduction of linear combinations of hydrogen bond distances as the collective variables making use of a specially adapted Principal Component Analysis (PCA); i.e., to make structured conformations more pronounced, only the formed bonds are included in determining the principal components. It is shown that a three-dimensional (3D) subspace gives a meaningful representation of the folding behavior. The first component, to which eight native hydrogen bonds make the major contribution (four in each beta hairpin), is found to play the role of the reaction coordinate for the overall folding process, while the second and third components distinguish the structured conformations. The representative points of the trajectory in the 3D space are grouped into conformational clusters that correspond to locally stable conformations of beta3s identified in earlier work. A simplified kinetic network based on the three components is constructed and it is complemented by a hydrodynamic analysis. The latter, making use of “passive tracers” in 3D space, indicates that the folding flow is much more complex than suggested by the kinetic network. A 2D representation of streamlines shows there are vortices which correspond to repeated local rearrangement, not only around minima of the free energy surface, but also in flat regions between minima. The vortices revealed by the hydrodynamic analysis are apparently not evident in folding pathways generated by transition-path sampling. Making use of the fact that the values of the collective hydrogen bond variables are linearly related to the Cartesian coordinate space, the RMSD between clusters is determined. Interestingly, the transition rates show an approximate exponential correlation with distance in the hydrogen bond subspace. Comparison with the many published studies shows good agreement with the present analysis for the parts that can be compared, supporting the robust character of our understanding of this “hydrogen atom” of protein folding. PMID:23621790

Precise carbon control of fabricated stainless steel

DOEpatents

Nilsen, R.J.

1975-12-01

A process is described for controlling the carbon content of fabricated stainless steel components including the steps of heat treating the component in hydrogen atmospheres of varying dewpoints and carbon potentials.

Adsorption process to recover hydrogen from feed gas mixtures having low hydrogen concentration

DOEpatents

Golden, Timothy Christopher; Weist, Jr., Edward Landis; Hufton, Jeffrey Raymond; Novosat, Paul Anthony

2010-04-13

A process for selectively separating hydrogen from at least one more strongly adsorbable component in a plurality of adsorption beds to produce a hydrogen-rich product gas from a low hydrogen concentration feed with a high recovery rate. Each of the plurality of adsorption beds subjected to a repetitive cycle. The process comprises an adsorption step for producing the hydrogen-rich product from a feed gas mixture comprising 5% to 50% hydrogen, at least two pressure equalization by void space gas withdrawal steps, a provide purge step resulting in a first pressure decrease, a blowdown step resulting in a second pressure decrease, a purge step, at least two pressure equalization by void space gas introduction steps, and a repressurization step. The second pressure decrease is at least 2 times greater than the first pressure decrease.

Method and apparatus for the selective separation of gaseous coal gasification products by pressure swing adsorption

DOEpatents

Ghate, M.R.; Yang, R.T.

1985-10-03

Bulk separation of the gaseous components of multi-component gases provided by the gasification of coal including hydrogen, carbon monoxide, methane, and acid gases (carbon dioxide plus hydrogen sulfide) are selectively adsorbed by a pressure swing adsorption technique using activated carbon zeolite or a combination thereof as the adsorbent. By charging a column containing the adsorbent with a gas mixture and pressurizing the column to a pressure sufficient to cause the adsorption of the gases and then reducing the partial pressure of the contents of the column, the gases are selectively and sequentially desorbed. Hydrogen, the least absorbable gas of the gaseous mixture, is the first gas to be desorbed and is removed from the column in a co-current direction followed by the carbon monoxide, hydrogen and methane. With the pressure in the column reduced to about atmospheric pressure the column is evacuated in a countercurrent direction to remove the acid gases from the column. The present invention is particularly advantageous as a producer of high purity hydrogen from gaseous products of coal gasification and as an acid gas scrubber. 2 figs., 2 tabs.

Volatile loss during homogenization of lunar melt inclusions

NASA Astrophysics Data System (ADS)

Ni, Peng; Zhang, Youxue; Guan, Yunbin

2017-11-01

Volatile abundances in lunar mantle are critical factors to consider for constraining the model of Moon formation. Recently, the earlier understanding of a ;dry; Moon has shifted to a fairly ;wet; Moon due to the detection of measurable amount of H2O in lunar volcanic glass beads, mineral grains, and olivine-hosted melt inclusions. The ongoing debate on a ;dry; or ;wet; Moon requires further studies on lunar melt inclusions to obtain a broader understanding of volatile abundances in the lunar mantle. One important uncertainty for lunar melt inclusion studies, however, is whether the homogenization of melt inclusions would cause volatile loss. In this study, a series of homogenization experiments were conducted on olivine-hosted melt inclusions from the sample 74220 to evaluate the possible loss of volatiles during homogenization of lunar melt inclusions. Our results suggest that significant loss of H2O could occur even during minutes of homogenization, while F, Cl and S in the inclusions remain unaffected. We model the trend of H2O loss in homogenized melt inclusions by a diffusive hydrogen loss model. The model can reconcile the observed experimental data well, with a best-fit H diffusivity in accordance with diffusion data explained by the ;slow; mechanism for hydrogen diffusion in olivine. Surprisingly, no significant effect for the low oxygen fugacity on the Moon is observed on the diffusive loss of hydrogen during homogenization of lunar melt inclusions under reducing conditions. Our experimental and modeling results show that diffusive H loss is negligible for melt inclusions of >25 μm radius. As our results mitigate the concern of H2O loss during homogenization for crystalline lunar melt inclusions, we found that H2O/Ce ratios in melt inclusions from different lunar samples vary with degree of crystallization. Such a variation is more likely due to H2O loss on the lunar surface, while heterogeneity in their lunar mantle source is also a possibility. A similar size-dependence trend of H2O concentrations was also observed in natural unheated melt inclusions in 74220. By comparing the trend of diffusive H loss in the natural MIs and in our homogenized MIs, the cooling rate for 74220 was estimated to be ∼1 °C/s or slower.

Influence of dissolved hydrogen on the fatigue crack growth behaviour of AISI 4140 steel

NASA Astrophysics Data System (ADS)

Ramasagara Nagarajan, Varun

Many metallic structural components come into contact with hydrogen during manufacturing processes or forming operations such as hot stamping of auto body frames and while in service. This interaction of metallic parts with hydrogen can occur due to various reasons such as water molecule dissociation during plating operations, interaction with atmospheric hydrogen due to the moisture present in air during stamping operations or due to prevailing conditions in service (e.g.: acidic or marine environments). Hydrogen, being much smaller in size compared to other metallic elements such as Iron in steels, can enter the material and become dissolved in the matrix. It can lodge itself in interstitials locations of the metal atoms, at vacancies or dislocations in the metallic matrix or at grain boundaries or inclusions (impurities) in the alloy. This dissolved hydrogen can affect the functional life of these structural components leading to catastrophic failures in mission critical applications resulting in loss of lives and structural component. Therefore, it is very important to understand the influence of the dissolved hydrogen on the failure of these structural materials due to cyclic loading (fatigue). For the next generation of hydrogen based fuel cell vehicles and energy systems, it is very crucial to develop structural materials for hydrogen storage and containment which are highly resistant to hydrogen embrittlement. These materials should also be able to provide good long term life in cyclic loading, without undergoing degradation, even when exposed to hydrogen rich environments for extended periods of time. The primary focus of this investigation was to examine the influence of dissolved hydrogen on the fatigue crack growth behaviour of a commercially available high strength medium carbon low alloy (AISI 4140) steel. The secondary objective was to examine the influence of microstructure on the fatigue crack growth behaviour of this material and to determine the hydrogen induced failure mechanism in this material during cyclic loading. The secondary objective of this investigation was to determine the role of inclusions and their influence in affecting the fatigue crack growth rate of this material. Compact tension and tensile specimens were prepared as per ASTM E-647, E-399 and E-8 standards. The specimens were tested in three different heat treated conditions i.e. annealed (as received) as well as two austempered conditions. These specimens were precharged with hydrogen (ex situ) using cathodic charging method at a constant current density at three different time periods ranging from 150 to 250 hours before conducting fatigue crack growth tests. Mode 1 type fatigue tests were then performed in ambient atmosphere at constant amplitude using load ratio R of 0.1. The near threshold fatigue crack growth rate, fatigue threshold and the fatigue crack growth rate in the linear region were determined. Fatigue crack growth behaviour of specimens without any dissolve hydrogen were then compared with the specimens with different concentration of dissolved hydrogen. The test results show that the dissolved hydrogen concentration increases with the increase in charging time in all three heat treated conditions and the hydrogen uptake shows a strong dependence on the microstructure of the alloy. It was also observed that the microstructure has a significant influence of on the fatigue crack growth and SCC behaviour of the alloy with dissolved hydrogen. As the dissolved hydrogen concentration increases, the fatigue threshold was found to decrease and the near threshold crack growth rate increases in all three heat treated conditions showing the deleterious effect of hydrogen, but to a different extent in each condition. Current test results also indicate that the fatigue crack growth rates in the linear region increases as the dissolved hydrogen content increases in all three heat treated conditions. It is also observed that increasing the austempering temperature decreases the resistance to hydrogen embrittlement. An interesting phenomenon was also observed in annealed specimen charged with hydrogen for 250 h which had an unusually high fatigue threshold (DeltaKth).

Devices and methods to measure H2 and CO2 concentrations in gases released from soils and low temperature fumaroles in volcanic areas

NASA Astrophysics Data System (ADS)

di Martino, R. M. R.; Camarda, M.; Gurrieri, S.; Valenza, M.

2009-04-01

Hydrogen solubility and diffusion have a great relevance to change the redox state of magmas, usually expressed by oxygen fugacity. This influences many chemical and physical properties, such as oxidation state of multivalent elements, kind and abundance of minerals and gas species. These processes change the phase ratios into the volcanic system and so the magma movement capability toward the earth surface and the eruptive dynamics. In past studies several authors (Carapezza et al., 1980; Sato et al., 1982; Sato and McGee, 1985; Wakita et al., 1980) proposed the application of the fuel cells in order to measure reducing capacity of volcanic gases. Their found some clear correlations between variation peaks and volcanic activity but a few reducing capacity changes showed no correlation with it. In this study we characterize a fuel cell device designed to measure hydrogen concentration in a gas mixture. We present test results obtained in laboratory and in field trip, carried out to verify the major interferences of others reducing gas species, commonly present in volcanic emissions, in the measurement carried out with a hydrogen fuel cell sensor. Tests were performed at controlled temperature ad pressure conditions and at air saturated pressure vapour in the cell cathode. A new device to measure simultaneously hydrogen (H2) and carbon dioxide (CO2) concentrations in soil and in low temperature fumaroles in volcanic areas was proposed. The H2-detector is a hydrogen fuel cell, whereas CO2 is measured using an I.R. spectrometer. To build a continuous monitoring station of volcanic activity both sensors were put in a case together with a data logger. Our device has 0.2 mV ppm-1 sensitivity, accuracy of ± 5 ppm and about 10 ppm resolution whit respect to the hydrogen concentration. These instrumental characteristics were obtained applying a 500 ohm resistor to the external circuit that represents the best compromise between sensitivity, resolution, instrumental response time, and linearity of signal. We determine the CO2 concentration in the gas mixture with an I.R. spectrometer that has a measuring range of 0-100% with accuracy of ± 2% of the range and response time of 10 seconds. The laboratory results confirm our hypothesis of interference between H2, H2S and CO in the full concentration range of contaminant species. Therefore, according to our studies, the assignment of the fuel cell signal output variations only to H2 variation of concentration as in past studies, without physical separation of different reducing species may be misleading. Continuous measurements and periodical measurement field trip were performed at Torre Del Filosofo site on the upper part of the Etna volcano from the end of July to the middle October 2008. In field applications, H2S was removed with a Pb(COOH)2 trap whereas CO interference was neglected because H2/CO ratios in volcanic gases are typically high. Field time-series measurements of H2 and CO2 in gases emitted by low temperature fumaroles at Torre del Filosofo site showed a close positive correlation between explosion activity and the major peaks in the hydrogen concentration.

Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution

DOE PAGES

Lu, Qi; Hutchings, Gregory S.; Yu, Weiting; ...

2015-03-16

One of the key components of carbon dioxide-free hydrogen production is a robust and efficient non-precious metal catalyst for the hydrogen evolution reaction. We report that a hierarchical nanoporous copper-titanium bimetallic electrocatalyst is able to produce hydrogen from water under a mild overpotential at more than twice the rate of state-of-the- art carbon-supported platinum catalyst. Although both copper and titanium are known to be poor hydrogen evolution catalysts, the combination of these two elements creates unique copper-copper-titanium hollow sites, which have a hydrogen-binding energy very similar to that of platinum, resulting in an exceptional hydrogen evolution activity. Moreover, the hierarchicalmore » porosity of the nanoporous-copper titanium catalyst also contributes to its high hydrogen evolution activity, because it provides a large-surface area for electrocatalytic hydrogen evolution, and improves the mass transport properties. Moreover, the catalyst is self-supported, eliminating the overpotential associated with the catalyst/support interface.« less

Measurement of the para-hydrogen concentration in the ISIS moderators using neutron transmission and thermal conductivity

NASA Astrophysics Data System (ADS)

Romanelli, Giovanni; Rudić, Svemir; Zanetti, Matteo; Andreani, Carla; Fernandez-Alonso, Felix; Gorini, Giuseppe; Krzystyniak, Maciej; Škoro, Goran

2018-04-01

We present an experimental study to determine the para-hydrogen concentration in the hydrogen moderators at the ISIS pulsed neutron and muon source. The experimental characterisation is based on neutron transmission experiments performed on the VESUVIO spectrometer, and thermal conductivity measurements using the TOSCA para-hydrogen rig. A reliable estimation of the level of para-hydrogen concentration in the hydrogen moderators is of crucial importance in the framework of a current project to completely refurbish the first target station at ISIS. Moreover, we report a new measurement of the total neutron cross section for normal hydrogen at 15 K on the broad energy range 3 meV -10 eV suggesting a revision of the most recent nuclear libraries for incident neutron energies lower than 10 meV. Finally, we characterise systematic errors affecting the para-hydrogen level estimation due to conversion from para to ortho hydrogen, as a function of the time a batch of gas spends in every component of our gas panel and apparatus.

Hydrogen-enhanced fatigue crack growth in steels and its frequency dependence.

PubMed

Matsunaga, Hisao; Takakuwa, Osamu; Yamabe, Junichiro; Matsuoka, Saburo

2017-07-28

In the context of the fatigue life design of components, particularly those destined for use in hydrogen refuelling stations and fuel cell vehicles, it is important to understand the hydrogen-induced, fatigue crack growth (FCG) acceleration in steels. As such, the mechanisms for acceleration and its influencing factors are reviewed and discussed in this paper, with a special focus on the peculiar frequency dependence of the hydrogen-induced FCG acceleration. Further, this frequency dependence is debated by introducing some potentially responsible elements, along with new experimental data obtained by the authors.This article is part of the themed issue 'The challenges of hydrogen and metals'. © 2017 The Author(s).

Homogeneous catalyst formulations for methanol production

DOEpatents

Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

1991-02-12

There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.-), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

Homogeneous catalyst formulations for methanol production

DOEpatents

Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

1990-01-01

There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.13 ), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

Overview of the Design, Development, and Application of Nickel-hydrogen Batteries

NASA Technical Reports Server (NTRS)

Thaller, Lawrence H.; Zimmerman, Albert H.

2003-01-01

This document provides an overview of the design, development, and application of nickel-hydrogen (Ni-H2) battery technology for aerospace applications. It complements and updates the information presented in NASA RP-1314, NASA Handbook for Nickel- Hydrogen Batteries, published in 1993. Since that time, nickel-hydrogen batteries have become widely accepted for aerospace energy storage requirements and much more has been learned. The intent of this document is to capture some of that additional knowledge. This document addresses various aspects of nickel-hydrogen technology including the electrochemical reactions, cell component design, and selection considerations; overall cell and battery design considerations; charge control considerations; and manufacturing issues that have surfaced over the years that nickel-hydrogen battery technology has been the major energy storage technology for geosynchronous and low-Earth-orbiting satellites.

Hydrogen Fueling Station Using Thermal Compression: a techno-economic analysis

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

Kriha, Kenneth; Petitpas, Guillaume; Melchionda, Michael

The goal of this project was to demonstrate the technical and economic feasibility of using thermal compression to create the hydrogen pressure necessary to operate vehicle hydrogen fueling stations. The concept of utilizing the exergy within liquid hydrogen to build pressure rather than mechanical components such as compressors or cryogenic liquid pumps has several advantages. In theory, the compressor-less hydrogen station will have lower operating and maintenance costs because the compressors found in conventional stations require large amounts of electricity to run and are prone to mechanical breakdowns. The thermal compression station also utilizes some of the energy used tomore » liquefy the hydrogen as work to build pressure, this is energy that in conventional stations is lost as heat to the environment.« less

Liquid-hydrogen rocket engine development at Aerojet, 1944 - 1950

NASA Technical Reports Server (NTRS)

Osborn, G. H.; Gordon, R.; Coplen, H. L.; James, G. S.

1977-01-01

This program demonstrated the feasibility of virtually all the components in present-day, high-energy, liquid-rocket engines. Transpiration and film-cooled thrust chambers were successfully operated. The first liquid-hydrogen tests of the coaxial injector was conducted and the first pump to successfully produce high pressures in pumping liquid hydrogen was tested. A 1,000-lb-thrust gaseous propellant and a 3,000-lb-thrust liquid-propellant thrust chamber were operated satisfactorily. Also, the first tests were conducted to evaluate the effects of jet overexpansion and separation on performance of rocket thrust chambers with hydrogen-oxygen propellants.

Hydrogen-Fuel Engine Component Tests Near Completion

NASA Technical Reports Server (NTRS)

2003-01-01

Gaseous hydrogen is burned off at the E1 Test Stand the night of Oct. 7 during a cold-flow test of the fuel turbopump of the Integrated Powerhead Demonstrator (IPD) at NASA Stennis Space Center (SSC). The gaseous hydrogen spins the pump's turbine during the test, which was conducted to verify the pump's performance. Engineers plan one more test before sending the pump to The Boeing Co. for inspection. It will then be returned to SSC for engine system assembly. The IPD is the first reusable hydrogen-fueled advanced engine in development since the Space Shuttle Main Engine.

Hydrogen-Fuel Engine Component Tests Near Completion

NASA Image and Video Library

2003-11-05

Gaseous hydrogen is burned off at the E1 Test Stand the night of Oct. 7 during a cold-flow test of the fuel turbopump of the Integrated Powerhead Demonstrator (IPD) at NASA Stennis Space Center (SSC). The gaseous hydrogen spins the pump's turbine during the test, which was conducted to verify the pump's performance. Engineers plan one more test before sending the pump to The Boeing Co. for inspection. It will then be returned to SSC for engine system assembly. The IPD is the first reusable hydrogen-fueled advanced engine in development since the Space Shuttle Main Engine.

Distillation Kinetics of Solid Mixtures of Hydrogen Peroxide and Water and the Isolation of Pure Hydrogen Peroxide in Ultrahigh Vacuum

NASA Technical Reports Server (NTRS)

Teolis, B. D.; Baragiola, R. A.

2006-01-01

We present results of the growth of thin films of crystalline H2O2 and H2O2.2H2O (dihydrate) in ultrahigh vacuum by distilling an aqueous solution of hydrogen peroxide. We traced the process using infrared reflectance spectroscopy, mass loss on a quartz crystal microbalance, and in a few cases ultraviolet-visible reflectance. We find that the different crystalline phases-water, dihydrate, and hydrogen peroxide-have very different sublimation rates, making distillation efficient to isolate the less volatile component, crystalline H2O2.

21 CFR 178.3280 - Castor oil, hydrogenated.

Code of Federal Regulations, 2014 CFR

2014-04-01

... polymers used in the manufacture of articles or components of articles authorized for food-contact use For... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Castor oil, hydrogenated. 178.3280 Section 178.3280 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED...

The Use of Hydrogen as a Fuel for Engines in the Energy Cycle of Remote Production Facilities

NASA Astrophysics Data System (ADS)

Ivanov, M. F.; Kiverin, A. D.; Smygalina, A. E.; Zaichenko, V. M.

2018-01-01

The approach to using hydrogen as fuel, which ensures the smooth operation of autonomous power systems that use renewable energy sources (wind or solar power installations) with the stochastic mode of power generation, has been presented. The fundamental possibility of implementing the nondetonation combustion of hydrogen via the addition of ecologically clean components or a small percentage of methane has been demonstrated by methods of mathematical modeling.

Component geochronology in the polyphase ca. 3920 Ma Acasta Gneiss

USGS Publications Warehouse

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

2014-01-01

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

Measurement component technology. Volume 1: Cryogenic pressure measurement technology, high pressure flange seals, hydrogen embrittlement of pressure transducer material, close coupled versus remote transducer installation and temperature compensation of pressure transducers

NASA Technical Reports Server (NTRS)

Hayakawa, K. K.; Udell, D. R.; Iwata, M. M.; Lytle, C. F.; Chrisco, R. M.; Greenough, C. S.; Walling, J. A.

1972-01-01

The results are presented of an investigation into the availability and performance capability of measurement components in the area of cryogenic temperature, pressure, flow and liquid detection components and high temperature strain gages. In addition, technical subjects allied to the components were researched and discussed. These selected areas of investigation were: (1) high pressure flange seals, (2) hydrogen embrittlement of pressure transducer diaphragms, (3) The effects of close-coupled versus remote transducer installation on pressure measurement, (4) temperature transducer configuration effects on measurements, and (5) techniques in temperature compensation of strain gage pressure transducers. The purpose of the program was to investigate the latest design and application techniques in measurement component technology and to document this information along with recommendations for upgrading measurement component designs for future S-2 derivative applications. Recommendations are provided for upgrading existing state-of-the-art in component design, where required, to satisfy performance requirements of S-2 derivative vehicles.

COMMON ISSUES IN HUMAN AND ECOSYSTEM EXPOSURE ASSESSMENT: THE SIGNIFICANCE OF PARTITIONING, KINETICS, AND UPTAKE AT BIOLOGICAL EXCHANGE SURFACES

EPA Science Inventory

Exogenous chemicals enter organisms through critical surfaces in the lung, gills, gut, and skin. Transfer across these boundaries is the first step in characterizing the ratio of tissue dose to external exposure. Surface processes and fugacity are important elements of both human...

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

DOE PAGES

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

2017-01-26

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

Evaluating the multimedia fate of organic chemicals: A level III fugacity model

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

Mackay, D.; Paterson, S.

A multimedia model is developed and applied to selected organic chemicals in evaluative and real regional environments. The model employs the fugacity concept and treats four bulk compartments: air, water, soil, and bottom sediment, which consist of subcompartments of varying proportions of air, water, and mineral and organic matter. Chemical equilibrium is assumed to apply within (but not between) each bulk compartment. Expressions are included for emissions, advective flows, degrading reactions, and interphase transport by diffusive and non-diffusive processes. Input to the model consists of a description of the environment, the physical-chemical and reaction properties of the chemical, and emissionmore » rates. For steady-state conditions the solution is a simple algebraic expression. The model is applied to six chemicals in the region of southern Ontario and the calculated fate and concentrations are compared with observations. The results suggest that the model may be used to determine the processes that control the environmental fate of chemicals in a region and provide approximate estimates of relative media concentrations.« less

A novel and simple model of the uptake of organic chemicals by vegetation from air and soil.

PubMed

Hung, H; Mackay, D

1997-09-01

A novel and simple three-compartment fugacity model has been developed to predict the kinetics and equilibria of the uptake of organic chemicals in herbaceous agricultural plants at various times, including the time of harvest using only readily available input data. The chemical concentration in each of the three plant compartments leaf, stem which includes fruits and seeds, and root) is expressed as a function of both time and chemical concentrations in soil and air. The model was developed using the fugacity concept; however, the final expressions are presented in terms of concentrations in soil and air, equilibrium partition coefficients and a set of transport and transformation half-lives. An illustrative application of the model is presented which describes the uptake of bromacil by a soybean plant under hydroponic conditions. The model, which is believed to give acceptably accurate prediction of the distribution of chemicals among plant tissues, air and soil, may be used for the assessment of exposure to, and risk from contaminants consumed either directly from vegetation or indirectly in natural and agricultural food chains.

Electrical properties of granite with implications for the lower crust.

USGS Publications Warehouse

Olhoeft, G.R.

1981-01-01

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

Organochlorine pesticides in soils of Mexico and the potential for soil-air exchange.

PubMed

Wong, Fiona; Alegria, Henry A; Bidleman, Terry F

2010-03-01

The spatial distribution of organochlorine pesticides (OCs) in soils and their potential for soil-air exchange was examined. The most prominent OCs were the DDTs (Geometric Mean, GM=1.6 ng g(-1)), endosulfans (0.16 ng g(-1)), and toxaphenes (0.64 ng g(-1)). DDTs in soils of southern Mexico showed fresher signatures with higher FDDTe=p,p'-DDT/(p,p'-DDT+p,p'-DDE) and more racemic o,p'-DDT, while the signatures in the central and northern part of Mexico were more indicative of aged residues. Soil-air fugacity fractions showed that some soils are net recipients of DDTs from the atmosphere, while other soils are net sources. Toxaphene profiles in soils and air showed depletion of Parlar 39 and 42 which suggests that soil is the source to the atmosphere. Endosulfan was undergoing net deposition at most sites as it is a currently used pesticide. Other OCs showed wide variability in fugacity, suggesting a mix of net deposition and volatilization. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

On the Coupling Time of the Heat-Bath Process for the Fortuin-Kasteleyn Random-Cluster Model

NASA Astrophysics Data System (ADS)

Collevecchio, Andrea; Elçi, Eren Metin; Garoni, Timothy M.; Weigel, Martin

2018-01-01

We consider the coupling from the past implementation of the random-cluster heat-bath process, and study its random running time, or coupling time. We focus on hypercubic lattices embedded on tori, in dimensions one to three, with cluster fugacity at least one. We make a number of conjectures regarding the asymptotic behaviour of the coupling time, motivated by rigorous results in one dimension and Monte Carlo simulations in dimensions two and three. Amongst our findings, we observe that, for generic parameter values, the distribution of the appropriately standardized coupling time converges to a Gumbel distribution, and that the standard deviation of the coupling time is asymptotic to an explicit universal constant multiple of the relaxation time. Perhaps surprisingly, we observe these results to hold both off criticality, where the coupling time closely mimics the coupon collector's problem, and also at the critical point, provided the cluster fugacity is below the value at which the transition becomes discontinuous. Finally, we consider analogous questions for the single-spin Ising heat-bath process.

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

NASA Technical Reports Server (NTRS)

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

2009-01-01

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

Highly oxidising fluids generated during serpentinite breakdown in subduction zones.

PubMed

Debret, B; Sverjensky, D A

2017-09-04

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

Thermodynamic characterization of hydrogen interaction with iridium polyhydride complexes

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

Zidan, R.A.; Rocheleau, R.E.

1999-01-01

Hydrogen interaction with solid iridium complexes IrXH{sub 2}(PPr3{sup i}){sub 2} (X=Cl, I) was investigated. Gaseous hydrogen was found to react reversibly with solid chloro-iridium complex IrClH{sub 2}(PPr3{sup i}){sub 2} forming IrClH{sub 2}(PPr3{sup i}){sub 2}H{sub 2}. The relative partial molal enthalpy and entropy were obtained from equilibrium isotherms at different hydrogen concentrations. The decrease in entropy with increasing hydrogen concentration and the absence of plateaus in the equilibrium isotherms were consistent with a single phase solid solution with two chemical components. Hydrogen release from solid iodo-iridium complex IrIH{sub 2}(PPr3{sup i}){sub 2}H{sub 2} was not observed at temperatures up to 350 K,more » indicating stronger hydrogen bonding. {copyright} {ital 1999 Materials Research Society.}« less

Potential improvement to a citric wastewater treatment plant using bio-hydrogen and a hybrid energy system

NASA Astrophysics Data System (ADS)

Zhi, Xiaohua; Yang, Haijun; Berthold, Sascha; Doetsch, Christian; Shen, Jianquan

Treatment of highly concentrated organic wastewater is characterized as cost-consuming. The conventional technology uses the anaerobic-anoxic-oxic process (A 2/O), which does not produce hydrogen. There is potential for energy saving using hydrogen utilization associated with wastewater treatment because hydrogen can be produced from organic wastewater using anaerobic fermentation. A 50 m 3 pilot bio-reactor for hydrogen production was constructed in Shandong Province, China in 2006 but to date the hydrogen produced has not been utilized. In this work, a technical-economic model based on hydrogen utilization is presented and analyzed to estimate the potential improvement to a citric wastewater plant. The model assesses the size, capital cost, annual cost, system efficiency and electricity cost under different configurations. In a stand-alone situation, the power production from hydrogen is not sufficient for the required load, thus a photovoltaic array (PV) is employed as the power supply. The simulated results show that the combination of solar and bio-hydrogen has a much higher cost compared with the A 2/O process. When the grid is connected, the system cost achieved is 0.238 US t -1 wastewater, which is lower than 0.257 US t -1 by the A 2/O process. The results reveal that a simulated improvement by using bio-hydrogen and a FC system is effective and feasible for the citric wastewater plant, even when compared to the current cost of the A 2/O process. In addition, lead acid and vanadium flow batteries were compared for energy storage service. The results show that a vanadium battery has lower cost and higher efficiency due to its long lifespan and energy efficiency. Additionally, the cost distribution of components shows that the PV dominates the cost in the stand-alone situation, while the bio-reactor is the main cost component in the parallel grid.

Selective gas-chromatographic detection using an ion-selective electrode-II Selective detection of fluorine compounds.

PubMed

Kojima, T; Ichise, M; Seo, Y

1972-04-01

Components in samples are separated on a gas chromatography column using hydrogen as carrier gas. The individual components from the column are passed through a platinum tube heated at 1000 degrees , where they undergo hydrogenolysis, and fluorine compounds are converted into hydrogen fluoride. The hydrogen fluoride is dissolved in a slow stream of an absorption solution, and the fluoride ion concentration in the resulting solution is monitored in a flow-cell with a fluoride ion electrode. The potentiometric output of the cell is converted into a signal, which is proportional to the concentration of fluoride ion, by an antilogarithmic converter, and recorded. The response of the detector to fluorine compounds was about 10,000 times that to an equal quantity of other organic compounds, and 5 x 10(-11) mole of fluorobenzene could be detected.

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

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

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

2008-11-20

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

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

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

NASA Astrophysics Data System (ADS)

Roller, G.

2015-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-07-01

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

Oxygen Fugacity in Large Metal Capsules

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

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

NASA Astrophysics Data System (ADS)

Sugawara, Toru

2001-06-01

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

Sensing the flux of volatile chemicals through the air-water interface

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

Mackay, D.; Schroeder, W.H.; Ooijen, H. von

1997-12-31

There are several situations in which there is a need to assess the direction and magnitude of the flux across the air-water interface. Contaminants may be evaporating or absorbing in wastewater treatment systems in natural lake, river, estuarine and marine systems, and any attempt to compile a mass balance must include this process. In this study the authors review the theory underlying air-water exchange, then describe and discuss a sparging approach by which the direction and magnitude of the flux can be ascertained. The principle of the method is that a known flow rate of air is bubbled through themore » sparger and allowed to equilibrate with the water. The gas exiting the water surface is passed through a sorbent trap and later analyzed. The concentration, and hence the fugacity, of the contaminant in the sparged air can be deduced. In parallel, a similar flow of air from the atmosphere above the water is drawn through another sparger at a similar flow rate for a similar time and the trapped chemical analyzed giving the concentration and fugacity in the air. These data show the direction of air-water exchange (i.e. from high to low fugacity) and with information on the mass transfer coefficients and area, the flux. Successful tests were conducted of the system in a laboratory tank, in Lake Ontario and in Hamilton Harbour. Analyses of the traps showed a large number of peaks on the chromatogram many of which are believed to be of petroleum origin from fuels and vessel exhaust. The system will perform best under conditions where concentrations of specific contaminants are large, as occurs in waste water treatment systems. The approach has the potential to contribute to more accurate assessment of air-water fluxes. It avoids the problems of different analytical methodologies and the effect of sorption in the water column.« less

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

NASA Astrophysics Data System (ADS)

Basu, A. R.; Das, S.

2017-12-01

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

Occurrence and air-soil exchange of organochlorine pesticides and polychlorinated biphenyls at a CAWNET background site in central China: Implications for influencing factors and fate.

PubMed

Zhan, Lingxi; Lin, Tian; Wang, Zuwu; Cheng, Zhineng; Zhang, Gan; Lyu, Xiaopu; Cheng, Hairong

2017-11-01

Ambient air and soil samples were collected between March 2012 and March 2013 at Jinsha, a regional background site in central China, to measure the concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). The average concentrations of total OCPs and total PCBs were 191 ± 107 and 39.4 ± 27.1 pg/m 3 in air (gaseous and particulate phase) and 0.585 ± 0.437 and 0.083 ± 0.039 ng/g in soil, respectively. The higher concentrations of p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT) and p,p'-DDT/p,p'-DDE ratios in the soil indicated recent p,p'-DDT input to the soil. A strong positive temperature dependence and average fugacity fraction value > 0.5 were observed for p,p'-DDT, suggesting that volatilization of residual DDT in the soil was the main influencing factor on atmospheric p,p'-DDT. Highly average fugacity fractions (>0.7) of trans-chlordane (TC) and cis-chlordane (CC) and high TC/CC ratios both in the soil and atmosphere suggested fresh inputs. Higher gaseous concentrations of hexachlorobenzene (HCB) were observed in winter and negative temperature dependence was directly attributed to the surrounding ongoing source (e.g. fuel consuming activities), especially in winter. Overall, most targeted OCPs and PCBs were influenced by long-range transport, and fugacity fraction values indicated highly volatile compounds (e.g. α-hexachlorocyclohexane (α-HCH) and lower chlorinated PCBs) were volatilized and low volatility compounds (e.g. p,p'-DDE and higher chlorinated PCBs) were deposited at the air-soil interface. Knowing the source and sink of OCPs and PCBs can help to control their pollution in this area and provide a reference for other studies. Copyright © 2017 Elsevier Ltd. All rights reserved.

Gas solubility in hydrophobic confinement.

PubMed

Luzar, Alenka; Bratko, Dusan

2005-12-01

Measured forces between apolar surfaces in water have often been found to be sensitive to exposure to atmospheric gases despite low gas solubilities in bulk water. This raises questions as to how significant gas adsorption is in hydrophobic confinement, whether it is conducive to water depletion at such surfaces, and ultimately if it can facilitate the liquid-to-gas phase transition in the confinement. Open Ensemble molecular simulations have been used here to determine saturated concentrations of atmospheric gases in water-filled apolar confinements as a function of pore width at varied gas fugacities. For paraffin-like confinements of widths barely exceeding the mechanical instability threshold (spinodal) of the liquid-to-vapor transition of confined water (aqueous film thickness between three and four molecular diameters), mean gas concentrations in the pore were found to exceed the bulk values by a factor of approximately 30 or approximately 15 in cases of N2 and CO2, respectively. At ambient conditions, this does not result in visible changes in the water density profile next to the surfaces. Whereas the barrier to capillary evaporation has been found to decrease in the presence of dissolved gas (Leung, K.; Luzar, A.; and Bratko, D. Phys. Rev. Lett. 2003, 90, 065502), gas concentrations much higher than those observed at normal atmospheric conditions would be needed to produce noticeable changes in the kinetics of capillary evaporation. In simulations, dissolved gas concentrations corresponding to fugacities above approximately 40 bar for N2, or approximately 2 bar for CO2, were required to trigger expulsion of water from a hydrocarbon slit as narrow as 1.4 nm. For nanosized pore widths corresponding to the mechanical instability threshold or above, no significant coupling between adsorption layers at opposing confinement walls was observed. This finding explains the approximately linear increase in gas solubility with inverse confinement width and the apparent validity of Henry's law in the pores over a broad fugacity range.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

An AAA-DDD triply hydrogen-bonded complex easily accessible for supramolecular polymers.

PubMed

Han, Yi-Fei; Chen, Wen-Qiang; Wang, Hong-Bo; Yuan, Ying-Xue; Wu, Na-Na; Song, Xiang-Zhi; Yang, Lan

2014-12-15

For a complementary hydrogen-bonded complex, when every hydrogen-bond acceptor is on one side and every hydrogen-bond donor is on the other, all secondary interactions are attractive and the complex is highly stable. AAA-DDD (A=acceptor, D=donor) is considered to be the most stable among triply hydrogen-bonded sequences. The easily synthesized and further derivatized AAA-DDD system is very desirable for hydrogen-bonded functional materials. In this case, AAA and DDD, starting from 4-methoxybenzaldehyde, were synthesized with the Hantzsch pyridine synthesis and Friedländer annulation reaction. The association constant determined by fluorescence titration in chloroform at room temperature is 2.09×10(7)  M(-1) . The AAA and DDD components are not coplanar, but form a V shape in the solid state. Supramolecular polymers based on AAA-DDD triply hydrogen bonded have also been developed. This work may make AAA-DDD triply hydrogen-bonded sequences easily accessible for stimuli-responsive materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemistry and catalysis of coal liquefaction catalytic and thermal upgrading of coal liquid and hydrogenation of CO to produce fuels. Quarterly progress report, July-September 1980

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

Wiser, W.H.

1981-02-01

Studies on the basic properties of supported sulfide catalysts showed that different supports have a profound influence on catalytic activities of CoMo catalysts. The three functions of hydrodesulfurization, hydrogenation and cracking were differently affected depending on the support used and the manner of preparation of the catalyst. Also, incorporation of additives to the support showed that the different catalytic functions can be selectively affected. A systematic study concerned with catalytic cracking of coal-derived liquids, viz., an SRC-II middle-heavy distillate and four hydrotreated SRC-II products was carried out in the range of 375 to 500/sup 0/C (LHSV, 0.2 to 3.9 h/supmore » -1/). Hydrotreatment, even to a limited extent, results in a remarkable improvement in the yield of gasoline-range products from the SRC-II distillate. This improvement is ascribed to: (a) hydrogenolysis reactions leading to lower molecular weight feedstock components and (b) limited hydrogenation of aromatic rings leading to polycyclic feed components with sufficient concentration of hydroaromatic rings needed for effective cracking. The results with model compounds and the data on hydrogen consumption during hydrotreatment of SRC-II liquids indicate that for tricyclic, tetracyclic, and pentacyclic coal-liquid components the optimal concentration of hydroaromatic rings for effective subsequent cracking is at least two rings per molecule.« less

A prolific catalyst for dehydrogenation of neat formic acid

PubMed Central

Celaje, Jeff Joseph A.; Lu, Zhiyao; Kedzie, Elyse A.; Terrile, Nicholas J.; Lo, Jonathan N.; Williams, Travis J.

2016-01-01

Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments. PMID:27076111

Multi-component hydrogen storage material

DOEpatents

Faheem, Syed A.; Lewis, Gregory J.; Sachtler, J.W. Adriaan; Low, John J.; Lesch, David A.; Dosek, Paul M.; Wolverton, Christopher M.; Siegel, Donald J.; Sudik, Andrea C.; Yang, Jun

2010-09-07

A reversible hydrogen storage composition having an empirical formula of: Li.sub.(x+z)N.sub.xMg.sub.yB.sub.zH.sub.w where 0.4.ltoreq.x.ltoreq.0.8; 0.2.ltoreq.y.ltoreq.0.6; 0

Indirect measurements of hydrogen: The deficit method for a many-component system

NASA Astrophysics Data System (ADS)

Levine, Timothy E.; Yu, Ning; Kodali, Padma; Walter, Kevin C.; Nastasi, Michael; Tesmer, Joseph R.; Maggiore, Carl J.; Mayer, James W.

We have developed a simple technique for determining hydrogen atomic fraction from the ion backscattering spectrometry (IBS) signals of the remaining species. This technique uses the surface heights of various IBS signals in the form of a linear matrix equation. We apply this technique to in situ analysis of ion-beam-induced densification of sol-gel zirconia thin films, where hydrogen is the most volatile species during irradiation. Attendant errors are discussed with an emphasis on stopping powers and Bragg's rule.

Computer simulations of adsorption and diffusion for binary mixtures of methane and hydrogen in titanosilicates.

PubMed

Mitchell, Martha C; Gallo, Marco; Nenoff, Tina M

2004-07-22

Equilibrium molecular dynamics (MD) simulations of equimolar mixtures of hydrogen and methane were performed in three different titanosilicates: naturally occurring zorite and two synthetic titanosilicates, ETS-4 and ETS-10. In addition, single-component MD simulations and adsorption isotherms generated using grand canonical Monte Carlo simulations were performed to support the mixture simulations. The goal of this study was to determine the best membrane material to carry out hydrogen/methane separations. ETS-10 has a three-dimensional pore network. ETS-4 and zorite have two-dimensional pore networks. The simulations carried out in this study show that the increased porosity of ETS-10 results in self-diffusion coefficients for both hydrogen and methane that are higher in ETS-10 than in either ETS-4 or zorite. Methane only showed appreciable displacement in ETS-10. The ability of the methane molecules to move in all three directions in ETS-10 was demonstrated by the high degree of isotropy shown in the values of the x, y, and z components of the self-diffusion coefficient for methane in ETS-10. From our simulations we conclude that ETS-10 would be better suited for fast industrial separations of hydrogen and methane. However, the separation would not result in a pure hydrogen stream. In contrast, ETS-4 and zorite would act as true molecular sieves for separations of hydrogen and methane, as the methane would not move through membranes made of these materials. This was indicated by the near-zero self-diffusion coefficient of methane in ETS-4 and zorite.

Computer simulations of adsorption and diffusion for binary mixtures of methane and hydrogen in titanosilicates

NASA Astrophysics Data System (ADS)

Mitchell, Martha C.; Gallo, Marco; Nenoff, Tina M.

2004-07-01

Equilibrium molecular dynamics (MD) simulations of equimolar mixtures of hydrogen and methane were performed in three different titanosilicates: naturally occurring zorite and two synthetic titanosilicates, ETS-4 and ETS-10. In addition, single-component MD simulations and adsorption isotherms generated using grand canonical Monte Carlo simulations were performed to support the mixture simulations. The goal of this study was to determine the best membrane material to carry out hydrogen/methane separations. ETS-10 has a three-dimensional pore network. ETS-4 and zorite have two-dimensional pore networks. The simulations carried out in this study show that the increased porosity of ETS-10 results in self-diffusion coefficients for both hydrogen and methane that are higher in ETS-10 than in either ETS-4 or zorite. Methane only showed appreciable displacement in ETS-10. The ability of the methane molecules to move in all three directions in ETS-10 was demonstrated by the high degree of isotropy shown in the values of the x, y, and z components of the self-diffusion coefficient for methane in ETS-10. From our simulations we conclude that ETS-10 would be better suited for fast industrial separations of hydrogen and methane. However, the separation would not result in a pure hydrogen stream. In contrast, ETS-4 and zorite would act as true molecular sieves for separations of hydrogen and methane, as the methane would not move through membranes made of these materials. This was indicated by the near-zero self-diffusion coefficient of methane in ETS-4 and zorite.

Energy Systems High-Pressure Test Laboratory | Energy Systems Integration

Science.gov Websites

Facility | NREL Energy Systems High-Pressure Test Laboratory Energy Systems High-Pressure Test Laboratory In the Energy Systems Integration Facility's High-Pressure Test Laboratory, researchers can safely test high-pressure hydrogen components. Photo of researchers running an experiment with a hydrogen fuel

Hydrogen purification: MOF membranes put to the test

DOE PAGES

Nenoff, Tina M.

2015-03-30

Membranes are essential components for the removal of greenhouse gases during fuel generation processes, such as hydrogen production, but simultaneous permeability and selectivity is difficult to obtain. This has now been achieved in ultrathin membranes that use the size-selective porosity of metal–organic frameworks to separate CO 2 from H 2.

Nickel-hydrogen battery with oxygen and electrolyte management features

DOEpatents

Sindorf, John F.

1991-10-22

A nickel-hydrogen battery or cell having one or more pressure vessels containing hydrogen gas and a plurality of cell-modules therein. Each cell-module includes a configuration of cooperatively associated oxygen and electrolyte mangement and component alignment features. A cell-module having electrolyte includes a negative electrode, a positive electrode adapted to facilitate oxygen diffusion, a separator disposed between the positive and negative electrodes for separating them and holding electrolyte for ionic conductivity, an absorber engaging the surface of the positive electrode facing away from the separator for providing electrolyte to the positive electrode, and a pair of surface-channeled diffusion screens for enclosing the positive and negative electrodes, absorber, and separator and for maintaining proper alignment of these components. The screens, formed in the shape of a pocket by intermittently sealing the edges together along as many as three sides, permit hydrogen gas to diffuse therethrough to the negative electrodes, and prevent the edges of the separator from swelling. Electrolyte is contained in the cell-module, absorbhed by the electrodes, the separator and the absorber.

Nature of hydrogen embrittlement of steel

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

Archakov, Yu. I.; Grebeshkova, I.D.

1986-01-01

The hydrogen embrittlement of metals is the result of the origin and development of microcracks, which are formed as the result of the occurence of internal stresses. The specific feature of the appearance of hydrogen embrittlement are the result of the physical properties of the metals and the character of their interaction with hydrogen. The tendency of metals toward hydrogen embrittlement is determined by the following characteristics: their capacity to dissolve hydrogen and its maximum solubility; the chemical activity of the metals and other phases in relation to hydrogen, that is, the capacity toward hydride formation and failure of themore » carbided sand oxides, and the tendency of the metal toward the occurence and propagation of cracks. The authors cite and discuss two general forms of action of hydrogen on metals, the physical action of hydrogen on metals and the physicochemical action when chemical interaction of hydrogen with the different phases and the individual components of the alloy on the surface and in the volume occurs. The tendency toward hydrogen embrittlement is shown to increase with an increase in the strength of the steel. In addition to the strength, this characteristic also depends upon the chemical composition and structural condition of the steel.« less

Backbone amide 15N chemical shift tensors report on hydrogen bonding interactions in proteins: A magic angle spinning NMR study.

PubMed

Paramasivam, Sivakumar; Gronenborn, Angela M; Polenova, Tatyana

2018-08-01

Chemical shift tensors (CSTs) are an exquisite probe of local geometric and electronic structure. 15 N CST are very sensitive to hydrogen bonding, yet they have been reported for very few proteins to date. Here we present experimental results and statistical analysis of backbone amide 15 N CSTs for 100 residues of four proteins, two E. coli thioredoxin reassemblies (1-73-(U- 13 C, 15 N)/74-108-(U- 15 N) and 1-73-(U- 15 N)/74-108-(U- 13 C, 15 N)), dynein light chain 8 LC8, and CAP-Gly domain of the mammalian dynactin. The 15 N CSTs were measured by a symmetry-based CSA recoupling method, ROCSA. Our results show that the principal component δ 11 is very sensitive to the presence of hydrogen bonding interactions due to its unique orientation in the molecular frame. The downfield chemical shift change of backbone amide nitrogen nuclei with increasing hydrogen bond strength is manifested in the negative correlation of the principal components with hydrogen bond distance for both α-helical and β-sheet secondary structure elements. Our findings highlight the potential for the use of 15 N CSTs in protein structure refinement. Copyright © 2018 Elsevier Inc. All rights reserved.

National Combustion Code Used To Study the Hydrogen Injector Design for Gas Turbines

NASA Technical Reports Server (NTRS)

Iannetti, Anthony C.; Norris, Andrew T.; Shih, Tsan-Hsing

2005-01-01

Hydrogen, in the gas state, has been proposed to replace Jet-A (the fuel used for commercial jet engines) as a fuel for gas turbine combustion. For the combustion of hydrogen and oxygen only, water is the only product and the main greenhouse gas, carbon dioxide, is not produced. This is an obvious benefit of using hydrogen as a fuel. The situation is not as simple when air replaces oxygen in the combustion process. (Air is mainly a mixture of oxygen, nitrogen, and argon. Other components comprise a very small part of air and will not be mentioned.) At the high temperatures found in the combustion process, oxygen reacts with nitrogen, and this produces nitrogen oxide compounds, or NOx--the main component of atmospheric smog. The production of NOx depends mainly on two variables: the temperature at which combustion occurs, and the length of time that the products of combustion stay, or reside, in the combustor. Starting from a lean (excess air) air-to-fuel ratio, the goal of this research was to minimize hot zones caused by incomplete premixing and to keep the residence time short while producing a stable flame. The minimization of these two parameters will result in low- NOx hydrogen combustion.

U.S. Clean Energy Hydrogen and Fuel Cell Technologies: A Competitiveness Analysis

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

Fullenkamp, Patrick; Holody, Diane; James, Brian

The objectives of this project are a 1) Global Competitiveness Analysis of hydrogen and fuel cell systems and components manufactured including 700 bar compressed hydrogen storage system in the U.S., Europe, Asia, and other key areas to be identified to determine the global cost leaders, the best current manufacturing processes, the key factors determining competitiveness, and the potential means of cost reductions; and an 2) Analysis to assess the status of global hydrogen and fuel cell markets. The analysis of units, megawatts by country and by application will focus on polymer electrolyte membrane (PEM) fuel cell systems (automotive and stationary).

Robot-Powered Reliability Testing at NREL's ESIF

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

Harrison, Kevin

With auto manufacturers expected to roll out fuel cell electric vehicles in the 2015 to 2017 timeframe, the need for a reliable hydrogen fueling infrastructure is greater than ever. That's why the National Renewable Energy Laboratory (NREL) is using a robot in its Energy Systems Integration Facility (ESIF) to assess the durability of hydrogen fueling hoses, a largely untested-and currently costly-component of hydrogen fueling stations. The automated machine mimics the repetitive stress of a human bending and twisting the hose to refuel a vehicle-all under the high pressure and low temperature required to deliver hydrogen to a fuel cell vehicle'smore » onboard storage tank.« less

Robot-Powered Reliability Testing at NREL's ESIF

ScienceCinema

Harrison, Kevin

2018-02-14

With auto manufacturers expected to roll out fuel cell electric vehicles in the 2015 to 2017 timeframe, the need for a reliable hydrogen fueling infrastructure is greater than ever. That's why the National Renewable Energy Laboratory (NREL) is using a robot in its Energy Systems Integration Facility (ESIF) to assess the durability of hydrogen fueling hoses, a largely untested-and currently costly-component of hydrogen fueling stations. The automated machine mimics the repetitive stress of a human bending and twisting the hose to refuel a vehicle-all under the high pressure and low temperature required to deliver hydrogen to a fuel cell vehicle's onboard storage tank.

Robot-Powered Reliability Testing at NREL's ESIF

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

Harrison, Kevin

With auto manufacturers expected to roll out fuel cell electric vehicles in the 2015 to 2017 timeframe, the need for a reliable hydrogen fueling infrastructure is greater than ever. That's why the National Renewable Energy Laboratory (NREL) is using a robot in its Energy Systems Integration Facility (ESIF) to assess the durability of hydrogen fueling hoses, a largely untested—and currently costly—component of hydrogen fueling stations. The automated machine mimics the repetitive stress of a human bending and twisting the hose to refuel a vehicle—all under the high pressure and low temperature required to deliver hydrogen to a fuel cell vehicle'smore » onboard storage tank.« less

Koster van Groos, A F

NASA Astrophysics Data System (ADS)

Guggenheim, S.

2008-12-01

The deep-ocean environment, including the ocean floor and crust, represents one of the last scientific frontiers on earth. The surprising lack of information on the mineralogy, the geochemical processes, or the biota of the ocean floor is the result of the inability to simulate ocean-floor conditions and to study geochemical systems at these conditions. A proto-type high-pressure environmental chamber (HPEC) has been constructed for use on a transmission- mode X-ray diffractometer to study geochemical processes at the deep-ocean sediment cover and crust. The HPEC has a designed pressure range to 1000 bars and temperature range from -20 oC to 200 oC. In this chamber, a liquid (e.g., sea water) plus sample in suspension can be pressurized either by gas or liquid. A cell-pump system continuously agitates the liquid to keep particles in suspension, thereby allowing the examination of mineral phases, including clays minerals. A major feature of the HPEC is that the mineral component moves freely and can react with its environment while being illuminated by the X-ray beam. The cell-pump also allows applied gas, such as CH4 or CO2, or O2, to interact efficiently with the aqueous liquid so that the system may rapidly reach equilibrium. In addition, mixing these gases with inert gases, e.g. He or Ar, allows control of the fugacity of these gas components. The design components and how data are manipulated to remove X-ray dispersion effects caused by the liquid will be discussed, along with examples showing the effects of temperature, pressure, and salt content on smectite clay.

Liquefaction process wherein solvents derived from the material liquefied and containing increased concentrations of donor species are employed

DOEpatents

Fant, B. T.; Miller, John D.; Ryan, D. F.

1982-01-01

An improved process for the liquefaction of solid carbonaceous materials wherein a solvent or diluent derived from the solid carbonaceous material being liquefied is used to form a slurry of the solid carbonaceous material and wherein the solvent or diluent comprises from about 65 to about 85 wt. % hydroaromatic components. The solvent is prepared by first separating a solvent or diluent distillate fraction from the liquefaction product, subjecting this distillate fraction to hydrogenation and then extracting the naphthenic components from the hydrogenated product. The extracted naphthenic components are then dehydrogenated and hydrotreated to produce additional hydroaromatic components. These components are combined with the solvent or diluent distillate fraction. The solvent may also contain hydroaromatic constituents prepared by extracting naphthenic components from a heavy naphtha, dehydrogenating the same and then hydrotreating the dehydrogenated product. When the amount of solvent produced in this manner exceeds that required for steady state operation of the liquefaction process a portion of the solvent or diluent distillated fraction will be withdrawn as product.

Bio-oil Stabilization by Hydrogenation over Reduced Metal Catalysts at Low Temperatures

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

Wang, Huamin; Lee, Suh-Jane; Olarte, Mariefel V.

Biomass fast pyrolysis integrated with bio-oil upgrading represents a very attractive approach for converting biomass to hydrocarbon transportation fuels. However, the thermal and chemical instability of bio-oils presents significant problems when they are being upgraded, and development of effective approaches for stabilizing bio-oils is critical to the success of the technology. Catalytic hydrogenation to remove reactive species in bio-oil has been considered as one of the most efficient ways to stabilize bio-oil. This paper provides a fundamental understanding of hydrogenation of actual bio-oils over a Ru/TiO2 catalyst under conditions relevant to practical bio-oil hydrotreating processes. Bio-oil feed stocks, bio-oils hydrogenatedmore » to different extents, and catalysts have been characterized to provide insights into the chemical and physical properties of these samples and to understand the correlation of the properties with the composition of the bio-oil and catalysts. The results indicated hydrogenation of various components of the bio-oil, including sugars, aldehydes, ketones, alkenes, aromatics, and carboxylic acids, over the Ru/TiO2 catalyst and 120 to 160oC. Hydrogenation of these species significantly changed the chemical and physical properties of the bio-oil and overall improved its thermal stability, especially by reducing the carbonyl content, which represented the content of the most reactive species (i.e., sugar, aldehydes, and ketones). The change of content of each component in response to increasing hydrogen additions suggests the following bio-oil hydrogenation reaction sequence: sugar conversion to sugar alcohols, followed by ketone and aldehyde conversion to alcohols, followed by alkene and aromatic hydrogenation, and then followed by carboxylic acid hydrogenation to alcohols. Hydrogenation of bio-oil samples with different sulfur contents or inorganic material contents suggested that sulfur poisoning of the reduced Ru metal catalysts was significant during hydrogenation; however, the inorganics at low concentrations had minimal impact at short times on stream, indicating that sulfur poisoning was the primary deactivation mode for the bio-oil hydrogenation catalyst. Reducing the sulfur content in bio-oil could significantly increase the lifetime of the hydrogenation catalyst used. The knowledge gained during this work will allow rational design of more effective catalysts and processes for stabilizing and upgrading bio-oils.« less

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

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

Durable regenerable sorbent pellets for removal of hydrogen sulfide from coal gas

DOEpatents

Siriwardane, R.V.

1999-02-02

Pellets for removing hydrogen sulfide from a coal gasification stream at an elevated temperature are prepared in durable form, usable over repeated cycles of absorption and regeneration. The pellets include a material reactive with hydrogen sulfide, in particular zinc oxide, a binder, and an inert material, in particular calcium sulfate (drierite), having a particle size substantially larger than other components of the pellets. A second inert material and a promoter may also be included. Preparation of the pellets may be carried out by dry, solid-state mixing of components, moistening the mixture, and agglomerating it into pellets, followed by drying and calcining. Pellet size is selected, depending on the type of reaction bed for which the pellets are intended. The use of inert material with a large particle size provides a stable pellet structure with increased porosity, enabling effective gas contact and prolonged mechanical durability.

Durable regenerable sorbent pellets for removal of hydrogen sulfide from coal gas

DOEpatents

Siriwardane, R.V.

1997-12-30

Pellets for removing hydrogen sulfide from a coal gasification stream at an elevated temperature are prepared in durable form usable over repeated cycles of absorption and regeneration. The pellets include a material reactive with hydrogen sulfide, in particular zinc oxide, a binder, and an inert material, in particular calcium sulfate (drierite), having a particle size substantially larger than other components of the pellets. A second inert material and a promoter may also be included. Preparation of the pellets may be carried out by dry, solid-state mixing of components, moistening the mixture, and agglomerating it into pellets, followed by drying and calcining. Pellet size is selected, depending on the type of reaction bed for which the pellets are intended. The use of inert material with a large particle size provides a stable pellet structure with increased porosity, enabling effective gas contact and prolonged mechanical durability.

Pore size engineering applied to starved electrochemical cells and batteries

NASA Technical Reports Server (NTRS)

Abbey, K. M.; Thaller, L. H.

1982-01-01

To maximize performance in starved, multiplate cells, the cell design should rely on techniques which widen the volume tolerance characteristics. These involve engineering capillary pressure differences between the components of an electrochemical cell and using these forces to promote redistribution of electrolyte to the desired optimum values. This can be implemented in practice by prescribing pore size distributions for porous back-up plates, reservoirs, and electrodes. In addition, electrolyte volume management can be controlled by incorporating different pore size distributions into the separator. In a nickel/hydrogen cell, the separator must contain pores similar in size to the small pores of both the nickel and hydrogen electrodes in order to maintain an optimum conductive path for the electrolyte. The pore size distributions of all components should overlap in such a way as to prevent drying of the separator and/or flooding of the hydrogen electrode.

Durable regenerable sorbent pellets for removal of hydrogen sulfide from coal gas

DOEpatents

Siriwardane, Ranjani V.

1997-01-01

Pellets for removing hydrogen sulfide from a coal gasification stream at an elevated temperature are prepared in durable form usable over repeated cycles of absorption and regeneration. The pellets include a material reactive with hydrogen sulfide, in particular zinc oxide, a binder, and an inert material, in particular calcium sulfate (drierite), having a particle size substantially larger than other components of the pellets. A second inert material and a promoter may also be included. Preparation of the pellets may be carried out by dry, solid-state mixing of components, moistening the mixture, and agglomerating it into pellets, followed by drying and calcining. Pellet size is selected, depending on the type of reaction bed for which the pellets are intended. The use of inert material with a large particle size provides a stable pellet structure with increased porosity, enabling effective gas contact and prolonged mechanical durability.

Durable regenerable sorbent pellets for removal of hydrogen sulfide coal gas

DOEpatents

Siriwardane, Ranjani V.

1999-01-01

Pellets for removing hydrogen sulfide from a coal gasification stream at an elevated temperature are prepared in durable form, usable over repeated cycles of absorption and regeneration. The pellets include a material reactive with hydrogen sulfide, in particular zinc oxide, a binder, and an inert material, in particular calcium sulfate (drierite), having a particle size substantially larger than other components of the pellets. A second inert material and a promoter may also be included. Preparation of the pellets may be carried out by dry, solid-state mixing of components, moistening the mixture, and agglomerating it into pellets, followed by drying and calcining. Pellet size is selected, depending on the type of reaction bed for which the pellets are intended. The use of inert material with a large particle size provides a stable pellet structure with increased porosity, enabling effective gas contact and prolonged mechanical durability.

Precise tuning in platinum-nickel/nickel sulfide interface nanowires for synergistic hydrogen evolution catalysis

PubMed Central

Wang, Pengtang; Zhang, Xu; Zhang, Jin; Wan, Sheng; Guo, Shaojun; Lu, Gang; Yao, Jianlin; Huang, Xiaoqing

2017-01-01

Comprising abundant interfaces, multicomponent heterostructures can integrate distinct building blocks into single entities and yield exceptional functionalities enabled by the synergistic components. Here we report an efficient approach to construct one-dimensional metal/sulfide heterostructures by directly sulfuring highly composition-segregated platinum-nickel nanowires. The heterostructures possess a high density of interfaces between platinum-nickel and nickel sulfide components, which cooperate synergistically towards alkaline hydrogen evolution reaction. The platinum-nickel/nickel sulfide heterostructures can deliver a current density of 37.2 mA cm−2 at an overpotential of 70 mV, which is 9.7 times higher than that of commercial Pt/C. The heterostructures also offer enhanced stability revealed by long-term chronopotentiometry measurements. The present work highlights a potentially powerful interface-engineering strategy for designing multicomponent heterostructures with advanced performance in hydrogen evolution reaction and beyond. PMID:28239145

Water's Interfacial Hydrogen Bonding Structure Reveals the Effective Strength of Surface-Water Interactions.

PubMed

Shin, Sucheol; Willard, Adam P

2018-06-05

We combine all-atom molecular dynamics simulations with a mean field model of interfacial hydrogen bonding to analyze the effect of surface-water interactions on the structural and energetic properties of the liquid water interface. We show that the molecular structure of water at a weakly interacting ( i.e., hydrophobic) surface is resistant to change unless the strength of surface-water interactions are above a certain threshold. We find that below this threshold water's interfacial structure is homogeneous and insensitive to the details of the disordered surface, however, above this threshold water's interfacial structure is heterogeneous. Despite this heterogeneity, we demonstrate that the equilibrium distribution of molecular orientations can be used to quantify the energetic component of the surface-water interactions that contribute specifically to modifying the interfacial hydrogen bonding network. We identify this specific energetic component as a new measure of hydrophilicity, which we refer to as the intrinsic hydropathy.

Fabrication and testing of silver-hydrogen cells

NASA Technical Reports Server (NTRS)

Klein, M. G.

1978-01-01

The development and life testing of single electrode and multi electrode stacks to optimize the individual components and characterize the performance of a silver hydrogen battery system are described. A NASA-developed inorganic separator material was used as the main separator within the cells. Single electrode test cells were cycled at 75% of nominal capacity out through approximately 1,000 cycles in a number of cases where deterioration in performance was observed. This deterioration appears to be a decay in usable capacity of the silver electrode; but the exact mechanism is still unidentified. Twenty ampere-hour boilerplate test cells consisting of a stack of ten silver electrodes and twenty hydrogen electrodes were cycled also at 75% depth of discharge. The oldest stack achieved 522 stable cycles to the end of the program. Weight analysis of light-weight cells showed that 50 ampere-hour cells with improved components could be capable of as much as 40 watt hours per pound.

Liquid Iron Alloys with Hydrogen at Outer Core Conditions by First Principles

NASA Astrophysics Data System (ADS)

Umemoto, K.; Hirose, K.

2015-12-01

Since the density of the outer core deduced from seismic data is about 10% lower than that of pure iron at core pressures and temperatures (P-T), it is widely believed that the outer core includes one or more light elements. Although intensive experimental and theoretical studies have been performed so far, the light element in the core has not yet been identified. Comparison of the density and sound velocity of liquid iron alloys with observations, such as the PREM, is a promising way to determine the species and quantity of light alloying component(s) in the outer core. Here we report the results of a first-principles molecular dynamics study on liquid iron alloyed with hydrogen, one of candidates of the light elements. Hydrogen had been much less studied than other candidates. However, hydrogen has been known to reduce the melting temperature of Fe-H solid [1]. Furthermore, very recently, Nomura et al. argued that the outer core may include 24 at.% H in order to be molten under relatively low temperature (< 3600 K) [2]. Since then hydrogen has attracted strong interests. We clarify the effects of hydrogen on density and sound velocity of liquid iron alloys under outer core P-T conditions. It is shown that ~1 wt% hydrogen can reproduce PREM density and sound velocity simultaneously very well. In addition, we show the presence of hydrogen rather reduces Gruneisen parameters. It indicates that, if hydrogen exists in the outer core, temperature profile of the outer core could be changed considerably from one estimated so far. [1] Sakamaki, K., E. Takahashi, Y. Nakajima, Y. Nishihara, K. Funakoshi, T. Suzuki, and Y. Fukai, Phys. Earth Planet. Inter., 174, 192-201 (2009). [2] Nomura, R., K. Hirose, K. Uesugi, Y. Ohishi, A. Tsuchiyama, A. Miyake, and Y. Ueno, Science 31, 522-525 (2014).

Pollutants in Plastics within the North Pacific Subtropical Gyre.

PubMed

Chen, Qiqing; Reisser, Julia; Cunsolo, Serena; Kwadijk, Christiaan; Kotterman, Michiel; Proietti, Maira; Slat, Boyan; Ferrari, Francesco F; Schwarz, Anna; Levivier, Aurore; Yin, Daqiang; Hollert, Henner; Koelmans, Albert A

2018-01-16

Here we report concentrations of pollutants in floating plastics from the North Pacific accumulation zone (NPAC). We compared chemical concentrations in plastics of different types and sizes, assessed ocean plastic potential risks using sediment quality criteria, and discussed the implications of our findings for bioaccumulation. Our results suggest that at least a fraction of the NPAC plastics is not in equilibrium with the surrounding seawater. For instance, "hard plastic" samples had significantly higher PBDE concentrations than "nets and ropes" samples, and 29% of them had PBDE composition similar to a widely used flame-retardant mixture. Our findings indicate that NPAC plastics may pose a chemical risk to organisms as 84% of the samples had at least one chemical exceeding sediment threshold effect levels. Furthermore, our surface trawls collected more plastic than biomass (180 times on average), indicating that some NPAC organisms feeding upon floating particles may have plastic as a major component of their diets. If gradients for pollutant transfer from NPAC plastic to predators exist (as indicated by our fugacity ratio calculations), plastics may play a role in transferring chemicals to certain marine organisms.

Structural determinants of enzyme binding affinity: the E1 component of pyruvate dehydrogenase from Escherichia coli in complex with the inhibitor thiamin thiazolone diphosphate.

PubMed

Arjunan, Palaniappa; Chandrasekhar, Krishnamoorthy; Sax, Martin; Brunskill, Andrew; Nemeria, Natalia; Jordan, Frank; Furey, William

2004-03-09

Thiamin thiazolone diphosphate (ThTDP), a potent inhibitor of the E1 component from the Escherichia coli pyruvate dehydrogenase multienzyme complex (PDHc), binds to the enzyme with greater affinity than does the cofactor thiamin diphosphate (ThDP). To identify what determines this difference, the crystal structure of the apo PDHc E1 component complex with ThTDP and Mg(2+) has been determined at 2.1 A and compared to the known structure of the native holoenzyme, PDHc E1-ThDP-Mg(2+) complex. When ThTDP replaces ThDP, reorganization occurs in the protein structure in the vicinity of the active site involving positional and conformational changes in some amino acid residues, a change in the V coenzyme conformation, addition of new hydration sites, and elimination of others. These changes culminate in an increase in the number of hydrogen bonds to the protein, explaining the greater affinity of the apoenzyme for ThTDP. The observed hydrogen bonding pattern is not an invariant feature of ThDP-dependent enzymes but rather specific to this enzyme since the extra hydrogen bonds are made with nonconserved residues. Accordingly, these sequence-related hydrogen bonding differences likewise explain the wide variation in the affinities of different thiamin-dependent enzymes for ThTDP and ThDP. The sequence of each enzyme determines its ability to form hydrogen bonds to the inhibitor or cofactor. Mechanistic roles are suggested for the aforementioned reorganization and its reversal in PDHc E1 catalysis: to promote substrate binding and product release. This study also provides additional insight into the role of water in enzyme inhibition and catalysis.

Component and System Sensitivity Considerations for Design of a Lunar ISRU Oxygen Production Plant

NASA Technical Reports Server (NTRS)

Linne, Diane L.; Gokoglu, Suleyman; Hegde, Uday G.; Balasubramaniam, Ramaswamy; Santiago-Maldonado, Edgardo

2009-01-01

Component and system sensitivities of some design parameters of ISRU system components are analyzed. The differences between terrestrial and lunar excavation are discussed, and a qualitative comparison of large and small excavators is started. The effect of excavator size on the size of the ISRU plant's regolith hoppers is presented. Optimum operating conditions of both hydrogen and carbothermal reduction reactors are explored using recently developed analytical models. Design parameters such as batch size, conversion fraction, and maximum particle size are considered for a hydrogen reduction reactor while batch size, conversion fraction, number of melt zones, and methane flow rate are considered for a carbothermal reduction reactor. For both reactor types the effect of reactor operation on system energy and regolith delivery requirements is presented.

Electrosorption of organic acids from aqueous bio-oil and conversion into hydrogen via microbial electrolysis cells

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

Park, Lydia Kyoung-Eun; Satinover, Scott J.; Yiacoumi, Sotira

Neutralization of the bio-oil pH has been shown to generate a neutralized bio-oil aqueous phase (NBOAP) that includes most of the acidic components and a neutralized bio-oil organic phase (NBOOP) that includes hydrophobic organics, such as phenols. NBOOP can be used for fuel production, while NBOAP can be fed to microbial electrolysis cells (MECs) for hydrogen production. After pH neutralization, some organic acidic components remain in NBOOP. This work is focused on capturing acidic compounds from NBOOP through water extraction and electrosorption, and demonstrating hydrogen production via MECs. Capacitive deionization (CDI) is proven effective in capturing ions from NBOOP-contacted watermore » and NBOAP via electrosorption. Captured acidic compounds enable the MEC application to effectively produce renewable hydrogen. Chemical oxygen demand (COD) removal of 49.2%, 61.5%, and 60.8% for 2, 4, and 10 g/L-anode/day loading were observed, corresponding to a total COD degradation of 0.19 g/L, 0.79 g/L, and 1.3 g/L, respectively. A maximum hydrogen productivity of 4.3 L-H 2/L-anode/day was obtained. Major compounds in the water phase such as fatty acids, sugar derivatives, furanic and phenolic compounds were converted to hydrogen with an efficiency of 80–90%. Lastly, this approach may lead the entire biomass pyrolysis process to be an overall carbon-neutral process.« less

Electrosorption of organic acids from aqueous bio-oil and conversion into hydrogen via microbial electrolysis cells

DOE PAGES

Park, Lydia Kyoung-Eun; Satinover, Scott J.; Yiacoumi, Sotira; ...

2018-02-17

Neutralization of the bio-oil pH has been shown to generate a neutralized bio-oil aqueous phase (NBOAP) that includes most of the acidic components and a neutralized bio-oil organic phase (NBOOP) that includes hydrophobic organics, such as phenols. NBOOP can be used for fuel production, while NBOAP can be fed to microbial electrolysis cells (MECs) for hydrogen production. After pH neutralization, some organic acidic components remain in NBOOP. This work is focused on capturing acidic compounds from NBOOP through water extraction and electrosorption, and demonstrating hydrogen production via MECs. Capacitive deionization (CDI) is proven effective in capturing ions from NBOOP-contacted watermore » and NBOAP via electrosorption. Captured acidic compounds enable the MEC application to effectively produce renewable hydrogen. Chemical oxygen demand (COD) removal of 49.2%, 61.5%, and 60.8% for 2, 4, and 10 g/L-anode/day loading were observed, corresponding to a total COD degradation of 0.19 g/L, 0.79 g/L, and 1.3 g/L, respectively. A maximum hydrogen productivity of 4.3 L-H 2/L-anode/day was obtained. Major compounds in the water phase such as fatty acids, sugar derivatives, furanic and phenolic compounds were converted to hydrogen with an efficiency of 80–90%. Lastly, this approach may lead the entire biomass pyrolysis process to be an overall carbon-neutral process.« less

Hydrogen bond disruption in DNA base pairs from (14)C transmutation.

PubMed

Sassi, Michel; Carter, Damien J; Uberuaga, Blas P; Stanek, Christopher R; Mancera, Ricardo L; Marks, Nigel A

2014-09-04

Recent ab initio molecular dynamics simulations have shown that radioactive carbon does not normally fragment DNA bases when it decays. Motivated by this finding, density functional theory and Bader analysis have been used to quantify the effect of C → N transmutation on hydrogen bonding in DNA base pairs. We find that (14)C decay has the potential to significantly alter hydrogen bonds in a variety of ways including direct proton shuttling (thymine and cytosine), thermally activated proton shuttling (guanine), and hydrogen bond breaking (cytosine). Transmutation substantially modifies both the absolute and relative strengths of the hydrogen bonding pattern, and in two instances (adenine and cytosine), the density at the critical point indicates development of mild covalent character. Since hydrogen bonding is an important component of Watson-Crick pairing, these (14)C-induced modifications, while infrequent, may trigger errors in DNA transcription and replication.

Research on Improving Low Rank Coal Caking Ability by Moderate Hydrogenation

NASA Astrophysics Data System (ADS)

Huang, Peng

2017-12-01

The hydrogenation test of low metamorphic coal was carried out by using a continuous hydrogen reactor at the temperature of (350-400)°C and the initial hydrogen pressure of 3 ~ 6Mpa. The purpose of the experiment was to increase the caking property, and the heating time was controlled from 30 to 50min. The test results show that the mild hydrogenation test, no adhesion of low metamorphic coal can be transformed into a product having adhesion, oxygen elements in coal have good removal, the calorific value of the product has been improved significantly and coal particles during pyrolysis, swelling, catalyst, hydrogenation, structural changes and the combined effects of particles a new component formed between financial and is a major cause of coal caking enhancement and lithofacies change, coal blending test showed that the product can be used effectively in the coking industry.

Composite hydrogen separation element and module

DOEpatents

Edlund, D.J.; Newbold, D.D.; Frost, C.B.

1997-07-08

There are disclosed improvements in multicomponent composite metal membranes useful for the separation of hydrogen, the improvements comprising the provision of at least one common-axis hole through all components of the composite membrane and the provision of a gas-tight seal around the periphery of the hole or holes through a coating metal layer of the membrane. 11 figs.

Hydrogen from coal cost estimation guidebook

NASA Technical Reports Server (NTRS)

Billings, R. E.

1981-01-01

In an effort to establish baseline information whereby specific projects can be evaluated, a current set of parameters which are typical of coal gasification applications was developed. Using these parameters a computer model allows researchers to interrelate cost components in a sensitivity analysis. The results make possible an approximate estimation of hydrogen energy economics from coal, under a variety of circumstances.

Induction of low-level hydrogen peroxide generation by unbleached cotton nonwovens as potential or wound healing applications

USDA-ARS?s Scientific Manuscript database

Greige cotton is an intact plant fiber. The cuticle and primary cell wall near the outer surface of the cotton fiber contains pectin, peroxidases, superoxide dismutase (SOD), and trace metals, which are associated with hydrogen peroxide (H2O2) generation during cotton fiber development. The compon...

Composite hydrogen separation element and module

DOEpatents

Edlund, David J.; Newbold, David D.; Frost, Chester B.

1997-01-01

There are disclosed improvements in multicomponent composite metal membranes useful for the separation of hydrogen, the improvements comprising the provision of at least one common-axis hole through all components of the composite membrane and the provision of a gas-tight seal around the periphery of the hole or holes through a coating metal layer of the membrane.

Transport hysteresis and hydrogen isotope effect on confinement

NASA Astrophysics Data System (ADS)

Itoh, S.-I.; Itoh, K.

2018-03-01

A Gedankenexperiment on hydrogen isotope effect is developed, using the transport model with transport hysteresis. The transport model with hysteresis is applied to case where the modulational electron cyclotron heating is imposed near the mid-radius of the toroidal plasmas. The perturbation propagates either outward or inward, being associated with the clockwise (CW) hysteresis or counter-clockwise (CCW) hysteresis, respectively. The hydrogen isotope effects on the CW and CCW hysteresis are investigated. The local component of turbulence-driven transport is assumed to be the gyro-Bohm diffusion. While the effect of hydrogen mass number is screened in the response of CW hysteresis, it is amplified in CCW hysteresis. This result motivates the experimental studies to compare CW and CCW cases in order to obtain further insight into the physics of hydrogen isotope effects.

Methane and Hydrogen Production from Anaerobic Fermentation of Municipal Solid Wastes

NASA Astrophysics Data System (ADS)

Kobayashi, Takuro; Lee, Dong-Yeol; Xu, Kaiqin; Li, Yu-You; Inamori, Yuhei

Methane and hydrogen production was investigated in batch experiments of thermophilic methane and hydrogen fermentation, using domestic garbage and food processing waste classified by fat/carbohydrate balance as a base material. Methane production per unit of VS added was significantly positively correlated with fat content and negatively correlated with carbohydrate content in the substrate, and the average value of the methane production per unit of VS added from fat-rich materials was twice as large as that from carbohydrate-rich materials. By contrast, hydrogen production per unit of VS added was significantly positively correlated with carbohydrate content and negatively correlated with fat content. Principal component analysis using the results obtained in this study enable an evaluation of substrates for methane and hydrogen fermentation based on nutrient composition.

TOGA: A TOUGH code for modeling three-phase, multi-component, and non-isothermal processes involved in CO 2-based Enhanced Oil Recovery

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

Pan, Lehua; Oldenburg, Curtis M.

TOGA is a numerical reservoir simulator for modeling non-isothermal flow and transport of water, CO 2, multicomponent oil, and related gas components for applications including CO 2-enhanced oil recovery (CO 2-EOR) and geologic carbon sequestration in depleted oil and gas reservoirs. TOGA uses an approach based on the Peng-Robinson equation of state (PR-EOS) to calculate the thermophysical properties of the gas and oil phases including the gas/oil components dissolved in the aqueous phase, and uses a mixing model to estimate the thermophysical properties of the aqueous phase. The phase behavior (e.g., occurrence and disappearance of the three phases, gas +more » oil + aqueous) and the partitioning of non-aqueous components (e.g., CO 2, CH 4, and n-oil components) between coexisting phases are modeled using K-values derived from assumptions of equal-fugacity that have been demonstrated to be very accurate as shown by comparison to measured data. Models for saturated (water) vapor pressure and water solubility (in the oil phase) are used to calculate the partitioning of the water (H 2O) component between the gas and oil phases. All components (e.g., CO 2, H 2O, and n hydrocarbon components) are allowed to be present in all phases (aqueous, gaseous, and oil). TOGA uses a multiphase version of Darcy’s Law to model flow and transport through porous media of mixtures with up to three phases over a range of pressures and temperatures appropriate to hydrocarbon recovery and geologic carbon sequestration systems. Transport of the gaseous and dissolved components is by advection and Fickian molecular diffusion. New methods for phase partitioning and thermophysical property modeling in TOGA have been validated against experimental data published in the literature for describing phase partitioning and phase behavior. Flow and transport has been verified by testing against related TOUGH2 EOS modules and CMG. The code has also been validated against a CO 2-EOR experimental core flood involving flow of three phases and 12 components. Results of simulations of a hypothetical 3D CO 2-EOR problem involving three phases and multiple components are presented to demonstrate the field-scale capabilities of the new code. This user guide provides instructions for use and sample problems for verification and demonstration.« less

An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation

PubMed Central

Gao, Min-Rui; Liang, Jin-Xia; Zheng, Ya-Rong; Xu, Yun-Fei; Jiang, Jun; Gao, Qiang; Li, Jun; Yu, Shu-Hong

2015-01-01

The electroreduction of water for sustainable hydrogen production is a critical component of several developing clean-energy technologies, such as water splitting and fuel cells. However, finding a cheap and efficient alternative catalyst to replace currently used platinum-based catalysts is still a prerequisite for the commercialization of these technologies. Here we report a robust and highly active catalyst for hydrogen evolution reaction that is constructed by in situ growth of molybdenum disulfide on the surface of cobalt diselenide. In acidic media, the molybdenum disulfide/cobalt diselenide catalyst exhibits fast hydrogen evolution kinetics with onset potential of −11 mV and Tafel slope of 36 mV per decade, which is the best among the non-noble metal hydrogen evolution catalysts and even approaches to the commercial platinum/carbon catalyst. The high hydrogen evolution activity of molybdenum disulfide/cobalt diselenide hybrid is likely due to the electrocatalytic synergistic effects between hydrogen evolution-active molybdenum disulfide and cobalt diselenide materials and the much increased catalytic sites. PMID:25585911

Tetracycline removal and effect on the formation and degradation of extracellular polymeric substances and volatile fatty acids in the process of hydrogen fermentation.

PubMed

Hou, Guangying; Hao, Xiaoyan; Zhang, Rui; Wang, Jing; Liu, Rutao; Liu, Chunguang

2016-07-01

Many research indicate antibiotics show adverse effect on methane fermentation, while few research focus on their effect on hydrogen fermentation. The present study aimed to gain insight of the effect of antibiotics on hydrogen fermentation with waste sludge and corn straw as substrate. For this purpose, tetracycline, as a model, was investigated with regard to tetracycline removal, hydrogen production, interaction with extracellular polymeric substances (EPSs) of substrate and volatile fatty acids (VFAs) on concentration and composition. Results show that tetracycline could be removed efficiently by hydrogen fermentation, and relative low-dose tetracycline (200mg/l) exposure affects little on hydrogen production. While tetracycline exposure could change hydrogen fermentation from butyric acid-type to propionic acid-type depending on tetracycline level. Based upon three-dimensional excitation-emission matrix fluorescence spectroscopy and UV-vis tetracycline changed the component and content of EPSs, and static quenching was the main mechanism between EPSs with tetracycline. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigation of a para-ortho hydrogen reactor for application to spacecraft sensor cooling

NASA Technical Reports Server (NTRS)

Nast, T. C.

1983-01-01

The utilization of solid hydrogen in space for sensor and instrument cooling is a very efficient technique for long term cooling or for cooling at high heat rates. The solid hydrogen can provide temperatures as low as 7 to 8 K to instruments. Vapor cooling is utilized to reduce parasitic heat inputs to the 7 to 8 K stage and is effective in providing intermediate cooling for instrument components operating at higher temperatures. The use of solid hydrogen in place of helium may lead to weight reductions as large as a factor of ten and an attendent reduction in system volume. The results of an investigation of a catalytic reactor for use with a solid hydrogen cooling system is presented. Trade studies were performed on several configurations of reactor to meet the requirements of high reactor efficiency with low pressure drop. Results for the selected reactor design are presented for both liquid hydrogen systems operating at near atmospheric pressure and the solid hydrogen cooler operating as low as 1 torr.

Development of a solid polymer electrolyte electrolysis cell module and ancillary components for a breadboard water electrolysis system

NASA Technical Reports Server (NTRS)

Porter, F. J., Jr.

1972-01-01

Solid polymer electrolyte technology in a water electrolysis system along with ancillary components to generate oxygen and hydrogen for a manned space station application are considered. Standard commercial components are utilized wherever possible. Presented are the results of investigations, surveys, tests, conclusions and recommendations for future development efforts.

Potential low cost, safe, high efficiency propellant for future space program

NASA Astrophysics Data System (ADS)

Zhou, D.

2005-03-01

Mixtures of nanometer or micrometer sized carbon powder suspended in hydrogen and methane/hydrogen mixtures are proposed as candidates for low cost, high efficiency propellants for future space programs. While liquid hydrogen has low weight and high heat of combustion per unit mass, because of the low mass density the heat of combustion per unit volume is low, and the liquid hydrogen storage container must be large. The proposed propellants can produce higher gross heat combustion with small volume with trade off of some weight increase. Liquid hydrogen can serve as the fluid component of the propellant in the mixtures and thus used by current rocket engine designs. For example, for the same volume a mixture of 5% methane and 95% hydrogen, can lead to an increase in the gross heat of combustion by about 10% and an increase in the Isp (specific impulse) by 21% compared to a pure liquid hydrogen propellant. At liquid hydrogen temperatures of 20.3 K, methane will be in solid state, and must be formed as fine granules (or slush) to satisfy the requirement of liquid propellant engines.

Hydrogen peroxide catalytic decomposition

NASA Technical Reports Server (NTRS)

Parrish, Clyde F. (Inventor)

2010-01-01

Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated through the use of concentrated hydrogen peroxide fed as a monopropellant into a catalyzed thruster assembly. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50%-70% by volume, and may be increased in concentration in a continuous process preceding decomposition in the thruster assembly. The exhaust of the thruster assembly, rich in hydroxyl and/or hydroperoxy radicals, may be fed into a stream containing oxidizable components, such as nitric oxide, to facilitate their oxidation.

Spectral line profiles for a planetary corona

NASA Technical Reports Server (NTRS)

Chamberlain, J. W.

1976-01-01

The Lyman and Balmer emissions of a planetary corona depend on the exospheric temperature, the integrated column density of solar-illuminated hydrogen, and the region of phase space occupied by particles. Measurements of the intensity alone are incapable of defining the exosphere unambiguously. Line profiles with high spectral resolution can show whether a nonthermal component of the escaping hydrogen is present and can indicate at what altitude orbits of hydrogen atoms are depleted. It is necessary, however, to plan the observations carefully if they are to be fitted usefully to a model.

Utilization of Low-Pressure Plasma to Inactivate Bacterial Spores on Stainless Steel Screws

PubMed Central

Stapelmann, Katharina; Fiebrandt, Marcel; Raguse, Marina; Awakowicz, Peter; Reitz, Günther

2013-01-01

Abstract A special focus area of planetary protection is the monitoring, control, and reduction of microbial contaminations that are detected on spacecraft components and hardware during and after assembly. In this study, wild-type spores of Bacillus pumilus SAFR-032 (a persistent spacecraft assembly facility isolate) and the laboratory model organism B. subtilis 168 were used to study the effects of low-pressure plasma, with hydrogen alone and in combination with oxygen and evaporated hydrogen peroxide as a process gas, on spore survival, which was determined by a colony formation assay. Spores of B. pumilus SAFR-032 and B. subtilis 168 were deposited with an aseptic technique onto the surface of stainless steel screws to simulate a spore-contaminated spacecraft hardware component, and were subsequently exposed to different plasmas and hydrogen peroxide conditions in a very high frequency capacitively coupled plasma reactor (VHF-CCP) to reduce the spore burden. Spores of the spacecraft isolate B. pumilus SAFR-032 were significantly more resistant to plasma treatment than spores of B. subtilis 168. The use of low-pressure plasma with an additional treatment of evaporated hydrogen peroxide also led to an enhanced spore inactivation that surpassed either single treatment when applied alone, which indicates the potential application of this method as a fast and suitable way to reduce spore-contaminated spacecraft hardware components for planetary protection purposes. Key Words: Bacillus spores—Contamination—Spacecraft hardware—Plasma sterilization—Planetary protection. Astrobiology 13, 597–606. PMID:23768085

Robot-Powered Reliability Testing at NREL's ESIF

ScienceCinema

Harrison, Kevin

2018-02-14

With auto manufacturers expected to roll out fuel cell electric vehicles in the 2015 to 2017 timeframe, the need for a reliable hydrogen fueling infrastructure is greater than ever. That's why the National Renewable Energy Laboratory (NREL) is using a robot in its Energy Systems Integration Facility (ESIF) to assess the durability of hydrogen fueling hoses, a largely untested—and currently costly—component of hydrogen fueling stations. The automated machine mimics the repetitive stress of a human bending and twisting the hose to refuel a vehicle—all under the high pressure and low temperature required to deliver hydrogen to a fuel cell vehicle's onboard storage tank.

NASA Orbit Transfer Rocket Engine Technology Program

NASA Technical Reports Server (NTRS)

1984-01-01

The advanced expander cycle engine with a 15,000 lb thrust level and a 6:1 mixture ratio and optimized performance was used as the baseline for a design study of the hydrogen/oxgyen propulsion system for the orbit transfer vehicle. The critical components of this engine are the thrust chamber, the turbomachinery, the extendible nozzle system, and the engine throttling system. Turbomachinery technology is examined for gears, bearing, seals, and rapid solidification rate turbopump shafts. Continuous throttling concepts are discussed. Components of the OTV engine described include the thrust chamber/nozzle assembly design, nozzles, the hydrogen regenerator, the gaseous oxygen heat exchanger, turbopumps, and the engine control valves.

5-Amino-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde hemihydrate: a polarized electronic structure within hydrogen-bonded sheets of R(10)(8)(34) rings.

PubMed

Quiroga, Jairo; Trilleras, Jorge; Cobo, Justo; Glidewell, Christopher

2010-01-01

In the title compound, C(11)H(11)N(3)O.0.5H(2)O, the water molecule lies across a twofold rotation axis in the space group Pbcn. The bond distances in the organic component provide evidence for polarization of the electronic structure. The molecular components are linked into puckered sheets of R(10)(8)(34) rings by a combination of O-H...N and N-H...O hydrogen bonds; adjacent sheets are weakly linked by an aromatic pi-pi stacking interaction. Comparisons are made with some fused-ring analogues.

The causes for geographical variations in OS187/OS186 at the Cretaceous-Tertiary boundary

NASA Technical Reports Server (NTRS)

Turekian, K. K.; Esser, B. K.; Ravizza, G. E.

1988-01-01

Researchers at Yale has approached the problem of the osmium isotopic composition of marine deposits formed in contact with both oxidized and reduced bottom waters. The measured (187) Os/(186) Os ratios of modern bulk sediment can be explained using mixing equations involving continental detrital, volcaniclastic, cosmogenic and hydrogeneous components. These studies show that sediments deposited under reducing marine conditions contain a hydrogenous component which is enriched in Re and has a radiogenic (187) Os/(186) Os ratio. The presence of such a hydrogenous component in the marine fish clay at Stevns Klint can account for the elevation of its (187) Os/(186) Os ration above the expected meteoritic value. Mass balance considerations require the Re/Os ratio of the phase precipitated from the terminal Cretaceous sea at Stevns Klint to have been about one tenth the value observed in contemporary deposits in the Black Sea, assuming Re has not been lost (or Os gained) subsequent to precipitation. In continental sections, the elevation of the (187) Os/(186) Os ratio in boundary layers may be due to precipitation from continental waters of crustally-derived radiogenic osmium either contemporaneous with the meteoritic (or mantle) osmium deposition or later during diagenesis.

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

NASA Astrophysics Data System (ADS)

Davis, F. A.; Cottrell, E.

2014-12-01

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

Re-Os isotopic systematics of primitive lavas from the Lassen region of the Cascade arc, California

USGS Publications Warehouse

Borg, L.E.; Brandon, A.D.; Clynne, M.A.; Walker, R.J.

2000-01-01

Rhenium-osmium isotopic systematics of primitive calc-alkaline lavas from the Lassen region appear to be controlled by mantle wedge processes. Lavas with a large proportion of slab component have relatively low Re and Os abundances, and have radiogenic Os and mid ocean ridge basalt-like Sr and Pb isotopic compositions. Lavas with a small proportion of slab component have higher Re and Os elemental abundances and display mantle-like Os, Sr, Nd, and Pb isotopic compositions. Assimilation with fractional crystallization can only generate the Re-Os systematics of the Lassen lavas from a common parent if the distribution coefficient for Re in sulfide is ~40-1100 times higher than most published estimates and if most incompatible element abundances decrease during differentiation. High Re/Os ratios in mid ocean ridge basalts makes subducted oceanic crust a potential source of radiogenic Os in volcanic arcs. The slab beneath the southernmost Cascades is estimated to have 187Os/188Os ratios as high as 1.4. Mixing between a slab component and mantle wedge peridotite can generate the Os isotopic systematics of the Lassen lavas provided the slab component has a Sr/Os ratio of ~7.5X105 and Os abundances that are 100-600 times higher than mid ocean ridge basalts. For this model to be correct, Os must be readily mobilized and concentrated in the slab component, perhaps as a result of high water and HCl fugacities in this subduction environment. Another possible mechanism to account for the correlation between the magnitude of the subduction geochemical signature and Os isotopic composition involves increasing the stability of an Os-bearing phase in mantle wedge peridotites as a result of fluxing with the slab component. Melting of such a source could yield low Os magmas that are more susceptible to crustal contamination, and hence have more radiogenic Os isotopic compositions, than magmas derived from sources with a smaller contribution from the slab. Thus, the addition of the slab component to the mantle wedge appears to result in either the direct or indirect addition of radiogenic Os to arc magmas. (C) 2000 Elsevier Science B.V. All rights reserved.

Metastable equilibria among dicarboxylic acids and the oxidation state during aqueous alteration on the CM2 chondrite parent body

NASA Astrophysics Data System (ADS)

McAlister, Jason A.; Kettler, Richard M.

2008-01-01

Linear saturated dicarboxylic acids are present in carbonaceous chondrite samples at concentrations that suggest aqueous alteration under conditions of metastable equilibrium. In this study, previously published values of dicarboxylic acid concentrations measured in Murchison, Yamato-791198, and Tagish Lake carbonaceous chondrites are converted to aqueous activities during aqueous alteration assuming water:rock ratios that range from 1:10 to 10:1. Logarithmic plots of the aqueous activities of any two dicarboxylic acids are proximal to lines whose slope is fixed by the stoichiometry of reactions describing the oxidation-reduction equilibrium between the two species. The precise position of any line is controlled by the equilibrium constant of the reaction relating the species and the hydrogen fugacity for the reaction of interest. Reactions among succinic (C4), glutaric (C5), and adipic (C6) acids obtained from CM2 chondrites show evidence of metastable equilibrium and yield logf values that agree to within 0.3 log units at 298.15 K and 0.6 log units at 473.15 K. At a water:rock ratio of 1:1, metastable equilibrium among succinic, glutaric, and adipic acids results in calculated logf values during aqueous alteration that range from -6.2 at 298.15 K to -3.3 at 373.15 K. These values are consistent with those obtained in previous work on carbonaceous chondrites and with metastable equilibrium at temperatures ranging from 300 to 355 K in contact with cronstedtite + magnetite.

Condensation of an ideal gas obeying non-Abelian statistics.

PubMed

Mirza, Behrouz; Mohammadzadeh, Hosein

2011-09-01

We consider the thermodynamic geometry of an ideal non-Abelian gas. We show that, for a certain value of the fractional parameter and at the relevant maximum value of fugacity, the thermodynamic curvature has a singular point. This indicates a condensation such as Bose-Einstein condensation for non-Abelian statistics and we work out the phase transition temperature in various dimensions.

Workshop on Parent-Body and Nebular Modification of Chondritic Materials

NASA Technical Reports Server (NTRS)

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

1997-01-01

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

Modeling the effect of water on mantle rheology

NASA Technical Reports Server (NTRS)

Bounama, CH.; Franck, S.

1994-01-01

To study the thermal history of the Earth we use a parameterized model of mantle convection. This model includes a mathematical description of de- and regassing processes of water from the Earth's mantle. The rates of this processes are considered to be directly proportional to the seafloor spreading rate. The kinematic viscosity of the mantle depends on the temperature/pressure as well as on the volatile content. Dissolved volatiles such as water weaken the minerals by reducing their activation energy for solid state creep. Karato and Toriumi showed a power law dependence between creep rate and water fugacity derived from experimental results. Therefore, we use such flow parameters of diffusion creep in olivine under wet and dry conditions to calculate the mantle viscosity as a function of the water content. Because the creep rate is proportional to the concentration of water-related point deflects we assume that the water fugacity is proportional to the water weight fraction. An equation for the steady-state strain rate under wet conditions is established. To assess the unknown constant K in this equation, we use flow law parameters given by Karato and Wu as well as the results of McGovern and Schubert.

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

NASA Technical Reports Server (NTRS)

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

2015-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2013-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2006-01-01

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

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

NASA Technical Reports Server (NTRS)

Dehghan-Banadaki, A.

1983-01-01

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

Hydrogen adsorption and diffusion, and subcritical-crack growth in high strength steels and nickel base alloys

NASA Technical Reports Server (NTRS)

Wei, R. P.; Klier, K.; Simmons, G. W.; Chornet, E.

1973-01-01

Embrittlement, or the enhancement of crack growth by gaseous hydrogen in high strength alloys, is of primary interest in selecting alloys for various components in the space shuttle. Embrittlement is known to occur at hydrogen gas pressures ranging from fractions to several hundred atmospheres, and is most severe in the case of martensitic high strength steels. Kinetic information on subcritical crack growth in gaseous hydrogen is sparse at this time. Corroborative information on hydrogen adsorption and diffusion is inadequate to permit a clear determination of the rate controlling process and possible mechanism in hydrogen enhanced crack growth, and for estimating behavior over a range of temperatures and pressures. Therefore, coordinated studies of the kinetics of crack growth, and adsorption and diffusion of hydrogen, using identical materials, have been initiated. Comparable conditions of temperature and pressure will be used in the chemical and mechanical experiments. Inconel 718 alloy and 18Ni(200) maraging steel have been selected for these studies. Results from these studies are expected to provide not only a better understanding of the gaseous hydrogen embrittlement phenomenon itself, but also fundamental information on hydrogen adsorption and diffusion, and crack growth information that can be used directly for design.

Nuclear Thermal Rocket Element Environmental Simulator (NTREES) Upgrade Activities

NASA Technical Reports Server (NTRS)

Emrich, William

2013-01-01

A key technology element in Nuclear Thermal Propulsion is the development of fuel materials and components which can withstand extremely high temperatures while being exposed to flowing hydrogen. NTREES provides a cost effective method for rapidly screening of candidate fuel components with regard to their viability for use in NTR systems. The NTREES is designed to mimic the conditions (minus the radiation) to which nuclear rocket fuel elements and other components would be subjected to during reactor operation. The NTREES consists of a water cooled ASME code stamped pressure vessel and its associated control hardware and instrumentation coupled with inductive heaters to simulate the heat provided by the fission process. The NTREES has been designed to safely allow hydrogen gas to be injected into internal flow passages of an inductively heated test article mounted in the chamber.

Generation of tunable infrared radiation by stimulated Raman scattering on hydrogen in a prism-lens optical delay line

NASA Astrophysics Data System (ADS)

Andreev, R. B.; Butylkin, V. S.; Evtiushkin, V. A.; Fisher, P. S.; Khabarov, V. V.

1983-03-01

The threshold of stimulated Raman scattering was lowered by filling an optical delay line with hydrogen. Pumping was by a tunable neodymium laser. Lens-prism combinations were used as phase correctors in the delay line. The dependences of the energy of the Stokes component on the pump energy determined experimentally for different numbers of transits through the delay line were compared with the results of a calculation allowing for the losses in the components of this line. When the frequency conversion was by a factor of at least 2 and the tuning range was wide (tens of percent), the optimal performance was obtained from the optical delay line when total-internal-reflection prisms and lenses were combined in a single component and oriented at the Brewster angle.

BRIEF COMMUNICATIONS: Generation of tunable infrared radiation by stimulated Raman scattering on hydrogen in a prism-lens optical delay line

NASA Astrophysics Data System (ADS)

Andreev, R. B.; Butylkin, V. S.; Evtyushkin, V. A.; Fisher, P. S.; Khabarov, V. V.

1983-03-01

The threshold of stimulated Raman scattering was lowered by filling an optical delay line with hydrogen. Pumping was by a tunable neodymium laser. Lens-prism combinations were used as phase correctors in the delay line. The dependences of the energy of the Stokes component on the pump energy determined experimentally for different numbers of transits through the delay line were compared with the results of a calculation allowing for the losses in the components of this line. When the frequency conversion was by a factor of at least 2 and the tuning range was wide (tens of percent), the optimal performance was obtained from the optical delay line when total-internal-reflection prisms and lenses were combined in a single component and oriented at the Brewster angle.

[Energetics of complex formation of the DNA hairpin structure d(GCGAAGC) with aromatic ligands].

PubMed

Kostiukov, V V

2011-01-01

The energy contributions of various physical interactions to the total Gibbs energy of complex formation of the biologically important DNA hairpin d(GCGAAGC) with aromatic antitumor antibiotics daunomycin and novantron and the mutagens ethidium and proflavine have been calculated. It has been shown that the relatively small value of the total energy of binding of the ligands to the hairpin is the sum of components great in absolute value and different in sign. The contributions of van der Waals interactions and both intra- and intermolecular hydrogen bonds and bonds with aqueous environment have been studied. According to the calculations, the hydrophobic and van der Waals components are energetically favorable in complex formation of the ligands with the DNA pairpin d(GCGAAGC), whereas the electrostatic (with consideration of hydrogen bonds) and entropic components are unfavorable.

Stability of the magnetosonic wave in a cometary multi-ion plasma

NASA Astrophysics Data System (ADS)

Sreekala, G.; Varghese, Anu; Jayakumar, Neethu; Michael, Manesh; Sebastian, Sijo; Venugopal, Chandu

2017-05-01

A generalized dispersion relation of the magnetosonic wave in a four component plasma consisting of electrons and hydrogen ions of solar origin and positively and negatively charged oxygen ions of cometary origin has been derived by using the Vlasov-Maxwell kinetic model. Parallel to the magnetic field, the hydrogen and electron components are modeled by a drifting Maxwellian distribution; perpendicular to the magnetic field, we use a loss cone type distribution obtained by the subtraction of two Maxwellian distributions having different temperatures. The effect of change in the drift velocity of streaming components and number densities and temperatures of each species in driving the instability has been analyzed both analytically and numerically. For typical parameters at comet Halley, we find that both positively and negatively charged oxygen ions can drive the wave unstable.

Capacitance‐Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation

PubMed Central

Lamb, Katie J.; Dowsett, Mark R.; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D.

2017-01-01

Abstract An electrochemical cell comprising a novel dual‐component graphite and Earth‐crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero‐carbon energy source. PMID:29171724

In situ measurements of fuel retention by laser induced desorption spectroscopy in TEXTOR

NASA Astrophysics Data System (ADS)

Zlobinski, M.; Philipps, V.; Schweer, B.; Huber, A.; Stoschus, H.; Brezinsek, S.; Samm, U.; TEXTOR Team

2011-12-01

In future fusion devices such as ITER tritium retention due to tritium co-deposition in mixed material layers can be a serious safety problem. Laser induced desorption spectroscopy (LIDS) can measure the hydrogen content of hydrogenic carbon layers locally on plasma-facing components, while hydrogen is used as a tritium substitute. For several years, this method has been applied in the TEXTOR tokamak in situ during plasma operation to monitor the hydrogen content in space and time. This work shows the LIDS signal reproducibility and studies the effects of different plasma conditions, desorption distances from the plasma and different laser energies using a dedicated sample with constant hydrogen amount. Also the LIDS signal evaluation procedure is described in detail and the detection limits for different conditions in the TEXTOR tokamak are estimated.

Hydrogen storage and hydrolysis properties of core-shell structured Mg-MFx (M=V, Ni, La and Ce) nano-composites prepared by arc plasma method

NASA Astrophysics Data System (ADS)

Mao, Jianfeng; Zou, Jianxin; Lu, Chong; Zeng, Xiaoqin; Ding, Wenjiang

2017-10-01

In this work, core-shell structured Mg-MFx (M = V, Ni, La and Ce) nano-composites are prepared by using arc plasma method. The particle size distribution, phase components, microstructures, hydrogen sorption properties of these composites and hydrolysis properties of their corresponding hydrogenated powders are carefully investigated. It is shown that the addition of MFx through arc plasma method can improve both the hydrogen absorption kinetics of Mg and the hydrolysis properties of corresponding hydrogenated powders. Among them, the Mg-NiF2 composite shows the best hydrogen absorption properties at relatively low temperatures, which can absorb 3.26 wt% of H2 at 373 K in 2 h. Such rapid hydrogen absorption rate is mainly due to the formation of Mg2Ni and MgF2 on Mg particles during arc evaporation and condensation. In contrast, measurements also show that the hydrogenated Mg-VF3 composite has the lowest peak desorption temperature and the fastest hydrolysis rate among all the hydrogenated Mg-MFx composites. The less agglomeration tendency of Mg particles and VO2 covered on MgH2 particles account for the reduced hydrogen desorption temperature and enhanced hydrolysis rate.

Radiation Shielding Materials Containing Hydrogen, Boron, and Nitrogen: Systematic Computational and Experimental Study. Phase I

NASA Technical Reports Server (NTRS)

Thibeault, Sheila A.; Fay, Catharine C.; Lowther, Sharon E.; Earle, Kevin D.; Sauti, Godfrey; Kang, Jin Ho; Park, Cheol; McMullen, Amelia M.

2012-01-01

The key objectives of this study are to investigate, both computationally and experimentally, which forms, compositions, and layerings of hydrogen, boron, and nitrogen containing materials will offer the greatest shielding in the most structurally robust combination against galactic cosmic radiation (GCR), secondary neutrons, and solar energetic particles (SEP). The objectives and expected significance of this research are to develop a space radiation shielding materials system that has high efficacy for shielding radiation and that also has high strength for load bearing primary structures. Such a materials system does not yet exist. The boron nitride nanotube (BNNT) can theoretically be processed into structural BNNT and used for load bearing structures. Furthermore, the BNNT can be incorporated into high hydrogen polymers and the combination used as matrix reinforcement for structural composites. BNNT's molecular structure is attractive for hydrogen storage and hydrogenation. There are two methods or techniques for introducing hydrogen into BNNT: (1) hydrogen storage in BNNT, and (2) hydrogenation of BNNT (hydrogenated BNNT). In the hydrogen storage method, nanotubes are favored to store hydrogen over particles and sheets because they have much larger surface areas and higher hydrogen binding energy. The carbon nanotube (CNT) and BNNT have been studied as potentially outstanding hydrogen storage materials since 1997. Our study of hydrogen storage in BNNT - as a function of temperature, pressure, and hydrogen gas concentration - will be performed with a hydrogen storage chamber equipped with a hydrogen generator. The second method of introducing hydrogen into BNNT is hydrogenation of BNNT, where hydrogen is covalently bonded onto boron, nitrogen, or both. Hydrogenation of BN and BNNT has been studied theoretically. Hyper-hydrogenated BNNT has been theoretically predicted with hydrogen coverage up to 100% of the individual atoms. This is a higher hydrogen content than possible with hydrogen storage; however, a systematic experimental hydrogenation study has not been reported. A combination of the two approaches may be explored to provide yet higher hydrogen content. The hydrogen containing BNNT produced in our study will be characterized for hydrogen content and thermal stability in simulated space service environments. These new materials systems will be tested for their radiation shielding effectiveness against high energy protons and high energy heavy ions at the HIMAC facility in Japan, or a comparable facility. These high energy particles simulate exposure to SEP and GCR environments. They will also be tested in the LaRC Neutron Exposure Laboratory for their neutron shielding effectiveness, an attribute that determines their capability to shield against the secondary neutrons found inside structures and on lunar and planetary surfaces. The potential significance is to produce a radiation protection enabling technology for future exploration missions. Crew on deep space human exploration missions greater than approximately 90 days cannot remain below current crew Permissible Exposure Limits without shielding and/or biological countermeasures. The intent of this research is to bring the Agency closer to extending space missions beyond the 90-day limit, with 1 year as a long-term goal. We are advocating a systems solution with a structural materials component. Our intent is to develop the best materials system for that materials component. In this Phase I study, we have shown, computationally, that hydrogen containing BNNT is effective for shielding against GCR, SEP, and neutrons over a wide range of energies. This is why we are focusing on hydrogen containing BNNT as an innovative advanced concept. In our future work, we plan to demonstrate, experimentally, that hydrogen, boron, and nitrogen based materials can provide mechanically strong, thermally stable, structural materials with effective radiation shielding against GCR, SEP, and neutrons.

Hydrogen mitigation in submerged arc welding

NASA Astrophysics Data System (ADS)

Klimowicz, Steven

With the role of hydrogen in weld metal well understood in its relation to cold cracking, there has been a push to produce welds with lower and lower diffusible hydrogen contents. The push for lower diffusible hydrogen contents has placed pressure on consumables manufactures to create consumables that can achieve the requirements for lower diffusible hydrogen content. Currently EM12K flux is produced so that it can achieve below 4 ml of diffusible hydrogen for every 100g of weld metal deposited (ml/100g) for submerged arc welding (SAW). The recent trend for industry is to preferentially achieve diffusible hydrogen contents below 3 ml/100g. Making it necessary to find a way to modify the flux to achieve a lower diffusible hydrogen content for the welds it produces. To achieve this goal a two phase plan was developed. The first phase was to characterize the entire welding system for hydrogen. Since the goal of the project is hydrogen mitigation, any amount of hydrogen that could be reduced is helpful and therefore must first be discovered. Sources of hydrogen may be found by analyzing the welding wire and base metal, as well as breaking the flux down into its components and production steps. The wire was analyzed for total hydrogen content as was the base metal. The flux and its components were analyzed using differential thermal analysis-simultaneous thermal analysis (DTA-STA) and later vacuum degassing for moisture content. The analysis of the wire showed that the copper coating on the wire was the largest contributor of hydrogen. There was lubricant present on the wire surface as well, but it did not contribute as much as the copper coating. It was found that a simple low temperature baking of the wire was enough to remove the lubricant and coating moisture. The base metal was found to have a similar total hydrogen content to that of the wire. The breakdown of the flux and production process for moisture content analysis revealed that the production process removes the moisture that is added by the water based binder. The second phase of the project was to modify the flux with fluoride additions to remove hydrogen from the arc while welding. The introduction of fluorine into the arc would lower the amount of hydrogen that may be absorbed as diffusible hydrogen by the weld metal. To select the fluorides a series of thermodynamic calculations were performed as well as simple tests to determine the fluorides behavior in a welding arc and flux. From these tests the following fluorides were selected to be used to be added to EM12K flux as oneweight percent additions: SrF 2, K2TiF6, K2SiF6, and LiF. Welds were then run with the experimental fluxes according to AWS A4.3 standard for diffusible hydrogen testing. From these tests it was found that none experimental fluxes were able to achieve a diffusible hydrogen content lower than the original EM12K flux. It was also found that fluoride reduction in a simple flux is a better predictor of fluoride effectiveness than decomposition temperature.

On-board diesel autothermal reforming for PEM fuel cells: Simulation and optimization

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

Cozzolino, Raffaello, E-mail: raffaello.cozzolino@unicusano.it; Tribioli, Laura

2015-03-10

Alternative power sources are nowadays the only option to provide a quick response to the current regulations on automotive pollutant emissions. Hydrogen fuel cell is one promising solution, but the nature of the gas is such that the in-vehicle conversion of other fuels into hydrogen is necessary. In this paper, autothermal reforming, for Diesel on-board conversion into a hydrogen-rich gas suitable for PEM fuel cells, has investigated using the simulation tool Aspen Plus. A steady-state model has been developed to analyze the fuel processor and the overall system performance. The components of the fuel processor are: the fuel reforming reactor,more » two water gas shift reactors, a preferential oxidation reactor and H{sub 2} separation unit. The influence of various operating parameters such as oxygen to carbon ratio, steam to carbon ratio, and temperature on the process components has been analyzed in-depth and results are presented.« less

Multiphysics Thermal-Fluid Design Analysis of a Non-Nuclear Tester for Hot-Hydrogen Materials and Component Development

NASA Technical Reports Server (NTRS)

Wang, Ten-See; Foote, John; Litchford, Ron

2006-01-01

The objective of this effort is to perform design analyses for a non-nuclear hot-hydrogen materials tester, as a first step towards developing efficient and accurate multiphysics, thermo-fluid computational methodology to predict environments for hypothetical solid-core, nuclear thermal engine thrust chamber design and analysis. The computational methodology is based on a multidimensional, finite-volume, turbulent, chemically reacting, thermally radiating, unstructured-grid, and pressure-based formulation. The multiphysics invoked in this study include hydrogen dissociation kinetics and thermodynamics, turbulent flow, convective, and thermal radiative heat transfers. The goals of the design analyses are to maintain maximum hot-hydrogen jet impingement energy and to minimize chamber wall heating. The results of analyses on three test fixture configurations and the rationale for final selection are presented. The interrogation of physics revealed that reactions of hydrogen dissociation and recombination are highly correlated with local temperature and are necessary for accurate prediction of the hot-hydrogen jet temperature.

A study of the efficiency of hydrogen liquefaction

NASA Technical Reports Server (NTRS)

Baker, C. R.; Shaner, R. L.

1976-01-01

The use of liquid hydrogen as a jet aircraft fuel has a number of environmental and technological advantages over conventional fuels. The liquefaction of hydrogen requires a large expenditure of energy. There are many inefficiencies that are a part of any practical liquefaction process. Current technology was investigated for the best available system. Parametric studies were made to identify where inefficiencies occur and to optimize and integrate the component parts. Flowsheets are presented for a module that produces 250 tons per day of liquid hydrogen. Approximately ten of these modules is needed for a major airport in the 1990's. The advantages of producing a product with a minimum amount of ortho to para hydrogen conversion are pointed out. The optimum degree of conversion was determined for a liquid hydrogen product that will be used within a given time. An assessment was made regarding the potentials for improvement of the processing schemes and equipment over the next 10 to 25 years.

Theoretical investigation of the effect of hydrogen addition on the formation and properties of soliton in direct current argon plasma

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

Saikia, P., E-mail: partha.008@gmail.com; Goswami, K. S.; Saikia, B. K.

2014-03-15

In this study the effect of hydrogen addition on the formation and properties of soliton in direct-current (DC) argon plasma is theoretically investigated. By coupling fluid equations with Poisons equation for such multi-component plasma, the Mach number and amplitude of the soliton are determined following pseudo potential method. Addition of hydrogen in argon discharge leads to the decrease of electron, Ar{sup +} ion density while a reverse trend was observed for ArH{sup +} and hydrogen like ions. It was found that presence of hydrogen like ions in argon plasma affects the formation of soliton with its amplitude significantly decreases asmore » concentration of hydrogen increases. On the other hand, increase in ion to electron temperature ratios of the lighter ions in the discharge also has a significant influence on the amplitude and formation of soliton. The inverse relation between solitons width and amplitude is found to be consistent for the entire range of study.« less

Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds

DOEpatents

Jackson, James E.; Lam, Chun Ho; Saffron, Christopher M.; Miller, Dennis J.

2018-04-24

A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with the organic reactants. Biomass fast pyrolysis-derived bio-oil is a liquid mixture containing hundreds of organic compounds with chemical functionalities that are corrosive to container materials and are prone to polymerization. A high surface area skeletal metal catalyst material such as Raney Nickel can be used as the cathode. Electrocatalytic hydrogenation and/or hydrodeoxygenation convert the organic substrates under mild conditions to reduce coke formation and catalyst deactivation. The process converts oxygen-containing functionalities and unsaturated bonds into chemically reduced forms with an increased hydrogen content. The process is operated at mild conditions, which enables it to be a good means for stabilizing bio-oil to a form that can be stored and transported using metal containers and pipes.

Development of Technology and Installation for Biohydrogen Production

NASA Astrophysics Data System (ADS)

Pridvizhkin, S. V.; Vyguzova, M. A.; Bazhenov, O. V.

2017-11-01

The article discusses the method for hydrogen production and the device this method application. The relevance of the use of renewable fuels and the positive impact of renewable energy on the environment and the economy is also considered. The presented technology relates to a method for hydrogen production from organic materials subject to anaerobic fermentation, such as the components of solid municipal waste, sewage sludge and agricultural enterprises wastes, sewage waste. The aim of the research is to develop an effective eco-friendly technology for hydrogen producing within an industrial project To achieve the goal, the following issues have been addressed in the course of the study: - development of the process schemes for hydrogen producing from organic materials; - development of the technology for hydrogen producing; - optimization of a biogas plant with the aim of hydrogen producing at one of the fermentation stages; - approbation of the research results. The article is recommended for engineers and innovators working on the renewable energy development issues.

Flow-Control Unit For Nitrogen And Hydrogen Gases

NASA Technical Reports Server (NTRS)

Chang, B. J.; Novak, D. W.

1990-01-01

Gas-flow-control unit installed and removed as one piece replaces system that included nine separately serviced components. Unit controls and monitors flows of nitrogen and hydrogen gases. Designed for connection via fluid-interface manifold plate, reducing number of mechanical fluid-interface connections from 18 to 1. Unit provides increasing reliability, safety, and ease of maintenance, and for reducing weight, volume, and power consumption.

Preliminary design of an auxiliary power unit for the space shuttle. Volume 3: Details of system analysis, engineering, and design for selected system

NASA Technical Reports Server (NTRS)

Hamilton, M. L.; Burriss, W. L.

1972-01-01

Numerous candidate APU concepts, each meeting the space shuttle APU problem statement are considered. Evaluation of these concepts indicates that the optimum concept is a hydrogen-oxygen APU incorporating a recuperator to utilize the exhaust energy and using the cycle hydrogen flow as a means of cooling the component heat loads.

Impact of Molecular Hydrogen on Chalcopyrite Bioleaching by the Extremely Thermoacidophilic Archaeon Metallosphaera sedula▿

PubMed Central

Auernik, Kathryne S.; Kelly, Robert M.

2010-01-01

Hydrogen served as a competitive inorganic energy source, impacting the CuFeS2 bioleaching efficiency of the extremely thermoacidophilic archaeon Metallosphaera sedula. Open reading frames encoding key terminal oxidase and electron transport chain components were triggered by CuFeS2. Evidence of heterotrophic metabolism was noted after extended periods of bioleaching, presumably related to cell lysis. PMID:20190092

Development of novel active transport membrande devices

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

Laciak, D.V.

1994-11-01

Air Products has undertaken a research program to fabricate and evaluate gas separation membranes based upon promising ``active-transport`` (AT) materials recently developed in our laboratories. Active Transport materials are ionic polymers and molten salts which undergo reversible interaction or reaction with ammonia and carbon dioxide. The materials are useful for separating these gases from mixtures with hydrogen. Moreover, AT membranes have the unique property of possessing high permeability towards ammnonia and carbon dioxide but low permeability towards hydrogen and can thus be used to permeate these components from a gas stream while retaining hydrogen at high pressure.

Cations in component reactions of `malic' enzyme catalysis

PubMed Central

Tsai, C. S.; Tsai, Y. H.; Samad, R. A.

1971-01-01

The `malic' enzyme (EC 1.1.1.40) has been purified (300-fold) from wheat germ and its abilities to catalyse the decarboxylation and the hydrogenation of oxaloacetic acid and oxaloacetate esters was studied. The free 1-carboxyl group is essential for the interaction of oxaloacetates and substituted oxaloacetates with the enzyme via cations. The free 4-carboxyl group is required for the decarboxylation but is not indispensable for the hydrogenation. At high concentrations, cations inhibit the enzymic hydrogenation of oxaloacetic acid but not that of 4-ethyl oxaloacetate. A plausible inhibitory mechanism is proposed. PMID:4399519

Synthesis and Characterization of Cluster-Derived Supported Bimetallic Catalysts

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

Adams, Richard D; Amiridis, Michael D

2008-10-10

New procedures have been developed for synthesizing di- and tri-metallic cluster complexes. The chemical properties of the new complexes have been investigated, particularly toward the activation of molecular hydrogen. These complexes were then converted into bi- and tri-metallic nanoparticles on silica and alumina supports. These nanoparticles were characterized by electron microscopy and were then tested for their ability to produce catalytic hydrogenation of unsaturated hydrocarbons and for the preferential oxidation of CO in the presence of hydrogen. The bi- and tri-metallic nanoparticles exhibited far superior activity and selectivity as hydrogenation catalysts when compared to the individual metallic components. It wasmore » found that the addition of tin greatly improved the selectivity of the catalysts for the hydrogenation of polyolefins. The addition of iron improves the catalysts for the selective oxidation of CO by platinum in the presence of hydrogen. The observations should lead to the development of lower cost routes to molecules that can be used to produce polymers and plastics for use by the general public and for procedures to purify hydrogen for use as an alternative energy in the hydrogen economy of the future.« less

Tribological properties of amorphous hydrogenated (a-C:H) and hydrogen-free tetrahedral (ta-C) diamond-like carbon coatings under jatropha biodegradable lubricating oil at different temperatures

NASA Astrophysics Data System (ADS)

Mobarak, H. M.; Masjuki, H. H.; Mohamad, E. Niza; Kalam, M. A.; Rashedul, H. K.; Rashed, M. M.; Habibullah, M.

2014-10-01

The application of diamond-like carbon (DLC) coatings on automotive components is emerging as a favorable strategy to address the recent challenges in the industry. DLC coatings can effectively lower the coefficient of friction (CoF) and wear rate of engine components, thereby improving their fuel efficiency and durability. The lubrication of ferrous materials can be enhanced by a large amount of unsaturated and polar components of oils. Therefore, the interaction between nonferrous coatings (e.g., DLC) and vegetable oil should be investigated. A ball-on-plate tribotester was used to run the experiments. Stainless steel plates coated with amorphous hydrogenated (a-C:H) DLC and hydrogen-free tetrahedral (ta-C) DLC that slide against 440C stainless steel ball were used to create a ball-on-plate tribotester. The wear track was investigated through scanning electron microscopy. Energy dispersive and X-ray photoelectron spectroscopies were used to analyze the tribofilm inside the wear track. Raman analysis was performed to investigate the structural changes in the coatings. At high temperatures, the CoF in both coatings decreased. The wear rate, however, increased in the a-C:H but decreased in the ta-C DLC-coated plates. The CoF and the wear rate (coated layer and counter surface) were primarily influenced by the graphitization of the coating. Tribochemical films, such as polyphosphate glass, were formed in ta-C and acted as protective layers. Therefore, the wear rate of the ta-C DLC was lower than that of the-C:H DLC.

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

PubMed

Righter, K; Ghiorso, M S

2012-07-24

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

Stable Vanadium Isotopes as a Redox Proxy at High Temperatures?

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Vegetated Ditches for the Mitigation of Pesticides Runoff in the Po Valley.

PubMed

Otto, Stefan; Pappalardo, Salvatore E; Cardinali, Alessandra; Masin, Roberta; Zanin, Giuseppe; Borin, Maurizio

2016-01-01

In intensive agricultural systems runoff is one of the major potential diffuse pollution pathways for pesticides and poses a risk to surface water. Ditches are common in the Po Valley and can potentially provide runoff mitigation for the protection of watercourses. The effectiveness depends on ditch characteristics, so there is an urgent need for site-specific field trials. The use of a fugacity model (multimedia model) can allows recognition of the mitigation main processes. A field experiment was conducted in order to evaluate the mitigation capacity of a typical vegetated ditch, and results were compared with predictions by a fugacity model. To evaluate herbicide mitigation after an extreme runoff, the ditch was flooded with water containing mesotrione, S-metolachlor and terbuthylazine. Two other subsequent floods with uncontaminated water were applied 27 and 82 days later to evaluate herbicides release. Results show that the ditch can immediately reduce runoff concentration of herbicides by at least 50% even in extreme flooding conditions. The half-distances were about 250 m. As a general rule, a runoff of 1 mm from 5 ha is mitigated by 99% in 100 m of vegetated ditch. Herbicides retention in the vegetated ditch was reversible, and the second flood mobilized 0.03-0.2% of the previous one, with a concentration below the drinking water limit of 0.1 μg L(-1). No herbicide was detected in the third flood, because the residual amount in the ditch was too low. Fugacity model results show that specific physical-chemical parameters may be used and a specific soil-sediment-plant compartment included for modelling herbicides behaviour in a vegetated ditch, and confirm that accumulation is low or negligible for herbicides with a half-life of 40 days or less. Shallow vegetated ditches can thus be included in a general agri-environment scheme for the mitigation of pesticides runoff together with wetlands and linear buffer strips. These structures are present in the landscape, and their environmental role can be exploited by proper management.

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

PubMed

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

2008-11-28

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

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Vegetated Ditches for the Mitigation of Pesticides Runoff in the Po Valley

PubMed Central

Pappalardo, Salvatore E.; Cardinali, Alessandra; Masin, Roberta; Zanin, Giuseppe; Borin, Maurizio

2016-01-01

In intensive agricultural systems runoff is one of the major potential diffuse pollution pathways for pesticides and poses a risk to surface water. Ditches are common in the Po Valley and can potentially provide runoff mitigation for the protection of watercourses. The effectiveness depends on ditch characteristics, so there is an urgent need for site-specific field trials. The use of a fugacity model (multimedia model) can allows recognition of the mitigation main processes. A field experiment was conducted in order to evaluate the mitigation capacity of a typical vegetated ditch, and results were compared with predictions by a fugacity model. To evaluate herbicide mitigation after an extreme runoff, the ditch was flooded with water containing mesotrione, S-metolachlor and terbuthylazine. Two other subsequent floods with uncontaminated water were applied 27 and 82 days later to evaluate herbicides release. Results show that the ditch can immediately reduce runoff concentration of herbicides by at least 50% even in extreme flooding conditions. The half-distances were about 250 m. As a general rule, a runoff of 1 mm from 5 ha is mitigated by 99% in 100 m of vegetated ditch. Herbicides retention in the vegetated ditch was reversible, and the second flood mobilized 0.03-0.2% of the previous one, with a concentration below the drinking water limit of 0.1 μg L-1. No herbicide was detected in the third flood, because the residual amount in the ditch was too low. Fugacity model results show that specific physical-chemical parameters may be used and a specific soil-sediment-plant compartment included for modelling herbicides behaviour in a vegetated ditch, and confirm that accumulation is low or negligible for herbicides with a half-life of 40 days or less. Shallow vegetated ditches can thus be included in a general agri-environment scheme for the mitigation of pesticides runoff together with wetlands and linear buffer strips. These structures are present in the landscape, and their environmental role can be exploited by proper management. PMID:27070781

Preburner of Staged Combustion Rocket Engine

NASA Technical Reports Server (NTRS)

Yost, M. C.

1978-01-01

A regeneratively cooled LOX/hydrogen staged combustion assembly system with a 400:1 expansion area ratio nozzle utilizing an 89,000 Newton (20,000 pound) thrust regeneratively cooled thrust chamber and 175:1 tubular nozzle was analyzed, assembled, and tested. The components for this assembly include two spark/torch oxygen-hydrogen igniters, two servo-controlled LOX valves, a preburner injector, a preburner combustor, a main propellant injector, a regeneratively cooled combustion chamber, a regeneratively cooled tubular nozzle with an expansion area ratio of 175:1, an uncooled heavy-wall steel nozzle with an expansion area ratio of 400:1, and interconnecting ducting. The analytical effort was performed to optimize the thermal and structural characteristics of each of the new components and the ducting, and to reverify the capabilities of the previously fabricated components. The testing effort provided a demonstration of the preburner/combustor chamber operation, chamber combustion efficiency and stability, and chamber and nozzle heat transfer.

Capacitance-Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation.

PubMed

Lamb, Katie J; Dowsett, Mark R; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D; Aguiar, Pedro M; North, Michael; Parkin, Alison

2018-01-10

An electrochemical cell comprising a novel dual-component graphite and Earth-crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero-carbon energy source. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Tritium levels in milk in the vicinity of chronic tritium releases.

PubMed

Le Goff, P; Guétat, Ph; Vichot, L; Leconte, N; Badot, P M; Gaucheron, F; Fromm, M

2016-01-01

Tritium is the radioactive isotope of hydrogen. It can be integrated into most biological molecules. Even though its radiotoxicity is weak, the effects of tritium can be increased following concentration in critical compartments of living organisms. For a better understanding of tritium circulation in the environment and to highlight transfer constants between compartments, we studied the tritiation of different agricultural matrices chronically exposed to tritium. Milk is one of the most frequently monitored foodstuffs in the vicinity of points known for chronic release of radionuclides firstly because dairy products find their way into most homes but also because it integrates deposition over large areas at a local scale. It is a food which contains all the main nutrients, especially proteins, carbohydrates and lipids. We thus studied the tritium levels of milk in chronic exposure conditions by comparing the tritiation of the main hydrogenated components of milk, first, component by component, then, sample by sample. Significant correlations were found between the specific activities of drinking water and free water of milk as well as between the tritium levels of cattle feed dry matter and of the main organic components of milk. Our findings stress the importance of the metabolism on the distribution of tritium in the different compartments. Overall, dilution of hydrogen in the environmental compartments was found to play an important role dimming possible isotopic effects even in a food chain chronically exposed to tritium. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol.

PubMed

Zhao, Hailiang; Tang, Shanshan; Xu, Xiang; Du, Lin

2016-12-30

Amides are important atmospheric organic-nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH) with amides (formamide, N -methylformamide, N , N -dimethylformamide, acetamide, N -methylacetamide and N , N -dimethylacetamide) have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH-amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O-H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components.

Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol

PubMed Central

Zhao, Hailiang; Tang, Shanshan; Xu, Xiang; Du, Lin

2016-01-01

Amides are important atmospheric organic–nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH) with amides (formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide and N,N-dimethylacetamide) have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH–amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O–H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components. PMID:28042825

Overview of the U.S. DOE Hydrogen Safety, Codes and Standards Program. Part 4: Hydrogen Sensors; Preprint

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

Buttner, William J.; Rivkin, Carl; Burgess, Robert

Hydrogen sensors are recognized as a critical element in the safety design for any hydrogen system. In this role, sensors can perform several important functions including indication of unintended hydrogen releases, activation of mitigation strategies to preclude the development of dangerous situations, activation of alarm systems and communication to first responders, and to initiate system shutdown. The functionality of hydrogen sensors in this capacity is decoupled from the system being monitored, thereby providing an independent safety component that is not affected by the system itself. The importance of hydrogen sensors has been recognized by DOE and by the Fuel Cellmore » Technologies Office's Safety and Codes Standards (SCS) program in particular, which has for several years supported hydrogen safety sensor research and development. The SCS hydrogen sensor programs are currently led by the National Renewable Energy Laboratory, Los Alamos National Laboratory, and Lawrence Livermore National Laboratory. The current SCS sensor program encompasses the full range of issues related to safety sensors, including development of advance sensor platforms with exemplary performance, development of sensor-related code and standards, outreach to stakeholders on the role sensors play in facilitating deployment, technology evaluation, and support on the proper selection and use of sensors.« less

Developing Planetary Protection Technology: Recurrence of Hydrogen Peroxide Resistant Microbes from Spacecraft Assembly Facilities

NASA Astrophysics Data System (ADS)

Kempf, M. J.; Chen, F.; Quigley, M. S.; Pillai, S.; Kern, R.; Venkateswaran, K.

2001-12-01

Hydrogen peroxide vapor is currently the sterilant-of-choice for flight hardware because it is a low-heat sterilization process suitable for use with various spacecraft components. Hydrogen peroxide is a strong oxidizing agent that produces hydroxyl free radicals ( .OH) which attack essential cell components, including lipids, proteins, and DNA. Planetary protection research efforts at the Jet Propulsion Laboratory (JPL) are focused on developing cleaning and sterilization technologies for spacecraft preparation prior to launch. These efforts include research to assess the microbial diversity of spacecraft assembly areas and any extreme characteristics these microbes might possess. Previous studies have shown that some heat-tolerant Bacillus species isolated from the JPL Spacecraft Assembly Facility (SAF) are resistant to recommended hydrogen peroxide vapor sterilization exposures. A Bacillus species, which was related to a hydrogen peroxide resistant strain, was repeatedly isolated from various locations in the JPL-SAF. This species was found in both unclassified (entrance floors, ante-room, and air-lock) and classified (class 100K) (floors, cabinet tops, and air) areas. The phylogenetic affiliation of these strains was carried out using biochemical tests and 16S rDNA sequencing. The 16S rDNA analysis showed >99% sequence similarity to Bacillus pumilus. In order to understand the epidemiology of these strains, a more highly evolved gene (topoisomerase II β -subunit, gyrB) was also sequenced. Among 4 clades, one cluster, comprised of 3 strains isolated from the air-lock area, tightly aligned with the B. pumilus ATCC 7061 type strain (97%). The gyrB sequence similarity of this clade was only 91% with the 3 other clades. The genetic relatedness of these strains, as per pulse field gel electrophoresis patterns, will be presented. The vegetative cells and spores of a number of isolates were tested for their hydrogen peroxide resistance. Cells and spores were separately treated with 5% liquid hydrogen peroxide. After 60 minutes of exposure, the samples were diluted in tryptic soy broth and incubated at 32oC. Vegetative cells of one of the isolates, FO-036b, were the only cells to survive the exposure to hydrogen peroxide. In contrast, spores of several of the isolates survived exposure to hydrogen peroxide. Spores of these isolates do not appear to have any obvious morphological changes. We are in the process of analyzing these hydrogen peroxide resistant spores and comparing them to spores of microbes that are not as hydrogen peroxide resistant. The impact and implications of the identification and recurrence of these hydrogen peroxide microbes, and their spores, will be discussed.

Valorization of crude glycerol and eggshell biowaste as media components for hydrogen production: A scale-up study using co-culture system.

PubMed

Pachapur, Vinayak Laxman; Das, Ratul Kumar; Brar, Satinder Kaur; Le Bihan, Yann; Buelna, Gerardo

2017-02-01

The properties of eggshells (EGS) as neutralizing and immobilizing agent were investigated for hydrogen (H 2 ) production using crude glycerol (CG) by co-culture system. Eggshells of different sizes and concentrations were used during batch and repeated-batch fermentation. For batch and repeated-batch fermentation, the maximum H 2 production (36.53±0.53 and 41.16±0.95mmol/L, respectively) was obtained with the EGS size of 33μm

Crystal structures of the three closely related compounds: bis-[(1H-tetra-zol-5-yl)meth-yl]nitramide, tri-amino-guanidinium 5-({[(1H-tetra-zol-5-yl)meth-yl](nitro)-amino}-meth-yl)tetra-zol-1-ide, and di-ammonium bis-[(tetra-zol-1-id-5-yl)meth-yl]nitramide monohydrate.

PubMed

Mitchell, Lauren A; Imler, Gregory H; Parrish, Damon A; Deschamps, Jeffrey R; Leonard, Philip W; Chavez, David E

2017-07-01

In the mol-ecule of neutral bis-[(1 H -tetra-zol-5-yl)meth-yl]nitramide, (I), C 4 H 6 N 10 O 2 , there are two intra-molecular N-H⋯O hydrogen bonds. In the crystal, N-H⋯N hydrogen bonds link mol-ecules, forming a two-dimensional network parallel to (-201) and weak C-H⋯O, C-H⋯N hydrogen bonds, and inter-molecular π-π stacking completes the three-dimensional network. The anion in the molecular salt, tri-amino-guanidinium 5-({[(1 H -tetra-zol-5-yl)meth-yl](nitro)-amino}-meth-yl)tetra-zol-1-ide, (II), CH 9 N 6 + ·C 4 H 5 N 10 O 2 - , displays intra-molecular π-π stacking and in the crystal, N-H⋯N and N-H⋯O hydrogen bonds link the components of the structure, forming a three-dimensional network. In the crystal of di-ammonium bis-[(tetra-zol-1-id-5-yl)meth-yl]nitramide monohydrate, (III), 2NH 4 + ·C 4 H 4 N 10 O 2 2- ·H 2 O, O-H⋯N, N-H⋯N, and N-H⋯O hydrogen bonds link the components of the structure into a three-dimensional network. In addition, there is inter-molecular π-π stacking. In all three structures, the central N atom of the nitramide is mainly sp 2 -hybridized. Bond lengths indicate delocalization of charges on the tetra-zole rings for all three compounds. Compound (II) was found to be a non-merohedral twin and was solved and refined in the major component.

Reduction of interferences in the analysis of Children's Dimetapp using ultraviolet spectroscopy data and target factor analysis

NASA Astrophysics Data System (ADS)

Msimanga, Huggins Z.; Lam, Truong Thach Ho; Latinwo, Nathaniel; Song, Mihyang Kristy; Tavakoli, Newsha

2018-03-01

A calibration matrix has been developed and successfully applied to quantify actives in Children's Dimetapp®, a cough mixture whose active components suffer from heavy spectral interference. High-performance liquid chromatography/photodiode array instrument was used to identify the actives and any other UV-detectable excipients that might contribute to interferences. The instrument was also used to obtain reference data on the actives, instead of relying on the manufacturer's claims. Principal component analysis was used during the developmental stages of the calibration matrix to highlight any mismatch between the calibration and sample spectra, making certain that "apples" were not compared with "oranges". The prediction model was finally calculated using target factor analysis and partial least squares regression. In addition to the actives in Children's Dimetapp® (brompheniramine maleate, phenylephrine hydrogen chloride, and dextromethorphan hydrogen bromide), sodium benzoate was identified as the major and FD&C Blue #1, FD&C Red #40, and methyl anthranilate as minor spectral interferences. Model predictions were compared before and after the interferences were included into the calibration matrix. Before including interferences, the following results were obtained: brompheniramine maleate = 481.3 mg L- 1 ± 134% RE; phenylephrine hydrogen chloride = 1041 mg L- 1 ± 107% RE; dextromethorphan hydrogen bromide = 1571 mg L- 1 ± 107% RE, where % RE = percent relative error based on the reference HPLC data. After including interferences, the results were as follows: brompheniramine maleate = 196.3 mg L- 1 ± 4.4% RE; phenylephrine hydrogen chloride = 501.3 mg L- 1 ± 0.10% RE; dextromethorphan hydrogen bromide = 998.7 mg L- 1 ± 1.6% RE as detailed in Table 6.

Sensor for measuring hydrogen partial pressure in parabolic trough power plant expansion tanks

NASA Astrophysics Data System (ADS)

Glatzmaier, Greg C.; Cooney, Daniel A.

2017-06-01

The National Renewable Energy Laboratory and Acciona Energy North America are working together to design and implement a process system that provides a permanent solution to the issue of hydrogen buildup at parabolic trough power plants. We are pursuing a method that selectively removes hydrogen from the expansion tanks that serve as reservoirs for the heat transfer fluid (HTF) that circulates in the collector field and power block components. Our modeling shows that removing hydrogen from the expansion tanks at a design rate reduces and maintains dissolved hydrogen in the circulating HTF to a selected target level. Our collaborative work consists of several tasks that are needed to advance this process concept to a development stage, where it is ready for implementation at a commercial power plant. Our main effort is to design and evaluate likely process-unit operations that remove hydrogen from the expansion tanks at a specified rate. Additionally, we designed and demonstrated a method and instrumentation to measure hydrogen partial pressure and concentration in the expansion-tank headspace gas. We measured hydrogen partial pressure in the headspace gas mixture using a palladium-alloy membrane, which is permeable exclusively to hydrogen. The membrane establishes a pure hydrogen gas phase that is in equilibrium with the hydrogen in the gas mixture. We designed and fabricated instrumentation, and demonstrated its effectiveness in measuring hydrogen partial pressures over a range of three orders of magnitude. Our goal is to install this instrument at the Nevada Solar One power plant and to demonstrate its effectiveness in measuring hydrogen levels in the expansion tanks under normal plant operating conditions.

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

NASA Astrophysics Data System (ADS)

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

2013-11-01

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

Photosynthesis at the Microscale

DTIC Science & Technology

2013-03-25

cobalt(II) system reported by Lehn and co- workers, 10 the photocatalytic activity of the dyads decreased by a factor of 1/3 on addition of water to...more active than the corresponding multi-component systems, the non-conjugated bridge (A7) exhibited higher activity for hydrogen production.38 There...water as a feedstock, many potential hydrogen-evolving catalysts are tested for catalytic activity in organic solvents, as they often are not

Evaluating the Energetic Driving Force for Cocrystal Formation

PubMed Central

2017-01-01

We present a periodic density functional theory study of the stability of 350 organic cocrystals relative to their pure single-component structures, the largest study of cocrystals yet performed with high-level computational methods. Our calculations demonstrate that cocrystals are on average 8 kJ mol–1 more stable than their constituent single-component structures and are very rarely (<5% of cases) less stable; cocrystallization is almost always a thermodynamically favorable process. We consider the variation in stability between different categories of systems—hydrogen-bonded, halogen-bonded, and weakly bound cocrystals—finding that, contrary to chemical intuition, the presence of hydrogen or halogen bond interactions is not necessarily a good predictor of stability. Finally, we investigate the correlation of the relative stability with simple chemical descriptors: changes in packing efficiency and hydrogen bond strength. We find some broad qualitative agreement with chemical intuition—more densely packed cocrystals with stronger hydrogen bonding tend to be more stable—but the relationship is weak, suggesting that such simple descriptors do not capture the complex balance of interactions driving cocrystallization. Our conclusions suggest that while cocrystallization is often a thermodynamically favorable process, it remains difficult to formulate general rules to guide synthesis, highlighting the continued importance of high-level computation in predicting and rationalizing such systems. PMID:29445316

Evaluating the Energetic Driving Force for Cocrystal Formation.

PubMed

Taylor, Christopher R; Day, Graeme M

2018-02-07

We present a periodic density functional theory study of the stability of 350 organic cocrystals relative to their pure single-component structures, the largest study of cocrystals yet performed with high-level computational methods. Our calculations demonstrate that cocrystals are on average 8 kJ mol -1 more stable than their constituent single-component structures and are very rarely (<5% of cases) less stable; cocrystallization is almost always a thermodynamically favorable process. We consider the variation in stability between different categories of systems-hydrogen-bonded, halogen-bonded, and weakly bound cocrystals-finding that, contrary to chemical intuition, the presence of hydrogen or halogen bond interactions is not necessarily a good predictor of stability. Finally, we investigate the correlation of the relative stability with simple chemical descriptors: changes in packing efficiency and hydrogen bond strength. We find some broad qualitative agreement with chemical intuition-more densely packed cocrystals with stronger hydrogen bonding tend to be more stable-but the relationship is weak, suggesting that such simple descriptors do not capture the complex balance of interactions driving cocrystallization. Our conclusions suggest that while cocrystallization is often a thermodynamically favorable process, it remains difficult to formulate general rules to guide synthesis, highlighting the continued importance of high-level computation in predicting and rationalizing such systems.

Method for the continuous production of hydrogen

DOEpatents

Getty, John Paul; Orr, Mark T.; Woodward, Jonathan

2002-01-01

The present invention is a method for the continuous production of hydrogen. The present method comprises reacting a metal catalyst with a degassed aqueous organic acid solution within a reaction vessel under anaerobic conditions at a constant temperature of .ltoreq.80.degree. C. and at a pH ranging from about 4 to about 9. The reaction forms a metal oxide when the metal catalyst reacts with the water component of the organic acid solution while generating hydrogen, then the organic acid solution reduces the metal oxide thereby regenerating the metal catalyst and producing water, thus permitting the oxidation and reduction to reoccur in a continual reaction cycle. The present method also allows the continuous production of hydrogen to be sustained by feeding the reaction with a continuous supply of degassed aqueous organic acid solution.

Fuel quality combustion analysis

NASA Technical Reports Server (NTRS)

Naegeli, D. W.; Moses, C. A.

1979-01-01

A high pressure research combustor operating over a wide range of burner inlet conditions was used to determine the effects of fuel molecular structure on soot formation. Six test fuels with equal hydrogen content (12.8%) were blended to stress different molecular components and final boiling points. The fuels containing high concentrations (20%) of polycyclic aromatics and partially saturated polycyclic structures such as tetralin, produced more soot than would be expected from a hydrogen content correlation for typical petroleum based fuels. Fuels containing naphthenes such as decalin agreed with the hydrogen content correlation. The contribution of polycyclic aromatics to soot formation was equivalent to a reduction in fuel hydrogen content of about one percent. The fuel sensitivity to soot formation due to the polycyclic aromatic contribution decreased as burner inlet pressure and fuel/air ratio increased.

Low-Cost High-Pressure Hydrogen Generator

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

Cropley, Cecelia C.; Norman, Timothy J.

Electrolysis of water, particularly in conjunction with renewable energy sources, is potentially a cost-effective and environmentally friendly method of producing hydrogen at dispersed forecourt sites, such as automotive fueling stations. The primary feedstock for an electrolyzer is electricity, which could be produced by renewable sources such as wind or solar that do not produce carbon dioxide or other greenhouse gas emissions. However, state-of-the-art electrolyzer systems are not economically competitive for forecourt hydrogen production due to their high capital and operating costs, particularly the cost of the electricity used by the electrolyzer stack. In this project, Giner Electrochemical Systems, LLC (GES)more » developed a low cost, high efficiency proton-exchange membrane (PEM) electrolysis system for hydrogen production at moderate pressure (300 to 400 psig). The electrolyzer stack operates at differential pressure, with hydrogen produced at moderate pressure while oxygen is evolved at near-atmospheric pressure, reducing the cost of the water feed and oxygen handling subsystems. The project included basic research on catalysts and membranes to improve the efficiency of the electrolysis reaction as well as development of advanced materials and component fabrication methods to reduce the capital cost of the electrolyzer stack and system. The project culminated in delivery of a prototype electrolyzer module to the National Renewable Energy Laboratory for testing at the National Wind Technology Center. Electrolysis cell efficiency of 72% (based on the lower heating value of hydrogen) was demonstrated using an advanced high-strength membrane developed in this project. This membrane would enable the electrolyzer system to exceed the DOE 2012 efficiency target of 69%. GES significantly reduced the capital cost of a PEM electrolyzer stack through development of low cost components and fabrication methods, including a 60% reduction in stack parts count. Economic analysis indicates that hydrogen could be produced for $3.79 per gge at an electricity cost of $0.05/kWh by the lower-cost PEM electrolyzer developed in this project, assuming high-volume production of large-scale electrolyzer systems.« less

Long-Term Heating to Improve Receiver Performance

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

Glatzmaier, Greg C.; Cable, Robert; Newmarker, Marc

The buildup of hydrogen in the heat transfer fluid (HTF) that circulates through components of parabolic trough power plants decreases receiver thermal efficiency, and ultimately, it decreases plant performance and electricity output. The generation and occurrence of hydrogen in the HTF provides the driving force for hydrogen to permeate from the HTF through the absorber tube wall and into the receiver annulus. Getters adsorb hydrogen from the annulus volume until they saturate and are no longer able to maintain low hydrogen pressure. The increase in hydrogen pressure within the annulus significantly degrades thermal performance of the receiver and decreases overallmore » power-plant efficiency. NREL and Acciona Energy North America (Acciona) are developing a method to control the levels of dissolved hydrogen in the circulating HTF. The basic approach is to remove hydrogen from the expansion tanks of the HTF subsystem at a rate that maintains hydrogen in the circulating HTF to a target level. Full-plant steady-state models developed by the National Renewable Energy Laboratory (NREL) predict that if hydrogen is removed from the HTF within the expansion tanks, the HTF that circulates through the collector field remains essentially free of hydrogen until the HTF returns to the power block in the hot headers. One of the key findings of our modeling is the prediction that hydrogen will reverse-permeate out of the receiver annulus if dissolved hydrogen in the HTF is kept sufficiently low. To test this prediction, we performed extended heating of an in-service receiver that initially had high levels of hydrogen in its annulus. The heating was performed using NREL's receiver test stand. Results of our testing showed that receiver heat loss steadily decreased with daily heating, resulting in a corresponding improvement in receiver thermal efficiency.« less

Perron-Frobenius theorem on the superfluid transition of an ultracold Fermi gas

NASA Astrophysics Data System (ADS)

Sakumichi, Naoyuki; Kawakami, Norio; Ueda, Masahito

2014-05-01

The Perron-Frobenius theorem is applied to identify the superfluid transition of the BCS-BEC crossover based on a cluster expansion method of Lee and Yang. Here, the cluster expansion is a systematic expansion of the equation of state (EOS) in terms of the fugacity z = exp (βμ) as βpλ3 = 2 z +b2z2 +b3z3 + ⋯ , with inverse temperature β =(kB T) - 1 , chemical potential μ, pressure p, and thermal de Broglie length λ =(2 πℏβ / m) 1 / 2 . According to the method of Lee and Yang, EOS is expressed by the Lee-Yang graphs. A singularity of an infinite series of ladder-type Lee-Yang graphs is analyzed. We point out that the singularity is governed by the Perron-Frobenius eigenvalue of a certain primitive matrix which is defined in terms of the two-body cluster functions and the Fermi distribution functions. As a consequence, it is found that there exists a unique fugacity at the phase transition point, which implies that there is no fragmentation of Bose-Einstein condensates of dimers and Cooper pairs at the ladder-approximation level of Lee-Yang graphs. An application to a BEC of strongly bounded dimers is also made.

Mass balance modelling of contaminants in river basins: a flexible matrix approach.

PubMed

Warren, Christopher; Mackay, Don; Whelan, Mick; Fox, Kay

2005-12-01

A novel and flexible approach is described for simulating the behaviour of chemicals in river basins. A number (n) of river reaches are defined and their connectivity is described by entries in an n x n matrix. Changes in segmentation can be readily accommodated by altering the matrix entries, without the need for model revision. Two models are described. The simpler QMX-R model only considers advection and an overall loss due to the combined processes of volatilization, net transfer to sediment and degradation. The rate constant for the overall loss is derived from fugacity calculations for a single segment system. The more rigorous QMX-F model performs fugacity calculations for each segment and explicitly includes the processes of advection, evaporation, water-sediment exchange and degradation in both water and sediment. In this way chemical exposure in all compartments (including equilibrium concentrations in biota) can be estimated. Both models are designed to serve as intermediate-complexity exposure assessment tools for river basins with relatively low data requirements. By considering the spatially explicit nature of emission sources and the changes in concentration which occur with transport in the channel system, the approach offers significant advantages over simple one-segment simulations while being more readily applicable than more sophisticated, highly segmented, GIS-based models.

Nucleation barrier reconstruction via the seeding method in a lattice model with competing nucleation pathways.

PubMed

Lifanov, Yuri; Vorselaars, Bart; Quigley, David

2016-12-07

We study a three-species analogue of the Potts lattice gas model of nucleation from solution in a regime where partially disordered solute is a viable thermodynamic phase. Using a multicanonical sampling protocol, we compute phase diagrams for the system, from which we determine a parameter regime where the partially disordered phase is metastable almost everywhere in the temperature-fugacity plane. The resulting model shows non-trivial nucleation and growth behaviour, which we examine via multidimensional free energy calculations. We consider the applicability of the model in capturing the multi-stage nucleation mechanisms of polymorphic biominerals (e.g., CaCO 3 ). We then quantitatively explore the kinetics of nucleation in our model using the increasingly popular "seeding" method. We compare the resulting free energy barrier heights to those obtained via explicit free energy calculations over a wide range of temperatures and fugacities, carefully considering the propagation of statistical error. We find that the ability of the "seeding" method to reproduce accurate free energy barriers is dependent on the degree of supersaturation, and severely limited by the use of a nucleation driving force Δμ computed for bulk phases. We discuss possible reasons for this in terms of underlying kinetic assumptions, and those of classical nucleation theory.

A thermodynamic study of pyrite and pyrrhotite

USGS Publications Warehouse

Toulmin, P.; Barton, P.B.

1964-01-01

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

Detailed Investigation of Separation Performance of a MMM for Removal of Higher Hydrocarbons under Varying Operating Conditions

PubMed Central

Mushardt, Heike; Müller, Marcus; Shishatskiy, Sergey; Wind, Jan; Brinkmann, Torsten

2016-01-01

Mixed-matrix membranes (MMMs) are promising candidates to improve the competitiveness of membrane technology against energy-intensive conventional technologies. In this work, MMM composed of poly(octylmethylsiloxane) (POMS) and activated carbon (AC) were investigated with respect to separation of higher hydrocarbons (C3+) from permanent gas streams. Membranes were prepared as thin film composite membranes on a technical scale and characterized via scanning electron microscopy (SEM) and permeation measurements with binary mixtures of n-C4H10/CH4 under varying operating conditions (feed and permeate pressure, temperature, feed gas composition) to study the influence on separation performance. SEM showed good contact and absence of defects. Lower permeances but higher selectivities were found for MMM compared to pure POMS membrane. Best results were obtained at high average fugacity and activity of n-C4H10 with the highest selectivity estimated to be 36.4 at n-C4H10 permeance of 12 mN3/(m2·h·bar). Results were complemented by permeation of a multi-component mixture resembling a natural gas application, demonstrating the superior performance of MMM. PMID:26927194

Positronium hydride in hydrogen-laden thermochemically reduced MgO single crystals

NASA Astrophysics Data System (ADS)

Pareja, R.; de La Cruz, R. M.; Pedrosa, M. A.; González, R.; Chen, Y.

1990-04-01

Thermochemical reduction of hydrogen-laden MgO single crystals at T~2400 K results in a large concentration of both hydride (H-) ions and anion vacancies (>1024 m-3). Positron-lifetime experiments of these crystals provide evidence for bound positronium hydride states also referred to as [e+-H-] or PsH states. The presence of the anion vacancies was found to inhibit the formation of these states. After thermally annealing out these vacancies, such that H- concentration remains intact, two long-lived components appear in the lifetime spectrum. Furthermore, these two components correlate with the presence of the H-ions. These results suggest the existence of bound [e+-H-] states when positrons are trapped by the H- ions, and the subsequent formation of positronium (Ps) states by the dissociation of the [e+-H-] states. From the values of the intermediate lifetime component, a value of (570+/-50) ps is obtained for the lifetime of the PsH state located in an anion vacancy in MgO. The longest lifetime component ~(1-3) ns is attributed to pick-off annihilation of ortho-Ps states.

Arc-Heater Facility for Hot Hydrogen Exposure of Nuclear Thermal Rocket Materials

NASA Technical Reports Server (NTRS)

Litchford, Ron J.; Foote, John P.; Wang,Ten-See; Hickman, Robert; Panda, Binayak; Dobson, Chris; Osborne, Robin; Clifton, Scooter

2006-01-01

A hyper-thermal environment simulator is described for hot hydrogen exposure of nuclear thermal rocket material specimens and component development. This newly established testing capability uses a high-power, multi-gas, segmented arc-heater to produce high-temperature pressurized hydrogen flows representative of practical reactor core environments and is intended to serve. as a low cost test facility for the purpose of investigating and characterizing candidate fueUstructura1 materials and improving associated processing/fabrication techniques. Design and development efforts are thoroughly summarized, including thermal hydraulics analysis and simulation results, and facility operating characteristics are reported, as determined from a series of baseline performance mapping tests.

From flavoenzymes to devices: The role of electronic effects in recognition

NASA Astrophysics Data System (ADS)

Deans, Robert

Acylated aminopyridines provide models for specific flavoenzyme-cofactor interactions, allowing isolation and observation of the effects of hydrogen bonding on flavin NMR. To determine the relative hydrogen bond affinities of O(2) and O(4) of the flavin, a 2-aminopyridine based receptor was investigated. Additionally, this receptor allowed the effects of hydrogen bonding at O(2) and O(4) on the electron distribution in the flavin nucleus to be determined using sp{13}C NMR. A new family of receptors for flavins based on 6-aryl-2,4-(acyldiamino)-s-triazines was synthesized. In these synthetic hosts, systematic variation of the spatially remote substituents on the 6-aryl ring altered the hydrogen bond donating abilities of the amide functionality and the hydrogen bond accepting properties of the triazine N(3). This variation resulted in a strong modulation of the efficiency of flavin binding, with association constants for the receptor flavin complexes ranging over an 8-fold range. In addition, the communication of electronic information over extended distances was also investigated. Polymers can provide relevant media for the modeling of biological processes, including molecular recognition. To explore this possibility, a diaminotriazine-functionalized polymer was synthesized, starting from Merrifield's peptide resin. This polymer selectively bound a flavin derivative through hydrogen bonding, efficiently extracting it from a chloroform solution, as monitored by UV-vis extraction studies. The temperature profile of this polymer-flavin binding was also investigated and compared to the analogous solution-phase triazine-flavin dyad. Hydrogen bonding and aromatic stacking are fundamental interactions in molecular recognition. These interactions are sensitive to the redox states of the components of the host-guest complex. To explore the interplay of recognition and redox processes, a system consisting of two hosts and one guest, where guest binding interactions (hydrogen bonding and aromatic stacking) were modulated via choice of redox state was examined. Proper choice of receptors then provided a device where the competition between the two hosts was controlled by the redox state of the guest. The efficient reversal of host preference in this assembly provided an electrochemically-controlled three-component, two-pole, molecular switch.

A synergetic use of hydrogen and fuel cells in human spaceflight power systems

NASA Astrophysics Data System (ADS)

Belz, S.

2016-04-01

Hydrogen is very flexible in different fields of application of energy conversion. It can be generated by water electrolysis. Stored in tanks it is available for re-electrification by fuel cells. But it is not only the power system, which benefits from use of hydrogen, but also the life support system, which can contain hydrogen consuming technologies for recycling management (e.g. carbon dioxide removal and waste combustion processes). This paper points out various fields of hydrogen use in a human spaceflight system. Depending on mission scenarios, shadow phases, and the need of energy storage, regenerative fuel cell systems can be more efficient than secondary batteries. Here, different power storage concepts are compared by equivalent system mass calculation, thus including impact in the peripheral structure (volume, thermal management, etc.) on the space system. It is also focused on the technical integration aspect, e.g. which peripheral components have to be adapted when hydrogen is also used for life support technologies and what system mass benefit can be expected. Finally, a recommendation is given for the following development steps for a synergetic use of hydrogen and fuel cells in human spaceflight power systems.

Ground and Excited-Electronic-State Dissociations of Hydrogen-Rich and Hydrogen-Deficient Tyrosine Peptide Cation Radicals

NASA Astrophysics Data System (ADS)

Viglino, Emilie; Lai, Cheuk Kuen; Mu, Xiaoyan; Chu, Ivan K.; Tureček, František

2016-09-01

We report a comprehensive study of collision-induced dissociation (CID) and near-UV photodissociation (UVPD) of a series of tyrosine-containing peptide cation radicals of the hydrogen-rich and hydrogen-deficient types. Stable, long-lived, hydrogen-rich peptide cation radicals, such as [AAAYR + 2H]+● and several of its sequence and homology variants, were generated by electron transfer dissociation (ETD) of peptide-crown-ether complexes, and their CID-MS3 dissociations were found to be dramatically different from those upon ETD of the respective peptide dications. All of the hydrogen-rich peptide cation radicals contained major (77%-94%) fractions of species having radical chromophores created by ETD that underwent photodissociation at 355 nm. Analysis of the CID and UVPD spectra pointed to arginine guanidinium radicals as the major components of the hydrogen-rich peptide cation radical population. Hydrogen-deficient peptide cation radicals were generated by intramolecular electron transfer in CuII(2,2 ':6 ',2 ″-terpyridine) complexes and shown to contain chromophores absorbing at 355 nm and undergoing photodissociation. The CID and UVPD spectra showed major differences in fragmentation for [AAAYR]+● that diminished as the Tyr residue was moved along the peptide chain. UVPD was found to be superior to CID in localizing Cα-radical positions in peptide cation radical intermediates.

Thermodynamic Stability of Ice II and Its Hydrogen-Disordered Counterpart: Role of Zero-Point Energy.

PubMed

Nakamura, Tatsuya; Matsumoto, Masakazu; Yagasaki, Takuma; Tanaka, Hideki

2016-03-03

We investigate why no hydrogen-disordered form of ice II has been found in nature despite the fact that most of hydrogen-ordered ices have hydrogen-disordered counterparts. The thermodynamic stability of a set of hydrogen-ordered ice II variants relative to ice II is evaluated theoretically. It is found that ice II is more stable than the disordered variants so generated as to satisfy the simple ice rule due to the lower zero-point energy as well as the pair interaction energy. The residual entropy of the disordered ice II phase gradually compensates the unfavorable free energy with increasing temperature. The crossover, however, occurs at a high temperature well above the melting point of ice III. Consequently, the hydrogen-disordered phase does not exist in nature. The thermodynamic stability of partially hydrogen-disordered ices is also scrutinized by examining the free-energy components of several variants obtained by systematic inversion of OH directions in ice II. The potential energy of one variant is lower than that of the ice II structure, but its Gibbs free energy is slightly higher than that of ice II due to the zero-point energy. The slight difference in the thermodynamic stability leaves the possibility of the partial hydrogen-disorder in real ice II.

The controlled relay of multiple protons required at the active site of nitrogenase.

PubMed

Dance, Ian

2012-07-07

The enzyme nitrogenase, when reducing natural and unnatural substrates, requires large numbers of protons per chemical catalytic cycle. The active face of the catalytic site (the FeMo-cofactor, FeMo-co) is situated in a protein domain which is largely hydrophobic and anhydrous, and incapable of serial provision of multiple protons. Through detailed analysis of the high quality protein crystal structures available the characteristics of a chain of water molecules leading from the protein surface to a key sulfur atom (S3B) of FeMo-co are described. The first half of the water chain from the surface inwards is branched, slightly variable, and able to accommodate exogenous small molecules: this is dubbed the proton bay. The second half, from the proton bay to S3B, is comprised of a single chain of eight hydrogen bonded water molecules. This section is strictly conserved, and is intimately involved in hydrogen bonds with homocitrate, an essential component that chelates Mo. This is the proton wire, and a detailed Grotthuss mechanism for serial translocation of protons through this proton wire to S3B is proposed. This controlled serial proton relay from the protein surface to S3B is an essential component of the intramolecular hydrogenation paradigm for the complete chemical mechanisms of nitrogenase. Each proton reaching S3B, instigated by electron transfer to FeMo-co, becomes a hydrogen atom that migrates to other components of the active face of FeMo-co and to bound substrates and intermediates, allowing subsequent multiple proton transfers along the proton wire. Experiments to test the proposed mechanism of proton supply are suggested. The water chain in nitrogenase is comparable with the purported proton pumping pathway of cytochrome c oxidase.

Hydrogen Embrittlement of Automotive Advanced High-Strength Steels

NASA Astrophysics Data System (ADS)

Lovicu, Gianfranco; Bottazzi, Mauro; D'Aiuto, Fabio; De Sanctis, Massimo; Dimatteo, Antonella; Santus, Ciro; Valentini, Renzo

2012-11-01

Advanced high-strength steels (AHSS) have a better combination between strength and ductility than conventional HSS, and higher crash resistances are obtained in concomitance with weight reduction of car structural components. These steels have been developed in the last few decades, and their use is rapidly increasing. Notwithstanding, some of their important features have to be still understood and studied in order to completely characterize their service behavior. In particular, the high mechanical resistance of AHSS makes hydrogen-related problems a great concern for this steel grade. This article investigates the hydrogen embrittlement (HE) of four AHSS steels. The behavior of one transformation induced plasticity (TRIP), two martensitic with different strength levels, and one hot-stamping steels has been studied using slow strain rate tensile (SSRT) tests on electrochemically hydrogenated notched samples. The embrittlement susceptibility of these AHSS steels has been correlated mainly to their strength level and to their microstructural features. Finally, the hydrogen critical concentrations for HE, established by SSRT tests, have been compared to hydrogen contents absorbed during the painting process of a body in white (BIW) structure, experimentally determined during a real cycle in an industrial plant.

Hydrogen and the materials of a sustainable energy future

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

Zalbowitz, M.

1997-02-01

The National Educator`s Workshop (NEW): Update 96 was held October 27--30, 1996, and was hosted by Los Alamos National Laboratory. This was the 11th annual conference aimed at improving the teaching of material science, engineering and technology by updating educators and providing laboratory experiments on emerging technology for teaching fundamental and newly evolving materials concepts. The Hydrogen Education Outreach Activity at Los Alamos National Laboratory organized a special conference theme: Hydrogen and the Materials of a Sustainable Energy Future. The hydrogen component of the NEW:Update 96 offered the opportunity for educators to have direct communication with scientists in laboratory settings,more » develop mentor relationship with laboratory staff, and bring leading edge materials/technologies into the classroom to upgrade educational curricula. Lack of public education and understanding about hydrogen is a major barrier for initial implementation of hydrogen energy technologies and is an important prerequisite for acceptance of hydrogen outside the scientific/technical research communities. The following materials contain the papers and view graphs from the conference presentations. In addition, supplemental reference articles are also included: a general overview of hydrogen and an article on handling hydrogen safely. A resource list containing a curriculum outline, bibliography, Internet resources, and a list of periodicals often publishing relevant research articles can be found in the last section.« less

Sensor for Measuring Hydrogen Partial Pressure in Parabolic Trough Power Plant Expansion Tanks

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

Glatzmaier, Greg C.; Cooney, Daniel A.

The National Renewable Energy Laboratory and Acciona Energy North America are working together to design and implement a process system that provides a permanent solution to the issue of hydrogen buildup at parabolic trough power plants. We are pursuing a method that selectively removes hydrogen from the expansion tanks that serve as reservoirs for the heat transfer fluid (HTF) that circulates in the collector field and power block components. Our modeling shows that removing hydrogen from the expansion tanks at a design rate reduces and maintains dissolved hydrogen in the circulating HTF to a selected target level. Our collaborative workmore » consists of several tasks that are needed to advance this process concept to a development stage, where it is ready for implementation at a commercial power plant. Our main effort is to design and evaluate likely process-unit operations that remove hydrogen from the expansion tanks at a specified rate. Additionally, we designed and demonstrated a method and instrumentation to measure hydrogen partial pressure and concentration in the expansion-tank headspace gas. We measured hydrogen partial pressure in the headspace gas mixture using a palladium-alloy membrane, which is permeable exclusively to hydrogen. The membrane establishes a pure hydrogen gas phase that is in equilibrium with the hydrogen in the gas mixture. We designed and fabricated instrumentation, and demonstrated its effectiveness in measuring hydrogen partial pressures over a range of three orders of magnitude. Our goal is to install this instrument at the Nevada Solar One power plant and to demonstrate its effectiveness in measuring hydrogen levels in the expansion tanks under normal plant operating conditions.« less

Integrated investigation of the mixed origin of lunar sample 72161,11

NASA Technical Reports Server (NTRS)

Basu, A.; Des Marais, D. J.; Hayes, J. M.; Meinschein, W. G.

1975-01-01

The comminution-agglutination model and the solar-wind implantation-retention model are used to postulate the origins of the particulate components of lunar sample (72161,11), a submillimeter fraction of a surface sample for the dark mantle regolith at LRV-3. Grain-size analysis was performed by wet sieving with liquid argon, and analyses for CO2, CO, CH4, and H2 were carried out by stepwise pyrolysis in a helium atmosphere. The results indicate that the present sample is from a mature regolith, but the agglutinate content is only 30% in the particle-size range between 90 and 177 microns, indicating an apparent departure from steady state. Analyses of the carbon, methane, and hydrogen concentrations in size fractions larger than 149 microns show that the volume-correlated component of these species increases with increased grain size. It is suggested that the observed increase can be explained in terms of mixing of a dominant local population of coarser agglutinates having high carbon and hydrogen concentrations with an imported population of finer agglutinates relatively poor in carbon and hydrogen.

Effects of the non-extensive parameter on the propagation of ion acoustic waves in five-component cometary plasma system

NASA Astrophysics Data System (ADS)

Mahmoud, Abeer A.

2018-01-01

Some important evolution nonlinear partial differential equations are derived using the reductive perturbation method for unmagnetized collisionless system of five component plasma. This plasma system is a multi-ion contains negatively and positively charged Oxygen ions (heavy ions), positive Hydrogen ions (lighter ions), hot electrons from solar origin and colder electrons from cometary origin. The positive Hydrogen ion and the two types of electrons obey q-non-extensive distributions. The derived equations have three types of ion acoustic waves, which are soliton waves, shock waves and kink waves. The effects of the non-extensive parameters for the hot electrons, the colder electrons and the Hydrogen ions on the propagation of the envelope waves are studied. The compressive and rarefactive shapes of the three envelope waves appear in this system for the first order of the power of the nonlinearity strength with different values of non-extensive parameters. For the second order, the strength of nonlinearity will increase and the compressive type of the envelope wave only appears.

Protective effect of ursolic acid from Cornus officinalis on the hydrogen peroxide-induced damage of HEI-OC1 auditory cells.

PubMed

Yu, Hyeon-Hee; Hur, Jong-Moon; Seo, Se-Jeong; Moon, Hae-Dalma; Kim, Hyun-Jin; Park, Rae-Kil; You, Yong-Ouk

2009-01-01

The fruits of Cornus officinalis have been used in traditional oriental medicine for treatment of inner ear diseases, such as tinnitus and hearing loss. In the present study, we investigated the protective effect of C. officinalis on hydrogen peroxide-induced cytotoxicity in HEI-OC1 auditory cells. The results from bioassay-guided fractionation of methanol extract of C. officinalis fruits showed that ursolic acid is a major active component. Ursolic acid (0.05-2 microg/ml) had protective effect against the HEI-OC1 cell damage and reduced lipid peroxidation in a dose-dependent manner. In addition, pre-treatment with ursolic acid significantly attenuated the decrease of activities of catalase (CAT) and glutathione peroxidase (GPX), but superoxide dismutase (SOD) activity was not significantly affected by ursolic acid. These results indicate that ursolic acid protects hydrogen peroxide-induced HEI-OC1 cell damage through inhibition of lipid peroxidation and induction of antioxidant enzymes, CAT and GPX, and may be one of the active components responsible for these effects of C. officinalis fruits.

Catalytic Combustion for Ultra-Low NOx Hydrogen Turbines

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

Etemad, Shahrokh; Baird, Benjamin; Alavandi, Sandeep

2011-06-30

Precision Combustion, Inc., (PCI) in close collaboration with Solar Turbines, Incorporated, has developed and demonstrated a combustion system for hydrogen fueled turbines that reduces NOx to low single digit level while maintaining or improving current levels of efficiency and eliminating emissions of carbon dioxide. Full scale Rich Catalytic Hydrogen (RCH1) injector was developed and successfully tested at Solar Turbines, Incorporated high pressure test facility demonstrating low single digit NOx emissions for hydrogen fuel in the range of 2200F-2750F. This development work was based on initial subscale development for faster turnaround and reduced cost. Subscale testing provided promising results for 42%more » and 52% H2 with NOx emissions of less than 2 ppm with improved flame stability. In addition, catalytic reactor element testing for substrate oxidation, thermal cyclic injector testing to simulate start-stop operation in a gas turbine environment, and steady state 15 atm. operation testing were performed successfully. The testing demonstrated stable and robust catalytic element component life for gas turbine conditions. The benefit of the catalytic hydrogen combustor technology includes capability of delivering near-zero NOx without costly post-combustion controls and without requirement for added sulfur control. In addition, reduced acoustics increase gas turbine component life. These advantages advances Department of Energy (DOE’s) objectives for achievement of low single digit NOx emissions, improvement in efficiency vs. postcombustion controls, fuel flexibility, a significant net reduction in Integrated Gasification Combined Cycle (IGCC) system net capital and operating costs, and a route to commercialization across the power generation field from micro turbines to industrial and utility turbines.« less

Alternative method for steam generation for thermal oxidation of silicon

NASA Astrophysics Data System (ADS)

Spiegelman, Jeffrey J.

2010-02-01

Thermal oxidation of silicon is an important process step in MEMS device fabrication. Thicker oxide layers are often used as structural components and can take days or weeks to grow, causing high gas costs, maintenance issues, and a process bottleneck. Pyrolytic steam, which is generated from hydrogen and oxygen combustion, was the default process, but has serious drawbacks: cost, safety, particles, permitting, reduced growth rate, rapid hydrogen consumption, component breakdown and limited steam flow rates. Results from data collected over a 24 month period by a MEMS manufacturer supports replacement of pyrolytic torches with RASIRC Steamer technology to reduce process cycle time and enable expansion previously limited by local hydrogen permitting. Data was gathered to determine whether Steamers can meet or exceed pyrolytic torch performance. The RASIRC Steamer uses de-ionized water as its steam source, eliminating dependence on hydrogen and oxygen. A non-porous hydrophilic membrane selectively allows water vapor to pass. All other molecules are greatly restricted, so contaminants in water such as dissolved gases, ions, total organic compounds (TOC), particles, and metals can be removed in the steam phase. The MEMS manufacturer improved growth rate by 7% over the growth range from 1μm to 3.5μm. Over a four month period, wafer uniformity, refractive index, wafer stress, and etch rate were tracked with no significant difference found. The elimination of hydrogen generated a four-month return on investment (ROI). Mean time between failure (MTBF) was increased from 3 weeks to 32 weeks based on three Steamers operating over eight months.

Commercial aerospace and terrestrial applications of nickel-hydrogen batteries

NASA Astrophysics Data System (ADS)

Caldwell, Dwight B.; Coates, Dwaine K.; Fox, Chris L.; Miller, Lee E.

1996-03-01

The nickel-hydrogen battery system, used extensively in the aerospace industry to supply electrical power to earth-orbital satellites for communications, observation, and military applications, is being developed for commercial, terrestrial applications. Low-cost components, electrodes, cell designs, and battery designs are currently being tested. Catalytic hydrogen electrodes have been developed which are compatible with commercial nickel battery cost. Prismatic and spiral-wound cell designs have been built and tested. Common pressure vessel and dependent pressure vessel battery designs are also being evaluated. The nickel-hydrogen battery offers potential cycle life unequaled by any other battery system. This makes the battery ideal for many commercial and terrestrial energy storage applications such as telecommunication, remote stand-alone power systems, utility load-leveling, and other applications which require long life and a truly maintenance-free and abuse-tolerant battery system.

Hydrodesulfurization of dibenzothiophene (DBT) catalyzed by sulfided CoO-MoO/sub 3//. gamma. -Al/sub 2/O/sub 3/: the reaction kinetics

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

Broderick, D.H.; Gates, B.C.

1980-01-01

Rates of the two competing conversion routes of DBT, a model compound for components of heavy oils and coal liquids, i.e., aromatic ring hydrogenation followed by hydrodesulfurization of the tetra- and hexahydro-DBT intermediates to cyclohexylbenzene (the hydrogenation route) and direct DBT hydrodesulfurization to biphenyl (the hydrogenolysis route) were measured independently at 548/sup 0/, 573/sup 0/, and 598/sup 0/K and 178 atm over an in-situ desulfurized commercial CoO-MoO/sub 3//..gamma..-Al/sub 2/O/sub 3/ catalyst. The rate data were fitted to Langmuir-Hinshelwood equations derived by nonlinear least-squares regression analysis, and all the kinetic parameters were accurately estimated. The selectivity for the hydrogenolysis route canmore » be increased, and hence hydrogen consumption minimized, by increasing temperature, reducing hydrogen sulfide concentration in the system through recycle gas scrubbing, or by adding quinoline which acts as inhibitor of the hydrogenation route preferentially.« less

Nickel-hydrogen. [metal hydrides, electrochemical corrosion, and structural design

NASA Technical Reports Server (NTRS)

Mchenry, E. J.

1977-01-01

Because of the disintegration of LaNi5 as the lattice expands on absorbing hydrogen, a nickel hydrogen cell similar to a nickel cadmium cell was designed. The positive electrode is wrapped in a microporous separator and the leads are insulated. A negative conducting grid is inserted and welded to the top of the can into an open ended container which is then turned upside down and filled so that LiNa5 powder occupies all the space not used by the rest of the components. The bottom of the can is then welded on. A fill tube is located either on the bottom or on the top of the can. When welded shut, the cell is put into a pressure bomb and the lanthanum nickel is activated at about 1,000 pounds of hydrogen. Electrolytes are added to the cell as well as whatever amount of hydrogen precharge desired, and the cell is sealed. Advantages and disadvantages of the cell are discussed.

Diffusion coefficient of hydrogen in a cast gamma titanium aluminide

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

Sundaram, P.A.; Wessel, E.; Ennis, P.J.

1999-06-04

Gamma titanium aluminides have the potential for high temperature applications because of their high specific strength and specific modulus. Their oxidation resistance is good, especially at intermediate temperatures and with suitable alloying additions, good oxidation resistance can be obtained up to 800 C. One critical area of application is in combustion engines in aero-space vehicles such as hypersonic airplanes and high speed civil transport airplanes. This entails the use of hydrogen as a fuel component and hence the effect of hydrogen on the mechanical properties of gamma titanium aluminides is of significant scientific and technological utility. The purpose of thismore » short investigation is to use an electrochemical method under galvanostatic conditions to determine the diffusion coefficient of hydrogen in a cast gamma titanium aluminide, a typical technical alloy with potential application in gas turbines under creep conditions. This result will be then compared with that obtained by microhardness profiling of electrolytically hydrogen precharged material.« less

Gaining electricity from in situ oxidation of hydrogen produced by fermentative cellulose degradation.

PubMed

Niessen, J; Schröder, U; Harnisch, F; Scholz, F

2005-01-01

To exploit the fermentative hydrogen generation and direct hydrogen oxidation for the generation of electric current from the degradation of cellulose. Utilizing the metabolic activity of the mesophilic anaerobe Clostridium cellulolyticum and the thermophilic Clostridium thermocellum we show that electricity generation is possible from cellulose fermentation. The current generation is based on an in situ oxidation of microbially synthesized hydrogen at platinum-poly(tetrafluoroaniline) (Pt-PTFA) composite electrodes. Current densities of 130 mA l(-1) (with 3 g cellulose per litre medium) were achieved in poised potential experiments under batch and semi-batch conditions. The presented results show that electricity generation is possible by the in situ oxidation of hydrogen, product of the anaerobic degradation of cellulose by cellulolytic bacteria. For the first time, it is shown that an insoluble complex carbohydrate like cellulose can be used for electricity generation in a microbial fuel cell. The concept represents a first step to the utilization of macromolecular biomass components for microbial electricity generation.

Safety Standard for Hydrogen and Hydrogen Systems: Guidelines for Hydrogen System Design, Materials Selection, Operations, Storage and Transportation. Revision

NASA Technical Reports Server (NTRS)

1997-01-01

The NASA Safety Standard, which establishes a uniform process for hydrogen system design, materials selection, operation, storage, and transportation, is presented. The guidelines include suggestions for safely storing, handling, and using hydrogen in gaseous (GH2), liquid (LH2), or slush (SLH2) form whether used as a propellant or non-propellant. The handbook contains 9 chapters detailing properties and hazards, facility design, design of components, materials compatibility, detection, and transportation. Chapter 10 serves as a reference and the appendices contained therein include: assessment examples; scaling laws, explosions, blast effects, and fragmentation; codes, standards, and NASA directives; and relief devices along with a list of tables and figures, abbreviations, a glossary and an index for ease of use. The intent of the handbook is to provide enough information that it can be used alone, but at the same time, reference data sources that can provide much more detail if required.

4-Aza-1-azoniabicyclo­[2.2.2]octa­ne–2-amino­benzoate–2-amino­benzoic acid (1/1/1)

PubMed Central

Arman, Hadi D.; Kaulgud, Trupta; Tiekink, Edward R. T.

2011-01-01

A 4-aza-1-azoniabicyclo­[2.2.2]octane cation, a 2-amino­benzoate anion and a neutral 2-amino­benzoic acid mol­ecule comprise the asymmetric unit of the title compound, C6H13N2 +·C7H6NO2 −·C7H7NO2. An intra­molecular N—H⋯O hydrogen bond occurs in the anion and in the neutral 2-amino­benzoic acid mol­ecule. The cation provides a charge-assisted N—H⋯O hydrogen bond to the anion, and the 2-amino­benzoic acid mol­ecule forms an O—H⋯N hydrogen bond to the unprotonated amino N atom in the cation. In this way, a three-component aggregate is formed. These are connected into a three-dimensional network by amino–carboxyl­ate N—H⋯O hydrogen bonds. N—H⋯N hydrogen bonds are also observed. PMID:22219964

H2 production by the photocatalytic reforming of cellulose and raw biomass using Ni, Pd, Pt and Au on titania

PubMed Central

Jones, W.; Hardacre, C.; Bowker, M.

2016-01-01

Here, we report a method for sustainable hydrogen production using sunlight and biomass. It is shown that cellulose can be photoreformed to produce hydrogen, even in solid form, by use of metal-loaded titania photocatalysts. The experiments performed verified that the process is enabled by initial hydrolysis via glucose, which itself is shown to be efficiently converted to produce hydrogen by photocatalysis. Importantly, it is shown that not only precious metals such as Pt, Pd and Au can be used as the metal component, but also much more economic and less environmentally damaging Ni is effective. Even more importantly, we show for the first time, to the best our knowledge, that fescue grass as raw biomass can be effective for hydrogen production without significant pre-treatment. This provides additional benefits for the efficiency of biomass hydrogen production, because fewer processing steps for the raw material are required than in the production of purer forms of cellulose, for example. PMID:27493561

Hydrogen-extraction experiments on grossular

NASA Astrophysics Data System (ADS)

Kurka, A.; Blanchard, M.; Ingrin, J.

2003-04-01

Grossular generally contains the highest amount of hydrogen within the garnet-group and is a minor component in many pyrope-rich mantle garnets, despite some mantle garnets are known showing significant grossular-component. Gemmy, orange-brown colored, grossular-samples from Madagascar of composition Gr 83.2 Py 2.2 An 14.3 were used to study the hydrogen-extraction behaviour. Five doubly polished, single crystal-slices with a thickness ranging from about 350 to 500 microns were cut. The slices were heated in air at temperatures of 800^o, 900^o, 950^o, 1000^o and 1050^o C for 2 hours up to 900 hours. The hydrogen content was determined using FTIR-spectroscopy. Our material shows a spectra characteristic for grossular with about 12 absorption-bands in the OH-region. The initial OH content was determined as 0.022 wt% H_2O. The diffusion coefficients calculated using the equation proposed by Hercule &Ingrin (1999) range from 7 10-15 to 2 10-12 (m2/s) leading to an activation energy for H-extraction in grossular at about 260 kJ/mol, which is similar to that of pyrope from Dora Maira (personal communication M. Blanchard) but slightly higher than pyrope investigated by Wang et al. (1996). It should be further noticed that the extraction rate of some bands at lower energies shows slightly different behaviour than that of other bands. This may affect the model of H-incorporation in grossular, that is usually described by the classic hydrogen-incorporation via O_4H_4 - SiO_4, and may support more sophisticated models of OH-substitution in garnet as proposed recently by Andrut et al. (2002). This study was financially supported by the EU through the Human Potential Program HPRN-CT-2000-0056. References: [1] Wang, L., Zhang, Y., Essene, E. (1996) Diffusion of the hydrous component in pyrope. Am. Mineral., 81, 701-718. [2] Hercule, S. and Ingrin, J. (1999) Hydrogen in diopside: Diffusion, kinetics of extraction-incorporation, and solubility. Am. Mineral., 84, 1577-1587. [3] Andrut, M., Wildner, M. and Beran A. (2002) The crystal chemistry of birefrigent natural uvarovites. Part IV. OH defect incorporation mechanisms in non-cubic garnets derived from polarized IR spectroscopy. Eur. J. Mineral., 14, 1019-1026.

The 1985 Goddard Space Flight Center Battery Workshop

NASA Technical Reports Server (NTRS)

Morrow, G. (Editor)

1986-01-01

The subjects covered include: advanced energy storage, lithium cell technology, nickel-cadmium design evaluation and component testing, simulated orbital cycling and flight experience, and nickel-hydrogen technology.

Characterization of exhaust emissions from diesel-powered passenger cars with particular reference to unregulated components

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

Lies, K.H.; Postulka, A.; Gring, H.

Besides regulated components VW's research program in the field of characterization of diesel emissions comprises a detailed analysis of the particulates and a comprehensive study of a number of unregulated gaseous compounds. The following chemical compounds and classes of compounds are measured: particulates, traces of metals, major elements, sulfates, sulfur dioxide, hydrogen sulfide, hydrogen cyanide, aldehydes, ammonia, phenols, individual hydrocarbons, and odor (DOAS). The test fleet of this investigation included a number of VW and Audi cars equipped with 4-, and 5-cylinder diesel engines (naturally aspirated and turbocharged). All measurements were performed on a chassis dynamometer in accordance with themore » specification of the known US-test-procedures: Federal Test Procedure, Sulfate Emission Test, Fuel Economy Test. For sampling , in principle, the dilution tunnel technique was used combined with an automatically working collection system. This micro-processor controlled system involves 13 individual sample lines, 8 for gaseous and 5 for particulate components.« less

Gelatinized wheat starch influences crystallization behaviour and structure of roll-in shortenings in laminated bakery products.

PubMed

Mattice, Kristin D; Marangoni, Alejandro G

2018-03-15

One hydrogenated and one non-hydrogenated shortening were baked with isolated components of a croissant matrix, including crystalline wheat starch, gelatinized wheat starch, gluten, and formed gluten network. The impact of the matrix components on fat crystallization was analyzed for polymorphism using powder X-ray diffraction, solid fat content by pulsed nuclear magnetic resonance and thermal behaviour by differential scanning calorimetry. When compared to results obtained from croissants prepared with the respective shortenings, samples containing gelatinized wheat starch displayed notably similar results: polymorphic conversion, from the β' to β form over storage, and visually broader peaks in the melting endotherms indicating a greater temperature was required to completely melt all of the fat. All other component mixtures behaved similar to the respective fats in bulk. The measured rate of crystallization was greater in samples containing gelatinized wheat starch, indicating that the gelatinized starch could act as a nucleation site to speed crystallization. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interaction between xanthan gum and cationic cellulose JR400 in aqueous solution.

PubMed

Li, Haiping; Hou, Wanguo; Li, Xiuzhi

2012-06-05

The electrostatic and hydrogen bonding interactions between xanthan gum (XG) and semisynthetic cationic cellulose (JR400) in aqueous solution are investigated via stability map, FT-IR spectra, thermogravimetric analysis, potentiometric measurement and rheological method. The stability map shows three regions, a stable region with XG as the major component, a flocculated region and another stable region with JR400 as the major component. The stability of mixing system depends on both the concentration fraction of JR400 (fJR) and the overlapping concentrations of these two polymers. In the region near the stoichiometric fJR, the mixture shows stoichiometric flocculation, which is independent of the total polymer concentration. However, in the regions away from the stoichiometric fJR, the mixtures are stable when the concentration of major polymer component is higher than its overlapping concentration. In stable regions, the electrostatic and hydrogen bonding interactions can enhance the viscosity of mixing system at appropriate fJR values. Copyright © 2012 Elsevier Ltd. All rights reserved.

Redox state of earth's upper mantle from kimberlitic ilmenites

NASA Technical Reports Server (NTRS)

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

1983-01-01

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

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

NASA Technical Reports Server (NTRS)

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

1973-01-01

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

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

PubMed

Weill, D F; Drake, M J

1973-06-08

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

Universal FFM Hydrogen Spectral Line Shapes Applied to Ions and Electrons

NASA Astrophysics Data System (ADS)

Mossé, C.; Calisti, A.; Ferri, S.; Talin, B.; Bureyeva, L. A.; Lisitsa, V. S.

2008-10-01

We present a method for the calculation of hydrogen spectral line shapes based on two combined approaches: Universal Model and FFM procedure. We start with the analytical functions for the intensities of the Stark components of radiative transitions between highly excited atomic states with large values of principal quantum numbers n,n'γ1, with Δn = n-n'≪n for the specific cases of Hn-α line (Δn = 1) and Hn-β line (Δn = 2). The FFM line shape is obtained by averaging on the electric field of the Hooper's field distribution for ion and electron perturber dynamics and by mixing the Stark components with a jumping frequency rate ve (vi) where v = N1/3u (N is electron density and u is the ion or electron thermal velocity). Finally, the total line shape is given by convolution of ion and electron line shapes. Hydrogen line shape calculations for Balmer Hα and Hβ lines are compared to experimental results in low density plasma (Ne˜1016-1017cm-3) and low electron temperature in order of 10 000K. This method relying on analytic expressions permits fast calculation of Hn-α and Hn-β lines of hydrogen and could be used in the study of the Stark broadening of radio recombination lines for high principal quantum number.

Effect of the components' interface on the synthesis of methanol over Cu/ZnO from CO2/H2: a microkinetic analysis based on DFT + U calculations.

PubMed

Tang, Qian-Lin; Zou, Wen-Tian; Huang, Run-Kun; Wang, Qi; Duan, Xiao-Xuan

2015-03-21

The elucidation of chemical reactions occurring on composite systems (e.g., copper (Cu)/zincite (ZnO)) from first principles is a challenging task because of their very large sizes and complicated equilibrium geometries. By combining the density functional theory plus U (DFT + U) method with microkinetic modeling, the present study has investigated the role of the phase boundary in CO2 hydrogenation to methanol over Cu/ZnO. The absence of hydrogenation locations created by the interface between the two catalyst components was revealed based on the calculated turnover frequency under realistic conditions, in which the importance of interfacial copper to provide spillover hydrogen for remote Cu(111) sites was stressed. Coupled with the fact that methanol production on the binary catalyst was recently believed to predominantly involve the bulk metallic surface, the spillover of interface hydrogen atoms onto Cu(111) facets facilitates the production process. The cooperative influence of the two different kinds of copper sites can be rationalized applying the Brönsted-Evans-Polanyi (BEP) relationship and allows us to find that the catalytic activity of ZnO-supported Cu catalysts is of volcano type with decrease in the particle size. Our results here may have useful implications in the future design of new Cu/ZnO-based materials for CO2 transformation to methanol.

Inhibitory activity of honey against foodborne pathogens as influenced by the presence of hydrogen peroxide and level of antioxidant power.

PubMed

Taormina, P J; Niemira, B A; Beuchat, L R

2001-09-28

Antimicrobial activity of honey has been attributed to hydrogen peroxide, which is produced by naturally occurring glucose oxidase, and phenolic compounds, although lethality of and inhibition by these and other components against microorganisms vary greatly, depending on the floral source of nectar. This study was undertaken to compare honeys from six floral sources for their inhibitory activity against Escherichia coli O157:H7, Salmonella typhimurium, Shigella sonnei, Listeria monocytogenes, Staphylococcus aureus, and Bacillus cereus. A disc assay revealed that development of zones of inhibition of growth depends on the type and concentration of honey, as well as the test pathogen. Growth of B. cereus was least affected. The inhibition of growth of S. sonnei, L. monocytogenes, and S. aureus in 25% solutions of honeys was reduced by treating solutions with catalase, indicating that hydrogen peroxide contributes to antimicrobial activity. Darker colored honeys were generally more inhibitory than light colored honeys. Darker honeys also contained higher antioxidant power. Since antimicrobial activity of the darker colored test honeys was not eliminated by catalase treatment, non-peroxide components such as antioxidants may contribute to controlling the growth of some foodborne pathogens. The antibacterial properties of honeys containing hydrogen peroxide and characterized by a range of antioxidant power need to be validated using model food systems.

Odyssey/NS

NASA Image and Video Library

2002-12-10

These two views of Mars were made with data taken by the neutron spectrometer component of NASA Mars Odyssey spacecraft and show epithermal neutron flux, which is sensitive to the amount of hydrogen present.

Accurate calculation of dynamic Stark shifts and depopulation rates of Rydberg energy levels induced by blackbody radiation. Hydrogen, helium, and alkali-metal atoms

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

Farley, J.W.; Wing, W.H.

1981-05-01

A highly excited (Rydberg) atom bathed in blackbody radiation is perturbed in two ways. A dynamic Stark shift is induced by the off-resonant components of the blackbody radiation. Additionally, electric-dipole transitions to other atomic energy levels are induced by the resonant components of the blackbody radiation. This depopulation effect shortens the Rydberg-state lifetime, thereby broadening the energy level. Calculations of these two effects in many states of hydrogen, helium, and the alkali-metal atoms Li, Na, K, Rb, and Cs are presented for T = 300 K. Contributions from the entire blackbody spectrum and from both discrete and continuous perturbing statesmore » are included. The accuracy is considerably greater than that of previous estimates.« less

Assembly of multiple components in a hybrid microcapsule: designing a magnetically separable Pd catalyst for selective hydrogenation.

PubMed

Amali, Arlin Jose; Sharma, Bikash; Rana, Rohit Kumar

2014-09-15

In analogy to the role of long-chain polyamines in biosilicification, poly-L-lysine facilitates the assembly of nanocomponents to design multifunctional microcapsule structures. The method is demonstrated by the fabrication of a magnetically separable catalyst that accommodates Pd nanoparticles (NPs) as active catalyst, Fe3O4 NPs as magnetic component for easy recovery of the catalyst, and silica NPs to impart stability and selectivity to the catalyst. In addition, polyamines embedded inside the microcapsule prevent the agglomeration of Pd NPs and thus result in efficient catalytic activity in hydrogenation reactions, and the hydrophilic silica surface results in selectivity in reactions depending on the polarity of substrates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electromagnetic dampers for cryogenic applications

NASA Technical Reports Server (NTRS)

Brown, Gerald V.; Dirusso, Eliseo

1988-01-01

Cryogenic turbomachinery of the type used to pump high-pressure liquid hydrogen at -423 F and liquid oxygen at -297 F to the main engines of the Space Shuttle are subjected to lateral rotor vibrations from unbalance forces and transient loads. Conventional dampers which utilize viscous fluids such as lubricating oil cannot be used in turbopumps because the bearing components are filled with either liquid hydrogen or liquid oxygen, which have viscosity comparable to air and, therefore, are not effective in viscous dampers. Electromagentic dampers are currently being explored as a means of providing damping in cryogenic turbopumps because their damping effectiveness increases as temperature decreases and because they are compatible with the liquid hydrogen or liquid oxygen in the turbopumps.

Determination of the delta(2H/1H)of Water: RSIL Lab Code 1574

USGS Publications Warehouse

Revesz, Kinga; Coplen, Tyler B.

2008-01-01

Reston Stable Isotope Laboratory (RSIL) lab code 1574 describes a method used to determine the relative hydrogen isotope-ratio delta(2H,1H), abbreviated hereafter as d2H of water. The d2H measurement of water also is a component of the National Water Quality Laboratory (NWQL) schedules 1142 and 1172. The water is collected unfiltered in a 60-mL glass bottle and capped with a Polyseal cap. In the laboratory, the water sample is equilibrated with gaseous hydrogen using a platinum catalyst (Horita, 1988; Horita and others, 1989; Coplen and others, 1991). The reaction for the exchange of one hydrogen atom is shown in equation 1.

Turbojet Performance and Operation at High Altitudes with Hydrogen and Jp-4 Fuels

NASA Technical Reports Server (NTRS)

Fleming, W A; Kaufman, H R; Harp, J L , Jr; Chelko, L J

1956-01-01

Two current turbojet engines were operated with gaseous-hydrogen and JP-4 fuels at very high altitudes and a simulated Mach number of 0.8. With gaseous hydrogen as the fuel stable operation was obtained at altitudes up to the facility limit of about 90,000 feet and the specific fuel consumption was only 40 percent of that with JP-4 fuel. With JP-4 as the fuel combustion was unstable at altitudes above 60,000 to 65,000 feet and blowout limits were reached at 75,000 to 80,000 feet. Over-all performance, component efficiencies, and operating range were reduced considerable at very high altitudes with both fuels.

Wind-To-Hydrogen Energy Pilot Project

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

Ron Rebenitsch; Randall Bush; Allen Boushee

2009-04-24

WIND-TO-HYDROGEN ENERGY PILOT PROJECT: BASIN ELECTRIC POWER COOPERATIVE In an effort to address the hurdles of wind-generated electricity (specifically wind's intermittency and transmission capacity limitations) and support development of electrolysis technology, Basin Electric Power Cooperative (BEPC) conducted a research project involving a wind-to-hydrogen system. Through this effort, BEPC, with the support of the Energy & Environmental Research Center at the University of North Dakota, evaluated the feasibility of dynamically scheduling wind energy to power an electrolysis-based hydrogen production system. The goal of this project was to research the application of hydrogen production from wind energy, allowing for continued wind energymore » development in remote wind-rich areas and mitigating the necessity for electrical transmission expansion. Prior to expending significant funding on equipment and site development, a feasibility study was performed. The primary objective of the feasibility study was to provide BEPC and The U.S. Department of Energy (DOE) with sufficient information to make a determination whether or not to proceed with Phase II of the project, which was equipment procurement, installation, and operation. Four modes of operation were considered in the feasibility report to evaluate technical and economic merits. Mode 1 - scaled wind, Mode 2 - scaled wind with off-peak, Mode 3 - full wind, and Mode 4 - full wind with off-peak In summary, the feasibility report, completed on August 11, 2005, found that the proposed hydrogen production system would produce between 8000 and 20,000 kg of hydrogen annually depending on the mode of operation. This estimate was based on actual wind energy production from one of the North Dakota (ND) wind farms of which BEPC is the electrical off-taker. The cost of the hydrogen produced ranged from $20 to $10 per kg (depending on the mode of operation). The economic sensitivity analysis performed as part of the feasibility study showed that several factors can greatly affect, both positively and negatively, the "per kg" cost of hydrogen. After a September 15, 2005, meeting to evaluate the advisability of funding Phase II of the project DOE concurred with BEPC that Phase I results did warrant a "go" recommendation to proceed with Phase II activities. The hydrogen production system was built by Hydrogenics and consisted of several main components: hydrogen production system, gas control panel, hydrogen storage assembly and hydrogen-fueling dispenser The hydrogen production system utilizes a bipolar alkaline electrolyzer nominally capable of producing 30 Nm3/h (2.7 kg/h). The hydrogen is compressed to 6000 psi and delivered to an on-site three-bank cascading storage assembly with 80 kg of storage capacity. Vehicle fueling is made possible through a Hydrogenics-provided gas control panel and dispenser able to fuel vehicles to 5000 psi. A key component of this project was the development of a dynamic scheduling system to control the wind energy's variable output to the electrolyzer cell stacks. The dynamic scheduling system received an output signal from the wind farm, processed this signal based on the operational mode, and dispatched the appropriate signal to the electrolyzer cell stacks. For the study BEPC chose to utilize output from the Wilton wind farm located in central ND. Site design was performed from May 2006 through August 2006. Site construction activities were from August to November 2006 which involved earthwork, infrastructure installation, and concrete slab construction. From April - October 2007, the system components were installed and connected. Beginning in November 2007, the system was operated in a start-up/shakedown mode. Because of numerous issues, the start-up/shakedown period essentially lasted until the end of January 2008, at which time a site acceptance test was performed. Official system operation began on February 14, 2008, and continued through the end of December 2008. Several issues continued to prevent consistent operation, resulting in operation of the system in fits and starts. During the operational period, three ramp tests were performed on the electrolyzer cell stacks to evaluate cell stack degradation, if present. In addition, from December 23 - 30 2008, the hydrogen system was operated using Mode 1 protocol. From February 14, 2008 - December 31, 2008, the system produced a total of just less than 26,000,000 liters (2320 kg), including approximately 3,300,000 liters (295 kg) of hydrogen during Mode 1 operation. Unfortunately, the chronic shutdown issues prevented consistent operation and, therefore, did not allow for any accurate economic analysis as originally intended. With that said, much valuable experience was gained in the form of "lessons learned," and the project served as an extremely valuable platform for educating the public.« less

The Multiple Continuum Components in the White-Light Flare of 16 January 2009 on the dM4.5e Star YZ CMi

NASA Astrophysics Data System (ADS)

Kowalski, A. F.; Hawley, S. L.; Holtzman, J. A.; Wisniewski, J. P.; Hilton, E. J.

2012-03-01

The white light during M dwarf flares has long been known to exhibit the broadband shape of a T≈10 000 K blackbody, and the white light in solar-flares is thought to arise primarily from hydrogen recombination. Yet, a current lack of broad-wavelength coverage solar flare spectra in the optical/near-UV region prohibits a direct comparison of the continuum properties to determine if they are indeed so different. New spectroscopic observations of a secondary flare during the decay of a megaflare on the dM4.5e star YZ CMi have revealed multiple components in the white-light continuum of stellar flares, including both a blackbody-like spectrum and a hydrogen-recombination spectrum. One of the most surprising findings is that these two components are anti-correlated in their temporal evolution. We combine initial phenomenological modeling of the continuum components with spectra from radiative hydrodynamic models to show that continuum veiling causes the measured anti-correlation. This modeling allows us to use the components' inferred properties to predict how a similar spatially resolved, multiple-component, white-light continuum might appear using analogies to several solar-flare phenomena. We also compare the properties of the optical stellar flare white light to Ellerman bombs on the Sun.

Graphene Derivative in Magnetically Recoverable Catalyst Determines Catalytic Properties in Transfer Hydrogenation of Nitroarenes to Anilines with 2-Propanol.

PubMed

Das, Vijay Kumar; Mazhar, Sumaira; Gregor, Lennon; Stein, Barry D; Morgan, David Gene; Maciulis, Nicholas A; Pink, Maren; Losovyj, Yaroslav; Bronstein, Lyudmila M

2018-06-14

Here, we report transfer hydrogenation of nitroarenes to aminoarenes using 2-propanol as a hydrogen source and Ag-containing magnetically recoverable catalysts based on partially reduced graphene oxide (pRGO) sheets. X-ray diffraction and X-ray photoelectron spectroscopy data demonstrated that, during the one-pot catalyst synthesis, formation of magnetite nanoparticles (NPs) is accompanied by the reduction of graphene oxide (GO) to pRGO. The formation of Ag 0 NPs on top of magnetite nanoparticles does not change the pRGO structure. At the same time, the catalyst structure is further modified during the transfer hydrogenation, leading to a noticeable increase of sp 2 carbons. These carbons are responsible for the adsorption of substrate and intermediates, facilitating a hydrogen transfer from Ag NPs and creating synergy between the components of the catalyst. The nitroarenes with electron withdrawing and electron donating substituents allow for excellent yields of aniline derivatives with high regio and chemoselectivity, indicating that the reaction is not disfavored by these functionalities. The versatility of the catalyst synthetic protocol was demonstrated by a synthesis of an Ru-containing graphene derivative based catalyst, also allowing for efficient transfer hydrogenation. Easy magnetic separation and stable catalyst performance in the transfer hydrogenation make this catalyst promising for future applications.

An experimental aluminum-fueled power plant

NASA Astrophysics Data System (ADS)

Vlaskin, M. S.; Shkolnikov, E. I.; Bersh, A. V.; Zhuk, A. Z.; Lisicyn, A. V.; Sorokovikov, A. I.; Pankina, Yu. V.

2011-10-01

An experimental co-generation power plant (CGPP-10) using aluminum micron powder (with average particle size up to 70 μm) as primary fuel and water as primary oxidant was developed and tested. Power plant can work in autonomous (unconnected from industrial network) nonstop regime producing hydrogen, electrical energy and heat. One of the key components of experimental plant is aluminum-water high-pressure reactor projected for hydrogen production rate of ∼10 nm3 h-1. Hydrogen from the reactor goes through condenser and dehumidifier and with -25 °C dew-point temperature enters into the air-hydrogen fuel cell 16 kW-battery. From 1 kg of aluminum the experimental plant produces 1 kWh of electrical energy and 5-7 kWh of heat. Power consumer gets about 10 kW of electrical power. Plant electrical and total efficiencies are 12% and 72%, respectively.

Recent insights into the cell immobilization technology applied for dark fermentative hydrogen production.

PubMed

Kumar, Gopalakrishnan; Mudhoo, Ackmez; Sivagurunathan, Periyasamy; Nagarajan, Dillirani; Ghimire, Anish; Lay, Chyi-How; Lin, Chiu-Yue; Lee, Duu-Jong; Chang, Jo-Shu

2016-11-01

The contribution and insights of the immobilization technology in the recent years with regards to the generation of (bio)hydrogen via dark fermentation have been reviewed. The types of immobilization practices, such as entrapment, encapsulation and adsorption, are discussed. Materials and carriers used for cell immobilization are also comprehensively surveyed. New development of nano-based immobilization and nano-materials has been highlighted pertaining to the specific subject of this review. The microorganisms and the type of carbon sources applied in the dark hydrogen fermentation are also discussed and summarized. In addition, the essential components of process operation and reactor configuration using immobilized microbial cultures in the design of varieties of bioreactors (such as fixed bed reactor, CSTR and UASB) are spotlighted. Finally, suggestions and future directions of this field are provided to assist the development of efficient, economical and sustainable hydrogen production technologies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Regenerative Fuel Cell Test Rig Completed and Operational at Glenn Research Center

NASA Technical Reports Server (NTRS)

Bents, David J.

2004-01-01

The NASA Glenn Research Center has completed construction of its first closed-cycle hydrogen-oxygen regenerative fuel cell (RFC). The RFC is an electrochemical system that collects and stores solar energy during the day then releases that energy at night, thus making the Sun's energy available all 24 hours. It consists of a dedicated hydrogen-oxygen fuel cell stack and an electrolyzer stack, the interconnecting plumbing and valves, cooling pumps, water transfer pumps, gas recirculation pumps, phase separators, storage tanks for oxygen (O2) and hydrogen (H2), heat exchangers, isolation valves, pressure regulators, nitrogen purge provisions, instrumentation, and other components. It includes all the equipment required to (1) absorb electrical power from an outside source and store it as pressurized hydrogen and oxygen and (2) make electrical power from the stored gases, saving the product water for reuse during the next cycle.

Hydrogen: What's Different Now

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

Gearhart, Chris C

This is an exciting time for hydrogen fuel-cell electric vehicles (FCEVs). They seem to be on the verge of a major market breakthrough. However, those of us who have been working in the hydrogen and FC industry for a while are familiar with the boom and bust cycle of FCEV hype-it feels like we have been here before. The first FC automobile was designed as far back as the 1960s. NASA was using FCs to power its spacecraft, and, in 1966, General Motors (GM) used this space-age technology in the prototype GM Electrovan. The Electrovan used the body and chassismore » of GM's Handivan, their production utility van at the time. The FC and hydrogen components for this vehicle filled nearly the entire available space of the van. At this point, FCs were clearly too expensive and impractical for production vehicles.« less

Hydrogenated 5-carbon compound and method of making

DOEpatents

Elliott, Douglas C.; Frye, John G.

1999-01-01

The present invention is based upon the surprising discovery that a 5-carbon compound selected from the group of 4-oxopentanoic acid, at least one lactone of 4-oxopentanoic acid, and combinations thereof, may be hydrogenated with a bimetallic catalyst of a noble metal in combination with a second metal and preserve the pendant methyl group. It was further unexpectedly discovered that the same conditions of bimetallic catalyst in the presence of hydrogen are useful for catalyzing the different intermediate reactions for example angelicalactone to gamma-valerolactone and gamma-valerolactone to 1,4-pentanediol. Finally, it was surprising that levulinic acid could be converted to 2-methyltetrahydrofuran with heating in the presence of the bimetallic catalyst and hydrogen in a single process vessel. The method of the present invention unexpectedly produced a fuel or fuel component having 2-methyltetrahydrofuran either in a yield greater than 4.5 mol % or in combination with alcohols.

Hydrogenated 5-carbon compound and method of making

DOEpatents

Elliott, D.C.; Frye, J.G.

1999-03-16

The present invention is based upon the surprising discovery that a 5-carbon compound selected from the group of 4-oxopentanoic acid, at least one lactone of 4-oxopentanoic acid, and combinations thereof, may be hydrogenated with a bimetallic catalyst of a noble metal in combination with a second metal and preserve the pendant methyl group. It was further unexpectedly discovered that the same conditions of bimetallic catalyst in the presence of hydrogen are useful for catalyzing the different intermediate reactions, for example, angelicalactone to gamma-valerolactone and gamma-valerolactone to 1,4-pentanediol. Finally, it was surprising that levulinic acid could be converted to 2-methyltetrahydrofuran with heating in the presence of the bimetallic catalyst and hydrogen in a single process vessel. The method of the present invention unexpectedly produced a fuel or fuel component having 2-methyltetrahydrofuran either in a yield greater than 4.5 mol % or in combination with alcohols. 8 figs.

Mineral chemistry of Pangidi basalt flows from Andhra Pradesh

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

Organochlorine pesticides in soils and air of southern Mexico: Chemical profiles and potential for soil emissions

NASA Astrophysics Data System (ADS)

Wong, Fiona; Alegria, Henry A.; Jantunen, Liisa M.; Bidleman, Terry F.; Salvador-Figueroa, Miguel; Gold-Bouchot, Gerardo; Ceja-Moreno, Victor; Waliszewski, Stefan M.; Infanzon, Raul

The extent of organochlorine pesticides (OCs) contamination in southern Mexico was investigated in this study. Biweekly air samplings were carried out in two sites in the state of Chiapas (during 2002-2003), and one in each state of Veracruz and Tabasco (during 2003-2004). Corresponding to the air sampling locations, soil samples were also collected to gauge the soil-air exchange of OCs in the region. ∑DDTs in soils ranged from 0.057 to 360 ng g -1 whereas those in air ranged from 240 to 2400 pg m -3. DDT and metabolite DDE were expressed as fractional values, FDDTe = p, p'-DDT/( p, p'-DDT + p, p'-DDE) and FDDTo = p,p'-DDT/( p,p'-DDT + o,p'-DDT). FDDTe in soils ranged from 0.30 to 0.69 while those in air ranged from 0.45 to 0.84. FDDTe in air at a farm in Chiapas (0.84) was closer to that of technical DDT (0.95) which is suggestive of fresh DDT input. Enantiomer fractions (EF) of o,p'-DDT in air were racemic at all locations (0.500-0.504). However, nonracemic o,p'-DDT was seen in the soils (EFs = 0.456-0.647). Fugacities of OCs in soil ( fs) and air ( fa) were calculated, and the fugacity fraction, ff = fs/( fs + fa) of DDTs ranged from 0.013 to 0.97 which indicated a mix of net deposition ( ff < 0.5) and volatilization ( ff > 0.5) from soil among the sites. It is suggested that DDTs in Mexico air are due to a combination of ongoing regional usage and re-emission of old DDT residues from soils. Total toxaphene in soils ranged from 0.066 to 69 ng g -1 while levels in air ranged from 6.2 to 230 pg m -3. Chromatographic profiles of toxaphenes in both air and soil showed depletion of Parlar congeners 39 and 42. Fugacity fractions of toxaphene were within the equilibrium range or above the upper equilibrium threshold boundary. These findings suggested that soil emission of old residues is the main source of toxaphenes to the atmosphere. Results from this study provide baseline data for establishing a long-term OC monitoring program in Mexico.

Lipid Extraction and the Fugacity of Stable Isotope Values

NASA Astrophysics Data System (ADS)

Padula, V.; Causey, D.; Wolf, N.; Welker, J. M.

2013-12-01

Stable isotope analysis of blood, feathers, and other tissues are often used to infer migration patterns, diet composition and trophic status of seabirds. Tissues contain variable amounts of lipids that are depleted in the heavy carbon isotope (13C) and may introduce a bias in these values. There is evidence that lipid extraction may affect other stable isotope ratios, such as δ15N. Consequently, correction factors need to be applied to appropriately interpret δ13C and δ15N values for individual species and tissue type. In this study, we collected seven species of seabirds from the Near Islands, the western most group of islands in the Aleutian Island archipelago. We sampled kidney, liver, heart and muscle samples from each bird and after freeze drying, individual tissue samples were divided into two subsamples. We left one subsample unaltered and extracted lipids from the other subsample using a 2:1 chloroform-methanol solution. We found that the change in δ13C values after lipid extraction (Δδ13C) varied widely among categories (eg., species, tissue type) from 0 - 4 ‰, while Δδ15N values ranged from 0 to 2‰. Notably, within category variation was nonsignificant and the Δδ values were linear against the covariant C:N ratio of the isotopic data, which allows us to use arithmetic corrections for categorical values. Our data strongly indicate that the effects of lipid extraction on stable isotopic values, while linear within category, vary widely by species, tissue, geographic area, year of collection, and isotope. Fugacity is usually employed as a thermodynamic quantity related to the chemical potential or activity that characterizes the escaping tendency from a phase (eg. Mackay & Paterson 1982). Here we use fugacity in the earlier, broader sense of fleeting, transitory, or instable states (eg., S. Johnson 1751), and its measure may be approximated by the higher order variance of Δδ13C and Δδ15N among data categories. Clearly, understanding the nature of variation and the physiological processes responsible for stable isotope values from biological tissues are critical for their interpretation. Change in carbon and nitrogen stable isotopes (ΔδC13, Δδ15N) after lipid extraction for Tufted Puffins (Fratercula cirrhata) collected July 2010 at Attu Island, Aleutians.

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

NASA Astrophysics Data System (ADS)

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

1997-01-01

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

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

PubMed Central

Righter, K.; Ghiorso, M. S.

2012-01-01

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

Investigation on drug solubility enhancement using deep eutectic solvents and their derivatives.

PubMed

Li, Zheng; Lee, Ping I

2016-05-30

Deep eutectic solvent (DES) is a room temperature liquid typically formed by mixing two solid compounds, such as a quaternary ammonium salt (QAS) (e.g. choline chloride) and a hydrogen bond donor (HBD) (e.g. urea or a carboxylic acid) at their eutectic composition. Very often, a range of room temperature liquids can also be obtained near the eutectic composition. Hence, it is more convenient to introduce a more general term deep eutectic solvent derivatives (DESDs) to describe a wide range of DES-like derivatives including those derived from ternary mixtures. The melting point of the mixture is lowered because the hydrogen bonding between DESD components reduces the lattice energy of components of the eutectic system. Based on the analysis of available data for 22 such choline chloride-based DES pairs, we found that the observed melting point depression can be statistically correlated with the difference between the hydrogen bonding contribution (δh) and the polar contribution (δp) to the solubility parameter of the hydrogen bond donor (HBD) component. The correlation was validated with a new DESD based on glycolic acid and choline chloride, which form DESDs at a molar ratio between 1:1 and 1:4 with DES-like properties. As a room temperature liquid, this DESD exhibits a wide range of solubility enhancement on several weakly basic poorly water-soluble drugs. For example, the solubility of itraconazole, piroxicam, lidocaine, and posaconazole has been observed to increase by 6700, 430, 28, and 6400-fold, respectively as compared to their aqueous solubility at room temperature. Furthermore, another new ternary DESD based on choline chloride, glycolic acid, and oxalic acid at a molar ratio of 1:1.6:0.4 is shown to further increase the solubility of itraconazole to a remarkable level of 5.36mg/mL (a 53,600-fold increase!). Because the components of such DESDs can include those biodegradable ones that had previously been used in formulated human products, the potential applicability of suitable DESDs to drug delivery, especially in enhancing drug solubility for topical formulations could be very attractive. Copyright © 2016 Elsevier B.V. All rights reserved.

Components of a standardised olive leaf dry extract (Ph. Eur.) promote hypothiocyanite production by lactoperoxidase.

PubMed

Flemmig, Jörg; Rusch, Dorothea; Czerwińska, Monika Ewa; Rauwald, Hans-Wilhelm; Arnhold, Jürgen

2014-05-01

We investigated in vitro the ability of a standardised olive leaf dry extract (Ph. Eur.) (OLE) as well as of its single components to circumvent the hydrogen peroxide-induced inhibition of the hypothiocyanite-producing activity of lactoperoxidase (LPO). The rate of hypothiocyanite (⁻OSCN) formation by LPO was quantified by spectrophotometric detection of the oxidation of 5-thio-2-nitrobenzoic acid (TNB). By using excess hydrogen peroxide, we forced the accumulation of inactive enzymatic intermediates which are unable to promote the two-electronic oxidation of thiocyanate. Both OLE and certain extract components showed a strong LPO-reactivating effect. Thereby an o-hydroxyphenolic moiety emerged to be essential for a good reactivity with the inactive LPO redox states. This basic moiety is found in the main OLE components oleuropein, oleacein, hydroxytyrosol, caffeic acid as well as in different other constituents including the OLE flavone luteolin. As LPO is a key player in the humoral immune response, these results propose a new mode of action regarding the well-known bacteriostatic and anti-inflammatory properties of the leaf extract of Olea europaea L. Copyright © 2014 Elsevier Inc. All rights reserved.

Conceptual Design of Optimized Fossil Energy Systems with Capture and Sequestration of Carbon Dioxide

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

Nils Johnson; Joan Ogden

2010-12-31

In this final report, we describe research results from Phase 2 of a technical/economic study of fossil hydrogen energy systems with carbon dioxide (CO{sub 2}) capture and storage (CCS). CO{sub 2} capture and storage, or alternatively, CO{sub 2} capture and sequestration, involves capturing CO{sub 2} from large point sources and then injecting it into deep underground reservoirs for long-term storage. By preventing CO{sub 2} emissions into the atmosphere, this technology has significant potential to reduce greenhouse gas (GHG) emissions from fossil-based facilities in the power and industrial sectors. Furthermore, the application of CCS to power plants and hydrogen production facilitiesmore » can reduce CO{sub 2} emissions associated with electric vehicles (EVs) and hydrogen fuel cell vehicles (HFCVs) and, thus, can also improve GHG emissions in the transportation sector. This research specifically examines strategies for transitioning to large-scale coal-derived energy systems with CCS for both hydrogen fuel production and electricity generation. A particular emphasis is on the development of spatially-explicit modeling tools for examining how these energy systems might develop in real geographic regions. We employ an integrated modeling approach that addresses all infrastructure components involved in the transition to these energy systems. The overall objective is to better understand the system design issues and economics associated with the widespread deployment of hydrogen and CCS infrastructure in real regions. Specific objectives of this research are to: Develop improved techno-economic models for all components required for the deployment of both hydrogen and CCS infrastructure, Develop novel modeling methods that combine detailed spatial data with optimization tools to explore spatially-explicit transition strategies, Conduct regional case studies to explore how these energy systems might develop in different regions of the United States, and Examine how the design and cost of coal-based H{sub 2} and CCS infrastructure depend on geography and location.« less

Volatile-rich lunar soil - Evidence of possible cometary impact.

NASA Technical Reports Server (NTRS)

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

1973-01-01

A subsurface Apollo 16 soil, 61221, is much richer in volatile compounds than soils from any other locations or sites as shown by thermal analysis-gas release measurements. A weight loss of 0.03% during the interval 175 to 350 C was associated with the release of water, carbon dioxide, methane, hydrogen cyanide, hydrogen, and minor amounts of hydrocarbons and other species. These volatile components may have been brought to this site by a comet, which may have formed North Ray crater.

Supramolecular Polymers Based on Non-Coplanar AAA-DDD Hydrogen-Bonded Complexes.

PubMed

Mendez, Iamnica J Linares; Wang, Hong-Bo; Yuan, Ying-Xue; Wisner, James A

2018-03-01

Non-coplanar triple-hydrogen-bond arrays are connected as telechelic groups to alkyl chains and their properties as AA/BB type supramolecular polymers are examined. Viscosity studies at three temperatures are used to study the ring-chain equilibrium and determine the critical concentrations where polymer chains are formed. It is observed that neither the temperature range studied nor the alkyl chain length of one component significantly affect the polymerization properties in this system. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The role of the reactor wall in hydrothermal biomass conversions.

PubMed

Fábos, Viktória; Yuen, Alexander K L; Masters, Anthony F; Maschmeyer, Thomas

2012-11-01

The processing of renewable feedstocks to platform chemicals and, to a lesser degree, fuels is a key part of sustainable development. In particular, the combination of lignocellulosic biomass with hydrothermal upgrading (HTU), using high temperature and pressure water (HTPW), is experiencing a renaissance. One of the many steps in this complicated process is the in-situ hydrogenation of intermediate compounds. As formic acid and related low-molecular-weight oxygenates are among the species generated, it is conceivable that they act as a hydrogen source. Such hydrogenations have been suggested to be catalyzed by water, by bases like NaOH, and/or to involve "reactive/nascent hydrogen". To achieve the temperatures and pressures required for HTU, it is necessary to conduct the reactions in high-pressure vessels. Metals are typical components of their walls and/or internal fittings. Here, using cyclohexanone as a model compound for more complex biomass-derived molecules, iron in the wall of high-pressure stainless steel reactors is shown to be responsible for the hydrogenation of ketones with low-molecular-weight oxygenates acting as a hydrogen source in combination with water. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water: two liquids divided by a common hydrogen bond.

PubMed

Soper, Alan K

2011-12-08

The structure of water is the subject of a long and ongoing controversy. Unlike simpler liquids, where atomic interactions are dominated by strong repulsive forces at short distances and weaker attractive (van der Waals) forces at longer distances, giving rise to local atomic coordination numbers of order 12, water has pronounced and directional hydrogen bonds which cause the dense liquid close-packed structure to open out into a disordered and dynamic network, with coordination number 4-5. Here I show that water structure can be accurately represented as a mixture of two identical, interpenetrating, molecular species separated by common hydrogen bonds. Molecules of one type can form hydrogen bonds with molecules of the other type but cannot form hydrogen bonds with molecules of the same type. These hydrogen bonds are strong along the bond but weak with respect to changes in the angle between neighboring bonds. The observed pressure and temperature dependence of water structure and thermodynamic properties follow naturally from this choice of water model, and it also gives a simple explanation of the enduring claims based on spectroscopic evidence that water is a mixture of two components. © 2011 American Chemical Society

Neutron scattering shows a droplet of oleic acid at the center of the BAMLET complex.

PubMed

Rath, Emma M; Duff, Anthony P; Gilbert, Elliot P; Doherty, Greg; Knott, Robert B; Church, W Bret

2017-07-01

The anti-cancer complex, Bovine Alpha-lactalbumin Made LEthal to Tumors (BAMLET), has intriguing broad-spectrum anti-cancer activity. Although aspects of BAMLET's anti-cancer mechanism are still not known, it is understood that it involves the oleic acid or oleate component of BAMLET being preferentially released into cancer cell membranes leading to increased membrane permeability and lysis. The structure of the protein component of BAMLET has previously been elucidated by small angle X-ray scattering (SAXS) to be partially unfolded and dramatically enlarged. However, the structure of the oleic acid component of BAMLET and its disposition with respect to the protein component was not revealed as oleic acid has the same X-ray scattering length density (SLD) as water. Employing the difference in the neutron SLDs of hydrogen and deuterium, we carried out solvent contrast variation small angle neutron scattering (SANS) experiments of hydrogenated BAMLET in deuterated water buffers, to reveal the size, shape, and disposition of the oleic acid component of BAMLET. Our resulting analysis and models generated from SANS and SAXS data indicate that oleic acid forms a spherical droplet of oil incompletely encapsulated by the partially unfolded protein component. This model provides insight into the anti-cancer mechanism of this cache of lipid. The model also reveals a protein component "tail" not associated with the oleic acid component that is able to interact with the tail of other BAMLET molecules, providing a plausible explanation of how BAMLET readily forms aggregates. Proteins 2017; 85:1371-1378. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Adsorption, hydrogenation and dehydrogenation of C2H on a CoCu bimetallic layer

NASA Astrophysics Data System (ADS)

Wu, Donghai; Yuan, Jinyun; Yang, Baocheng; Chen, Houyang

2018-05-01

In this paper, adsorption, hydrogenation and dehydrogenation of C2H on a single atomic layer of bimetallic CoCu were investigated using first-principles calculations. The CoCu bimetallic layer is formed by Cu replacement of partial Co atoms on the top layer of a Co(111) surface. Our adsorption and reaction results showed those sites, which have stronger adsorption energy of C2H, possess higher reactivity. The bimetallic layer possesses higher reactivity than either of the pure monometallic layer. A mechanism of higher reactivity of the bimetallic layer is proposed and identified, i.e. in the bimetallic catalyst, the catalytic performance of one component is promoted by the second component, and in our work, the catalytic performance of Co atoms in the bimetallic layer are improved by introducing Cu atoms, lowing the activation barrier of the reaction of C2H. The bimetallic layer could tune adsorption and reaction of C2H by modulating the ratio of Co and Cu. Results of adsorption energies and adsorption configurations reveal that C2H prefers to be adsorbed in parallel on both the pure Co metallic and CoCu bimetallic layers, and Co atoms in subsurface which support the metallic or bimetallic layer have little effect on C2H adsorption. For hydrogenation reactions, the products greatly depend on the concentration and initial positions of hydrogen atoms, and the C2H hydrogenation forming acetylene is more favorable than forming vinylidene in both thermodynamics and kinetics. This study would provide fundamental guidance for hydrocarbon reactions on Co-based and/or Cu-based bimetallic surface chemistry and for development of new bimetallic catalysts.

HyPEP FY06 Report: Models and Methods

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

DOE report

2006-09-01

The Department of Energy envisions the next generation very high-temperature gas-cooled reactor (VHTR) as a single-purpose or dual-purpose facility that produces hydrogen and electricity. The Ministry of Science and Technology (MOST) of the Republic of Korea also selected VHTR for the Nuclear Hydrogen Development and Demonstration (NHDD) Project. This research project aims at developing a user-friendly program for evaluating and optimizing cycle efficiencies of producing hydrogen and electricity in a Very-High-Temperature Reactor (VHTR). Systems for producing electricity and hydrogen are complex and the calculations associated with optimizing these systems are intensive, involving a large number of operating parameter variations andmore » many different system configurations. This research project will produce the HyPEP computer model, which is specifically designed to be an easy-to-use and fast running tool for evaluating nuclear hydrogen and electricity production facilities. The model accommodates flexible system layouts and its cost models will enable HyPEP to be well-suited for system optimization. Specific activities of this research are designed to develop the HyPEP model into a working tool, including (a) identifying major systems and components for modeling, (b) establishing system operating parameters and calculation scope, (c) establishing the overall calculation scheme, (d) developing component models, (e) developing cost and optimization models, and (f) verifying and validating the program. Once the HyPEP model is fully developed and validated, it will be used to execute calculations on candidate system configurations. FY-06 report includes a description of reference designs, methods used in this study, models and computational strategies developed for the first year effort. Results from computer codes such as HYSYS and GASS/PASS-H used by Idaho National Laboratory and Argonne National Laboratory, respectively will be benchmarked with HyPEP results in the following years.« less

Final Report: Investigation of Catalytic Pathways for Lignin Breakdown into Monomers and Fuels

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

Gluckstein, Jeffrey A; Hu, Michael Z.; Kidder, Michelle

2010-12-01

Lignin is a biopolymer that comprises up to 35% of woody biomass by dry weight. It is currently underutilized compared to cellulose and hemicellulose, the other two primary components of woody biomass. Lignin has an irregular structure of methoxylated aromatic groups linked by a suite of ether and alkyl bonds which makes it difficult to degrade selectively. However, the aromatic components of lignin also make it promising as a base material for the production of aromatic fuel additives and cyclic chemical feed stocks such as styrene, benzene, and cyclohexanol. Our laboratory research focused on three methods to selectively cleave andmore » deoxygenate purified lignin under mild conditions: acidolysis, hydrogenation and electrocatalysis. (1) Acidolysis was undertaken in CH2Cl2 at room temperature. (2) Hydrogenation was carried out by dissolving lignin and a rhodium catalyst in 1:1 water:methoxyethanol under a 1 atm H2 environment. (3) Electrocatalysis of lignin involved reacting electrically generated hydrogen atoms at a catalytic palladium cathode with lignin dissolved in a solution of aqueous methanol. In all of the experiments, the lignin degradation products were identified and quantified by gas chromatography mass spectroscopy and flame ionization detection. Yields were low, but this may have reflected the difficulty in recovering the various fractions after conversion. The homogeneous hydrogenation of lignin showed fragmentation into monomers, while the electrocatalytic hydrogenation showed production of polyaromatic hydrocarbons and substituted benzenes. In addition to the experiments, promising pathways for the conversion of lignin were assessed. Three conversion methods were compared based on their material and energy inputs and proposed improvements using better catalyst and process technology. A variety of areas were noted as needing further experimental and theoretical effort to increase the feasibility of lignin conversion to fuels.« less

The Local ISM and its Interaction with the Winds of Nearby Late-type Stars

NASA Technical Reports Server (NTRS)

Wood, Brian E.; Linsky, Jeffrey L.

1998-01-01

We present new Goddard High-Resolution Spectrograph (GHRS) observations of the Ly-alpha and Mg II absorption lines seen toward the nearby stars 61 Cyg A and 40 Eri A. We use these data to measure interstellar properties along these lines of sight and to search for evidence of circumstellar hydrogen walls, which are produced by collisions between the stellar winds and the Local InterStellar Medium (LISM). We were able to model the Ly-alpha lines of both stars without hydrogen-wall absorption components, but for 61 Cyg A the fit required a stellar Ly-alpha, line profile with an improbably deep self-reversal, and for 40 Eri A the fit required a very low deuterium-to-hydrogen ratio that is inconsistent with previous GHRS measurements. Since these problems could be rectified simply by including stellar hydrogen-wall components with reasonable attributes, our preferred fits to the data include these components. We have explored several ways in which the hydrogen-wall properties measured here and in previous work can be used to study stellar winds and the LISM. We argue that the existence of a hydrogen wall around 40 Eri A and a low H I column density along that line of sight imply that either the interstellar density must decrease toward 40 Eri A or the hydrogen ionization fraction (chi) must increase. We find that hydrogen-wall temperatures are larger for stars with faster velocities through the LISM. The observed temperature-velocity relation is consistent with the predictions of hydromagnetic shock jump conditions. More precise comparison of the data and the jump conditions suggests crude upper limits for both chi and the ratio of magnetic to thermal pressure in the LISM (alpha): chi less than 0.6 and alpha less than 2. The latter upper limit corresponds to a limit on the LISM magnetic field of B less than 5 micro G. These results imply that the plasma Mach number of the interstellar wind flowing into the heliosphere is M(sub A) greater than 1.3, which indicates that the collision is supersonic and that there should therefore be a bow shock outside the heliopause in the upwind direction. Finally, we estimate stellar wind pressures (P sub wind) from the measured hydrogen-wall column densities. These estimates represent the first empirical measurements of wind properties for late-type main-sequence stars. The wind pressures appear to be correlated with stellar X-ray surface fluxes, F(x), in a manner consistent with the relation P(wind) varies as F(x)(exp -1/2), a relation that is also consistent with the variations of P(sub wind) and F(sub x) observed during the solar activity cycle. If this relation can in fact be generalized to solar-like stars, as is suggested by our data, then it is possible to estimate stellar wind properties simply by measuring stellar X-rays. One implication of this is that stellar wind pressures and mass-loss rates are then predicted to increase with time, since F(sub x) is known to decrease with stellar age.